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HYDROCARBONS AND AIR POLLUTION:
1 AN ANNOTATED BIBLIOGRAPHY ;;
{,•:?. • '•-•' '* W -^ r
Part I. Categories A to E
O 4 ",.v •- .
U. S. DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE
Public Health Service
Environmental Health Service
-------
AP75A
HYDROCARBONS AND AIR POLLUTION:
AN ANNOTATED BIBLIOGRAPHY
PART I
Office of Technical Information and Publications
Air Pollution Technical Information Center
U.S. DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE
Public Health Service
Environmental Health Service
National Air Pollution Control Administration
Raleigh, North Carolina
October 1970
-------
The AP series of reports is issued by the National Air Pollution Control Adminis-
tration 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 NAPCA intramural activities and of cooperative studies con-
ducted in conjunction with state and local agencies, research institutes, and indus-
trial organizations. Copies of AP reports maybe obtained upon request, as
supplies permit, from the Office of Technical Information and Publications,
National Air Pollution Control Administration, 1033 Wade Avenue, Raleigh, North
Carolina 27605.
National Air Pollution Control Administration Publication No. AP-75
For sale by [he Superintendent of Documents, U.S. Government Printing Offict
Washington, B.C. 20402 - Price S5 per two volume .et
11
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CONTENTS
PART I.
INTRODUCTION 1
ANNOTATED BIBLIOGRAPHY
A. General . . 3
B. Emission Sources 19
C. Atmospheric Interaction 193
D. Measurement Methods . . . 227
E. Control Methods . 467
PARTH.
F. Effects - Human Health 583
G. Effects - Plants and Livestock 737
H. Effects - Materials 771
I. Effects - Economic 777
j. Air Quality Measurements 781
K. Legal and Administrative 849
L. Standards and Criteria 865
M. Basic Science and Technology 877
AUTHOR INDEX 1041
TITLE INDEX 1061
SUBJECT INDEX 1147
GEOGRAPHIC LOCATION INDEX 1181
United States 1181
Foreign 1182
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HYDROCARBONS AND AIR POLLUTION:
AN ANNOTATED BIBLIOGRAPHY
INTRODUCTION
As the level of air pollution attributed to automotive and stationary sources
increases, so does the necessity to extend our knowledge of hydrocarbon pollutants.
Certain hydrocarbon derivatives may have direct carcinogenic effects on lung
tissue. One of the ma^or concerns -with hydrocarbons as pollutants, however, is in
the indirect effects attributed to their role in the formation of smog through photo-
chemical reactions -with other substances. Photochemical smog has been associated
with plant damage, eye and respiratory tract irritation, and reduced atmospheric
visibility.
In urban areas, aerosols and exhaust gases have been found to contain not
only parafinic, aromatic, acetylenic, and olefinic hydrocarbons but also ketones,
aldehydes, phenols, alcohols, and halogenated hydrocarbons.
This bibliography represents an effort to collect, condense, and organize the
literature on the hydrocarbons in relation to air pollution. The approximately
2,300 documents abstracted here are all included in the information storage and
retrieval system of the National Air Pollution Control Administration's (NAPCA)
Air Pollution Technical Information Center (APTIC). Most of them are from
recent literature (1959-1970); however, some -were -written earlier in this century.
The abstracts are arranged in 13 categories listed in the table of contents.
Each category is designated by a letter of the alphabet; each abstract is designated
by its APTIC accession number. Since accession numbers are assigned as litera-
ture is received in APTIC, recent literature will more likely bear higher accession
numbers.
A subiect index, a geographical location index, an author index, and a title
index follow the abstracts; they refer to the abstracts by category letter and APTIC
number. The author index lists the first and second authors separately; -when there
are two or more, the first author is indicated by an asterisk (*). The geographical
location index has two major divisions; United States, and Foreign.
This bibliography is composed of selected references. It is intended as a
balanced sample of available literature, and no claim of all-inclusiveness is made.
All documents abstracted herein are on file at the Air Pollution Technical
Information Center, 1033 Wade Avenue, Raleigh, North Carolina. Readers outside
NAPCA may secure duplicates of the abstracted documents from libraries,
publishers, or from the authors.
-------
A. GENERAL
00164
STATISTICS ON PARTICULATE CONTAMINANTS - SAN DIEGO COUNT* AIR
POLLUTION CONTROL DISTRICT (FIRST QUARTER 1966). San
Diego Dept. of Public Health, Calif. Bar. 1966. 7 pp.
First Quarter 1966 Statistics on Participate Contaminants
San Diego County Air Pollution Control District are
presented. Data are included on weight concentrations from high
volume filter samples, soiling indexes, and hourly averages of
gaseous contaminants.##
00233
W.L. Faith
THE NATURE, SOURCES, AND FATE OF AIR CONTAMINANTS. J. Air
Pollution Control Assoc. 13, (10) 483-5, Oct. 1963.
(Presented at the 56th Annual Meeting, Air Pollution Control
Association, Detroit, Mich., June 9-13, 1963.)
A brief synopsis of air pollution specifying the types of
pollutants, their habitat, the importance of aerosols and gases,
and effect of meteorology on air pollution is presented. In
broad terms, the problem of air pollution as it relates to health
impairment is discussed.##
00599
J.J. schueneman
THE NEW JERSEY AIR SANITATION PROGRAM - A REVIEW AND
PROPOSALS FOR THE FUTURE. Preprint. 1964.
In order ot carry on a reasonably adequate air resource
management program which will insure a desirable air
supply for the State and provide for continuing growth
of population, industry and commerce, a major expansion
of activities of the Air Sanitation Program is needed.
Major decisions concerning land and air use, degree of
control of air pollutant emissions, economics and public
welfare must be amde in the next few years. Some of these
(for example: auto exhaust control; sulfur compound,
nitrogen oxides and odor control; refuse disposal problems)
involve potential expenditures in the hundreds of millions of
dollars. It would be wise to spend enough money on evaluation
•13-
-------
of the situation, effects of pollution, education of the public,
and study of control problems to provide a sound basis for
these decisions. It is further essential that adequate
expenditures be made to implement the measures found to
be necessary. While it is impossible to arrive at an
entirely adequate estimate on the basis of the work
done in this review, it appears that the Air Sanitation
Program should be allocated about $900,000 per year and
be staffed with about 75 people. This amounts to about
15 cents per capita per year, based on the 1960 population.
The present budget of $190,000 per year (3 cents per capita),
is grossly inadequate. The proposed level should be reached
in stages ov.er a period of three years of expansion. (Author's
abstract) f #
00984
S. Tilson
AIR POLLUTION. Intern. Sci. Technol. No. 42:22-31, 1965.
The problem and the approaches to solving it are reviewed.
Pollution sources, research, air quality criteria, the need for
controls, social attitudes, standards, photochemical reactions,
and future prospects are included.##
01073
V.G. MacKenzie
AIR POLLUTION - WHOSE PROBLEM? Preprint. (Presented at A
Panel Discussion on Air Pollution at the Board of
Directors Meeting, National Petroleum Refiners Association,
Washington, D.C., Sept. 20, 1965.)
The need for conservation of air as a natural resource is
discussed, with emphasis on the role of the petroleum industry.
Wats and means for improving on past patterns of conservation
effort through Federal authority under the Clean Air Act,
establishment of automotive emission standards, and application
of technology, to control of sulfur oxides and automotive emissions
are delineated. Attention is called to the need for research
on oxides of nitrogen and lead contamination. It is suggested
that business leaders, by their leadership in research and
education, can play a significant part in alleviating environmental
health problems.##
01211
J. A. Maga
AIR RESOURCE MANAGEMENT IN THE SAN FRANCISCO BAY AREA.
(California State Dept. of Public Health, Bureau of Air
Sanitation). California Oniv., Berkeley, Inst. of
Governmental Studies. 1965. «2 pp.
Author reviews the problems of air pollution in the San
Francisco Bay Area, stressing the need for effective air
HYDROCARBONS AND AIR POLLUTION
-------
quality standards. Topics covered in 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 Pollution 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.tt
01378
I. Baxter
DETERMINATION AND SIGNIFICANCE OF GASEOUS FUEL OCTANE
NUMBERS. J. Eng. Power, Vol. 87:166-168, April 1965.
(Presented at the Oil and Gas Power Conference and
Exhibit, American Society of Mechanical Engineers, Dallas,
Tex., Apr. 12-16, 1964, Paper No. 64-OGP-6.)
Gaseous fueled engines have for many years been built without an
undue concern for the octane number of the fuel, as long as it
contained a substantial amount of methane. The steady
increase in engine power ratings in recent years has made the
determination of octane numbers on specific gas mixtures desirable.
The introduction of turbocharging for gas engines places further
stress on fuel quality. A standardized apparatus and technique
for determining octane numbers of gaseous fuels in the ASTM-CFR
knock test engine is available. The means for making such
rating are described. While ratings on mixtures of saturate
hydrocarbon gases can be calculated with acceptable accuracy, the
presence of unsaturates or of antiknock additives make an engine
test necessary. (Author abstract)f#
016KO
M. Katz
SOME ASPECTS OF THE PHYSICAL AND CHEMICAL NATURE OF AIR
POLLUTION. World Health Organization Monograph Ser.
(Air Pollution). No. 46 1961. pp. 97-158.
This chapter of the WHO Monograph reviews works on air
pollution accomplished within the last ten to 15 years. The
subject of the physical and chemical nature of air pollution is so
broad and covers many fields of physics, chemistry and medicine
that only the most important works have been highlighted.
Discussed among others were the following problems: The
development of improved methods and techniques for the measurement,
separation and identification of air contaminants, the
standardization of methods of sampling and analysis of common air
pollutants, the application of meteorological concepts and
diffusion theory to the study of the dispersion of pollutants in
the atmosphere, the formation of smog'and the prediction of
pollution levels, the development of improved analytical
techniques, instrumentation and studies of motor vehicle exhaust
gas composition under, various operating conditions and the
development of catalytic and other exhaust gas system control
devices, the study of the action of sunlight on motor vehicle and
traffic gas and of photochemical atmospheric reaction in general.
A. General
-------
the determination of the health and other effects of irradiated
gaseous and vapour pollutants, the continued study of carcinogenic
and other toxic substances presented in the urban environment and
the evaluation of their effects on health, and the study of
radioactive pollutants and their effects in connection with the
development of industrial uses of nuclear energy for power and
transportation.##
02237
J.P. Dixon J.P. Lodge
AIR CONSERVATION REPORT REFLECTS NATIONAL CONCERN. Science
148, 1.060-6, May 21, 1965.
Pollutants, sources, political and economic factors, and the
role of scientists in the formulation of public policy is
examined in the light of present knowledge.##
02951
A. C. Stern
AIR POLLUTION AND ITS ABATEMENT IN THE UNITED STATES. De
Ingenieur 77, (29) G83-93, July 16, 1965 and 77, (31) G97-104,
July 30, 1965. (Presented before the Dept. for Public Health
Engineering, Royal Inst. of Engineers, Hague,
Netherlands, July 3, 1964.)
'i
In the United States, visible smoke is no longer a major
problem. Present concern is principally with gases; their
chemical reactions in the atmosphere; the effects of both gases and
reaction products on humans, animals, plants, materials and
visibility; and their abatement. Considerable emphasis is placed
on the relation of meteorological conditions to air pollution
levels. Forecasting of weather conditions conducive to build—up
of pollution is now done routinely in the United States.
Although air pollution research is conducted nationally, abatement
is on local basis. The new Federal Clean Air Act seeks to
improve the effectiveness of local agencies, and to provide for
Federal abatement of interstate air pollution. (Author summary)
03058
A. P. Altshuller.
AIR POLLUTION: PHOTOCHEMICAL ASPECTS. Science 151, (3714)
1105-6, Mar. 4, 1966
This paper gives a brief summary of presentations at the
Symposium on the photochemical aspect of air pollution, which was
held April 1965 in Cincinnati, Ohio. Topics ranged from the
measurement of solar radiation in the ultraviolet region of the
biological aspects of irradiation of model systems in the
laboratory to the relation between meteorological parameters and
chemical effects in polluted atmospheres.#f
HYDROCARBONS AND AIR POLLUTION
-------
03085
i.e. Stern
PRESENT STATUS OF ATMOSPHERIC POLLUTION IN THE UNITED STATES.
Am. J. Public Health (Presented at the 86th Annual
Meeting, American Public Health Association, St. Louis,
Mo., Oct. 29, 1958.) 50, (3) 346-56, Bar. 1960
The status of air pollution in the,United States is reviewed
in terms of knowledge availabe and action taken to deal with
this problem. Studies by the National Air Sampling
Network, state, and local health agencies are reviewed.
Facilities for training persons for air,pollution work ,are
discussed, andtthe Federal Air Pollution Engineering
Research and Technical Assistance Program is surveyed.
(Author abstract)f #
03205
D. Epstein.
DETECTION AND PREVENTION OF'. AIR POLLUTION IN THE DSSR.
Detection et prevention de la pollution atmospherique en U.R.S.
S. Pollut. Atmos. (Paris) 8, (31) 273-83, Sept. 1966.
The problems of the toxic amounts of air pollutants (CO, S02,
H2S01, NO, and 3, U-benzopyrene) are described and the
criteria for standardization in Russia'given. The methods for
detecting toxic proportions of these,pollutants are given in
detail, the techniques used for animal experimentation, and studies
of the tests applicable to mankind and the techniques of applying
them are described in particular. The paper mentions that since
chronaxie was judged insufficiently sensitive, the Soviet authors
resorted to electroencephalcgraphic methods which reveal an
electrocortical reflex for small amounts of polluting agents.
These tests involving instantaneous maximum admissible
concentration are supplemented by statistically analyzed
experiments on animals.'" (Author summary) *#
03U01
F. Bonamassa
DESIGN CONSIDERATIONS OF A PHOTOCHEMICAL-ATMOSPHERE
ENVIRONMENTAL TEST FACILITY. Am. SOC. Testing Mater.,
Spec. Tech. Publ. 352, 32-9 pp., Dec. 1963. (Presented
at the Symposium on Air-Pollution Measurement Methods,
Los Angeles. Calif., Oct. 5, 1962.)
A photochemical-atmosphere environmental test facility is a
system designed to stimulate in the laboratory conditions
existing in polluted atmospheres. These test environments are
finding increasing .applications in studying the effects of
contaminated atmospheres on humans, animals, plants, or
inaminate objects; evaluating air-pollution control systems;
establishing air quality standards and permissible contaainant-
A. General
-------
emission levels; idenitfying atmospheric pollutants and their
reaction products; and investigating the mechanisms of
reactions of polluted atmospheres. Many interdependent
factors influence the design of a photochemical-environment
test facility. Careful study of the proposed experimental program
and its objectives is needed to determine the required test volume
and operating conditions. The design and choice of
construction materials reflect certain compromises, usually
dictated by the relative importance of the various test conditions.
Although probably no simulated photochemical atmosphere can ever
completely reproduce all the conditions of the natural.
atmosphere, enough control over significant variables can be
achieved to enable the test environment to assume an
increasingly important role in increasing our understanding of
the complex reactions and effects of photochemical air pollution
and in providing much needed information for its effective
control.ftt
03«38
B. C. Blakeney and n. D. High.
CLEANER AIR FOR NORTH CAROLINA (A SURVEY AND APPRAISAL FOR AIH
POLLUTION PROBLEHS). North Carolina State Board of
Health, Raleigh, Div. of Sanitary Engineering and Public
Health Service, Washington, D.C. Div of Air Pollution.
Sept. 1959. 62 pp.
The most frequently occurring air pollution problems attributed to
industrial and municipal establishments results from emissions of
smoke, soot, or fly ash from fuel burning equipment. The
lumber, wood and furniture industries are frequently sources of
dust. Asphalt paving material plants create more acute
air pollution problems than any other industry. Pulp and paper
mills are the cause of odor complaints and are considered the cause
of some property damage. A variety of waste disposal operations
emit excessive smoke and odors. In eight cities, open dumps have
caused complaints and in five cities semi-landfills (burning before
covering) have resulted in public request for relief. Control
of gases, dusts, and other pollutants cannot be legally required
by the State except through the Nuisance Code or indirectly
through some other statue. The lack of specific State
legislation limits the control of air pollution to the
jurisdictional area of a few cities, whereas pollution of community
air is not confined to man-made boundaries or jurisdiction.
Existing and potential air pollution problems requiring further
investigation are discussed.t#
035U7
M. W. Korth, H. cT Steward, R. C. Stahman
DEVELOPMENT OF A CYCLE CONTROLLER FOE CHASSIS DYNAMOMETER.
Preprint. (Presented at the 57th Annual Meeting, Air
Pollution Control Association, Houston, Tex., June 21-25,
196«, Paper No. 64-82.)
HYDROCARBONS AND AIR POLLUTION
-------
A closed-loop speed feedback ccntroi system has been
developed for a chassis dynamometer; the system permits precise
speed control of an automobile following a cycle that represents
average driving conditions. This system, when used in
conjunction with a variable-length cruise-mode device, permits
the generation of consistent exhaust emissions from an automobile
being used to charge large irradiation chambers with dilute
exhaust gas during lengthy air pollution experiments. The
application of this control system is being extended to include
operation with a range of vehicles having widely varying power and
response characteristics, (Author abstract)##
03556
M. Katz.
SOME TOXIC EFFECTS OF AIR POLLUTION ON PUBLIC HEALTH. Med.
Serv. J. (Can.) 16, 50«-25, June 1960.
Nature of atmospheric contamination is reviewed. Brief
descriptions are given of air pollution episodes, legislation,
epidemiology, sources of air pollution and their effect on health.
Air pollution research in Canada is summarized.##
03674
J. P. Lodge, Jr.
AIR POLLUTION (REVIEW OF APPLICATION OF ANALYSIS). Anal.
Chem. 33 (5) :3R-13R, Apr. 1961.
This review covers the years 1959 and 1960, which have seen great
activity in the air pollution research field. It supplements the
previous review, with the exception that the growth of the
literature has been so great that explicit coverage of
radioactive pollutants has been omitted from this review. The
trend toward increased interest in automotive exhaust and
atmospheric carcinogens, noted in the previous review, has
continued. In addition, there has been a renewal of interest in
atmospheric lead. For the most part, these observations hold only
for the United States. The bulk of research in Europe
continues to be directed toward improved methods for measurement
and control of sulfur dioxide and dust. Meetings and conferences
were numerous. The annual symposia organized by the Committee on
Air Pollution, American Chemical Society, featured sessions
on automotive exhaust and on polynuclear hydrocarbons in 1959, and
on photochemistry and fine particles in 1960. The Air Pollution
Control Association continued its regular schedule of meetings.
A conference on air pollution research was sponsored by the U.S.
Public Health Service in New Orleans in early 1960,
continuing a series of meetings intended primarily fpr the Public
Health Service contractors and grantees in the field. More
specialized meetings included a conference on dust in Vienna, one
on adhesion of fine particles at Leatherhead,
England, and a symposium at Oxford on atmospheric diffusion and
turbulence. Increasing public interest in air pollution resulted
in the publication of a large number of papers intended primarily
A. General
-------
for public consumption. These are too numerous and in general too
lacking in novelty to warrant mention here. On the other hand, a
substantial number of books and review articles of a general nature
were published having high scientific merit.##
04052
H. Haddad 'and J. J. Blooufield
ATMOSPHERIC POLLUTION IN LATIN AMERICA. Bol. Ofic. Sanit.
Panam. 58, 2U1-9, Sept. 1964. Sp. (Tr.) (Presented at the
Inter-Regional Symposium on Criteria for Air Quality and
Methods of Measurement, Geneva, Switzerland, Aug. 6-12, 1963.)
Latin America is an area which is experiencing a very rapid
population and industrial expansion. Although this growth is very
irregular, the cities which exceed a million inhabitants and the
industrial concentration in them is growing yearly. This
phenomenon has resulted in serious problems of air pollution in
Sao Paulo, Brazil, Santiago, Chile, Mexico City, Mexico,
which are in need of further investigation and control as quickly
as possible. There are potential problems in Buenos Aires,
Argentina, and in all those large metropolitan centres which are
growing and industrializing rapidly. The situation created in
Lima, Peru, because of the fishmeal industry, seems to be fairly
well controlled. The greatest necessity is to train personnel
capable of conducting studies in measuring air quality and
controlling the contamination of the air. There is also a
necessity to create a consciousness of the seriousness of the
problem among government authorities and the public in general.
It is hoped that the future development of the Institute of
Occupational Health and Air Pollution Research in Santiago^
Chile, will contribute effectively to achieve these objectives.#f
OK212
S. Abe
THE PRESENT STATUS OF AIR POLLUTION. Clean Air Heat
Management (Tokyo) 15, (7-8) 7-18, Aug. 1966. Jap.
The present status of air pollution in Japan is given naming the
kinds of contaminants and their origin, factors affecting
contamination density, and various types of smog. The types of
contaminants are: 1) minute particles (less than 1 micron in size)
such as found in soot, carbon, ashes, dust; 2) coarse particles
(greater than 1 micron in size), as found in dust, ashes,'and
minerals; 3) reactive substances found in mist, fog, and vapor
such as 502, S03, H2S, C02, CO, N02, N203, 03,
aldehydes, HC1, NH3, HF, Pb, Hg, Cd, As, Be and 3,
i*-benzpyrene. The contaminants originate from factories, chemical
plants, power stations, domestic heating, public baths, hotels,
laundries, dry cleaning establishments, hospitals, schools, and
public buildings. Also discussed are the human factors affecting
air pollution such as 'public awareness and interest, seasonal,
weekly, and daily changes in heating and cooking. Meteorological
aspects are covered such as wind direction and velocity, turbu-
lence, temperature, rain and snow. The types of smog found in New
York, London, Los Angeles, Pittsburgh, and Yokkaichi are
10 HYDROCARBONS AND AIR POLLUTION
-------
described. Graphs and tables list symptoms and diseases affecting
plants and humans and give the density of dust particles and
S02 in the main cities of Japan. Data on the sulfur content
of various oils produced by Japanese refineries and on the number
of Japanese automobiles produced is included for information on
emission sources of pollutants.##
041*87
B. T. Commins
CHEHISTRY OF TOWN AIR. Research (London) 15, 421-6, Oct.
1962.
A review of the chemistry of urban air pollution in London and
other cities is presented. Topics briefly discussed and
summarized included: sources of air pollutants; fuel combustion
principles; pollutant measurements; concentrations; air
pollutant properties; chemical reactions affecting air
pollution. Chief sources of air pollution are seen to be
fuels burnt for domestic, industrial and commercial heating, and
for power generation and transportation. The more important
pollutants are considered to be smoke (and associated particulate
matter including H2S04 and tar) S02, C02, oxides of
nitrogen, hydrocarbons, and ground deposits. The more important
meteorological factors affecting pollutant concentration are seen
to be timperature (highest in cold weather), turbulence and wind,
and temperature inversion. Factors which illustrate the
differences in air pollution characteristics to be found in
various cities are evident in a comparison between London and
Los Angeles, the latter being more affected by vehicular
exhaust contaminants and photochemical reactions than London where
the atmosphere contains more heating fuel exhausts such as S02
and smoke.##
06146
W. Rayher* and J. T. Middleton
THE CASE FOR CLEAN AIR (SPECIAL REPORT). Mill Factory 80,(4)
41-56, Apr. 1967,
The introduction in the form of a series of questions put to Dr.
Biddleton is of special interest in indicating the forward thrust
of the Federal government in air pollution control since he is the
Director of the National Center for Air Pollution Control
which has the responsibility for the administration of the Federal
air pollution control laws and regulations. His answers indicate
vigorous activity by the Federal authorities where local authori-
ties fail to act. The major provisions of the proposed Air
Quality Act of 1967 are outlined as well as the existing Federal
authority under the Clean Air Act of 1963. With this hack-
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 methods of control. In the section
A. General
-------
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.f#
06722
A. Goetz
PARAMETERS. Symp. Environ. bSmeasurements, Cincinnati, Ohio,
1963. (PHS Publ. No. 999-AP-15.) (July 1964). pp. 29-34.
Air and water as gaseous and liquid components of the environment
are considered essential ingredients for human, animal, and plant
life — ingredients that are also acted upon by these live forms.
Air and water are evaluated in terms of chemical and physical
parameters relating to their occurrence in the natural regenerative
and degradative cycle and to their physiological assimiliation.
Particulate pollutants and reactive gases are discussed.
Emphasis is given to the physical and chemical characteristics of
aerosols and their potential role as pollutants of environmental
significance. (Author's summary)t#
06723
J. S. Nader
DATA ACQUISITION SYSTEMS IN AIR QUALITY. Symp. Environ.
Measurements, Cincinnati, Ohio, 1963, (PHS Publ. No.
999-AP-15.) (July 1964). pp. 107-23.
Two major automated data acquisition systems are now being used in
the United States for air quality measurements. These systems,
operated by the Los Angeles County Air Pollution Control
District and by the U.S. Public Health Service (Continuous
Air Honitoring Program), are reviewed in detail; 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)##
06744
T. Suzuki
AIR POLLUTION IN JAPAN. Kulci Seijo (Clean Air - J. Japan.
Air Cleaning Assoc., Tokyo) 2, (2) 1-4, 1964. Jap.
The nature of air pollution in Japan has been changing.
-Pollution from the chemical industry, petroleum processing, and
automobiles has become more prevalent than dust and soot from coal
and heavy fuel oil. At present, the degree of air pollution is
indicated primarily by the amount of dust and soot fall and
concentration of S02 and floating dust, and secondarily by the
concentration of carbon monoxide, nitrogen oxides, and
hydrocarbons. Use of heavy oil and coal of very low grade Bakes
12 HYDROCARBONS AND AIR POLLUTION
-------
the situation worse. General considerations of the effects of
pollutants on the human body are given. Studies made by the
Yamaguchi Medical School on floating dust and S02 indicate a
correlation between concnetration and death rate. Mention is made
of the now familiar "Yokohama Asthma". It was found that in
Yokkaichi city, air pollution is especially heavy when the wind"
velocity is greater than 5 m/sec and S02 is highly concentrated.
The death rate from lung cancer in Hokkaido for 1950 to 1960 was
1.6 times as great as the mean value for the rest of Japan.
Maximum allowable concentrations of various pollutants are
tabulated for the United States, Soviet Union, and West
Germany.#f
07181
F. Begemann
TBITIUH IN THE ATMOSPHERE. Tritium in der atmosphare.
Umschau (Berlin) No. 22 741-2 (1966). Ger.
The current state of knowledge about tritium in the atmosphere is
reviewed. Tritium originates in the stratosphere through
bombardment of nitrogen and oxygen by cosmic radiation. Having a
half life of 12.3 years, it can be used as a tracer to study
various atmospheric problems. Since tritium is also contained in
radioactive fallout, the concentration has doubled every 1.5 years
during the last 12 years. Tritium is also found in methane in the
atmosphere, but this probably stems from a leak in an industrial
facility.ft
07204
S. Somazzi and G. Zezzo
LIQUID FUELS IN CENTRAL HEATING INSTALLATIONS FOR URBAN HEATING.
I Combustibili Liguidi Nelle Centrali Termiche per II
Riscaldamento Urbano. Fumi Polveri (Milan) 7 (4) , 79-84
(Apr. 1967) . (It.)
Various sources of energy used throughout the world are compared
for the years 1900 and 1960. In 1900, 57.8% carbon, 2.2%
petroleum, 38.7% wood, 1.0% natural gas, 0.1% hydroelectric energy,
and 0.2% other were used, whereas in 1960, 41.6% carbon, 26.6*
petroleum, 19.1% wood, 11.6% natural gas, 1.1% hydroelectric
energy, and 0.0% others were employed. A similar study in Italy
from 1920 to 1960 also shows that the use of petroleum has
increased. By 1970 it is estimated that 101.7 million tons of
combustible oil will be burned compared to 70 million tons in 1965.
The use of solid fuels is expected to decrease in the future and
liquid fuels such as petroleum and natural gas, as well as nuclear
energy will increase. Liquid fuels are divided into distillate
oils such as kerosene and gas oil and residual oil such as naphtha,
paraffins, and aromatic hydrocarbons. Air pollution results from
combustion of residual oil if the combustion chamber is not large
enough, if there is no turbulent mixing, and if the temperature is
not high enough to ensure complete combustion. The best source
A. General 13
-------
of fuel would be distilled gas oil with a low sulfur content. The
use of central heating systems in a manner which will produce
optimum conditions for heat output and eliminate air pollution is
mentioned.##
07599
Barnes, J. H., P. Bonnevie, G. H. Fair, P. J.
Lawther, M. Hollis, H. Laird, and R. Pavanello
MICROCHEHICAL POLLUTANTS IN THE ENVIRONMENT. Preprint, World
Health Organization, Geneva, Switzerland, ((20p.)), 1963.
(Paper No. WHO/PA/110.&3.)
An attempt is made by the World Health Organization to assess
the contamination of air, soil, food and water by the many organic
chemicals man synthesizes. The problem, with respect to air
pollution, is the contamination of air by the products of
combustion, complete and incomplete, of carbonaceous fuels and
their contained impurities. Pollution of industrial atmospheres
by synthetic organic chemicals and their intermediates is
common. The problems involved in this transient type of
pollution are likely to be local in extent and, since the chemical
concerned is already identified and its properties known,
precautions against its inhalation can be applied accordingly.
Pollution of the communal air by synthetic organic chemicals is
probably insignificant. It is doubtful whether the synthetic
pesticides, whether formulated as liquids or powders, can easily be
redispersed in inhalable form since their formulations and the
methods by which they are dispersed are designed to produce
maximum retention by the surfaces to which they are directed.
Emissions of synthetic organic chemicals by industry are likely to
be very small since they are prime products and not wastes.
Within a factory, any waste synthetic organic chemicals can be
destroyed in the same way as odoriferous gases. The
destruction of scrap organic material such as waste plastics ought
always to be complete and such material should never be burnt on
open dumps. There is good reason to deduce from investigations on
the pollution of air by motor vehicle exhausts that the ultimate
fate of organic matter in the air may be complete oxidation. Some
chemicals may take part in reactions by which irritant new
substances are formed as more or less long-lived intermediates.
This type of pollution can hardly be said to be due to synthetic
organic chemicals, but exemplifies what might follow the emission
into the air of truly synthetic chemicals.t#
07845
Parker, A.
WHAT'S IN THE AIR J. Inst. Fuel, 40 (315): 173-175, April
1967.
He each breathe about 35 Ib of air in a day, consume 3 to 4 Ib of
drinking water and 1 1/2 Ib of dry food. This provides energy by
oxidation of carbon and hydrogen of which the thermal value is
about 12,000 Btu. equivalent to that provided when 1 Ib of coal is
burnt. Some of this energy is given out as heat, say about 400
H HYDROCARBONS AND AIR POLLUTION
-------
Btu/h. Hecords of smogs in various countries since 1873 exist,
but that in London in 1952 had great effect leading to the
bSbeaver Report and the bSclean Air b8act, 1956. 2.7 million ton
of smoke were discharged into the air during 1938 in Britain, of
which 63% was from domestic sources, 10% from railways and 27% from
industry. This was reduced to 1.1 million tons in 1965-, of which
0.9 million, 80%, was from domestic sources. This reduction was
also helped by the rationing of coal.during the years of World
War II and by the desire for cleaner domestic heating methods.
<*.1 million tons of sulphur dioxide were discharged into the
atmosphere in Britain in 1938 and 6.4 million tons in 1965, but
the concentration of S02 in the air near the ground has stayed
the same. The problem is not yet solved. About 1t million
motor vehicles in the U. K. emitted perhaps 5 million tons of
carbon monoxide and 1/4 million tons of hydrocarbons in 1965.
The interaction of hydrocarbons, oxides of nitrogen and ozone, in
sunlight causes the smogs of Los Angeles in which visibility is
scarcely reduced and so they are of a different character from
London smogs. The International Union of Air Pollution
Prevention Associations was recently founded. Its first
international clean air congress was held in London in October,
1966. (Author's abstract)**
08071
Gammelgard, P. N.
CURRENT STATUS AND FUTURE PROSPECTS — HEFINEBY AIR POLLUTION
CONTROL. Preprint, 13p., ((1966)). (Presented at the
National Conference on Air Pollution, Washington, D. C. ,
Dec. 13, 1966.)
The oil industry has been engaged in air conservation research and
practice for almost two decades, both through the efforts of
individual companies and through programs of its trade association,
the American Petroleum Institute. The present status and
prospective methods for controlling smoke, hydrocarbons, oxides of
sulfur, particulates, and carbon monoxide in the petroleum
industry are discussed briefly.##
08273
&IR POLLUTION AND THE UBIQUITOUS AUTO. Environ. Sci. Technol.,
1 (11) :878-880, Nov. 1967.
The recent report of the Commerce Department]s Panel on
Electrically Powered Vehicles is discussed. "The Automobile
and Air Pollution: A Program for Progress" details 16 specific
recommendations to serve as a basis for immediate action. There is
an urgent need for more extensive information regarding the
significance of specific and combined air pollutants on public
health. Little is known of the social and economic costs of air
pollution., The entire area of meteorological effects of air
pollutants, is speculative at present and only a beginning has been
made in the design of meaningful research programs. The panel
feels that (the Federal Government should continue to establish
A. General 15
-------
standards for all harmful automotive emissions and realistic
timetables tor the achievement of such standards.| Lead emissions
particularly concerned the panel, because of possible impact on
human health, increased levels of hydrocarbon in auto exhaust;
modification of atmospheric processes; and deactivation of
catalysts or absorbants which may be necessary to reduce emission
of other pollutants. The panel feels that the emission standards
should specify total mass of specific pollutants. The National
Center for Air Pollution Control in its current organization does
not appear appropriate for effective action. The panel would like
to see an advisory board at the highest departmental level. The
use of low pollution performance criteria rather than detailed
product specification in the vehicle procurement process would
provide strong incentives. To meet future emission standards, more
and better technology must be developed. The panel feels that:
During the next decade, in the normal course of events, no
significant reduction in total air pollution will be achieved
through the introduction of unconventional low-polluting vehicles.
Gas turbines are reasonable alternatives to internal combustion
engines in the large sizes used in trucks, trains, and buses.
Hybrid power plants might provide satisfactory performance.
Because two separate energy sources are needed, such hybrids might
be too expensive for private passenger autos.
09310
Kalika, Peter W.
THE GROWING PROBLEM. Mach. Des. , 39 (17) :19-21,
July 20, 1967.
The facts, figures, and concern about the national problem of .air
pollution are covered. Past air pollution episodes, sources and
types of pollutants released in the atmosphere, and the mechanisms
and characteristics of temperature inversions are reviewed.
09780
Environmental Science Services Corp., Stamford, Conn.
AIR POLLUTION CONTROL PRIMER. 35 p., ((1968)).
The main sources of air pollution are combustion processes,
especially internal combustion engines. in a general manner the
following are discussed: causes and effects of air pollution;
legal aspects; automobile emissions; fossil fuels and lead
additives; and control eguipment and its market potential.
11227
J. E. Yocom
AIR QUALITY. In: Instructional Material for the
Connecticut Air Pollution Simulation Model Program
16 HYDROCARBONS AND AIR POLLUTION
-------
Travelers Research Center, Inc., Hartford, Conn., 10p., 1968.
2 refs. (Presented at the TRC Seminar, Hartford, Conn.,
Oct. 12, 1968.)
The nature and composition of clean air itself is reviewed.
An almost infinite number of individual chemical compounds,
singly and in combination, and existing in a variety of
physical forms contribute to community air pollution. The most
important pollutants and classes of pollutants found in
majority of communities may be listed within five categories:
carbon monoxide, hydrocarbons, nitrogen oxides, sulfur oxides,
particulate matter. A discussion of each is presented to show
their sources and importance in air pollution problems.
Criteria background information which is required-prior to
setting air.quality criteria for 302 and other pollutants is
presented.#f
12177
John T. Middleton
AIR QUALITY AS A CONTROLLING FACTOR IN LIFE PROCESSES. In:
Biometeorology, Proceedings of the Twenty-Eighth Annual
Biology Colloquium, 1967, William P. Lowry (ed.) p. 67-79,
1967. (i») refs.
The quality of air is determined by the uses made of it and by
the pollutants injected into it by man. The quality of air
varies for a number of reasons, but principally because of
contaminants arising from economic and social developments
throughout the world. Air pollution is one of the undesirable
side effects of this growth and development. The extent,
severity, and character of man-made air pollution are determined
by the kind, number, and location of contaminant sources, the
chemical reactivity and interaction of the pollutants, the
topography of the land, the weather, the nature of the
community, and the characteristics of the airshed.**
14479
Biersteker, Klaas
AIR POLLUTION IN THE NETHERLANDS. Tijdschr. Soc. Geneesk.
(Assen), 47(3):66-70, Jan. 31, 1969. 24 refs.
In a survey conducted in 1965, all Dutch municipalities with
populations above 50,000 reported experiences with air pollution.
Many complaints center on local nuisances, particularly the odors
caused by a potato plant in Gronigen, textile industries in the
eastern part of the country, spice, timber, and oil operations
north of Amdsterdam, and oil refineries and phosphate plants in
Rotterdam. The odors are frequently a result of water pollution,
indicating a connection between the two types of pollution, at
least in the Netherlands. Because of the increasing concentration
of population and industries in the area comprising Rotterdam,
Amsterdam, and The Hague, a further increase in air pollution
problems is anticipated. Tables give the standard smoke
concentrations in central Rotterdam in the winter months for the
A, General 17
-------
years 1957 to 1968 and the 3,1-benzopyrene content at two
sampling stations in Rotterdam from 1961 to 1967. Also tabulated
are the distribution of Dutch municipalites according to the
number of inhabitants since 1900 and the population densities of
The Netherlands and other countries.
16523
Urrutia, D. Jose Llado Fernandez
ASPECTS OF INDUSTRIAL CONTAMINATION. (Aspectos de la contaminacion
industrial). Text in Spanish. Eev. San. Hig. (Spain), 43(9-10):
663-713, Sept.-Oct. 1969. (Pages 691-710 are pertinent to air
pollution.) (Presented at the Conference of the Sociedad de
Higiene y Hedicina Social, April 16, 1969.)
The industrialization processes, the increase in industrial water
and air pollution, the causes of contamination, and Spanish
legislation for the control of air and water pollution are
discussed. The principal atmospheric contaminants are carbon
oxides, sulfur oxides, nitrogen oxides, hydrocarbons, and
particulates. The amounts were estimated and it was found that
half of the pollutants are concentrated in the major cities. The
main sources of pollutants are 'automobiles, heaters, incinerators,
and industrial processes. Industrial emissions are not controlled
because of poor equipment, insufficient finances, and inefficient
legislation. Another important source is radioactive contamination
from laboratories, 'hospitals, and nuclear centers. The irritant
effects of pollutants on the eyes, nose, and throat were briefly
discussed. Foreign legislation was also briefly discussed.
Generally, foreign regulations prohibit the emission' of gases-and
smoke above certain pre-established limits, provide vehicle
emission standards and regulation of some control equipment.
Spanish legislation is scarce and inefficient. Old regulations
include provision for industries to emit noxious gases with the
consent of Sanitation inspectors and weekly atmospheric analyses'
for chemicals and bacteria. Other eld regulations prohibit
the establishment of vapor-producing industries within 500 m of
a town and a maxmimum emission limit for sulfur anyhydrides at
8 g/cu m. More recent legislation established maximum allowable
concentrations for smoke, particulates, sulfur anhydrides, and
carbon anhydrides, and an opacity index. The amounts of sulfur
allowed in combustible liquids for industrial use were prescribed.'
Carbon monoxide emissions from vehicles and dust emissions from
cement industries were also regulated. It was concluded that
public and industrial responsibility and enthusiasm for control
should be encouraging and more flexible, realistic legislation
should be passed.
18 HYDROCARBONS AND AIR POLLUTION
-------
B. EMISSION SOURCES
00020
0. R. Goldsmith and L. H. Rogers
HEALTH HAZARDS OF AUTOMOBILE EXHAUST. Public Health Rept.,
74(6):551-558, June 1959.
Of the substances which occur in automobile exhaust and their
reaction products,, hygienic standards have been established for
industrial exposure to carbon motaoxide, nitrogen dioxide, lead, and
ozone. Establishing a full set of levels for community exposures
to these substances is very difficult because of the sensitivity of
frail or ill individuals, the indeterminate period of exposure, the
effect of agents in combination, and the cumulative effect of
exposure from other sources, such as cigarette smoking. The
hazard of automobile exhaust to the population of a large community
will depend, among other things, on the extent and way that
vehicles are used, and the meteorology of the area. In the
absence of effective control for air pollution from automobile
exhaust, the public health hazard should be evaluated. (Author)#f
00027
A. H. Rose, Jr., H. Corn, R- R. Horsley, D. R.
Allen, and P. W. Kolp
AIR POLLUTION EFFECTS OF INCINERATOR FIRING PRACTICES AND
COMBUSTION AIR DISTRIBUTION. J. Air Pollution Control
Assoc. 8(4) .-297-309, Feb.1959.
The relationships between incinerator design criteria and
resulting atmospheric contaminant discharges were investigated...
Tests were made by burning a fuel of constant composition in a
prototype, multiple-chamber incinerator under controlled
conditions. Effects of variables were measured by analyzing the
flue gases for solids, hydrocarbons, oxides of nitrogen, and CO.
The series of tests reported was made to (1) provide information
on the relative importance of such variables as stoking and amount
of fuel per charge insofar as they affect the production of
atmospheric pollutants, and (2) evaluate the chosen levels of
variables such as excess combustion air, underfire and secondary
air distribution, and fuel charging rate. Production of
particulates was highly dependent on the amount of excess
combustion air and the percentage of this air entering under the
fuel bed. At the 50% excess air level, particulate discharge
increased when underfire air was increased from 15% to 30% of the
total combustion air. This did not hold true for the 150% excess
air level. Reduction of hydrocarbons and CO appeared to be
more dependent on the level of excess combustion air available than
19
-------
on its distribution between overfire, underfire, and secondary air.
These pollutants were produced under combustion with 50% excess
air but not with 150% excess. Production of oxides of nitrogen
depended on the rate of fuel charging- the amount of excess air,
and the gas temperature in the ignition zone. (Author)#t
00030
W. S. Smith
ATMOSPHERIC EMISSIONS FROM FUEL OIL COMBUSTION (AN INVENTORY
GUIDE). Public Health Service, Cincinnati, Ohio, Div. of
Air Pollution, (999-AP-2.) Nov. 1962. 102p.
This review provides a guide for the inventorying and control of
emissions arising from the combustion of fuel oil. Information
was collected from the published literature and other sources.
The report is limited to information on oil used as a source of
heat or power (exclusive of process heaters). The data were
abstracted, assembled, and converted to common units of
expression to facilitate understanding. From these data, emission
factors were established that can be applied to fuel oil combustion
to determine the magnitude of air-contaminating emissions. Also
discussed are the compositions of fuel oils; the preparation and
combustion of fuel oil; and the rates of emission, their variables,
and their control. (Author)##
00052
MOTOR VEHICLES, AIE POLLUTION AND HEALTH (A REPORT OF THE
SURGEON GENERAL TO THE U.S. CONGRESS IN COMPLIANCE WITH PUBLIC LAW
86-493, THE SCHENCK ACT). Public Health Service,
Washington, B.C., Div. of Air Pollution. June 1962. 463
pp.
"Motor Vehicles, Air Pollution, and Health" is a report
prepared by the Division of Air Pollution of the Public Health
Service as directed by the Congress in Public Law 86-i»93.
The Report is presented in three parts as follows: Part I.
Summary—A Review of the Problem; Part II. Effects of
Motor Vehicle Pollution on Health; Part III. Air
Pollution from Motor Vehicles. Part I summarizes current
information and theories of the nature of air pollution
resulting from emissions from motor vehicles. It also
examines approaches to the reduction of such pollution, and some
of the problems associated with control measures. Finally, it
presents an appraisal of the biological effects, proven or
potential, of such pollution. Part II reviews, in detail,
information which has been reported concerning the influence
of air pollution on health, with particular reference to the
effects from pollution arising from the operation of
motor vehicT.es. The results of mortality and morbidity surveys,
of laboratory research, and of other pertinent investigations
are given. The responses of vegetation and animals, as well as of
humans, to individual contaminants as well as to mixtures, such
20 HYDROCARBONS AND AIR POLLUTION
-------
as are encountered in the atmosphere, are examined. Part III
describes, in some detail, how motor vehicle operation elates to
emissions of pollutants, the magnitude of the pollution problem,
the nature of chemical reactions in the atmosphere, factors
affecting concentrations, methods for reducing pollution, and
the subject of ambient air and emission standards.*#
0005U
A STUDY OF AIR POLLUTION IN THE INTERSTATE REGION OF LEWISTON,
IDAHO, AND CLARKSTON, WASHINGTON. Public Health Service,
Cincinnati, Ohio, Div of Air Pollution. (999-AP-8.) Dec.
196«. 166p.
As a result of an increasing number of complaints from citizens
about reduced visibility, damage to house paint, tarnishing
of silver, undesirable odors, and suspected effects of air
pollution on health, Idaho and Washington and Leviston and
Clarkston officials requested assistance from the U.S. Public
Health Service. Subsequently, the Public Health Service, the
two states, and the two cities agreed to undertake a
cooperative study; the two cities participated in the study.
The purpose of the study was to determine the nature and extent
of air pollution in the two-city area and to assemble information
to be used as a basis for technical and official action needed to
conserve air quality in the area. Because of its unique valley
location, the two-city area is susceptible to meteorological
conditions conducive to pollutant accumulation. Either city
can contaminate the other, and this creates a multi-
jurisdictional problem that requires joint and cooperative action
to control air pollution. As a first step to solve the problem,
an Air Resources Management Council consisting of county,
city, and state officials is to be organized. This council
will be responsible for planning surveys and studies to determine
air quality guides and legislation and administration necessary
to control air pollution in this multi-jurisdictional area. The
Public Health Service in its advisory capacity will provide
technical assistance. (Author)ft
00081
R.T. Arnest
ATMOSPHERE CONTROL IN CLOSED SPACE ENVIRONMENT (SOB-MARINE)
Naval Medical Research Lab., New London, Conn., Bureau
of Medicine and Surgery, (Rept. No. 367.) Dec. It, 1961. 39
pp.
CFSTI, DDC: AD 270896
The purpose of this work was to make a general summary of the
toxicological problems associated with the closed space environment
of submarines and to review the current state of development of
tools for measuring and removing the problem substances involved.
Bore than twenty-five atmospheric contaminants are listed, their
sources, and their maximum allowable concentrations (MAC) are
given, as well as the symptoms they cause, the long-term effects;
tools for measuring the amounts of contaminants present are
described and methods of removal indicated, in so far as known.*t
B. Emission Sources 21
-------
00107
S. S. Griswold
CONTROL OF STATIONAEY SOURCES (TECHNICAL PHOGRESS REPT, 70LOBE
1). Los Angeles County Air Pollution Control District,
Calif. Apr. 1960. 191 pp.
As a result of the intensive source control measures adninistered
in Los Angeles County, Virtually all industrial operations have
been brought within the scope of the air pollution control
program. From the melting of metal to the painting of
manufactured goods, specific industrial processes and equipment
have been subject to air pollution control measures. This volume
provides individual discussion of control techniques applied to the
most significant stationary sources of air contamination. Certain
source emission problems, such as those traceable to the operation
of railroad locomotives and ships, are not discussed in this volume
in view of the current unimportance of the source. The material
reported in this volume generally contains only those developments
occurring subsequent to the publication of the Second Technical
and Administrative Report on Air Pollution Control in Los
Angeles County, 1950-51. (Author.) **
00109
A. P. Altshuller
REACTIVITY OF ORGANIC SUBSTANCES IN ATBOSPHERIC PHOTOOXIDATION.
Public Health Service, Cincinnati, Ohio, Division of Air
Pollution.(999-AP-14.) July 1965. 29 pp.
The organic vapors emitted to urban atmospheres by motor vehicles
and other sources of emissions consist not only of paraffinic,
acetylenic, aromatic, and olefinic hydrocarbons, but also of
aldehydes, ketones, alcohols, phenols, and chlorinated
hydrocarbons. To estimate the contribution of each of these
classes of compounds to photochemical smog, one must know both
their atmospheric concentrations and their relative reactivities in
atmospheric reactions. A review of the available literature on
concentration levels of organic vapors in urban atmospheres
indicates that much more analytical work is needed. The existing
data are adequate, however, for the formulation of useful
estimates. Reactivities of organic substances in photooxidation
reactions can be considered from many standpoints. Rates of
disappearance of the organic substances, rates of disappearance of
nitric oxide or of formation and disappearance of nitrogen dioxide,
and rates or maximum yields of various products such as oxidant or
organic nitrates all can be used as chemical measurements of
reactivity. Eye irritation, various types of plant damage, and
aerosol formation are indicators of reactivity that can be related
only to a limited extent to chemical measurements of reactivity.
The problems of developing a single index of reactivity are
considered. The application of reactivity measurements to
automobile exhaust composition, to control devices, and to
improvements in atmospheric purity is discussed. (Author)#*
22 HYDROCARBONS AND AIR POLLUTION
-------
0015«
Beckman, E. H., W. S. Fagley, and Jorma 0. Sarto
EXHAnST EHISSIOH CONTROL BY CHRYSLE8 - THE CLEANER AIR PACKAGE.
In: Vehicle Emissions, Part II, SAE Progress in
Technology Series, Vol. 12, New York, Society of Automotive
Engineers, Inc. 1966, p. 178-191. 16 refs. Also: 90th
Congress ("Air Pollution—1967, Part I (Automotive Air
Pollution) " Hearings before the Subcommittee on Air and Water
Pollution of the Committee on Public Works, U.S. Senate,
Feb. 13-14, 20-21, 1967, p. H11-421.)
Air pollution problems in California required control of
vehicle exhaust emissions. The early development of catalytic
converters and direct flame afterburners led to relatively complex
mechanisms with substantial added cost to the vehicle. An
evaluation of the primary factors affecting exhaust emissions
indicated the feasibility of control by engine modification alone.
A series of engine modifications were subsequently developed
which reduced the exhaust emissions to below the California
standard of 275 ppm hydrocarbons and 1.5X carbon monoxide. bSthe
primary changes were to employ optimum combinations of fuel-air
mixture and spark timing at all operating conditions. These
changes are known as the "cleaner Air Package" (CAP).
50,000 mile tests indicated that with normal maintenance the
exhaust emissions were stable and remained at a low level. The
CAP system was put into production on 1966 model Chrysler
Corporation passenger cars and light trucks marketed in
California.##
00171
THE CONTROL OF AOTOHOBILE EMISSIONS. (FORD CRANKCASE
EHISSIONS CONTROL SYSTEM. FORD THEHBACTOR SYSTEH FOR EXHAUST
CONTROL.) Ford Motor Co., Dearborn, Mich., Engineering
Staff. 1966. 6 pp.
An explanation of both Ford's Engine crankcase Ventilation and
Thermactor Exhaust Emissions Control Systems, complete with
schematic drawings of cross-sections of the automobile engines is
presented. The rationale for its development, the chemistry
involved, and the future implications of the systems are
discussed.tf
00186
J. H. Ludwig
SEMINAR ON AIR POLLUTION BY MOTOR VEHICLES. Public Health
Service, Cincinnati, Ohio, Division of Air Pollution. 1966.
52 pp.
B. Emission Sources 23
-------
The contribution of motor vehicle emissions to community-wide air
pollution is discussed and related to other factors involved in air
pollution such as commercial and industrial sources, the size of
-he community and source distribution, topographical and
meteorological factors, and the degree of control exercised on
the sources. In particular, one section of the publication
analyzes the different pollutant types emitted from diesel and
gasoline engines. Another section discusses the photochemical
reactions in the atmosphere kncwn to produce air pollutants.f#
00220
J. P. Sheehy, J. J. Henderson, C. I. Harding, and A.
L. Danis
AIR POLLUTION IN JACKSONVILLE, FLORIDA (A PILOT
STDDY - AUG.-SEPT. 1961). Public Health Service,
Cincinnati, Ohio, Div. of Air Pollution (AP-3). Apr.
1963. 65 pp.
GPO: 802-899-6
The objectives of this pilot study were: (1) To develop a
preliminary opinion as to whether the city of Jacksonville has a
generalized air pollution problem. (2) To determine whether
certain pollutants - fluorides and S02, were present in the
atmosphere in concentrations capable of producing the damage to
vegetation that had been experienced in the Jacksonville-Duval
County area. To accomplish the first objective, a one-week
intensive investigation was carried on in downtown Jacksonville,
at (emming Park, from August 3 to 10, 1961. To accomplish to
second objective, additional studies were conducted during the
periods August « to 12, and September 5 to 13, 1961, in the area
in which damage to vegetation had occurred. The two fertilizer
plants, located in the industrial area of Jacksonville, were not
in production during the first phase of this study. Pollutants
sampled in this study included fluorides, S02, H2S, N02,
nitrogen dioxide, and particulates. As a result of the
investigations it was concluded that: (1) Photochemical snog was
being produced in the air over Jacksonville. (2) Concentrations
of fluorides occurred in certain parts of Jacksonville during the
period of the study that could cause damage to sensitive plants.
(3) Pollutants from the city of Jacksonville can be transported
across the St. John's River. H2S concentrations measured
during this study were not of the magnitude known to cause
discoloration of paints containing lead pigments and/or mercury
base fungicides. Subsequent to the study, an incident of
darkening of paints occurred in the arlington area. Therefore, it
is evident that an H2S problem exists in this area. SO2
concentrations observed during this study did not reach levels
known to"cause damage to vegetation. However, it appears
possible for S02 concentrations to reach levels during the
heating season capable of causing damage to sensitive plants,
particularly in localized areas downwind of major sources of
S02.*#
24 HYDROCARBONS AND AIR POLLUTION
-------
00221
L. E. Reed, H. D. Fawell, and P. J. Lawther
VEHICLE EXHAUSTS AND HEALTH. Smokeless Mr, (London)
198-202, 1966. (Presented at the Royal Society of Health
Symposium, London, England, Feb. 16, 1966.)
A brief report is given of three papers on Vehicle Exhausts and
Health presented at the Hoyal Society of Health, London, Feb.
1966. Subjects covered include motor vehicle exhausts, petrol and
diesel engine emissions, and problems of controlling such
pollutants as hydrocarbons and carbon monoxide.##
00225
V.G, HacKenzie K. Flieger
THE CLEAN AIR ACT AMENDMENTS AND SOLID WASTE DISPOSAL ACT OF
1965 (P. L. 89-272). Health, Education, and Welfare
Indicators. Nov. 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 program 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
problem of air pollution.##
00268
E, H, Brice and J. F. Boesler
THE EXPOSURE TO CARBON HONOXIDE OF OCCUPANTS OF VEHICLES HOVING IN
HEAVY TRAFFIC. J. Air Pollution Control Assoc.
16(11):597-600, Nov. 1966. (Presented at the 58th Annual
Heeting, Air Pollution Control Association, San Francisco,
Calif., June 20-24, 1966.)
Carbon nonoxide and hydrocarbons were sampled at operator's nose
height inside vehicles moving in moderate to heavy traffic in six
cities. The samples were integrated over 20 to 30 minutes by
collection in Mylar bags. Carbon monoxide and hydrocarbons
were analyzed by infrared and flame ionization, respectively, with
instruments at the Continuous Air Monitoring Program (CAMP)
station in each city. Detector tubes for carbon monoxide were
also used to determine 5-minute concentrations at suspected high
points in the field. Estimates of traffic density were aade.
Three types of traffic arteries were considered: 1) heavily
traveled, wide expressways, 2) main city streets with moderately
rapid vehicular traffic, and 3) center city streets with
slow-moving traffic. Integrated half-hour CO concentrations
B. Emission Sources i 25
-------
obtained within the vehicles while in traffic were generally
considerably higher than the concurrent concentrations measured at
the CAMP sites. In-traffic CO values in all cities sampled
exceeded 30 ppm in at least 10% of the integrated samples. The
range of city averages was 21 to 39 ppm carbon monoxide and the
range of individual integrated samples was 7 to 77 ppm of carbon
monoxide. (Author abstract)ft
00271
W. F. McMichael and J. E. Sigsby, Jr.
AUTOHOTIVE EMISSIONS AFTER HOT AND COLD STARTS IN SUMMER AND
HINTEH. J. Air Pollution Control Assoc., 16 (9):U84-488,
Sept. 1966. (Presented at the 59th Annual Heeting, Air
Pollution Control Association, San Francisco, Calif., June
22, 1966.)
The 0. S. Public Health Service, as part of its continuing
investigations of automotive emissions, began a study early in 1965
to determine the effects of hot-start and cold-start engine
operation on exhaust emissions. This study was conducted in the
Cincinnati area in summer and winter ambient temperatures. The
effects of hot and cold starts on the mass and composition of
exhaust gases were compared. Emissions from the test vehicles
were measured in actual traffic with a proportional sampler. The
test route was developed in earlier work to represent average urban
driving conditions. Data from this study reflect the effects of
traffic density, route, and climate on hot-start and cold-start
engine operation. (Authors' abstract)ft
00288
H. C, Johnson, J. D. Coons, and D. M. Keagy
CAN MUNICIPAL INCINERATORS MEET TOMORROW'S REGULATIONS?
Preprint. (Presented at the 59th Annual Meeting, Air
Pollution Control Association, San Francisco, Calif., June
20-2U, 1966, Paper No. 66-131.)
Over the last two decades, Los Angeles, the San Francispo
Bay Area, and other Hest Coast areas have gone far beyond most
other parts of the country in the nature and extent of limitations
legally imposed on incinerator design and performance. Kith the
increasing population of these areas, and the problems of other
solid waste disposal methods, it seems prudent to consider whether
additional or tighter limitations may be imposed as rapidly as the
'technology permits. It is the purpose of this paper to consider
briefly some of the implications of these possibilities. It is,
therefore, primarily speculative in nature. Present and future
standards for incinerator emission control, incinerator performance
and design considerations are discussed. (Authors' abstract)*!
26 HYDROCARBONS AND AIR POLLUTION
-------
00319
SURVELLIANCE OF MOTOR VEHICLE EMISSIONS IN CALIFORNIA
(QUARTERLY PROGRESS REPT. NO. 1, JULY - SEPT., 1965).
California Dept. of Public Health, Los Angeles, Vehicle
Pollution Lab. Spet. 1965. 77 pp.
The 1966 model automobiles which are sold and registered in
California must be equipped with exhaust control systems or
control devices which will meet California standards for the
emissions of hydrocarbons and carbon monoxide. Although all
control systems were thoroughly tested prior to certification
these tests were performed on a limited number of
preproduction model cars and their performance in the hands of the
general public may differ substantially from that of the earlier
test vehicles. Moreover, since the maintenance requirements
recommended by the car manufacturers are not enforceable by
law, the effects of quality and frequency of voluntary
maintenance on emission levels need further study. Under the
Federal surveillance Grant the above conditions will be
investigated on a large sampling of cars at 3 separate surveillance
test stations in the Southern California area, each equipped
with a chassis dynamometer and an analytical sampling train for
the accurate determination of emission levels. The 1966
model vehicles equipped with exhaust control systems were not
available for testing during this report period. However,
test data were obtained and compiled on 2 groups of fleet
vehicles. In general, both groups of vehicles were driven
in a manner considered representative of the type of driving
expected of private owners. Servicing of the fleet vehicles
may have been different from the maintenance procedure of
private owners. Results of the survey are expressed in both
tabular and graphic form for cold and hot starts showing the
changes in emission levels of hydrocarbon and CO with respect
to mileage accumulation and/or engine adjustments. The data
are presented in categories by manufacturer. State-owned Fleet,
General Motors Corp., Ford Motor Co., American Motors,
2nternational Harvester, Kaiser-Willys. Data derived from the
testing of the fleet vehicles will provide a basic reference
pattern for comparing fleet-maintanined vehicles with: (1) the
1966 assembly line production models (with control system) sold
to private owners in California; (2) the 1965 unequipped vehicles
maintained by the general public. ##
0032i»
G. C. Hass, F. Bonamassa, P. Reward, N. Kayne
THE INFLUENCE OF VEHICLE OPERATING VARIABLES ON
EXHAUST EMISSIONS. J. Air Pollution Control Assoc. 17(6)
384-7, June 1967. (Presented at the 59th Annual Meeting, Air
Pollution Control Assoc., San Francisco,
Calif., June 20-21, 1966, Paper No. 66-69.)
This paper is a report of the operating variables and enission
characteristics of a 1961 283 cubic inch V-8 Chevrolet
B, Emission Sources 27
-------
automobile. This vehicle was used as a laboratory tool in a
project to develop an improved driving cycle to represent Los
Angeles peak hour driving. As a result it became necessary to
run many expoloratory tests to determine the relationships
between the primary variables of intake manifold vacuum,
engine rpm, and vehicle speeds and acceleration rates.
Emissions of hydrocarbons, carbon monoxide, and nitrogen oxides
were also determined for the entire range of operating conditions.
The effect of prior operating modes on closed-throttle
unburned hydrocarbon concentrations was also determined.
The results of these tests are presented in tables and
graphs which make a comprehensive picture of one typical
automobile as a generator of air pollutants. (Author's
abstract)##
00337
VJ. B. Grouse and N. E. Flynn
SOURCE INVENTORY IBM SYSTEM FOR PARTICIPATE AND GASEOUS
POLLUTANTS. Preprint. (Presented at the 59th Annual
Meeting, Air Pollution Control Association, San Francisco,
Calif., June 20-24, 1966, Paper No. 66-10.)
A source inventory IBM system of air pollutants is described
which makes use of an existing IBM card index-registration
system in an established air pollution control district and which
employs efficient utilization of engineering time, including
computer services, to establish and maintain current a detailed
source inventory of point sources of emissions. An emission
inventory specifies the (1) amounts, and (2) sources of air
pollution in a community. The knowledge of air pollution can be
relegated to three simple questions: (1) "What" the pollution
problem is in terms of primary air pollutants, (2) the "where" of
the problem — i.e., a description of the industrial, commercial,
or domestic sources by tabulation of either (a) types and location
of basic equipment discharging pollutants, (b) a description in
broad source categories of industry, or (c) actual tabulation of
locations of plants in the community, and (3) the "how
much" or extent of air pollutants. In the case of gases, namely
organic compounds, the oxides of nitrogen and sulfur, and CO,
future regulation and enforcement of invisible gaseous emissions
requires an inventory which predetermines or estimates levels of
emissions and directs enforcing officers or inspectors to point
locations. This capability is discussed as well as the
description of the method of construction of a recent source
inventory, calculated on the basis of average emission factors and
known plant throughput data and plant locations (registered plant
equipment).##
00375
Br A. Prindle
AIB POLLUTION AND COMMUNITY HEALTH (CHAPTER EIGHTEEN).
Hedical Climatology 505-18, 196U.
28 HYDROCARBONS AND AIR POLLUTION
-------
In this chapter author reviews major pollution episodes which
have occurred since 1930 in various parts of the world. These
episodes have demonstrated the danger and the lethality that may
result when certain meteorologic phenomena occur in geographical
areas where potentially high concentrations of air pollutants may
form. Certain pollutants that might be tolerated in low
concentrations in some inhabited areas might become dangerous when
mixed with pollutants from other sources that could exert an
accentuating or synergistic action. S02, particulates, CO,
beryllium, lead, fluoride, photochemical, and allergenic
pollutants and their effect on man and animals are discussed. The
most important animal experiments as well as other research are
reviewed.t#
00379
G. A- Jansen and D. F. Adams
ABSORPTION AND CHLORINE OXIDATION OF SULFUR COHPOUNDS
ASSOCIATED WITH KRAFT BILL EFFLUENT GASES. Preprint. 1966.
Absorption of methyl mercaptan and H2S into agueous solutions of
Cl, NaOH, and Cl plus NaOH has been studied using a 2 in
diameter absorption column packed with 1/U in. Intalox saddles.
Absorption rates were noticeably affected by chemical reactions
occurring in agueous Cl and OH media. Potentiometric methods
were used to follow the reactions of mercaptan and sulfide in
agueous chlorine solutions. Mercaptan apparently was converted by
aqueous Cl absorption media to dimethyl disulfide and stripped off
in the effluent gas. The percentage conversion increased with
increasing pH. The absorption of H2S in aqueous Cl (pH 2 to
13) was highly pH dependent. The absorption rate increased
slowly as the pH of the feed solution increased to pH 11.
Sulfate was the resulting oxidation product. At pH 11, the rate
of absorption dropped slightly, then rose sharply at pH 12.
Elemental S became the major product at pH 12 and above and
fouling of the packed column occurred. The effect of pH on
formation of sulfate and/or elemental S in chlorine-sulfide
reactions was explained by Choppin and Faulkenberry (1937).
The absorption of sulfide in agueous NaOH increased until the
feed hydroxide to sulfide ratio was 1. At higher ratios, the
absorption rate remained constant. Apparently, sodium bisulfide
was the absorption product. The results of these studies indicate
that aqueous Cl solutions at pH above 12 can be effectively used
for removal of H2S in absorption equipment designed to handle
S in suspension. The absorption of methyl mercaptan in
aqueous Cl solution appeared to be impractical since dimethyl
disulfide was apparently the only product formed and was stripped
from the tower by the gas stream. Hydroxide solution was
effective for absorption of both methyl mercaptan and H2S when
hydroxide to sulfide or mercaptan feed ratios were greater than 1
or 1.8 respectively. (Author)#f
6. Emission Sources 29
-------
00388
E. C. Tabor
CONTAMINATION OF URBAN AIR THROUGH THE DSE OF INSECTICIDES.
Trans. N.Y. Acad. Sci. 28(5) 569-78, Mar. 1966:
Results of this investigation show that the air over many
communities is contaminated with substantial amounts of a
vide variety of insecticides. The concentrations observed
represent minimum values, since the sampling method did not
collect pesticide vapors and some of the collected aerosols could
have been lost by vaporization during the sampling period.
These minimum values, nevertheless, demonstrate that the ambient
air can be a route for the nonoccupational exposure of people to
insecticides. The actual significance of this route requires
considerable further definition, particularly with respect to the
total pesticide concentrations. Before total air-borne pesticide
concentrations can be determined and potential physiological
effect on humans, flora, and fauna evaluated, suitable methods must
be developed for the simultaneous collection of both aerosol and
vapor forms and for subsequent analysis of the resulting samples.
Levels reported herein indicate the need for the development of
improved techniques and the further definition of the ambient air
concentrations. (Author)f#
OOH64
C.F. Ellis
CHEHICAL ANALYSES OF AUTOMOBILE EXHAUST GASES FOR OXYGENATES.
Bureau of nines, Washington, B.C. (Rept. of Investigations
No. 5822). 1961. 39 pp.
This report presents procedures for chemical analyses of
certain oxygenated compounds, procedures for sampling the
exhaust gases for these analyses, and the analytical results
of some experimental work in which these procedures were
used. A stationary 1956 model, 170 horsepower, V-8,
dynamometer-mounted engine, operated to simulate vehicular cruise
conditions, was used for the study. Exhaust gsees produced
from a regular-grade Midcontinent gasoline during 15- , to- ,
and 60-mile-per-hour cruise operations were analyzed by chemical
methods for formaldehyde, total aldehydes, total carbonyls-; total
alcohols, carvon associated with the oxygenated compounds, and the
oxides of nitrogen. Experimental results indicate: (1) The
range of concentrations of the total of the functional
groups of oxygenated compounds, expressed as moles per million
moles of water-free exhaust gases, is about 90-100; the
concentrations increase with engine speed; (2) Aldehydes
comprise about 80-90 mole-percent of the total of the
oxygenated groups, and formaldehyde accounts for about
50 mole-percent of the total aldehydes; (3) The order of
magnitude of the concentration of the carbonyls is the same as
that for the aldehydes, indicating that ketones are not a
major group. A colorimetric test indicates that methyl ketones
consititute about 2 mole-percent of the oxygenated compounds;
30 HYDROCARBONS AND AIR POLLUTION
-------
(4) The concentration of the alcohols is of the order of 10
mole-percent of the oxygenated compounds; (5) The total
carbon associated with the oxygenated compounds is about 175 moles
per million moles of water-free exhaust gas for all 3 speeds;
and (6) The concentration of N oxides, expressed as
moles of K02 per million moles of water-free exhaust gas,
is about 150, 1,600, and 2,800 at 15, «0, and 60 miles per hour,
respectively.##
0050i»
D.A, Jensen
SEPARATING FACT FROM FICTION IN AUTO SMOG CONTROL. Arch.
Environ. Health, 14 (1):150-155, Jan. 1967. (Presented at
the American Medical Association Air Pollutron Medical
Research Conference, Los Angeles, Calif., March 2-U, 1966.)
Author gives a status state-of the -art summary of the various
sources of emissions from automobiles. Topics covered ar'e:
crankcase emission controls; servicing and maintenance; requirement
of a "closed" system or one equally effective, exhaust emission
controls; evaporative emissions; oxides of nitrogen emission
controls; diesel smoke and odor emission controls; cars .and
fuels of the future. In addition, author discusses the impending
vehicle emission control which will be put into effect for
1968 motor vehicles.#f
00566
W. L. Faith
ECONOMICS OF MOTOR VEHICLES POLLUTION CONTROL. Chem. Eng.
Progr., 62 (10):41-«3, Oct. 1966. (Presented before the
Symposium on Economics of Air Pollution Control, 59th
National Meeting, American Inst. of Chemical Engineers,
Columbus, Ohio, Hay 15-18, 1966, Paper No. 21 G.)
The cost of air pollution control devices to the motorist, for the
reduction of hydrocarbons, carbon monoxide and nitrogen oxides in
general and per smog day, are discussed, cost of the device, of
the installation and cost of maintenance are calculated. Results
are summarized in tables.#f
00592
T. A. Huls, P. S. Byers, and 0. A. Oyehara
SPARK IGNITION ENGINE OPERATION AND DESIGN FOR MINIMUM EXHAUST
EMISSION. In: Vehicle Emissions, Part II, SAB
Progress in Technology Series, Vol. 12, Society of
Automotive Engineers, Inc., New York, 1966, p. 71-91. 28
refs. (Presented at the Society of Automotive Engineers
Meeting, June 6-10, 1966.
B. Emission Sources 31
-------
The purpose of the tests conducted on a single-cylinder
laboratory engine was to determine what can be done in the design
and operation of a spark-ignition engine to minimize emission
of air pollutants. For the engine used in this study, the
exhaust emissions were found to have the following dependence on
various engine variables. Hydrocarbon emission was reduced by
lean operation, increased manifold pressure, retarded spark,
increased exhaust temperature, increased coolant temperature,
increased exhaust back pressure and decreased compression
ratio. Carbon monoxide emission was affected by air-fuel ratio
and premixing the charge. SO and N02 emission is primarily a
function of the 02 available and the peak temperature attained
during the cycle. Decreased manifold pressure and retarded spark
decrease NOx emission. Hydrocarbons were found to react to sone
extent in the exhaust port and exhaust system. This reaction
appears to follow the Arrhenius rate "equation, relationship.
Calculations of theoretical HC concentrations were made
based on quench theory using measured combustion pressures and
surface temperatures. It was assumed that the only source
of HC's in the exhaust is the quench volume, i.e., the thin
layer adjacent to the chamber walls through which the flame does
not propagate. The difference between actually measured HC
emission levels>and the levels that quench theory predicts is
resolved by assuming 2/3 of the contents of the quench
volume leave the engine and Arrhenius type reaction during the
exhaust portion of the combustion cycle. It was also concluded
that the HC' left unburned after flame passage in-the combustion
chamber are proportional to the area swept by the flame per unit
charge. (Authors' abstract)##
00621
D.J. Von Lehmden, R. P. Hangebrauck, J.E. Heeker
POLYNUCLEAR HYDROCARBON EMISSIONS FROM SELECTED INDUSTRIAL
PROCESSES. J.,Air Pollution Control issoc. Vol. 15(7):306-
312, July 1965.
A number of selected industrial .processes considered as
potential sources of benzo (a)pyrene and other polynuclear
hydrocarbons was surveyed. Polynuclear hydrocarbon
emission levels were measured directly for asphalt hot
road mix preparation and asphalt air blowing. Emissions
of other pollutants, including particulate matter, carbon
monoxide, and total gaseous hydrocarbons were also measured, and
are reported together with pertinent data on process design and
operation. Results are discussed with reference*to the type
of process; the type of equipment used, including control
devices; and other factors. The significance of sone additional
processes as contributors of polynuclear hydrocarbons
was examined indirectly by collecting atmospheric sanples of
polynuclear hydrocarbons in residential areas in the vicinity of
(1) a carbon black manufacturing area, (2) a steel and coke
manufacturing area, (3) an organic chemical industry complex, and
(4) a residential and small-industry coal burning area. (Author
abstract) f *
32 HYDROCARBONS AND AIR POLLUTION
-------
00650
B.C. Battigelli
EFFECTS OF DIESEL EXHAUST. Arch. Environ. Health Vol.
10(2)165-167, Feb. 1965. (Presented at the Seventh Annual
Air Pollution Hedical Research Conference, Los Angeles,
Calif., Feb. 10-11, 196U.)
Over the past three years the author's work at the School of
Public Health in Pittsburgh has been directed to the possible
detrimental effects brought about through exposure to diesel
motor exhaust. Attention was directed to railroad workers
employed in locomotive repair shops. Neither respiratory
complaints nor impaired pulmonary function, could be related
to this type of occupational exposure. As a second phase in
this investigation, volunteers were exposed to diesel exhaust
gas for short periods and pulmonary resistance was measured. The
levels utilized for these controlled exposures are
comparable to realistic values such as those found in railroad
shops. No effect could be measured in these volunteers after
they had been exposed at these varying levels of pollution
from diesel exhaust for short periods up to one hour.tf
00673
H.H. Hovey, A. Wisman, J.F. Cunnans
THE DEVELOPMENT OF AIR CONTAMINANT EMISSION TABLES FOR
NONPROCCESS EMISSIONS J. Air Pollution Control Assoc.
Vol. 16 (7) :362-366, July 1966. (Presented at the 58th
Annual Meeting, Air Pollution Control Association, Toronto,
Canada, June 20-24, 1965, Paper No. 65-17.)
In New York State, the calculation of air contaminant
emissions from a variety of sources is an essential part of
comprehensive air pollution studies. The tables used to
calculate emissions were obtained from an extensive
literature search and modified to apply to New York State
conditions. For example, sulfur dioxide emission factors for
coal were selected to reflect the average sulfur content of the
coal sold in New York State. Since the literature contains a
wide array of emission factors,##
00679
W. E, Jackson
AIR POLLUTION FROM AUTOMOBILES IN PHILADELPHIA. Preprint.
(Presented at the 58th Annual Meeting, Air Pollution
Control Association, Toronto, Canada, June 20-24, 1965,
Paper No. 65-137.)
This report has been prepared with the objectives of describing
the problem created by automobiles in Philadelphia and
recommending the action which must be taken. The action
B. Emission Sources 33
-------
recommended is as follows: (1) Positive crankcase ventilation
systems and exhaust control systems should be required on all new
cars registered in Pennsylvania. A well planned program of
controlling only the new cars with factory installed devices will
minimize the problem over a ten year period. If initiated
immediately, this reasonable approach would eliminate the need for
a crash program at some future date. All mechanical devices
require maintenance to insure proper and efficient.operation; and
(2) The State-wide inspectional system should require a
maintenance check of all appropriate parts of the automobiles to
insure satisfactory operation (as related to pollution emissions)
and to reject those cars with visibly excessive exhaust emissions.
This should apply to both new and used automobiles and all other
types of motor vehicles.#t
00746
R. Piper
THE HAZARDS OF PAINTING AND VARNISHING 1965 . Brit. J. Ind.
aed. (London) 22(4):2«7-266, Oct. 1965.
A review of paint hazards is made, giving brief descriptions of
methods of application in use in 1965, of paint usage according
to resin base, and of paint ingredients. The most
interesting and complex of these are the resin bases, which have
much in common with plastics. Reference is made to some of the
many minor ingredients. The problem of keeping abreast of the
possible toxic effects, so that paint manufacturers and their
customers may be warned and protected is emphasized.
(Author's abstract)#f
00798
R.I. Larsen
VEHICLE EHISSIONS AND EFFECTS, A SUHBARY OF THE DECEHBER 1961
AIR POLLUTION RESEARCH CONFERENCES. Preprint. (Presented
at the New England Section Annual-Meeting, Air Pollution
Control Association, Worcester, Mass., Apr. 25, 1962).
In December 1961 air pollution research findings to that date
were presented at two conferences held in Los Angeles. The
conferences were the Fifth Air Pollution Medical Research
Conference and the Joint Research Conference on Motor
Vehicle Emissions and Their Effects. A few highlights follow.
Air pollution damages plants, animals, and property, and is
harmful to people. Plant damage in the United States exceeds
$25 million per year. Present community air pollution^levels
weaken an individual's resistance to respiratory diseases such
as colds, pneumonia, and lung cancer. Smoking and air pollution
•age and deteriorate lungs. In one study, smokers' lungs aged
50% faster than non-smokers' lungs. In another study, 90% of
heavy smokers (more than two packs per day) had respiratory
disease. The disease rate for several respiratory ills was 3 to
5 times greater in these heavy smokers than in individuals vho had
34 HYDROCARBONS AND AIR POLLUTION
-------
never smoked. The death rate from emphysema (deteriorated' lungs)
has increased 400% in the last 10 years. A recently identified
photochemical pollutant, peroxyacyl nitrate (PAN), at
concentrations as low as 5 parts per billion (ppb), damages
plants. It is quite possible that this pollutant is responsible
for most "oxidant-type" damage in Los Angeles. Five times as
much exhaust gas from low-olefin fuel was required to produce
similar damage. Russian air quality standards probably have
at least one present use in the United States.
In a given community, pollution concentrations that do not
exceed the Russian standards tentatively could be considered to
not be problems. The contribution of the internal combustion
engine to smog could be reduced significantly by improved
carburetor design, improved production control, and imporved
carburetor and ignition system maintenance. If' the
conventional engine without an afterburner is considered beyond
redemption, a lean-fuel engine (such as gas urbine, stratified
charge, or diesel) could be used to meet present emission
standards. If an automobile that does not contribute to smog is
to be achieved, a new sense of mission, a lot more money, and
additional competent researchers will be required. (Author
abstract modified)f#
00835
B.P. Gourinoff
CANCEROGENIC SUBSTANCES IN THE AIP OF CITIES AND POSSIBLE
PREVENTIVE MEASURES. Acta, Unio Intern. Contra Cancrum,
Vol. 19, 737-738, 1963.
Cancerogenic properties as identified in emissions from
motor vehicles, fuels, and industrial exhaust, are considered
an important factor in human cancer epidemiology. This paper
reviews briefly studies at hone and abroad. Exhaust from
carburetor and diesel engines are compared, and other sources of
carcinogenic properties investigated. It is briefly
mentioned that use of coal tars for road surfacing is
prohibited in the U.S.S.R.tt
00895
V.L. Lur'e
(STUDY OF THE HARMFUL INDUSTRIAL EXHAUSTS IN THE ATMOSPHERE
IN THE SYNTHETIC RUBBER PLANTS IN VORONEZH AND YEFHEBOV.)
Obsledovanie vrednykh Proizvodstvennykh Vybrosov v
Atmosferu na Voronezhskom i Efremovskom Zavodakh SK.
Kauchuk i Rezina No. (3):36-37, 1966. Text in Russian
Waste emissions both in the factory area and in the hygienic
control zone around it (300-500 m from the factory) were studied
both qualitatively and quantitatively. While
pollution did not exceed the established limits in the factory
areas, it did in the control zone surrounding the factories.
Contaminants were butadiene, isobutylene, styrene, benzene and
ethanol vapors. Host of the pollution was caused by styrene-
B. Emission Sources 35
-------
butadiene rubber processing in the belt casting machine. Large
amounts of hydrocarbons were given off by shops producing isopcene
and latex. Pollution of the surrounding air also came from
exhaust ventilation of the factories and open pits of chemical
waste. This resulted in a fall of 1200 metric tons in Voronezh
and 700 tons in Efremov per year. Measures for the control of
exhaust ventilation from the factories are urged.##
00905
0. Buchta
HYGIENIC CONDITIONS ON MOLDING POLYESTER GLASS REINFORCED
PLASTICS. Hygienicke Pomery Pri Lisovani Polyesterovvch
Skelnych. Plasticke moty Kaucuk (Prague), 3 (6): 177-182,
1966.
Hygienic problems associated with the manufacture of polyester
glass reinforced plastics are discussed. Results are given for
the polarographic measurement of styrene vapor concentration in
the atmosphere of the general pressing room and the hand pressing
room.##
0.0962
R. I. Larsen
AIH POLLUTION FROM HOTOR VEHICLES. Ann. N. Y. Acad. Sci.,
136(12):275-301, Aug. 26, 1966. (Presented at a meeting of the
New York Academy of Sciences, April 6, 1966.)
Motor vehicles are a major source of urban air pollution. They
emit carbon monoxide that reduces man's ability to transport oxygen
to his tissues; lead that increases man's body burden of this toxic
metal; cancerigenic hydrocarbons; and reactive hydrocarbons and
nitrogen oxides that combine with sunlight to produce
eye-irritating, plant-damaging, visibility-obscuring photochemical
smog in New York as well as in California. Present and
predicted air pollutant concentrations are compared with pollutant
effects and air quality standards. Emission-reduction features
presently used in new cars sold in California will improve air
quality, but will not completely solve the problem. Indications
are that 95 percent reduction in emissions of carbon monoxide,
hydrocarbons, and nitrogen oxides from new cars sold in the United
States jnay be needed by 1975. Such a "clean-air car" by 1975 is
suggested as a research goal for automobile manufacturers. At
present, improved fuel cells or improved battery power seem to be
the most likely means for achieving this goal. (Author
abstract)*t
36 HYDROCARBONS AND AIR POLLUTION
-------
00969
P. A. Leighton
KAN AND AIR IN CALIFORNIA. Preprint. (Presented at the
Statewide Conference on Man in California, 1980's,
Sacramento, Calif., Jan. 27, 196«.)
Author discusses polluted air in respect to automobile emissions
and projects the concentrations that can be expected by 1980.
Presented are charts and tables which easily delineate the
salient points of the article.##
00972
M. Mayer
A COMPILATION OF AIR POLLDTANT EMISSION FACTORS FOR COMBUSTION
PROCESSES, GASOLINE EVAPORATION, AND SELECTED INDUSTRIAL
PROCESSES. Public Health Service, Cincinnati, Ohio, Div.
of Air Pollution, May 1965, 53 p.
The source emission factors presented in this report were compiled
primarily for use in conducting an air pollutant emission
inventory. The compilation is the result of an extensive
literature survey and includes emission factors for the principal
combustion and industrial processes. Obviously, the best
emission factor to use for any specific source of air pollution is
that resulting from source tests of the specific source.
Unfortunately, many urban areas are not equipped to conduct the
numerous and expensive stacfc testing studies needed for an emission
inventory. The purpose of this compilation of emission factors is
to provide the best available substitute to air pollution control
agencies unable to conduct extensive source test programs. In
certain cases, particularly in the combustion and refuse disposal
areas, a single number is presented for the emission factor for a
specific pollutant. It should be understood that the number is
usually a weighted average of several different values found in the
listed references. The compilation of source emission factors
presented is, in our judgment, the most accurate currently
available. As new technical advances are made, however, and
additional emission data become available in the literature, the
present compilation should be revised to reflect the newer data and
developments.##
00975
M. I. Weisburd, (Compiler and Ed.)
AIR POLLUTION CONTROL FIELD OPERATIONS MANUAL (A GUIDE FOR
INSPECTION AND ENFORCEMENT). Public Health Service, Washing-
ton, D, C., Div. of Air Pollution, 1962. 291p.
Author discusses sources, control methods, training
techniques and related aspects of air pollution. Document is an
B. Emission Sources 37
-------
excellent source for specific information on equipment being used
in air pollution control. Pictures, diagrams, schematics and
charts are given.**
00985
R.E. Waller, B.T. Commins, P.J. Lawther
AIR POLLUTION IN A CITY STBEET. Brit. J. Ind. Med.
(London), Vol. 22:128-138, 1965.
Reasurements of the concentrations of smoke, lead, and
five polycyclic hydrocarbons in the air have been made in the
City of London in the middle of a busy street and at two control
sites. Samples were taken only throughout the daytime hours on
weekdays to enable us to assess the maximum contribution made by
traffic to the pollution in the street. The results showed that
during these periods the air in the middle of the street contained
three times as much smoke, four times as much "lead, and 1.7 tines
as much 3:<»-benzpyrene as were present in the general atmosphere
of the City of jLondon as estimated from samplesjtaken at the
control sites. One of these sites was chosen because it was only
150 feet from the street; analyses yielded no evidence that the
traffic contributed itosthe pollution sampled there. Sulphur
dioxide concentrationsrwere[determined in-the early part^of the
study and the .results showed that traffic appeared to add little
to the background level. The concentrations of lead found
were below those held ,to be safe by many authorities, carbon
monoxide concentrations, reported in greater detail-elsewhere,
sometimes reached,the accepted industrial maximum allowable
concentration of 100 ppm. (Author abstract)##
01008
S. K. Say and E. Long
POLYCYCLIC AKOMATIC HYDROCARBONS FROH DIFFUSION FLAHES
AND DIESEL ENGINE COHBUSTION. Combust. Flame 8, 139-:51, June
1964.
A study has been.made.of the effects of air flow rate and of
several additives to the fuel of a laminar diffusion, flame on the
formation of: (1) soot, (2) carbonaceous residue (i.e.
chloroform insoluble material), (3) pentane-soluble material
(shown to be essentially polycyclic aromatic hydrocarbons), and
(4) 3,U-benzpyrene contained in the latter. Increasing air flow
rate leads to a decrease in both soot and carbonaceous residue
which reach limiting values. Pentane-soluble material and
3,4-benzpyrene decline continuously with increase in air flow rate
but at a diminishing rate. Dichloromethane as additive increases
the formation of soot and carbonaceous residue to a considerable
extent without having any appreciable effect on the formation of
pentant-soluble material and 3,4-benzpyrene. Nitroethane,
1-nitropropane, ethyl nitrate and t-butylhydroperoxide all bring
about significant reductions in the formation of chloroform-soluble
material, including pentane-soluble material and 3,i»-benzpyrene.
38 HYDROCARBONS AND AIR POLLUTION
-------
Total soot formation is reduced slightly but the .formation of
carbonaceous residue is virtually unaffected. Similar results
are obtained in a study of the particulate matter in diesel exhaust
when the additives are blended with a diesel fuel, and conditions
of inefficient operation are simulated. t-Butylhydroperoxide is
found to be most effective in reducing the formation of
3,4-benzpyrene. Both the diffusion flame and diesel engine
results are in conflict with the hypothesis that carbon formation
occurs through polycyclic aromatic hydrocarbons as intermediates;
these may be the end products of side-reactions, probably
free-radical in nature. (Author abstract)#t
01038
L. J. Goldwater, A. J. Rosso, and H. Kleinfeld
BLADDER TUHOBS IN A COAL TAB DYE PLANT, Arch. Environ.
Health Vol. 11:814-817, Dec, 1965.
This study was undertaken in order to assemble additional
information on the occurrence and natural history of malignant
tumors in workers exposed to coal tar dyes and dye intermediates.
Specific points to be investigated were: 1. To determine the
incidence of urinary bladder tumors, especially in workers
exposed to beta-naphthylamine, benzidine, and alpha-napthylamine.
2. To establish the "incubation" period from the start of exposure
to the onset of first genitourinary complaints suggestive of
bladder tumor. 3. To establish survival time after diagnosis of
bladder tumor. 4, to determine the incidence of malignant tumors
other than those of the bladder. The major conclusions from this
study of the records of 366 male employees in a coal tar dye
factory are: 1.- The incidence of malignant tuaors of the bladder
was 26.2%. 2. The time elapsed from first exposure to first
abnormal signs or symptoms ranged from 1 to 35 years, with a Bean
of 18.4 years. 3. The time elapsed from first exposure to
diagnosis of bladder malignancy ranged from 2 to 42 years, with a
mean of 22.9-years. 4. The mean survival time following diagnosis
of bladder malignancy was about three years for all types of
exposure except beta-naphthylamine alone for which it was about
eight years. 5. There was no evidence of any unusual incidence of
malignancies other.than those of the urinary bladder. 6. The
findings were similar to those reported by other observers.fi
01059
P.J. Lawther, B.T. Commins, R.E. Waller
A STUDY OP THE CONCENTRATIONS OF POLYCYCLIC AROHATIC
HYDROCARBONS IN GAS WORKS RETORT HOUSES. Brit. J. Ind. Bed.
Vol. 22:13-20, 1965.
Heasurements of the concentration of 3:4-benzpyrene and other
polycyclic aromatic hydrocarbons have been made in gas works
retort houses of several types. The tarry fumes which
escaped from retorts contained extremely high concentrations
of polycyclic hydrocarbons, but in general men were only
B. Emission Sources 39
-------
exposed to these very briefly. The mean concentration of 3:4-
benzpyrene determined from long-period samples at sites
representative of normal working conditions in three works was 3
micro g./cu.m., over 100 times the normal level in the City of
London. Above the retorts in an old horizontal retort house
the concentration was over 200 micro g./cu.m., about 10,000 tines
that in the City, and the "top-man" working there could be exposed
to this in the normal course of his duty. The authors
found no working areas in the vertical retort houses where men
could be exposed to such massive concentrations of polycyclic
hydrocarbons. Apart from defining these special conditions
above horizontal retorts the results did not reveal any gross
differences in pollution of the general air in horizontal and
continuous vertical retort houses. (Author abstract)##
01076
E. F. Darley, F. H. Burleson, E. H. Hateer, J. T.
Hiddleton, and V. P. osterli
CONTRIBUTION OF BURNING OF AGRICULTURAL WASTES TO PHOTOCHEMICAL
AIR POLLUTION. J. Air Pollution Control Assoc. Vol.
16(12):685-90, Dec. 1966. (Presented at the 59th Annual
Meeting, Air Pollution Control Association, San Francisco,
Calif., June 20-25, 1966.)
Agricultural wastes from orchards, grain fields, and range lands
are burned each year in California as the nost practical means
of ridding the land of these wastes. In order to determine the
relative contribution of the burning of such material to
photochemical air pollution, the effluent from 123 fires of known
weights of range brush, both dry and green, barley and rice
stubble, and prunings from various fruit and nut trees were
monitored in a special tower which provided an open burning
situation. Analyses were made for total hydrocarbon, expressed as
C, by flame ionization detection, and for 24 individual
hydrocarbons by gas chromatography, as well as for CO and C02
by infrared spectroscopy. A few analyses were made for oxides of
nitrogen. These data, coupled with temperature and airflow
measurements, allowed calculations to be made on pounds of
effluent per ton of material burned and demonstrated that the
emissions from agricultural burning are much less than those fro«
the automobile, a principal source of such emissions. (Author
abstract) ##
01132
G. B. Niepoth and S. H. Mick
THE GENERAL MOTORS AIR INJECTION REACTOR SYSTEM FOR THE CONTROL OF
EXHAUST EMISSIONS . Gen. Motors Eng. J., 13(3):20-29, 1966.
The Air Injection Reactor (AIR) system developed by
General Motors, and initially applied on most 1966 GH car and
light truck models produced for sale in California, provides an
effective means for controlling hydrocarbon and carbon monoxide
exhaust emissions without a sacrifice in automotive perforaance.
40 HYDROCARBONS AND AIR POLLUTION
-------
The AIR system, which meets California standards for emission
control, is basically simple in operation. Fresh air is injected
into the exhaust ports of an engine to provide complete burning of
hydrocarbons and carbon monoxide in the exhaust manifold. The
development of the system, however, involved much design effort
and testing to prove its effectiveness, reliability, and
durability. System components, including a specially-designed
air pump, had to be designed to be compatible with all
engine-carburetor—transmission combinations used in GM car
models, in addition, the AIR system had to be designed to
reguire minimum maintenance. (Author summary)f#
01133
W. B. Thompson
THE DESIGN AND DEVELOPMENT OF THE AIR POHP FOR THE GENERAL MOTORS
AIR INJECTION REACTOR SYSTEM. General Motors Engineering J.,
13(3):30-35, 1966.
The development of the General Motors Air Injection Reactor
system for controlling the concentrations of unburned hydrocarbons
and carbon monoxide in vehicle exhaust emissions required engine
modifications and the design of new components. The most vital
component in the system is the air pump, designed and manufactured
by the Saginaw steering Gear Division. The pump developed by
Saginaw engineers is a semi-articulated vane type positive
displacement pump. The design displacement is 19.3 cu in. per
revolution with high volumetric efficiency and low horsepower
consumption. Additional design criteria included durability
consistent with the life of the vehicle and satisfactory
performance without maintenance. (Author summary) ##
01165
H. B. Holland
AIR QUALITY CONTROL BY PETROLEUM REFINERS. Preprint.
(Presented at the Third Annual Meeting, Pacific Northwest
International Section, Air Pollution Control Association,
Vancouver, British Columbia, Nov. 2-4, 1965.)
Air quality can best be maintained by controlling pollution on a
regional basis. Close cooperation between.the technical staffs
of the province, municipalities and industries in the region is
required to achieve the best solution to the regional problem.
Beans are available to control the emissions from petroleum
refineries to the degree required by our current understanding of
the problems.##
01228
L. Rispler and C. R. Ross
VENTILATION FOR ENGINE EXHADST GASES. Occupational Health
Rev. Ottawa 17, (U) 19-22, 1965.
B. Emission Sources 41
-------
Engine exhaust gases are capable of affecting health in varying
degrees, and confusion as to their relative importance often
arises. This is partly because most exhaust analyses are reported
only as concentrations within the exhaust system, without
specifying the total exhaust volume. For clarification, a
comparison is made of the actual amounts in which these components
are emitted from various engines. These data exemplify the
difference in ventilation requirements for diesel engines and
gasoline engines. The toxic effects of carbon monoxide and so»e
basic ventilation considerations are outlined. (Author abstract)I
01362
E.K. Diehl E.A. Zawadzki
CONTAMINANTS IN FLUE GASES - AND METHODS FOR REMOVAL. Coal
Age, Vol. 70:70-74, Dec. 1965. (Presented at Technical
Sales Conference, National Coal Association and Annual
Meeting of Bituminous Coal Research, Inc., Sept. 1965.)
The relative importance of the harmful pollutants in stack
gases from coal combustion is described. Polynuclear
hydrocarbons, ocides of nitrogen, particulates, and sulfur oxides
are considered. Sulfur dioxide removal methods are described.t*
01375
E.S. Starkman H.K. Newhall
CHARACTERISTICS OF THE EXPANSION OF REACTIVE GAS MIXTURES AS
OCCURRING IN INTERNAL COMBUSTION ENGINE CYCLES. California
Univ., Berkeley, Dept. of Mechanical Engineering, 1965, 13 p.
(Presented at the Mid-Year Meeting, Society of Automotive
Engineers, Chicago, 111., May 17-21, 1965, Paper No. 650509.)
The influence of nonequilibrium in the expansion gases of
spark ignition engines has been studied theoretically to determine
how power output and exhaust gas composition might be affected.
Comparing a gas which is frozen in composition during
expansion with a composition which continuously is in
equilibrium shows the difference in expansion work can be as
large as 10S. Maximum influence is in the fuel-air ratio range
of chemically correct mixture. It was found that carbon monoxide
and nitric oxide concentrations in the exhaust more nearly reflect
the frozen composition than the equilibrium expansion. This is
particularly true for the range of mixture ratios - from lean to
chemically correct.t#
01381
B.W. Hum
COMPREHENSIVE ANALYSES OF AUTOMOTIVE EXHAUSTS. Arch.
Environ. Health, Vol. 5:592-596, Dec. 1962. (Presented at the
session on Constituents of Motor Vehicle Exhaust at the
Air Pollution Research Conferences, Los Angeles, Calif.,
Dec. 5, 1961.)
42 HYDROCARBONS AND AIR POLLUTION
-------
The nature of the gaseous or volatilized components of automotive
exhaust is reviewed. Recent work conducted to define more
precisely variations in exhaust-gas stream composition is reported.
Information on the simultaneous occurrences of the several
classes of components is presented. Analytical methods; inert,
reactive, and noxious constituents; and hydrocarbon measurements
are considered.**
01382
B.H. Hum, T.C. Davis
GAS CHROMATOGRAPHIC ANALYSIS SHOWS INFLUENCE OF FUEL ON
COMPOSITION OF AUTOMOTIVE ENGINE EXHAUST. Proc. An. Petrol,
Inst. 38(3):353-375, 1958. (Presented at the 23rd Midyear
Meeting, American Petroleum Institute's Division of Refining,
Los Angeles, Calif., Hay 12, 1958.)
Chemical differences in the exhaust products from different fuels;
and the effect of engine speed and load on these differences are
reported. Experimental data were obtained with the use of a late
model automotive V-8 engine on a dynamometer block. Fuels which
were used included pure isooctane, commercial LPG (butane and
propane, separately), and seven gasoline stocks from different
refining processes. Analytical data obtained by gas
chromatography show that exhaust composition varies with engine
speed and load according to consistent trends. These trends are
influenced by fuel composition, and the degree of fuel influence
depends upon mode of engine operation—some basic fuel
characteristics are more heavily reflected in the exhaust than are
others. Generally, differences in the composition of exhausts
from different fuels are guantitatively small, but they are
reproducible, (Author abstract modified)*#
01383
K.W. Hurn, T.C. Davis, P.E. Tribble
DO AUTOMOTIVE EMISSIONS INHERIT FUEL CHARACTERISTICS?
Am. Petrol, Ins., Proc HO(3) :352-357, 1960. (Presented
at the 25th Midyear Meeting, American Petroleum Institute's
Division of Refining, Detroit, Mich., May 11, 1960.)
In general, the composition of the hydrocarbon component of
exhaust produced during engine deceleration is closely related to
the fuel. However, during acceleration and cruise the
hydrocarbons emitted may be guite dissinilar to the fuel. In
this latter instacne the amount of olefin emitted bears ao direct
relation to fuel olefin. Moreover, reduced fuel olefin with
increased paraffinicity generally results in increased enissions
of olefin. In all engine cycles, the aromatic content of the
exhausts follows the aromatic content of the fuel. Thus,
hydrocarbons which are emitted inherit the fuel's characteristics
during only a portion of the average driving cycle. During the
remainder of the cycle many of the original fuel characteristics
are erased and the emissions become no more than characteristic
mutations. (Author abstract modified)**
B. Emission Sources 43
-------
01384
B.W. Hum, C.L. Dozois, J.O. Chase, C.F. Ellis,
P.E, Ferrin
THE POTPOURRI THAT IS EXHAUST GAS. Proc. Am.'Petrol. Inst.,
12(3):657-664, 1962. (Presented at the 27th Midyear Meeting,
American Petroleum Institute's Division of Refining, San
Francisco, Calif., Hay 17, 1962.)
Information concerning the myriad compositions and hydrocarbon
distributions that accompany changes in engine mode and that define
the variable character of an exhaust gas stream is given. Data
were obtained on exhaust gases produced using an engine
dynamometer cycled through steady-state and transient modes to
simulate demands on the engine in city traffic. Test procedures
were designed to optimize reproducibility of the tests. Moreover,
analyses were scheduled in a manner to permit determination of all
components on the same or on comparable samples. Carbon
hydrocarbons by major types, oxygen, oxides of nitrogen, and
hydrocarbon-derived ocygenates were determined. Concentrations
that were measured fell within a range of values that had been
reported in the literature. However, the analyses are unique in
that they provide information on the simultaneous, concurrent
concentrations of materials that constitute the exhaust gas flow
and on how these concentrations vary with steady-state and
transient engine operation. The data also show the manner in
which both absolute and relative distributions of hydrocarbon in
the exhausts vary with change in engine mode. (Author abstract
modified) ##
0.1404
H. P. Hangebrauck, 8. P. lauch, and J. E. Meeker
EMISSIONS OF POLYNUCLEAB HYDROCARBONS FROM AUTOMOBILES AND
TRUCKS. Am. Ind. Hyg. Assoc. J,, Vol. 27:47-56, Feb. 1966.
As part of a screening survey to determine the origin of the
benzo (a)pyrene found in urban atmospheres in the United States,
emission rates of several polynuclear hydrocarbons, including
benzo(a)pyrene, were measured on several automobiles and trucks
powered by gasoline engines. The vehicles were road-tested over
typical driving routes. The total exhaust was sampled by passing
it through a multi-plate condenser followed by large high
efficiency filters. Operating and emission data are given. The
combined effects of vehicle-model age and mileage on polynuclear
emissions are discussed, as are the relationships between
polynuclear hydrocarbon emissions and the emissions of other
products of incomplete combustion. (Author abstract)**
01413
A. H. Eose, Jr., R. Smith, H, F. McMichael, and R.
E. Kruse
44 HYDROCARBONS AMD AIR POLLUTION
-------
COMPARISON OF AUTO EXHAUST EMISSIONS IN TWO MAJOR CITIES . J.
Air Pollution Control Assoc. 15, (8) 362-6, Aug. 1965.
Direct measurement of emissions from vehicles operating under
actual traffic conditions in Los Angeles, California, and
Cincinnati, Ohio are presented- Exhaust emissions expressed as
pounds of contaminant emitted per vehicle mile traveled are a
function of average speed of the vehicles over the designated
route (average route speed) regardless of the characteristics of
the specific route and can be best shown as a logarithmic function
of pounds of contaminant emitted per vehicle mile versus average
route speed. Exhaust emissions expressed as concentration provide
a less valid measurement of atmospheric contamination than
emissions expressed as pounds per vehicle mile traveled. The
reason is believed to be the variability in consumption of
combustion air by vehicles and in characteristics of the test
routes. The emission data expressed as a logarithmic function of
pounds of contaminant emitted per vehicle mile versus average
route speed show no significant differences between Los Angeles
and Cincinnati. The effects of peak versus offpeak traffic on
emissions expressed by weight are basically a function of the
changes in average route speed. (Author summary modified)tf
01453
8. Tye, K. J. Burton, E. Bingham, 2. Bell, and A. W.
Horton
CARCINOGENS IN A CBACKED PETROLEUM RESIDUUM (THE CONTRIBUTIONS
OF VARIOUS POLYCYCLIC AROMATIC HYDROCARBONS TO THE CARCINOGENIC
POTENCY OF A CATALYTICALLY CRACKED OIL). Arch. Environ.
Health, 13 (2) :202-207, Aug. 1966.
An extensive examination, which involved the preparation and
bioassay of more than 100 fractions, of a petroleum residuum, K8,
from commercial fluid catalytic cracking, was performed. The
preparation of the fractions involved distillation at reduced
pressures, solvent extraction, chemical reactions, and
chromatography. The fractions were assayed for carcinogenic
potency by repeated application to the skin of C3H mice. It was
possible to categorize the carcinogens and to evaluate the
contribution of each category to carcinogenic potency of the
whole residuum. The major carcinogens in this oil were
categorized according to whether they were found in the relatively
high boiling portion (438-455C) characterized by the presence of
5-ringed or alkyl it-ringed PAH, in intermediate fractions
(404-438 C) characterized by unsubstituted and methyl substituted
4-ringed PAH, and in lower boiling fractions characterized by
assorted smaller compounds including alkyl 3-ringed PAH. In the
same order the percentages by weight (of the whole oil) of
characteristic carcinogens found in each category were as follows:
benzo (a)pyrene, 0.45S; benz (a)anthracene and alkyl honologs 0.4%;
and benzo (c)phenanthrenes, 0.01%. Larger quantities of
benzo (c)phenanthrenes may have been present in the intermediate
fractions, which were not analyzed for these compounds. In spite
of the small percentage that was found, the presence of this
class of carcinogens may be significant because they were the
dominant carcinogens in the most volatile portion of the oil.
(Author summary modified)##
B. Emission Sources 45
-------
01182
S. T. Cuffe and H. W. Gerstle
EMISSIONS FBOM COAL-FIRED POWER PLANTS: A COMPREHENSIVE
SUMMARY. Public Health Service, Cincinnati, Ohio,
National Center for Air Pollution Control. (Presented at the
American Industrial Hygiene Association Meeting, Houston,
Tex., May 1965.) (PHS Publ. No. 999-AP-35.) 1967. 30 pp.
A series of tests on six coal-burning power plants has been
conducted to determine certain stack gas components of interest in
atmospheric pollution. The six units tested included three
dry-bottom pulverized coal-burning units, two wet-bottom units, and
a large spreader-stoker traveling-grate unit. Measurements of
sulfur oxides indicate that essentially 90 to 100 percent of the
sulfur in the coal appears as sulfur oxides in the stack gas. Of
this amount 1 to 2 percent is in the form of sulfur trioxide and
the balance is sulfur dioxide. Neither the type of furnace, the
conditions of firing, nor the reinjection of fly ash affected
sulfur oxide emissions significantly. Concentrations of sulfur
oxides are thus essentially determined by the amount of sulfur in
the coal entering the furnace. Concentrations of nitrogen oxiees
varied widely, ranging from 221 ppm for the vertically fired unit
to 1201 ppm for the cyclone-type furnace. Concentrations of
nitrogen oxides apparently are determined by: (1) initial flame
temperatures in the firebox, (2) decomposition in the
high-temperature region of the furnace, and (3) guenching of the
decomposition reaction as the gases are cooled in the
boiler section of the furnace. Control of particulate emissions
varied considerably in coal-fired power plants. Combination
cyclone and electrostatic-precipitator-type fly-ash collectors
gave collection efficiencies of about 96 percent and an outlet
grain loading of 0.20 grain/scf at full load. Electrostatic
precipitators and mechanical cyclone collectors, when used
separately, gave average collection efficiencies ranging fron 75 to
85 percent, with loadings at the fly-ash collector outlet varying
from 0.19 to 0.68 grain/scf. Additional emissions determined
included polynuclear hydrocarbons, carbon monoxide, gaseous
hydrocarbons, formaldehyde, and trace metals. None of these
components was found in appreciable quantities during normal
furnace operating conditions. (Author summary)**
01188
Ludwig, J. H.
SEMINAR ON AIR POLLUTION BY MOTOB VEHICLES. Technology
Research and Development Programs, Washington, D.C.
((51)) p., 1968. 1 ref.
The contribution of motor vehicle emissions to community-wide air
pollution levels; emissions from gasoline and diesel engines; and
photochemical reactions in the atmosphere are reviewed.**
46 HYDROCARBONS AND AIR POLLUTION
-------
01534
H. Bozniczek
AIR POLLUTION BY MOTOR CAB EXHAOST GASES) ZATROCIE
Powietrza Przez Spaling Samochodowe. Ochrona Pracy
(Warsaw), 21(5):14-17, May 1966.,
Pollution of towns and cities by automotive emissions is
described. Chemical analyses of the various constituents of
exhaust gases are given. Toxicity of these constituents is
discussed.##
01544
J.D. Kalasky
VENTILATION AND METHANE DBAINAGE IN LONGWALL MINING. MINING
Engineering 18 (8):79-82, Aug. 1966.
The facilities and procedures necessary for adequate
ventilation and methane drainage in longwall mines are described.
Schematic diagrams showing air coursing and air inspection
stations are presented. Company standards reguire that methane
concentration be kept below 0.50%.##
01546
J.J. Hanks H.D. Kube
INDUSTRY ACTION TO COMBAT POLLUTION. Harvard Bus. ReT. ,
44 (5):49-62, Oct. 1966.
The responsibilities of individual corporations in air
pollution abatement are emphasized. Sources of pollution
discussed include the paper, steel, electric power, transportation
and petroleum industries. Principal equipment for removal of
aerosols and particulates is described. It is concluded that
although air pollution equipment increases costs in certain
industries, recovery of pollutant, such as fly ash, may help to
offset the costs. Government activities in air pollution programs
are summarized.ft
01558
H. Hayer, M. Handl, and J. Doubek
DE7ICE FOR SAMPLING AND ANALYSIS OF METALLURGICAL FURNACE
ATMOSPHERES. Zarizeni pro odber a analyzu hutnich atmosfer.
HUTNICKS LISTY (PRAGUE), 21(8) 532-538, AUG. 1966.
Two types of devices for sampling furnace atmospheres and an
instrument for analyzing waste .gases and furnace atmospheres based
on gas chromatography are described. Specimens can be sampled
and delivered to the analyzer within seconds. Sampling from
B.IEmission Sources 47
-------
several points can be carried out manually or automatically.
Chromatographic analysis of 02, N2, CO, C02 or CHU can be
performed within five minutes. The system can be adapted for
other gases.#i
01565
E. S. Starkman
ENGINE GENERATED AIH POLLUTION - A STUDY OF SOURCE AND
SEVERITY. Preprint. (Presented at the Federal International
Societes Ingeneures Techniques De L'Sutomobile, Germany,
June 15, 1966.)
A brief comprehensive view of the state of knowledge, legislation,
research and application of devices to control the influence of
reciprocating engine emissions on man and his environment is
presented from the viewpoint and experiences of a California
observer. The pollutants considered are: unburned hydrocarbons;
carbon monoxide; oxides of nitrogen; carcinogens; 'particulate
matter; lead; odor; and oxides of sulfur. Engine operating modes
and severity of emissions; engine factors and emissions: and
legislative control of emissions are considered.i#
01572
OXIDES OF NITROGEN IN THE ATMOSPHERE (CHAPTER V OF THE OXIDES
OF NITROGEN IN AIR POLLUTION). California State Dept. Of
Public Health, Berkeley, Bureau of Air Sanitation, p. 33-51.
Jan. 1966.
This article discusses the air monitoring systems in California
which detect the concentrations of nitrogen oxides.
Concentrations are given for hourly, daily, monthly and seasonal
variations. Statistics are also stated for hydrocarbon emissions
but not in as much detail as for the oxides of nitrogen.#t
01575
PHOTOCHEHICAL EFFECTS OF NITROGEN OXIDES (CHAFER VIII OF THE
OXIDES OF NITROGEN IN AIH POLLUTION). California State
Dept. of Public Health, Berkeley, Bureau of Air
Sanitation. p. 69-89, Jan. 1966.
The chemistry of the photochemical reaction is reviewed,-with
emphasis on the role of nitrogen oxides,._.It is concluded that
quantitative predictions cannot be made-about-the changes in the
photochemical smog effects that would result from various degrees
of control of either hydrocarbons or nitrogen oxides from motor
vehicles.#f . •
48 HYDROCARBONS AND AIR POLLUTION
-------
01582
H.W, Gerstle D.A. Kemnitz
ATMOSPHERIC EHISSIOSS FROM OPEN BURNING. J. Air
Pollution Control Assoc. 17 (5), 324-7 (Bay 1967).
(Presented at the 60th Annual Meeting, Air Pollution Control
Association, Cleveland, Ohio, June 11-16, 1967, Paper No.
67-135.)
Open burning of municipal refuse, of landscape refuse, and of
automobile components was simulated. Carbon monoxide
emissions were: 85 pounds per ton of material burned when municipal
refuse was burned, 65 pounds per ton when landscape refuse was
burned, and 125 pounds per ton when auto components were burned.
These values are all very high when compared to emissions from
municipal incinerators or other combustion processes. Gaseous
hydrocarbon emissions paralleled the carbon monoxide concentrations
and averaged 30 pounds per ton of material burned for all tests.
The organic acid concentrations were also fairly high, averaging
about 15 pounds per ton of material originally present in all
tests. Formaldehyde concentrations varied from 0.095 pound
per ton for municipal refuse to as low as 0.006 pound per ton
for the landscape refuse. These formaldehyde concentrations also
exceed those normally found in incinerators. Emissions of
nitrogen oxides varied widely and depended on the intensity of
burning. Highest values occurred during the initial burning
period when temperatures were high. After the initial intense
burning period of about 10 minutes, the nitrogen oxides
concentrations dropped off rapidly. Particulate emissions
averaged 16 pounds per ton of material burned when municipal refuse
was burned and 17 pounds per ton when landscape refuse was burned.
Emissions jumped to 100 pounds per ton when auto components were
burned. Emissions of polynuclear hydrocarbons were also quite
high, but for municipal or landscape refuse they were comparable
to emissions from small commercial incinerators. For auto
components, the concentrations were very high, comparable to
those found in emissions from small coal-burning furnaces.
(Author summary modified)##
01616
AIR POLLUTION CONTROL IN CONNECTION WITH DDT PBODUCTION
(INFORMATIVE HEPT. NO 6). J. Air Pollution Control Assoc.
14, (3) 94-5, Mar. 1964. (TI-2 Chemical Industry Committee).
DDT (Dichlorodiphenyltrichloroethane) is made from chloral,
monochlorbenzene and sulphuric acid. The air pollution aspects
of the process and of storage are considered-##
01620
THE PETHOLEtJB REFINING INDUSTRY - AIR POLLUTION PHOBLEBS AND
CONTROL METHODS (INFOEHATIVE HEPT, NO. 1). J. Air Pollution
Control Assoc. 14, (1) 30-3, Jan. 1964. (TI-3 Petroleum
Committee).
B. Emission Sources 49
-------
Possible air-borne contaminants from refining operations are
covered. Control methods for gaseous and particulate emissions,
and the industry's research projects are reviewed.!*
0162«
D.A. Jensen
SOURCES AND KINDS OF CONTAMINANTS FROM MOTOR VEHICLES
(INFORMATIVE REFT. NO. 4). J. Air Pollution Control ASSOC.
14, (8) 327-8, Aug. 1964. (TA-10 Vehicular Exhaust
Committee).
The sources of the pollutants, the important compounds, and the
magnitude of the several contaminant sources from both gasoline
and diesel powered motor vehicles are indicated.#f
01626
C. H. Festerfield
LITERATURE AND RESEARCH SURVEY TO DETERMINE NECESSITY AKD
FEASIBILITY OF AIR POLLUTION RESEARCH PROJECT ON COMBUSTION OF
COMMERCIALLY AVAILABLE FUEL OILS. J. Air Pollution Control
Assoc. 14, (6) 203-7, June 1964. (TA-4 Committee, Oil
Burner Equipment.)
The basic purpose of this preliminary survey was to determine:
(a) whether the combustion^ of fuel oil presented a serious air
pollution problem by nature of its being a serious
pollutant contributor; (b) what work has been done to evaluate its
pollution contribution; (c) what work is being done; '(d) what needs
to be done; (e) if there is need and justification for a fuel oil
combustion study.##
01654
A,C. Stern
THE REGULATION OF AIR POLLUTION FKOM POWER PLANTS IN THE UNITED
STATES. Rev. Soc. Roy. Beige Ingrs. Ind., Brussels
(Presented at the International Symposium on Immission
Regulations, sponsored by the Haus der Technik E.W. Essen and
the Arbeitt; -und Sozialministerium (Dept. of Labor and
Social Welfare) of North-Rhine-Westfalia, Essen,
Germany Mar. 9, 1966; and before the 'Societe Royale Beige
des Igenieurs et des Industrials, Brussels, Belgium, Mar. 16,
1966.)
Author discusses the types, concentrations, and levels of
control (state, federal and local) that the United States has
initiated for the abatement of air pollution from power generating
sources. Statistics are presented for various localities as well
as specific pollutants which are emitted. The Clean Air Acts
(88-206 and 89-272) as they apply to the abatement of air
pollution are explained.*#
50 HYDROCARBONS AND AIR POLLUTION
-------
01673
C.J. Conlee, P.A. Kealine, R.L. Cumsins, V.J.
Konopinsfci
MOTOR VEHICLE EXHAUST STUDIES AT THREE SELECTED SITES. Arch.
Environ- Health IK, (3) 429-K6, Mar. 1967.
Air quality was studied in relation to motor vehicle densities
at three selected sites: the Suaner Tunnel between Boston and
East Boston, Hassachusetts; the International Peace Bridge
across the upper Niagara River between Fort Erie, Ontario,
and Buffalo, Hew York; and Laidlaw Avenue near the Air
Pollution Research Facility in Cincinnati, Ohio.
Pollutant concentrations and aeteorological findings are
presented for each site. Concentrations of pollutants known to
be associated with auto exhaust were greater at sites of higher
traffic density. A comparison or particulate pollution levels
at the Suaner Tunnel operated as a one-way tube in 1963 with
the tunnel carrying two-way traffic in 1961, indicates a definite
decrease in pollutant levels. Other pollutants sere assuaed to
be dispersed in air in the sase way as carbon nonoxide in
determing the contribution by aotor vehicles to ambient air for
the Sumner Tunnel. Auto exhaust appears to be a prise
contributor (greater than SOS) for carbon monoxide, aliphatic
aldehydes, benzene-soluble particulate, and oxides of nitrogen.
Lead, beuzo(g,h,i)pyrene, and coronene nay also be assuaed to be
important pollutants froo auto exhaust, but they do not Beet the
requirements for contribution calculations. (Author abstract)**
01687
S.C. Ttothman
ESGISEEHIS3 CONTROL OF INDUSTRIAL AIH POLLDTIOS: STATE OF THE
ART, 1966. Heating, Piping, Sir Conditioning Bar. 1966.
1*1-8 pp. (Presented before the First Borld Air
Pollution Congress, Buenos Aires, Argentina, HOT. 1965.)
Probleas encountered by the engineer are illustrated through
analysis of air pollution control in the aluminas production
industry. Prebaked pots and Soderburg pots and their fluoride
enissions are considered.**
Q17SK
J. A. Adans, and E. G. Basdin
THE SDPPRESSIOH OF C4RBOS FOKHATIOS IN PARTIAL-COHBDSTION
GASIFIE3S. Die Terhntung von Kohlenstoffausscheidungen in
Gaserzeugern nit nnterstcchiometrischer Veibrennung. Erdel
Kohle (aanbnrn) 19, (8) 560-72, Aug. 1966. Text in Ger.
Bide industrial application of partial-combustion, liquid fuel
gasifiers is United by the occurrence of solid carbon in the
resultant fuel gases. The theory of solid carbon formation and
B. Emission Sources 51
-------
its inhibition is discussed. Experiments are described in which
carbon formation was suppressed in a partial—combustion distillate
fuel gasifier by vaporizing the fuel in the presence of steam,
carbon dioxide or nitrogen prior to combustion. In the presence
of steam the amount of carbon formed is inversely proportional to
the steam/fuel ratio at constant air/fuel ratio. (Author
summary) t#
01763
ORGANIC HALOGEN COMPOUNDS. (METHODS FOR THE DETECTION OF TOXIC
SUBSTANCES IN AIE.) Ministry of Labour, London, England
(Booklet No. 12) 1966. 10 pp.
The booklet first describes industries and processes in which
organic halogen fumes may be encountered, i.e. artificial silk,
bleaching, dyeing and dye-making, dry cleaning, electroplating,
engineering, lithography, refrigeration and rubber. It then
describes the toxic effects, notably liver damage as a long-term
effect and narcosis. The chief method of detection described is a
halide detector lamp in which the halogen will react with a copper
invert, in the lamp to give a typical green copper color in the
flame. It is emphasized that this is not a quantitative test
although approximate limits of coloration for various organic
halogen compounds are given; chlorobenzene, for example will show
color at a minimum concentration of 35 ppm, while 1,2 dibromoethane
will show color at 5 ppm. Approximately 50 compounds are thus
classified.f#
01788
R.P. Hangebrauck, D.J. Von Lehmden, J.E. Meeker
EMISSIONS OF POLYNUCLEAR HYDROCARBONS AND POLLUTANTS FROM
HEAT-GENERATION AND INCINERATION PROCESSES. J. Air Pollution
Control Assoc. 1«, (7) 267-78, July 196U. (Presented at the
56th Annual Meeting, Air Pollution Control Association,
Detroit, Mich., June 11, 1963.)
This paper presents emission data from a series of tests, for
which the sources tested included typical combustion processes
involving the burning of conventional fuels (coal, oil, and gas)
and of certain commercial and municipal solid wastes. In addition
to obtaining over-all emission data from different sizes
and types of combustion units, a primary objective of the study
was to establish the relative importance of various combustion
processes as contributors of benzo (a)pyrene (3,4 benzpyrene) and
other polynuclear hydrocarbons with demonstrated or potential
carcinogenic properties. The other pollutants measured included
particulate matter, carbon monoxide, total gaseous hydrocarbons,
oxides of nitrogen, oxides of sulfur, and formaldehyde. Two
categories of c/mbusticn sources were tested. Those burning
conventional fuels were designated as heat-generation processes,
and those burning waste materials were classed as incineration
processes. Design and operation data for the units studied are
given in tables.#f
52 HYDROCARBONS AND AIR POLLUTION
-------
01803
D. Hoffmann
A STUDY OF MS POLLUTION CAFCINOGENESIS. II. THE ISOLATION AND
IDENTIFICATION OF POLYNUCLEAS AROKATIC HYDROCARBONS FROH
GASOLINE ENGINE EXHAUST CONDENSATE. Cancer 15, 93-102, Feb.
1962.
1. Polynuclear aromatic hydrocarbons, both carcinogenic and
noncarcinogenic in animal tests, have been identified in
automobile exhaust "tar". These data do not indicate the
nature or the amount of these substances in the air.
2. The results are based upon automobile exhaust obtained from
a conventional engine under road load, a typical gasoline, and
used under "city driving" conditions. Present evidence suggests
that the mileage run by an engine does have an influence on the
formation of polynuclear aromatic hydrocarbons.*t
01815
A.P. Altshuller P.W. Leach
REACTIVITY OF AROMATIC HYDROCARBONS IN IRRADIATED AUTOMOBILE
EXHAUST. Intern. J. Air Water Pollution 8, 37-42, 1964.
Gas chromatographic analyses for up to 14 aromatic hydrocarbons
in the 7-10-carbon range and for ethylene and propylene were Bade
in irradiated auto exhaust containing total hydrocarbons
at 3-, 6- and 12-carbon ppn. The total and individual hydrocarbon
concentrations corresponded to the range of atmospheric levels
which have been measured in Los Angeles, and San Francisco.
About 40 per cent of the m-xylene and p-xylene and of the 1,3-
methyl-ethylbenzene and 1,4-methyl ethyl benzene reacted to form
products. Over 70 per cent of the trialkylbenzenes reacted
to form products. The average percentage conversion of the
7-1 carbon aromatic hydrocarbons measured vas approximately
the same as the percentage conversion for the ethylene plus
propylene. These results provide confirmation at atmospheric
concentration levels, of the reactivity of aromatic hydrocarbons.
(Author abstract)**
01837
H. F. HcBichael and A. H. Rose, Jr.
A COMPARISON OF AUTOMOTIVE EMISSIONS IN CITIES AT LOH AND HIGH
ALTITUDES. Preprint. (Presented at the 58th Annual 7eeting,
Air Pollution Control Association, Toronto, Canada, June
20-24, 1965, Paper 65-22.)
Automobile exhaust emissions were studied in Denver, Colorado.
Denver is unigue among large cities in the United States in that
it is situated at an altitude of approximately 5,000 feet; the
opportunity was thus provided for observing the effects of altitude
on auto exhaust emissions. The emissions measured in Denver in
B. Emission Sources 53
-------
1963 are compared with the emissions obtained in a similar,
previously reported study in los Angeles, California, and
Cincinnati, Ohio. The survey techniques and the instrumentation
used to colect and analyze the exhaust samples were the same.
Emission measurements were made on test vehicles driven under
actual traffic conditions while equipped with a proportional
sampler. This method produces data that reflect the effects of
traffic density, route, climate, and altitude.*f
01838
T. D., Nevens and F. A. Rohrman
GASEOUS AND PARTICIPATE EMISSIONS FROM SHALE OIL OPERATIONS'.
Preprint. (Presented at the American Chemical Society
Meeting, Pittsburgh, Pa., 1966.)
World-wide and domestic demands for hydrocarbons tend to seek the
most economical and convenient sources for potential exploitation.
It has been said that the oil shale deposits of the world
constitute many times the total of the world's
reserves of liquid petroleum. The vast shale oil industry is
nearly upon us as the problems of finding new economical sources
of liquid petroleum are becoming more acute. The next 5 or 10
years could see the emergence of shale oil industry producing a
million or more barrels a day in this small area of the Bocky
Mountains. Any ripples of unfavorable prices on imported crude
or finished products could cause abrupt waves of decision as to the
tin e of arrival of this industry. It is hoped that all
operations involving a future shale oil industry will take
cognizance of the potential air pollution problem. To disregard
air pollution at the early stages of development nay require later
intensive and extensive engineering at a much higher cost.tt
018U8
A. H. Rose
SUMMARY BEPORT OF VEHICULAR EMISSIONS AND THEIR CONTROL.
Preprint. (Presented at the Winter Annual Meeting,
American Society of Mechanical Engineers, Chicago, 111.,
Nov. 1965.)
The report summarizes average emissions from the four sources of
contaminants in the present day automobile: the exhaust, the
crankcase, the fuel tank, and the carburetor. Levels of
contaminants presented are for emissions under average urban
driving conditions, in contrast to earlier work in which values
were based on cyclic dynamometer tests. Emission levels are
expressed as pounds per day emitted and, where applicable, as
concentration. Emissions are considered by general chemical
classes to indicate the relative photochemical reactivities of
compounds from each of the four sources. Control approaches are
briefly discussed. (Author abstract)##
54 HYDROCARBONS AND AIR POLLUTION
-------
01863
AUTOMOTIVE AIB POLLUTIOB; (3ECOBI/ BEPOBT 07 THE SECBETABY OF
HEALTH, ED0CATIOB, ABB HELFABE TO THE 13.3. COSGRESS PUBSUAHT
TO PUBLIC LAW 33-206 - THE CLEAB AIB ACT.) 39th Congress
(1st Session (Docuoent «2) July 15, 1965- 17 pp.
Progress is reported on the resolution of the following problems;
exhaust enissions, crankcase emission, fuel evaporative losses,
maintenance, fuel, and diesels. The relevant literature is
reviewed,**
01868
AOTOHOTIVE SIB POLLOTIOH. (THIHD BEPOET OP THE SECRETABY OF
HEALTH, EDUCATIOB, ABD BELFABE TO THE U.S. COBGBESS PDBSDAHT
TO PUBLIC LAW 38-206 - THE CLEAH AIB ACT.) 89th Congress
(2nd Session) (Document 83) Bar. 25, 1966. 17 pp.
Seduced exhaust emissions of hydrocarbons and carbon monoxide
have become a reality in California, with the introduction of the
1966-nodel passenger cars and light commercial vehicles.
Recognition of the need for still farther control measures
is evidenced by the adoption of nitrogen oxide standards by
the California "Board, of Wealth. The Department of Wealth,
Education, and Welfare is implementing the new responsibilities
and authories conferred by the Hotor Vehicle Air Pollution
Control Act. Standards for the control of emissions froia
gasoline-fueled vehicles are being deveoped accordingly, to
become effective with the 1958 models. Some additional
technical information has become available. Further studies of
the effect of ambient temperature on exhaust enissions indicate
that low temperatures tend to increase exhaust hydrocarbons and
carbon monoxide, particularly following cold engine starts.
Preliminary results obtained from a study of the effect of
leaded fuels indicate that combustion chamber deposits may not
significantly affect the quantities of hydrocarbons and carbon
monoxide emitted in exhaust gases. A survey conducted to measure
carbon monoxide levels in urban communities suggests that
human exposure to carbon monoxide may be greater than routine
atmospheric monitoring data had indicated. A number of new
projects are being initiated by the Government to study the
performance characteristics of production-type exhaust emission
controls in varied environments, to develop more definitive
data on exhaust emissions from small cars and diesel-powered
vehicles, to learn more about human tolerance of lead and carbon
monoxide, and to effect control of oxides of nitrogen. An
expansion of industry research in automotive air pollution and its
control is indicated by the recent activities of technical
associations. (Author summary)*#
01885
W. T. BcKean, Jr., B. F. Hrutfiord, and K. V. Sarkanen
KIHETIC ABALTSIS OF ODOB FOBHATIOH IH THE KBAFT PULPIHG
PBOCESS I. Paper Trade J. 149, (35) 41-2, Aug. 30, 1965
B,: Emission Sources "55
-------
and Tappi «8, (12) 699-704, Dec. 1965. (Presented at the
National Meeting, American Inst. of Chemical Engineers, San
Francisco, Calif., May 1965.)
The kinetics of the consecutive formation of methyl mercaptan and
dimethyl sulfide at constant liquor composition were determined at
several temperatures using a novel gas analysis based on vapor
phase sampling. Comparison of kraft pulping of softwood and
hardwood species shows that more organic sulfur compounds are
produced from the latter group. In softwood pulping, a general
enhancement in the reactivity of the lignin methoxyls occurs
during the alkaline delignification process which results in
accelerated odor formation during the last phase of pulping. The
activation energies of these reactions suggest a substantial
reduction in total formation of organic sulfur compounds may be
accomplished by raising the reaction temperature and shortening the
time of the kraft cook. The significance of the results to actual
kraft pulping process is discussed. (Author abstract)##
01890
Williams, J. D., G. Ozolins, J. W. Sadler, and J. R.
Farmer
INTERSTATE AIR POLLUTION STUDY: PHASE II PROJECT BEPORT.
VIII. A PROPOSAL FOP AN AIR RESODECE MANAGEMENT PROGRAM.
Public Health Service, Cincinnati, Ohio, National Center
for Air Pollution Control, 132p., Hay 1967. 7 refs
This report is devoted to the development of an air use plan for
the St. Louis metropolitan area. An air use plan may be
thought of as a link between the potential pollutant emissions of a
community and the air quality goals. Its function is to optimize
the use of the air with respect to the amount of pollutants
emitted, by considering the dilution capacity of the air basin and
the configuration of the pollutant sources in the area. The air
use plan may then be used as the basic framework for achieving the
desired air quality by the various means available such as limiting
the emissions from individual sources, limiting the emissions from
sources in certain areas, or even disallowing new pollution
sources in overburdened areas. In short, it provides the basis
for enacting control regulations and provides a guide for future
planning activities.#f
01894
P.' A. Bennett, M. H. Jackson, C. K. Murphy, and B. A.
Randall
CEANKCASE GAS CAUSES U0% OF AUTO AIR POLLUTION. SAE (SOC.
Automot. Engrs.) J. 68, 31-6, Mar. 1960.
Crankcase gas is a major contributor to air pollution. In fact,
tests show that hydrocarbon emission from the crankcase is of the.
same order of magnitude as that due to exhaust. Composition of
exhaust and crankcase vent or blowby gases of five test cars was
determined by: Orsat analyses (carbon dioxide, oxygen, and carbon
56 HYDROCARBONS AND AIR POLLUTION
-------
monoxide) of grab samples obtained before and after a combustion
train; and a BecXman L/B Model 15A infrared analyzer, which
continuously measured exhaust and crankcase vent or blowby
concentrations. It was equipped with an n-hexane detector and
quartz optics. By using gas chromatography, measured Beckman
concentrations were converted to absolute hydrocarbon
concentrations. Blowby gases were shown to be predominantly
carbureted mixture. This led to the conclusion that the specific
hydrocarbons in the fuel determine the specific hydrocarbons in the
crankcase gases. Therefore, in cars whose crankcase emissions are
not controlled, the fuel used will determine the crankcase
hydrocarbons emitted. Feeding engine crankcase gases back to the
intake system eliminates crankcase hydrocarbon emissions without
appreciably affecting exhaust emissions. An internal crankcase
ventilating system can thus eliminate approximately 40% of the
engine hydrocarbon emissions (considering crankcase plus exhaust,
under all operating conditions) exclusive of carburetor vent
losses.*#
01902
H. Mukai, J. F. Thomas, and B. D. Tebbens.
AROMATIC HYDROCARBONS PRODUCED DUHIH.G COMBUSTION OF SIMPLE
ALIPHATIC FUELS. Anal. Chem. 37, 398-403. Bar. 1965.
(Presented before the Division of Water, Air and Haste
Chemistry, 148th Meeting, American Chemical Society,
Chicago, 111., Sept. 1965.)
The combustion of simple aliphatic fuels such as methane and
propane at atmospheric pressure results in the formation of _a. wile
array of products. Previous work has been concerned with
arene-type products. Current work has shown the relative
production of benzene, toluene, ethybenzene, as well as other
simple alkyl substituted derivatives of benzene. The practical
aspects include an index of relative abundance of the latter type
of compounds that might be found in polluted atmospheres as well as
indicating a method for predicting the relative contribution of
automobile exhaust to atmospheric pollution. (Author abstract)*t
01941
M. B. Jacobs
HEALTH ASPECTS OF AIR POLLUTION FROM INCINERATORS. Proc.
Natl. Incinerator Conf., New York, 1964. pp. 128-31.
The public health aspects of incinerator exhaust gases are
discussed first in the light of the physiological response
induced by specific contaminants such as sulfur oxides, nitrogen
oxides, and other inorganic gases and aldehydes, organic acids,
esters, polynuclear hydrocarbons, and other organic compounds;
second, with respect to their relation to illness caused by air
pollution in general such as emphysema and other respiratory
diseases, allergenic responses, and cancer; and third on the
character of the effluent gases, namely domestic, municipal, or
industrial. One aspect of doaestic incinerator effluents is
B. Emission Sources , 57
-------
particularly stressed, that is, the effect on nearby residents.
The contribution that incinerator exhaust gases make to the air
pollution of any given community depends on the ratio of the
amount of refuse and garbage burned to the total amount of fuel
used and consumed in that region.f#
01958
P. W. Leach, L. J. Leng, T. A. Bellar, J. E. Sigsby,
Jr., and A. P. Altshuller
EFFECTS OF HC/NOX RATIOS ON IRRADIATED AUTO EXHAUST, PAST II.
J. Air Pollution Control Assoc. 1tt, (5) 176-83, May 196U-
(Presented at the 56th Annual Meeting, Air Pollution Control
Association, Detroit, Mich., June 11-13, 1963.)
The relative concentrations of individual hydrocarbons have been
shown to be independent of autoexhaust concentration in dynamic
irradiation experiments. The absolute concentrations of the
individual hydrocarbons are linearly related to total hydrocarbon
concentration. The decrease in the concentration of reactive
hydrocarbons during irradiation is found to be independent of
whether a 120- or a 180-minute average irradiation time is used.
A fourfold reduction in initial -hydrocarbon concentration at
constant hydrocarbon to nitrogen oxide level causes a slight
increase in the relative amounts (percent) of hydrocarbon consumed
during irradiation. The same fourfold reduction in initial
hydrocarbon concentration at constant nitric oxide level results in
a decrease in the percent of olefins reacted, but does not affect
the percent of aromatics reacted. If the hydrocarbon level is
kept constant, while the nitrogen oxide level is varied, an
increase in nitrogen oxides causes a marked reduction in the
percent of olefinic and aromatic hydrocarbons reacted during
irradiation. The aldehyde yields are linearly related to the
total hydrocarbon level. No significant effect on aldehyde yields
was found when the average irradiation time was varied from 120 to
180 minutes. The aldehyde yields did vary with a decrease in
yield both at very high and very low ratios of hydrocarbon to
nitrogen oxide. The individual hydrocarbon and aldehyde
concentrations are shown to fall well within the range of
atmospheric concentrations. Although the aldehydes may be
responsible in part for the eye irritation, the presence of other
eye-irritating species must be postulated to explain the shape of
the eye-irritation response curves when plotted against nitrogen
oxide concentration.t#
02001
B. Gills E.L. Hove
OIL BURNEHS FOR DOMESTIC APPLICATION: PRESENT DESIGN AND FUTURE
DEVELOPMENTS. Proc. (Part I) Intern. Clean Air Cong.,
London, 1966. (Paper HI/2.) pp. 37-UU.
Published work from various research organizations in Europe
and the U.S.A. concerning malfunctioning of domestic pressure
jet burners is reviewed. It is shown that when poor combustion
98 HYDROCARBONS AND AIR POLLUTION
-------
performance of pressure jet burners is experienced the cause can be
traced to one, or a combination of the following factors: 1.
Poor design of the air/fuel mixing system. 2. Bad
maintenance. 3. Bad matching of the burner characteristics to the
heating appliance requirements. Bad performance of any
combustion system is reflected in the composition of the
final exhaust products. Hesults are presented which show that a
combustion system can generally be operated so that it products
no smoke, carbon monoxide or unburnt hydrocarbons. Due
to attention which has recently been drawn to "exhaust odor" from
oil-fired appliances reference is made to methods of measuring
the total hydrocarbon content of flue gases. Recent
developments with the objective of impo
developments with the objective of improving the combustion
performance and reliability of domestic oil burners are described,
together with references to research into methods of distillate
fuel atomization and combustion using novel principles.
(Author abstract modified)##
02017
M.A. Termeulen
AIR POLLUTION CONTROL BY OIL REFINERIES. Proc. (Part I)
Intern. Clean Air Cong., London, 1966 (Paper IV/5) .
pp. 92-5.
Stichting CONCAHE has been established by the Oil Companies'
International Study Group for Clean Air and Hater
Conservation (Western Europe). Its Working Group on
Atmospheric Dispersion is active in the field of abatement
and control of air pollution originating from both domestic and
industrial complexes. Major air-borne contaminations, from oil
refining operation but not petrochemical operations, such a
hydrocarbons, mercaptans, carbon monoxide, hydrogen sulphide
and sulphur oxides other than from refinery flue gas, are
discussed. Host common sources of the above contaminants are
discussed, together with the general refinery practices for
preventing or reducing emission of these contaminants. The
effectiveness of modern refinery processes in reducing air
pollution is reviewed and examples of local conditions and the way
they affect the setting of practical limits of emissions are
discussed. In conclusion, the general oil industries views with
respect to the air pollution problem are summarized. (Author
abstract modified)##
02023
G.J. Cleary
POLYCYCLIC HYDROCARBON RATIOS: THEIR USE IN STUDYING THE
SEQUENCE OF COMBUSTION IN A HAND-FIHED INTERMITTENT BRICK KILN.
Proc. (Part I) Intern. Clean Air Cong., London, 1966,
Paper IV/11). pp. 111-4.
Concentration ratios of polycyclic aromatic hydrocarbons have
been used to study combustion inn a hand-fired intermittent brick
B. Emission Sources 59
-------
kiln. Soot samples were obtained at various stages in the heating
cycle using a scrolltype high efficiency cyclone located at the
base of the stack. There is a gradation in the nature of the
tar adsorbed by the soot, that collected early in the drying
stage being primary, as the temperature rises there is a
transition to secondary tar. The highest concentration of
polycyclic aromatic hydrocarbons coincides with the highest
soot fall from the kiln. Two possible mechanisms are
examined. In both it is assumed that soot with absorbed primary
tar is deposited on kiln walls and product surfaces during the
steaming period and that towards the end of the preheating period
the higher flue gas velocities and greater temperature gradients
dislodge the soot: (a.) in the early part of the steaming period, as
successive layers of soot deposit they prevent colatilization of
the tar adsorbed on previous deposits. When the soot is
dislodged the adsorbed tar, no longer shielded, is thermally
cracked on the surface of the carbon particles; (b) the primary
tar is alternatively cracked on the surface of the soot
before the latter is dislodged and this assumes that the
adsorptive forces are sufficiently strong to prevent the
mass transfer of the adsorbed tar into the flue gas stream.
(Author abstract)tt
02066
W. Breuer, and K. Winkler.
SOOBCES AND DISTRIBUTION OF AIR POLLUTIONS ASCERTAINED BY
STATIONARY RECORDING OF GASEODS COMPONENTS. Herkunft Ond
Ausbreitung Von Luftverunreinigungen, Ermittelt Durch
Stationare Registrierung Mehrerer Immissionskomponenten.
Proc. (Part I) Intern. Clean Air Cong., London, 1966.
(Paper VII/10). pp. 239-42.
Simultaneous, continuous and stationary measurement of'the
concentration of gas components. (CO, C02, S02, H2S, C12,
nitrous gases, hydrocarbons) combined with the recording of
meteorological factors (wind direction, speed of wind, atmospheric
stability etc.) enable the identifying of the source of air
pollutions (motor vehicle exhaust, domestic heating, power
stations, chemical works). The examination of special air
conditions and statistical evaluation gives information on the
process of distribution. (Author abstract)##
02152
G. Weston.
EXCESSIVE EMISSIONS OF FIREDAMP IN THE WEST LANCASHIRE AND NORTH
WALES COALFIELDS. MINING ENGR. (LONDON) 126, (74) 81-96,
Nov. 1966.
Several recent sudden emissions of firedamp in the Lancashire and
North Wales coalfields are reported; steps taken to deal with the
emissions and recognition of common factors indicating when similar
occurrences might be expected are recorded and analyzed. Firedamp
60 HYDROCARBON SAND AIR POLLUTION
-------
drainage by boring holes into the seams close below the one being
worked was one method employed. The system should be capable of
dealing with more firedamp than is normally encountered to protect
against sudden substantial emissions, Regular monitoring of
firedamp emitted from wastes and in the tunnels is necessary.
Emissions of firedamp from the seam being worked may be reduced if
steps are taken to "harden" the coal.##
02153
C. A. Bogus.
CONTROL OF AIR POLLUTION AND HASTE HEAT. RECOVERY FROM
INCINERATION. PUBLIC WORKS 97, (6) 100-3, JUNE 1966.
Europe has had for some time rigid government standards
controlling air pollution with many large scale air pollution
control installations, particularly of refuse incineration
facilities. The nature of air pollutants from refuse incineration
is discussed. The chemical analysis of fly ash is given as well
as the size distribution of stack dust emissions. Air pollution
abatement equipment is described. The approximate characteristics
and costs of major collector systems are tabulated.##
02232
R.L. Stenburg, T.P. Hangebrauck, D.J. Von Lhdmden,
A.H. "Rose, Jr.
EFFECTS OF HIGH VOLATILE FUEL ON INCINERATOR EFFLUENTS.
J. Air Pollution Control Assoc. 11, 376-83, Aug. 1961
(Presented at the 53rd Annual Meeting, Air Pollution Control
Association, Cincinnati, Ohio, May 22-26, 1960.)
A readily vaporizable solid fuel normally considered as being
more difficult to burn than ordinary cellulose was treated in a
multiple chamber incinerator having an 8.5 sg, ft. grate area
in a 19.5 cu. ft. primary combustion chamber, a downpass mixing
chamber and a 16,5 cu ft. final combustion chamber. One part
shredded asphalt saturated felt roofing composed of 60%
petroleum base asphalt, 37 T/2% felt, and 2 ~\/2% ash with one
part 1" sguares of newpaper was the fuel mixture. . The effects
of combinations of excess air (100 and 200%), fuel feed rate (100
and 150 Ib/hr) , fuel per charge, underfire air (15 and 6056), and
secondary air on the emission of particulates, oxides of nitrogen,
hydrocarbons, carbon monoxide, formaldehyde, and smoke were
evaluated. Optimum conditions imply a temperature range of 1800
to 2000 F in the secondary chamber, 15 to 20* underfire air, and
small batch on continuous charging.##
02234
CHEMICAL INDUSTRY REPORT (REVISED INFORMATIVE REPORT NO. 1).
J. Air Pollution Control Assoc. (TI-2 Chemical
Committee). 13, (10) 496-9, Oct. 1963,
BJ Emission Sources 61
-------
The chemical industry uses raw materials from mine, forest, sea,
air, and farm; from oil, brine and gas wells; and from by-product
materials of many other industries. It converts these widely
diversified raw materials into more than 8,850 compounds, called
"end chemicals," in more than 12,000 plants operated by hundreds
of chemical manufacturers. since World War II the chemical
industry has become so diversified that it is difficult even
to classify it accurately. Today, petroleum producers are now
important chemical manufacturers; paper companies, rubber
companies, even manufacturers of electrical machinery and farm
equipment are chemical producers. This report will discuss in
general terms some of the characteristics of emissions from certain
kinds of operations and the relation of the plant operators to
the Air Pollution Control Officials.**
02236
HYDROCHLORIC ACID MANUFACTURE, REPORT NO. 3. J. Air
Pollution Control Assoc. 13, (10) 502-5,7, oct. 1963.(TI-2
Chemical Committee.)
This report, published as Informative Rpt. No. 3 of the Air
Pollution Control Association's TI-2 Chemical Committee
represents the "best thingking of the Association" on the
subject. The manufacture of hydrochloric acid involves the
generation of hydrogen chlorid gas and its absorption in water
for the aqueous solutions. There are three principal processes
used to produce hydrogen chloride: (1) Reaction of salt and
H2SOU (Hahnheim Process) resulting in the production of
hydrogen chloride gas and sodium sulfate; (2) Burning chlorine in
a slight excess of hydrogen; (3) As a by-product from
chlorination of organic compounds. Up until the early thirties
more acid was made by the salt-acid process; by 1961 the hydrogen-
chlorine process was more in use. Air pollution aspects of the
processes are reviewed.**
0224H
A.H. Rose, Jr., B.C. Stahman, M.V. Korth
DYNAMIC IRRADIATION CHAMBER TESTS OF AUTOMOTIVE EXHAUST, PART I.
J. Air Pollution Control Assoc. 12, «68-73, Oct. 1963.
(Presented at the 55th Annual Meeting, Air Pollution
Control Association, Chicago, 111., Bay 20-21, 1962,)
The data from this series of tests run under dynamic
irradiation conditions show differences attributable to: (1) the
concentration of exhaust gas at which the irradiation was made, and
(2) the composition of the fuel used to produce the exhaust gas.
Evaluations of the variations in chemical reaction and
biological effects show: (1) The rate of N02 formation
increased proportionately with both exhaust concentration and
olefin content of the fuel. (2) The percentage of N02 reacting
with unreacted fresh exhaust components and with secondary reaction
products varied inversely with the increase of the exhaust
concentration level. (3) No consistent change in oxidant
concentration level (primarily ozone) resulted from an inarease
in the hydrocarbon concentration level at which the irradiation
62 HYDROCARBONS AND AIR POLLUTION
-------
was made. {«) Formaldehyde formation increased in direct
proportion to the increase in hydrocarbon concentration at
irradiation. (5) Plant effects indicate a shift in the type
of phytotoxicant developed and a decrease in damage level
with increase in the hydrocarbon concentration level at which
the irradiation was made. (6) Bacterial effect showed a
significant increase in degree of kill with increase in
hydrocarbon concentration level at which the irradiation was
made. {Author summary)#t
02335
H. K. Hewhall.
THEORETICAL AND EXPERIMENTAL INVESTIGATION OF CHEMICAL KINETICS
DURING RAPID EXPANSIONS OF HIGH TEMPEBATURE COHBUSTION PRODUCTS
(DOCTOR'S THESIS). (For the degree of Doctor of
Philosophy in Engineering, California Univ., Berkeley,
Graduate Div.) Sept. 1966. 198 pp.
Theoretical analysis predicts that during expansion of combustion
products occurring in internal combustion engines, the rate of
atom and free radical recombination is sufficient for
equilibration of these species. It is further predicted that as a
result of kinetic limitations, nitric oxide persists in
hyper-equilibrium concentrations. Theoretical analysis of the
kinetics of the expansion process was performed, through use of a
digital computer. Overall reactions considered were the
decomposition of nitric oxide and the recombination of atonic
oxygen, atomic hydrogen and the hydroxyl free radical. Rate
expressions for the overall reactions were formulated through
consideration of all significant elementary reactions. Reaction
rate data for the elementary reactions were obtained from a large
number of published sources. Nitric oxide is of considerable
importance in the problem of automotive air pollution and' an
experimental study of nitric oxide decomposition occurring during
engine cycle expansion was undertaken. A single cylinder
research engine was equipped with an infrared transmitting
window. The emergent infrared radiation was studied by means of
spectroscopic equipment making possible the determination of
nitric oxide concentrations throughout expansion. The results
indicate that nitric oxide concentration remains fixed throughout
the entire expansion process. (Author summary modified)##
02362
J.H. Ludwig
STATUS OF VEHICLE EMISSIONS IN AIR POLLUTION. Preprint.
(Presented at the Eighth Annual Environmental Health Inst.,
Colorado Association of Sanitarians, Denver, Apr. 26, 1963.)
Review of the various classes of motor vehicles in use today
and associated power plants indicates that as a group the
gasoline-powered passenger car accounts for the major share
of auto exhaust emissions associated with production of
photochemical snog. Of the various sources of emissions from
B. Emission Sources 63
-------
all types of vehicles, tailpipe emissions from gasoline-powered
vehicles are the most significant, followed by crankcase
02375
J. E. Sigsby, Jr. and M. H. Korth.
COMPOSITION OF BLOWBY EMISSIONS. Preprint. (Presented at the
57th Annual Meeting, Air Pollution Control Association,
Houston, Tex., June 21-25,,196U, Paper No. 64-72.)
The composition of blowby emissions was evaluated from ten
different cars with displacements ranging from 52 cu in. to 365
chromatographic analyses were made of the blowby hydrocarbon
composition covering a group of approximately 75 components.
Nondispersive infrared and flame ionization equipment were also
used to determine CO, C02 and hydrocarbon concentrations.
(Author abstract)t#
02U28
M. P. Sweeney
THE POTENTIAL OF MODIFICATIONS TO THE ENGINE INDUCTION
SYSTEM ON PERFORMANCE AND EMISSIONS. Scott Research Labs.,
San Bernardino, Calif. 31 pp., 1966
This paper describes approaches to combining reduction in exhaust
emissions from spark ignition internal combustion engines with
equal improved "performance". In view of the new legislation of
vehicle emissions, a new criterion of engine design is being added,
so that now the basic criteria are: Power capabilities, economy,
driveability and emissions. The induction system modifications
discussed in this study are believed to play a large and increasing
part in exhaust emission reduction. Furthermore author states
that these improvements will contribute to improved general
operation and performance of spark ignition internal combustion
engines in the very near future.##
02527
D. S. Smith and E. S. Starkman
PERFORMANCE OF ANHYDROUS AMMONIA AS A SPARK IGNITION ENGINE
FUEL. California Univ., Berkeley, Dept. of Mechanical
Engineering. 62 pp., Feb. 1966.
CFSTI, DDC: AD 633632
The operating characteristics of anhydrous NH3 as a fuel for a
spark ignition engine were determined and compared, experimentally
and theoretically, to those of iso-octane, the reference
hydrocarbon fuel. Experimental data obtained over a. wide range of
parameters—compression ratio, engine speed, manifold
pressure—displayed no grossly divergent fuel characteristics for
NH3 compared to iso-octane. Anhydrous SH3 was demonstrated to
operate successfully as a fuel for spark ignition engines.
€4 HYDROCARBONS AND AIR POLLUTION
-------
Principal requirements are that it be introduced into the
engine in the vapor phase and be partly dissociated to H2 and
HH3, Dissociation was accomplished in a temperature controlled
catalytic dissociator using pelletized activated iron catalyst.
The optimal weight concentration of H2 to insure against power
loss is approximately 5%. The maximum theoretically possible
indicated output using ammonia vapor when adjusted for 5^ hydrogen
dissociation is about 75% of that with hydrocarbon. The
presently obtained maximum experimental level is 12% at a
compression ratio of 10. Specific fuel consumption, both by
theory and experiment, is twofold at maximum power and 2-1/2 fold
at maximum economy when using ammonia as a replacement for
hydrocarbon. Spark timing for maximum performance must be
advanced slightly for ammonia but sensitivity to spark timing is
very little greater than with hydrocarbons. (Author summary
modified)##
025U8
F. I. Dubrovskaya, I. A. Pinigina, and V. M. Styazhkin
POLLUTION OF AIR BY SYNTHETIC FATTY ALCOHOLS AROUND A FACTORY
PRODUCING FAT SUBSTITUTES. (Zagryaznenie atmosfernogo
vozdukha sinteticheskimi zhirnymi spirtami vokrug proizvodstva
zhirozamenitelei.) Hyg. Sanit. 31, (1) 113-5, Jan. 1966.
CFSTI: TT66-51160/1-3
The qualitative and quantitative composition of alcohols
contaminating the air around factories producing synthetic fatty
alcohols and synthetic fatty acids, is described for the first
time. Such air may contain volatile lower alcohols, as well as
less volatile higher alcohols. Since aliphatic alcohols differ
in their toxic properties, the maximum permissible atmospheric
concentration should be established for each alcohol separately.**
025«9
L. V. Buzunova, A. N. Bokov, A. M. Gurevich, and Z.
P. Nikitinskaya
SLAG HEAPS AS i SOURCE OF ATMOSPHERIC POLLUTION. (Otvaly
ugol'nykh shakht kak istochnik zagryazeniya atmosfernogo vozdukha.)
Hyg. Sanit. 318 (1) 118-20, Jan. 1966.
CFSTI: TT66-51160/1-3
The burning slag heaps of the coal mining districts in the
Rostov Region, where the principle combustible component is
anthracite, do not present any carcinogenic hazard. However,
this conclusion cannot be extended to burning rocks in slag heaps
containing quantities of other grades of coal, such as
bituminous coal, and particularly coal which processes a higher
content of tarry substances. The burning slag heaps give rise to
considerable pollution of the atmosphere by carbon monoxide and
sulfur dioxide,**
B. Emission Sources 65
-------
02573
N.Y,A. Yanysheva, .L.G. Andrienko, N.V. Balenko, I.S.
Kireeva
THE CARCINOGENIC PROPERTIES OF COKE OVEN WASTES. (0
kantsergennykh svoistvakh vybtosov koksovykh pechei.) Hyg.
Sanit. 29, (5) 6-11, May 1964.
CFSTI: TT65-50023/5
The authors present data on the concentration of 3,4-benzpyrene,
anthracene, 1,2-benzanthracene, phenatrene, pyrene, phryzene in
the discharges of coke oven into the air and the effect exerted by
these discharges on animals in a biological test. It was shown
that the coke gas resin in the coke oven discharges contains 0.3X
of benzpyrene and certain other polycyclic aromatic carbonhydrates
and has a strongly marked blastogenic effect on experimental
animals. As a means of control of atmospheric air pollution with
cancerigenic substances the authors suggest a smokeless method of
charging coke ovens. (Author abstract)tf
02610
C. V. Ranter, and R. G, Lunche
EMISSIONS AND POLLUTANT LEVELS (TRENDS IN LOS ANGELES).
Arch. Environ. Health 8, (1) 5-11, Jan. 1964. (Presented at
the Sixth Annual Air Pollution Medical Research Conference,
San Francisco, Calif., Jan. 28-29, 1963.)
For accurate assessment of the problems, needs, and progress of an
air pollution control program, accurate information must be
obtained on emissions of contaminants from sources, and on
contaminant levels. This is a very large task, requireing the
acquisition of a great mass of data on a continuing basis. In a
large community suffering the blight of smog, the acguisition of
data is imperative in order to take effective action to stop the
advancing menace and to begin a trend back toward clean air. In
Los Angeles total air pollution surveys and air monitoring
activities have provided the means for understanding the basic
causes of the smog problem, and for guiding actions which have
slowed the advance of smog and which will turn it back.
Inspection of trends of emissions and contaminant levels in Los
Angeles County affirms that a vigorous control program on
stationary sources can slow and even reverse trends. It is clear
though, that permanence of these effects cannot be achieved until
the increasing emissions frcm motor vehicles are controlled. Of
the major contaminants discussed, only sulfur dioxide, which is not
significantly affected by motor vehicles emissions, has regressed.tt
02635
J. H. Boddy and D. Turner
A DEFINITION OF THE PROBLEM AND SIGNIFICANCE OF AIR POLLUTION FROB
PETROL-ENGINED VEHICLES (PART I OF ATMOSPHERIC POLLUTION: A
66 HYDROCARBONS AND AIR POLLUTION
-------
SURVEY OF SOME ASPECTS OF THE EMISSIONS FHOH PETROL-ENGINED
VEHICLES AND THEIR TREATMENT). British Technical Council of
the Motor and Petroleum Industries, England. Sept. 1965.
pp. 1-34.
Horld-wide legislation is reviewed; the existing and probable
restriction on vehicle use and design is presented. The notor
vehicle pollutants are detailed. The public health significance
is examined. Automotive emissions are compared to those from
other sources. Existing legislation in the western and
non-Communist world, other than the Californian legislation,
imposes negligible restrictions on the gasoline engine at present,
but shows indications of imminent action. Legislation in many
countries is framed in such a way that regulations against emission
from gasoline vehicles could be enforced without major revision of
legislation. This is most apparent in recent revisions of
legislation, e.g. Ireland, France, and Belgium. When and if
the present legislation in the O.K. is successful in controlling
pollution from industrial and domestic sources, more attention oust
inevitably focus on the motor vehicle. The gasoline-engined
vehicle makes a major contribution to the following pollutants:
carbon monoxide, unburnt hydrocarbons, and oxides of nitrogen.
Of these pollutants referred to, carbon monoxide is certainly the
most undesirable. Oxides of nitrogen may be more damaging in
respect to chronic exposure but evidence is limited. Onburnt
hydrocarbons in vapour form appear significant only in relation to
photochemical smogs. Heavy hydrocarbons in association with
non-particulate matter, like oxides of nitrogen, have possible
significance in relation to effects of chronic exposure. The use
of lead in gasolines appears to have minor significance as a health
hazard in respect to its pollution of the atmosphere. Major
attention should be immediately devoted to the reduction of carbon
monoxide emission from automotive vehicles. In the interests of
clarifying the situation and, as a safeguard against possible
legislation of an unnecessarily restrictive nature, the motor and
petroleum industries should support research into the significance
of such emissions as oxides of nitrogen and heavy hydrocarbons and
methods of reducing these.f#
02636
J. A. Walker
INFLUENCE OF GASOLINE COMPOSITION ON THE CONSTITUTION OF ENGINE
EXHAUST (PABT II OF ATMOSPHERIC POLLUTION: A SURVEY OF SOHE
ASPECTS OF THE EMISSIONS FBOM PETROL-ENGINED VEHICLES AND THEIR
TREATMENT). British Technical Council of the Motor and
Petroleum Industries, England. Sept, 1965. 35-6U pp.
The major component, adverse to health, in gasoline engine
exhausts is carbon monoxide. Fuel composition has no
influence on the production of this toxic compound and it is
recommended therefore that work is carried out to develop other
practicable methods of minimixing CO in engines of European
design. Traces of unburned hydrocarbons are also present in
exhaust gases and in California they contribute to smog formation
by participating in photochemical reactions promoted by sunlight.
This reaction rarely occurs in Europe, and thus hydrocarbons are
of importance only because they may make a small contribution to
B. 'Emission Sources 67
-------
the presence of carcinogenic compounds in the air. The AHA has
stated that in some 1966 model cars, an engine afterburner system
will be fitted as original equipment which will convert CO and
hydrocarbons to the harmless compounds C02 and water. Any
method adopted in Europe for removing CO from exhaust gases
is likely to be of a similar type and inevitably the major part of
the hydrocarbons present in the exhaust will also be converted into
innocuous materials. It is recommended that work is carried out
to assess the importance of the presence of oxides of nitrogen in
the air, and if necessary to develop means of preventing their
emission from gasoline engine exhausts. Particulate natter is
emitted from engine exhausts consisting of sulphur compounds,
carbon, compounds of lead and other materials. At the present it
is not considered that these represent any appreciable health
hazards, but it is recommended that close touch is maintained with
workers in the U.S.A. and in the U.K. who are measuring the
concentration and nature of particulate matter in the air,
particularly under high traffic density conditions. Evaporation
of gasoline vapours from the car fuel tanks and carburetors will
probably be controlled in the D.S.A. The contribution to
atmospheric pollution from these sources must be extremely small,
but it is recommended that some work is carried out in European
engines to investigate the factors involved. (Author summary)*!
02806
F. J. Schuette
AUTOMOTIVE EXHAUST STUDY CONDUCTED AT U.S. BUEEAD OF BINES
PETROLEUM RESEARCH CENTER, BARTLESVILLE, OKLAHOMA (FINAL
REPT, JULY 17-NOV. 10, 1959). California State Dept. of
Public Health, Berkeley, Air and Industrial Hygiene Lab.
(Rept. No. AIHL-1) June 9, 1960. 28 pp.
Based on the data included in this report it may be said that
exhaust hydrocarbon analyses by n-hexane-sensitized non-dispersive
infrared analyzers are reproducible from one instrument to another
when instrument variables are kept constant. For this reason,
they make valuable survey instruments. It must be borne in Bind
that n-hexane sensitized analyzers "see" only a fraction of the
total exhaust hydrocarbons, the fraction depending on the
instrument characteristics and the composition of the exhaust gas.
Analyzers sensitized to acetylene, benzene and ethylene used in
this study were not reliable. Efforts to obtain two analyzers
with comparable responses did not produce satisfactory results.
Preliminary investigations into flame ionization detection for
exhaust hydrocarbon analyses indicate this instrument to be
promising as a true carbon counter. Gas-liquid partition
chromatography, although very time consuming, still appears to be
the best method for analysis of exhaust hydrocarbons. Of course,
there is still need for further refinement of techniques in this
method. (Author conclusion)**
02911
R. L. Chass, R. G. Holmes, A. P. Fudurich, and H. H.
Burlin
68 HYDROCARBONS AND AIR POLLUTION
-------
EMISSIONS FROM UNDERGROUND GASOLINE STORAGE TANKS. J. Air
Pollution Control Assoc. 13, (11) 52U-30, Nov. 1963.
(Presented at the 56th Annual Meeting, Air Pollution Control
Association, Detroit, Mich., June 9-13, 1963, Paper No. 63-
i»6.)
A test program was designed and carried out in two phases: a
study of current service station filling losses, and determination
of variations in these losses using a prototype vapor return
system. Emissions from the filling of underground tanks amount
to 11.5 Ib of vapor for each 1000 gal of gasoline delivered; in
Los Angeles County, this totals 38 tons per'day, assuming
splashloading techniques are used at all locations. Equipment
auxiliary to the delivery and loading of this gasoline is
responsible for an additional controllable total of five tons per
day of vapor emissions. Use of various combinations of equipment
and techniques could provide vapor control of the following
magnitudes: A 37X reduction merely by converting from splash
filling to submerged filling techniques. A 93S reduction by
returning the vapors .to the tank truck, but retaining the normal
vent line from the underground tank to the atmosphere.
Essentially complete reduction by using submerged filling,
returning the vapors to the tank truck, and eliminating the
atmospheric vent line. (Author summary modified)##
02956
G. B. Warren
FUEL-ECONOMY GAINS FROM HEATED LEAN AIR-FUEL MIXTURES IN MOTORCAR
OPERATION. Preprint. (Presented at the Winter Annual Meeting,
American Society of Mechanical Engineers, Chicago, 111.,
Nov. 7-11, 1965, Paper No. 65-HA/APC-2.)
Following suggestions resulting from previously published
results a 1963 225 cu in., 8.2 to 1 compression ratio six cylinder
sedan with automatic transmission was modified to permit cruising-
speed operation with 10 to 25* leaned mixtures, the leaning air
being separately heated by an exhaust heat exchanger. The heated
leaning air vas introduced into the intake manifold through fixed-
area orifices below the-throttle valve, "with this arrangement, of
course, opening of the main throttle valve by depressing the
accelerator would drop the vaccuum in the intake manifold and
reduce or eliminate entirely the induction of leaning air and
return the motor to full throttle, cold inlet, and normal throttle
mixture immediately, and so result in no diminution of full-
throttle performance. Slightly less than 10% gain in normal fuel
consumption was demonstrated on a new and already very
economical motorcar; analysis indicates that up to 15* may be
obtainable. With the heated leaning air inlet no surging
difficulties were encountered except at very low idling speeds,
which it is believed could be obviated by refinements in controls
or adjustments. Also, the smog-making properties of the exhaust
should be'reduced by this system. This is not to be confused wit'h
the more normal preheating of the air to the carburetor, which
will also result in simultaneously enriching the fuel-air ratio,
and will also reduce full-power performance. (Author abstract) it
B. Emission Sources 69
-------
03113
R.W. Gerstle, S.T. Cuffe, A.A. Orning, C..H. Schwartz
AIR POLLUTANT EMISSIONS FROM COAL-FIRED POWER PLANTS, REPORT
NO. 2. J. Air Pollution Control Assoc. 15, (2) 59-64,
Feb. 19659
The Public Health Service and the Bureau of Bines are
conducting a joint study to evaluate a number of flue-gas-stream
components from coal-burning power plants. Emissions of fly
ash, sulfur oxides, nitrogen oxides, polynuclear hydrocarbons,
tota.1 gaseous hydrocarbons, formaldehydes, certain metals,
and carbon dioxide are determined. A previous paper
covered air pollutant emissions from vertical-fired and front-wall-
fired power plant boilers. This paper includes a comparative
evaluation of emissions from a tangential-fired and a turbo-fired
power plant boiler. (Author abstract)t#
03122
B. Brunner, P. Lemaigre
METHODS OF REDUCING POLLUTION CAUSED BY INTERNAL COMBUSTION
ENGINES. (Motor Vehicles). European Conf. on Air
Pollution Strasburg, 196<*. p. 191-258.
As a result of the growth of industry and the subsequent
development of motor vehicles, European countries are faced with
an air pollution problem the nature and size of which depend not
only on the degree of industrialisation and the number of motor
vehicles in sue but also on the density of population and industry,
traffic conditions and geographical and climatic conditions.
The problem of pollution from motor vehicles in Ireland or
Norway is different from that in Germany. The problem in
France as a whole is not the same as the problem in Paris.
The problem in Paris is, in turn, different from the smog
problem in London, while the latter problem is different
again from the smog problem in Los Angeles. In Belgium,
Ireland, Norway, the Netherlands, Sweden, Switzerland and
even Italy, the interest of the public, the police and
legislature is concentrated mainly on the visible smoke from
diesel vehicles, while petrol-driven vehicles are not yet regarded
as a very serious source of pollution. In Switzerland, the
inspection authorities have been primarily concerned from the
outset (apart from gas emissions by factories) with the
quantities of CO and lead compounds to be found in the air
along traffic routes. This work began in the years immediately
following the appearance of ethyl motor spirit on the market
(19U7). In the United Kingdom, attention also seems to be
directed mainly towards other sources of pollution. In the
Federal Republic of Germany and France mortality and
morbidity statistics, reports on pollution t*ends in
particular areas, the effects of pollution on people, plants and
masonry have made doctors and learned societies alive to the
changes, led to Press campaigns and impressed public opinion
and government departments. The issue is not only the nuisance
7° HYDROCARBONS AND AIR POLLUTION
-------
caused by smoke, but, abovs all, the poisonous nature of
the exhaust gases of petrol engines. Considered are: (1) - the
organisation of anti-pollution action in each state; (2) -
studies and research; organisation, co-ordination and results;
(3) - methods and equipment which can be used to reduce pollution;
and (4) - anti-pollution legislation in Europe.*!
03129
C. Padovani
HETHODS OF REDUCIHG POL10TIOS CAUSED BY SPECIFIC IHDUSTBIES
(CHAPTER V. OIL INDUSTRY). European Conf. on Air Pollution,
Strasbourg. 196<*. pp 323-36.
One general observation that can be made concerning the national
reports received is that the information they contain is not full
enough or specific enough particularly as regards pollution
statistics, the cost of anti-pollution equipment and the results
obtained. Furthermore, as regards sources of pollution and
methods of control, the reports mention nothing vhich cannot be
found in technical literature. Becent years have seen enormous
refinery developaent in Europe owing to a steady increase in
consumption and the transfer of processing plants from the areas
where the crude oil is obtained to those where petroleum products
are consumed. There are also signs of a tendency to concentrate
production in increasingly large refineries and of a continuous
increase in secondary or vertical refining processes as compared
with primary or horizontal refining processes. The pollution
problem has naturally been aggravated by the tendency to bring
refineries closer to consumption areas. By their very appearance,
the enormous size of the storage tanks, the tall distillation
towers, the flares for burning the surplus gases, petrol
refineries make a strong impression on the public at large and give
rise to suggestions out of all proportion to the actual threat
presented to public health. It should further be pointed out
that the European oil industry was almost completely reconstructed
after the second world war and that, even in the field of pollution
control, it is in the van of progress. However, the oil industry
still needs to improve on the measures it has adopted.**
03129
Avy., A. P.
BETHODS OF SEDUCING P011UTIOH CAUSED BY SPECIFIC IKDUSTBIES.
(CHAPTEB VI. CHEHICA1 IHDUSTBY). European Conf. of Air
Pollution, Strasburg, 196«. p. 337-356.
The pollutants discharged by the chemical industry may be
subdivided into several classes. The first and most important
class is that of harmful products emitted, in large quantities by
the "heavy" chemical industry and, in particular, organic
chemical works: Sulphur dioxide, sulphuric acid, chlorine,
whether manufactured or in the form of impurities in the basic
•aterial: fluorine in the case of fertilizers and fluorine again
in aluminum electro-chemistry. The chemical industry has a wide
B. Emission Sources 71
-------
range of special problems which is in a constant state of flux
owing to the wide and ever-increasing variety of new synthetic
products (intermediate and finished) in the organic chemical
industry. From the technical point of view, the prevention of
pollution by such products depends on their presentation and
manner of application. A problem directly connected with
chemical manufacture is that of smell: mercaptans, hydrogen
phosphide, methylamines, etc., although, of course, it does not
arise in the chemical industry alone. Technical methods used to
reduce pollution are highly devellped for dusts and smoke and there
is a wide choice of apparatus. The chemical industry, like all
others, is subject to laws and regulations governing industrial air
pollution. A fairly sharp distinction, however, should be drawn
between laws, which lay down in general terms the objects to be
attained and the obligations to be fulfilled, and the regulations
which embody detailes of the limits imposed and the degree of
reduction demanded. In this last report, caution is necessary and
impossible or unnecessary standards should not be set. It is
clear that international liaison or even international
collaboration is not only desirable, but necessary.#f
03158
N. C. Kailos
UTILIZATION OF AMMONIA AS AN ALTERNATE FUEL IN AHMY AIFCSAFT
ENGINES, Army Aviation Material Labs., Fort Eustis, Va.
(Technical Report No. 66-52.) June 1966. 68 pp.
CFSTI, DDC AD 638360
The successful application of the Nuclear Powered Energy Depot
Concept is partly dependent upon the practicability of
ammonia-fueled gas turbine engines. The purpose of this
investigation was to assess the feasibility of ammonia-fueled gas
turbine engines in Army aircraft. In accordance with this
objective, engine performance in the DH-1D helicopter and in the
CV-7A fixed-wing aircraft was compared utilizing both
hydrocarbon and anhydrous ammonia fuels. Aircraft fuel system
reguirements were investigated, and an elementary cost comparison
was made for engine conversion kits and production engines.
Engine maintenance was considered briefly. From this study, it
is concluded that the use of ammonia as a gas turbine fuel results
in considerably lower aircraft productivity than the productivity
obtained from the use of hydrocarbon fuels. (Author abstract)f#
0316U
M. E. LePera
INVESTIGATION OF THE AUTOXIDATION OF PETROLEUM FUELS (INTEBIM
SEPT.). Army Coating and Chemical Lab., Aberdeen Proving
Ground, Md. (CCL Kept. 20U) (Project 1C024U01A106).
JUNE 1966. 24 PP.
CFSTI,DDC AD 611270
The deterioration of petroleum fuels was studied by investigation
of their autoiidation susceptibilities. Federal and Military
72 HYDROCARBONS AND AIR POLLUTION
-------
Specification fuels and coaaercial gasolines were subjected to a
six-week accelerated aging test with analyses for generated
aydroperosides deterained at weekly intervals. The resulting
peroxide-tine curves revealed autoxidation tendencies to vary
considerably. Dnder the conditions of this aging technique, there
is evidence that the bulk storage supply of conbat gasoline
(HIL—6—3056B) at Aberdeen Proving Ground is experiencing a
gradual depletion of antioxidant quality. (Author abstract)**
03202
7. Del Vecchio.
TEE PHOBLEHS OF BASIC UHBAK AIB POLLUTIOI. II problema
dell'inguiBasento di fondo urbane dell'aria ataosferica. Funi
Polveri (Hilan) 6, (6) 177-8, June 1966.
Basic urban air pollution refers to the discharge into the air of
exhaust gases from aotor vehicles and froa heating units, which
are prevalently inefficient. Both sources discharge respirable
dusts and gases, the latter including some aliphatic and aronatic
hydrocarbons which have proven carcinogenic in experiaental
animals. The problem arising frojs the incomplete coabustion of
Rotor fuels is aggravated by the presence, in Italian cities, of
narrow streets and relatively high buildings which becoae
repositories of enitted fuaes and dust fron slow-moving vehicles.
is Buch as 12 to 135 CO aay be present in gasoline-driven motor
car exhaust. Shile gross measurement of pollutants present in the
urban air is of high indicative value, public health aspects of the
problea deaand that granulometric studies of the dust particles
also be conducted, since size is a factor in respirability. In
addition, photocheaical studies involving the interaction between
the pollutants in the air and the sun's rays indicate that solar
radia'tion transforms the originally present contaminants into
biologically Bore receptive compounds, guite different fron their
precursors. Thus peroiacetylnitrate(PAH) is produced fron
HOx, and the new substance is a powerful irritant of the BUCUS
membranes. The draaatic episodes of sass illness resulting froa
saog in various places in recent years were caused by the
phenoaenon of thermal inversion which prevented the dispersion of
the irritants present in the air.**
03255
H. L. Cuaains and V. J. Konopinski
BOTOH VEHICLE EXHAUST COHCEHTBiTIOHS IH A ROAD TUHHEL.
Preprint. (Presented at the Conference of the American
Industrial Hygiene Association, Philadelphia, Pa., Apr. 29,
1964.)
The contribution of actor vehicle exhaust to ambient air pollution
was studied by using a vehicular—road taimel as a saapling site.
An intensive aerometric study was conducted April 20 through 28,
1963, at the Suaner Tunnel in Boston, Bassachusetts. The
tunnel is now operated as a one-way tube. Air quality was
determined on the fresh air supplied to the tunnel (inlet air), on
B. Emission Sources 73
-------
the air exhaust from the tunnel (exhaust air), and at three sites
within the tunnel. Particulate pollutants were analyzed for total
suspended particulates, benzene-soluble organics, sulfates,
nitrates, metals, and polycyclic hydrocarbons. Concentration of
S02, oxides N, N02, aliphatic aldehydes, and CO were also
determined. The average concentration of total suspended
particulates in the inlet air was 86 micrograms/cu m while that of
the exhaust air was i»21 micrograms/cu m. The concentrations of
total particulates, benzene-soluble organics, sulfates, and
nitrates for the inlet and exhaust air were less than reported in a
previous study. The ranges of concentrations of oxides N, N02,
and aliphatic aldehydes in the tunnel were, respectively, 11.3 to
13.0, 3.5 to 8.8, and 3.1 to 12.6 parts per hundred million
(hereafter referred to as pphm). S02 concentrations ranged from
0.1 to 0.5 pphm, and were less than ambient concentrations. The
mean daily concentration of CO was 2.3 ppm in the inlet air and
50.8 ppm in the exhaust air. Mean concentrations in the tunnel
ranged from 20.5 to 54.2 ppm and increased with increasing
distance into the tunnel. Other pollutants exhibited a similar
gradient. The particulate pollutant concentrations measured
during April 1963 study are less than those measured in 1961.
This decrease may be attributable to operation of the tunnel with
one-way traffic and the concomitant piston effect, and to a 36
percent decrease in the average number of motor vehicles using the
tunnel. Values for polycyclic hydrocarbons reported for the 1961
study were in error; corrected values are given in this report.
(Author abstract)##
0326«
J. N, Pattison and E, R. Stephens
COMPOSITION OF AUTOMOTIVE ELOHBY GASES. Proc. Tech. Meeting
West Coast Sect., Air Pollution Control Assoc., 3rd,
Monterey, Calif., 1963. 37-50 pp.
Blowby emissions from internal combustion engines have been
analyzed, and it has been experimentally shown that they have the.
same carbon content as exhaust and carbureted mixture. It has
also been found that blowby is composed of approximately two-thirds
carbureted mixture and one-third exhaust. Gas chromatographic
analyses have been made of the blowby from ten cars using the same
fuel, and it was found that the ratio of one component to the next
(in the CT to C5 range) was very similar for all cars and that
the total emission level only varied by a factor of 2 or 3.
Cracked products accounted for about one per cent of the organic
carbon in blowby. The actual concentration of these compounds was
found to be the same in blowby and exhaust, which indicates that
some reaction occurs during the compression stroke before any
appreciable amount of blowby occurs. Gas chromatographic analysis
of the aromatic portion of the blowby showed variations similar
in amount to that found in the light hydrocarbons. The
composition of the blowby aromatics resembles the composition of
the fuel. (Author summary)tf
74 HYDROCARBONS AND AIR POLLUTION
-------
03265
A. F. Bush, E. A. Slater, G. Richards, and J. Dyer
EFFECT OF ENGINE EXHAUST ON THE ATMOSPHEBE WHEN AUTOMOBILES ABE
EQUIPPED WITH AFTEBBURNEBS. Proc. Tech. Meeting West Coast
Section, Air Pollution Control Assoc., 3rd, Monterey,
Calif., 1963.)
"Typical" smog damage of the conventional type if induced in
Nicotiana glutinosa when the ratio of pure air to automobile
exhaust is in the range of 1000 to 1 in the test facility, A
specific cycle of engine operation involving acceleration, cruise,
deceleration and idle produced typical damage. The absence of
cruise in the cycle caused no damage to occur. With an after
burner on the exhaust of internal combustion engines, it becomes
apparent that a new type of injury was being induced in
Nicotiana glutinosa plants. Fumigations with afterburner
exhausts consistently produced atypical plant damage, whereas
automobile exhaust fumigations, without afterburner devices,
usually produced typical oxidant damage. 2t is considered that
since the concentration of hydrocarbons is reduced using the
afterburner, one of the principal air polluting agents has been
eliminated; typical air pollution therefore, does not occur. This
does not mean that plant damage is eliminated, only that the usual
type of plant damage appears to have replaced it (atypical).
Some of the exceptions to the trends described in f1 above can be
explained on the basis of lack of sweep of the tunnel so that
residual smog-forming materials may have remained behind. The
tunnel must therefore be carefully swept with air passed through
beds of activated charcoal for at least 15 hours before the
fumigation can have validity. Plant damage does not correlate
well with measured concentrations of nitric oxide. Atypical
damage is produced however in almost every instance of
afterburner exhaust fumigation. Since the fumigation period
includes the period when the oxides of nitrogen are high (ppm or
so) it may be speculated that the new damage is due to oxides of
nitrogen in the absence of high hydrocarbon. There is fair
correlation between hydrocarbon concentrations and the appearance
of typical damage when no afterburner is used. Afterburner
exhaust in the chamber showed no appreciable human eye irritation
resulting from the new atmosphere while automobile exhaust without
afterburner produced eye irritation of the type described by
Buchberg, (Author conclusions)t#
03352
J. P. Morris and A. B. Calongne
CONTAMINATION GENERATION OF INTERNAL COMBUSTION ENGINES.
Preprint. (Presented at the Fourth Annual Technical
Meeting and Exhibit, American Association for Contamination
Control, Miami Beach, Fla., May 25-28, 1965.)
The contamination generated by various types of mobile equipment
used to support inplant operations was studied at the NASA
Michoud Operations in New Orleans. The contamination
sensitivity of various systems on the Saturn C-IC made it
mandatory that all contamination generating operations be studied
in order to effect the best possible control. Vehicles used
B. Emission Sources 75
-------
inplant had to be selected on the basis of minimum contamination
generation. The exhaust gases of six vehicles were tested to
determine the generated waste products. One of these vehicles
was a crane that had two separate engines which increased the
number of tests to seven. Two U,000 pound fork lifts; a 6,000
pound fork lift; a crane mobile power motor; and a crane boon
motor, all powered with liquid petroleum gas; and a gasoline
powered 6,000 pound fork lift and a Diesel fuel air compressor
were the vehicles used for these tests. The exhaust gases from
each engine were analyzed on a Fisher Orsat apparatus for"the
following constituents: carbon dioxide, oxygen, carbon monoxide,
hydrocarbons, hydrogen, water (calculated), and nitrogen
(calculated). In addition, the sampling tubes from each vehicle
were saved and photographed to show, candidly, the particulate and
oily contamination which was generated. The results of this test
show that all of the internal combustion engines are contamination
generators. The amount of contamination generated is dependent
upon two factors: (1) Condition of the engine, and (2)
Efficiency of engine operation. In some cases, the carbon
monoxide content was high enough to present a health hazard if the
vehicles were operated in a confined space. Cleaning by
trichlorethylene and by hot alkaline is not adeguate if
carbonaceous particles from internal combustion engines
contaminate parts. Engines must be kept in perfect condition.
Exhaust gases should be analyzed frequently to determine engine
conditions. Hater-cooled manifolds or water mufflers should be
used to precipitate contaminants. Exhaust gases should be
filtered.##
03U20
A. H. Rose, Jr., a. H. Black, R.C. Hanta
AIB AND WATER POLLDTION STUDIES RELATED TO PROPOSED PETROLEUM
REFINERY FOR SAND ISLAND - OAHU, TERRITORY OF HAWAII (--REPORT
TO BOARD OF HEALTH, TERRITORY OF HAWAII). Public Health
Service, Cincinnati, Ohio, Div. of Air Pollution. Dec.
1955. 60 pp.
HEW
The objective of the atmospheric pollution phase of this
study was na evaluation of the possible effect on the
atmosphere of the City of Honolulu which may result from the
operation of a 2t,000-barrel-per-day modern fluid catalytic
cracking refinery. Two factors were investigated, first
the extent and causes of the current atmospheric pollution level,
and second the potential impact on the pollution level which may
result from the refinery operation. Process design for the
proposed refinery was tentative in that only process flow and
major process units were fixed; interflow of components between
process units and their elements had not been finalized. Data
covering the operation of and ataospheric contaminant discharge
from existing industrial operations were relatively meager. Data
on the concentrations of specific contaminants in the Honolulu
atmosphere were not available. Only published climatological data
were available . The quantity of specific atmospheric
contaminants from both existing sources and the proposed refinery
are presented as determined from the best available data.**
76 HYDROCARBONS AND AIR POLLU FION
-------
03513
B. J. Steigerwald
CARCINOGEN APPRAISAL STUDY. Preprint. 1960.
The purpose of this study is the development of sampling and
analytical techniques which will allow and encourage more
widespread source and air sampling and analysis for suspected
carcinogenic and cocarcinogenic compounds. A sampling program for
the first year has been worked out which allows rapid advancement
toward the goals outlined: Development of source sampling
techniques for the appraisal of carcinogens in hot stack
gases, and exploration of the possibility of correlating short
chemical tests for aromatics, or indicator tests for CO with
the aliphatic and polynuclear aromatic content' of combustion
gases or automobile exhausts. Development of routine
analytical methods for long-chain aliphatics. Some estimates
of the possible importance of many other industrial sources
of these compounds. Additional information on the distribution
of heavy hydrocarbons in urban areas, and estimates of possible
Maximum exposure levels of polynuclear aromatic and long-chain
aliphatics near some of the suspected sources of such emissions.
A broad screening of the emission of polynuclear aromatic
hydrocarbons and aliphatic from major combustion sources and the
development of emission factors for automobile internal combustion
engines. ##
03562
A. H. Rose, Jr. and R. C. Stahman.
THE ROLE OF ENGINE BLOHBY IN AIR POLLUTION. J. Air Pollution
Control Assoc. 11, (3) 11«-7, Bar. 1961. (Presented at the
53rd Annual Meeting, Air Pollution Control Association,
Cincinnati, Ohio, May 22-26, 1960.)
The results are presented of a survey of 13 late model cars j,n
which measurements were made of the concentration and quantity of
both crankcase and exhaust gas emissions during various modes of
vehicle operation. Measurements of C02 concentration and flow
rate have established that the composition of the blowby gas is
approximately 75 to 85S carbureted fuel-air mixture. As such, the
specific composition of the crankcase gases will be controlled by
the composition of the fuel used in the engine. A high
correlation was found between manifold vacuum and both blowby
emission rate in cfm and gross emission in pounds per hour. Both
factors decrease with increasing manifold vacuum resulting in
substantially zero emissions at the low manifold vacuums
associated with closed throttle deceleration. A further effect
also apparent from the data is a twofold increase in crankcase
emission rate and gross emission for the eight cylinder engine as
compared to the six. The effect of these variables for all
driving conditions was based on the average driving cycle developed
by the Traffic Survey Panel of the Automobile Manufacturers
Association. It was found that crankcase emissions account for
2tX of the over-all automotive emission for the six cylinder engine
and 33% for the eights.**
B. Emission Sources 77
-------
03580
P. A. Bennett, H. W .Jackson, C. K. Murphy, and B. A.
Randall
REDUCTION OF AIR POLLUTION BY CONTROL OF EMISSION FROM AUTOMOTIVE
CRANKCASES. Vehicle Emissions (Selected SAE Papers) 6,
224-53, 268, 1964. (Presented at the Annual Meeting, Society
of Automotive Engineers, Detroit, Mich., Jan. 11-15, 1960.)
Analyses of crankcase vent'gases by several methods have shown
that crankcase and exhaust hydrocarbon emissions from automobiles
are of the same order of magnitude. Internal ventilation of the
crankcase to the engine intake system eliminates crankcase
emission, thus providing a practical control of this important
source of air pollution. (Author abstract)tf
03584
G. R. Cann, K. H. Noble, and G. P. Larson
DETECTION OF SMOG FORMING HYDROCARBONS IN AUTOMOBILE EXHAUST
GASES USING PLANTS AS INDICATORS. Air Repair 4, (2) 83-6,
Aug. 1954.
Following the identification of hydrocarbons in the 4, 5 and 6
carbon atom range in automobile exhaust gases, it became necessary
to determine whether these hydrocarbons, mixed with other exhaust
gases, could produce typical snog effects. A study was carried
out in which the atmospheric reaction of hydrocarbons was
duplicated in the Air Pollution Control District's plexiglas
house. Certain plants, which had already been proved susceptible
to smog damage, were used as indicators. Gasoline vapor was used
as the standard against which the plant damaging effects of
automobile exhaust gases were compared. Results show that
automobile exhaust hydrocarbons are capable of producing effects
eguivalent to those resulting from snog. (Author abstract)ft
03761
P. P. Mader, M. Eye, J. A. Orcutt, and L. A. Chambers
EFFECTS OF FUEL OLEFIN CONTENT ON COMPOSITION AND SHOG FOBBING
CAPABILITIES OF ENGINE EXHAUST (INTERIM SEPT. 2). Los
Angeles County Air Pollution Control District, Calif. Apr.
1959. 24 pp.
A proportionate sampling system was used which made it possible to
collect continuously representative composite exhaust samples from
all all driving cycles in proportion to exhaust volume, under
actual driving conditions. six gasolines, with olefinic contents
ranging from 1.0% to 30.9S were used (bromine number 1.6 to 49.4).
The exhaust was irradiated for one hour by means of mercury lamps.
A panel of laboratory personnel (usually eight in number, but
never less than six) was then exposed to the contents of the flask
by the use of a specially designed eye mask, which fitted the mouth
of the flask as well as the eyes of the individual. The eye
piece was built with a shutter to open and close quickly, thereby
78 HYDROCARBONS AND AIR POLLUTION
-------
enabling an exact measurement of time of exposure. The number of
seconds required for each individual to detect the initial eye
irritation was recorded, and the arithmetic mean of the
observations was calculated as an index of the eye irritation
potential of the exhaust sample. The olefin content of the fuels
used to drive the automobiles is directly related to the quantities
and relative distributions of olefins in the exhaust. The
amount of olefins present in the exhaust is directly related to the
intensity of eye irritation which is produced when the exhaust
gases are irradiated. Since a direct relationship exists between
olefins in fuels and olefins in the engine exhaust on the one
hand, and between exhaust olefins and eye irritation on the other,
it is reasonable to assume that the determination of total exhaust
olefin indicates the intensity of eye irritation that can be
expected from a given fuel composition.##
03871
L. B. Hitchcock
AIB POLLUTION AND THE OIL INDUSTRY. Proc. Am. Petrol.
Inst., Sect. IV. 35, 150-U, 1955. (Presented at the spring
meeting. Pacific Coast District, American Petroleum Inst.
Division of Production, Los Angeles, Calif., Apr. 28, 1955.)
While most of Los Angeles' air pollution is traceable to
petroleum products, by far the largest share arises from the use
to which these products are put. Motor-vehicle exhaust accounts
for the largest single source of pollution. Fuel oil and gas also
contribute. Incineration of refuse and metallurgical and
miscellaneous industrial emissions account for most of the
balance. The public, through its motor vehicles and
rubbish burning, contributes more than half the total
pollution. The oil industry, indispensable to the community's
growth, has done more than all the rest of the area in
developing and adopting corrective measures, and has reduced
its emissions very substantially. Petroleum production in Los
Angeles County contributes a very minor part to air pollution.
Hydrocarbons and nitrogen oxides in combination produce snog
effects, although neither alone, at concentrations found, is
known to be deleterious. Cleaner air costs money, but less
than smog. Intevsive application of science and engineering
to the overall problem is the only road to success. (Author
abstract)##
03883
E, A. Schuck and G. J. Doyle
A STCDY OF IEEADIATED AUTO EXHAUST. Stanford Hesearch Inst.,
South Pasadena, Calif., Southern California Labs. (Kept. 9
and Technical Rept. 11.) Feb. 1958. 65 pp.
Aerosol was formed by irradiation of exhaust-air mixtures. The
aerosol thus formed was in the submicron size region but was of
sufficient concentration to reduce visibility appreciably—in some
instances from around 40 miles down to 2 or 3 miles. The
severity of eye irritation is dependent on the concentrations of
B. Emission Sources 7<9
-------
hydrocarbons and nitrogen oxides. Here particularly, a
relationship has been established between 'the concentration ratio
of hydrocarbons and oxides of nitrogen and the degrees of eye
irritation, the degree of irritation being dependent on the
concentration ratio. This ratio also influences the rate of
formation of the aerosol, oxidant, and indicated nitrogen dioxide.
Varying the relative humidity in the exhaust-air mixtures between
40% and 80% and the temperature between 26 C and HO C had no
detecta le effect on any of the measured syaptoms. Eye irritation
increased as the light intensity was increased from zero to 3/U the
intensity of noonday sunlight, but did not appear to increase with
a further increase in intensity up to about twice that of noonday
sunlight. Eye irritation intensity was found to be a function of
residence time under irradiation. The results indicate that the
length of time that pollutants reside under irradiation has an
effect on the severity of smog symptoms, i.e., leads to an increase
and then a decrease in eye irritation with time. The snog
potential from an auto exhaust mixture appears to be intimately
associated with hydrocarbon concentration, oxides of nitrogen
concentration, the concentration ratio of hydrocarbons to oxides of
nitrogen, light intensity, and residence time under irradiation.
The half life of the eye irritant produced by irradiating dilute
auto exhaust was determined to be in the order of 2H hr, indicating
the presence of a rather stable irritant. The half life of the
aerosol was found to be 12 hr, and that of the oxidant or indicated
nitrogen dioxide was less than one hour. Thus, from the measure
of halt life, the aerosol, oxidant, and indicated nitrogen dioxide
do not appear to be intimately associated with eye irritation.#f
03887
W. J. Sweeney and C. E. Heath
THE FUEL CELL: ITS PROMISE AND PROBLEMS. Proc. Am.
Petrol. Inst., Sect. Ill 41, 121-6, 1961. (Presented at the
26th Midyear Meeting, American Petroleum Inst. Division of
Refining, Houston, Tex., May 9, 1961.)
The inherent high efficiency of the fuel cell and its promise of
simple, trouble-free conversion of chemical energy to electricity
have prompted a research effort which extends to approximately 100
laboratories throughout the world. This paper discusses the
advantages of the fuel cell and the chemical and engineering
problems to be solved before its potential is realized. Recent
work has encouraged the prospects for development of a
general-purpose fuel cell. The question of its ultimate technical
and economic feasibility will depend on making the cell work
efficiently and dependably on conventional fuels and air. (Author
abstract) ##
03935
L. M. Shabad, A. Y. Khezina, Y. S. Fridman
POSSIBLE COKTABINATION 0? CHEMICAL PRODUCTS WITH 3,4-BENZPYHEHE
DURING THEIR MANUFACTURE. Hyg. Sanit, 31, (U-6) 30U-6, Apr.-
June 1966. Buss. (Tr.)
CFSTI, TT 66-51160/4-6
80 HITDRQCARBONS AND AlR POLLUTION
-------
Increasing attention is directed to the possible carcinogenic
effects of different industrial products with which man may cone
into contact in the course of manufacture or consumption. The
relationship between the manufacture of ammonium sulfate and
coking industry led to the investigation of industrial samples
for their contents of 3,4-benzpyrene. The samples were
investigated according to the following scheme, A 10-g sample
was repeatedly washed, with vigorous shaking, with distilled
benzene until the resulting benzene extracts were no longer
luminescent. Luminescence was induced with filtered light
from a mercury lamp. This was followed by measurement
of the volume of the extract and by quantitative analysis to
detect 3,4-benzpyrene. Quantitative determination of 3,4-
benzpyrene was made by the method of addition from the
flucrescence spectrum of the n-octane solution at 77K, The
sample contained 1400 micrograms 3,4-benzpyrene per 1 kg ammonium
sulfate. The contents of this carcinogenic hydrocarbon
exceeded 1000 micrograms per 1 kg in all investigated
samples.##
03989
J. H. Freeman, Jr. H. C. Stahman
FUEL INJECTION INCREASES ECONOMY SEDUCES EXHAUST EMISSIONS.
S.A.E. (Soc. Automotive Engrs.) J. 74, (10) 70-5, Oct. 1966
The standard carburetors on three test cars were replaced with a
fuel injection system. The automobiles were tested on a chassis
dynamometer and on four driving routes. Fuel consumption,
C02 and hydrocarbon emission were reduced.**
OH008
J. T. Gray, Jr., E. Dimitroff, N. T. Meckel, and R.
D. Quillian, Jr.
AMMONIA FUEL - ENGINE COMPATIBILITY AND COMBUSTION.
S.A.E. (Soc. Automotive Engrs.), Preprint. (Presented at
the Automotive Engineering Congress, Detroit, Mich., Jan.
10-14, 1966.)
Full-scale engine studies were conducted to determine the
feasibility and compatability of ammonia combustion in various
systems. Briefly outlined is the spark-ignition investigation
undertaken by the Army Laboratory to learn the potential and
effect of ammonia as a fuel and to study the influence of engine
variables on combustion. A study of compression-ignition
performance was made to ascertain the ability of ammonia to be
pumped in existing injection systems and various means of achieving
ammonia combustion were explored. Compatibility of ammonia and
its combustion products with engineering materials and lubricants
presents no substantial problem. Satisfactory delivery of
ammonia may be accomplished by cooling the inlet to the injection
pump. Ammonia—only combustion reguires high compression ratios
and temperatures (35:1 compression ratio, 300 F air and coolant).
Ammonia may be ignited by pilot fuels at compression ratios as Ion
B. , Emission Sources 31
-------
Oi»028
R. E. Kruse and D. M, Hill
EXHAUST EMISSIONS FHOM COMPACT CARS. Preprint. (Presented
at the Society of Automotive Engineers Meeting, Dayton, Ohio,
Mar. 14. 1967.)
The purpose of this study was to develop basic emission data that
will provide background information for the setting of Federal
emission standards that weigh as equitably as possible the relative
contributions to air pollution of different passenger cars varying
both in gross vehicle weight and in engine displacement. This was
accomplished by determining for a variety of imported and domestic
compact vehicles the concentrations and mass levels of emissions
of hydrocarbons, carbon monoxide, and oxides of nitrogen during
operation on the road and on a chassis dynamometer (7-mode cycle,
hot start) . The compact vehicle was defined as any car weighing
less than 3,000 pounds with an engine displacement of less than
200 cu. in.##
04098
V. A. Gofmekler, M. D. Manita, Zh. V. Hanusadzhants,
and L. L. Stepanov
CORRELATION BETWEEN 3,4-BENZPYRENE AND CARBON KONOXIDE
CONCENTRATIONS IN AUTOMOBILE EXHAUST GASES. Gigiena i Sanit.
28, (8) 3-8, Aug. 1963. Russ. (Tr.) (Translated by B. S.
Levine in U.S.S.R. Literature on Air Pollution and
Related Occupational Diseases, Vol. 12.)
One of the most widely occurring cancerogenic substances in
ambient air, 3,4-benzpyrene, is also a component of automobile
exhaust gases. Seemingly, there exists a correlation between the
formation and discharge of 3,4-benzpyrene and carbon monoxide, as
both may result from incomplete liguid fuel combustion. A better
understanding of this 3,4-benzpyrene and carbon monoxide
correlation in dealing with the problem of sanitary protection of
atmospheric air was the aim of this investigation. Concentrations
of 3,4-benzpyrene in auto exhaust gases were determined by the
spectral-fluorescent method. Carbon monoxide concentration in
automobile exhaust gases ran in correlation with the concentration
of simultaneously occurring 3,4-benzpyrene; accordingly, CO
concentration can be used as an indicator of the rate at which 3,4-
benzpyrene is discharged into the atmosphere with the automobile
exhaust gases. Automobiles with properly adjusted carburetors
generated and discharged into the atmospheric air less carbon
monoxide and less 3,4-benzpyrene. The highest concentration of 3,
4-benzpyrene and of carbon monoxide was discharged with exhaust
gases coming from automobiles operated at low rpm, usually at the
as 12:1, depending upon the cetane number of the pilot. None of
the fuel additives investigated significantly lowered the energy
level requirement for ammonia ignition. Gases introduced into
the intake manifold resulted, in ammonia combustion although
amounts required were high: (10% hydrogen, 15-20% acetylene).
High temperature glow coils were suitable ignition sources but
spark plugs and standard glow plugs failed to initiate
combustion.#tt
82 HYDROCARBONS AND AIR POLLUTION
-------
time of starting or accelerating atmospheric air pollution with
3,4-benzpyrene and carbon monoxide can be reduced substantially
as follows: by controlled carburetor operation at all times,
particularly when starting and moving into line with the traffic,
and most of all by keeping the carburetor clean and well adjusted;
by reducing to a minimum the number of stops and starts at cross
sections and light signals. This can be done by proper manual and
signal traffic regulations and by instituting overhead and
underground auto routes which would allow automobiles to travel
without making many stops.##
04108
N- Ya. Yanysheva, I. S. Kireeva, and N. N. Serzhantova
3,4-BENZPYRENE IN CRUDE OIL AND IN BITUMENOUS PRODUCTS.
Gigiena i Sanit. 28, (11) 71-38 Nov. 1963. Russ. (Tr.)
(Translated by B. S. Levine in D.S.S.H. Literature on Air
Pollution and Related Occupational Diseases, Vol. 12.)
CFSTI: TT 66 61429
The present authors investigated the 3,4-benzpyrene concentrations
in crude oil tars of different trademarks. The investigation
aimed at finding which of the products contained the least amount
of 3,4-benzpyrene so their use could be recommended in the place
of other products which contained higher cancerogenic hydrocarbon
concentrations. The investigation included crude oil, tar and
pitch products trademarked BN-IV and VN-V, obtained from
cracking residuals BN-V produced by the Kherson plant. This
plant processed crude oil coming from the Ukraine and partly
from Povolzh'ya. Samples for the investigation came in a variety
of forms of processed crude oil, such as crude oil asphalt
resulting from direct vertical crude oil distillation, and cracking
residuals resulting from processing crude oil break down products.
The composition of products resulting from direct vertical crude
oil distillation depended largely upon the nature of the crude oil,
and the composition of cracking products characterized by high
content of aromatic polycyclic hydrocarbons is determined basically
by the production technology. Trademarked crude oil bitumens are
distinguished by their melting point and viscosity. Results
indicated that even the maximal 3,4-benzpyrene concentrations found
in the crude oil tar residues were consiberably below the maximal
concentration of 3,4-benzpyrene found in coal pitch. Therefore,
it appears that replacing the coal tar pitch as a binder by crude
oil tar residue should reduce considerably the amount of•
cancerogenic coal products in coal dust brickettes. It should be
remembered, however, that crude oil tar residue binders may contain
cancerogenic substances other than 3,4—benzpyrene, the
concentration of which may be different in different types of the
crude oil binders. In view of this, final recommendations for
the use of the safest crude oil residue binders of different
trademarks should be based on experimental studies with animals.tt
04114
N. V. Dmitrieva, A. I. Kukhovkaya, and I. S. Khazanov
HETHODS FOR LOWERING SOLVENT CONCENTRATIONS IN THE AIR OF PLANTS
ENGAGED IN DRY CLEANING CLOTHES. Gigiena i Sanit. 28, (12) 71-
3, Dec. 1963. Russ. (Tr.) (Translated by B. S. Levine in
B. Emission Sources 83
-------
U.S.S.R. Literature*on Air Pollution and Related
Occupational Diseases, Vol. 12.)
CFSTI: TT 66 61429
Indoor air pollution with organic solvent vapors in dry cleaning
plants constituted a hazard to the health of the workers. The
following air pollution sources were found in dry cleaning plants:
open manual method of applying solvents in the spot removing
department; non-observance of safety regulations, ..primitive and
manual technological procedures in loading and unloading the
rotating cleaning drums, unorganized leakage, etc. The method
used in unloading dry cleaned clothes from the solvent containing
drums constituted a particularly hygienically unfavorable condi-
tion. Comparative evaluation of equipment and machines used showed
that highest solvent vapor air pollution was noted in dry cleaning
plants equipped with USA machines. Therefore, it is recommended
that the use of American machines be discontinued. Prevention
of air pollution with solvent vapors in dry cleaning plants can
be attained by the following means; (a) strict adherence to most
advanced technological defatting processes; (b) elimination of all
leakage sources, especially in the pipes and conduits; (c)
installation of a properly planned up-to-date overall ventilation
system supplemented by the installation of local exhaust devices at
points of workers exposure to the inhalation of the solvent vapor
polluted air. The present practice of manual spot removing froa
clothes in the open should be unconditionally prohibited,
appropriate local exhaust ventilation devices be installed; the
rate of fresh air inflow should be increased. Employees of dry
cleaning establishments should be examined periodically by
industrial medical personnel, and persons unfit for such
occupation should be replaced. (Author conclusions)##
OU233L
A. R. Poirier
ENGINEERING INVESTIGATION OF DIRECT LIQUID HYDROCARBON-AIR FUEL
CELLS. (FINAL TECHNICAL KEPT). ONAN Engine-Generator
Div. of Studebaker Corp., Minneapolis, Minn. (Bept. No. 2.)
Dec. 31, 1966. 50 pp.
DDC: AD 4877981
The objective was to perform preliminary engineering design
studies that will lead to the development of a direct liquid
hydrocarbon-air fuel cell power plant operating on logistic
military fuels at moderately low temperatures. The basic cell
design approach is a matrix-type using phosphoric acid as the
electrolyte. Commercially available electrodes were evaluated
for their electrical performance in direct liquid hydrocarbon-air
fuel cells. American Cyanamid electrodes, type 1-AA, show
promise as both hydrocarbon and air electrodes with phosphoric
acid electrolyte at temperatures below 200 C. These electrodes
have delivered as high as 10 watts/square foot on JP-t, 15 watts/
square foot on combat aviation gasoline, and 60 watts/square foot
on propane. Air was used as the oxidant in all three cases.
There is a strong influence on the initial performance of the
present American Cyanamid hydrocarbon electrodes with platinum
loadings under 30 grams/square foot. Higher anode platinum
loadings lose their sensitivity to initial performance, bat becone
important in the operating life of the electrodes. Humidification
of the fuel was found to have a pronounced effect on the
84 HYDROCARBONS AND AIR POLLUTION
-------
electrochemical performance. As much as 10-fold increase in the
power output of the JP-1 fuel cells was observed upon
humidification of the fuel feed. A six-cell matrix-type nodule/
employing 1/U square foot electrodes, was fabricated and tested.
Gas leakage problems at operating temperature were encountered.
The cause of the gas seal failure was attributed to the "flowing"
of the hypalon asbestos gaskets under compressive loading at
operating temperature. A new current collector was designed to
employ silicone "o" rings along its perimeter. The Hydroform
Process which uses only one machined die was found suitable
for fabricating a variety of current collector designs at low cost.
A design layout of a direct liquid hydrocarbon-air fuel cell
system was established. The total weight and volume
estimates of a state-of-the-art 1 KW direct JP-t/air fuel
cell system are 621 pounds and 12 cubic feet respectively. The
high system weight is contributed primarily to the present-day
performance of the electrodes on J.P-1 fuel.f#
0423U
J. V. Pustinger, Jr., F, N, Hodgson, and H. D. Ross
IDENTIFICATION OF VOLATILE CONTAHINANTS OF SPACE CABIN
MATERIALS. Monsanto Research Corp., Dayton, Ohio. (Rept.
No. AMRL-TR-66-53.) June 1966. 210 pp.
CFSTI: AD 642051*
Fifty-five candidate materials' for space cabin construction were
stored for 30, 60 and 90 day periods at 23-25 C, and 20-«OX R.
H. in environments of air at a pressure of one atmosphere and
oxygen at 5 psia. The composition of the gas-off products was
determined by mass spectroaetry and gas chromatography.
Considerable amounts of gas-off products were detected from
candidate materials prepared immediately prior to testing, e.g.,
coatings, paints, and adhesives. Very little, if any, gas-off
products were evolved from materials submitted as fabricated
sections, e.g., polycarbonates, polyvinyl-fluorides, and nylon
based material. In general, the major gas-off products were
solvents, plasticizers, and monomers. some coatings desorbed
considerable amounts of carbon monoxide. Others gave off
relatively large quantities of trimethyl silanol and low
molecular weight methyl siloxane polymers. Although slight
differences in relative amounts of alcohols and aldehydes were
observed in some gas-off atmospheres, no large changes in
atmospheric composition were observed that could be attributed to
increased oxidation when materials were exposed at 23-25 C to
oxygen at 5 psia. Quantitative analyses of the gas-off products
were influenced by: uniformity of sample lots, sample homogeneity,
freshness of sample, free surface area, adsorptive characteristics
of the encapsulating chamber, method'of sampling the gaseous
atmosphere, and method of analysis. Additional analyses were
performed on desorbates from four carbon canisters from space cabin
simulators and the hydrolysis products of MCS 198. (Author
abstract)f #
OH272L
0. J. Adlhart and A. J. Hartner
FDEL CELL CATALYSTS (REPT. NO. 3, THIBD QUARTERLY REPT.-NOV.
1, 1965 TO JAN. 31, 1966). Engelhard Industries, Inc.,
B. Emission Sources 85
-------
Newark, N. J., Res. Dev. Div. Hay 1966. 36 pp.
DDC: AD «82110L
The work consists of an investigation of fuel cell catalysts
permitting complete oxidation of hydrocarbon fuels under
conditions which all reaction products are rejected from the
electrolyte. Anodic catalysts and catalysts for oxygen reduction
were evaluated. A study was carried out on fuel cell catalyst
carriers used in oxidation of hydrocarbons. The carriers studied
were graphite, boron carbide, and because of its specific grain
structure industrial diamond. The crystallite sizes of the
applied noble metal and its distribution on the carrier were
determined by X-ray and electron micrographic technigues. It has
been demonstrated that whereas certain carriers may assure the
deposition of platinum with the desired small crystallite size,
they may not be able to retain it on their surface in a uniformly
distributed fashion. At an unfavorable and low surface area of
the carrier the noble metal may agglomerate or even separate from
the carrier. The anodic oxidation of propane and of carbon
monoxide containing hydrogen has been studied on supported
catalyst. For both types of fuel, utilization of precious metal
is improved by dispersing the metal on a carrier. Of the carriers
tested, graphite was found to be the best carrier for the
oxidation propane. Alloying supported platinum with ruthenium is
particularly beneficial for the oxidation of carbon monoxide
containing hydrogen. On the cathode the amount of precious metal
needed for a given current output could not be substantially
decreased by the use of catalysts on carrier.#f
04315
AUTOMOTIVE AIR POLLUTION (A REPORT TO THE D.S. CONGRESS PURSUANT
TO PUBLIC LAW 88-206, THE CLEAN AIR ACT). 89th Congress
(|st Session.) (Document No. 7.) 1965. 26 pp.
Based on the information presented in this report the following
conclusions are made: (1) That all necessary steps should be
taken to assure the reduction of pollutant emissions from motor
vehicles. For this purpose, there is need for (a) further
development of emission criteria, and (b) development of means for
insuring the national application of currently available technical
knowledge for reduction of such emissions; (2) That the need
should be recognized for an expanded automotive vehicle air
pollution research program to accelerate further development of
emission criteria and improve technical capabilities for controls
on automotive vehicles; (3) That means be developed through
vehicle inspection programs or otherwise to insure appropriate
maintenance of vehicle emission control systems; and (U) That
all practicable measures should be taken to expedite the flow of
traffic in urban areas, since this will, in itself, accomplish
significant reduction in vehicle pollutant emissions.f*
Oi»316
FUEL CELLS. FOA Orienterar Om (5) 2U-9, Apr. 1966.
The fuel cell has many acceptable properties. It has a high
efficiency, 60-80%, which means that with a given amount of fuel
a long time of action is obtained. Operating costs moreover
remain very low as cheap fuel can be utilized. Since the fuel
cell lacks movable parts it operates quietly and in addition has a
86 HYDROCARBONS AND AIR POLLUTION
-------
greater effect per unit weight and volume than the conventional
battery. The fuel cell is utilized in applications where the
properties quoted are particularly valued. For current
maintenance of space ships for instance a high effect per unit
weight and volume is required with maximum utilization of the fuel.
Fuel cells answer this need perfectly, and they are used in fact
in the space capsules in the American Gemini project and will be
utilized in the Apollo project. The fuel cell is ideal for
submarines. No interruption for charging is required. Swedish,
German, and American developments are reviewed with special
mention of cells for hydrocarbon fuels.##
04361T
B. G. Gills, E. L. Howe
OIL BURNERS FOB DOMESTIC USE: PRESENT STATE, RECENT
IMPROVEMENTS AND FUTURE DEVELOPMENTS. ( (Olbrenner fur den
Hausbrand: Gegenwartiger Stand, erzielte Verbesserungen und
Moglichkeiten der Weiterentwicklung.)) Schweiz. Arch.
(Zurich), 31 (4) :119-126, April 1965. 7 refs.
An oil furnace well built and maintained should cause no
intolerable air pollution. Soot and a smell of oil will occur
only in case of improper adjustment or perhaps in starting up.
In the latter case an inadequate means of ignition, too low
carburetor temperature, or excessive cooling of the flame may be
the cause. Some methods of combating this difficulty are
described here (beginning injection of fuel only after an adequate
oil pressure is achieved, in the pressure atomizer burner; as
nearly continuous operation as possible for evaporator furnaces;
use of higher pressure for the air of combustion) . In pressure
atomizer burners such difficulties can usually be traced to
defective nozzles or to poor combustion from other causes.
Installations which give reise to complaints must therefore
be overhauled and if necessary replaced. Determination of
concerns itself among other things with the following problems:
improved mixing of air and oil mists; influence of systems
for recirculating smoke gases; ultrasonic and airfoan atomizer
burners; electrostatic oil atomizing; total evaporation of the
fuel in the vaporizer burner; and speed of combustion.lt
04419
M. W. First, F. J. Viles, and S. Levin
CONTROL OF TOXIC AND EXPLOSIVE HAZARDS IN BOILDINGS ERECTED ON
LANDFILLS. Public Health Rept., (U.S.) 81, (5) 419-28,
May 1966.
The principal hazard associated with construction on refuse-filled
land arises from anaerobic production of combustible gases by
methane-producing bacteria. Gas-tight construction over landfills
appears to be difficult, if not impossible, because of gas
pressures under the structure resulting from biological gas
production. During investigations of gas levels in a housing
development constructed on sanitary landfills, unsafe methane
concentrations were found in a high proportion of the
buildings. A concrete slap laid on top of the fill did not
prevent gases produced in the fill from penetrating into the
B. Emission Sources 87
-------
buildings. Several sealants were tested and found inadequate.
The results of periodic gas samplings conducted over several
years in the sub-basement spaces of a number of buildings
indicated that organic fill located around and under heated
buildings becomes completely degraded in approximately 5 years,
releasing methana at a proportionately rapid rate. This produces
a severe explosion hazard unless suitable methods of aerating and
venting are employed. Continuous mechanical ventilation at a rate
of one or two air changes per hour adeguately reduced methane
concentrations. (Author summary)##
04460
J. C. Gagliardi
THE EFFECT OF FUEL ANTI-KHOCK COMPOUNDS AND DEPOSITS ON EXHAUST
EMISSIONS. 90th Congress ("Air Pollution—1967, Part I
(Automotive Air Pollution)" Hearings before the Subcommittee
on Air and Water Pollution of the Committee on Public Works,
U.S. Senate, Feb. 13-14, 20-21, 1967, pp. 487-554.)
(Presented at the Automotive Engineering Congress, Detroit,
Hich., Jan. 9-13, 1967, Paper No. 670128.)
The effect of fuel anti-knock compounds and combustion chamber
deposits on exhaust hydrocarbon emissions was investigated. Six
Ford Galaxies equipped with production non-Thermactor 289-CID,
2V engines were operated on a light-duty driving schedule for '
periods of 12- 30,000 miles at Ford's Michigan Proving Grounds.
Three fuel blends were used in mileage accumulation-Indolence
Clear (a full boiling range nonleaded gasoline), Indolence 30
(Indolence Clear plus 3.0 ml/gallon of motor mix blend), and
Indolence 30 plus 0.2 theory of an organic phosphorous compound.
Two engine lubricants were evaluated for the first 12,000 miles -
a petroleum base SAE - POH - 30 used for Ford factory fill and
a synthetic oil, di-2-ethyl hexal sebacate. After 12,000 miles,
all test engines were operated on the petroleum based lubricant.
Exhaust emissions were monitored at 3,000-mile intervals on the
chassis dynamometer using the California Motor vehicle
Pollution Control Board seven-mode procedure. Additional
seven-mode cycles were conducted on each engine after combustion
chamber deposits were removed at the completion of the mileage
accumulation phase. The increase in exhaust hydrocarbon (HC)
emissions of the vehicles operating on Indolene 30 and Indolene
30 plus 0.2T phosphorus was substantially higher than the HC
increase of vehicles operated on Indolene Clear (an average
HC increase of 15 ppm for Indolene Clear versus an average
HC increase of 171 ppm for Indolene 30). operation of
nonleaded fuel showed no deleterious effect on intake or exhaust
valves or other engine components. (Author abstract)tf
04492
C. B. Smith
NDCLEAE POSER AND THE AIB POLLUTION PROBLEM. Preprint.
(Presented at the Conference: "Engineering Solutions to Air
Resource Problems" Sept. 9, 1966.)
88 HYDROCARBONS AND AIR POLLUTION
-------
After reviewing the air pollution problem, the role of nuclear
power in Southern California and its potential are considered in
terms of cost and feasibility. Nuclear power has promise of
reducing air pollution in Los Angeles, and has the added
advantages of safety and economic savings. In the long run,
clean air will require improved control techniques, new sources
of power, or perhaps a replacement for gasoline powered
vehicles. The scope of these measures - requiring substantial
engineering and scientific development - indicates the
magnitude of the effort that will be required to "bring back 1940
air to Los Angeles." Nuclear power will undoubtedly help
attain that goal.t#
01599
R. L. Chass
THE STATDS OF ENGINEERING KNOWLEDGE FOR THE CONTBOL OF AIH
POLLUTION, Proc. Natl. Conf. lir Pollution, Washington,
D. C., 1962- pp. 272-80. 1963.
Control programs are discussed and particular the control progran
of Los Angeles County, also its demography, urban growth which
is paralelled by increase in automobiles. Los Angeles, in spite
of stringent air pollution regulations, has continued to increase
its industries and to expand existing industries. In spite of the
growth pattern, the engineering and enforcement functions of the
District have resulted in preventing 1,500 tons of air
contaminants from stationary sources, from entering the Los
Angeles atmosphere each day. As it is pointed out in this paper,
the air pollution problems can be solved, using sound technical and
engineering approaches coupled with enlightened administrative and
legislative action.##
04621
A. S. Bhullar
BEACTION KINETICS IN DIESEL COMBUSTION. J. Inst. Engrs.
(India) (Calcutta) 46, (3) 41-4, Nov. 2, 1965.
The combustion process of injected fuel particle is analyzed.
The reaction kinetics theory has been utilized to obtain a gas
phase molecular mixture by allowing the fuel to evaporate in snail
doses from the combustion chamber in H-combustion system used in
Indian army vehicles. In this system, fuel is sprayed onto the
walls of a direct combustion chamber, formed on the piston head, in
a pencil shaped spray with no attempt for atomization. Host of
the spray reaches the spherical combustion chamber walls. A
portion of the spray suspended in the air begins to absorb heat,
forms a vapor envelope, and commences to burn. The upper layer
of fuel on the combustion chamber vaporizes by absorbing heat from
the walls of the chamber. Thus, instead of liquid
particles, vapor is supplied into the combustion chamber. It is
mixed with air by an induction induced swirl. The mixture
becomes more or less like a carburetor mixture, i.e., a gas phase
molecular mixture, instead of a suspended liquid particles
mixture. Thus, a gas phase molecular mixture can be burnt in very
high compression ratio Diesel engine. The M-combustion chamber
B. Emission Sources 89
-------
not only gives better oxygen utilization, less smoke, less
Diesel knock, but comprises a multifuel system which can burn
petrol, Diesel or heavy oils.#t
OIJ630
Rose, A. H., Jr. and R. Smith
A DIRECT MEASUREMENT TECHNIQUE FOB AUTOMOTIVE EXHAUST EMISSIONS.
Arch. Environ. Health 5, (6) 609-15, Dec. 1962. (Presented at
the session on constituents of Motor Vehicle Exhaust at the
Air Pollution Research Conference, Los Angeles, Calif.,
Dec, 5, 1961.)
A new sampling approach was developed using direct measurements of
the composite exhaust emissions from vehicles moving in actual
traffic. Contaminant emissions were expressed at vt. of emission
per vehicle mile traveled within the metropolitan areas. The
effect of engine power demand on contaminant emissions was also
evaluated, since this factor is influenced not only by traffic
volume but by'average traffic speed, terrain, and operating
modes. Emissions were measured under both peak and offpeak
traffic conditions for all routes except the neighborhood route.
These measurements were made in 8 metropolitan areas chosen to
represent different types of geographic areas: Cincinnati,
Chicago, Detroit, Los Angeles, New Orleans, Philadelphia,
San Francisco, and Washington, D.C. The key to the
successful measurement of the exhaust emissions was the
proportional sampler. The sampler obtained a composite exhaust
sample that is proportional to the exhaust flow under all
operating conditions. An electromechanical servo mechanism
system controled the amount of exhaust gas allowed to enter a
noncontaminating bag in a fixed proportion to the exhaust flow.
The sampling rate was 0.25% of the total exhaust emitted to the
atmosphere. Air-fuel ratios also indicate a marked dependence on
the effects of the various routes on engine power demand. Mean
air-fuel ratio for the downtown routes is 10.8:1; for arterial
and residential routes, 12.2:1; for freeways, 13.8:1. This
effect on air-fuel ratio is consistent with the effects of engine
power demands on hydrocarbon emissions. The effects of olefin
production in the exhaust do not show the same degree of
correlation as do hydrocarbon emission trends. The conclusions
drawn from the limited data thus far are necessarily tentative.#t
04663
B. S. Murthy, L. G. Pless
EFFECTIVENESS OF FUEL CETANE NUBBER FOR COMBUSTION CONTROL IN
BI-FUEL DIESEL ENGINE. Instn. Engrs. (India), U5 (7):155-183,
March 1965.
Four fuels covering a broad range of cetane number were
carburetted while injecting either a high or low cetane fuel.
The carburation rate was about 2556 of the total heat input, which
was held constant for all tests. Ignition delay, as compared
with full load injection only, was reduced with all except
the. lowest cetane fuel carburetted. Delay decreased with
increasing cetane number of the carburetted-fuel.
90 HYDROCARBONS AND AIR POLLUTION
-------
Audible combustion noise was greatly reduced with the
carburation of high cetane fuels when the low cetane fuel
was injected. with high cetane fuel injection, the entire
combustion noise level was lower. Further reductions were not
evident when either high or low cetane fuel was carburetted.
Concurrent carburation of fuel improved the full load thermal
efficiency up to a certain cetane number range. At a
carburation rate of 12% of total heat input, methanol did not
fire at the compression ratio for standard ignition delay of high
cetane injected fuel. The ignition delay with methanol at the
higher compression ratio used when injecting the low cetane fuel
was longer than with any of the other fuels tested. Audible
combustion noise, peak cyclinder pressure and rate of pressure
rise increased with the increasing rate of propane carburation.
When low cetane fuel was injected, exhaust temperature was
slightly lower and smoke density slightly higher with methanol
carburation. With the injection of higher cetane fuel, the
exhaust temperature was lower with carburation of all fuels
compared with full load injection only. Exhaust smoke density was
reduced with carburation of high cetane fuels, but was increased
slightly with methanol carburation. This small effect
of dual-fuel operation on exhaust smoke does not agree with
large smoke reductions reported by other workers. The difference
may be due to the fuels used, percentage of total heat input carbu-
retted, combustion chamber design of the engines used and/or meth-
ods of measuring smoke density.##
04731
H. Alperstein and H. L, Bradow
INVESTIGATIONS INTO THE COMPOSITION OF END GASES FEOM OTTO CYCLE
ENGINES. S.A.E. (Soc. Automotive Engrs.) Preprint.
(Presented at the Mid-Year Meeting, Society of Automotive
Engineers, Detroit, Mich., June 6-10, 1966.)
Techniques are described for determining the chemical nature of
the end gas in a normally fired CFE Otto cycle engine.
Apparatus for obtaining and chromatographically analyzing
representative end-gas samples is described, and its utility
illustrated using isooctane as a fuel. Twenty-seven carbon
containing slow combustion products were identified before flame
arrival; these consist principally of olefins, ring ethers,
carbonyls, CO, and C02. Product formation is shown to
increase with increasing pressure and temperature stress and to .be
inhibited by octane number appreciating additives. Distinct
product formation trends from the slow combustion of
isooctane were observed. (Author abstract)##
04792
R. E. George and R. M. Burlin
AIR POLLUTION FROM COMMERCIAL JET AIHCBAFT IN LOS ANGELES
COUNTY. Los Angeles County Air Pollution Control
District, Calif. (Apr. 1960). 67 pp.
B. Emission Sources 91
-------
An investigation of commercial jet aircraft operations at Los
Angeles International Airport to determine the daily emission of
atmospheric air contaminants was made. Smoke emissions and other
air contaminants are byproducts from the combustion of fuel used in
the turbojet engines. The jet exhaust was tested for particnlate
matter, aldehydes, oxides of nitrogen, hydrocarbons, carbon
monoxide, carbon dioxide and oxygen. Evaluation of the data
suggest that the total contaminant emissions from jet aircraft
operations are insufficient to produce any generalized
deterioration of air quality. Visible smoke emission from
commercial jet aircraft do occur during take off and landing but on
take-off the emission of smoke in excess of' legally allowable
opacity limits is well within the allowable three minute time
limit and on landing the smoke emissions do not exceed the opacity
limits.##
0«808
3. H. Ludwig
THE VEHICLE POLLUTION PROBLEM. Preprint. (Presented at the
American Public Power Association Conference, Denver, Colo.,
May 8-11, 1967,
The problem of emissions from motor vehicles is reviewed from
the standpoints of the contribution of vehicles to community air
pollution, present progress in control regulations and application
of devices, and the immediate and longer-term outlook for
additional controls. (Author abstract)##
04922
W. F. Deeter and F. G. Jewell
FACTORS AFFECTING CARBURETOR VAPOR LOSSES. Am. Petroleum
Institute, Preprint. (Presented at a Session on Automobiles,
Hydrocarbons, and Clean Air, 25th Midyear Heeting, American
Petroleum Inst. Division of Hefining, Detroit, Mich., May
11, 1960.)
Gasoline vapor, escaping from carburetors of motor vehicles during
operation, has been considered as a source of air pollution.
During a study made to establish the magnitude of this loss the
various contributing factors were investigated. Carburetor vapor
loss is affected by: 1, the temperature of the carburetor bovl; 2,
the volatility of the fuel; 3, the manner in which the vehicle is
operated (driving pattern); and, U, the carburetor vent design.
Carburetors can be divided into two classifications depending upon
their venting: 1, those with restricted internal venting capacity
(e.g., a single 1/16-in. diameter vent) from which large vapor
losses may occur; and, 2, those with adequate internal venting
capacity from which vapor losses will be small or nil.
Carburetors in the second category include those which htive no
external vents, and externally vented models equipped with either
multiple internal vents or a single internal vent of approximately
1/4 in. diameter. Bench unit data indicated that vapor loss is a
function of carburetor bowl temperature, but tests with three
different vehicles using and 8-lb Rvp (Reid vapor pressure) fuel
indicated that such a relationship only exists for specific
driving patterns, such as low-speed cruising and extended periods
92 HYDROCARBONS AND AIR POLLUTION
-------
of idle. Under these conditions carburetor bowl temperatures may
rise by as much as 40 F to 80 F above the ambient, as a result
of pickup of engine heat by the fuel. Limited testing indicated
that carburetor vapor loss is also a function of fuel vapor
pressure, but analyses of the recovered vapors (70 percent of
C5+) suggested that fuel composition and front-end volatility were
also important factors. The driving pattern affects carburetor
vapor loss by influencing the pressure differential across the
external vent. At low cruising speeds and during extended periods
of idle, a positive pressure differential may exist and losses
occur. At higher cruising speeds, the pressure differential tends
to become negative, thereby preventing losses. A survey of the
California car population (as of July 1957) indicated that
approximately 26 per cent of the vehicles were equipped with
carburetors from which substantial vapor loss could occur.
(Author abstract)t#
04993
J. Q. Payne H. W. Sigworth
THE COMPOSITION AND NATURE OF BLOHBY AND EXHAUST GASES FKOM
PASSENGER CAR ENGINES. Proc. Natl. Air Pollution Symp.,
2nd, Pasadena, Calif., 1952 pp. 62-70
The purpose was to present results of work wherein over-all
rates and composition of blowby and exhaust from the engines
of three passenger cars were studied as a function of
operating conditions. Particular emphasis was placed on the
so-called noxious products in exhaust and blowby. The tests
were carried out on a chassis dynamometer where actual road
conditions could be duplicated in an automobile operating
on a stationary test bed. Analyses were made using a mass
spectrometer Blowby and exhaust rates increase with increasing
power output. Engine mechanical condition has little effect on
exhaust rates, but poor mechanical condition can cause a greater
than tenfold increase in the rate of blowby under some conditions.
Materials such as CO, C02, H20, H2, 02, and N2, were
found to comprise over 99 percent of the composition of both
exhaust and blowby. The remaining less than one percent
contains the noxious materials. Except under decelerating
conditions exhaust gases contain a lower proportion of noxious
products than blowby gases and no materials of mass greater than
58. Common conditions of engine malfunctioning such as misfiring
and retarded timing can increase the concentration of noxious
products in the exhaust. The concentration of noxious products in
blowby was affected by fuel type, carburetor adjustment, and power
output. The following classes of compounds were identified as
present or probably present in blowby: Paraffins, olefins,
aromatics, cyclics, acids, alcohols, aldehydes, and an organic
hydroperoxide. No material of mass number higher than 86 was
found in greater than trace guantities.t#
04994
P. L. Magill, D. H. Hutchison, J. M. Stormes
HY.DBOCARBON CONSTITUENTS OF AUTOMOBILE EXHAUST GASES.
Proc, Natl. Air Pollution Symp., 2nd, Pasadena, Calif.,
1952. pp. 71-83.
8. Emission Sources 93
-------
The aim was to present the results of mass spectrometer
analyses of hydrocarbons exhausted by passenger car exhausts.
The ultimate objective was to arrive at an estimate of the amount
of hydrocarbons released into the Los Angeles atmosphere by
gasoline-burning vehicles. The exhaust gases of automobile
passenger cars were analyzed for C1 to C7 ; hydrocarbon content
passenger cars were analyzed for b8c1 to C7 * hydrocarbon content
with the mass spectrometer. The hydrocarbons found include
methane, acetylene, paraffins, and olefins from b8c2 to C7+,
The exhaust composition was found to be independent of the
type of gasoline burned, using gasolines ranging from premium
gasoline of current-day producers to saturated
straight-run gasoline typical of prewar production. New cars
and old cars showed relatively little difference in exhaust
composition during acceleration and steady driving. Under
conditions of idling and deceleration, the hydrocarbon
content exhausted from prewar cars was approximately twice that
of postwar cars. Over the range of driving conditions encountered
in city traffic, there is a loss of hydrocarbon out of the
exhaust ranging from 5 percent of the weight of fuel entering the
carburetor under conditions of steady driving to 19 percent
during periods of deceleration. The total guantity of C1 to C7+
hydrocarbons released by automobile exhausts to the atmosphere over
Los Angeles County during a twenty-four-hour day is
estimated to be about 850 tons.#*
04995
E- L. Hall
PRODUCTS OF COMBUSTION OF GASEOUS FUELS. Proc. Natl. Air
Pollution Symp., 2nd, Pasadena, Calif., 1952. pp. 814-9-
Data on the combustion products of fuel gases is
reviewed. Work on the photochemistry of smog is related to work
on vapor phase gum produced in manufactured gas by
hydrocarbons and N02 catalytically oxidized from NO in the
presence of butadiene.f#
05005
R. P. Hangebrauck, D. J. von Lehmden, and J. E. Meeker
SOURCES OF POLYNUCLEAR HYDROCARBONS IN THE ATMOSPHERE. Public
Health Service, Cincinnati, Ohio, National Center for Air
Pollution Control. (PHS Publ. No. 999-AP-33'.) 1967. i»8
pp.
Rates of emissions of polynuclear hydrocarbons were measured at
several sources considered likely to produce such emissions. The
sources included heat generation by combustion of coal, oil, and
gas; refuse burning; industrial processes; and motor vehicles.
The annual emissions of benzo (a)pyrene in the United States were
estimated for each of the sources surveyed, to provide a rough
gauge of the importance of each source. small, inefficient
residential coal-fired furnaces appear to be a prime source of
polynuclear hydrocarbons; other sources may be of local importance.
Production of polynuclear hydrocarbons was generally associated
with conditions of incomplete combustion. (Author abstract)M
94 HYDROCARBONS AND AIR POLLUTION
-------
05007
J- H. Ludwig
SEBIHAB OS AIB POLL0TIOH BY MOTOB VEHICLES. Preprint. 1967.
54 pp.
The various facets of the vehicle pollution problem from the
standpoint of both effects on community atmospheres nationwide and
the source of variables are summarized. The problems that
reaain today encompass a number of considerations, which may be
enumerated as follows: (1) The importance of the diesel problea
as it relates to saioke and odor control, the means for securing
reduction of smoke and odors, and the development of test
procedures for the setting of standards; (2) The importance of
relative reactivity of the various organic species, particularly
hydrocarbons, and the effects of reactivity on both standards and
control methods; (3) The importance of various emission sources
(exhaust, crankcase ventilation, fuel tank evaporation and
carburetor evaporation losses) in relation to reactivity and need
for control and the development of test procedures for these
sources from all types of vehicles (passenger cars, trucks and
buses) ; (4) The need for control of nitrogen orides from
vehicular sources, both gasoline engine and diesel engine power
sources and concurrently for stationary sources; (5) The
iiaportance of instrumentation in measurement of pollution
parameters for research, enforcement (certification) procedures,
surveillance and inspection; (6) The problems of maintenance of
devices on vehicles to insure their continued operation
(surveillance and inspection) , and/or the upgrading of such devices
such that they will be essentially maintenance free; and (8) The
importance of in-traffic carbon monoxide levels, particularly
their significance relative to driver fatigue. ##
05011
A. A, Orning, C. H. Schwartz, and J. 7. Smith
HINOB PBODUCTS OF COMBUSTION IB IAEGE COAL-EIBED STEAM GEKEHATOHS
American Society Mechanical Engineers lew York Paper 64-
wA/FU-2.
(Presented at the Winter Annual Meeting, American Society
of Mechanical Engineers, Hew York City, Hov. 29-Dec. 4, 1964.)
An analysis is given of the minor products of combustion
large coal-fired steam generators in relation to theraodynamic
equilibria, unit design and operating conditions. Concentrations
of nitrogen oxides and the ratios of sulfur trioiide to total
sulfur oxides are near equilibrium values at the furnace outlet.
Significant amounts of low molecular weight organic acids and
comparatively small amounts of polynuclear aromatic hydrocarbons
are found under good combustion conditions. (Author abstract) ##
05012
A, A. Orning, C. H. Schwartz, and J. E. Smith
A STODY OF THE MIHOB PBODDCTS OF COAL COMBUSTION. American
Society Mechanical Engineers, Sew York. Paper 64-PHB-4.
B. Emission Sources 95
-------
(Presented at the IEEE-ASME National Power Conference, Tulsa
, OKla., Sept. 27-Oct. 1, 196U.)
A study of the minor products of combustion from large coal-fired
steam generators is described. Concentrations were determined for
sulfur oxides, nitrogen oxides, various organic materials including
organic acids and polynuclear aromatic compounds, and particulate
matter with spectrographic analyses for various metals. Analyses
of the data in relation to thermodynamic equilibria, operating
conditions, and unit design are in progress. Some of the oore
obvious conclusions are given. Purpose of the paper is to
describe the testing plan and the difficulties involved, and their
importance in relation to extension of such studies to include oil
and gas-fired units. (Author abstract)#t
05067
S. T. Cuffe, R. H. Gerstle, A. A. Orning, and C. H.
Schwartz
AIR POLLUTANT EMISSIONS FROH COAL-FIRED POWER PLANTS; REPORT NO.
1. J. Air Pollution Control Assoc. 14, (9) 353-62, Sept.
196« (Presented at the 56th Annual Meeting, Air Pollution
Control Association, Detroit, Hich., June 9-13, 1963.)
Air pollutant emissions from two types of coal burning power plant
furnaces were studied. Particulates entering the fly-ash
collector from the low-intensity-mixing, vertically fired boiler of
Unit A accounted for 60% of the ash contained in the coal charge.
In the high-intensity-mixing, horizontally fired Unit B, 85* of
the total ash entering the boiler in the coal was carried to the
fly-ash collector. The fly-ash collectors effectively removed
85 to 95% of the particulate matter and showed essentially the
same efficiency in removal of common trace metal compounds.
Concentrations of sulfur trioxide ahead of the dust collector
varied widely. For Unit A, the vertically fired boiler, they
averaged about «% of the SO2 concentration; for Unit B, the
horizontally fired boiler, formation of S03 was lower,
averaging less than one percent of the S02 concentration. The
fly-ash collectors effected an appreciable reduction in sulfur
trioxide emissions on Unit A but not on Unit B. For both
units S03 emissions were less than one percent of their S02
emissions. Nitrogen oxide concentrations during normal full-load
operation were increased 30 to U0% by passage through an
electrical precipitator. Organic acid concentrations were
appreciably higher than those of gaseous hydrocarbons,
formaldehyde, and carbon monoxide. The very small concentrations
of gaseous hydrocarbons, formaldehyde, and carbon monoxide
indicated very complete and efficient combustion during both
full-load and partial-load operation. Emissions of
polynuclear hydrocarbons from large power plant boilers were found
to be very small in comparison with those from smaller coal-fired
units having less efficient combustion processes.»i
'05097
R. E. Neligan
A COHPAHISOH BETWEEN THE HYDROCAHBOHS IN AUTOHOBILE EXHAUST AND
THOSE FOUND IN THE LOS ANGELES ATMOSPHERE. Preprint.
96 HYDROCARBONS AND AIR POLLUTION
-------
(Presented at the Joint Research Conference on Motor Vehicle
Exhaust Emissions and Their Effects, Los Angeles, Calif.,
Dec, 5, 1961.)
ftmbient air samples obtained from the central Los Angeles
business district were analyzed by gas chromatography.
Hydrocarbons in the C2-C7 molecular weight range were
identified and their concentrations determined. The results
obtained from these analyses are compared to those obtained from
diluted automobile exhaust and diluted automobile exhaust that
had been irradiated for a period of four hours. Gas
chromatography was found to be an accurate reproducible
procedure for the analysis fo C3 to C7 hydrocarbons present in
the atmosphere. The procedure is limited by the inability to
determine the methane concentration as well as the C8
hydrocarbons. In the sixteen samples analyzed, it was found that
the relative concentrations of the individual hydrocarbon groups
did not change significantly with total concentration. This
would indicate that the hydrocarbon emissions to the atmosphere
are relatively constant. A linear relationship was also found to
exist between total hydrocarbons recovered and the sum of the
nitric oxide - nitrogen dioxide levels. Comparison of
atmospheric hydrocarbons to those produced by automobile exhaust
indicates that natural gas could be a major source of the low
boiling hydrocarbons present in the atmosphere. The
relatively low acetylenic level found in the ambient air samples,
as compared to diluted automobile exhaust, also indicate
significant contributions are made by automobile blowby emissions
as well as carburetor and fuel tank evaporation losses.#t
05106
G. W. Fiero
PROTECTIVE COATINGS AND BOLE 66. Am. Paint J. 52 (29), 70-1.
71, 76, 78, 80, 82 (Jan. 9, 1967).
Eule 66 defines "photochemically reactive" solvents as those
containing more than 20 per cent total of the substances listed or
more than: (1) 5 percent olefinic or cyclo-olefinic hydrocarbons,
alcohols, aldehydes, esters, ethers or ketones, (2) 8 percent
c8 or higher aromatics except ethylbenzene. (3) 20 per cent
ethylbenzene, toluene, branched ketones or trichloroethylene.
Eule 66 reguires reduction of 85 per cent of emissions of
solvents from various industrial applications if "photochemically
reactive" solvents are used. There are some uncertainties with
regard to the rule. For example, both state and federal
protective coatings specifications in many cases specify the
solvents employed and often they are the "photoreactive" variety.
To make matters worse. Presidential Orders require Federal
facilities to abide by local air pollution regulations. After
many consultations with industry, in Harch and April 1966
LA APCD, in conjunction with California Manufacturers Assn.,
conducted a series of tests on solvents and Eule 66 was finalized.
The reason for this rule was that an estimated 345 tons of
solvents were emitted each day in 1965 from the drying of
protective coatings. After the final Hule 66 was adopted, the
Bay Area APCD followed suit and in its current draft it
prohibits the sale or use of guart or larger sizes of building
coatings containing more than 8 per cent "reactive organic
compounds" plus 12 per cent of monosubstituted aromatics.
B. Emission Sources 97
-------
Industrial coatings are limited to 20 per cent of "reactive
organic compounds." Thus, in the current draft. Bay Area APCD
regulations are somewhat less restrictive than LA APCD Pule 66,
but the number of pounds exempt per facility is less than LA.
The Bay Area APCD estimates 196U emission of solvents to be
297 T/D of solvents. Industry is compiling data for a more
up-to-date figure. It should be borne in mind that this is a
draft; final Regulation 3 is expected to issue in January of
1967 to become effective January 1, 1968.##
05109
H. L. Falk, P. Kotin, and A. Hiller
AROMATIC POLYCYCLIC HYDROCARBONS IN POLLUTED AIR AS INDICATORS OF
CARCINOGENIC HAZARDS. Intern. J. Air Pollution 2, 201-9
(1960). (Presented at the Air Pollution Symposium, 136th
National Meeting, American Chemical Society, Atlantic City,
N.J., Sept. 17, 1959.)
The concentration of 3,4-benzpyrene in air samples has been used
as an indicator of carcinogenic risks in breathing polluted air,
and rapid and reliable methods for the determination of benzpyrene
have been worked out. This approach has two shortcomings. First,
polluted air frequently contains carcinogens other than
polycyclic aromatic hydrocarbons. Second, there is no accounting
for other effects of polluted air. These effects may enhance the
carcinogenic process by inhibiting the normal physiologic process
by which foreign materials are eliminated from the lung. The
conditions under which quantitation of 3,4-benzpyrene in air
samples is carried out in the laboratory may be far different from
those existing in the lung. The liberation of benzpyrene from
rubber tire dust by an aqueous protein solution, as is encountered
in the lung, occurs rapidly. In the case of soots, particle size
plays an important role in determining whether elution of
polycyclic aromatic hydrocarbons will take place. . The smaller
particles that retain their hydrocarbons may also adsorb additional
hydrocarbons that have been eluted from larger size particles in
the immediate neighborhood. Competitive effects have been
observed between aromatic polycyclic hydrocarbons as found on soot
and dust with regard to the production of tumors. As there is
narked structural similarity between cancer-producing and inactive
compounds, the intracellular site of action may be common for both
groups and the latter may thus inhibit the action of the former in
producing cancer. A chemical method for the evaluation of the
carcinogenic potency of polluted air requires determination of all
polycyclic aromatic hydrocarbons elutable by protein solutions.
There are still a number of unidentified hydrocarbons present.
The stability of these compounds adsorbed on soot when exposed to
the atmosphere differs from one compound to the next.tt
05113
N. Ar Renzetti
ANALYSIS OF AIB NEAR HEAVY TRAFFIC ARTERIES. Air Pollution
Found. Los Angeles Rept. 16. Dec. 1956. 30 pp.
The primary objective of this work was to obtain the range of
concentration of the principal constituents of automobile
98 HYDROCARBONS AND AIR POLLUTION
-------
exhaust in the vicinity of heavy traffic. Samples were taken at
essentially ground level (five feet) within 60 to 75 feet of the
traffic artery and analyzed for carbon monoxide, hydrocarbons, and
carbon dioxide by infrared spectrometry. The carbon monoxide
values ranged from 4 to 93 ppm (by vol.); the hydrocarbons, from
0.25 to 2.3 ppm (by vol. as hexane); and carbon dioxide, from 0.05
to 0.14 per cent (by vol.). Samples were taken from 6 a.m. to
9 a.m., local time, on week: days of the period from September 4 to
October 2, 1956. This period was characterized by low
inversions, low winds, and high solar radiation, and on a large
number of the days high oxidant values and eye irritation were
experienced. Meteorological data and atmospheric oxidant and
eye irritation values for these days are tabulated at the end
of the report. (Author summary)##
05133
Hasser, J., R. P. Hangebrauck, and A. J. Schwartz
EFFECTS OF AIB-FUEL STOICHIOMETSY ON AIR POLLUTANT EMISSIONS
FROM AN OIL-FIRED TEST FURNACE. J. Air Pollution Control
Issoc., 18(5):332-337, May 1968, 19 refs. (Presented at the
60th Annual Meeting, Air Pollution Control Association,
June 11-16, 1967, Paper No. 67-124.)
An experimental, domestic-sized, oil fired test furnace to be
used for evaluation of fuel additives and combustion process
modifications in reducing air pollutant emissions is described.
Operating data and emissions of particulate matter, smoke, carbon
monoxide, gaseous hydrocarbons, oxides of nitrogen, and oxides of
sulfur are reported over the range of operable air-fuel ratio.
Emission levels are interpreted in terms of key operating
parameters and potential areas for reduction of emission.
(Authors' abstract modified)##
05171
f. g. r ounds, P. A. Bennett, and G. J. Nebel
SOME EFFECTS OF ENGINE-FUEL VARIABLES ON EXHAUST GAS HYDROCARBON
CONTENT. J. Air Pollution Control Assoc. 5 (2), 109-19 (Aug.
1955) and Trans. SM
1955) and Trans. ASME (Am. Soc. Hech. Engrs.) 63, 591-601
(1955). (Presented at the Annaul Meeting, Society of
Automotive Engineers, Detroit, Mich., Jan. 10-14, 1954.)
The aim was to obtain a better understanding of the factors
influencing the concentration of hydrocarbons in engine exhaust.
Initially, tests were made to determine the fraction of the total
fuel supplied to the engine which appeared as hydrocarbons in the
exhaust at different driving conditions. Later, more exhaustive
tests were made to determine the effect of common engine-fuel
variables at each driving condition. The data are based on mass
spectrometer and/or Orsat analyses of exhaust gas samples obtained
from 163 passenger cars and 8 public transit buses. Reductions
in exhaust gas hydrocarbon content can be achieved through proper
maintenance and design. Mass spectrometer analyses have indicated
that the hydrocarbon content of engine exhaust gas varies
appreciably with driving condition. The most important engine-
B. Emission Sources 99
-------
fuel variable affecting the hydrocarbon content at idle was mixture
ratio with the highest hydrocarbon contents being observed at rich
mixtures. A substantial reduction in the average hydrocarbon
content could be obtained by adjustment of the idle mixture ratio
of all cars to the range resulting in best idle operation. The
current trend toward the overhead valve V-8 engine should also
help to reduce idle hydrocarbon losses since these engines will
idle acceptably with leaner mixtures than either 6 cyclinder or
line 8 engines. Fuel type was found to have essentially no effect
on the exhaust gas hydrocarbon content. None of the engine-fuel
variables investigated at part throttle were observed to affect
significantly the hydrocarbon content. These included mixture
ratio, compression ratio, fuel type, coolant temperature, engine
type, engine speed, and engine load. The most important engine-
fuel variable affecting the hydrocarbon content during simulated
deceleration was manifold vacuum. The hydrocarbon content was
found to increase sharply to high values at manifold vacuums above
21 inches of mercury. Since manifold vacuum during a closed
throttle deceleration depends upon engine speed, the trend toward
automatic transmissions and lower rear axle ratios made possible
by higher output engines tends to reduce hydrocarbon losses by
reducing engine speed at a given car speed. Limited studies using
gasoline, LPD, and Diesel powered public transit buses have
suggested that there is no significant difference in the total
amount of hydrocarbon released to the atmosphere by the three
different engines provided that the overall fuel consumption is
comparable.ft
05184
V. N. Trefilov, and M. D. Skanavi
HYGIENIC CHARACTERIZATION OF LABOR CONDITIONS IN THE CHLOROPHOS
INDUSTRY. Gigiyena Truda I Professional1 Nyye Zabolevaniya.
Translated from Russian. «1-3, 1963. Russ. (Tr.)
Analysis established the atmosphere of the chlorophos
production department ot be contaminated mostly by chloral,
dimethylphosphate and chlorophos vapours. Judging by the
available clinical data the detected concentrations of
organophosphorus compound (chlorophos and dimethylphosphite)
vapours reached dangerous levels, which, as it was noted, gave
rise to the development of intoxications. In reconstruction
and erecting new analogous plants it is recommended that
particular attention be attached to proper sealing of equipment and
to elimination of manual operations. It is also suggested to
make provisions for automatic pouring of chlorophos, its
measuring, weighing and washing of barrels to be effected in
special shielded chambers. (Author summary)t*
05292
J. H. Chandler
EFFECTS OF ENGINE-OPERATING VARIABLES ON THE COMPOSITION OF
AUTOMOTIVE EXHADST GASES . Proc., Am. Petrol. Inst.,
Sect. Ill 38, 32U-35 (1958). (Presented before a session on
air pollution, 23rd Midyear Meeting, American Petroleum lost.
Division of Refining, Los Angeles, Calif., May 15, 1958.)
100
HYDROCARBONS AND AIR POLLUTION
-------
The factors affecting hydrocarbon concentration in exhaust gas to
the greatest extent are manifold vacuum, engine detuning
(maladjustment and/or poor mechanical condition), and cold as
compared to hot engine starting. Manifold vacuum of more than
approximately 21.5-in. Hg (mercury) accounts for high
concentrations of hydrocarbons during deceleration. This effect
is accentuated by high speeds at the start of deceleration and by
manual transmissions as compared to automatic transmissions.
Accelerating and cruising conditions at various engine speeds
produce similar hydrocarbon concentrations, generally in the range
of 1 per cent to 5 per cent of the supplied fuel, with hydrocarbon
concentrations tending to decrease with increasing engine speed.
Enriched carburetor idle setting increase hydrocarbon emission
during cruise up to approximately 30 mph. One misfiring plug may-
more than double the average hydrocarbon concentration. A deposit
-fouled spark-plug set can increase the rate of hydrocarbon
emission moe than 2 1/2 time during a wide-open-throttle
acceleration. Among variables which affect oxides of nitrogen,
air-fuel ratio is of primary importance. Lean mixtures promote
the formations of oxides of nitrogen and increase the relative
effects of other engine variables. Under full throttle, rich
mixture conditions, concentrations of oxides of nitrogen are
relatively low. Under part-throttle conditions, however,
mixtures are sufficiently lean to permit varying degrees of
importance to be attached to ignition timing advance, manifold
pressure increase, and compression ratio increase, all of which
promote oxides of nitrogen formation. under road-load cruise
conditions and during full-throttle accelerations, higher speeds
produce higher concentrations. During part-throttle accelerations
, there is no general effect of speed, and high concentrations may
be exhausted even at low speeds. During idling and deceleration,
oxides of nitrogen concentrations are so low as to be considered
insignificant.f#
05312
Chironis, N. P.
SMOG: THE DEADLY POISONS PERIL LIFE IN ALL CITY ABEAS. Prod. Eng.
37, 33-41 (Dec. 19, 1966).
The air pollution problem is national in scope. Pollution-control
officers continue to make a point of cracking down on offending
factories, power stations, and incinerators. But, behind the
scenes, the case against automotive contaminants is building up,
and nothing less than a revolution in automotive engineering will
satisfy tomorrow's standards. This design revolution is chartered
for three stages: Modification of existing engines—improved
carburetors, timing systems, cylinder-head design—and the addition
of devices to burn off hydrocarbons and noxious gases. A search
for new types of internal combustion engine—fuel injection
engines, improved gas turbines, rotary engines. Entirely new
propulsion systems that don't use fossil fuels—electric cars with
batteries or fuel cells, linear motors for mass transportation
systems, perhaps nuclear power either indirectly to charge
batteries or directly to drive vehicles. It was indicated that
pollutants from all sources amount to 135 million tons a year. So
motor vheicles account for about 60 percent of the nation's
atmospheric wastes, by weight. Moreover, government figures
indicate that vehicles are responsible for about 97 percent of the
olefin hydrocarbons and HO percent to 60 percent of the nitrogen
B. Emission Sources 101
-------
oxides. Controls are aimed at three specific targets: emissions
from the tailpipe, from crankcase ventilations, and from carburetor
and gas tank evaporation. The tailpipe is by far the greatest
source of emissions, accounting for up to 65 percent of the
hydrocarbons and almost all the carbon monoxide and nitrogen
oxides. But the crankcase emission is the easiest to control, and
California chose it as the first target six years ago. These allow
275 ppm of hydrocarbons and 1.5 percent carbon monoxide by volume.
Effective Jan. 1, 1970, however, California will cut these
allowables to 180 ppm hydrocarbons and 1 percent CO. The state is
also considering a proposal to adopt a standard of 350 ppm of
nitrogen dioxide.
05323
Jackson, Marvin W.
EFFECTS OF SOME ENGINE VARIABLES AND CONTROL SYSTEMS ON
COMPOSITION AND REACTIVITY OF EXHAUST HYDROCARBONS. In:
Vehicle Emissions, Part II, SAE Progress in Technology
Series, Vol. 12, Society of Automotive Engineers, Inc.,
N. Y., 1966, P.
N. Y., 1966, p. 241-267. {(«1)) refs. (Presented at the
Mid-Year Meeting, society of Automotive Engineers, Detroit,
Bich., June 3-10, 1966.)
The effects of air-fuel ratio, spark timing, an engine
modification system, and the Air Injection Reactor System on
the composition and reactivity of the exhaust hydrocarbons are
reported. The reactivity index and composition changes are
compared to those indicated by the nondispersive infrared analyzer.
Either retarding the spark timing or leaning the air-fuel ratio
reduced the hydrocarbon concentration measured by the infrared
analyzer. In contrast, the reactivity index increased as the
spark timing was retarded and the decrease in the reactivity index
due to leaning the air-fuel ratio was only 1/2 the decrease in the
concentration measured by the infrared analyzer. For equal
reductions in the concentration measured by the infrared
analyzer, the reactivity index with the engine modification system
was 37% higher than that with the Air Injection Reactor
System. Conversely, in order to produce an exhaust with the same
level of reactivity, the engine modification system has to reduce
the concentration measured by the infrared analyzer about 70 ppm
n-hexane more than the Air Injection Reactor System. The
use of the reactivity index points out significant differences in
smog-forming potential resulting from both changes in engine design
variables and exhaust control systems; these differences are not
revealed by measurements made using the infrared analyzer.
(Author's abstract)i#
05337
G. G. Esposito
IDENTIFICATION OF AEROSOL PROPELLANTS IN PAINT PRODUCTS BY
GAS-LIQUID CHROMATOGEAPHY (FINAL REPT.) Aroy Coating and
Chemical Lab., Aberdeen Proving Ground, Md. (Rept. No.
226.) Mar. 1967. 15 pp.
102 HYDROCARBONS AND AIR POLLUTION
-------
Aerosol packaged paint products have gained widespread
acceptance in recent years. Because of safety and toxicity
factors, the type o± propellant employed is of vital importance.
This report describes a rapid, specific procedure for the
identification of propellants using gas-liquid chromatography. A
chilled can of paint is sprayed into a test tube and the atmosphere
above the liquid is sampled. The analysis is conducted on
silicone grease and porous polymer columns. (Author abstract)M
05111
E, S. Starkman
VARIOUS COMPONENT GASES OF ENGINE GENERATED POLLUTION POSE
DIFFERING HEALTH HAZARDS. S.A.E. (Soc. Automot. Engrs.)
J. 75, (3) 85-7, Mar. 1967
Onburned hydrocarbons, oxides of nitrogen, carbon monoxide, and
carcinogens are among the emissions generated by engines. Each
produces hazards of varying importance and each presents a
different control problem. For example, the ultimate method of
reducing the hydrocarbon emissions is to supply a completely
stratified charge. As with the hydrocarbons, many engine
variables influence the concentration of nitric oxide. carbon
monoxide concentration follows directly the fuel-air ratio, and a
rich mixture operation must be avoided at all times. Reduction
in carcinogen content should occur as the concentration of
unburned hydrocarbons is reduced.*#
05077
K. Gasiorowski
(ENERGY GENERATION FROM LIQUID FUELS.) Energieerzeugung aus
fluessigen Brennstoffen. Gesundh. Ingr. (Munich) 86 (t),
116-22 (Apr. 1965.) Ger.
Air pollution due to oil-fired installations is caused by
sulfur dioxide, carbon dioxide, nitrogen oxides, and products of
incomplete combustion (carbon monoxide, hydrocarbons, ashes, and
soot). Percentual share of these agents in flue gases produced
froa different fuel oils under various combustion
conditions is giben. Efficiency of high smoke stacks in
dispersing S02 is discussed and presented graphically.
Statistical data are presented on share of automobile engines,
domestic furnaces, and industrial furnaces in cities' air
pollution due to S02.##
05479
A. Goetz
AEHOSOL FORMATION IN NATURAL AND POLLUTED AIR.
(Aerosolbildung in naturlichen and verunreinigten Luftmassen.)
B. Emission Sources 103
-------
Preprint. Ger. Tr. (Presented at the
Internationales Immissionsschutz Forum, Essen, Germany, 1966.)
The nature, type, and the effects resulting from modifications by
aerosols of reactive gaseous constituents contained in the
biosphere are reviewed. aerosols modify the physical as well
as the chemical reaction pattern of the molecular-disperse
gaseous phase to a considerable degree in spite of the fact
that the total mass of this colloid substance is minimal
10 to the minus 7th to 10 to the minus 8th compared to that
of the gases which suspend the colloids. The increase in
concentration of aerocolloids becomes obvious through a rapidly
increasing visibility restriction due to contrast reduction by
light scattering should also be considered. The growth of
aerosols demonstrates the presence of reactive emission components
by increased haze formation. It also has to be realized that the
origin of the haze production is not necessarily tied to the
locality of the pollution source because such reactions
proceed relatively slowly, especially when different reaction
partners originate at different localities or when a high
particulate level is already present due to climate conditions.
The formation of aerocolloids is by far not restricted to
industrial and other man-made pollutions but results also from many
processes in nature which go on continuously over the earth's
surface in large variety. Consequently the final effect
of emissions depends to a large extent on the geographical
and climatic conditions and the natural aerosol levels, so that
knowledge about their origin and formation rate is necessary to
judge the final effect of various emission types over specific
population areas. The sources, chemical and physical interactions
, and methods for determining the size distribution of aerosols
are considered.tf
05596
C. J. Domke, D. J. Lindley, and C. N. Sechrist
HOW TO STUDY EFFECT OF BLOWBT GAS. Hydrocarbon Process.
45 (9), 303-6 (Sept. 1966).
A new technigue for the study of blowby gas uses an engine which
contains Teflon parts and thus can operate without lubricating
oil. This allows the generation and collection of uncontani&ated
gas samples for studying vehicle emissions, engine sludge and
deposit formation. The character and chemical composition of
blowby gases were explored by ducting them from the engine and
fractionating them in a series of traps at 32, minus 100, and minus
326F. Each fraction was analyzed by (1) infrared absorption,
(2) mass spectrometry, and (3) gas chromatography. Changing
air-fuel ratio had little or no effect on the composition of the
hydrocarbons being emitted from the crankcase. The hydrocarbon
portion of the blowby gas was roughly 50% aromatics, 35% saturates,
and 15% olefins. The composition of the hydrocarbon portion was
approximately the same whether the fuel was a fall range boiling
range gasoline or isooctane. The appearance of a broad spectrua
of paraffinic hydrocarbons, olefins, and aromatics when using
isooctane fuel is evidence of extensive chemical reactions
talcing place within the combustion chamber of an engine. The
TO4 HYDROCARBONS AND AIR POLLUTION
-------
combined concentration of oxygenated organic compounds present in
the blowby gas, collected in our studies, was less than five parts
per million. This includes all oxys to C12. Only the simplest
of these oxygenated compounds, formaldehyde, acetaldehyde,
methanol, and ethanol, were identified. The blowby gas from the
operating engine was bubbled through oil samples maintained at
275F. As a control, air at the same rate was passed through
another sample of the same oil, maintained at the same temperature.
Analyses showed that the rate of oxy compound generation in the
oil contacted by blowby gas was 10 times greater than that in the
oil contacted by air. Details of engine modification, operating
conditions and gas evaluation are presented.##
05632
T. S. Legatski
THE ENGINE BEHAVIOR CHABACTEHISTICS OF L.P.-GAS FUELS.
Preprint. (1959).
The purpose was to offer a further analysis of the findings of a
research program on engine requirements''under severe operating
conditions and on fuel behavior characteristics as related to fuel
composition. Eight two-component and two three—component
IP-Gas blends were tested in one or more of four 1958 model
IP-Gas truck engines of different makes or models. The
permissible knock-limited spark advance was determined throughout
the speed range. Neither ASTH Motor or ASTH Research
octane numbers, as calculated from a knowledge of fuel
composition, nor any combination of them reflects fuel behavior in
the more severe types of current LP-Gas engines. Behavior
of LP-Gas fuel formulations in severe engines and under severe
service conditions can be predicted from fuel composition using a
new and different scale of values which has been designated as the
ESSU scale. Since the ESBD (service octane scale) numbers
are only significant when related to an engine of assigned high
severity, the numbers lack utility as an overall quality yardstick.
Both propane and propylene are depreciated by about the same
amount in current severe types of LP-Gas engines. Behavior of
LP—Gas fuels in the more common mild engines, operated under
mild conditions, can be predicted from fuel composition and some
scale of antiknock values lying in between those of the
ASTM-Research and ASTB-Hotor methods of test.**
05633
London, A. L.
THE APPLICATION OF RESEARCH TO MOTOR VEHICLE EMISSION CONTROL—CAN
BE AVOID AFTERBURNERS? (Presented at a Session of the
Air Pollution Research Conference on "The Application of
Research to Motor Vehicle Emission Control," Los Angeles,
Calif., Dec. 7, 1961.)
B. Emission Sources
-------
Basic improvements in the design, production control, and
maintenance of the carburetor and distribution system of the
conventional spark-ignition four-stroke cycle automobile engine,
and a change of engine type to one having inherently the potential
for low hydrocarbon emissions are reviewed. Chemical
considerations, especially fuel-air ratio, are discussed. Engine
test results are considered. The low pollution potential of the
following possible alternate automotive power plants is discussed:
diesel engines, gas turbine engines, and stratified charge engines.
The cost factor is mentioned.
05648
J, H. Elliott, N. Kayne, and M. F. LeDuc
EXPERIMENTAL PROGRAM FOR THE CONTROL OF ORGANIC EMISSIONS FROM
PROTECTIVE COATING OPERATIONS (INTERIM REPT. NO. 7). Los
Angeles County Air Pollution Control District, Calif. Jan.
1961. 26 pp.
The progress made on the experimental program for the control of
solvent emissions from surface coating operations is reported.
The results of 16 runs made with two industrial finishes, an air
dry lacquer and a high temperature baking enamel, are discussed
with respect to particulate matter removal before the air stream
enters the carbon unit. Various filters and combinations of
filters were used in this study. Additional runs were made using
single and mixed solvents with the four-tray adsorber. The
results are analyzed with respect to the effect of using saturated
versus superheated steam on the retentivity of the carbon for
these solvents, carbon life, pressure drop, and temperature rise
for the four-tray absorber are also discussed. The status of the
program, together with the questions that have been answered, and
the questions to be answered, are delineated. A modification of
the first conical unit adsorber is described. The experimental
work on this modified unit, now under construction, will conclude
the work on the spray booth phase of this project.tf
05649
Smith, I. D.
NITROGEN TETFOXIDE DISPOSAL UNIT COHBUSTION PRODUCTS. National
Aeronautics and Space Administration, Las Cruces, N. Hex., Manned
Spacecraft Center. May 1967. 7pp. (Hept. No. NASA TN D-3965.)
A test program was conducted to determine the identity of the
combustion products released to the atmosphere by the vapor
disposal units which dispose of nitrogen tetroxide by burning with
propane. The burner unit, which is designed to dispose of at least
10 Ib of nitrogen tetroxide per minute, consists of an injector
system for the propane and the nitrogen tetroxide, a nixing
chamber, a burner head constructed to minimize flashback, and a
spark-plug igniter system controlled from a blockhouse. Samples of
the combustion products were collected and analyzed by infrared
106 HYDROCARBONS AND AIR POLLUTION
-------
spectroscopy. Hhen the unit was operated in the normal, slightly
fuel-rich mode, the detectable combustion products were carbon
dioxide, water vapor, and unburned propane or other carbon-hydrogen
bond-containing materials. The hydrocarbon emission, which would
be undesirable in a smog-prone area, can be controlled to a degree
by adjustment of the propane feed. The propane adjustment becomes
important when disposing of an oxidized feed that continuously
diminishes in nitrogen tetroxide. The combustion products do not
contain any materials which present any toxicity problems. After a
year of usage, the Hhite Sands Test Facility concludes that the
disposal units provide d convenient, rapid, and safe method for the
disposal of excess nitrogen tetroxide.
05716
Ourusoff, L.
CLEANED AIR AND THE GAS INDOSTRY (PAET I) . Am. Gas J. 194 (3) , 32-
5; 38; <*0; 42 (Bar. 1967) .
The background of air pollution is briefly reviewed from both a
universal and a gas industry viewpoint. The principal causes and
sources of air pollution in the United States are discussed. The
physiological effects of air pollution are considered. Current
methods and means of controlling air pollution are reviewed.
Regional aspects of the problem are examined as they affect its
severity and bear on the attitudes of the public, the federal and
local authorities, commerce, and industry, and more specifically
the public utility companies.
058UU
THE EFFECT OF ORGANIC MATERIALS IN THE ATHOSPHERE ON VEGETATION.
Preprint. California Univ., Riverside. (This is a
continuation of the report dated Jan. 21, 1957.)
A study on the effect of irradiated auto exhaust on plant daaage
isjresented. No satisfactory amount of plant damage was produced
in any of the combinations of conditions available. These
included varying residence time, light intensity, plant exposure
time, ratios of the auto operating cycles, and additions of
nitrogen dioxide, ozone or raw gasoline. In a few experiments,
very slight, but typical oxidant damage was produced along the
margins of some leaves, but the amount was too small to be of use
in evaluating fuels. Of particular interest is the fact that when
ozone was added to the exhaust, no damage occurred. Similarly,
when raw gasoline and nitrogen dioxide were irradiated ozone was
formed, but no oxidant damage was obtained. No explanation for
the failure to obtain plant damage can be offered until the test
facilities are made available for intensive trials.*f
B. Emission Sources 107
-------
05850
M. A. Elliott, G. J. Nebel, and F. G. Rounds
THE COMPOSITION OF EXHAUST GASES FROM DIESEL, GASOLINE AND
PROPANE POWERED MOTOR COACHES. 3. Air Pollution Control
Assoc. 5 (2), 103-8 (Aug. 1955). (Presented at the 48th innual
Heeting, Air Pollution Control Association, Detroit, Mich.,
May 22-26, 1955.)
Exhaust-gas samples were obtained from Diesel, gasoline, and
propane-powered motor coaches of similar passenger capacity under
idling, accelerating, cruising, and decelerating driving
conditions. The samples were analyzed for carbon monoxide, oxides
of nitrogen, formaldehyde, and hydrocarbons. In addition, the
exhaust-gas flow rates were measured to permit calculation of the
emission rate for each constituent at each driving condition.
Based on a typical city driving pattern, it was concluded that:
1. The carbon monoxide emission from the Diesel coaches was only
a small fraction of that from the gasoline and propane coaches.
2. The differences observed in the emission of oxides of nitrogen,
formaldehyde, and hydrocarbons by the 3 coach types were relatively
small. No one coach type discharged either the greatest or least
amounts of all of these 3 constituents.##
05912
Larsen, R. I.
MOTOR VEHICLE EMISSIONS AND THEIR EFFECTS (CONFERENCE
REPORT). Public Health Rept. (U.S.) 77(11), 963-9 (Nov. 1962)
(Presented at the Annual Meeting, New England Section, Air
Pollution Control Association, Worcester, Hass., April 25, 1962.)
Highlights of the papers presented at the Fifth Air Pollution
Medical Research Conference on December 4, 1961, and at the Joint.
Research Conference on Motor Vehicle Emissions and Their Effects on
December 5-7, 1961 are presented. Current research findings on
quantities and types of air pollutants from motor vehicles and the
effects of these pollutants on the health of man, plants, and
laboratory animals are reviewed.
06031
E. E. Lemke, N. R. Shaffer, J. A. Verssen, and R. G.
Lunche
AIR POLLUTION FROM AIRCRAFT IN LOS ANGELES COUNTY - A DEPORT OF
THE ENGINEERING DIVISION, DEC. 1965. 90th Congress. pp.
248-61. ("Air Pollution-1967, Part I (Automotive Air
Pollution)" Senate Committee on Public Works, Washington,
D. C., Subcommittee on Air and Water Pollution, Feb. 13-14,
20-21, 1967.
108 HYDROCARBONS AND AIR POLLUTION
-------
The amount of air contaminants emitted into the atmosphere of Los
Angeles County as the result of the operation of aircraft was
surveyed. The emissions from aircraft with which the District is
concerned are those occurring below 3,500 feet altitude and within
the geographical boundaries of Los Angeles County. This
altitude (3,500 feet) is used as a parameter for the mixing height
below which atmospheric dispersion of pollution is inadequate.
Observations were made from airport control towers to establish
the average time duration of the various operational flight phases
for different types of aircraft. These phases are: (1) Taxiing
from the terminal to the end of the runway and idling while
awaiting clearance from the control tower; (2) Take-off and
climb-out through 3,500 feet altitude; (3) Descent from 3,500 feet
altitude to touchdown on the runway; and (4) Taxiing from
touchdown to the unloading terminal. In observing the departure
phase, radio contact was maintained with the pilot in order to
learn when the aircraft had climbed-out to 3,500 feet altitude.
The distance in miles from the airport when the aircraft was at
3,500 feet altitude was established by radar for both arrival and
departure. In the arrival phase, the pilot notified the control
tower as the aircraft descended downward through 3,500 feet
altitude. It was thus possible to determine the average elapsed
time for an aircraft to travel from take-off to 3,500 feet
altitude, and from 3,500 feet altitude to touchdown on the runway.
Emission factors were then applied.f#
06039
K. J. Springer
INVESTIGATION OF DIESEL POKERED VEHICLE ODOB AND SHORE - PART 2
(MONTHLY PROGPESS REPT. NO. 4, APE. 15, - MAY 15, 1967).
Southwest Research Inst. , San Antonio, Tex., Vehicle
Emissions Research Lab. (Bay 26, 1967) 12p.
Studies of the effect of engine derating on exhaust smoke and odor
are in progress. The 6-month fleet test of a smoke suppressant
additive, which began on April 1, is continuing. Preparations
for the evaluation of the three types of catalytic mufflers for
use with two-cycle powered buses are nearing completion.
Preliminary studies are under way to establish the feasibility in
the laboratory of relating an instrumental odor measurement method
with the human odor panel.f#
06055
HEALTH PROBLEMS RESULTING PROM PROLONGED EXPOSURE TO AIR
POLLUTION IN DIESEL BUS GARAGES. Ind. Health (Japan) 4(1):
1-10 (1966).
An environmental and a health survey of two diesel bus garages in
Alexandria (Egypt) have shown an air pollution problem due to the
exhaust of engines containing S02, N02, aldehydes and
hydrocarbons within permissible levels and a relatively higher
concentration of smoke. The examination of workers revealed the
occurrence of upper respiratory tract disease, chronic bronchitis.
B. Emission Sources 109
-------
asthma, peptic ulcer, gastritis, and high blood pressure in
prevalences higher than expected. Respiratory diseases were
probably due to a synergistic effect of smoke and irritants as well
as the presence of acrolein and adsorbed hydrocarbons and the
smoking habits of workers. Cases of chronic dyspepsia and peptic
ulcers were probably related to the nervous tension of night
shifts, and other factors as the irregularity of meals and the
probable swallowing of dissolved irritants. The blood pressure
was relatively "higher" among night shift workers. (Authors'
abstract, modified)ft
06086
E- L. Stenburg, R. H. Horsley, H. A. Herrick, A. H.
Rose, Jr.
EFFECTS OF DESIGN AND FUEL MOISTURE ON INCINERATOR EFFLUENTS.
J- Air Pollution Control Assoc. 10 (2), 114-20 (Apr. 1960).
(Presented at the 52nd Annual Meeting, Air Pollution Control
Association, Los Angeles, Calif., June 21-26, 1959,)
Tests were made to determine the effects of fuel moisture
content on pollutant emissions from an experimental incinerator
of fixed dimensions while varying (1) the amount and distribution
of combustion air, and (2) the burning rate as measured by the
amount of fuel charged per hour. Overfire combustion air was
introduced into the front of the ignition chamber at the grate
level, and swept the surface of the burning fuel bed.
Underfire air entered through the ash pit and passed up
through the fuel bed. Secondary air was introduced through
a duct built into the top of the bridge—wall and was
discharged through a series of ports opening into the top of the
mixing chamber. Dry components of the fuel include equal parts,
by weight, of newspaper and corrugated cardboard, mixed in a ratio
of three to one with wood chips. Chopped potatoes were
substituted for leafy vegetables as the wet component
because of their year-round availability. Five-pound charges
were prepared with the wet-to-dry components adjusted to provide
a fuel with an average moisture content of either 25 or 50S.
Particulate, oxides of nitrogen, hydrocarbons, carbon monoxide,
and smoke were measured. Because of the basic physical and
chemical laws involved, factors demonstrated by this study
as affecting the increase or decrease of air pollutants
should be the same as those affecting production of pollutants
from larger scale incinerators.#t
710
HYDROCARBONS AND AIR POLLUTION
-------
06104
Swartz, D, J., K. B. Vilson and W. J. King
HERITS OF LIQUEFIED PETROLEUM GAS FUEL FOB AUTOMOTIVE AIR POLLUTION
ABATEMENT J. Air Pollution Control Assoc. 13 (4), 154-9 (April
1963). (Presented at the 51th Annual Meeting, Air Pollution
Control Association, New York City, June 11-15, 1961.)
The purpose of this investigation is to establish trends and to
present some material which sould be both interesting and revealing
as regards the use of LPG as a motor fuel. Particular emphasis is
directed towards its potential for reducing atmospheric air
pollution. A major result of this investigation is to provide new
data emphasizing the striking differences in the composition of
exhaust gas from similar engines operating on Liquefied Petroleum
Gas fuel as contrasted with their operation on gasoline. Tests show
that in the case of LPG exhaust there are essentially no heavy
hydrocarbons (C4 or greater) present. Since the olefins are the
worst offenders as regards smog formation from gasoline exhaust,
the absence of heavy olefins in LPG exhaust suggests the
possibility of a significant reduction in automotive smog if enough
vehicles in a given area use LPG fuel. The scaled fuel system
offers an additional advantage by eliminating the evaporation of
fuel to the atmosphere, which is currently a source of added
expense to the motorist as well as adding to the total amount of
air pollution from cars.
06108
Hoffman, D. and E. L. Wynder
STUDIES ON GASOLINE ENGINE EXHAUST. J. Air Pollution Control
Assoc. 13(7), 322-7 (July 1963). (Presented at the 55th
Annual Meeting, Air Pollution Control Association, Chicago,
111., May 20-24, 1962.)
Results of the chemical analysis of exhaust gas of a gasoline
engine under city driving schedule and road load are presented.
Various carcinogenic and noncarcinogenic hydrocarbons, as well as
phenols and nitro compounds, were isolated and identified. A
benzene extract of the exhaust gas particulate phase and condensate
was applied in five different concentrations to mouse skin. An
attempt has been made to explain the observed development of
papillomas and carcinomas in terms of its chemical constituents.
The analyses of various standard runs with different fuels were
reported and the possibility of the most pertinent precursors for
phenols and aromatic hydrocarbons are dicussed. Caution must be
used in regard to the interpretation of these findings in respect
to their effect on man. (Authorsl summary)
06280
Folke Hedlund, Gustav Ekberg, Sten Erik Mortstedt
DIESEL EXHAUST GASES. INVESTIGATION WITH PROPOSALS FOR ACTION.
(Communications Dept., Stockholm, Sweden, Guidance Group
Concerning Development Work in the Field of Motor
B. Emissidn Sources
-------
Vehicle Exhaust Gas, Sept. 1967. Translated from Swedish,
Joint Publications Hesearch Service R-8913-D, 7Up., Dec. 12,
1967. 27 refs.
Diesel exhaust emissions and methods of controlling these
emissions in Sweden are reviewed. The diesel engine differs
from the gasoline engine in several respects, which have a decisive
influence on the pollution it emits. It uses a fuel that is
less volatile than gasoline. It normally works with a higher
excess of air (leaner mixture) and the devices for feed and
ignition of the fuel are quite different. Due to the discharge
by individual vehicles of dense smoke and by the discharge of
foul-smelling substances they have been pointed out by the
public as qualified air polluters. Poor maintenance of the
engine or intentionally wrong pump adjustments can result in the
giving off of such dense smoke that this can constitute a hazard
for overtaking vehicles due to impaired or obscured visibility.
Diesel engines can give off various types of smoke. One type is
the heavy load smoke, which arises through load on a hot engine.
Exhaust gases from diesel vehicles, especially under certain
driving conditions, contain substances that are irritating
to eyes, nose and throat. These include: oxides of nitrogen,
hydrocarbons, polycyclic aromatic hydrocarbons, carbon monoxide
and sulfur dioxide. The smoke from a diesel engine can
be limited by various measures, undertaken on the engine or the
fuel pump, the fuel, and finally on the exhaust gases.
Regular maintenance of the engine is necessary to keep the smoke
values at the lowest possible level. Current and proposed
regulation of diesel exhaust emissions are discussed.##
06299L
Bureau of Mines, Pittsburgh, Pa., Coal Research Center
pp. 51-61 (1966) .
FLAHE CHARACTERISTICS CAUSING AIR POLLUTION. (SECTION VI OF
AIH POLLUTION RESEARCH PROGRESS REPORT FOR QUARTER ENDED
DECEMBER 31, 1966.)
A study is in progress of the factors that lead to or limit
emission of oxides of nitrogen, carbon monoxide, and light
hydrocarbons by gas appliances, such as space heaters and hot water
heaters. The separate and combined effect of thermally or
chemically perturbing the combustion gases above primary flames
of lean, stoichiometric, and rich propane-air mixtures are being
determined theoretically and also experimentally by means of
factorial experiments. Concentrations of oxides of nitrogen
with and without flue gas were determined at sampling
stations at the top of the primary flames and
concentration of oxides of nitrogen was reduced by the
addition of either of two simulated flue gases. Flue gas A
(containing no air) was more effective in reducing the
concentration of oxides of nitrogen than flue gas B
(containing air). The data also indicate that for most of the
flames with or without flue gas the major increase in
concentration of oxides of nitrogen occurred within about the
first inch above the primary flames. The effect of
addition of flue gas on concentration of hydrocarbons was
measured at the top of the primary combustion zone. Hydrocarbons
occurred at the edge of all flames when a flue gas was added.
Since the addition of flue gas caused partial flame lift it is
VIZ HYDROCARBONS AND AIR POLLUTION
-------
possible that some of the initial hydrocarbon plus other
hydrocarbons formed from it may be escaping through the dead space
between the burner grid and the base of the flame. (Author's
summary, modified)##
06300L
CHARACTERISTICS AND PHOTOCHEMICAL REACTIVITY OF VEHICULAR
EMISSIONS. (Section VII of air pollution research progress
report for quarter ended December 31, 1966.) Bureau of
Bines, Pittsburgh, Pa., Coal Research Center, 1966, pp.
BH/63-BM/67.
The effects of halogens, S02, and humidity on reactivity of a
standard ethylene plus NO plus air mixture were studied. The
results showed no effects on the system's chemical reactivity as a
result of the presence of halogen and S02; the ozone meter's
response to oxidant and N02, however, was reduced in the
presence of S02. Humidity was found to interfere with the
chemical processes in a way that affected significantly
the reactivity-measuremnt results. Further studies on
background reactivity in the irradiation chamber showed that
the background oxidant formation result of photochemical
reactions involving NOx and hydrocarbon at extremely low
concentrations. (Author summary)##
06350
California State Dept. of Public Health, Berkeley, Bureau
of Air Sanitation. (Sept. 1, 1965). 8pp.
CONSIDERATION OF EMISSION STANDARDS FOR EXHAUST HYDROCARBONS
IN TERMS OF QUANTITY (PRELIMINARY REPORT.)
The quantity of exhaust contaminants emitted from motor vehicles
is proportional to the product of contaminant concentration and
exhaust volume (which in turn is proportional to fuel
consumption); a concentration standard essentially allows quantity
of emissions from individual vehicles proportional to fuel
consumption. By requiring the same concentration of contaminants
to be emitted by all vehicles, the concentration standards are
perhaps more restrictive to small cars. For this reason, it has
been suggested that standards based on quantity would be more
equitable. summarized in this report are data on contaminant
concentration in exhaust, and exhaust volume flow rates for
vehicles classified according to engine displacement. There
is no simple relationship between engine size and quantity of
hydrocarbon, carbon monoxide and oxides of nitrogen emitted.
Quantity emissions of hydrocarbon from all classes of
vehicles fall within a narrow range, whereas those of carbon
monoxide and oxides of nitrogen vary markedly from class to class-
Exhaust hydrocarbon concentration measured on one group of 50
Class A cars (displacement less than 110 cu in) had a range
of 2840 ppm; the smallest value was UHO ppm while the
largest was 3180 ppm. Similar variations also exist in the
data for other classes of vehicles. The exhaust flow rates are
lower in smaller displacement engines. The exhaust flow rates,
as well as the fuel consumption rates were determined from
testing vehicles on a seven-mode dynamometer cycle. Exhaust
B. Emission Sources ITS
-------
flow rates might be expected to be closely proportional to fuel
consumption rates. However, the relative exhaust flow rates
between classes do not follow closely the relative fuel consumption
rates, although similar trends are apparent. The difference
nay be due to an insufficient number of cars tested for exhaust
volume.##
06H88
Squires, Arthur M.
CLEAN-FUEL POWER CYCLES. American Society of Mechanical
Engineers, New York, 67-WA/PWR-3, 16p.. 1967. 58 refs.
(Presented at the Winter Annual Meeting, American Society
of Mechanical Engineers, Pittsburgh, Pa., Nov. 12-17, 1967.
A number of supercharged-loiler power cycles are surveyed which
are regarded as especially suited for use with clean fuels, i.e.,
fuels which are dust-free and sulfur-free. The cycles are
intended for use in "clean power" systems, which offer the
prospect that power can be generated not only without discharge of
objectionable atmospheric pollutants but also more cheaply. In
such systems, dirty fuels would first be converted to a clean fuel
gas by processes which recover elemental sulfur for the market, and
the clean gas would be committed to an advanced power cycle
engineered for clean fuel and affording higher efficiency. The
cycles have in common the feature that an unusually large amount of
superheat is added to the steam, so that steam exhausts fron an
expansion in a highly superheated condition. The exhaust is
preferably at atmospheric pressure or above. The superheated
steam is cooled against boiler feed water, and is then sent to a
low-temperature power-recovery step. In some cycles, high-level
heat is added indirectly by heat exchange from flue gases at high
pressure. In others, high-level heat is added to the steam
directly in the form of products of combustion of a clean fuel
either with air or with oxygen provided by an improved version of
the historic Brin process. Heat rates are given postulating
methane as fuel, with steam at 2,100 psia, indirect additions of
heat limited to 1200 F, and direct additions of heat limited to
1500 F. Detailed economic evaluations of the several cycles are
not yet available, and only qualitative statements can now be made
concerning their probable relative worth. (Author's abstract)ft
06791
P, Lemaigre
AIE POLLUTION BY MOTOB VEHICLES. LA POLLUTION DE
1'Air par les Vehicules Automobiles. Pollut Atmos (Paris)
8, (32) 439-82, Dec. 1966, Fr.
A general review is presented of the air pollution caused
by motor vehicles. The known facts and the current research on
air pollution is presented on the basis of papers given before
the Strasbourg Conference in June of 196U. The various
polluting agents are considered and the control measures which
involve the fuels and the engines are described. Recent work
carried out in both France and the United States is
discussed with the differences between the motor
traffic conditions taken into account. French legislation is
114 HYDROCARBONS AND AIR POLLUTION
-------
discussed emphasizing the importance of proper engine
maintenance in air pollution control. The results of proper
carburetor adjustment during idling are a good example of a simple
method of control. It is concluded that the eventual solution
will not be easy. The necessity ot preserving "green areas" as
method of air pollution control is brought out since these
plots have a considerable absorbent role.f*
06808
G. Scassellati-Sforzolini
TOBACCO SHORE IN AN ENCLOSED SPACE. II Fumo di Tabacco
Negli Ambienti Confinati. Fumi Polveri (Milan) 7 (2-3),
38-U1 {Mar. 1967) It.
The amount of polycyclic aromatic hydrocarbons present in
cigarette smoke as well as the amount of tar and nicotine present
in filtered and unfiltered cigarette smoke (the part inhaled and
the part in the surrounding air) was investigated. For the smoke
parameters, the following standards were used: length of stub, 23
mm; period of inhalation, 2 sec; intermittence period, 60 sec;
volume inhaled, 35 ml. The method used to determine the amount
of polycyclic hydrocarbons present was based on chemical treatment
of the liquid through which smoke was bubbled, then
separation of alumina and silica gel columns, followed by
spectrophotometric analysis of the eluates. The following
hydrocarbons were obtained in the smoke inhaled and in the smoke in
the ambient air, respectively: Anthracene - 4.85, 5.40 -
gamma/100 cigarettes; Pyrene - 4.56, 1.88 - gamma/100 cigarettes;
3/4-Benzopyrene - 2.99, 0.38 - gamma/100 cigarettes.
Chloroform extraction was used in the determination of the tar
content. The nicotine content was determined by distilling the
acetic extract after addition of 30% NaOH. The results
indicate that the amount of tar and nicotine is greater in the
ambient smoke than in the inhaled smoke. Among the Italian
cigarettes studied, those with filters showed higher tar and
nicotine content than the non-filtered cigarettes.M
06950
Liebhafsky, H. A.
FUEL CELLS AND FUEL BATTERIES—AN ENGINEEBING VIEW. IEEE
(Inst, Elec. Electron- Engrs.) Spectrum, 3(12):48-56, Dec.
1966. 9 refs.
Fuel cells electrically connected (in series, parallel or series-
parallel) make fuel batteries. Fuel cells should react
conventional fuels (by which is meant the fossil fuels and
substances readily derived therefrom) electrochemically with oxy-
gen, preferably from air. A fuel cell, therefore, is an
electrochemical cell in which energy from such a reaction is
converted directly and usually into low-voltage dc energy. Fuel
batteries are discussed in terms of the various types of fuels,
effiency, reliability, life, and operating temperatures. Ill of
these properties are tied in with the important consideration of
economics.##
B. Emission Sources 115
-------
07089
Rosen, A.A., B. T. Skeel, and B. B. Ettinger
RELATIONSHIP OF RIVER WATER ODOR TO SPECIFIC ORGANIC
CONTAMINANTS. J. Hater Pollution Control Federation
(Presented at the 35th Annual Heating, Water Pollution
Control Federation, Toronto, Canada, Oct. 7-11, 1962.)
35(6):777-782, June, 1963.
The results of odor tests conducted in conjunction with a study of
organic contaminants in the Kanawha Biver at (itro, West
Virginia are reported. A major part of the odor of the river
can be ascribed to 11 organic chemical compounds that were
identified and measured. Naphthalene, Tetralin, Styrene,
Acetophenone, Ethyl benzene. Bis (2-chloro-isopropyl) ether,
2-Ethyl hexanol, Bis (2-chloroethyl)ether, Di-isobutyl carbinol,
Phenyl methyl carbinol and 2-Methyl-5-ethyl pyridine.
Threshold odor concentrations for each of these compounds were
determined from the responses of an odor panel. A mixture of all
the identified pollutants, in the same proportions as found in the
river, was shown to contribute nearly twice the amount of odor that
can be calculated on the basis of the sum of the individual
contributions. Thus, it was indicated that odor synergism plays
its role as effectively in polluted streams as in the simulated
instances tested in the laboratory.##
07187
E. C. Larson and H. E. Sipple
LOS ANGELES HOLE 66 AND EXEMPT SOLVENTS. J. Paint
Technol. 39 (508) :258-26« (May 1967). (Presented at the Los
Angeles Society for Coatings Technology, Calif., Oct. 12,
1966; at the Golden Gate Society, San Francisco, Calif.,
Oct. 17, 1966; and at the Portland, Seattle, abd Vancouver
Sections of the Pacific Northwest Society, Washington,
Oct. 19, 20, and 21, 1966.)
The implications of Rule 66 of the Los Angeles County Air
Pollution Control District, which controls the emissions of
volatile organic solvents, are reviewed for their effect on the
paint industry. The various provisions of Rule 66 are discussed
to illustrate the desirability of using exempt solvents.
Saturated hydrocarbons (iso, normal, and cycloparaffins),
alcohols, esters, ether-alcohols, and non-branched ketones are
entirely exempt. The exempt limits for photochemical reactive
materials are as follows: olefins - 5*, C8 plus aromatics - 8%,
and toluene, ethylbenzene, branched ketones, and
trichloroethylene - 20%. With mixtures of these photochemical
reactives the total allowable amount is 20%. The problem facing
the paint industry is the replacement of the aromatic solvents
which are good solvents, but are photochemically reactive. (igh
solvency napthenic base stocks will help offset the solvency of the
displaced aromatics for the long oil alkyds and many medium oil
alkyds. Small quantities of non-exempt solvents can be used
provided the escaping vapors are condensed or burned efficiently.
The General Services Administration has asked for a revision
of all their purchasing specifications to conform to Rule 66.ft
116 HYDROCARBONS AND AIR POLLUTION
-------
0721K
Bethge, Per Olof and Lalla Ehrenborg
IDENTIFICATION OF VOLATILE COMPOUNDS IN KRAFT HILL EKISSIONS.
Svensk Papperstid. (Stockholm), 70 (10) : 3
-------
07299
Gorelova, D. N. and P. P. Dikun
THE DETECTION OF 3,4 BENZPYEENE IN SOME SPECIES OF SMOKED FISH.
(FLUORESCENCE-SPECTRAL ANALYSIS). Text in Russian. Vopr.
Onkol., 4 (4) :398-405, 1958. 7 refs. Engl. transl. by B. S.
Levine, O.S.S.R. Lit. on Air Pollut, £ Helat. Occup. Dis.,
Vol. 2, p. 126-134, March 1960.
CFSTI TT60-21188
An investigation was made of the presence of 3,4-benzpyrene in
smoked fish commonly used in the U.S.S.R. The fish were
subjected to saponification. Chromatographic partitioning was
made with a 50 g column of aluminum oxide. The unsaponifiable
fraction dissolved in 30 - 50 ml of benzene was adsorbed by the
aluminum oxide column. Smoke used for processing fish
contained 3,4-benzpyrene, which, together with other substances
contained in the smoke, was deposited on the walls of smokehouses
and on the surface of the processed products. It was shown that
3,4-benzpyrene penetrated into the inner part of the fish;
especially fish not covered with heavy fish scales, and split fish,
in which the contact between the flesh of the fish and the smoke
was direct. In the case of the sprat, smoked by the hot or cold
processes, 33 to 38S of the total 3,4-benzpyrene contained in the
fish penetrated into the flesh; in the case of the bream or split
Rutilus, 26% of 3,4-benzpyrene penetrated into the flesh; and for
the split Barbel up to 87% penetrated into the flesh. In cases
of smoked whole bream, Rutilus, Pelecus and Chalcalburnus,
which are covered with heavy scales, the 3,4-benzpyrene content of
the flesh was many times less than its content in the same types
of fish processed after splitting. The results of the
investigation indicated that the content of 3,4-benzpyrene in
smoked fish did not depend solely on the process by which it was
smoked, whether cold or hot, or whether the smoke came from
openly burned wood or from special smoke generators.##
07300
Dikun, P. P. and I. I. Nikberg
A STUDY OF AIR POLLUTION WITH 3,4-BENZPYRENE IN THE VICINITY OF
AN OLD PITCH-COKE PLANT. Vopr. Onkol., 4(6):669-674, 1958. 6
refs. Translated from Russian by B. S. Levine, U.S.S.R.
Lit. on Air Pollut. 6 Relat. Occup. Dis., Vol. 2, p. 135-
140, March 1960.
CFSTI: TT60-21188
Analyses were made of three sets of samples collected in the area
of the pitch-coke plant at different times, different distances,
and in different directions from the plant: set 1 consisted of 6
samples of dust sweepings; set 2 consisted of 4 sedimentation dust
samples, and set 3 consisted of 3 aspiration samples. A
comparison of pollution before and after the plant was
modernized shows that 3,4-benzpyrene content of sweepings
collected between the inside and storm windows before the plant «as
modernized was 100 times greater than after the improvements were
installed. (0.03 to 0.05* as against 0..0003S) Dust collected
in 1955 from the bricks stored on the plant grounds contained 10
times as much 3,4-benzpyrene as the dust collected between the
118 HYDROCARBONS AND AIR POLLUTION
-------
windows in 1957 (0.003 to 0.009X against 0.0003%). The fact
window pane washings gave negative or trace tests for
3,4-benzpyrene demonstrated the significant reduction in air
pollution attained by the plant combustion modernization. This is
further confirmed by a comparison of analyses of aspiration
samples. After the introduction of the improvefments aspiration
samples of 15 to 45 cubic meter of air contained only traces of
pollutants. Comparison of analytical results collected in 1958
with samples similarly collected in 1955 also shows a substantial
reduction in total pollution (95, 370 and 820 mg per cubic meter in
1955 as against 2.5 mg in 1957) and in 3,4-benzpyrene (0.002,
0.005, 0.400 mg per cubic meter in 1955 as against 0.0004 mg in
1957). Thus, results of the 1957 investigation revealed that
pollution of the air in the vicinity of the pitch-coke plant
decreased sharply after the coke furnaces were modernized.##
07451
Scharf, P. B., B. B. Goshgarian, H. M. Nelson, and G.
L. Body
THE MEASUREMENT OF THE EXHAUST COMPOSITION OF SELECTED HELICOPTER
ARMAMENT. Air Force Rocket Propulsion Lab., Edwards
AFB, Calif, and Army Aeromed. Res. Unit, Fort Sucker,
Ala., Proj. No. 3AO 2560 1A 819, Task No. 051, Rept. No.
AFRPL-TR-67-203 and tJSAARU-67-10, 46p., June 1967. 4 refs.
S study of the exhaust composition of rapid fire machine guns and
rockets has been conducted. Methods of analysis were evaluated
and exhaust compositions for the 50 cal and 7.62mm machine gun and
the 2.75" rocket were determined. A rapid scan infrared
spectrophotometer was used for immediate examination of
effluent gases in order to detect reactive species. The exhaust
gases were analyzed at concentrations as high as 1000 times those
present in helicopters to minimize the chance of missing any
significant toxic product. A qualitative and quantitative
analysis of gas phase and aerosol components is given. It may
well be that the proportion of carbon monoxide in the exhaust is
so high that permissible exposure tines can be selected on the
basis of its concentration alone while still limiting exposures to
all other toxic materials to safe leevls. However, significant
amounts of nitrogen dioxide, ammonia, carbonyl sulfide, hydrogen
cyanide, lead and copper were found.##
07546
J. G. Terrill, Jr., E. D. Harward, I. P. Leggett, Jr.
ENVIROHHENTAL ASPECTS OF NUCLEAR AND CONVENTIONAL POWER PLANTS.
Ind. Med, Surg., 36 (6):412-419, June 1967. 24 refs.
(Presented at the 5th Inter-American Conference on
Toxicology and Occupational Medicine, Miami, Fla,, Aug. 1-4,
1966.)
Inherent difficulties in comparing the health risks of
.conventional and nuclear power plants are pointed out, and
currently available data are presented. Efforts of the
Public Health Service to establish the relative health risks of
the power sources are indicated. There is a lack of accepted
B. Emission Sources 119
-------
standards for the permissible concentrations of nonradioactive
elements in the environment and also a limited amount of data
on the exact composition of the atmospheric radioactive releases
from operating nuclear plants. In the year 2000, the U.S.
power-generating capacity is expected to increase from the
present 11 x 10 to the 15th powerBTU/yr to 70 x 10 to the 15th
power BTU/yr with the proportion of this capacity provided
by nuclear power increasing from 1% in 1966 to U3% in 2000. The
production of oxides of sulfur produced by a 1000 MHi power
station when fired by coal, oil, or gas is given showing emission
rates in million 1b. per year of: 306 for coal;> 116 for oil; and
0.027 for gas. The generation of electricity in the U.S. is
responsible for 15.6 million tons of atmospheric pollutants per
year. There are some radioactive materials such as 1.1
ppm of 238U and 2.0 ppm of 232Th in coal. The only case
in which a nuclear plant might be close to requiring as much
dilution air as a fossil fuel plant to meet the required conditions
would be to prevent the contamination of milk by radioactive
iodine. The Public Health Service plans to conduct a study
of two oil-fired plants and two nuclear plants at the same
site to evaluate the environmental release and effects from both
types of plants with identical meteorological, hydrological,
population, and topographic features.f#
07561
Kaiser, E. E., J. Halitsky, H. B. Jacobs, and L. C.
HcCabe
PERFORMANCE OF A FLOE-FED INCINERATOR. J. Air Pollution
Control Assoc., 9(2):85-91, Aug. 1959. 7 refs. (Presented at
the 51st Annual Meeting, Air Pollution Control Assoc.,
Philadelphia, Pa., Hay 25-28, 1958.)
A limited survey of representative modes of operation and results
of one flue-fed incinerator is reported. The tests were conducted
to serve as a basis for comparison with fruture tests on identical
incinerators with modifications to improve combustion and reduce
air pollution. The incinerated refuse from a 128-apartment
building was approximately «30 Ib. a day. The flue-fed
incinerator reduced the apartment refuse to about 3751 of its
original weight and to about 10% of its original volume. The bulk
density of the refuse averaged i».1 Ib/cu ft. in the incinerator.
The residue had a bulk density of 15.4 Ib/cu ft. in the ash cans.
The residue averaged 6«% metal and glass, 12% ash, 16%
combustible, and 8% moisture, excluding quench water. The air
normally supplied to the furnace was 10 to 20 times the theoretical
air necessary for complete combustion. The high excess air
.reduced the furnace temperatures and undoubtedly affected
adversely the combustion of volatile matter and emission of fly
ash. The infiltration air entering the flue through vents on the
service doors and cracks averaged 35% more than entered the
furnace. Sealing the vents reduced the infiltration air to the
flue to 45%-of the furnace air during the period of fast burning.
The peak furnace temperatures varied from 970 to 1200 deg F.
The emissions of particulate matter to the atmosphere via the flue
gases ranged from 0.85 to 1.55% of the refuse weight. The weights
of particulate matter ranged from 2.5 to U.7 lb/1000 Ib of
furnace gas corrected to 12% C02. The emission of eight
noxious gases totaled 0.9 to 3.0 lb/100 Ib refuse. The presence
of additional unburned hydrocarbons in the flue gases was confirmed
120 HYDROCARBONS AND AIR POLLUTION
-------
by mass-spectrometer tests. The average odor concentrations
ranged from 2.5 to 100 5STM odor units. The incinerator had
inherent features of design and operation that caused high
emissions of particulate matter and unburned organic compounds.
The charging of refuse during burning could contribute to the
discharge of particulate matter. Suggested modifications to the
conventional incinerator include control of the furnace air supply,
better mixing of air and volatile products from the burning refuse
in a zone of high temperature, new furnace designs to eliminate
the necessity for hooking and raking the refuse and residue, and
residue removal with minimum air flow.##
07570
Kireeva, I. S.
ATHOSPHERIC POLLUTION WITH 3,it-BENZPYRENE IN THE VICINITY OF A
COAL BRIQUET FACTORY. (0 zagryaznenii atmosfernogo vozdukha
3,4-benzpirenom v raione briketnoi fabriki.) Text in Russian.
Gigiena i Sanit., 30(7), July 1965. 9 refs. Engl. transl.
by JPES, Hyg. Sanit., 307): 126-128, July 1967.
CFSTI: TT66-51033/3
An investigation was conducted of a large briquet factory which
uses 11% coal pitch for the binding of coal fines, so that the
3,1-benzpyrene content in the coal briguets reaches 0.14X. The
process of briqueting includes crushing bituminous coal and pitch,
mixing them in a certain ratio, and molding the briquets.
Determinations were made of the amounts of 3, i»-benzpyrene in the
gases discharged by the press shop, in the atmosphere, and in the
dust falling at distances of 200 to 1000m from the factory.
Tarry substances were extracted with pure nonfluorescent benzene
and fractionated on a chromatographic column with an activated
aluminum mixture. Identification of 3,4-benzpyrene was
accomplished by comparing the fluorescence spectra of the
individual fractions frozen in liquid nitrogen against
the fluorescence spectrum of a standard 3,4-benzpyrene. The
quantity of the latter was determined photoelectrically. Thus,
3,U-benzpyrene was found in all samples within the radius of 1 kn
from the factory, the concentration decreasing regularly with
increasing distance from the factory. However, concentrations
exceeded the control determinations made on the windward side
(0.1U—0.30 microgram/100 cu. m.) even at a distance of 1000 m.
The results indicate the need to eliminate coal pitch from the
technological process and introduce a new briqueting technology
using noncarcinogenic grades of petroleum bitumens as the
binder . *t#
07593
Panel on Electrically Powered Vehicles
THE AUTOMOBILE AND AIR POLLUTION: A PHOGKAH FOR PROGRESS.
Los Angeles County Air Pollution Control District, Calif.,
51p., Oct. 1967.
GPO: 0-278-482
Air pollution problems from the viewpoint of automotive
transportation were studied in general and all possible
"Alternatives to the current gasoline engine were investigated by
B. Emission Sources, 121
-------
the Panel on Electrically Powered Vehicles. The Panel made
sixteen recommendations for the Federal Government with respect
to its role concerning air pollution resulting from automotive
emissions. Technology and the control of automotive air
pollution and the role of industry are also discussed.f#
07596L
Styles, H. E-, J. Verbos, and J. Lawther
PUBLIC HEALTH ASPECTS OF AIR POLLUTION FROM DIESEL VEHICLES.
Preprint, London Transport, England; Transport
Administration, Brussels, Belgium and Medical Research
Council Air Pollution Research Unit, London, England,
(U6p.) , 1966. 8 refs. (Paper No. HHO/AP/67.28.)
An indication of the nature of air pollutants which may result
from the combustion of fuel, an explanation of the differences
between petrol and diesel engines which give rise to the emission
of exhaust products having different characteristics, and a
comparison between the two types of engines in respect of their
propensity to cause pollution of the atmosphere is presented.
Evidence derived from medical investigations concerning possible
health hazards arising from motor vehicle exhausts is reviewed.
An indication is then given as to means whereby satisfactory
operation of diesel engined vehicles may be achieved without
production of objectionably smoky exhausts. There follows a
description of the legislative procedure which one country
(Belgium) has introduced in the interests of ensuring that
vehicles are so operated as to ensure that they emit no unduly
offensive exhaust products and, as an appendix, an outline is
provided of measures taken by London Transport to prevent air
pollution by diesel-engined public service vehicles. The fact
that maladjustment or incorrect operation of a diesel engine almost
inevitably leads to the production of an objectionably smoky
exhaust has given rise to prejudice against the use of such engines
in road vehicles and an ill-informed impression that the exhaust
which they emit causes more serious atmospheric pollution than does
the exhaust from petrol engines.'tf
07623
Larson, Gordon P., John C. Chipman, and Erwin K, Kauper
DISTRIBUTION AND EFFECTS OF AUTOHOTIVE EXHAUST GASES IN
LOS ANGELES. In: Vehicle Emissions, SAE Tech, Progress
Series, Vol. 6, Society of Automotive Engineers, New York,
196U. p. 7-16. 12 refs. (Presented at the Annual Heeting>
Society of Automotive Engineers, Jan. 1955)
Hydrocarbons or gasoline vapors are known to be an important factor
in producing several of the deleterious effects of smog, however,
one question to be answered is whether or not the removal of
hydrocarbons from all other sources in the community would relieve
the burden on the air sufficiently to avoid any control measures on
auto exhaust. The measurements of the quantity of hydrocarbons
emitted by internal combustion engines another source of
hydrocarbons contributing to the buildup were explored. The areas
of exhaust gas concentration buildup were determined by a study of
122 HYDROCARBONS AND AIR POLLUTION
-------
Los Angeles traffic. Studies now clearly show that removal of all
other sources of hydrocarbons from refineries and from the
distribution of gasoline will not lower the concentration of
hydrocarbons in downtown los Angeles area and the north-central
section of the County sufficiently to relieve the eye irritation,
crop damage effects, and high ozone content of the air in those
areas. The Air Pollution Control District recommends that
engineering studies seeking to remove hydrocarbon vapors from
exhaust gases should strive for a 90S overall removal under
conditions of operation experienced in heavy traffic.
07625
Haas, G. C.
THE CALIFORNIA MOTOR VEHICLE EMISSION STANDARDS. In: Vehicle
Emissions, SAE Tech. Progress Series, Vol. 6, Society of Automotive
Engineers, New York, 1964, 39-14. 5 refs. (Presented at the
National West Coast Meeting, Society of Automotive Engineers, Aug.
1960) .
The legal and technical bases of the California standards are
reviewed and the air pollution laws of California summarized. The
evolution of air quality standards is described. The translation
of air quality standards into motor vehicle emission standards is
described along with a statement of the underlying assumptions
concerning the relationship of the photochemical smog effects to
the atmospheric concentrations of primary pollutants emitted to the
atmosphere from motor vehicles and other sources. Driving cycles,
analytical methods, evaluation of device warmup characteristics,
and related problems are also discussed.
07626
Neerman, J. C., and G. H. Millar.
DETERMINATION AND HYDROCARBON EMISSION BATE BY CONTINUOUS AIRFLOW
MEASUREHENT AND EXHAUST ANALYSIS. In: Vehicle Emissions, SAE
Tech. Progress series. Vol. 6, Society of Automotive
Engineers, New York, 1964, 70-80. 36 refs. (Presented at
the National West Coast Meeting, Society of Automotive
Engineers, Aug. 1957.)
Two instruments developed as part of a program of portable
instrumentation for measuring the emission of incompletely burned
hydrocarbons in the exhaust of automotive vehicles on the road are
described. The first instrument is an infrared interference filter
photometer which measures and records the concentrtion of
hydrocarbons in the exhaust by means of their optical absorption at
3.34 microns. The second instrument is a matrix flow meter
developed to measure and record total engine air consumption in a
moving vehicle operated in normal service. These two instruments
used together will determine the rate of emission of exhaust gas
components from hehicles operated in characteristic modes. The
instrumentation is relatively portable, compact, simple to use, and
adaptable to automobiles. (Authors' abstract, modified)
B. Emission Sources 123
-------
07629
Hay, Gilbert, and H. S. Fagley
FIELD SDRVEY OF EXHAUST GAS COMPOSITION. In: Vehicle Emissions
SAE Tech. Progress Series, Vol. 6, Society of Automotive Engineers,
New York, 1964, 102-120. (Presented at the Annual Meeting, Society
of Automotive Engineers, Jan. 1958O
The operations and results of a comprehensive field survey
conducted in Los Angeles are reported. The purpose was to measure
exhaust emissions from a representative group of cars during
operating conditions encountered in metropolitan driving.
Tvo hundred and ninety—three cars were tested under a schedule of
driving conditions which included a variety of accelerations,
cruise speeds, decelerations, and idle. During the test cycle,
exhaust gases were continuously analyzed by the Model 28 Liston-
Becker spectrometer for CO, C02, and unburned hydrocarbons and by
Bodel 15 Liston-Becker spectrometer for hydrocarbons. Airflow
was measured continuously by the viscous airflow meter. Indica-
tions from these instruments were registered by a recording oscil-
lograph. An oscillogram processor was used on location for deve-
loping the 10,000 ft of recordings taken during the test. Oxides
of nitrogen were determined by analyses of grab smaples taken dur-
ing the acceleration and cruise cycles. A description is given of
preparatory operations; survey operations including
instrumentation, test procedure, test cycle, and supporting
operations; data handling and calculations; and test results.
Details and examples of calculations of results and confidence
intervals, along with calibration charts for the instruments used
are appended.
07632
Wentworth, J. T.
CARBURETOR EVAPORATION LOSSES In: Vehicle Emissions SAE Tech
Progress Series, Vol. 6, Society of Automotive Engineers, New York,
1964, 146-156, 8 refs. of Automotive Engineers, Jan. 2958.)
An investigation was made of vapor losses from the carburetors of
five 1956-1957 automobiles during both 'suburban1 and 'city'
driving. The test cars were selected to represent several
different carburetor venting arrangements. Generally, carburetor
losses were found to increase with increasing carburetor
temperCarburetor vent design determined whether the vapor formed
was vented to the atmosphere, where it contributed to odor and air
pollution problems, or whether the vapor was consumed by the engine
where it could cause engine roughness at idle, especially under
high temperature conditions. (Author's abstract, modified)
07635
Hagen, D. F. and G. W. Holiday
THE EFFECTS OF ENGINE OPERATING AND DESIGN VARIABLES OH EXHAUST
EMISSIONS. In: Vehicle Emissions, SAE Tech. Progress Series
Vol. 6, Society of Automotive Engineers, New York, 1964, 206-223.
9 refs. (Presented at the Society of Automotive Engineers,
National Automobile Heek, March 1962.)
124 HYDROCARBONS AND AIR POLLUTION
-------
To determine the influence of engine variables on the composition
of exhaust gas, engine dynamometer tests were conducted on single
and multicylinder reciprocating engines. The following engine
variables were investigated; air-fuel ratio, power output, engine
speed, spark timing, exhaust back pressure, valve overlap,
combustion chamber deposits, and intake manifold pressure.
Hydrocarbon concentrations were found to be considerably affected
by changes in air-fuel ratio, spark timing, intake manifold
pressure. Hydrocarbon concentrations were found to be considerably
affected by changes in air-fuel ratio, spark timing, intake
manifold pressure, and combustion chamber deposits. Somewhat less
change in hydrocarbon concentration was obtained by varying valve
overlap and engine speed. Changes in engine power output and
exhaust back pressure had little effect on hydrocarbon
concentrations. Carbon monoxide concentrations were principally
affected by changes in the air-fuel ratio. No other variables
affected carbon monoxide concentration except where air-fuel ratio
was indirectly influenced. The influence of changes in the
variables on hydrocarbon and carbon monoxide emissions in pounds
per hour was also determined. Vehicles were tested on the road and
chassis dynamometer to investigate the effect of air-fuel ratio,
spark timing, and valve overlap on hydrocarbon and carbon monoxide
concentrations. Carburetion leaning, spark timing retardation, and
reduction of valve overlap produced concentration reductions in
line with those predicted from engine dynamometer studies.
(Author1 abstract)
07637
Nebel, G. J,
AUTOMOBILE EXHAUST GAS TREATMENT - AN INDUSTRY REPORT. In:
Vehicle Emissions, SAE Tech. Progress Series, Vol. 6, Soc-
iety of Automotive Engineers, New York, 1964. 269-273, 298.
(Presented at the National West Coast Meeting, Society of
Automotive Engineers, Aug. 1957.)
Various methods of treating automobile exhaust to remove
hydrocarbons have been explored. Most of the usual gas-phase
separation techniques were quickly rejected as impractical for
automotive use. Only devices employing the principle of oxidation
appear feasible. A number of experimental afterburners and
catalytic converters have been tested, and their performance
characteristics are briefly summarized. Experience to date has
shovn that exhaust treating devices will pose some special heat,
noise, and design problems for the automotive engineer. (Author's
abstract)
07638
Schaldenbrand, H., and J. H. Struck
DEVELOPMENT AND EVALUATION OF AUTOMOBILE EXHAUST CATALYTIC
CONVERTER SYSTEMS. In: Vehicle Emissions, SAE Tech. Progress
Series, Vol. 6, Society of Automotive Engineers, New York, 1964,
574-298. 14 refs. (Presented at the Society of automotive
Engineers, National Automobile Week, Harch, 1962.)
B. Emission Sources 125
-------
A program was conducted to determine the performance and catalyst
life of the low temperature catalytic converter system. A program
was also aimed at defining and resolving problems associated with
the operation of this sytem on vehicles. Much of this work
involved principles common to those encountered with any catalytic
converter system. An engine dynamometer screen test was later
devised and used to evaluate catalysts capable of oxidizing both
hydrocarbons and carbon monoxide. Catalysts were selected from
these tests for evaluation on vehicles. Tests of vehicle systems
employing catalysts selected from the screening tests showed the
systems to be inadequate from the standpoint of the catalysts
maintaining oxidation performance for extended mileage. If a
satisfactory catalyst can be found to improve the performance of
the systems to an acceptable level, much work remains to be done to
develop an acceptable catalytic converter system for vehicles.
(Authors' abstract, modified)
07690
Corainelli, A.
AS EASILY CONTB01LABLE AIP POLLUTION SOURCE: NAPHTHA
ENGINES. ((Una fonte di inguinamento atmosferico che e
relativamenta facile controllare: i motori a nafta.)) Text in
Italian. Ann. Sanita Pubblica (Rome), 28 (2):367-375, March-April
1967. 9 refs.
The exhaust from diesel engines (naphtha engines) in contrast to
that from gasoline engines is not usually an important source of
air pollution. When in good condition and operated properly it
emits less toxic gases (CO and hydrocarbons) than a spark ignition
engine. Atmospheric pollution from diesel engines depends to a
large extent upon the driver as well as on the mechanical condition
of the vehicle. Public education is needed and punitive action
against offenders. Switzerland has established norms to prevent
vehicular air pollution: rapid acceleration and deceleration must
be avoided, overloading is forbidden, the vehicle must be
frequently checked and kept in excellent working condition. Black
exhaust fumes quickly identify an offending vehicle. Maximum
permissible opacity for the exhaust fumes can be established by the
use of opacimeters. The ideal opacimeter should be ruggedly made
to withstand all road conditions and the 700 deg. C temperatures of
the gases emitted, it should be easily installed and easily read on
either a stationary vehicle or a moving one. The most frequently
used types (Hartridge, UTAC, Bosch) and the advantages and
disadvantages of each are discussed. Permissible values (Hartridge)
are given for different types of vehicles. A schematic drawing is
given of the Bosch opacimeter.
078««
Haga, J. A., H. Wong-Woo, and n. G. Mason
A STATUS REPORT ON MOTOR VEHICLE POLLUTION IN CALIFORNIA. J.
Air Pollution Control Assoc., 17(7):t35-U38, July 1967.
The accomplishments to date indicates problems that exist, and the
outlook for control are reviewed by analyzing emissions trends in
four urban areas in the state. To illustrate the effect of the
126 HYDROCARBONS AND AIR POLLUTION
-------
current anticipated control efforts in California, six charts
are presented showing the emission estimates in four areas from
1940 to 1980. A review of all the factors involved indicates that
there is no simple and inexpensive solution to the complex
problem of motor vehicle created air pollution. The problem has
many aspects. It is legal, political, social, economical', and
technological. The final solution must incorporate considerations
for all these aspects. The motor vehicle control program in
California has reduced emissions of hydrocarbons and carbon
monoxide into the atmosphere. In spite of the increasing number
of vehicles there has been a reversal in emission trends for the
first time. If the goal of prewar air quality is to be
achieved, there must be a high degree of emission control.
Consequently, the program requires that effective systems be
available, and that virtually no cars be exempt. Lack of
efficiency control of some emissions, large numbers of cars
uncontrolled, and deterioration in efficiency of control systems
will lead to air quality poorer than that desired. Under the
present program, which is oriented toward the installation of
control systems on new cars, the reduction of contaminants
emanating from motor vehicles will be gradual. In order to
accomplish a rapid improvement, within a few years, exhaust
emissions from all cars (new and used) must be controlled,#t
07853
Plust, H. G.
FUEL CELLS: PRINCIPLE OF OPERATION, DESIGN AND PRESENT STATE
OF THE ART IN FDEL CELL DEVELOPMENT. ((Die Brennstoffzellen:
Wirkungsweise, Aufbau und Heutiger Entwicklungsstand der
Brennstoffzellen,)) Neue Zuricher Zeitung, Technol. Suppl.
No. 133, Jan. 12, 1966. 4 refs. Engl. transl. no. J-1352,
13p., Dec. 22, 1966. Translated from German.
CFSTI, DDC: AD 805336
The fuel cell has achieved great progress in recent years. With
the aid of this cell it is pos'sible to convert the chemical energy
ot fuels directly into electrical energy without any limitation due
to the socalled Carnot's degree of effectiveness. The
present—day state of the art in fuel cell development is marked
by the fact that for greater output (above 1 kW) only those fuel
cells that operate on hydrogen as fuel and oxygen as oxydizer are
sufficiently far developed in order to test them for practical
applications. DC voltages of 700 volts could be achieved by
placing such cells in series; however, it is customary to use
batteries below 100 Volts. Performance weights of 10 to 45
kg/kH and performance volumes of 10 to 40 cu dm/kH are usually
stated for these batteries. These data are reduced by the
necessary accessories (control system, heat exchange, water
removal, converter, etc.) which must first be developed and newly
designed in many cases. It is possible to purchase a ikw fuel
cell for about 10,500 dollars.##
07925
Beighton, J.
THE SPECIAL INDDSTHIAL PROCESSES. Boy. Soc. Health J.
(London). 87(4):215-218, July-Aug. 1967. 2 refs. (London)
B. Emission Sources 127
-------
The air pollution problems of a group of industries which
produce: sulfuric acid, nitric acid, petroleum and petrochemicals,
iron and steel, copper, aluminum, gas, ceramics and electric power
are reviewed. The basic technical approach is to avoid the
formation of the emission by design of the process, then to
require the treatment of any unavoidable emission, and finally to
require adequate dispersal of any residual amount which has to be
discharged. The legislation is designed to compromise between
safeguarding of public health and amenities and providing for a
realistic acceptance with adequate control of special processes.
Although the loss of gases in the manufacture of sulfuric acid is
limited to 2% of the sulfur burned, the loss from a contact acid
plant with a 500-ton-per-day capacity may be considerable so that
chimney heights as high as 450 ft may be required. Acid mist from
contact plants burning sulfur is a special problem as it is
difficult to control and its occurrence is unpredictable. There
are two nitric acid plants in Britain equipped with catalytic
tail-gas reduction units which should solve the problem of
brown nitrous fume emission to the air. The use of special
flares is required to control H2S and mercaptans emitted by oil
refineries. In the steel industry the development of the
Fuel-Oxygen-Scrap process is regarded as an alternative to the
electric arc furnace. It is claimed that melting and
refining can be carried out without exceeding a fume level of
0.05 grains per cu ft.##
07945
A. Parker
REDUCTION AND PROBLEMS OF AIR POLLUTION IN CHEAT BRITAIN 1938
TO 1976. Roy Soc. Health J. (London), 87 (4) : 204-209,
July-Aug. 1967.
Air pollution from the use of fuels is discussed. 1938 was
chosen as the beginning date because the 1939-1945 war caused a
coal shortage. The smog of 1952, which killed 4,000 people in
Greater London, stirred public opinion. The Clean Air Act of
1956 which resulted produced a marked reduction in smoke emission
and an improvement in the fuel use efficiency. In spite
of the decrease in the use of coal by railways, collieries,
industrial processes, and domestic heating, there has been
an overall increase since 1938, This increase is largely due to
increased consumption by electrical powerplants. The total smoke
production is down, but S02 produced by power-generating plants
has increased five-fold since 1938 resulting in an increased S02
total in spite of reductions in other areas. There is no section
in the Clean Air Act of 1956 for S02 control except one for
chimney heights. The chief British complaint about
transportation is the unnecessary black smoke from diesels. It
is estimated that by 1976 the amount of smoke emitted will be
reduced; S02 will not be any greater; and 'co and hydrocarbons
from exhaust gases will be the same for the country as a whole.
In the cities, the situation is such that the traffic could
hardly be any worse, so that with main roads bypassing the center
of towns, and more efficient engines, there nay be an improvement
on the busiest streets.##
128 "HYDROCARBONS AND AIR POLLUTION
-------
07977
Conkle, J. R., W. E. Mabson, J. D. Adams, H. J.
Zeft, and B. E. Welch
DETAILED STUDY OF CONTAMINANT PRODUCTION IN A SPACE CABIN
SIMULATOR AT 760 HM. HG. USAF School of Aerospace
Medicine, Brooks AFB, Tex., Aerospace Medical Div.,
Contract NASA R-89, Prog. 7930, Task 793002, SAM-TR-67-16,
142p., Feb. 1967. 18 refs. (Also: Aerospace Med. ,
38 (5):491-499, May 1967.)
A 27-day experiment designed to determine man's contribution to
trace contaminants in a sealed environment was conducted. The
test cell used in this experiment was an advanced testing device
for simulating manned spacecraft atmospheres. A total of 97
compounds vere identified and quantified during the 27 days.
Twenty-one compounds were noted only during the manned portion of
the study. Direct analysis of the sealed environment was not
adequate for this type of comprehensive survey. The use of
ctyogenic fractionation and concentration, however, did provide
samples with sufficient concentration of contaminants for analysis
by means of gas chromatography, infrared spectroscopy, and mass
spectroscopy. Carbon monoxide was the only compound which was
produced by man at such a rate that clearly would require removal
in long—term scaled atmospheric system habitation. (Authors'
abstract, modified)##
07979
1. G. Austin
FUEL CELLS: A REVIEW OF GOVERNMENT-SPONSORED RESEABCH,
1950-1964. North Carolina State Univ., Raleigh, Dept. of
Chemical Engineering, NASA-SP-120, 439 p.. 1967.
Fuel-cell investigations funded by Government agencies of the
United States of America are reviewed. Primary Navy interest
is in more buoyant submarines; Army interest concerns silent
frontline power and more efficient use of fuel for motive power.
Both services need silent, portable electric generators. The
Air Force and NASA share the desire for minimum-weight
spacepower systems. The Advanced Research Projects Agency
of the Department of Defense considered direct energy
conversion important enough to carry multimillion-dollar Project
Lorraine for several years, which included sizable funds for
fuel-cell work. In addition, the Atomic Energy Commission is
looking into thermally regenerative fuel cells as possible adjuncts
to nuclear power plants. The high fuel efficiency of fuel cells
is a major advantage in vehicle propulsion. The fuel efficiency
of military vehicles is probably no greater than 15 to 25 percent
and a fuel cell unit with an efficiency of 50 percent would have a
great impact on the logistics of fuel supply. 3nly cheap fuels
with a high specific energy (Btu/lb or Btu/gal) can be
considered. The powerplant must be efficient and capable of
(-54 degrees C), and have reasonable weight and size. Electric
motors have excellent overload capability and can be run at
several times its continuous rated capacity for periods of
minutes. Therefore, electric motors probably need only about
one-fourth of the nominal rating of gasoline engine; e.g., 28
B.: Emission Sources 129
-------
kilowatts to replace 150 bhp. Power densities of 2kw/cu ft and
22 H/lb for fuel cells have been cited as requirements for vehicle
propulsion (assuming 60 percent efficiency), but could be too low
by a factor of 3. (o present direct or indirect hydrocarbon fuel
cells satisfy these requirements.##
08025
Conkle, James P.
CONTAMINANT STUDIES IN CLOSED ECOLOGICAL SYSTEMS AT THE SCHOOL
OF AEROSPACE MEDICINE. In: Proc. 2nd Ann. Conference
Atmospheric Contamination in Confined Spaces, 4 and 5 Hay
1966, Aerospace Medical Research Labs., Wright-Patterson
AFB, Ohio, Aerospace Medical Div., AMHL-TR-66-120, p.
31-50, Dec. 1966. 14 refs.
CFSTI, DDC: AD 646512
A 27-day experiment at 760 mm Hg (oxygen, 20%; nitrogen, BOX) was
conducted to define the contaminants associated with human
occupancy of a sealed environmental simulator. A second
experiment of 56 days duration was performed to evaluate the
suitability of a helium (30%) - oxygen (70%) atmosphere at 258
mm Hg. The atmospheres to which the four human subjects were
exposed were analyzed for trace contaminants. A total of 105
compounds were detected. The concentration of these compounds
remained below a level thought to cause a physiologic effect.
Carbon monoxide and carbon dioxide were the only compounds which
were produced by man at such a rate that clearly would require
removal in long-term sealed atmospheric habitation.tf
08033
J. V. Pustinger Jr., and F, N. Hodgson
IDENTIFICATION OF VOLATILE CONTAMINANTS OF SPACE CABIN
MATERIALS. Monsanto Research Corp., Dayton, Ohio, Contract
AF 33(615) - 3377, Proj. 6302, Task 630202, AHHL-TR-67-58,
164p,, June 1967.
CFSTI, DDC: AD 658203
Ninety eight candidate materials for space cabin construction were
—tested_to establish possible volatile gas-off and oxidation
products. These materials could be potential cabin contaminants.
Test conditions were designed to simulate the normal space cabin
environment. After pretreatment at 0.1 torr and at 25 degrees C,
candidate materials were stored in bench-scale simulators for 14
days at 68 degrees C, and for 30, 60, and 90 days at 25 degrees
C, in a 5 psia oxygen atmosphere with 20-40% relative humidity.
Individual components of the volatile contaminants vere identified
and the quantities evolved were estimated by gas chromatographic
and mass spectrometric analyses. Paints and coatings,
prepared immediately before testing, gave off considerable amounts
of entrapped solvents. Lesser, but significant, amounts of
contaminants result from oxidation and from hydrolysis. In some
cases, larger increases in carbon monoxide levels were observed
when the storage temperature was increased from 25 degrees C to 68
degrees C. In addition to the gas-off experiments, a cryogenic
system for serial trapping of atmospheric contaminants was
WO HYDROCARBONS AND MR POLLUTION
-------
constructed. Gas chromatographic and mass spectrometric analyses
were performed on four samples of atmospheres from
bio-environmental systems. (Authors' abstract, modified)#1
08165
Nedogibchenko, M, K.
PRESENT DAY CONDITIONS OF ATMOSPHERIC AIR POLLUTION BY
AUTOHOBILB EXHAtJST GASES IN CITIES AND PROBLEMS OF ITS
CONTROL, In: Survey of U.S.S.B. Literature on Air
Pollution and Related Occupational Diseases. Translated from
Russian by B. S. Levine. National Bureau of Standards,
Washington, D. C., Inst. for Applied Tech., Vol. 3, p.
195-199, May 1960.
CFSTI: TT 60-21475
Air quality measurements in Russian cities indicated that carbon
monoxide was the most important automotive exhaust pollutant. In
Moscow, maximum concentrations of carbon monoxide reached 100 —
200 mg/cu ra; in Leningrad 145 to 164 mg/cu m; in Saratov 20 to 60
mg/cu m; In Perm 40 to 60 mg/cu n, and in Ivanova 18 to 88
mg/cu m. In Sverdlovsk the lead content ia the exhaust gases
ranged between 0.069 to 3.70 mg/cu m, depending upon the Bade of
the motor vehicle. Investigations in 7oscow in connection with
the utilization of ethylated gasoline by the passenger auto
transport revealed only from 0.001 to 0.003 mg/cu m of lead in the
street air. Investigations disclosed in auto transport exhaust
gases the presence of a polycyclic hydrocarbon, 3, 4-benzpyrene,
generated at the rate of 0,75 mg/min. According to most recent
reports auto transport exhaust gases were polluting atmospheric air
also with nitrogen oxides; the more incomplete was the gas
combustion the greater was the quantity of formed carbon monoxide
and less of nitrogen oxides were emitted into the air; vice versa,
the more complete the gas combustion the less CO was formed and
the more nitrogen oxides were discharged into the air. Next in
importance to air pollution with carbon monoxide is air pollution
with soot discharged in large quantities with automobile exhaust
gases. The cause of this type of atmospheric air pollution lies
in the unsatisfactory technical construction and mechanical and
functional adjustment of the engines. The reduction of city air
pollution caused by auto-transport exhaust gases should be
carried out along the following basic lines: Improvement in the
design of automobile motors and carburetors with a view to
increasing degree of combustion and of gasoline utilization.
Development of methods to render harmless exhaust gases emitted
by auto-transport engines, preferably by oxidizing them to smaller
non-harmful or less harmful molecules.**
08200
Gurinov, B. P.
THE EFFECT OF COMBUSTION METHOD AND OF FUEL TYPE OH THE CONTENT OF
3. 4-BENZPYRENE IN SMOKE GLASS. Gigiena i Sanit., 23(12):6-9,
1958. 5 refs. Translated from Russian by B. S. Levine, D. S. S.
B. Literature on Air Pollution and Related Occupational Diseases,
Vol. 4, p. 260-264, Aug. 1960.
CFSTI: TT 60-21913
B. Emissibn Sources 13-1
-------
A study was made to determine the effect of different methods of
fuel burning on the content of 3,i»-benzpyrene in smoke gases.
Methods of burning hard fuel differ in different plants; the
pulverized and layer bed methods are examples of fuel burning
methods most commonly in practice. Both methods of fuel burning
were investigated. Dust samples were collected from boiler room
smoke flues by an appropriate aspiration method. Two of the
boilers burned coal from the vicinity of Moscow, one burned
anthracite, and one burned peat. Analogous investigations in
boiler rooms using oil as fuel showed that the process of oil
burning liberated the greatest amount of carcinogenic substances.
the method of layer or bed burning in non-mechanized furnaces
produced considerably greater quantities of 3,4-benzpyrene than in
mechanized furnaces; chamber burning of powdered fuel did not
produce any carcinogenic substances in smoke discharges. It is
recommended that boiler rooms using the bed or layer coal burning
method should be equipped with mechanized furnaces; boiler rooms
with non-mechanized furnaces should be replaced by central regional
boiler rooms and heating centers.
08359
Feuerstein, D. L-, J. F. Thomas, and D. L. Brink
MALODOROUS PRODUCTS FHOM THE COHBUSTION OF KKAFT BLACK LIQDOB.
I. PYROLYSIS AND COMBUSTION ASPECTS. TAPPI, 50 (6):258-262,
June 1967. 7 refs. (Presented at the 51st Annual Meeting of
the Technical Association of the Pulp and Paper Industry,
New York, N. Y., Feb. 21-24, 1966.)
The production of malodors is an undesirable side effect that has
always been associated with the kraft pulping process. Such
malodors may originate at six major points in the overall
digestion and combined recovery (inorganic chemical and heat) and
organic waste elimination processes. Based on information in the
literature, these points may be listed in order of decreasing
contribution to atmospheric pollution: the recovery furnace is the
major source, followed by evaporators, digester, lime kiln,
oxidation tower, and dissolving tank. In the present study it
was assumed that the recovery furnace operation covers a wide
spectrum, such as distillation and sublimation, pyrolysis,
auto-oxidation, stoichiometric combustion, and quenching. It was
found possible to carry single charges of spent reaction liquors
sequentially through the various steps in the laboratory under
controlled conditions as well as to quantitatively collect and
analyze all products. The contributions from individual,
simultaneously occurring processes within a furnace are thus being
considered for the first tine from the standpoint of air pollution.
Several unique control possibilities have been indicated as a
result of this work. Results of the work relating to
combustion techniques and sample collection are contained in this
paper. Analytical methods and a discussion of the results
obtained are presented in the second paper of this series.
(Authors1 abstract)t#
,V32 HYDROCARBONS AND AIR POLLUTION
-------
18373
'aum, Fritz and Wolfgang Steinbach
'flASTE INCINERATION IN SMALL UNITS. Staub (English translation),
27(7):23-25, July 1967. 10 refs.
CFSTI: TT 67-511*08/7
The incinerator investigated has a triple jacket combustion
'chamber, and is heated up and charged with dry paper waste. The CO
and C02 concentration was recorded by infrared gas analyzers.
'During charging, CO concentration rose rapidly to 0.4-0.6 vol.%
then dropped gradually. C02 concentration rose rapidly to
1.0 - 1.5 vol. percent, then dropped slowly. The CO and C02
concentrations were as a rule much lower than with medium units.
Measurements to determine the emission of solids were performed
with a Strohlein instrument at the chimney end. The results
yielded a solid concentration between 300 and 425 mg/ cu m. Large
quantities of hydrocarbons were deposited on the measuring filters
apart from solids, which gave an impression of a deceptively high
dust emission. The stong hydrocarbon development was confirmed by
observations and measurements. For a long time white-gray clouds
were emitted from the chimney, causing noxious odors in the
vicinity.
08376
Fiero, George H.
SOLVENTS, SMOG AND RULE 66. J. Am. Soc. Lubrication Engr.,
23(11):448-458, Nov. 1967. 29 refs. (Presented at the 22nd ASLE
Annual Meeting, Toronto, Canada, May 1-4, 1967.)
Solvents and cleaners evaporate into the air and some of them may
become pollutants. Their quantity, however, is relatively small
and their photochemical reactivity is relatively low. Since,
however, certain solvents when tested in smog chambers at
relatively hihg concentration (4ppm) do produce eye irritating
products, their use is restricted in Los Angeles by Rule 66 and in
the San Francisco Bay area by Regulation 3. These are discussed in
detail. The topographical and meteorological characteristics of
these locations are unique. Therefore, such restrictions should
not be imposed in other localities until a thorough study is made
to determine the extent, if any, which solvents may contribute to
smog.
08390
H. E. Benson, C. L. Tsaros
CONVERSION OF FOSSIL FUELS TO UTILITY GAS. Am. Che«. SOC,,
Pittsburg, Pa., Div. Fuel Chem., Preprints, 9 (2):104-113,
1965. 9 refs. (Presented at the 149th National
fleeting, American Chemical Society, Division of Fuel
Chemistry, Symposium on Fuel and Energy Economics,
Detroit, Hich., April 4-9, 1965.)
Natural gas has nearly completely replaced the use of coal
as a source of utility gas in the United Sates. The
B. Emission Sources 133
-------
production of gas from coal, shale, and distillate and
residual oils is discussed in terms of conversion costs. The
following processes for converting coal to gas are
described in detail; (1) Lurgi gasification, (2)
Hydrogasification, (3) Hydrogasification and the steam-iron
process. The raw material costs and the plant investments for
gas made by these processes are tabulated. Estimates of gas
costs averaged for a 20-year period, indicate that with an
improvement in coal gasification technology, it would be possible
to decrease the cost of utility gas made from coal by
10.43 per thousand cubic feet for a 90 x 106 BTO/Day
plant. Next is described the process for the conversion of shale
oil to gas. This can be accomplished by two means: (1) to
hydrogenate the shale directly, (2) to
retort the material first and then hydrogenate the shale oil.
Process schemes are shown for these routes. The hydrogenation
of the oil and the difficulties involved are described. A summary
is given of: raw material requirments, plant investments and gas
price. This shows that utility gas can be manufactured by the
hydrogasification of oil sh'ale at a reasonable cost. The most
important process variable influencing the cost of utility gas
is the hydrogen/shale ratio.t#
08391
n. D, Schlesinger, G. 0. Dinneen, S. Katell
CONVERSION OF FOSSIL FUELS TO LIQUID FUELS. Am. Chem.
Soc., Pittsburg, Pa., Div. Fuel Chem., Preprints,
9 (2):120-126, 1965. 12 fefs. (Presented at the 149th
National Meeting, American Chemical Society, Division of
Fuel Chemistry, Symposium on Fuel and Energy Economics,
Detroit, Mich., April 4-9, 1965.)
Supplies of crude petroleum and natural gas, although abundant,
are not inexhaustible, and provision is being made for the
time when our vast coal and oil shale "reserves will be called
upon to supply a significant quantity of liquid fuels. The
approach on coal research has been to continue theoretical
and practical studies to reduce costs by improving' stages in the
process or by developing new processes. Studies were made
in the following areas: coal hydrogenation, gas synthesis, oil
shale retorting systems, and bituminous sands and other
hydrocarbons. A flexible, integrated plant might
emphasize production of different fuels or byproducts under
different economic conditions and even at different times
of the year. To reduce hydrogen requirements, an alternative
is the partial conversion of coal whereby most of the
hydrogen is utilized as a hydrocarbon product. The char
product is used for generating power or. malting additional
hydrogen by gasification. In recent years, oil shale
research by the Bureau of Mines has been limited to small
scale laboratory studies on refining analysis. The cost of
producing gasoline from oil shale is almost competitive with
gasoline from petroleum on the West Coast. One of the Bain
problems is the isolated location of major deposits. The
recent process developments discussed have added more to refined
technology rather than to significant savings in cost. It has
been amply demonstrated both in the United States and
elsewhere in-the world, that liquid fuels can be made from
coal. Except in isolated cases, costs are too high for coal
W4 HYDROCARBONS AND AIR POLLUTION
-------
to be a real contender with petroleum at current prices.
Only by continued research will the remaining probleas be
solved.**
08393
John M. Ryan
UTILIZATION OF PETHOLEDH AND PETHOLEUM PRODUCTS. Am. Chem.
Soc., Pittsburg, Pa., Div. Fuel Chem., Preprints,
9 (2):223-230, 1965. 6 refs. (Presented at the 149th National
Heeting, American Chemical Society, Division of Fuel
Chemistry, Symposium on Fuel and Energy
Economics, Detroit, Mich., April 4-9, 1965.)
In discussing utilization of petroleum, the existing or
potential technology of oil consumption must be considered,
also the effects of potential changes in supply and of new
competitive forces. The demand for petroleum products
in the D. S. will probably grow at a rate of 2 or 3 per cent
a year. Abroad the annual growth rate will be perhaps twice as
great as the rate in the U. S. 50% of all the oil consumed in the
D. S. is used in the transportation sector. The growth
rate will be limited by the growth of the market.
General industry and power plant use constitute a second
market, accounting for 7% of steam and electric power plant
fuel, and 13% of the manufacturers' heat and power market.
Another major market is residential and commercial consumption
in which oil supplies about one third of the total energy consumed.
Resources will not be a limiting factor either in the U. S. or
the free world and there should be no significant shift in
relative fuel prices in the foreseeable future. It is
unlikely that oil demand will be increased appreciably in the
D. S. through research in utilization. Research on improved
exploratory and productive techniques will probably have a
greater influence on domestic oil demand than will research on
oil utilization. The changes in oil utilization which
appear most probable will not alter the growth rate of oil
demand in the I.S. so nuch as its composition. Finally, some
research is being conducted today on the supposition that crude
oil is in limited supply and hence that refined product
prices are likely to rise in the near future relative to prices
of competing fuels.!*
0839<4
Daniel Parson
GAS UTILIZATION TODAY AND IN THE FUTURE, Am. Chem. Soc.,
Pittsburg, Pa., Div. Fuel Chem., Preprints, 9(2):231-241,
1965. (Presented at the 149th National fleeting, American
Chemical Society, Division of Fuel Chemistry, Symposium on
Fuel and Energy Economics, Detroit, Hich., April 4-9, 1965.)
A comprehensive picture is given of the currrent and
future status of gas utilization in the United States.
Economic problems which affect all phases of industry, from
the wellhead to the consumer, are discussed. The research
and technological challenges within the industry are
examined.**
B.I Emission Sources 13S
-------
08106
Loquercio, Peter
AIR POLLUTION CONTBOL FOR SCREW MACHINE OPEBATIONS. Factory.
125(9):163-16«, Sept. 1967.
Generally there are three major sources of air pollution in screv
machine operations: machining, finishing, and heat treating and
quenching. The most common sources of pollution are the funes
created when cutting oils, lubricants and coolants break down
during machining processes. Metal dust is the most
significant pollutant in the finishing—grinding, polishing and
buffing—phase. Two types of air pollutants can arise from heat
treating; oil vapors from the quenching tanks, and toxic gases
emitted from heat-treating furnaces under special atmospheres.
Heat treating furnaces are suspected of emitting such toxic
pollutants as cyanides, carbon monoxide, nitrogen, methane, and
metallic oxides. Control equipment falls into several
categories. For "particulates" or solids (metal dust) removal,
dry and vet collectors are used. For general gaseous pollutants
(oil vapors, toxic emissions), afterburners and absorbers may do
the Job.##
08486
Marchenko, E. N.
FUNDAMENTAL PROBLEMS OF INDUSTRIAL HYGIENE IN PROCESSING OF
POLYFLUOBETHYLENE RESINS. ((Osnovnye voprosy gigieny truda
pri pererabotke ftoroplastov.)) Text in Russian. Gigiena
Truda i Prof. Zabolevaniya (Moscow), 10 (11):12-18, Nov.
1966. 9 refs.
A literature survey is presented on processes involved in the
degradation of polyfluoroethylene resins, studies of operating
conditions during heat treatment of polyfluoroethylene showed
that the atmosphere may be polluted with perfluoroisobutylene,
tetrafluoroethylene, oxyfluorides, hydrogen fluoride, carbon
monoxide, and polymer aerosols. A system of prophylactic
measures has been developed which drastically reduces toxic air
pollution. Heat processing of polyfluoroethylene resins requires
the special attention of hygienists and engineers.t#
08493
Shoji, Hikaru Takeo Yamamoto, Konosuke Nishida, Yoshimori
Ishikawa, Sasnma Takada, and Kaori Inoue
STDDIES ON AIB POLLUTION OWING TO THE AUTOHOBILE EXHAUST GASES.
THE CONCENTRATIONS OF C1-C6 HYDROCARBONS AND SOME INORGANIC
GASES IN THE EXHAUST GASES. Text in Japanese. Japan. J.
Hyg. (Tokyo), 22 (2) :341-353, June 1967. 34 refs.
The exhaust of an idling 1959 Datsun was analyzed, using gas
chromatography. Fuel consumption rate, air-fuel ratio, exhaust
gas temperature, intake air volume, emission gas volume and
concentration of the exhausted components were measured under
constant conditions (at 600 to 5,000 r.p.m.). Results, which are
736 HYDROCARBONS AND AIR POLLUTION
-------
abulated, were as follows: 1)?uel consumption at 600 r.p.m. was
227 gm./ps. hr. and decreased with increasing revolutions. The
volumetric efficiency of intake air-fuel mixtures was very low
31-515?) during idling. The air-fuel ratio was 10.1 at 600
r.p.m., while a lean fuel state was observed when rotation was
over 2,500 r.p.m. 2) Temperature of the emitted gases (at the
Tail pipe) was 60-80 deg C from 600 to 1,500 r.p.m. Temperatures
above 300 deg C were recorded at rotations above 4,000. 3) At
600 r.p.m., C02 content was found to be 2.1%. Maximum C02
level was observed at 3,000 to 4,000 r.p.m. The maximum
concentration of CO (9.9%) was found at 600 r.p.m.; concentration
decreased with increasing revolutions (4.4% at 5,000 r.p.m,).
These results suggest that exhaust gases containing 10% CO
would be discharged into the atmosphere when this car was stopped
it an intersection. 4) In the exhaust gases, 25 kinds of
short-chain hydrocarbons were identified: 3,645 p.p.m. total were
determined at 600 r.p.m. and 689,9 p.p.m. at 4,000 r.p.m.
relatively large proportions (5.5 to 23.7S) were found as
methane ethane, n-butane, iso-butane, ethylene, and propylene.
5) The composition of exhaust gases averaged: paraffin, 62%;
olefin, 33%; diolefin, 0.4%; and acetylene, 5%. 6) The ratio of
the emitted hydrocarbons to fuel was about .10 w/w at 600 r.p.m.
and .03 at 4,000 r.p.m. Emission of the hydrocarbons during the
idling was 1,79 gm./min. at 600 r.p.m. and 0.94 gm./min. at
3,500 r.p.m.**
08497
Hoffman, Heinz
EXHAUST GAS PROBLEMS WITH GASOLINE AND DIESEL ENGINES. II.
DIESEL ENGINES. ((Abgasprobleme bei Otto- und Dieselmotoren.
II. Dieselmotoren.)) Text in German. Erdoel Kohle
(Hamburg), 20 (9):644-648, Sept. 1967.
The various pollutants present in the smoke produced by diesel
engines were measured and discussed. The results, illustrated in
tables and graphs, show that CO emission is only 1/10 that
allowed for gasoline engines and is therefore of minor importance.
Aldehydes with their characteristic irritating odor are also
produced in small quantities and are considered annoying, but
medically unimportant. The nitrogen oxides, NO and N02, are
produced in sufficiently large quantities to cause lack of oxygen
in the blood, and inflammation of the respiratory tract. The
antechamber motor produces fewer nitrogen oxides than the direct
injection motor. Amount of S02 produced is negligible.
3,4-Benzopyrene is emitted in significant quantities when an
engine emits a large quantity of smoke and then only if the motor
is run under high pressure. As a control measure a reduction in
smoke quantity is recommended. The smoke characteristics can
also be greatly influenced by the design of the combustion chamber
and proper maintenance of the engines,##
08524
Kapkaer, E. A., L. V. Trofimova, N. A. Evikeeva, and
A. K. Bonkevich
HYGIENIC EVALUATION OP SOHE PETROCHEMICAL
IHDISTBIES. ((Gigienicheskaya otsenka nekotorykh neftekhimiches-
B Emission Sources 13V
-------
kykh proizvodstv.)) Text in Russian. Gigiena Truda i Prof.
Zabolevaniya (Moscow), 10 (11):22-28, Nov. 1966. 10 refs.
Deficiencies in planning and actual operation of petrochemical
plants are responsible for the discharge of acetylene,
polyethylene, phenol, acetone, methylstyrene, isoprene, divinyl and
other toxic complexes which are products of decomposition,
oxidation, and hydrolysis. Desorption of toxic substances fron
construction materials (concrete brick) plays an important part.
The authors recommend methods for improving working conditions in
petrochemical production facilities. (Authors* summary, modified)
08553
Coffnan, Q. H.
SOOTHERN CALIFORNIA AEROSPACE INDUSTBY'S PROGRAM TO CONTROL SMOG
PRODUCED BY CHEHICAL HILLING HASKASTS AND SHOP PROTECTIVE
COATINGS. S.A.E. (Soc. Autofflovite Engrs.), Preprint 670816,
10p., 1967. (Presented at the Aeronautic 6 Space Engineering 6
Manufacturing Meeting, Los Angeles, Calif., Oct. 2-6, 1967.)
The materials, test criteria results, and conclusions for chemical
milling maskants an d hand-peelable shop protective coatings which
comply with Rule 66 of the Los Angeles County Air Pollution Control
'District (APCD), and are used by the aerospace industry in Southern
California are discussed. The maskants were evaluated to deteraine
the material best suited under Rule 66 to perform chemical Billing,
and the shop protective coatings were evaluated to determine the
material best suited for protecting metal surfaces during
fabrication, adhesive bonding, and assembly operations. (Authorfs
abstract, modified)
08557
George, J. C. and G. R. Morris
AVAILABILITY AND EVALDATIOS OF MONPHOTOCHEHICALLY REACTIVE PRIHEHS
AND TOPCOATS FOR AEROSPACE APPLICATIONS. S.A.E. (SOC. AutOBO-
tive Engrs.), Preprint 670814, 7p., 1967, (Presented at the
Aeronautic S Space Engineering and Manufacturing Meeting, Los
Angeles, Calif., Oct. 2-6, 1967..)
New coatings with low snog producing potential have been and are
continuing to be evaluated for use in the aerospace industry..
These new coatings have been proved in laboratory and shop testing
to be equal in quality to the conventional coatings they are
replacing. Environmental exposure tests to date are satisfactory
and are continuing. However, difficulty has been encountered in
obtaining consistent quality in large production batches. Sose of
the new coatings contain solvents that are slightly more toxic.
Also, some of the modified coatings have lower flash points. These
new materials, which include both proprietary and nilitary
coatings, appear to be readily available. Coating costs of the new
materials generally are higher, bat vary from a reduction of
approximately 7 percent to an increase of 35 percent. (Authors*
abstract)
138 HYDROCARBONS AND AIR POLLUTION
-------
08633
Cleary, Sea ham J.
A IK POmmON &NC TUB &OTQHGH1I.E, Clean Air (0. Clean Air
See. Australia New Kealand) 1(1):7-9,11, June 1967. 18 refs.
magnitude and nature of the emissions from automobile engines
are examined, Host of the pollution is discharged through the tail
pipe (about 60 percent on a total hydrocarbon basis) , but erankcase
omissions (30 percent) are also appreciable. The remaining ten per
cent is made up ot evaporation losses from the fuel tank and from
the carburettor after the engine has stopped. By« irritation,
k'lant damage and cracking of typr« rubber have been found in
communities heavily polluted by automobile exhaust products.
Control measures to minimise pollution are considered. These
involve burning the exhaust gases from the tail pipe by means of
either thermal or catalytic afterburners, and recycling the vent
gases from the eranKcase to either the air manifold or the
carburettor. Statistics about the current car population in Sydney
and the anticipated future growth rate are presented, and an
estimate is made o£ the future date (1998) when the volume of
exhaust products in Sydney will be the same as that in los Angeles
in 1942, when conditions ot smog were first experienced, (Authorts
abstract)
0880:2
8-
THE cQBposrrtos OF SXHA.UST SA.SSS rsoa BIESEI aotoss. ((Die
£usaw»e.nsetxuu
-------
08851
Conkle, J. P., W. E. Mabson, J. D. Adams, H. J.
Zeft, and B. E. Welch
A DETAILED STDDY OF CONTAMINANTS PRODUCED BY HAN IN A SPACE CABIN
SIMULATOR AT 760 MM. HG. School of Aerospace Medicine,
Brooks AFB, Tex., Aerospace Hedical Div., Contract
NASA-R-89, Proj. 7930, Task 793002, 1U1p., March 1967. 18
ref s.
CFSTI, DDC: AD 653932
The atmosphere within the space cabin simulator contained 20%
oxygen and 80% nitrogen. The study was divided into three
parts: a preliminary stabilization period of 2 days; an
unmanned background period of 11 days; and a manned period of 14
days. The unmanned portion provided information as to the contam-
inant materials associated with the test cell, previous occupancy
by man, and support items required during the subsequent manned
portion. The four volunteer subjects were sustained on a liquid
diet and were permitted limited hygienic activity during their
occupancy of the test cell. Direct sampling and concentrating
technics with subsequent analysis were utilized for contaminant
detection. Dual flame-ionization gas chromatography and
microwave spectrometry were used for the analysis of unconcentrated
samples which were obtained directly from the chamber. Methane
and carbon monoxide were analyzed by flame-ionization gas
chromatography and infrared spectroscopy, respectively.
To concentrate the sample, multistage cryogenic trapping systems
were operated daily during the 27-day study. Four sample sets
were analyzed daily. Rapid initial increases in methane and
carbon monoxide were observed soon after man entered the test
cell. The methane concentration increased from 20.9 mg./cu B the
day after man entered the chamber to a high of 84.6 mg/cu m. The
concentration of carbon monoxide ranged from a low of 4.8 mg./cu a
to a high of 23.7 mg./cu m. No significant data relating to
organic compounds were obtained from the analyses of unconcentrated
samples during either portion of the study. Carbon monoxide and
carbon dioxide were identified as compounds which were produced by
man at a rate that would require removal in a closed system
operation.##
08873
Frysinger, Galen R.
FUEL CELL-ENERGY STORAGE HYBRID SYSTEMS FOR VEHICLES. Preprint,
Army Electronics command. Fort Monmouth, N. J., Electronic
Components Lab. , 25 p., 1967.
CFSTI, DDC: AD 662236
So called vehicle battery problems can be overcome through the use
of a fuel cell-battery hybrid power source. This power source
allows an electric vehicle full range capability, excellent
acceleration characteristics, and very fast energy refuel. To
achieve such performance for military vehicles, a 150 Hhr/lb «olten
electrolyte battery and a 20-30 Ibs./KH hydrocarbon fuel cell must
be developed. Research progress indicates that these goals should
be achieved in operational hardware within the next five to ten
years.
HO HYDROCARBONS AND AIR POLLUTION
-------
09023
Epstein, George and Edward F. Westlake, Jr.
MATERIALS FOB SPACE CABINS: THE FIRE HAZARD AND ATMOSPHERE
CONTAMINANT CONTROL PROBLEMS. Aerospace Corp., El
Segundo, Calif., Materials Science Lab., Contract
FOH695-67-C-0158, TR-0158 (3250-20)-8, SAMSO-TR-67-76, 27 p.,
Oct. 1967. 3 refs.
CFSTI: AD 663H18
The flammability and atmospheric contaminant hazards associated
with the use of plastics and other nonmetallic materials in manned
spacecraft cabins are discussed. Outgassing characteristics and
mechanisms of typical materials are described. Flammability and
combustion rates are discussed 'as highly important materials
selection factors. An approach' is presented for minimizing the
hazards through judicious selection and batch control of cabin
materials. (Authors' abstract, modified)ft
09094
AIR POLLUTION — A SPECIAL REPORT. Power, 18p., ((1967?)).
The results of research on each phase of air pollution are
reviewed. The nature of this planet's atmosphere, its natural.
pollutants and the mechanics of their transport are outlined.
The contribution to air pollution made by man as he lives and
works is described. The effects of air pollution on man's social
and economic existence are examined. Constructive approaches are
given to help communities meet the challenge of air
pollution control effectively and economically. It is shown how
intelligent plant design and location can eliminate pollution
problems from the start and then how problems of existing plants
can be mitigated.##
09106
Asher, William J., Robert H. Shabaker, and Carl R. Heath
FUEL CELL FUEL STUDIES. (INTERIM TECHNICAL REPORT, 10
JANUARY 1967 - 9 JULY 1967). Esso Research and Engineering
Co., Linden, N.J., Government Research Lab., Contract
DA-44-009 ARC -H»8U(T), ITR-3, 65p., 1967. 12 refs.
DDC: AD 823 283
Research and development aimed at processes for field treatnent of
military fuels to make them suitable for fuel cells have continued.
This program is divided into two tasks. Task A is directed to
the development of a process for removing components in jet fuel
which are harmful to fuel cell performance. Task B is concerned
with the feasibility of liquid phase reforming to generate
hydrogen fuel. In Task A, removal of naphthenes by
dehydrogenation has proved difficult. Molecular sieve absorption
processing can remove aromatics and sulfur or sulfur alone at an
increase yield. Desorption of the impurities adsorbed on the
sieve is the key to this process. A simple carbon dioxide
desorption process was ineffective. A new carbon dioxide-air
hybrid desorption process has shown promise in simulated operation.
B. Emission Sources 141
-------
The feasibility study on liquid phase reforming has been contin-
ued. High reaction rates equivalent to reforming catalyst
requirements of i» Ib/kw with a H2-air fuel cell have been
obtained at 600 F using pure n-C12 and n-C15 hydrocarbon feeds.
The reaction rates,declined with time on stream due to catalyst
oxidation in the intermittent once-through experiments. The
thermal efficiency of the system depends on the conversion level
per pass required for good hydrogen selectivity. Adequate
hydrogen selectivity has been obtained at conversion levels
100-fold higher than in the exploratory studies. Carbon monoxide
and hydrocarbon fragments remain undetectable.##
091U8
Heath, C. C,, E. H. Okrent, H. Beltzer, and G. Ciprios
DIRECT HYDROCARBON AND METHASOL-AIR FUEL CELLS. In: Power
Systems for Electric Vehicles. Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution Control,
PHS-Pub-999-AP-37, p. 307-312, 1967. 3 refs. (Presented at
the Symposium on Power Systems for Electric Vehicles, New
York, N. Y., April 6-8, 1967.)
Research on direct liquid hydrocarbon and methanol-air fuel cells
has identified some of the problems that must be solved before fuel
cells can meet the specific requirements for an automotive power
plant. The question of whether the fuel cell can reduce air
pollution cannot be conclusively answered yet. Direct hydrocarbon
cells, operating at temperatures below 500 degrees F, appear to
offer no serious source of contamination. Studies have shown that
hydrocarbons are completely consumed to carbon dioxide and water in
sulfuric acid electrolytes at 90 degrees c. Fuel cell fuels will
probably be sulfur and lead-free. Furthermore, the low
temperatures should minimize nitrogen oxide formation.
Hydrocarbon losses from manifolds and tanks may cause a problem,
but using low vapor pressure fuels and proper engineering should
minimize this contribution. No major obstacles to a low-emission
vehicle are known, but clearly much more experience will be
required to define pollution levels in operative systems. The
present state of ihydrocarbon fuel cell technology cannot meet the
requirements of a high-output, low-cost system suitable for
extensive vehicular application. Much progress has been made
during the past five years. If this progress continues and
suitable catalysts are developed, a fuel-cell-powered vehicle
could become practical. However, much more research and
development will be needed before this stage is reached.tt
09224
McDonald, James E.
VISIBILITY REDUCTION DUE TO JET-EXHADST CARBON
PARTICLES. J. Appl. Heteorol., 1 (3):391-390, Sept. 1962.
15 refs.
Pyrolysis of hydrocarbon fuels leads to emission of free carbon in
the exhaust of aircraft turbojet engines, visible as a faint dark
trail. Carbon formation rises markedly when water injection is
employed to augment thrust by 20-30 per cent in takeoffs under
142 HYDROCARBONS AND AIR POLLUTION
-------
heavy loads or at high temperatures, the enhanced pyrolysis
resulting from the lower combustion efficiency on such wet
takeoffs. During the takeoff run, while the aircraft is still
moving at low seeds bit with maximum thrust, dense dark smoke fills
the exhaust wake, reducing visual ranges to as little as a few
hundred feet. To cross -check recent measurements indicating carbon
particulate emissions of the order of 15 Ib per ton of fuel
consumed in wet takeoff, die extinction coefficients have been
computed for carbon particles of the size known to form as a sequel
to pyrolytic freeing of carbon. These are used to make theoretical
estimates of the maximum visual range to be expected if the carbon
loading measurements were correct. A discrepancy exists in the
sense that the predicted visual ranges are found to be some five
times larger than the observed. It is concluded that a large
fraction of total carbon emission leaves the tailpipe still
unaggregated into large soot particles, whence the reported carbon
loadings may be too low by a factor of as much as five.
Consequently the aircraft operational hazards as well as the air
pollution problems implicit in rising volume of jet traffic at
certain terminals may become rather more serious than has been
predicted. (Author1s abstract)
09331
Hiles L. Brubacher. Eric P. Grant
DO EXHAUST CONTROLS REALLY WORK? - SECOND DEPORT, Preprint,
Society of Automotive Engineers, 10p., 1968. 12 refs
(Presented at the West Coast Meeting of the Society of
Automotive Engineers, Portland, Oregon, Aug. 14-17, 1967,
Paper 670689.)
Emission tests on 739 cars (1966 and 1967 models) equipped with
exhaust controls in public use confirm that the vehicle
manufacturers have done a good job of designing cars with low
emissions. However, field data on emissions higher than proving
ground results, and deterioration of emissions with mileage,
indicate that much more effort is needed with regard to proper
engine adjustments and quality control on the production
line as well as better servicing of the engines in the field.
Continued effectibe emission control after initial sale of the
new car is the responsibility of the states. (Authors'
abstract)##
09341
Oberdorfer, P. E.
THE DETEBHISATION OF ALDEHYDES IN AUTOMOBILE EXHAUST GAS.
Preprint, Society of Automotive Engineers, 10p., 1967. 14
refs. (Presented at the Automotive Engineering Congress,
Detroit, Hich,, Jan. 9-13, 1967, Paper 670123.)
A method for the sampling and determination of exhaust
.aldehydes .and. ketoaes is described. The procedure consists of.
absorbing and converting these compounds to the solid 2,U
di-nitrophenylhydrazone derivatives. Results are reported as
total aldehydes and/or the derivatives separated into individual,
identifiable components by chronatographic techniques. Exhaust
emission data employing this procedure are presented for a limited
B. Emission Sources 143
-------
number of vehicles with and without exhaust control systems.
Total aldehyde levels (as formaldehyde) were found to range from
about 20 to over several hundred parts per million depending on
the mode of operation and the adjustment of such variables as
air-fuel ratio, spark timing, and exhaust emission control
devices. Effects of these variables on aldehyde emissions are
discussed. The relationship of the chemical structure of
inducted fuel to aldehyde emissions is also touched upon. The
amount of individual aldehydes was found to be related to the
parent fuel to a considerable extent for pure individual
hydrocarbon fuels. This relationship is greatly diminished,
however, within the design limitations of current full boiling
practical gasolines. (Author's abstract)##
093U7
D. T. Wade
FACTORS INCLUENCING VEHICLE EVAPORATIVE EHISSIONS. Preprint,
Society of Automotive Engineers, 13p., 1967. (Presented at the
Automotive Engineering Congress, Detroit, Hich., Jan. 9-13,
1967, Paper 670126.)
The basic factors influencing carburetor and fuel tank evaporative
emissions are explored. These factors are combined in a math-
ematical model to predict the magnitude and composition of evapo-
rative losses, A laboratory technique for simulating carburetor
losses is also described. The behavior of fuel in the carburetor
bowl during a short soak is adequately simulated by a one plate
eguilibrium distillation. Factors influencing carburetor hot soak
losses are: maximum bowl temperature; bowl volume (including after-
supply) ; and fuel temperature distillation curve from one plate
equilibrium distillation. Both quantity and conposition pf car-
buretor losses can be calculated from the following: original fuel
composition, maximum bowl temperature, effective bowl volume.
Fuel tank losses occur because of tank temperature increases which
cause an increase in fuel vapor pressure and thermal expansion of
the tank vapor. Factors influencing fuel tank losses are: tank
temperature; vapor volume; tank pressure; rate of equilibration of
liquid and vapor; fuel vapor pressure; molecular weight; and
density. If equilibrium between liquid and vapor exists, tank
losses can be calculated from a knowledge of the following: tank
temperatures, vapor volume, tank pressure, fuel vapor pressure,
fuel density, and molecular weight of fuel vapor.
09355
Pahnke, Alden J. and Edward C. Squire
LEAD IN GASOLINE: NO EFFECT ON EXHAUST EMISSIONS FOUND IN
18-HONTH CONSUMER-CAB TEST. Oil Gas J., 64 (50) :106-110,
Dec. 12, 1966.
Use of tetraethyl lead in gasoline does not significantly affect
exhaust emission characteristics of vehicles driven by the
motoring public. This is the conclusion reached after a test of
leaded and unleaded gasoline in 122 privately owned and
operated cars spanning a period of 18 months and covering a total
of 2,500,000 miles. Carbon monoxide and hydrocarbon-emission
144 HYDROCARBONS AND AIR POLLUTION
-------
levels of the cars operated on leaded gasoline were essentially
equivalent to those of the cars driven on unleaded gasoline.
Photochemical reactivity and nitrogen oxide levels for the two
car groups were also equivalent, further demonstrating the
absence of any effects of tetraethyl lead on vehicle emissions
either positive or negative.##
09385
Viroli, G. and E. Preite
AIR POLLOTION FROM ROOHS HEATED BY STOVES USING "LIQUID GAS".
(Sulla corruzione dell'aria dagli ambienti riscaldati da stufe a
gas liquido.) Text in Italian. Riv. Ital. 'Igiene (Pisa),
26(1-2): 113-126, Jan.-April 1966. 26 refs.
The use of liquid-gas fuel in stoves causes the accumulation of
CO, C02 and aliphatic hydrocarbons indoors. Measurements were
aade in two rooms, 92 sq. m, and 166 sq. m. on 6 different types of
gas stoves, two of them open flame. Gas chromatography and the
Fractovap D apparatus were utilized. Data for the levels of
C02, CO, and hydrocarbons liberated by combustion are tabulated.
CO levels ranged from traces to 130 p.p.m. After 2-4 hours of
burning, the amount of C02 in the room from open flame ovens was
5 percent or more, and , after 8 hours, up to 15.24 percent. The
effect of this type of indoor heating on pollution of the ambient
(outside) air is well below the limit considered toxic by present
standards, but increased use of such equipment would eventually
lead to considerable air pollution.
09389
Valorij P. A. Grella, C. Melchiorri, and N. Vescia
SPECTHOPHOTOMETBIC DETERMINATION OF AROMATIC POLYCYCLIC HYDRO-
CAKBONS. FURTHER DATA ON THE ATMOSPHERE OF HOME. (La deter-
minazione spettrofotometrica degli idrocarburi policiclici aroma-
tici. Ulterior! rilievi nell1atmosfera di Roma.) Text in
Italian. Nuovi Ann. "Ilgiene Microbiol. (Rone), 17(5):383-
414, Sept.-Oct. 1966. 23 refs.
From Jan. 1965 to March 1966, samples of polluted air, taken
three times a day, were analyzed spectrophotometrically after
column chromatography. The minimum and maximum values micrograms/
100 cu. m. of air) were: phenanthrene, 0.43-1.12; anthracene, 0.12-
0.22; pyrene, 2,40-4.62; fluoranthene, 2.10-4.92; chrysene, 2.50-
4.03; 1,2-benzanthracene, 1.10-3.09; perylene, 0.25-0.60; 3,4-
benzpyrene, 2.00-5.20; 1,12-benzperylene, 1.40-3.75; anthanthrene.
0.44-0.80; and corenene, 0.60-1.00. The highest levels were ob-
served during the winter months in morning rush hours and are due
to domestic heating and automotive traffic.
09393
Hettche, 0.
AIR POLLUTION IN LOCALITIES WITH HEAVY THAFFIC IN
METROPOLITAN CITIES. ((Die Verunreinigung der Atmosphare an
B. Emission Sources 145
-------
verkehrsreichen Punkten in Grossstadten.)) Text in German. Z,
Praeventivmed. 11 (2):122-133, March-April 1966. 27 refs.
Data on the variations in time of CO, SO2, NO, N02, hydrocarbons,
polycyclic hydrocarbons, lead compounds and dust in various
European cities such as Stuttgarg, Frankfurt, Hamburg, Essen and
London are discussed and compared with data from Los Angeles. In
heavy traffic, concentrations of up to 20 mg. CO, 0.2 nig. NO, 0.1
mg. NO2, 0.05-0.4 mg S02, 2-10 mg. hydrocarbons and 4 microgram of
lead per cubic meter were found. Polycyclic hydrocarbons such as
benzpyrene and coronene can be determined accurately only in
tunnels by analysis of the intake air and the air in the tunnel.
In Germany, more diesel engines are in operation than the 0.3
percent in Los .Angeles. Diesels generate only about 1 percent CO
but maintenance must be frequent and soot emission must be
controlled. Two-cycle engines give a very low CO emission.
Methods used in Germany for the determination of pollutants are
outlined. Standardization of analytical methods is emphasized.
09405
Candeli, A,, G. Barboni, and G. Berioli Galoforo
C&RCINOGENICITY OF POLLUTED AIR. I. ANALYSIS OF EXHAUST GAS FROH
A COMBUSTION ENGINE. ((11 problema della cancerogenicita
dell1aria inguinata. I. Analisi dei gas di scarico dei motori
a scoppio.)) Text in Italian. Riv. Ital. Igiene (Pisa),
26 (5-6):438-453, Sept.-Dec. 1966. 25 refs.
Study was made of the amounts of polycyclic aromatic hydrocarbons
exhausted from an Italian automobile which ran in neutral for two
hours on one liter of the most common commercial gasoline. A
filter was attached to the exhaust system and 0.3771 gm. of
particulate matter extracted from 112 cm of exhaust. The extract
was found to contain anthracene, fluoranthene, pyrene (703
microgram), coronene (612 microgram), 1,2-benzanthracene (381
microgram, 1,2-benzpyrene, 3,4-benzpyrene (52 micrograa), and a new
unidentified substance called "Compound 409". The extracts,
obtained with acetone, were chromatographed on an alumina column
and the eluates examined spectrophotometrically. Emphasis is put
upon the high level of 3,4-benzpyrene, a notorious carcinogenic
agent.t#
09421
Keller, J. L. and Joseph Byrne
WHAT VALUE FRONT-END VOLATILITY? Proc. Am. Petrol. Inst.,
Vol. 46, p. 407-426, 1966. 18 refs. (Presented at the 31st
Midyear Meeting of the American Petroleum Institute's Divi-
sion of Refining, Houston, Texas, May 11, 1966.)
Detailed estimates of the vapor lost from California cars for
several potential control methods, along with corresponding
estimates of fuel-associated costs, are presented. Factors
considered include tank and carburetor vapor loss, vehicle
performance and fuel economy, diversion of volatile hydrocarbons to
alternate uses, crude oil consumption, "and investment and operating
costs of alternate refining processes. It is estimated that the
146 HYDROCARBONS AND AIR POLLUTION
-------
average car in California loses 1.7 percent of its fuel by
evaporation and that nearly half the loss could be eliminated by a
general reduction of 3 Ib in Reid vapor pressure. However, fuel
consumption at equal warm-up performance would increase three times
as much as vapor loss decreased, adding more air pollutants to the
exhaust of pre-1966 cars than would be saved. Total fuel cost
would increase 85 dollars over the life of a car. A capital
investment of approximately 2 billion dollars would be required of
the O.S. petroleum industry to reduce volatility to this extent.
Alternately, a lossproof fuel system, for which one possible
arrangement is suggested, offers the possibility of eliminating
substantially all vapor emissions with no penalty in fuel
consumption, and a net reduction of U1 dollars in fuel costs per
car, or 127 dollars lower cost than with reduced volatility. If
such a fuel system permitted a general increase in volatility
equivalent to 3 Ib Rvp, achieved gradually over enough years to
retire present cars, not only would vapor loss be eliminated but
fuel consumption would decrease 6.5 percent and total fuel costs
would increase by an estimated $228 per car.
09655
Major, William D.
VARIATIONS IN POLPING PRACTICES HHICH BAY EFFECT EMISSIONS. In:
Proceedings of the International Conference on Atmospheric
Emissions from Sulfate Pulping, Sanibel Island, Fla.,
April 28, 1966. E. R. Hendrickson (ed.). Sponsored by: Public
Health Service, National Council for Stream Improvement, and
University of Florida. Detand, Fla., E. 0. Painter Printing Co.,
((1966)), p. 265-281. 8 refs.
Emissions from a kraft mill can be divided into two categories,
gaseous and particulate. Malodorous.emissions are subject to far
less control and precision of analysis than particulate enissions.
The magnitude of loss is more sensitive to operating variables, the
chemistry is more complicated and the sources are more numerous.
This discussion is concerned with the effect of operating variables
on gaseous sulfur losses. Evidence is given which indicates that
the wood species has a definite effect on the odor produced during
kraft pulping. Cooking variables include: sulfidity of the white
liquor, cooking time and cooking temperature. More recent cooking
variables are: continuous vs. batch digestion, and the use of
black liquor dilution in the digester as a means of controlling the
liquor -to-wood ratio. Hultiple-effeet evaporators are the second
largest source of gaseous sulfur losses in the process. The high
vacuums set up by condensers result in the release of low vapor
pressure sulfur compounds. Operating variables in direct contact
evaporation are: black liquor pH, sodium sulfide concentration,
and per cent C02 in the flue gas. Dust losses from the recovery
furnace are controlled with either a venturi scrubber or an
electrostatic precipitator. Operating variables which influence
the efficiencies of these two units are overloading, and the
temperature of the flue gas. The key to the effect of operating
variables on emissions from a kraft pulp mill is to recognize the
degree to which the various steps in the kraft process are
interrelated, especially in the case of gaseous sulfur losses.
B. Emissibn Sources H7
-------
09737
Ozolins, G. and C. Behmann
AIB POLLUTANT EMISSION INVENTORY OF NOBTHWEST INDI&Ni. (A PRELIM-
INARY SUBVEY, 1966.) Public Health Service, Durham, N. C. ,
National Center for Air Pollution Control, APTD-68-4, 36p.,
April 1968.
Sources of air pollutant emissions were surveyed to quantify the
total pollution load emitted to the air over the Northwest Indiana
communities of East Chicago, Gary, Hammond, and Whiting. The
emissions are reported on an annual basis and subdivided into the
five major pollutants: particulates, sulfur oxides, nitrogen
oxides, hydrocarbons, and carbon monoxide. The four major source
catagories that were utilized in reporting emissions from area and
point sources are: fuel combustion in stationary sources, fuel
combustion in mobile sources, combustion of refuse, and industrial
process losses. The results of this survey are reported by city
and illustrated on the grid system established by the Northwest
Indiana Air Resource Management Program. (Authors' abstract)
09751
Schmertzing, Hannibal and Julian H. Chaudet
UTILIZATION OF INFBABED•SPECTBOPHOTOBETRY IN BICROCONTABINANT
STUDIES IN SEALED ENVIRONBENTS. Melpar, Inc., Palls Church,
Va., Contract AF 41 (609)-1962, Task 793002, SAB-TR-67-2, 20
p., Jan. 1967.
CFSTI, DDC: AD 650000
Bicrocontaminants in a sealed environmental system were separated
and identified. The separation and identification of the collected
samples were accomplished with gas-liguid chromatography and
infrared spectrophotometry. Fifty-four sets of samples of the
atmosphere from a space cabin simulator, comprising 162 individual
samples, were analyzed. The method used was gas-liguid
chromatography using a flame ionization detector. The retention
time on the column was used for identification, while the peak area
was used for quantitative estimation of the compounds. A
collection of the vapor infrared spectra of 146 compounds, which
are possible contaminants for space cabin simulators, has been
compiled during 2 years. A computer program for sorting infrared
spectra with the aid of the ASTB deck of infrared cards has been
established. Analyses have been made of gases evolved from paint
panels, from the decomposition of a Teflon insulator, and from
human waste products.
09752
Beaver, Hugh
COBBITTEE ON AIR POLLUTION: BEPOBT. London. Her Bajesty's
Stationery Office, 1960, 80p. (Presented to Parliament by the
Minister of Housing and Local Government, the Secretary of
State for Scotland and the Minister of Fuel and Power by
Command of Her Majesty, Nov. 1954.)
H8 HYDROCARBONS AND AIR POLLUTION
-------
A committee on air pollution was established to examine the nature,
causes, and effects of air pollution and the efficacy of present
preventive measures; to consider what further preventive measures
were practicable; and to make recommendations. The report of the
committee examined current emission sources of pollutants, the
effects of air pollution on health, and the legislation and
administration of air pollution. Some recommendations made by the
committee were: prohibition of emission of dark smoke from
chimneys; arresting plant for grit and dust obligatory in new
industrial installations; control of smoke from railways;
establishment of smokeless zones and smoke control areas;
provisions of financial assistance by Local Authorities;
requirement of Local Authorities to submit annual reports on
progress of smoke abatement; preparation of documents on codes of
practice and standards; clean air should be national policy;
establishment of a "Clean iir Council" to coordinate and encour-
age research work.
09759
Sharpe, L. H.
ENERGY SODBCES AND POLICIES, THEIR IMPACT ON AIB POLLUTION,
CURRENT AND PROJECTED. Public Health Service, Washington, D.
C., Bureau of Disease Prevention and Environmental Control,
Contract PH-86-67-69, ((227))p., April 15, 1967. ((76)) refs.
There have been a number of energy studies over the last 15 - 20
years that have attempted to project the national energy needs to
various dates in the future. This study compiles energy
projections and the "mix" of energy sources to the year 2000, uade
as recently as 1967, and, on the basis of these data: estimates
the atmospheric pollution burden to be expected by the years 1980
and 2000 provided present fuel policies remain essentially
unchanged; summarizes some of the major technological developments
that could have an impact on energy source selection and total
energy requirements; identifies and discusses some of the major
government policies that affect both fuel source and energy demand;
outlines some approaches to an evaluation on a benefit/cost basis
of alternative policies that would reduce atmospheric pollution and
completes the analysis for the solvent refined coal process.
09781
Environmental science Services Corp., Stamford, Conn.
SOLVENT EMISSION CONTROL LAWS AND THE COATINGS AND SOLVENTS INDUS-
TRY. (A TECHNO/ECONOMIC STUDY.) 56 p., ((1967)). 6 refs.
The widespread adoption of the strict California solvent emission
laws will seriously effect practices and products in the surface
coating industry. The California codes contain three main
elements: the emission of photochemically reactive solvents is
restricted; the sale of coatings containing these materials is
banned; and the emission of these materials during the manufacture
of coating materials is restricted. Widespread adoption of these
codes would cause changes in the formulation of the coatings, and
would adversely affect the markets for mineral spirits, napthas,
substituted aromatics, branched ketones, olefins, and
trichloroethylene. However, alcohols, esters, odorless mineral
B. Emission Sources 149
-------
spirits, and glycolesters would gain markets at the expense of the
photochemically active solvents. Emission control methods,
analytical techniques, and measurement methods are outlined. The
effectiveness of various organic solvents in photochemical smog
formation is discussed. An evaluation of existing regulations,
with emphasis on California Rule 66, is presented along with lists
of exempt sources.
09784
Danielson, John A. (comp. and ed.)
AIR POLLUTION ENGINEERING MANUAL. (AIR POLLUTION CONTROL DISTRICT,
COUNTY OF LOS ANGELES.) Public Health Service, Cincinnati,
National Center for Air Pollution Control, PHS-Pub-999-AP-UO,
999-AP-40, 892p., 1967. ((314)) refs.
GPO: 806-614-30
The control of air pollution at individual sources peculiar to the
Los Angeles area is considered. The practical engineering problems
of design and operation for many sources of air pollution are
emphasized. There are 11 chapters, each by different authors, and
4 appendixes. The chapter titles are: (1) Introduction; (2)
Contaminants; (3) Design of Local Exhaust Systems; (4) Air
Pollution control Equipment for Particulate Batter; (5) Control
Equipment for Gases and Vapors; (6) Metallurgical Equipment; (7)
Control Equipment; (8) Incineration; (9) Combustion Equipment; (10)
Petroleum Equipment; and (11) Chemical Processing Equipment. The
introduction discusses the Los Angeles Basin, rules and regulations
in Los Angeles County, and the use of the manual. The appendixes*
titles are: (A) Rules and Regulations; (B) Odor-Testing
Techniques; (C) Hypothetical Available Heats from Natural Gas; and
(D) Hiscellaneous Data.
09785
Dickinson, Janet, Robert L. Chass, and R. J. Hamming
AIR CONTAMINANTS. In: Air Pollution Engineering Manual.
(Air Pollution Control District, County of Los Angeles.)
John A. Danielson (comp. and ed.), Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution Control,
PHS-Pub-999-AP-40, p. 11-21, 1967.
GPO: 806-614-30
The parameters of an air pollution problem, particularly the
problem in Los Angeles County; the measures taken to eliminate
the problem; and control measures still needed are described. The
air contaminants include: organic gases (hydrocarbons, hydrocarbon
derivatives); inorganic gases (NOx, SOx, CO); miscellaneous
inorganic gases (NH3, H2S, C12, F2); participates (carbon or soot
particles, metallic oxides and salts, oily or tarry droplets, acid
droplets, metallic fumes). Each is discussed indicating the sources
and significance in the air pollution problem.
150 HYDROCARBONS AND AIR POLLUTION
-------
09803
Thomas, G.
COSE OVENS. In: Air Pollution Engineering Manual.
(Air Pollution Control District, County of los Angeles.)
John A. Danielson (comp. and ed.). Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution
Control, PHS-Pub-999AP-<40, p. 309-315, 1967.
GPO: 806-614-30
Various types of core ovens are described. These include the
shelf, drawer, portable-rack, car, and conveyor ovens.
Heating core ovens, core binders, air contaminants from core
ovens, and control methods are discussed. In foundries, core
ovens are used to bake the core used in sand molds. Most cores
contain binders that require baking to develop the strength
needed to resist erosion and deformation by metal during the
filling of the mold. Core ovens supply the heat and, where
necessary, the oxygen necessary for the baking. Generally,
emissions from core ovens are a minor source of air pollution
when compared with other metallurgical processes. The air
contaminants discharged from core ovens consist of organic
acids, aldehydes, hydrocarbon vapors, and smoke. Host core ovens
are vented directly to the atmosphere through a stack.
Occasionally more than one vent is used, but if emissions are
such that air pollution control is needed, then ducting the
vents to a control device is all that is necessary. The use of
hoods or of eoccess air is not necessary to capture the
emissions. When operated below 400 Degrees F and when fired
with natural gas, most core ovens do not require air pollution
control equipment. Excessive emissions from core ovens have
been reduced to tolerable amounts by modifying the composition of
the core binders and lowering the baking temperature. When it
is not feasible or possible to reduce excessive emissions by
modifying the core mix or the baking temperature, afterburners
are the only control devices that have proved effective.f#
09818
Weiss, Sanford M.
SURFACE-COATING OPEEATIONS. In: Air Pollution
Engineering Manual. (Air Pollution Control District, County of Los
Angeles.) John A. Danielson (comp. and ed.), Public Health
Service, Cincinnati, Ohio, National Center for Air Pollution
Control, PHS-Pub-999-AP-40, p. 387-390, 1967.
GPO: 806-611-30
Basic coating operations include dipping, spraying, flovcoating,
and roller coating. Each operation is described. Air pollution
problems, hooding and ventilation requirements, and control
equipment are discussed. The discharge from a paint spray booth
consists of particulate matter and organic-solvent vapors. Air
contaminants from paint dipping, flowcoating, and roller coating
exist only in the form of organic-solvent vapors since no
particulate matter is formed. The usual spray booth ventilation
rate is 100 to 150 fpm per square foot of booth opening. Insurance
standards require that the enclosure for spraying operations be
designed and maintained so that the average velocity over the face
B. Emission Sources
-------
of the booth, during spraying operations, is not less than 100 fpm.
Dip tanks, flowcoaters, and roller coaters are frequently operated
without hoods. When local ventilation at the unit is desirable, a
canopy hood may be installed. Particulate matter in paint spray
booths is controlled by baffle plates, filter pads, or water spray
curtains. Known solvent recovery processes make use of
condensation, compression, absorption, distillation, or adsorption
principles. In view of the small solvent vapor concentration in
the airstream from the spray booth or applicator hood, the only
economically feasible solvent control method is adsorption. Decent
work indicates that adsorption by activated carbon can be a
feasible method for the control of paint solvents. This work
indicates that control efficiencies of 90 percent or greater are
possible, provided particulates are removed from the contaminated
airstream by filtration before the airstream enters the carbon
bed.
09820
Bailor, William C.
DRY CLEANING EQUIPMENT. In: Air Pollution
Engineering Hanual. (Air Pollution Control District, County of Los
Angeles.) John A. Danielson (comp. and ed.). Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution Control, PHS-
Pub-999-AP-HO, p. 393-397, 1967.
GPO: 806-6Ht-30
Dry cleaning equipment follows two basic designs. One design is
tailored for petroleum solvents, and the other, for chlorinated
hydrocarbon, or synthetic, solvents. In a petroleum solvent dry
cleaning plant, the equipment generally includes a washer,
centrifuge, tumbler, filter, and, in many instances, a batch still.
With perchloroethylene, the washer and extractor are combined in a
single unit. The tumbler is equipped with a condenser for recovery
of solvent vapor. The tumbler is a closed system while in operation
and is vented to the atmosphere only during a short deodorizing
period. A muck cooker is often used to reclaim solvent from filter
sludge. The dry cleaning industry contributes to air pollution by
the release of organic-solvent vapors to the atmosphere. The lint
generated when fabrics are tumbled dry is controlled by devices not
normally considered to be air pollution control equipment. The
synthetic-solvent tumblers are provided with a cloth bag to filter
the lint from the exhaust air. Because of safety requirements,
hooding and ducting are an integral part of all dry cleaning
equipment. In synthetic-solvent plants, vents are provided near
the doors of the washer-extractor and the tumbler. An exhaust
system is automatically activated whenever these doors are opened,
and the system exhausts the vapors resulting from transfer of the
.wet textiles. When a carbon adsorption unit is used to collect the
perchloroethylene vapors, floor vents are also provided to capture
vapors from other areas. Activated-carbon adsorption can also be
adapted to control the solvent emissions from the petroleum solvent
dry cleaning plant, but the lower value of the recovered solvent
requires a much longer period of time to pay the cost of the
equipment. Other methods of reducing emissions from dry cleaning
plants include operational procedures and equipment maintenance.
HYDROCARBONS AND AIR POLLUTION
-------
09825
Betzley, Arthur B. and John E- Williamson
HULTIPLE-CHABBEH ISCINEBATOHS FOB BUBHIBG HOOD WASTE. In: Air
Pollution Enin
Pollution Engineering Manual. (Air Pollution Control Dis-
trict, County of los Angeles.) John A. Danielson (comp. and
ed.). Public Health Service, Cincinnati, Ohio, National Cen
ter for Air Pollution Control, PHS-Pub~999-AP-40, p. 436-
4«7, 1967.
GPO: 806-614-30
Air pollution from the burning of wood waste can be reduced to a
minimum through the use of multiple-chamber incinerators. By
promoting complete combustion, multiple-chamber incinerators
produce considerably less air pollution than is emitted from single-
chamber incinerators or by open burning. The design of multiple-
chamber incinerators to burn all forms of wood waste—from large
pieces of lumber to sawdust particles that may comprise from 10 to
100 percent of the total weight of the charge is discussed. The
designs of mechanical feed systems are also included since the feed
system must be properly integrated with the design of the
incinerator to promote maximum combustion. An illustrative problem
shows calculations involved in designing a multiple-chamber
incinerator with a mechanical feed system. The calculations in
this problem fall into three general categories: (1) Combustion
calculations based upon refuse composition, projected air
requirements, and heat transfer; (2) gaseous flow calculations
based upon the products of combustion at elevated temperatures; and
(3) dimensional calculations based upon equations determined
empirically from source testing.
09830
Netzley, Arthur B.
WIBE BECLAKATIOH. In; Air Pollution Engineering
Manual. (Air Pollution Control District, County of Los Angeles.)
John A, Danielson {comp. and ed.). Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution Control,
PHS-Pub-999-AP-«0, p. 495-503, 1967.
GPO: 806-614-30
Scrap copper wire, with a diameter in the range 1U gage to one
inch, which has combustible insulation is reclaimed by burning off
the insulation in an incinerator, A great variety of materials
composes the combustible insulation: Bubber, paper, cotton, silk,
and plastics such as polyethylene and polyvinyl chloride.
Moreover, the wire itself may have a baked-on coating of plastics,
paint, or varnish. As received for burning, the total combustible
content of the insulated wire may vary widely from several percent
to over 50 percent by weight. Host commercial wire contains from 20
to 35 percent insulation. Burning in the open is accompanied by
copious quantities of dense smoke, disagreeable odors, inorganic
materials, and oxygenated hydrocarbons. Burning in single-chamber
incinerators produces somewhat less snoke, odors, and other air
contaminants than open burning does, since combustion air can be
regulated. The only practical industrial eguipnent available today
for controlling emissions from single-chamber insulation-burning
B. Emission Sources 153
-------
incinerators is an afterburner or secondary combustion chamber.
The composition of stack gases from equipment with and without
afterburners is presented. Design methods, materials of
construction, and operating procedures are discussed and
illustrated.
09835
Walters, Donald F.
HASTE-GAS DISPOSAL SYSTEMS. In: Air Pollution
Engineering Manual. (Air Pollution Control District, County of Los
Angeles.) John A. Danielson (comp. and ed.). Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution Control, PHS-
Pub-999-AP-40, p. 565-606, 1967.
GPO: 806-61«-30
Petroleum refineries must dispose of large quantities of
hydrocarbon vent, waste, blowdown, and emergency pressure release
gases. Types, design, instrumentation, and operating practices for
gas disposal flares are presented. These include elevated and
ground level flares, burner design, steam injection, ignition and
pilot light systems, flare sizes and capacities, removal of
entrained mists, and provision for emergency overloads. Pressure
relief systems are also thoroughly discussed. Commonly used terms
dealing with relief systems are defined. Design methods and
operating procedures for safety valves (standard and balanced),
rupture discs, vent lines, vent headers, and vent gas scrubbers are
discussed and illustrated.
09838
Cuffe, Stanley T.
CATALYST REGENERATION. In: Air Pollution
Engineering Manual. (Air Pollution Control District, County of Los
Angeles.) John A. Danielson (comp. and ed.). Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution Control,
PHS-Pub-999-AP-40, p. 6«2-652, 1967.
GPO: 806-61«-30
The regeneration of catalysts employed in petroleum refining
processes, such as fluid and Thermofor catalytic cracking, is
accomplished by burning coke and sulfur deposits from the catalyst
surface. Combustion gases from regeneration include the pollutants
CO, SOx, NOx, NH3, hydrocarbons, and particulate matter.
Tables of data collected in 1956 are presented which specify pro-
cess flow rates, catalyst circulation rates, regenerator air rates,
coke burn-off rates, flue gas temperatures, particulate losses,
^hydrocarbon emission and analysis, and stack gas composition and
volumes. Pollution control methods presented and discussed are:
wet and dry cyclones, carbon monoxide waste heat boilers, and elec-
trical precipitators. The economy of a CO boiler depends on the
catalyst regenerator flue gas volume, temperature, fuel value, and
C02/CO ratio. An analysis of flue gases from CO waste heat
boilers is presented for cases where ammonia has and has not been
injected into the gas stream before the electrostatic precipitator.
>54 HYDROCARBONS AND AIR POLLUTION
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09839
Kinsey, Bobert H.
OIL-WATEB EFFLUENT SYSTEHS. In: Air Pollution Control Dis-
trict, County of Los Angeles.) John A. Danielson (coup, and
ed.), Public Health Service, Cincinnati, Ohio, National Cen-
ter for Air Pollution Control, PHS-Pub-999-AP-40, p. 652-659
1967.
GPO: 806-614-30
Oil-water effluent systems found in the petroleum industry collect
and separate wastes recover valuable oils, and remove undesirable
contaminants before discharge of the water to ocean, rivers, or
channels. The type of liguid wastes may be classified as waste
water with: Oil present as free oil, emulsified oil, or as oil
coating on suspended matter; and chemicals include acids, alkalies,
phenols, sulfur compounds, clay, and others. The oil-water
separator design must provide for efficient inlet construction,
sediment collection mechanisms, and oil skimmers. Clarification of
final-effluent water streams is accomplished by filtration,
chemical flocculation, and biological treatment. The most
objectionable contaminants emitted from liguid waste streams are
hydrocarbons, sulfur compounds, and other malodorous materials. The
method presented may be used to estimate the hydrocarbon loss from
oil-water separators. The most effective means of control of
hydrocarbon emissions from oil-water separators has been the
covering of forebays or primary separator sections with fired roofs
or floating roofs. Isolation of certain odor-and chemical-bearing
liguid wastes at their source for treatment before discharge of the
water to the refinery waste—water gathering system is an effective
and economical means of minimizing odor and chemicals problems.
Principal streams that are treated separately are oil-in-water
emulsions, sulfur-bearing waters, acid sludge, and spent caustic
wastes. Gravity-type oil-water separators are ineffective in
breaking the oil—in—water emulsions. Beth ods of separation
include direct application of heat, distillation, centrifuging,
filtration, use of an electric field coagulating chemicals, air
flotation systems, and biological treatment. Sulfide —and mercaptan-
bearing water may be steam stripped, or the sulfides may be
oxidi-zed to form acceptable thiosulfates, will produce H. S. Acid
sludge is dumped, burned, or processed to recover acid or to
produce byproduct. Spent caustic wastes are generally dumped, or
can be used in the neutralization of acid wastes.
09840
Kinsey, B. H.
PDHPS. In: Air Pollution Engineering Hanual. (Air
Pollution Control District, County of Los Angeles.) John
A. Danielson (coop, and ed.), Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution
Control, PHS-Pub-999-AP-«0, p. 659-665, 1967.
GPO: 836-614-30
Pumps are used in every phase of the petroleum industry and are
available in wide variety of models, sizes, capacities and
materials used for construction. All the common machinable
metals and alloys, as well as plastics, rubber, and ceramics.
B. I Emission Sources 15S
-------
are used. Pumps may be classified under two general
headings, positive displacement and centrifugal.
Positive-displacement pumps have as their principle of operation
the displacement of the liquid from the pump case by reciprocating
action of a piston or diaphragm, or rotating action of a gear,
cam, vane, or screw. Centrifugal pumps operated by the
principle of converting velocity pressure generated by
centrifugal force to static pressure. Velocity is imparted to
the fluid by an impeller that is rotated at high speeds. The
fluid enters at the center of the impeller that is rotated at
high speeds. The fluid enters of the impeller and is discharged
from its periphery. Power for driving the various types of
pumps is usually derived from electric motors, internal combustion
engines, or steam drives. Any leak in the pumping equipment
causes emission of hydrocarbon vapors and malodorous sulfur
compounds. Several means have been devised for sealing the
annular clearance between pump shafts and fluid casings to
retard leakage. For most refinery applications, packed seals
and mechanical seals are widely used. Typical packed seal
generally consist of a stuffing box filled with sealing material
that encases the moving shaft. Lubrication of the contact
surfaces of the packing and shaft is effected by a controlled
amount of product leakage to the atmosphere. The second
commonly used means of sealing is the mechanical seal. This
type of seal can be used only in pump that have a rotary shaft
motion. A simple mechanical seal consists of two rings with
wearing surfaces at right angles to the shaft. One ring is
stationary while the other is attached to the shaft and rotates
with it. A spring and the action of fluid pressure keep the two
faces in contact. Lubrication of the wearing faces is effected
by a thin film of the material being pumped. The wearing faces
are precisely finished to ensure perfectly flat surfaces. For
cases not feasible to control with mechanical seals, specialized
types of pumps, such as canned, diaphragm, or electromagnetic, are
required. A pressure-seal-type application can reduce packing
gland leakage. A liquid, less volatile or gangerous than the
product being pumped, is introduced between two sets of packing
at a higher pressure than the product. Volatile vapors that leak
past a main seal may be vented to vapor recovery by using dual
09857
D'Imperio, Joseph
OIL AND SOLVENT HE-REFINING. In: Air Pollution Engineering
Hanual. (Air Pollution Control District, County of Los Angeles.)
John A. Danielson (comp. and ed.). Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution Control, PHS-
Pub-999-AP-40, p. 799-801, 1967.
GPO: 806-61
-------
10044
Starkman, E. S., G. E. James, and H. K. Newhall
AMMONIA AS A DIESEL ENGINE FUEL: THEORY AND APPLICATION. Society
of Automotive Engineers, Preprint, 20p., 1967. 8 refs (Present-
sented at the Combined Fuels and Lubricants, Powerplant and
Transportation Meetings, Pittsburgh, Pa., Oct. 30-Nov. 3,
portation Meetings, Pittsburgh, Pa., Oct. 30-Nov. 3, 1967.
1967. Paper 670946.)
Theoretical and experimental investigations were carried out fox
the purpose of predicting and measuring the performance which re-
sults from operating of compression.ignition engines when anhydrous
ammonia is used rather than diesel fuel. Predictions were that am-
monia would give slightly increased ouput but that fuel consumption
would also increase 2-1/ fold. By eguipping the engine with a
spark ignition system, it was possible to operate successfully on
ammonia at normal compression ratios and retain the same fuel injec
tion system. Fuel injection and spark timing were found to be cri-
tical. Indicated power output was reduced by about 105, which dif-
fered from prediction. The discrepancy was due to the poor combus-
tion characteristics of ammonia. Predicted increase in fuel con-
sumption were experienced. Because ammonia is not 'smoke limited*
as is diesel fuel, it was possible to increase the smoke free out-
put from the engine by going to richer mixtures with ammonia.
(Authors' abstract)
10075
Williams, A. F.
OIL FIRING AND ODOUR PROBLEMS. (Due Olfeuerung im Hinblick auf
Emissionsprobleme.) Text in German. Schweiz, Arch. Angew, Wiss,
Tech. 31 (4):105-112, April 1965. (presented at the S.V.B.T. Meeting
Zurich, Switzerland, Sept. 11, 1964, Preprint in English.)
Smoke and smells are indicative of incomplete combustion. He
propose to deal with underlying causes and curative measures which
concern mainly the design and operation of the combustion appliance.
We shall discuss the various types of burners which are being used,
particularly those which are prevalent in Switzerland for room and
whole house heating. These are mainly pressure Jet burners with som
pot burners rated 15000 k cal/h. and above and operated on
distillated gas oil. We shall comment on the relative merits of ON
OFF and HIGH/LOW fire operation and quote test results for smoke and
unburnt hydrocarbons produced by various burners during continuous
firing or intermittent operation. Such unburnt hydrocarbons can giv
rise to unpleasant odours. We shall show that a low smoke condition
is related primarily to good draught and an optimum excess air value
inside the fire box. Various new attempts to procude small, highly
efficient atomizing burners will be mentioned. These include
ultrasonic atomization and the Ventres blue flame, atomizing with
vaporising burner. Lastly, in reference to typical Swiss oil gualit
and the standards set by SNV Institute, we shall give some results
showing the influence of aromatic content of the oil on its smoking
propensity. Some mention will also be made about sulphur in the fue
and S02 emission from the chimney. (Author's summary, modified)
.; Emission Sources 1S7
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10135
Brubacher, Miles L. and Donel R. Olson
SMOG TUNE-UP FOE OLDER CARS. In: Vehicle Emissions, Part II
SAE Progress in Technology Series, Vol. 12, New York
Society of Automotive Engineers, Inc., 1966, p. 268-290. 20
refs. (Presented at the SAE Southern California Section,
April 1961.)
Surveys of smog forming pollutants from the exhaust of the
California car population have shown a tremendous range of
emissions between the worst and the best cars. A study was
conducted to determine the effectiveness and cost of various tune-
up approaches to the auto exhaust emission problem. Four phases of
tune-up were explored and pertinent facts and data .are included in
this paper. Three major engine systems affecting emissions of
older cars are ignition, carburetion, and exhaust valve leaks.
Exhaust control is predicted to be a $150,000,000 annual business
and the incentive exists to develop more effective and cheaper
control systems. The average annual tune-up cost was about $30.
(Authors abstract, modified)
10292
W. J. Mullin, N. Berkowitz
BECHANISHS OF COAL PYROLYSIS VIII—THE ISOTHERMAL DISENGiGEHENT
OF CO AND CHU IN THE RANGE 570-670C. Fuel, 17 (1):63-77,
Jan. 1968. 13 refs.
Isothermal rates of disengagement of CO and CHU from
anthracite, bituminous and sub-bituminous coal chars at
temperatures between 570 and 670 C follow pseudo-first order
kinetics, but indicate that the initial gas discharge is
governed by two concurrent control-mechanisms. Of these, the more
sustained can be identified with a diffusion process for which E
is less than 5 kcal/mole and D is about 1 times 10 the minus 8th
power cc/sec. The other, which superimposes itself on diffusion,
appears to be the actual rate of formation of CO (or CHU)
within the decomposing coal mass. The relative importance of
these two controls changes with rising reaction temperature,
diffusion governing virtually all gas discharge below about 600 C
but controlling only about 30-UO per cent of the total CO and
CHU flow at 670 C. It is suggested that these findings, and,
in particular, the dual rate control, are the inevitable
consequences of the existence of two partially interconnected but
strongly size-differentiated and effectively 'independent' pore
systems in coal and coal chars. (Authors' abstract, modified)f#
10128
Jenkins, G. I. and B. P. Walsh
QUICK BEASURE OF JET FUEL PROPERTIES. Hydrocarbon Process.
Petrol Refiner, U7 (5) : 16 1-16U, May 1968. 2 refs.
158 HYDROCARBONS AND AIR POLLUTION
-------
Luminometer number, smoke point, aromatics content, and hydrogen
content of kerosene type aviation fuels can be calculated directly
from the aniline point and gravity by using tables and graphs
compiled in this report. Calculated values for these properties hav
proven to be generally more precise than single experimental
determinations.
10Q29
Juntgen, H. and K. H. Van Beek
GAS RELEASE FROM COAL AS A FUNCTION OF THE HATE OF HEATING, Fuel
47(2):103-117, March 1968. 10 refs.
Fundamental work on the kinetics of coal pyrolysis at continuously
rising temperatures is described. The theory of non-isothermal
reaction kinetics is used to calculate the dependence of gas
releasing reactions on temperature, taking as parameters the reactio
order, the activation energy, the frequency factor and the rate of
heating. Furthermore, it is possible to calculate the reaction
parameters from curves established by measurements under non
isothermal conditions. This theory was checked against the thermal
decomposition of simple organic molecules and has been found to be i
good agreement with experiment. The simplest curves of gas emission
rate from coal as a function of temperature are obtained for higher
gaseous hydrocarbons. This type of curve is interpreted in terms of
a single reaction, whereas the release of methane and hydrogen is
more complicated. To show the influence of heating rate, the releas
of ethane from a finely—ground coal (19.15 VH) was measured at
different values between 0.01 and 100,000 deg. C/min. These
experiments agreed well with the theory, assuming a first order law
with a mean activation energy of 42.1 kcal/mol and a mean frequency
factor of 10 to the 11th power per min. Also, the theoretically
calculated shift of the reaction to higher temperatures with
increasing rates of heating was exactly confirmed by experiment.
(Authors' abstract)
10475
Sage, B. H.
PARTIAL OXIDATION PRODUCTS FORMED DDRING COHBDSTION. (SUMMARY
EEPOET.) California Inst. of Tech., Pasadena, Chemical
Engineering Lab., 26 p., 1968. 3 refs.
A research program dealing with the influence of oscillatory
combustion of various fuels on the residual quantities of nitrogen
oxides and other partial oxidation products is summarized.
Experiments were conducted at a pressure of 50 Ib./sq. in. employing
air and a range of fuels including natural gas, ethane, propane, and
butane. The highest NOx levels occurred at near stoichiometric
mixture levels, with a sharp decrease at richer mixtures, and a more
gradual decrease at leaner mixtures. The budget of the program,
along with a. list of publications and reports and personnel
requirements, is presented.
B. Emission Sources 159
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10631
Skvortsova, N. N. and S. N. Kimina
ATMOSPHERIC POLLUTION BY 3,4-BENZPYRENE IN THE VICINITY OF A
TIMBER-CHEMICAL PLANT. ((0 zagryazenii vozdushnoi sredy
3,1-benzpirenom v raione raspolozheniya osokhimicheskogo
proizvodstva.) ) Hyg. 6 Sanit. (English translation of:
Gigiena i Sanit.), 33 (1-3):159-163, Jan.-Harch 1968. 6 refs.
CFSTI: TT 68-5041*9/1
A timber-chemical plant with retort, tar-distilling, chemical
carburation, drying and other shops, was investigated.
Atmospheric pollution by 3,4-benzpyrene, tarry substances, free
silicon dioxide, sylvan, phenol, a acetic acid and methanol was
measured around the plant. Aspiration samples were taken in
summer and snow samples in winter. Samples from wood pyrolysis
were investigated to give information concerning accidental
discharge of 3,4-benzpyrene. Environmental studies were
accompanied by statistical studies of morbidity and mortality
among population residing around the plant and in a control area.##
10660
Laffey, William T. and Robert N. Manning
SOLVENT SELECTION FOR THE REDUCTION OF AIR POLLUTION. Hercules
Chem., No. 56:1-6, March 1968. 5 refs.
Regulations restricting the use of solvents which partake in
photochemical smog reactions have caused the solvent and surface
coating industries to develop alternate solvent formulations. A
system is presented whereby a restricted solvent can be simulated
using combinations of allowable materials. The procedure is
graphical and depends on the solvent parameters and solubility
characteristics of the materials. When several formulations are
found which possess the required solvent properties, the choice
of the best one then depends on economic or other factors.t#
10662
Cline, E. L. and Lee Tinkham
A REALISTIC VEHICLE EMISSION INSPECTION SYSTEM. Preprint, Clay-
ton Manufacturing Co., El Monte, Calif., Dynamometer Div.,
((12))p., 1968. (Presented at the 61st Annual Meeting of the
Air Pollution Control Association, St. Paul, Minn., June
23-27, 1968, Paper 68-152.)
A one minute mass vehicle exhaust emission inspection system is
described to aid those seeking to establish an appropriate effort
in compliance with the Air Quality Act of 1967. This proposed
inspection is suitable for both emission controlled and pre-
emission controled automobiles. It is oriented to appropriate Auto
Service Industry corrective measures since it provides guidelines
as to probable cause of unnecessarily high emissions for each
rejected vehicle. This capability is essential to avoid abnormal
corrective expense due to excessive repairs or continued high
160 HYDROCARBONS AND AIR POLLUTION
-------
emissions due to inadequate repairs. Low skill levels may be used
during the inspection process, yet results are repeatable and
consistent in a plurality of inspection stations. The net gain in
lover emissions through inspection of in-use vehicles is large
because the point of rejection is no longer dictated by the
inherently high emission vehicles. Not more than two rejection
standards are required for emission controlled vehicles, and only
one for pre-emission controlled vehicles. This includes all
domestic and foreign makes. These standards are flexible in that
they may be initially liberal and gradually tightened as
circumstances warrant. Such policy changes or future spark
ignition engine designs will not significantly obsolete the
hardware required to perform this inspection. The fundamental
techniques employed permit the use of greatly simplified equipment
and instrumentation with resultant lower initial cost and increased
reliability than previously envisioned meaningful inspection
methods. A study of nearly 1000 automobiles over a one year period
evolved and documented this proposed inspection system. Qualified
persons may study this work to any depth desired by contacting the
authors. (Authors abstract, modified)
1073U
Charles B. Begeman, and Joseph M. Colucci
BENZO(A)PYHENE IN GASOLINE PARTIALLY PERSISTS IN
AOTOHOBILE EXHAUST. Science, 161 (3838) :271, July 19, 1968.
On average 36 percent of the benzo(a)pyrene in an automobile's
exhaust gas comes from the benzo (a)pyrene originally in the
gasoline. Between 0.1 and 0.2 percent of the benzo (a)pyrene
in the gasoline survives the combustion process and is
recovered from the exhaust; 5 percent accumulates in the
crankcase oil. Some of the benzo(a)pyrene in the gasoline is
converted into other polynuclear aromatic hydrocarbons and other
more polar compounds. For our experiments we used commercial
gasoline containing benzo(a)pyrene at 1.0 part per million to
which was added benzo(a)pyrene—8,9 to the minus 11th power C at
1.1 parts per million as a radioactive tracer. (Authors'
abstract)#*
107U1
Chakraborty, B. B. , and R. Long
THE FOHHSTION OF SOOT AND POLICYCLIC AROMATIC HYDEOCARBOHS IN
DIFFUSION FLAHES—PART ONE. Combust, and Flame, 12 (3) :226-236,
June 1968.
The amount of chloroform soluble material, polycyclic arnatic
hydrocarbons (PCAH) and carbonaceous residue (CR), in the dry
soot recovered from an ethylene diffusion flame have been
determined and the effects on these of changes in the oxygen index
(i.e. the mole fraction of oxygen in the mixture) of
oxygen-nitrogen and oxygen-argon mixtures supplied to the flame
have been investigated. In the oxygen-nitrogen mixtures, there is
a rapid decline in the amount of PC1H in the soot as the oxygen
index increases from 0.18 to 0.26. The amount of soot reaches a
maximum at an oxygen index of about 0.26 and above this value it
declines rapidly being then composed almost entirely of
B. Emission Sources 161
-------
carbonaceous material. The decline in the amounts of individual
PCAH in the soot with increase in oxygen index has been
investigated. Substitution of nitrogen by argon leads to higher
temperatures in the reaction and pyrolysis zones and at lower
oxygen indices the effect is to favour the formation of CR and
to lead to a reduction in the amount of PCAH in the soot. At
higher oxygen indices, the amounts of soot (actually CR) are
less. From the point of view of air pollution, the results
emphasize the undesirability of either a general, or local,
depletion of oxygen. (Author's abstract)*#
107«8
Fenimore, C. P., and G. W. Jones
COMPARATIVE YIELDS OF SOOT FHOH PREMISED HYDROCARBON FLAMES,
Combust, and Flame, 12 (3):196-200, June 1968.
Ethylene and acetylene gave eight times more soot when burnt with
oxygen. The comparison was made in flames having the same
temperature, and about the same pack concentrations of species froa
which the soot is supposed to grow (hydrocarbon radicals, acetylene
and polyacetylene). We suggest that more effective oxidation of
the soot aggregates, particularly during their early stages of
growth occurred in oxygen flames, and this decreased the yield.
Hydrogen chloride added to acetylene-oxygen flames increased the
yield of soot without increasing the concentrations of
polyacetylenes. Here too, the yield may have been altered mainly
by changes in the oxidation of the early soot aggregates.
(Authors' abstract)*t
10775
Qader, S. A., W. H. Wiser, and G. B. Hill
KINETICS OF THE HYDROBEMOVAL OF SDLF0R, OXYGEN, AND NITROGEN FHOH
A LOW TEMPERATURE COAL TAR. Ind. Eng. Chem. Process
Design Develop., 7(3):390-397, July 1968. ((11)) refs.
The result of the batch hydrogenolysis of S, 0, and N compounds
of a low temperature tar in the presence of a HS2 catalyst
indicated that all the hetero atoms can be completely removed at
500 degree C. and a pressure of 1500 p.s.i. Cracking,
aromatization, and possibly dehydrogenation reactions start at
temperatures above 375 degree C. The hydrogenation of
aromatic hydrocarbons starts at a pressure of 1250 p.s.i. The
hydroremoval reactions of S, 0, and H are all first order
with respect to the heterocyclic molecules. Sulfur reaoval
follows a true Arrhenius Temperature dependence, but the removal
of 0 and N shows slight curvatures in the Arrhenius plot which
can be resolved into two parts, each approaching linearity with a
break at <»00 degree C. and having different activation energies.
The magnitude of energies of activation and enthalpies of
activation obtained suggests that chemical reactions but not
physical processes are rate controlling. The surface reaction
involving the rupture of the C- S, C- 0, and C- N bonds of
the heterocyclic molecules appears to be the rate-determining
step. (Authors' abstract)t#
162 HYDROCARBONS AND AIR POLLUTION
-------
11087
Bispoli, Jose A.
FIGHT AGAINST AIR POLLUTION IN ARGENTINA EDUCATIONAL, LEGAL
AND TECHNOLOGICAL ASPECTS. Preprint, Tecnica de Higienc
(Argentina), 20p.r June 1968. 31 refs-
Air pollution is an increasing problem in the Argentina cities of
Buenos Aires, Rosario, La Plata and Bar del Plata. Air
pollution control measures are not keeping pace with the growth of
industries, which are often located in neighborhoods of
populated areas. The Huniciple Director of Hygiene
supervisors the problems of automotive emissions and
industrial and domestic emissions. About one million vehicles
travel daily in Buenos Aires. Traffic throughfares are being
modified in order to eliminate congested traffic areas. The
Director of Hygiene studies daily the chemical control of the
pollutants of hydrocarbons, carbon monoxide and sedimented
particles. The "Argentina Association for Air Contamination
of sanitary education on all levels for the population.*f
11143
Dearden, P. and B. Long
SOOT FORMATION IN ETHYLENE AND PROPANE DIFFUSION FLAHES. J.
Appl. Chem., (London) 18 (8) :243-251, Aug. 1968.
Small sanples of gas have been withdrawn from the luminous regions
of the diffusion flames of ethylene and propane burning on a
flolfhard-Parker burner and these have been analysed by gas
chromatography. In general, the parent hydrocarbon is rapidly
decomposed on approaching and within the luminous region, acetylene
being the major hydrocarbon product found. The concentration of
acetylene falls rapidly near the interface with the oxidation zone
suggesting that the main hydrocarbon oxidised in the latter is
acetylene. The rates of soot collection, the uncorrected
temperatures in the flames and the concentration of stable
hydrocarbon species have also been measured when oxygen, hydrogen
and acetylene respectively were added to the fuel stream. Oxygen,
when introduced into the fuel, leads to increased temperatures and
sooting rates in the case of ethylene and to increased temperatures
but decreased sooting rates in the case of propane. The sooting
rates of flames of ethylene will acetylene or orygen as additives
increased linearly with the area under the acetylene concentration
profile in the luminous zone (measured at a height of approxinately
5 mm above the burner). This area is proportional to the amount of
acetylene present in the luminous z'one at this height, which
corresponds roughly with the onset of luminosity. Acetylene thus
appears to be the major stable species via which soot is formed in
such flames. Propane flames with oxygen as additive to the fuel,
however, behave differently in that although there is an increase in
temperature and in -the amount of acetylene in the luminous zone the
sooting rate decreases. This discrepancy remains unexplained and
requires further investigation. (Authors'1 abstract, modified)
B. Emission Sources 163
-------
11152
Heller, Austin N.
THE ROLE OF THE SCIENTIST IN URBAN ECOLOGY. Trans. N. Y.
Acad. Sci., 30(8):1027-10U4, June 1968.
Scientists play a central role in the management of air problems
in New York City. An emission inventory procedure has been
established for evaluation of the emissions into New York City's
air from hundreds of thousands of sources. The principal
objective of this inventory is to give an estimate of the spatial
and temporal distribution of emissions. The monitoring network
is based on a technical evaluation of the complex meteorological
problems. Pollutant systems must be viewed from the point of
view of multi-components, since the synergistic interaction of
pollutants has a profound effect on the problem. The air
resource management encompasses economic, sociological,
technological, and physiological factors. Only through effective
use of computer techniques can the interplay of these diverse
problems be handled in a reasonable time.f*
11171
Wheatley, R.N and B, J. Barge'r
WAY TO DETERMINE SULFUR IN PETROLEUM. Hydrocarbon Process.
Petrol. Refiner 47 (10):133-137, Oct. 1968.
Emphasis upon sulfur-free products for the benefit of man and
machine as well as low sulfur refinery feed stocks that permit
prolonged life of process catalysts has resulted in a concentrated
effort toward sulfur reduction. Because critical areas of analysis
are often in the range of 0 to 50 parts per million, a rapid and
accurate sulfur method in this range was sought. Such a method was
found in the application of the oxy-hydrogen Wickbold burner in
which the material is combusted and the reaction products absorbed
in water containing a small amount of hydrogen peroxide. The
sulfate formed in the combustion oxidation process is titrated with
standard bariun perchlorate using thorinmethylene blue indicator.
11231
J. H. Wasser, G. B. Martin, and 8. P. Hangebrauck
EFFECTS OF COMBUSTION GAS RESIDENCE TIME ON AIR POLLUTANT
EMISSIONS FROM AN OIL-FIRED TEST FURNACE. Preprint, Public
Health Service, Cincinnati, Ohio, National Air Pollution
Control Administration, ((20))p., 1968. 5 refs. (Presented at the
National Oil Fuel Institute Workshop, Linden, N. J.,
Sept. 17-18, 1968.)
The effects of increased combustion gas residence time on air
pollution emissions from an experimental oil furnace are
described and compared with earlier data to illustrate the
resultant reduction of carbonaceous emissions. Particulate matter,
smoke, carbon monoxide, and gaseous hydrocarbon emissions
were reduced, and satisfactory operation obtained at lower excess
164 HYDROCARBONS AND AIR POLLUTION
-------
air levels. Sulfur oxides emissions were essentially unchanged.
Nitrogen oxides emissions increased by a small amount. Oxygen
and carbon dioxide concentrations in the flue gas were closer to
theoretical values, indicating a significant improvement in
combustion efficiency. Revised combustion chamber design
criteria balanced with improved burner design should provide low
air pollutant emissions and optimum operating efficiency for fuel-
oil-fired domestic furnaces. (Authors' abstract, modified)##
11251
Springer, K. J., G. L. Williams, K. W. Olsen, and Kenneth
D. Hills
EMISSIONS FROM GASOLINE-POWEBED TRUCKS ABOVE 10,000-LB GVW
USING PHS PROPOETIONAL SAMPLING TECHNIQUES. Preprint,
American Institute of Chemical Engineers, New York, N. T.,
13p., 1968. 8 refs. (Presented at the 61st Annual Meeting,
Symposium on Research and Development in Automotive Air
Pollution Control, Los Angeles, Calif., Dec. 1-5, 1968,
Paper 53C.)
Exhaust emissions, including hydrocarbons, CO, C02, and NOx,
from three gasoline-powered trucks above 10,000-lb gross vehicle
weight are presented. Proportional techniques were used to
obtain exhaust samples, permitting emissions to be analyzed and
reported on a mass basis. A discussion of the preparations and
dynamometer test procedures is included. (Authors' abstract)##
11263
Reamer, H. H., Joan Jacobs, and B. H. Sage
OSCILLATORY COMBUSTION AT ELEVATED PRESSURE. EFFECT OF FUEL.
Preprint, California Inst. of Tech., Pasadena, Chemical
Engineering Lab., ( (29))p., ((1966)) 10 refs.
The effect of varying the fuel from natural gas to ethane, propane
and n-butane upon oscillatory combustion in a cylindrical chamber
1 in. i.d. and approximately 21 in. in length was investigated
experimentally. A significant effect upon the residual
guantities of nitrogen and upon the double amplitude of the
perturbation in normal stress was noted. Little, if any, effect
upon the freguency of the longitudinal perturbations was
experienced. The results are presented in tabular and graphical
form. (Authors' abstract)##
11265
Reid, Willian T.
KILOWATTS FOR CARS - A COMPARISON OF ENERGY COSTS FOE ELECTRIC
AUTOMOBILES. Boston, Mass., Battelle Memorial Inst.,
Columbus, Ohio, 7p., 1966. (Presented at the 3rd Annaul
Meeting, American Institute of Aeronautics and Astronautics,
Nov. 29-Dec. 2, 1966, Paper 66-978.)
B. Emission Sources 166
-------
Success of electric vehicles for passenger service will hinge
around costs as well as reliability, size, styling, and such
indirect advantages as the elimination of air pollution. Costs,
in turn, will depend mostly on the energy package, whatever it
may be eventually. Primary and secondary batteries, fuel cells,
combined cycles, and linear induction systems all have some place
in powering an electric automobile, but their price to the
eventual consumer is still uncertain. This paper outlines
briefly some of the basic cost factors underlying selection of the
optimum energy package. It points out where further scientific
and engineering development w}.ll be necessary to arrive at a
suitable compromise between what the average motorist will want and
what he can afford to pay. Hany of these costs must be based on
engineering assumptions, but reasonable estimates are furnished
based on the present state of the art and on expected advances in
the foreseeable future. (Author's abstract)t#
11H57T
Brunner, M., H. Hoffmann, 0. Hettche, L. Truffert, W.
Hess, T. Huller, D. Hogger, H. Brunner, J. Richter,
and R. Frick
AIR POLLUTION BY MOTOR VEHICLE EXHAUST GASES; ((Die
Verunreinigung der Atmosphare durch die Abgase der
tlotorf ahrzeuge.)) Translated from German. Alimenta
(Kilchfcerg) , ,<» (6) :213-220, 1965. (Summaries, of papers
presented at a symposium held.by the Swiss Commission for Air
Sanitation, Zurich, Sept. 22-23, 1965).
A review of several lectures presented at the Federal
Commission for Air Hygiene in Zurich, Switzerland on
pollution of the atmosphere by motor vehicle exhaust gases is
presented. The following lectures are included in the form of
brief communications: 1. The composition of exhaust gases
produced by gasoline-burning engines; 2. The composition of
exhaust gases of diesel engines; 3. The pollution of the
atmosphere in traffic centers of large cities Abroad; <». Air
pollution caused by the exhaust gases from the'automobile in
Paris and its environs; 5. Survey of investigations of the air
conducted in Zurich from 1961 to 1965; 6. The pollution of the
atmosphere-observations in Switzerland; 7. Effects of exhaust
gases on humans, animals, and plants; 8. The influence of the
fuel composition; 9. Traffic sanitation and hygiene of the air;
and 10. Police regulations and their enforcement. Pollution of
the atmosphere by motor vehicle exhaust gases in Switzerland is
emphasized.#t
11U93
Kaznina, N. I.
1IR POLLUTION BY 7OLATILES LIBERATED BY SOHE PLASTICS. ((0
zagryaznenii vozdukha letuchimi veshchestvami, uydelyaemymi
plastikami.))Hyg. Sanit. (English translation of: Gigiena i
Sanit.), 33(U-6):267-269, April-June 1968.
CFSTI: TT 68-50UH9/2
The liberation of volatiles from plastics based on polyester
resins PN-1 and PN-69 was investigated. Plastic saiples
166 HYDROCARBONS AND AIR POLLUTION
-------
Nos. 1 and 2 contained polyester resin PN-1, isopropylbenzene
hydroperoxide, cobalt naphthenate and cement, while sample No. 3
contained resin PN-1 and PN-69, isopropylbenzene hydroperoxide
and cobalt naphthenate. Styrene was used as the solvent for the
resins. The dynamics of the liberation of volatiles by these
plastics as a function of temperature were investigated
spectrophotometrically and chemically. The spectral
characteristics of samples suggested the liberation of organic
substances with an optical denisty of wavelength range 211-300 m.
The concentration of liberated substances was found to be
directly related to the temperature. The air of premises in which
polymer materials are used is liable to be polluted by a complex
mixture of volatiles which are extremely difficult to identify by
the available techniques. The chemical and spectrophotometric
data suggest that plastics based on polyester resins and
manufactured by cold cure liberate appreciable amounts of vola-
tiles, the concentrations of which are a function of temperature.**
11562
Ewald, Herbert and Gustav Emrich
ANALYSIS OF THE INTERESTING COMPONENTS OF EXHADST GASES.
((Die Analytik interessierender Abgasbestandteile von
Auspuffgasen.)) Text in German. Freiberger Forschungsh.,
(A387):133-161, 1966. 146 refs.
Becent methods for the determination of CO, C02, NO, N02,
hydrocarbons, and hydrocarbon combustion products in air and
exhaust gases are reviewed in detail, with a discussion of their
relative sensitivity, accuracy, and convenience. Data are also
presented on the concentrations of some of these components during
the operation of gasoline and diesel engines under various
conditions. The sensitivity of various methods for the
determination of some of these components and the prices of some
of the analytical eguipment (gas chromatographs, mass
spectrometers, photometers, other spectrometers, and gas
analyzers) required are given in tabular form. It is concluded
that rapid testing or testing performed in mobile laboratories
usually must be made by Orsat analysis or test capsules, while
continuous measurements of exhaust gas components for control
purposes can be done photometrically. For most purposes,
ultraviolet and mass spectrometery have been replaced by gas
chromatography, which is cheaper and more informative; however,
spectrometric techniques are useful for identifying component
detected by gas-chromatograph. Although basically a discontinuous
process, gas chronatography can be automated.**
11615
Nowakowski, Paul
LDHINESCENT SHORE GENERATION FEASIBILITY STUDY (FINAL REPORT).
Hissouri Research Labs., Inc., St. Louis, Ho., Contract
N61339-67-C-0095, Task 5709, NAVTRADEVCEN 67-C-0095-1, 25p.,
Hay 1968.
CFSTI: DDC AD 675503
The methods, test results and conclusions that comprise the effort
of expanding the potential of a smoke generating device into the
B.'Emission Sources 167
-------
realm of fluorescent, response are described. In order to satisfy
the requirements generated in this task, several areas of
investigation were included in this program. To determine
sources of fluorescent response and to ascertain the state of the
art, literature was surveyed. The next step involved a study of
the smoke generating device to determine the potential and the
limitations of the smoke generating mechanism. When the most
promising candidates for fluorescence had been procured, they were
tested in the apparatus varying the solvent and the concentration.
This physical testing prompted further work, using procured and
tested and when the most promising formulations were ascertained,
the stability of the fuel and the characteristics of the smoke
cloud were determined. The foments. (Author's summary,
modified)t#
1208«t
Fink, C. K. and J. E. Weigel
OXYGENATED SOLVENTS. REFOEHDLATING NITROCELLULOSE LACQUERS.
Paint, Varnish, Prod., 58 (12) :38-U3, Dec. 1968.
Oxygenated solvents in combination with allowable aromatic and
exempt hydrocarbon diluents have been accepted as an approach to
compliance with air pollution controls. A guide to reformulation
based on recent research into solvent composition-solution
viscosity relationships is presented. Data are presented
relating the composition of complying solvent systems to viscosity
of nitrocellulose solutions prepared with these solvents. In
addition to viscosity, a solvent mixture must have a balanced
evaporation rate. A .listing of acceptable solvents by relative
evaporation rate is also presented.##
12085
Greaves, D. A. and I. G. Smith
NATURAL GAS CHALLENGES THE GAS INDUSTRY. PART TWO. Gas
World, 168(J»39U) :422-U26, Nov. 2, 1968.
Natural gas at present supplies 16 to 17% of total world energy
needs on a heat content basis and this.may rise to about 25% by
1985 with the proportion varying widely from country to country.
Some of the problems encountered in burner design are discussed.
The need for ways of meeting peak loads cheaply is of importance.
Liquefied natural gas is more easily stored and transported.
Purification by removal of the acid gases is an important step
in liquefaction of natural gas. Some of the methods used are
discussed.t#
12159
Friesell, J. w.
BURNING DEVICE ELIMINATES AIR POLLUTION IN THE DISPOSAL OF WASTE
ALDHINUM ALKYLS. Preprint, Texas Alkyls, Inc., Houston,
Texas, 9p., 1964. (Presented at a meeting of the Air Pollution
Control Assoc., Houston, Texas, June 1961.)
168 HYDROCARBONS AND AIR POLLUTION
-------
Disposal of industrial wastes containing aluminum alkyls presents
a difficult problem in the control of air pollution. Aluminum
alykls are not toxic or explosive, but they are so active
chemically that they ignite and burn spontaneously on contact with
air, releasing dense smoke. Their reaction with water is violent
and liberates hydrocarbon vapors. The design,'construction and
performance of a unique smokeless burning device that has provided
a safe, efficient and economical method for eliminating air
pollution associated with disposal of waste aluminum alkyls is
described. The use of this device has been extended to disposal
of other materials such as kerosene, benzene and toluene.
However, its full potential as a tool for air pollution control
remains to be developed. (Author's abstract)##
12161
HcKee, Herbert C. and George C. lawrason
A STUDY OF ETHAHOL-GASOLINE BLENDS AS AUTOMOTIVE FUEL. Preprint,
Southwest Research Inst. , San Antonio and Houston, Texas, ,11p. ,
1964. (Presented at the 57th Annual Meeting of the Air Pollution
Control Association, Houston, Texas, June 21-25,. 1964.) paper
64-76.
An investigation of ethanol-gasoline blends as a fuel for modern
automotive engines was undertaken. Primary emphasis in the early
phases of the program was devoted to determining the operating
characteristics of typical automobile engines with various amounts
of ethanol added to conventional gasoline. Along with this
investigation, a few preliminary tests were made to determine the
amount of unburned organic vapor emitted in the exhaust, comparing
the emission of an ethanol-gasoline blend with the emission of a
leaded gasoline of the same octane number. It was immediately
evident that a significant reduction in hydrocarbon concentration
occurred with the ethanol-gasoline blends, and additional work was
performed to investigate this particular factor in more detail.
It is concluded, however, that before a large scale change in fuel
composition are undertaken, several factors needed extensive
investigation.
12521
H. U, Ayers
ALTERNATIVE NONPOLLUTING POWEB SOURCES. S.A.E. (Soc.
Autoraot. Engrs.) J., 76 (12):40-80, Dec. 1968.
An urban transportation crisis grips the nation—its symptoms:
thickening pollution, rising accidents, and ever increasing
congestion. Currently, emissions appear to be the most
pressing problem, therefore, responsible engineers must now
consider alternative nonpolluting power sources. External
combustion engines with steam or another fluid as the working
medium are available now as an economic alternative to the
internal combustion engine. The major virtue of the
external combustion engine is an almost complete lack of
emissions without compromise of engine performance. Steam
engines offer simplifications in power train design as they
possess high torque at zero speed eliminating the need for a
B. Emission Sources 169
-------
transmission. In hybrid systems, a small, constant speed
internal combustion or external combustion engine drives a high-
speed alternator-invertor which both powers electric motors at
the wheels and charges a battery. While overall
efficiency would equal that of present engines and emissions
would be drastically reduced, the cost penalties for private
automobiles would be substantial. Therefore, the use of hybrid
systems appears likely only for specialized situations which
might include trucks and buses. Electric propulsion systems
based on lead-acid batteries are possible now for small, limited
performance vehicles. If high energy batteries become an
economic reality, small cars comparable to the Volkswagen and
Renault will become possible. With the development of low cost
fuel cells, fuel cell-battery hybrids will present an attrative
alternative since the introduction of the fuel cell into the
system would give these vehicles a much neededyincrease in range.
The present state of development and a careful overview of the
potential of these alternative energy systems is presented in
detail.**
12967
Saito, Takeshi
INFLUENCE OF FUEL TYPES OF COMPOSITION OF AUTOMOTIVE ENGINE
EXHAUST. (Jidosha haiki gasu nr oyobosu nenryo sosei no eikyo).
Text in Japanese. Nenryo Kyokai Shi (J, Fuel Soc. Japan), <»8 (3) :
1U8-159, 1969. 8 refs.
A continuation of the investigation of the influence of different
fuels on the composition of automotive engine exhaust
constituents is reported. The relations between the olefin content
of fuel and exhaust constituents are experimentally shown using
an internal combustion engine on a dynamometer block. Test fuels
included two gasolines of different olefin content, commercial
LPG, and pure propane. Carbon monoxide, hydrocarbons, N2, 02,
C02, H2, and nitrogen oxides were analyzed by gas chromatography.
Unsaturated olefins were detected with an absorber reported by
H. B. Innes. A special sampling apparatus using a magnetic bulb
was constructed for analysis under acceleration. A hydrogen
flame ionization detector was used for hydrocarbon analysis;
molecular sieve and active charcoal were used for inorganic
analyses; phenol disulforic acid was used for nitrogen oxide
determinations. Analytical data are shown for various engine
loads and speeds. It is concluded that CO concentration depends
on air-fuel ratio only and is not influenced by fuel
composition. Differences in total hydrocarbon content of
exhausts from different fuels are quantitatively small, but
unsaturated hydrocarbons, which contribute, to air pollution
reactions, increase slightly with the fuel olefins.
13562
Chandler, J. H.
EFFECTS OF ENGINE-OPERATING VARIABLES ON THE COMPOSITION OF
AUTOHOTIVE EXHAUST GASES. Proc. Am. Petrol. Inst., Sect. Ill,
38:324-335, 1958. (Based on a report of the Variables Panel of
the Coordinating Research Council Group on composition of exhaust
gases, Aug. 1957.)
170 HYDROCARBONS AND AIR POLLUTION
-------
The effects of engine variables on the concentrations of
hydrocarbons and nitrogen oxides in automotive exhausts are
discussed. The factors affecting hydrocarbon concentration in
exhaust gas are manifold vacuum, engine detuning, and cold as
compared to hot engine starting. Manifold vacuum of more than
21.5 in. of mercury accounts for high hydrocarbon concentrations
during deceleration. This effect is accentrated by manual
transmissions as compared to automatic. Enriched carburetor idle
setting increases hydrocarbon emission at cruising speeds up to
30 mph. Sparlc-plug condition is important because one misfiring
plug may more than double the average hydrocarbon concentration.
Among the variables affecting nitrogen oxides, air-fuel ratio is
of primary importance. Lean mixtures promote the formation of
nitrogen oxides and increase the effects of other engine variables.
Under full throttle, rich mixture conditions, the concentrations
are relatively low. Under road-load cruise conditions and during
fuel throttle accelerations, higher speeds produce higher
concentrations. During part-throttle accelerations, speed has no
effect, and high concentrations may be exhausted even at low
speeds. During idling and deceleration, nitrogen oxides
concentrations are so low as to be considered insignificant.
13668
Robb, E. H. , H- R. Johnson, J. J. Westbrook, and R. B. Seligman
HODEL PYROLYSIS - THE STUDY OF CELLULOSE.
3(9):597-60«, Dec. 1966. « refs.
Beitr. Tabakforsch.,
Relating smoke products to smoke precursors is an ambiguous task
when burning any naturally occurring plant. TO facilitate
interpretation, a simple model pyrolysis system was studied using
cellulose as the smoke precursor and monitoring benzo(a)pyrene
as the smoke product. Data obtained show how pyrolysis was
affected by changes in atmospheres, varied pyrolysis temperatures,
the addition of inorganic materials, and chemical modifications
of the cellulose molecule. It is hypothesized that cellulose
can undergo pyrolysis by two different modes to form
benzo (a)pyrene. Large quantities of the hydrocarbon can be
formed by high-temperature (850 C) isothermal pyrolysis of
cellulose via an efficient gaseous reaction route. In this
reaction, the benzo(a)pyrene yield decreased in the presence
of iron, cobalt, and nickel, while the yield increased with
increasing temperatures and with the introduction of oxygen into
the system. In contrast, graduated heating experiments
demonstrated that benzo(a)pyrene began to form at 150 C. This
reaction was inefficient with respect to benzo (a)pyrene yield
and was unaffected by the presence of metals. The benzo (a)pyrene
precursors appeared to be nonvolatile, being formed from the
solid decomposition of cellulose. This reaction was inhibited
by nitric oxide or salts generating nitric oxide. Additionally,
oxidation of the cellulose molecule at the C6 position
produced a decreased benzo(a)pyrene yield. (Author summary
modified)
13795
Lawson, S. D., Sr., J. Byrne, A. R. Cunningham, D. L.
Hendrickson, and E. L. Winkler
B. Emission Sources
171
-------
ECONOMICS OF CHANGING VOLATILITY AND REDUCING LIGHT OLEFINS—
0. S. HOTOR GASOLINE. Proc. Am. Petrol. Inst., Div. Refining,
vol. 48:6
-------
13952
lindberg, Walter
AIR POLLUTION IN NORWAY. I. THE GENERAL AIR POLLUTION IN
NORWEGIAN CITIES AND INDUSTRIAL TOWNS. (Den alminnelige
luftforurensning i Norge. I. Generelt om luftfoturensning i
byer og tettbygde strok.) Translated from Norwegian. Oslo Univ.
(Norway), p. 1-65, 1968. 12 refs
General information is presented on air pollution in Norway
uith attention focused on (1) the sources and types of
pollutants: motor vehicles, heating plants, incinerators,
(2) air pollution levels in the cities, including dustfali,
S02, and smoke measurements in Oslo, Sweden, (3) special
investigations (sulfuric acid fog) , the chemical composition
of solid particulates in smoke and suspended dust,
polynuclear hydrocarbons and particulates, trace elements,
(») pollutants in Norwegian cities other than Oslo,
(5) directions for medicohygienic evaluation of pollution
levels in cities and other densely populated districts and
industrial regions, and (6) an evaluation of the economic
consequences of air pollution.
10033
Pahnke, Alden J. and James F. Conte
EFFECT OF COMBUSTION CHAMBER DEPOSITS AND DRIVING CONDITIONS ON
VEHICLE EXHAUST EMISSIONS. Preprint, Society of Automotive
Engineers, Inc., New York, B. Y., 2<*p., 1969. 15 refs.
(Presented at the International Automotive Engineering Congress,
Detroit, Mich., Jan. 13-17, 1969, Paper 690017.)
Hydrocarbon exhaust emission levels of new cars driven under
consumer-type conditions increase during the initial 5000 to
10,000 miles of operation; the magnitude of the increase is
less with vehicles eguipped with exhaust control systems.
The role of combustion chamber deposits in increasing hydrocarbon
exhaust emission levels during the initial period of vehicle
operation was considered. Analyses have shown these deposits
to contain high concentrations of lead salts originating from
the combustion of lead alkyls present in gasoline. Two consumer-
type vehicle tests to determine the effect of leaded and
unleaded gasoline on exhaust emissions were completed. One
test"involved 122 cars without exhaust control systems and the
other, 36 cars with exhaust control systems. In both tests,
hydrocarbon exhaust emissions of the leaded and unleaded cars
increased during the initial period of mileage accumulation
and then leveled out as equilibrium was reached. Average
hydrocarbon emission levels of the leaded cars were higher
than those of the unleaded cars with the difference or net lead
effect amounting to 7% in both the 122-car and the 36-car tests.
No significant differences in carbon monoxide or nitrogen oxide
emission levels were observed. Photochemical reactivity levels
were essentially the same for the leaded and unleaded car
groups in the two tests. A limited study of the effect of
mileage accumulation conditions on exhaust emission levels
was carried out. Results obtained under rapid or accelerated
mileage accumulation conditions did not correlate with consumer
test results. (Author abstract modified)
B. Emission Sources 173
-------
1UOU5
Davis, H. P., 0. A. Uyehara, and P. S. Myers
THE EFFECTS OF KNOCK ON THE HYDROCARBON EMISSIONS OF A SPABK-
IGNITION ENGINE. Preprint, society of Automotive Engineers, Inc.,
New York, 9p., 1969. 12 rets. (Presented at the International
Automotive Engineering Congress, Detroit, Mich., Jan. 13-17, 1969,
Paper ,690085.)
To determine the effects of knock in a spark ignition, single-
cylinder engine with cooled exhaust upon the exhaust composition,
exhaust products (CO, C02, and total hydrocarbons) were measured
by non-dispersive infrared analyzers (NDIHA) and by a flame
ionization detector (FID). Individual hydrocarbons were
separated on a gas-liquid chromatograph. In fuel-rich mixtures,
the FID indicated noticeable decreases in the hydrocarbon
concentrations in the presence of knock. The NDIRA did not
indicate a decrease in the hydrocarbons at knock of lower
intensities but showed decreases in hydrocarbons at knock of
higher intensities. Chromatograms indicated a preferential
decrease in acetylene at the time of knock, causing different
responses at lower intensities. In fuel-lean mixtures, no
apparent effect of knock on the hydrocarbons was indicated. Thus,
it was concluded that in fuel-rich to stoichiometric regions,
knock generally decreases the hydrocarbon concentration in the
exhaust and the extent of the decreases is greater with the
intensity of knock. (Author abstract modified)
1U07U
Leggewie, G. and I. Skunca
SOOT FORMATION TENDENCY OF LP-GAS IN ATMOSPHERIC BURNERS.
(Untersuchungen ueber die Russbildungsneigung von Fluessiggasen
in atmosphaerischen Brennern). Text in German. Intern. Z.
Gaswaerme, 18 (3):122-123, March 1969. 3 refs.
Using the cooker burner of a multi-gas range, the authors
determined the tendency to form soot when the range was
supplied with hydrocarbon gases under equal pressure. The
input of primary air was so adjusted as to cause incipient
yellow flame tips to occur. The tendency to form soot increases
in the order: propane, butane, propylene, and butylene.
1U116
Hurn, R. H.
AIR POLLUTION AND THE COMPRESSION-IGNITION ENGINE. Preprint.
Combustion Institute, Pittsburgh, 1 Up., 1968. 9 refs.
(Presented at The Combustion Inst. Twelfth International
Symposium on Combustion, Poitiers Univ., France, July 1U-20,
1968, Paper 61-7.)
The compression-ignition engine, popularly known as the diesel,
is examined as a contributor to metropolitan air pollution.
Smoke and odor are recognized as the primary targets of public
174 HYDROCARBONS AND AIR POLLUTION
-------
objection to the diesel, and factors relevant to the smoke and
odor problem are discussed. Problems ot diesel smoke are seen
as readily manageable, but a satisfactory solution to the diesel
odor problem is not yet available. Other pollutants, e.g.,
unburned or partially burned hydrocarbons, oxides of nitrogen,
and carbon monoxide, are significant products of diesel
combustion. Of these, only nitrogen oxides and possibly the
aldehydes are typically discharged in quantities that in
equivalent volumes may exceed the quantities discharged by
spark ignition reciprocating internal combustion engines.
Features unique to the diesel combustion process are discussed
as factors relevant to generation or avoidance of objectionable
pollutants. The high temperatures and oxygen availability in
diesel combustion are seen as serious impediments to
satisfactory reduction of the yield of nitrogen oxides, but they
are favorable in holding concentrations of pollutants in other
categories to acceptable low levels. To compound this advantage,
the diesel has advantages both in fuel economy and in higher
heat value of diesel fuel compared with lighter fuels. Thus,
it would appear that diesel power offers an excellent
opportunity for continued and expanded application to meet
increasingly stringent clean air requirements. (Author
abstract modified)
U12U
Elraenhorst, R. and W. Dontenwill
CARCINOGENIC HYDROCARBONS IN THE SMOKE FROM CHARCOAL GRILLING.
(Nachweis cancerogener Kohlenwasserstoffe im Rauch beim Grillen
uber Holzkohlenfeuer). Text in German. 2. Krebsforsch., vol.
70:157-160, Nov. 1967. 9 refs.
The smoke which is formed during the charcoal grilling of bacon
was analyzed for its content of polycyclic hydrocarbons. The
following polycyclic hydrocarbons were found: fluoranthene,
perylene, phenanthrene, pyrene, benzo(a)pyrene, benzo(e)pyrene,
chrysene, dibenzanthracene, anthracene, and benzanthracene. The
amount of carcinogenic benzo(a)pyrene in the smoke was 129
micrograms/kg of grilled bacon, and it was assumed that the
carcinogenic hydrocarbons in the grill smoke were produced by
pyrolysis of the fat which dropped on the glowing charcoal.
(Author summary modified)
14127
Stone, R. K. and B. H. Eccleston
VEHICLE EMISSIONS VS. FUEL COMPOSITION. Preprint, American
Petroleum Institute, Montreal, Can., Div. of Refining, 50p.,
1968. 9 refs. (Presented at the Session on Air and Hater
Conservation, 33rd Midyear Meeting of the American Petroleum
Institute Division of Refining, Philadelphia, Pa., May 16, 1968,
Preprint No, «3-68.)
Reduction of evaporation losses from motor vehicles was
investigated as a means of lessening the amount of pollutants
reaching the atmosphere. The effect of fuel volatility and of
front-end fuel composition on the quantity, composition, and
B. Emission Sources 175
-------
photochemical reactivity of vehicle emissions including both
tailpipe and fuel-system losses were studied. In addition, the
test variables included engine fuel-system features and ambient
temperature, which was varied over a range of 20-95 F. Results
of tests on eight 1966 model cars are given. Driving cycle and
instrumentation typical of current practices for emission studies
were used. Test results showed that at high ambient temperatures,
a large reduction in evaporation losses accompanied a reduction
in front-end fuel volatility. However, there was also a small
adverse effect on exhaust emissions from volatility reduction.
Reactive hydrocarbon emissions from evaporation were reduced
substantially by either volatility reduction or saturation of
light olefins. Light olefin reduction also reduced exhaust
reactivity. Carbon monoxide emissions showed a small increase as
fuel volatility was reduced, while nitrogen oxides and aldehydes
showed no significant fuel effect. (Author abstract modified)
14461
Hall, C. A., A. E. Felt, and H. J. Brown
EVALUATING EFFECTS OF FUEL FACTORS ON STABILIZED EXHAUST EMISSION
LEVELS. Preprint, Society of Automotive Engineers, Inc., New
York, 20p., 1969. 5 refs. (Presented at the International
Automotive Engineering Congress, Detroit, Hich., Jan. 13-17,
1969, Paper' 690014.)
Single-cylinder engine studies showed that the severity of the
test cycle used for deposit accumulation markedly affects the
level of exhaust emissions obtained with stabilized combustion
chamber deposits. These studies also show that the relative
stabilized emission levels with non-leaded and leaded fuels vary
significantly with the aromatic content of the base fuel. An
extensive evaluation in three groups of passenger cars operated
by their owners in normal service showed no significant
difference between the stabilized emission levels obtained with
commercial non-leaded and leaded fuels. A dynamometer engine
test procedure was developed that simulates short-trip, city-
type operation. The accelerated cooldown procedure allows for
rapid accumulation of test mileage. Use of this dynamometer
procedure showed that a prototype highly aromatic non-leaded fuel
produced a higher deposit stabilized emission level than that
obtained with an average presently used leaded fuel. (Author
abstract modified)
14462
Gagliardi, J. C. and F. E. Ghannam
EFFECTS OF TETRiETHYL LEAD CONCENTRATION ON EXHAUST EMISSIONS
IN'CUSTOMER TYPE VEHICLE OPERATION. Preprint, Society of
Automotive Engineers, inc.. New York,' 19p., 1969. 9 refs.
(Presented at the International, Automotive Engineering Congress,
Detroit, Mich., Jan. 13-17, 1969, Paper 690015.)
Effects of various concentrations of tetraethyl lead on exhaust
emissions were investigated. Eight Ford Galaxies equipped with
production non-exhaust emission-equipped 289-CID, 2-V engines
were operated in customer service for 18,000 miles in the Detroit
area. Four fuel blends were used in mileage accumulation. All
176 HYDROCARBONS AND AIR POLLUTION
-------
engines were operated on the same petroleum base engine lubricant.
Exhaust emissions were monitored at approximately 3000-mile
intervals using the California Motor Vehicle Pollution Control
Board seven-mode procedure. Additional seven-mode tests were
obtained on each engine after combustion chamber deposits were
removed at the completion of the mileage accumulation phase. The
increase in exhaust hydrocarbon emissions of vehicle operation
on the leaded fuels was substantially higher than the hydrocarbon
increase of vehicles operated on Indolene Clear (a full boiling
range non-lead gasoline). At the 12,000 mile point, for
example, the average hydrocarbon increase for the leaded fuels
was approximately 100 ppm as hexane, while the hydrocarbon
increase on Indolene Clear was negligible. No deleterious
effect, due to the fuel used, was observed on any engine component,
(Author abstract modified)
14487
Shoji, H., K. Nishida, H. Komatsu, S. Yamada, T. Denda, 5. Takada,
and A. Hasegawa
THE STUDIES ON THE AIR POLLUTION DUE TO AUTOMOBILE EXHAUST GASES
(HEPOHT 12). TOTAL AMODHT OF EXHAUST GASES IN KYOTO-CITY.
Jidosha haiki ni yoru taiki osen no kenkyu (Dai 12 ho). Kyoto-
shi ni okeru haiki seibun no hai shutsu). Text in Japanese.
Nippon Eiseigaku Zasshi (Japan J. Hyg.), 24(1):92, April 1969,
A method for calculating total automotive exhaust gases in Kyoto
is based on estimates of the average amount of exhaust gases
per automobile per running cycle and the ratio between traffic
density in center city and the surrounding areas. Assuming
that (1) the ratio between center city and outlying traffic
is 2.2 to 1.0; (2) the total number of cars varies between
200,000 to 300,000/day; (3) all have gasoline engines; and (4)
the running cycle for center city is the BC type and for the
circumferential area the HI type, the total amount of exhaust
would be 124.0 to 127.2 tons CO/day and 17.8 to 18.8 tons of
hydrocarbons per day for 200,000 cars and 186.0 to 198.8
tons CO/day and 26.8 to 28.2 tons of hydrocarbons per day for
300,000 cars.
1U619
Cejka, Milan
DIESEL ENGINE EXHAUST GASES. (Vyfukove plyny z naftovych
motoru) . Text in Czech. Ropa Uhlie, 9 (6-7):208-211, 1967.
Composition of engine exhaust gases depends largely on the
fuel-air ratio, which varies in accordance with the loading
of the engine from 18:1 to 100:1, and this greatly influences
the combustion process. In addition, the content of
exhaust gases is determined by the shape of the combustion
chamber, the type of fuel injection, whether the engine is
two or four stroke, habits o.f the driver, etc. Analysis gave
evidence of 47 different compounds in engine exhaust gas.
Nitrogen oxides comprised 40-85% of the emissions from diesel
engines compared to 10% from combustion engines. The content
of aldehydes in snoke is the main cause of toxic effects in
humans. It is believed that lighter fuels reduce smoke, but
B. Emission Sources 177
-------
they yield more irritant compounds. In a garage for 200
buses whose engines were in good condition, the measured
concentration of carcinogens was 2.7 to 2.9 micrograms/100 cu m,
which is less than values found in ambient air from burning
coal. The setting of maximum allowable concentration standards
is very difficult because of the wide range of individual
reactions to engine exhausts. Reduction of pollution may be
effected by supplying specially treated fuel with low sulfur
content, after burning of gases as practiced in the U. S., and
regular inspection of engines.
11680
Hagner, T. 0.
COMPOSITION OF DIESEL EXHAUST HYDROCARBONS. Franklin Inst.
Research Labs., Philadelphia, Pa., Haterials Science and
Engineering Dept. and Public Health Service, Durham, N. C.,
National Air Pollution Control Administration, Proc. First Natl.
Symp. on Heterogeneous Catalysis for Control of Air Pollution,
Philadelphia, Pa., Nov. 1968, p. 241-252.
The technology required to develop an odor standard for diesel
engines is being acquired. However, diesel exhausts contain
such a wide range of compounds that sampling and analytical
procedures are difficult. When no more than an inventory of
hydrocarbon compounds is desired, capillary-column chromatographic
analysis of a bag sample is adequate, even though many 'heavy'
hydrocarbons are lost. Such an analysis revealed the presence
of C1 to C18 paraffins. Few, if any, of the light and mid-boiling
compounds were present in the fuel. Compounds causing diesel
odor are in the C8 to C18 range, Diesel exhaust contains many
oxygenated compounds which may be relevant to odor, but their
concentrations are low. The effect of fuel on diesel emissions
is small. Concentrations of hydrocarbons in diesel exhaust,
adjusted for excess-air dilution, are generally below
passenger car emission standards.
me 97
Klinksiek, K. E.
PARTICULAR PROBLEMS WITH EXHAUST GAS ANALYSES AT
VOLKSWAGEHWERK AG. Preprint, society of Automotive Engineers,
Inc., New York, 12p.r 1968. 6 refs. (Presented at the
Automotive Engineering Congress, Detroit, Hich., Jan. 8-12, 1968,
Paper 680122.)
Emission and durability tests of 1968 Volkswagens are
reported. Exhaust emissions from cars made in Europe and the
United States were measured by a dynamometer and analyzed for
hydrocarbon and carbon monoxide content by infrared and flame
ionization detection methods. To determine if any correlation
exists between present or proposed emission standards and test
procedures, European, Japanese, and American tests were used to
calculate exhaust gas flows and quantity of pollutants. Carbon
monoxide concentrations in the European test procedure are 1.3
times higher than in the official 0. S. test procedure.
Concentrations of hydrocarbon in the European test procedure is
178 HYDROCARBONS AND AIR POLLUTION
-------
lower than in the D. S. procedure, reflecting the influence
of deceleration which is more rapid in the U. S. test. If U. S.
emission standards were based on mass emission rather than on
concentration, mass emissions of carbon monoxide would be higher
in U. S. test procedures. This is attributed to the relationship
between carbon monoxide and exhaust gas volume. Higher average
speed in the 0. S. test results in a higher exhaust gas volume.
Fuel consumption does not correlate significantly with emissions,
but combustion tends to be better with the 0. S. test procedure.
Worldwide legislation on emission standards with one common
test procedure is recommended.
1H767
Barkus, G. A., Yu. G. Ozerskii, and V. I. Oratovskii
DISCHARGES TO ATHOSPHERE AT THE PHENOL HORKS. Coke Chem.
(USSR) (English tanslation from Russian of: Koks i Khim.);
no. 1:37-39, 1969. 9 refs.
The quantity and composition of discharges from the phenol
worXs were determined. Discharges come from breather valves
in operational equipment as a result of evaporation from
equipment operating under a vacuum which discharges drawn-off
gases, and from spent gas leaving the unit for springing sodium
phenolates with carbon dioxide. The vacuum pump discharges
contain hydrogen sulfide and ammonia. Impurities such as
pyridine bases, phenols, neutral aromatic hydrocarbons, hydrogen
sulfide, and ammonia enter the common collector. Measurements
revealed that the volume of the gas-air mixture discharged to
the atmosphere through the collector is 600-800 cu m/hr. Two-
liter samples were taken over d 30-min period and analyzed.
The fluctuations of the various contents were ascribed to
changes in the composition of the raw materials that were
processed and in the operating conditions of the plants. The
maximum concentrations of the noxious discharges were calculated.
The results indicated that the content of phenols, hydrogen
sulfide, and other impurities exceeded the maximum standards
and must be reduced 10-20 times. It was concluded that work
should be done to reduce the volume of discharge by strict
observance of the process conditions to ensure that minimum
discharges and effective equipment be developed to trap noxious
impurities.
1U798
liedmeier, G. P.
PREVENTION OF ATMOSPHERIC POLLUTION IN PETROLEUM BEFINERIES.
(La prevention de la pollution atmospherique dans les
raffineries de petrole). Text in French. Pollut. Atmos. (Paris),
11 (Special):3-8, Feb. 1969.
A review of atmospheric pollution and problems in controlling it
in the refineries of Europe is presented. The author discusses
the founding of CONCAHE (Conservation of Clean Air and Water—
Western Europe), which is a group of oil companies and societies
representing 80$ of the refining capacity .in Western Europe. Its
functions are to process information pertaining to pollution
B. 'Emission Sources 179
-------
by refineries and the joint study of pollution problems. It
now has working groups in the following areas: study of the
height of chimneys and atmospheric dispersion; liquid effluents;
petroleum pipelines; subterranean migration of petroleum; and
noise abatement. The sources and effects of refinery pollution,
particularly by sulfur oxides, hydrocarbons, and malodorous
gases are reviewed. Particulate matter and nitrogen oxides
are considered of secondary importance. A brief review of methods
for combatting pollution is also included.
14892
Durrant, T.
TOWARDS CLEANEH SKIES. Aeroplane, 116(2966): 16, 20-21, Aug.
21, 1968.
The main contaminants produced by aircraft burning kerosene fuels
are exhaust smoke, unburned hydrocarbons, carbon monoxide, and
sulfur and nitrogen oxides. The presence of smoke in the engine
exhaust is a failure to control carbon production or consumption
processes or both, but experience has shown that elimination
of smoke is difficult at increased engine pressure ratios. By
changing combustion-chamber design and including airspray fuel
injectors, it is expected that new large transport gas-turbine
engines will have a barely visible level of smoke emission.
Annular chambers now being introduced have a smaller flame tube
wall surface area and therefore use less cooling air than the
tuboannular system. Consequently, unburned hydrocarbon and
carbon monoxide concentrations at idle and taxi conditions will
be lower on new engines than on those currently in service. The
most difficult contaminants to control are nitrogen oxides,
although concentrations are low compared with the automobiles.
Intensive investigations are being conducted to reduce these
emissions; it is suggested that one method of reducing their
concentration may be by running with a richer primary
combustion zone, although this is contrary to smoke-control
requirements and would involve design compromises.
15310
Friedlander, S. K. and J. H. Seinfeld
A DYNAMIC MODEL OF PHOTOCHEMICAL SMOG. Environ. Sci. Technol.,
3 (11) :1175-1181, Nov. 1969. 19 refs.
A simplified kinetic scheme is proposed as a dynamic model for
photochemical smog reactions. Unlike previous diffusion models,
which have been concerned with nonreacting pollutants, the
formulation of this model takes into account both the chemical
reaction and turbulent mixing aspects of the photochemical smog
problem. In the first part of the paper, a simplified kinetic
mechanism is presented for the formation of photochemical smog
from nitric oxide and unburned hydrocarbons. In the second part,
diffusion models based on the general eguation of conservation of
species are discussed. The model is a combination of the
transport and chemical kinetic equations and predicts the
behavior of a reacting pollutant cloud. The roles of sulfur
oxides and aerosols are not considered. Calculations basedon the
180 HYDROCARBONS AND AIR POLLUTION
-------
model lead to concentration dependence on time, similar in fora
to the experimental results for laboratory reaction chanbers. The
Lagrangian similarity hypothesis for the diffusion of nonreactive
components is extended to reacting species to take into account
the effect of atmospheric mixing. This leads to a set of
ordinary differential equations for the reactive species of the
type describing a chemical reactor of variable volume. as a
preliminary example of the application of the aodel, a
calculation was made for a single bimolecular reaction.
15352
Scofield, Francis
AIS POLLUTION FROM SOLVENTS. Am. Chem. Soc., Div. Org. Coatings
Plastics Chem., Preprints, 29(2):393, 1969. (Presented at the
158th Meeting of the Am. Chem. Soc., Div. Organic Coatings and
Plastics Chemistry, New Xork, Sept. 1969.)
The organics and plastics coatings industries are among the major
contributors to photochemical snog. A significant contribution
arises from the evaporation of organic solvents. The reactivity
of solvents varies over a wide range and a substantial reduction
in the amounts of reactive materials contributed by solvent
evaporation may be achieved without a corresponding reduction
of the total solvents. The only effective way to date of
establishing the relative reactivity of these compounds is an
empirical method which exposes a mixture of the solvent and
nitrogen oxides to irradiation. A number of photochemical
reactors of this type are in operation and many of them provide
for the direct determination of eye irritation. It is very
difficult to predict reactivity of individual solvents, and
since there is a wide variety of reactions which may take place,
not all of which lead to eye irritation or other damaging
products, even a high degree of reactivity is not necessarily
an indication that a solvent is objectionable. An accepted
order of reactivity by classes of compounds is that, in general,
olefins are the most reactive and should be controlled at the
lowest level. Aromatic compounds are less objectionable but
still require control, while most oxygenated and aliphatic
materials are relatively innocuous and under present conditions
do not appear to require control. However, within each of these
classes a wide range of reactivity can be encountered. (lore
information in this area is necessary in order to guide the
writing of future regulations and possibly the revision of current
controls.
15367
Eberan-Eberhorst, R.
PROBLEHS OF EXHADST GASES FROH OTTO ENGINES - RESULTS OF OTHERS
AND ORIGINAL MEASUREMENTS. (Probleme der Abgase von Ottomotoren
Ergebnisse fremder und eigener Messungen). Text in German.
AT2 (Automobiltechnische Zeitschrift) (Stuttgart), 70(2):40-«5,
1968. 19 refs.
Tests of the Otto engine on a dynamometer showed that all carbon
monoxide and hydrocarbons can be easily eliminated in the load
B. Emission Sources 181
-------
and speed range of the engine. Only when the engine acts as a
vehicle brake does the hydrocarbon (CH) content exceed 1000 ppm.
Optimum spark timing and diminishing of the valve overlap
reduces the idle rpm to 730 with a CH content of less than
1000 ppm. Above 1550 rpm, extremely high CH concentrations of
more than 5000 ppm occurred. This phenomenon was studied in
greater detail. For this purpose, the combustion pressure
in the cylinder was induced, and PV diagrams were obtained with
a piezo quartz pressure pick-off and a cathode ray oscillograph
at 2000 rpra and slowly closing throttle valve. Initially the
combustion was rather complete, as the emission concentrations
of 0.15% CO by volume and CH less than 30 ppm, show. By
further closing of the throttle valve, the pressure decreased
from 1.0 to 0.28 kg force/sq cm, combustion became markedly
irregular but still complete, and emissions decreased. At an
underpressure of i»88 mm Hg in the intake pipe, the engine began
to act as a brake, but the emissions were still only 50 ppn CH.
Upon closing of the throttle valve to 8 degrees, emissions
increased to KOOO ppm CH. There are two ways to avoid high
emission concentrations of CO and CH caused by misfiring;
namely, by prevention of the development of toxic exhaust
components in the engine, or by destroying the toxicants in the
exhaust system. A review of the major methods developed by the
various automobile manufacturers is given. In conclusion,
a regulator is described which maintains a constant fuel supply
and a constant underpressure in the intake pipe during all
operating states.
15392
^Bean, Samuel L. and Howard Wall, Jr.
ATflOSPHERIC EMISSIONS FROM HYDROCHLORIC ACID MANUFACTURING
PROCESSES. Public Health Service, Durham, N. C., National
Air Pollution Control Administration and Manufacturing Chemists
Association, Washington, D. C. , Pub. AP-5<*, 59p. Sept. 1969.
15 refs.
The basic characteristics of the manufacture of- hydrochloric
acid are presented, including growth rate of the industry,
manufacturing processes, product uses, and the number of
producing plants in the United States. The Mannheim, Hargreaves,
and Laury processes are discussed with respect to their
historical interest, even though the number of plants that use
them is decreasing. The concentration of hydrogen chloride
emitted to the atmosphere is usually less than 0.5* of the tail
gas volume emitted to the atmosphere. Emissions from hydrochloric
acid plants are adversely affected by high temperatures in the
absorption system, improper balance of absorption area and
contact time, faulty equipment, and inadequate tail gas scrubbing
systems. No correlation exists between exit gas volumes and
plant production rates because of the diverse methods of
production. However, smaller volumes of exit gas usually show
greater hydrogen chloride concentrations due to the varying
amounts of inert materials in this gas stream. Thus, the amount
of hydrogen chloride emitted in pounds per ton of acid produced
gives a more accurate description of the contaminant emissions.
The hydrogen chloride emissions are usually reduced by scrubbing
in a packed tower located behind the process tower. Water
scrubbers can reduce the concentration to less than 0.1 pound
per ton of acid produced. Hydrogen chloride absorption systeas
182 HYDROCARBONS AND AIR POLLUTION
-------
include falling film and adiabatic absorbers. Other
contaminants such as chloride, chlorinated organic compounds
and other hydrocarbons emitted to the atmosphere are mentioned.
15399
NATURE AND CONTROL OF AIRCRAFT ENGINE EXHAUST EMISSIONS.
Northern Research and Engineering Corp., Cambridge, Mass.
Contract PH22-68-27, Report 113U-1, 388p., Nov. 1968. 208 refs.
The results of a study of the emissions of air pollutants by
aircraft engines in the U. S. are presented. The study included
four aspects of aircraft engine emissions: the nature of aircraft
engine emissions and quantities emitted, the effects or impact
of aircraft engine emissions on the populace, the reduction of
emissions, and governmental control of the emissions. In
addition, emission control requirements were considered and
guidelines developed for determining the degree of control
needed. The principal conclusion drawn from the study is that the
nature and extent of air pollutant emission by aircraft can be
assessed with sufficient accuracy to allow a comparison between
aircraft and other emissions sources. On that basis, aircraft
are a snail contributor of pollutants in metropolitan areas.
In the vicinity of air terminals, however, the density of
pollutant emission by aircraft and the resulting pollutant
concentrations are comparable to emission densities and
concentrations in adjacent communities of the same pollutants
from other sources. Thus, the principle impact of aircraft
is local in nature and is expected to become more severe in
future years. It is also likely that aircraft emissions will
constitute a more significant portion of community-wide pollutant
loadings as new aircraft are introduced and as emissions from
other sources are reduced. It is further concluded that whenever
a reduction of aircraft emissions becomes desirable, a variety
of practical approaches exist to reduce both the quantities of
pollutants emitted and their impact on the community. Specific
conclusions relative to emission reduction and emission control
are presented. A program of activity with regard to aircraft
emission is recommended. All emission data is tabulated.
15769
Pursall, B. E.
POLLUTION IN ROAD TUNNELS. Consulting Eng., 33 (8):57-58, Aug.
1969. 9 refs.
The sources and causes of the build-up of pollutants in road
tunnels are discussed. The two main sources of poisonous exhaust
gases are gasoline and diesel engines. Diesel exhaust emits a
smaller percentage of carbon monoxide than the gasoline engine,
but because the diesel engine is larger, it emits a larger voluae.
The diesel engine also produces more nitric oxide and nitrogen "
peroxide. Vehicles emit up to 50% more carbon monoxide on the
up-gradient than on the level; on the down gradient, they emit
HQ% less. In calculations for two-way tunnels, an average figure
for carbon monoxide emission can safely be taken. Tests showed
that the amounts of carbon monoxide and other combustion
B. Emission Sources 183
-------
products vary directly with speed. Differences in tunnel
concentrations for the Sumner Tunnel in Boston and the Central
Tunnel in London were attributed to different vehicle speeds and
variations between British and American vehicles and fuels. The
variations resulted in higher concentrations of lead and
hydrocarbons in the Sumner Tunnel; carbon monoxide concentrations
were similar for average daytime periods in both tunnels. The
effects of carbon monoxide, nitrogen oxides, and lead compounds
are briefly discussed. It was concluded that if the concentration
of CO can be diluted to below 100 ppm, the concentration of
nitrogen oxides and other gases should be relatively harmless.
Visibility should also be satisfactory under these conditions.
In a 2 way tunnel, the maximum ventilation rate was calculated
to be 200 cu ft/min/ft. With one way traffic, ventilation is
induced from the portals by the moving vehicles, but additional
artificial ventilation would be necessary when the traffic is
stopped or moving slowly. In most large tunnels, alarms operate
if the CO concentration exceeds 250 ppm.
15883
Kinkier, G. t., S. S. Lestz, W. E. Meyer
EXHAOST GAS SAHPLING TECHNIQUE FOR RELATING EMISSIONS AND CYCLE
CHARACTERISTICS. Preprint, Society of Automotive Engineers, Inc.,
New York, 5p, 1968. 10 refs. (Presented at the National Fuels
and Lubricants Heeting, Tulsa, Okla., Oct. 29-31, 1968, Paper
680770.)
For investigating whether or not there is a correlation between
the irregularity of combustion processes in spark engine ignitions
and undesirable emissions, a sampling system was developed which
collects bag samples from specified cycles only. It consists of
an anolog portion for obtaining pressure and rate-of-pressure
change signals, a digital logic portion for discriminating between
signals according to selected criteria, and an electrically
actuated sampling valve in the engine exhaust system. Since
signal analysis and discrimination are instantaneous, gas sampling
is done during the exhaust stroke of the same cycle for which
the logic generated the command to sample. An analysis of the
total unburnt hydrocarbons from 600 bag samples shows that there
is a separation in the amount of unburnt hydrocarbons according to
:the magnitude of the peak rate of pressure change. The separation
is repeatable for a given engine condition and supports the
assumption of a relationship between exhaust gas composition and
the physical characteristics of the cycle. (Author abstract
modified)
15996
Campbell, Frank Leslie and Willis Conrad
INSECTICIDE COHPOUND AND HETHOD OF DISPENSING AN INSECTICIDE.
(Assignee not given.) U. S. Pat. 2,381,257. 2p., Aug. 7, 1945.
(Appl. July 24, 1941, 3 claims).
The invention provides an insecticide in a liquid or solid form
which decomposes at atmospheric pressure and room temperature, to
release a toxic gas for the destruction of insects. The method
184 HYDROCARBONS AND AIR POLLUTION
-------
consists of exposing insects to a compound of sulfur dioxide
and acetone which decomposes to release sulfur dioxide and acetone
vapors in a toxic volume. Other compounds for use as
insecticides include S02 and ethylene oxide, S02 and dioxan, S02
and trimethylamine, S02 and triethylamine, and 502 and
dimethylaniline. The invention makes it possible to pack and
ship sulfur dioxide in a readily usable form.
16017
Kurtzweg, J, A. and D. «. Heig
DCTBRHINING AIR POLLUTANT EMISSIONS FROM TRANSPORTATION SYSTEMS.
Preprint, Association for Computing Machinery, Nev York, N. Y-,
22p., 1969. 18 refs., (Presented at the Association for
Computing Machinery, Symposium on The Applications of Computers
to the Problems of an Urban Society, New York, Oct. 2U, 1969.)
Internal combustion vehicles are a source of five major air
pollutants: carbon monoxide, hydrocarbons, nitrogen oxides,
particulates, and sulfur oxides. Because vehicular pollution
is essentially a problem of urbanization, analysis of its
source must be carried out on a metropolitan or smaller scale.
A method is presented for estimating the quantity and spatial
distribution of motor vehicle emissions in a metropolitan area
from established speed-emission relationships and transportation
study data. On-the-road sampling of exhaust emissions from
a representative sample of automobiles indicates there is a
consistent relationship between average route speed and the
quantity of carbon monoxide and hydrocarbons emitted.
Metropolitan transportation study agencies developed detailed
descriptions of future street and highway networks. The
Seattle, Washington, metropolitan area was selected for the
initial application of the vehicle emission estimation method
because of the transportation characteristics of the area and
the nature of the transportation study data available.
Emissions are calculated for two 1985 street and highway
networks, one based on the land use pattern predicted if
existing trends within the region continue, and one based on a
pattern which will exist only if certain development policies are
implemented. The calculated vehicular emissions and estimated
emissions from non-vehicular sources can be used with a
meteorological diffusion model to predict future air quality.
(Author abstract modified)
1602U
Styles, B. E-, J. Vrebos, and 0. lawther
PUBLIC HEALTH ASPECTS OF AIB POLLUTION FKOB DIESEL VEHICLES.
Preprint, World Health Organization, Geneva, Switzerland,
36p,, Aug. 18, 1966. 8 refs. (WHO/4P/67,28.)
Diesel and gasoline engines are compared with regard to
differences between their design and operating characteristics
and differences between their exhaust products. Satisfactory
combustion in a diesel engine does not require the production
of an explosive admixture of vaporized fuel and air. Complete
combustion is largely a natter of ensuring a correct pattern of
B. Emission Sources 185
-------
fuel spray from injector nozzles and a suitable degree of air
swirl by proper combustion chamber design. In a diesel working
at rated capacity, an excess of oxygen is always present during
combustion and, in a properly maintained engine, the exhaust
seldom contains more than mere traces of carbon monoxide, even
though a haze of smoke is produced. As shown by analyses of
smoke from intentionally maladjusted engines, diesels are not
a major source of polycyclic hydrocarbons, while diesel soot has
produced tumors in laboratory animals, no excess of lung cancer
has been found among workers exposed to diesel exhausts. Diesel
engines can be developed which meet emission standards such as
those contained in the Belgian 'Royal Decree of 196U. Properly
adjusted and maintained, these engines will not emit dangerous
or dirty smoke. The use of smoke meters is recommended to check
diesel smoke. Included in the appendix are measures taken to
reduce air pollutio by diesel buses and coaches in London.
16125
Hasek, V.
DEPOSITION OF COAL AND PITCH DUST ON AND AROUND COKE OVENS.
Coke Chem. (USSR) (English translation from Russian of: Kaks i
Khim.), vol. 4:29-31, 1969.
The results of investigations on the amounts of dust, the
composition, and the method of dissemination in pitch-coke
batteries and coke oven batteries was described. Host of the dust
deposited on the pitch-coke batteries was in the form of spherical
particles with a minimum diameter of 0.3-0.5 micron. The majority
of the dust particles which settled on coke-oven batteries had a
characteristic crystalline structure. Samples of dust deposited
on the top of and in the vicinity of five coke-oven batteries vere
analyzed. No striking differences were obtained under winter and
summer conditions. Homogeneous samples were collected to
determine the contents of vitrain, clarain, durain, fusain, coke,
and other constituents. It was established that the major
component is vitrain. Results showed that with increasing
distance from the battery, the deposits contain larger
proportions of particles below 0.2 mm and smaller amounts of
3,1-benzopyrene. The highest content of 3,U-benzopyrene was
found in the pitch and dust on and around coke-oven batteries.
The amount of dust deposited on the coke-oven batteries depends
on the charging procedure. Observations showed that ramming
reduces dust emissions and loose charging increases the emissions.
The results support the conclusion that strict adherence to
battery operating instructions secures a major reduction in dust
pollution. A further improvement can'be effected by adopting the
smokeless charging technique.
16135
Hashimoto, nichio and Masahiro Fujiwara
EFFECTS OF .AUTOMOBILE EXHAUST GAS EHISSION ON AIR POLLUTION.
(Jidoshahaikigasu no taikiosen eno eikyo). Text in Japanese.
Jidosha Gijutsu (Automobile Eng.), 23 (11):1151-1163, 1969. 25
refs.
186 HYDROCARBONS AND AIR POLLUTION
-------
In 1968, automobile production in Japan was almost U,100,000 cars,
a million more than produced in Best Germany, and second only to
the United State's production of 11,000,000 cars in the same year.
While the United States, West Germany, France, England, and
Italy show no annual increase, automobile production in Japan is
increasing at an annual rate of 25-30%. If this rate is
maintained, the approximate annual output should match that of
the Onited Stated by 197U. It is difficult to imagine the extent
of pollution by automobile engine exhaust when automobile
production in a country approximately the area of California
approximates that of the United States. Based on the results of
measurements in several cities, the following aspects of pollution
by automobile exhaust are discussed in detail: carbon monoxide
emissions; dust fall including lead and pyrene; photochemical
contaminations; hydrocarbon emissions; and odors. The toxicity of
air pollutants for humans and vegetation is also examined.
Although work on carbon monoxide began late in Japan, air
quality criteria are now being formulated with respect to carbon
monoxide. Air pollution from automobile exhaust is found to be
increasing by approximately 10-15%. It is hoped that control
policies will be in effect before automobile production reaches
one car for every two individuals.
16263
ludwig, John H.
SEMINAB OH AI? POLLUTION BY HOTOB VEHICLES. Preprint, Assistant
Commissioner, Science and Technology, Washington, D. C. 6
-------
16298
Fiala, Ernst and Ernst-Georg Zeschmann
ANNOYANCE CAUSED BY ODOROUS EXHAOST GASES. (Laestigkeit VOD
Abgasgeruch). Text in German. VDI (Ver. Deut. Ingt.) Z.
(Duesseldorf), 109(2«):1139-1141, 1967. Srefs.
The intensity of odors caused by automobile exhaust gases was
evaluated by measuring the odor intensity of dilutions of the
exhaust gas with fresh air that exceeded the odor threshold.
The tests were performed with a water-cooled four-cylinder, four-
stroke Otto engine. The measurements were based on the following
considerations. At low traffic density i.e., on well-ventilated
streets, the exhaust gas odor is not noticeable; the odor
threshold is not reached. With increasing traffic density, i.e.,
less ventilation, odor threshold is exceeded. The mass flows
emitted under the latter condition were indicative of the dilution
which was the measure for the odor intensity. The results showed
the familiar independence of carbon monoxide and hydrocarbon
concentrations from engine operating state. Test personnel could
smell the exhaust gas independently of the operating state at
800- to 1000-fold dilution. The carbon monoxide and hydrocarbon
concentrations at the moment the odor threshold was exceeded were
between 1 and 100 ppm and 0.6 to 8 ppm, respectively. Addition
of air in the exhaust system reduced the concentrations, but
increased the odor intensity.
16318
Eisebrough, Robert and Virginia Brodine
HORE LETTERS IN THE HIND. Environment, 12(1):16-26, Jan.-Feb.
1970. 15 refs.
The accidental release to the atmosphere of toxic polychlorinated
biphenyls (PCB) is discussed. Like DDT, PCS contains chlorine,
hydrogen, and carbon; is soluble in fat and insoluble in water;
and is extremely persistent in the environment. It is found in
natural and synthetic rubber, electrical products, floor tile,
printer's inks, coatings for paper and fabrics, brake linings,
paints, varnishes, asphalt, adhesives, and resins. In addition,
PCB is used to suppress the vaporization of chlorinated
insecticides. Its detection began in 1967 with the identification
of 1980 ppm PCB in the fat of North American peregrine falcons and
17,000 ppm in the fat of Swedish white-tailed eagles. It is
unlikely that the insecticide is the only source of contamination.
Other suspected sources are stacks of the plant manufacturing
polychlorinated biphenyls, industrial wastes, and the gradual wear
and weathering of PCB-containing products. Little data is
available about PCB in people, but a sampling of mothers1 milk in
Berkeley and Los Angeles showed average concentrations of 0.06 ppm
of whole milk. Small amounts were present in a sample of cow's
milk and higher concentrations in fish eaten by humans.
Establishment of tolerance limits of PCB in food is clearly
essential. It is also necessary to identify the sources of the
environmental PCB residues and to trace the paths by which they
move through the environment.
18s HYDROCARBONS AND AIR POLLUTION
-------
16352
Del Vecchio, V., P. Valori, C. fielchiorri, and A. Grella
AROBATIC POLYCYCLIC HYDROCARBONS FODND IN THE EXHAUST GASES OF
ENGINES HUN ON GASOLINE AND LIQUEFIED PETROLEUM GAS.
(Idrocarburi policiclici aromatic! nei gas di scarico di motor!
alimentati a benzina e a gas liguido). Text in Italian. Nuovi
Ann. Igiene Hicrobiol (Rome), 20 (2) : 174-190, Harch-April 1969.
33 refs. (Presented at the Symposium on the Chemical Aspects of
Air Pollution, Cortina d'Ampezzo, July 9-10, 1969.)
Liguefied petroleum (LP) gas is seldom used for motor vehicles
on the highway, even though its use would reduce air pollution
problems, but is used in industry and commercial establishments
to operate the motors of lift trucks for loading, unloading,
transporting, and stacking goods. A series of experiments were
made with a Towmotor model lift truck, type 161 HF, with a
4-cylinder continental motor, 2400 rpm, lifting power 2000 kg.
The truck was operated for a total of 8450 hours during the
experiment. The fuels used wery 84 NO gasoline and propane-
butane (LP gas). It was operated under simulated operating
conditions with a load of 1000 kg as well as in an idling state
at approximately 500 rpm. The exhaust gases were collected,
dried, and filtered through glass wool and cellulose triacetate.
Aspiration was by means of a vacuum pump, with a constant flow of
2813 1/m. Extracts were prepared in a Soxhlet apparatus with
cyclohexane for a period of 20-30 hours. The extract was
adsorbed in a column of alumina and separated chromatographically.
Quantitative determinations of aromatic polycyclic hydrocarbons
(APH) were made by spectrophotometry. The gasoline exhaust
contained 19 identifiable APH, some of which were known to be
carcinogenic. The LP gas exhaust contained 18 APH. Qualitative
differences were very slight, but the APH emissions from the
gasoline exhaust were considerably higher in guantity, with the
exception of fluorene, anthracene, and antanthrene. Tests with
an idling motor at 500 rpm produced considerably less
concentrations of the individual hydrocarbons for both fuels,
with the exception of naphthalene.
16494
Akamatsu, Isao, Hiroshi Kamishina, and Yutaka Kimura
DEODORIZATION OF EXHAUST GAS IN KRAFT PULPING. (PAHT I). ON THE
FORMATION OF HALODOROUS COBPOBENTS IN KRAFT PULPING. (Kurafuto-
parupu seizo kotei haishutsu gasu no mushuka (1 ho): Jokai-chu
ni okeru akushu-seibun no seisei ni tsuite). Text in Japanese.
Kami-pa Gikyoshi (J. Japan Tech. Assoc. Pulp Paper Ind.), 22(8):
406-410, Aug. 1968. 3 refs.
The formation of malodorous substances, methy mercaptan (HBA) and
-dimethyl sulfide (DBS), in the process of kraft pulping was studied
in two types of Japanese pulp woods: softwoods (red pine, cedar and
Japanese cypress) and hardwoods (beech, poplar, cherry and pasania
oak). Alkaline (Na20) and sodium sulfide (NaS) were added to a
400 g dried pulpwood block in an electric autoclave and boiled for
5-1/2 hours at 185 C. Then 5 cc of exhaust gas (raw blow gas) was
sent into the cyclone-separator (a cylinder with the diameter
B. Emission Sources 189
-------
of 3 cm and the length of 18 cm) and analyzed for malodorous
substances (HHA and DMS) by the use of Yanagimoto GCG-5DH type
gas chromatograph. Larger amounts of MMA and DMS, especially
HBA, were produced by pulping hardwoods than by pulping softwoods.
In pulping the same wood type, the amount of malodorous substances
was increased with the increase of cooking hour and temperature,
and the concentration of NaS. The white,lauan produced the same
malodorous substances in quality and quantity as obtained in the
pulping of Japanese hardwoods. When the pulping was performed by
a batch system, the concentration of DMS was decreased to trace
with the depression of pressure in the autoclave.
16«98
Heuser, A. R.
TRENDS IN AIR CONSERVATION IN THE GRAPHIC ARTS INDUSTRY. Gravure,
1969:22-25, «5-U8, Feb. 1969. (Presented at the Fifth Graphic
Arts Conference of the Technical Association of the Pulp and Paper
Industry, Chicago, Nov. 1968.)
The main sources of pollution from processes involving printing
and coating operations is exhaust from ovens and dryers. The
principal contaminants are hydrocarbons from the solvents used
in the inks and coatings. In addition, there can be some
hydrocarbon residue from incomplete combustion of the fuel in
flame dryers and ovens, odors are also a problem, attributed
to complex organic products of cracking and partial oxidation
of resinous materials in solvents. In general, the solvents
themselves are not responsible for odor complaints. Solvent
emissions can be limited by direct-flame incineration or catalytic
combustion, the latter technique being the more economical.
Because of the possibility of catalyst poisoning or suppression,
catalytic combustion may not meet Los Angeles air pollution
regulations limiting solvent emissions to a maximum of 8% olefins
and 20% toluene. Direct-flame ionization has been approved by
the Los Angeles Air Pollution Control District. A newer approach
to curtailing emissions from graphic art processes involves the
use of inks and coatings which do not pollute air or require
expensive effluent treatment. Ways by which this goal might be
met are examined.
16526
Wheatley, G. A. and J. A. Hardman
INDICATIONS OF THE PRESENCE OF OHGANOCHLORINE INSECTICIDES IN
RAINWATER IN CENTRAL ENGLAND. Nature, 207 (U996) :«J86-«87, July
31, 1965. 5 refs.
Rainwater samples collected from a locality in central England
were analyzed for organochlorine insecticides by both thin-layer
and gas/liquid chromatographic techniques. Quantitative estimates
(90S for dieldrin, 70% for gamma benzene hexachloride (BBC), and
50% for DDT) were obtained by comparing the peak heights on the
gas chromatograms of samples extracted with hexane with those
given by standards prepared from analytical grade specimens of the
insecticides. All the rainwater samples examined yielded solutes
identical in behavior to gamma-BHC and dieldrin in both the
thin-layer and gas/liquid chromatographic systems. A solute
corresponding to the behavior of p,p' DDT was also detected.
190 HYDROCARBONS AND AIR POLLUTION
-------
The concentrations of the solutes varied from month to month
and appeared to be independent of the total monthly recorded
rainfall. It is concluded that apparent increases in residues
in untreated droplets could not be accounted for by fallout of
insecticide in the rain, since calculations showed that one part
of solute could deposit only 2.7 mg of solute per acre for a 21-in.
annual rainfall.
B. Emission Sources 19]
-------
C. ATMOSPHERIC INTERACTION
00139
E. R. Allen and R. D. Cadle
A STUDY OF THE EFFECT OF MOLECDLAH OXYGEN ON ATOMIC
OXYGEN-HYDROCARBON HEACTIONS. Photochem. Photobiol. 4,
979-87, 1965.
Investigations of the systems atomic oxygen-methane and atomic
oxygen-n-butane have been made, using techniques for producing
atonic oxygen in the presence and absence of ground state molecular
oxygen. The results indicated that the initial rate of removal of
atomic oxygen from both systems was accelerated by the presence of
molecular oxygen, whereas the initial rate of removal of
hydrocarbon, for n-butane, was affected little if at all.f*
00173
R. J. Engelmann, R. H. Perkins, D. I. Hagen, and W.
A. Haller
HASHOUT COEFFICIENTS FOR SEIECTED GASES AND PARTICULATES.
Battelle Memorial Inst., Richland, Wash., Pacific
Northwest Lab. (BNWL-SA-657,) (Presented at the 59th
Annual Meeting, Air Pollution Control Association, San
Francisco, Calif., June 20-24, 1966, Paper No. 66-118).
31 pp.
Precipitation scavenging is the primary cleansing mechanise for
airborne gases and fine particulates. Scavenging below cloud
base, called washout, acts to remove these from pollution clouds.
Advances in radiochemical techniques allow the measurement of
such washout coefficients during natural rain and snow. Washout
coefficients (fraction washed out per unit time) are presented for
several gases as a function of precipitation rate. Deviations
from theoretical predictions are discussed.lt
00177
H. Buchberg, M. H. Jones, K. G. Lindh, and K. W.
Hilson
AIR POLLUTION STUDIES WITH SIHULATED ATMOSPHERES. California
Univ., Los Angeles, Dept. of Engineering. (Eept. Ho,
61-14.) July 1961. 185 pp.
Part I of this report deals with the statistical relations
among interacting atmospheric variables. Also contained in this
report are the results of several auxiliary or supporting studies
as follows: Air Purification Studies; Development of an Eye
193
-------
Mask for the Heasurement of the Threshold of Eye
Irritation; Development of an Omnidirectional Solar Radiometer
for a Limited Spectral Region Centered about 0.36 microns; A
Comparison of Concentration and Duration as Measures of
Threshold for Eye Irritation; A Comparison of Threshold to
Eye Irritation Resulting from Reacted Air Mixtures Sampled
at Different Points in the Exposure System; A Comparison of
Odor Threshold and Eye Irritation Threshold for Formaldehyde,
Acrolein, and Ozone. (Author)**
002U2
W.W. Heck, C.S. Brandt, J.A. Dunning, F.L. Fox
ECOLOGICAL FACTORS INFLUENCING PLANTS AS MONITORS OF
PHOTOCHEMICAL AIR POLLUTION. Preprint. (Presented at the
59th Annual Meeting, Air Pollution Control Association, San
Francisco, Calif., June 20-24, 1966, Paper 66-48.)
The response of plant systems.to the oxidant complex of the air
must be interpreted in terms of the influence of the total
environment. Photoperiod, light intensity, carbon dioxide
concentration, soil conditions, time of day, plant age, and
frequency of exposures affect the response of pinto bean and
tobacco to ozone. Tobacco is suggested as a relatively simple
monitoring system for obtaining some data on photochemical
pollution. (Authors' abstract)*t
00302
A.. P. Altshuller
ATMOSPHERIC REACTION STUDIES RELATED TO AIR POLLUTION. Arch.
Environ. Health 8, 27-30, Jan. 1964.
Studies of air pollution in urban and adjacent rural areas by
particles and trace gases need to be related to studies of
composition of the earth's atmosphere. Han's activities generate
pollutants which in themselves or through photochemical reactions
contaminate the general atmosphere. Cooperative efforts need to
be made by air pollution and atmospheric science laboratories to
obtain monitoring data. Areas of such research in
measurement of pollutants and nonpollutants, .measurement methods,
instrumentation, and biological and chemical effects are reviewed
by the author. The proper selection of synthetic atmospheres
for laboratory studies so that real conditions are reflected is
emphasized. An important problem still requiring solution is the
obtaining of support, personnel, and facilities for research and
development on instrumentation for specialized applications.it
00344
W. L. Faith
RELATIVE REACTIVITY OF HYDROCARBONS IN PHOTOCHEMICAL SMOG
FOHHATION AND ITS PRACTICAL IMPLICATIONS. Preprint.
(Presented at the 59th Annual Meeting, Air Pollution Control
1,94 HYDROCARBONS AND AIR POLLUTION
-------
Association, San Francisco, Calif., June 20-24, 1966, Paper
No. 66-«0-)
Adequate and intelligent control of photochemical smog requires a
knowledge of the relative reactivity of the hydrocarbons emitted
from motor vehicles and a method of measuring them. An extensive
survey of the literature yields the following general
classification of hydrocarbons: (1) reactive (all olefins and all
aromatics except benzene and toluene) and (2) nonreactive (all
paraffins, acetylene, benzene and toluene). Hithin the olefin
series, there is a wide range of reactivity; ethylene is far less
reactive than other olefin species. In fact, ethylene provides a
good line of demarcation between reactive and unreactive
compounds, so far as photochemical smog formation is concerned. A
simple method of analysis that will distinguish between reactive
and non-reactive hydrocarbons is sorely needed. At present,
an instrument that would distinguish between olefins and
nonolefins would be useful. (Author)##
00345
J. C. Romanovsky, R. M. Ingels, and E. J. Gordon
ESTIMATION OF SHOG EFFECTS IN THE HYDBOCABBON-NITBIC OXIDE
SYSTEM. Preprint. (Presented at the Air
Pollution Control Assoc. Annual Meeting, June 20-24, 1966,
San Francisco, Calif., Paper No. 66-42).
The complex role of nitric oxide in photochemical snog has led to
conflicting conclusions concerning its relationship to end effects.
The confusion has not been dispelled by the tendency to employ
Kinetic parameters of the photochemical reactions accompanying the
formation of snog as indicators of the end effects. In an attempt
to resolve these differences a detailed study was carried out to
examine the effects of varying the concentrations and reactant
ratios of NO and "hydrocarbon" on a number of smog effects as
well as on various functions of the reaction rate. Hydrocarbon
components increasing in complexity from propylene through a
simulated auto exhaust to authentic auto exhaust were irradiated
in the presence of NO in large chambers instrumented for
measurements of numerous variables. Eye irritation was
measured using a selected panel of human subjects; formation of
ozone and formaldehyde was followed analytically. From other
analytical data it Has possible to derive half-lives for NO,
S02, and hydrocarbon, as well as maximum reaction rates for
propylene, either as the sole hydrocarbon or as a component of the
exhaust. The various dependent variables are presented as
functions of the reactant concentrations by means of contour
diagrams derived by computer treatment. The effect of
"hydrocarbon" and NO levels on smog effects are discussed; the
observed relationships between end effects and reaction rates are
considered. The study simulated the effects of varying degrees of
vehicular emissions control over one or both reactants and has a
bearing on the establishment of vehicle emission standards in
California. (Author)*t
C. Atmospheric Interaction 195
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00l»53
J.P. Detrie
(METHODS AND TECHNIQUES CABBIED OUT IN FB4HCE IN THE FIGHT
AGAINST ATMOSPHERIC POLLUTION.) Methodes et Boyens en
Oeuvre en France pour Lutter centre la Pollution
Atnospherigne. Rev. Soc. Roy. Beige Ingrs. Ind. (Brussels)
No. (5):207-217, May 1966. Text in French
Legislative proposals put into effect in the Paris region over
the last five years are reviewed. There is a close liaison
established between private organizations, representing the
hygiene specialists and private industry and public powers.
Studies carried out to determine the extent of pollution, that is,
emission, dispersion, type of environment and its effect on
pollution, demonstrated the problems involved with means of
combating pollution. The solution cannot be found in
generalized formulas which are too often recommended, and which
mask the detailed effort necessary to obtain good carburetion
and combustion of fuels and proper construction of buildings
and eguipment. (Author summary)#*
OOU65
A.P. Altshuller
AN EVALUATION OF TECHNIQUES FOR THE DETERMINATION OF THE
PHOTOCHEMICAL REACTIVITY OF ORGANIC EMISSIONS. J. Air Pol-
lution Control Assoc. 16 (5):257-260, May 1966.
The concept that control of organic substances in emissions
should be based on the relative ability to cause the effects
associated with photochemical air pollution (reactivity) rather
than on gross emission levels has gained wide acceptance.
Two general types of reactivity response scales have been
proposed. One of these is based on rates of hydrocarbon
reaction or nitrogen dioxide formation. This scale covers a wide
range because of the very high rates associated with
olefins having internal dougle-bonds. The other scale is based
on product yields combined with biological measurements. This
type of scale is considered superior to one based on rates. This
latter scale covers a narrow response range because olefins with
internal double bonds have only- slightly higher product yields and
biological effects than do other reactive olefins and
alkylbenzenes. Use of a response scale based on product yields
and biological effects also permits use of less detailed
instrumental procedures. A simple subrractive column technique
combined with a flame ionization analyzer should be sufficient
to estimate hydrocarbon emissions. Gas chromatographic analyses
of hydrocarbon emissions are of value when used with either type of
reactivity response scale. However, detailed gas chromatographic
analyses are essential for a response scale based
on rates. The response scale based on product yields and
biological effects indicates much less improvement in reactivity
from fuel composition changes than would be predicted fron a
response scale based on rates. The most desirable approach is
to use a variety of control and engine modification techniques
to reduce all reactive organics to the lowest level possible.tt
196 HYDROCARBONS AND AIR POLLUTION
-------
00502
H. J. Hamming, W.G. MacBeth, R.L. Chass
THE PHOTOCHEMICAL AIR POLLUTION SYNDROME AS EXHIBITED BY THE
ATTACK OF OCTOBER 1965. Arch. Environ. Health.,
14 (1) : 137-149, Jan. 1967. (Presented at the American
Medical Association Air Pollution Medical Research
Conference, Los Angeles, Calif., March 2-4, 1966.)
The photochemical air pollution syndrome which occurred on the
days of October 26, 27, 28, 1965, was typical and it followed
the pattern set by previous smog attacks. These factors
are: (1) low wind speeds to concentrate the pollution in one
area, (2) low inversion heights so that little vertical
mixing can occur to dilute the emitted materials, (3) a
trajectory which carries the emitted pollution to Los Angeles
Civic Center and to Pasadena and Azusa or Burbank in the
afternoon, and (4) sufficient sunlight to photodissociate
the N02 formed, and to form nitric oxide and atomic oxygen.
The results are high oxidant or ozone and large quantities of
sub-micron size particles. In addition, eye irritants and
"plant damaging" chemicals are formed. Some of these are, it
is believed, formaldehyde, acrolein, PAN, chemical free
radicals, other nitrates or nitroso compounds, and a peroxyformyl
activated complex. Authors present sixteen (16) charts and tables
to substantiate the events in this air pollution episode. They
include meterology, concentrations of various oxidants,
pulmonary blow resistance, and variations in eye irritation.#*
00510
M. Neiburger
METEOROLOGICAL ASPECTS OF AIR POLLUTION IN RELATION TO BIOLOGICAL
RESPONSES. Arch. Environ. Health 14(1):41-45, Jan. 1967.
(Presented at the American Medical Association Air Eollution
Medical Research Conference, Los Angeles, Calif., Mar. 2-4,
1966.)
This report presents a brief review of the meteorological
aspects of air pollution, as a background for the implications
they have on biological and medical effects. The
meteorological factors enter because they determine the rats
of diffusion of pollutants, and thus the concentrations of
contaminants in the air, given the configuration and intensity
of the sources. The two factors which enter are the wind velocity
and the vertical temperature gradient or lapse rate.
Meteorological considerations will have to enter into the
final determination of the air purity standards which will
have to be met. Much research will be needed regarding
the rates of diffusion from line and area sources, and
especially the rates of removal of pollution. Much data will
be reguired to define the air pollution potential of regions
throughout the world. But we cannot await the anwsers to
this research before requiring controls to the full extent
presently feasible. Regulations are needed to enforce liniting
every emission into the atmosphere to the lowest possible level,
at the same time as we push research and developemnt programs
seeking means of reducing further the contamination of the
atmosphere.ft
C. Atmospheric Interaction 197
-------
00602
J.N. Pitts, Jr., J.K. Foote, J.K.S. Wan
SOBE CORRELATIONS BETWEEN SPECTEOSCOPIC AND PHOTOCHEHICAL
PROCESSES. Photochenu Photobiol. Vol. «:323-333, 1965.
(Presented at the Photochemistry and Photobiology Symposium,
Fourth International Congress of Photochemistry and
Photobiology, July 26-30, 1961, Oxford, England.)
By applying the modifier 'Space' to the terms 'Photochemistry'
and 'Spectro-scopy' one implies a concern with electromagnetic
radiation of wavelengths less than that found at the earth's
surface and with energetic particles, particularly electrons.
It has been observed that for certain classes of organic
compounds useful empirical correlations exist between reactions
induced by electron impact, non-ionizing ultraviolet radiation
and ionizing radiation. These correlations allow qualitative
or semi-quantitative predictions of specific reactions and/or
reaction mechanisms which will occur during photolysis or
radiolysis, based on known optical or mass spectra. In accord
with recent spectroscopic evidence, benzene and toluene do not
significantly react photochemically in their first absorption
band (at about 2500 angstroms); however, they react with a quantum
yield approaching unity in their second and thired absorption
bands (at about 2000 and 1850 angstroms respectively). The
products of this decomposition are primarily carbon and/or
polymer which deposit on cell windows, however, small yields of
stable products have been isolated. Another example of this
extrapolation from one technique to another deals with the
correlation of cyclic elimination reactions observed in the
mass spectra, photochemistry and radiation chemistry of various
classes or organic compounds. Classic examples of this type
of reaction are the photolytic and radiolytic elimination of
olefins from esters and ketones having a hydrogen gamma to the
carbonyl group (i.e., the elimination of ethylene from ethyl
acetate and of propylene from methyl n-butyl ketone). Based
on mass spectral correlations with the above reactions, the
same type of elimination should be expected from a great
number of compuods which contain hydrogens gamma to unsaturated
groups. In those cases where the photochemistry or radiation
chemistry of these compounds have been studied, an intra-
molecular cycloelimination of olefin has been observed to be
an important process. It is suggested that mass spectra are a
useful diagnostic tool for at least gross predictions in
•space photochemistry' and 'space photobiology', as well as
in considering reactions of importance under primitive earth
conditions. (Author abstract)#*
00618
E. A. Schuck, J. N. Pitts, Jr., J.K.S. Han
RELATIONSHIPS BETWEEN CERTAIN HETEOBLOGICAL FACTORS AND
PHOTOCHEHICAL SHOG. Intern. J. Air Water Pollution Vol.
10(10):689-711, Oct. 1966. (Presented at Photochemistry
Symposium, Robert A. Taft Sanitary Engineering Center,
Cincinnati, Ohio, Apr. 20-22, 1961.)
By a method of averaging, involving a large amount of
atmospheric monitoring data, it has been shown that
198 HYDROCARBONS AND AIR POLLUTION
-------
interesting and perhaps valid information on the formation
and intensities of smog symptoms can be obtained.
For example, it has been shown that the concentration of
maximum daily oxidant is a function of day of the week
and that this function might be related to automotive
traffic patterns. Thus for certain time periods maximum
daily oxidant was at a minimum on weekends at stations in the
northern protion of the Los Langeles Basin (Burbank, Pasadena,
Azusa). During this same time period the maximum daily
oxidant was found to be at a maximum on weekends near
certain cities in the southern portion of the Basin (Inglewood,
Long Beach). These two distinctly different weekend patterns
correspond in part to the recreational activities of the
populace, and in addition, indicate that mixing is less than
complete in the Los Angeles Basin. In spite of this lack
of complete nixing the macimum daily oxidant at stations
within a 600 to 800 sguare mile area are directly proportional
to each other in a predictable fashion. The weekend
daily temperatures are also affected presumably by the same
factors which influence the weekend oxidant intensity. Changes
in inversion height and wind speed appear to account for
twofold changes in macimum daily oxidant values. Maximum
daily oxidant concentration was also found to be directly
related to the square root of light intensity with little
if any dependence on temperature. This study also indicates that
pollution levels are proportional to each other over large
areas of the Basin. The analysis of atmospheric data indicates
that variable hydrocarbon to oxides of nitrogen rations do exist in
the atmosphere and that there exists a dependence of atmospheric
smog symptom intensity upon this ratio.**
00629
P. Ausloos and S. G. Lias
H2S AS A FHEE-RiDICAL INTEBCEPTOB IN THE GAS-PHASE KADIOLYSIS
AND PHOTOLYSIS OF PKOPANE. J. Chem. Phys. Vol.
UH (2) : 521-529, Jan, 1966.
The gas-phase photolysis (1236 Angstrom units) and the gamma-ray
radiolysis of C3D8 has been investigated in the presence of
varying concentrations of H2S. Shen 10% or more H2S is
added to C3D8, the majority of the D, CD3, C2D3, and C2D5
radicals abstract an H atom from H2S to form HD, CD3H,
C2D3H, and C2D5H, respectively. The fully deuterated
molecules formed in these mixtures result from the uninolecular
elimination of a stable molecule from C3D8 or C3D8 (plus) and
from fast bimolecular processes such as ion-molecule reactions.
The mechanisms of the radiolysis and the photolysis proposed in
earlier studies have been re-examined in the light of the
information derived from the C3D8 - H2S experiments and of
some additional photolysis experiments on CD3CH2CD3 - NO
mixtures. The modes of decomposition of the neutral excited
propane molecule are indicated. The internally excited C2D1,
C2D5, C3D6, and C3D7 species formed in these primary
processes decompose to form D, CD3, C2D2, C2D3, and C2DU
unless they are collisionally stabilized. In the radiolysis of
C3D8 - H2S mixtures, yields of the free radicals can be
adequately accounted for by taking into account the modes of
fragmentation of the parent ion and of the excited propane. The
C2D5 (plus) ions are shown to react with H2S in part by the
C. Atmospheric Interaction 199
-------
deuteron-transfer reaction. The effect of pressure and the
effectiveness of HI as a free-radical interceptor in the
radiolysis have been examined. (Author abstract)#*
00757
A.P. Altshuller J.J. Bufalini
PHOTOCHEMICAL ASPECTS OF AIR POLLUTION: A REVIEW.
Photochem. Photobiol., Vol. 1, 97-TU6, 1965.
Materials that are emitted in the atmosphere are subjected to a
number of interesting and unusual reactions. These reactions
lead to many products whose deleterious effects have now been
recognized as one of the most pressing problems in urban areas
throughout the world. These effects can be observed in reduced
visibility, eye irritation, plant damage, cracking of rubber, and
corrosion of metals. This paper is concerned with the present
state of the problems in air pollution, with emphasis on recent
literature. The chemical aspects are covered in some detail
through 1963. The biological effects are surveyed more briefly,
with literature reviewed up to the fall of 1963.##
00773
J.J. Bufalini A.P. Altshuller
KINETICS OF VAPOR PHASE HYDROCARBON - OZONE REACTIONS. Can.
J. Chem. U3,2243-2250, 1965.
The reaction of nine olefinic and aromatic hydrocarbons with
ozone in the vapor phase have been investigated in static and
dynamic systems. Some of the rate constants for the olefin-
ozone reactions are in good agreement with previously published
data, whereas others are larger than values previously
reported. Rate constants for trans-2-bueene-, isobutene-, and
ethylene-ozone reactions were measured between 30 and 100 degrees
C. The activation energies for the reaction of ozone with
trans-2-butene, isobutene, and ethylene are 0.2 plus or minus 0.3,
2.8 plus or minus O.i», and U.2 plus or minus Q.U kcal/mole. In
general, the reactions of hydrocarbons with ozone are
nonstoichiometric. However, these reactions do appear to be
second order. The rates of reaction between alkylbenzenes
and ozone are too low to be of importance in air pollution
studies. (Author abstract)t#
00783
D.A. Lynn, B.J. Steigerwald, J.H. Ludwig
THE 1JOVEHBER-DECEHBER 1962 AIR POLLUTION EPISODE IN THE
EASTERN DNITED STATES. Public Health Service, Cincinnati,
Ohio, bSdiv. of Air Pollution. (999-AP-78) 196«. 28pp.
This report documents the subject "episode" with respect
to meteorology, air quality, and public reaction. Particulate
and gaseous air quality data are reported and discussed.
Meteorology and public reaction are discussed with reference to
BOO HYDROCARBONS AND AIR POLLUTION
-------
the Public Health Service program of Air Pollution
Potential Forecasts. Epidemiological aspects are not
considered. (Author abstract)t#
00789
J.N. Pitts, Jr., L.D. Hess, E. J. Baum, E.A. Schuck,
J. K. S. Han
THE TBANSFEH AND CONVERSION OF ELECTRONIC ENERGY IN SOME "HODEL"
PHOTOCHEHICAL SYSTEMS. Photochem. Photobiol., Vol. 4:305-21,
1965. (Presented at the Rapporteur Session, the Fourth
International Congress of Photobiology, Oxford, England,
July 26-30, 1964.)
Recent studies of the effects of molecular structure and
reaction environment on the mechanism of primary
photochemical processes involving transfer and conversion
of electronic energy in relatively 'simple1 organic molecules
are presented and discussed. A quantitative i.r.
spectroscopic method for studying intramolecular and intermolecular
photoprocesses of u.v. irradiated substrates dispersed in solid
alkali halide matrices at room temperature is described.
Current data for the substrates ortho-nitrobenzaldehyde,
anthracene and henzophenone—benzhydrcl are presented. A series of
'model' ketones containing cyclopropyl groups have been synthesized
and while their adsorption spectra are similar, the efficiency of
vapor-phase photodissociation into radicals is shown to be
strongly dependent on molecular structure. Butyrophenone and a
series of ring substituted derivatives have been photolyzed in the
liquid phase using the quantum yield of the photo-elimination of
ethylene (Type II split) as a "probe" to determine the effect
of substituents on the internal H atom abstracting power of the
excited carbonyl chromophore. Phi sub C2H4 is very
sensitive to ring substitution, dropping grom 0.24 in
butyrophenone to 0.20, 0.058 and 0.00 in the p-CH3, p-OCH3
and p-NH2 derivatives respectively, and to 0.00 in both ortho and
para hydroxy derivatives. This effect is correlated with their
absorption spectra in terms of the lowest states of these alkyl
aryl ketones. While several 'classic1 photochemical
reactions, unimolecular and bimolecular, proceed efficiently in
solid KBr matrices giving the sane product as in liquid systems,
the 'model' cyclopropyl compounds and the alkyl aryl ketones did
not undergo their usual intramolecular processes. Implications
of this molecular environment effect are pointed out. (Author
abstract)##
00834
C.S. Benson
ICE FOG: LOH TEHPERATDRE AIB POLLUTION (DEFINED WITH
FAIRBANKS, ALASKA AS TYPE LOCALITY). Alaska Univ.,
College, Geophysical Inst. Nov. 1965. 196 pp.
CFSTI, DDC: AD 631553
Ice fog crystals are an order of magnitude smaller than
diaaond dust, or cirrus cloud crystals, which in turn are
an order of magnitude smaller than common snow crystals
(0901, 0.1 and 1 to 5 mn respectively). The differences in
size are shown to result from differences in cooling rates over
C. Atmospheric Interaction 20]
-------
5 orders of magnitude. Most of the ice fog crystals have
settling rates which are slower than the upward velocity of air
over the city center. The upward air movement is caused
by convection cells driven by the 6 C "heat island" over
Fairbanks. This causes a reduced precipitation rate which
permits the density of ice fog in the city center to be three
times greater than that in the outlying areas. The inversions
which occur during cold spells over Fairbanks begin at ground
level and are among the strongest and most persistent in the
world. They are three times stronger than those in the
inversion layer over Los Angeles. Thus, the low-lying air over
Fairbanks stagnates and becomes effectively decoupled from the
atmosphere above, permitting high concentrations of all pollutants.
The combustion of fuel oil, gasoline, and coal provides daily
inputs of: U.I x 10 to the sixth power kg C02; 8.6 x 10 to the
third power kg S02; and 60, 46 and 20 kg of Pb, Br and Cl
respectively, into a lens-like layer of air resting on the surface
with a total volume less than 3 x 10 to the ninth power cubic
meter. The air pollution over Fairbanks during cold spells
couldn't be worse, because the mechanisms for cleaning the air
are virtually eliminated while all activities which pollute the
air are increased. (Author abstract modified)f#
00929
CONTINUOUS AIR MONITORING PROGRAM IN CINCINNATI, 1962-1963.
Public Health Service, Cincinnati, Ohio, Div. of Air
Pollution, (999-AP-21). Jan. 1965. 193 pp.
This report presents-results of the operation of the Public
Health Service Continuous Air Monitoring Program (CAMP) in
Cincinnati, Ohio, during 1962 and 1963. Data on atmospheric
levels of sulfur dioxide, nitric oxide, nitrogen dioxide, total
oxidants, total hydrocarbons, and carbon monoxide are
analyzed and discussed. The data are tabulated as hourly, daily,
and monthly mean concentration. Background information about
Cincinnati and descriptions of the instrumentation are included.
(Author abstract)*#
00935
J. N. Pitts, Jr., R. Simonaitis, and J. M. Vernon
LIQUID PHASE PHOTOLYSIS OF Y-BUTYROLACTONE. Tetrahedron
letters. No. 36:3209-3213, 1965.
In view of the variety of interesting photochemical reactions
reported for saturated eyelid ketones and acyclic esters and the
lack of similar studies on lactone, the authors have photolysed
representatives of the latter class of compounds and report here
preliminary results with-gamma-butyrolactone. Vacuum degassed
butyrolactone was irradiated-in a quartz cell (9 ml) with a*
Hanovia medium pressure SH lamp, and gaseous products were
separated by conventional high-vacuum techniques. The major
products, carbon monoxide, carbon dioxide, cyclopropane and
ethylene (relative amounts '2.5 : 0.9 : 0.9 : 1.0), were ' '-
identified by comparison of gas chromatographic retention* tines
(Hexadecane, 25 degrees) and mass spectra with those of authentic
materials. -In addition, traces of ethane, propane and 'propylene
were characterised by gas chromatographic comparisons.**
202 HYDROCARBONS AND AIR POLLUTION
-------
00952
A. C. Harkness and F. E. Murray
GAS PHASE OXIDATION OF METHYL SDLFIDE. Preprint. (Presented
at the 59th Annual Meeting, Air Pollution Control
Association, San Francisco, Calif., June 20-25, 1966, Paper
No. 66-58.)
Methyl sulfide and oxygen react explosively at temperatures as low
as 210 degrees. At 195 degrees, the nonexplosive 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
of initial methyl sulfide pressure. The activation energy of the
main stage is 42 kcal/mole. The extent of the initiation stage is
reduced by increasing oxygen pressure. The main oxidation
products are sulfur dioxide and carbon monoxide. Even with an
excess of oxygen not all methyl sulfide reacts. (Author
abstract)f#
01027
B. 3. Gordon
PHOTOCHEMICAL HEASUBEHENTS OF DLTBAVIOLET SDNLIGHT. Preprint.
(Presented at the 59th Annual Meeting, Air Pollution Control
Association, San Francisco, Calif., June 20-24, 1966, Paper
No. 66-38.)
Measurements of solar ultraviolet radiation intensity were made,
vising two photochemical reactions. These were the gas-phase bag
photolysis of N02 in nitrogen and the photoisoaerization of
o-nitrobenzaldehyde in liguid solution. Results of the two
methods were converted, as nearly as possible, to absolute light
intensities. The two sets were compared and, as applied, it
appears that the solution method is simpler and gives more
consistent results. It should be noted, however, that atmosphere
N02 will affect the two methods to different degrees. A
continuous recording actinometer based on the solution method was
developed and gave satisfactory initial trial runs.*#
01194
E. Grovenstein, Jr.
PHOTOCHEBICALLT INDUCED BEACTIONS OF ACETYLENES WITH AEOHATIC
COMPOUNDS (FINAL KEPT.) Georgia Inst. of Tech., Atlanta,
Engineering Experiment Station. Aug. 1965. 30 pp.
DDC: AD U709U6
Irradiation with ultraviolet light of a mixture of benzene and
acetylene under a variety of experimental conditions gave, at best,
only a trace of cyclooctatetraene. No photo-adduct could, be found
of acetylene with dimethyl phthalate, naphthalene, or anthracene.
Vinylene carbonate underwent no detectable photochemical
reaction with benzene. Chlorovinylene carbonate, however, upon
irradiation in benzene or cyclohexane solution undergoes reduction
to give vinylene carbonate in good yield. Benzene with a solution
C. Atmospheric Interaction 203
-------
of the monopotassium salt of acetylenedicarboxylic acid gives,
upon ultraviolet irradiation, a different product from that
obtained with dimethyl acetylenedicarboxylate. Naphthalene, upon
irradiation with a solution of dimethyl acetylenedicacboxylate,
gives a complex mixture of products which appear to be the result
of an initial 1,2-addition of the acetylenic ester to the various
aromatic multiple bonds of naphthalene. From the reaction
mixture a crystalline derivative has been isolated which seems to
have been detived from addition of dimethyl acetylenedicarboxylate
to the 1,2-position of naphthalene. Furthermore, vapor phase
chromatography (v.p.c.) provisionally indicates the presence of
dimethyl phthalate, dimethyl naphthalene-2,3-dicarboxylate,
dimethyl cycloooctatetraene-1,2-eicarboxylate, as well as
napthalene and dimethyl acetylenedicarboxylate in the purified
reaction product. Since it was demonstrated that all of the
naphthalene should have been removed by the purification process,
the v.p.c. results indicate that the naphthalene adducts are
undergoing pyrolysis under the conditions of the v.p.c.
analysis. Reaction schemes are proposed to account for the
observed products. Preliminary experiments show that
phenanthrene reacts readily with dimethyl acetylenedicarboxylate
upon irradiation with ultraviolet light. In experiments in which
benzophenone was added as a photo-sensitizer, benzophenone was
found to undergo addition of alcohol, especially methanol, to give
considerable amounts of mixed pinacol. (Author abstract)f#
012Ui»
J. J. Bufalini and J. C. Purcell
NITROGEN: FORMATION BY PHOTOOXIDATION OF ETHYLENE IN THE
PRESENCE OF ITS OXIDES . Science 150, (3700) 1161-2, Nov. 26,
1965.
The apparent lack of nitrogen balance for the photooxidation
systems cpntaining olefin and nitrogen oxides can be explained by
evidence for the production of molecular nitrogen; molecular
nitrogen was identified by gas chromatography and mass
spectrometry, (Author abstract)f#
0126«
F. C. Alley, G. B. Hartin, and W. H. Ponder
APPARENT RATE CONSTANTS AND ACTIVATION ENERGIES FOR THE
PHOTOCHEHICAL DECOMPOSITION OF VARIOUS OLEFINS . J. Air
Pollution Control Assoc. 15, (8) 348-50, Aug. 1965.
The photochemical reaction of various olefins and nitrogen dioxide
was studied under conditions of controlled temperature, pressure,
and humidity in a 200 liter stirred glass reactor. The
hydrocarbon concentration in the reactor during four and five hour
irradiation periods was monitored with a flame ionization
chromatograph. Reaction rate constants, based on three
consecutive first order reactions, were calculated for reactor
temperature of 20, 25, 30, and 35 degrees centigrade. Activation
energies for the three consecutive reactions were calculated from
the Arrhenius equation. Branched and straight chain olefins were
studied at initial concentrations of 5.0 to 10.0 parts per Billion.
(Author, abstract) #f
204 HYDROCARBONS AND AIR POLLUTION
-------
01K81
Nader, J. S. (ed.)
PILOT STtJDY OF ULTRAVIOLET RADIATION IN LOS ANGELES, OCTOBER
1965. (A REPORT ON CONCURRENT MEASUREMENTS MADE BY COOPERATING
ORGANIZATIONS BY VARIOUS METHODS.) Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution Control,
PHS-Pub-999-AP-38, 91 p., (Presented at the Fourth
International Biometeorological Congress, Rutgers Univ.,
New Brunswick, N.J., Aug. 26 - Sept. 2, 1966.)
Measurements of 300-380-nm UV radiation in Los Angeles were
conducted under varying conditions of smog environment, below and
above the urban smog layer, and at various elevations through the
smog atmosphere in October 1965. The UV energy incident on a
horizontal plane surface detector near ground level at solar noon
on a clear day (no smog) was 31 w/m square meter or 37% of the
maximum possible for that date based on the value of 85 w/sq m of
DV radiation entering the earth's atmosphere. Attenuation of
UV radiation varied with smog intensity. Transmission through
the atmosphere from 5700 feet (Mt. Hilson) to 350 feet
(Laboratory rooftop) above sea level, average through the day,
was 87% for a clear day and 65% for a moderate-to—heavy—smog day.
Outgoing radiation was significantly increased by the smog
environment. In heavy smog, values were higher by a factor of
about 2 than those obtained in a no-smog environment. Outgoing
radiation also tended to increase exponentially with elevation.
UV scatter or,transmission measurements appear to offer
potential as a sensitive method of monitoring environmental smog
levels as an alternative to visibility which is subjective and
semiquantitative. The high scattering capability of a snog
atmosphere points to the need of measurements of UV radiation in
all directions, particularly as this applies to photochemical
reactions in the atmosphere, and a correlation of such measureaents
with measurements of vertical components. (Author's summary)##
01501*
W. J. Hamming and J. S. Dickinson
CONTROL OF PHOTOCHEMICAL SMOG BY ALTERATION OF INITIAL REACT1NT
RATIOS. J. Air Pollution Assoc., 16 (6):317-323, June 1966.
A study of the variation in eye irritation with irradiation tine
demonstrates that the time at which eye irritation measurements are
taken is important in understanding the entire photochemical
mechanism underlying the smog problem in the summer in Los
Angeles. The data analyzed were obtained from 5 experimental
studies conducted under a variety of conditions. Analysis of the
data from chamber irradiation experiments indicate that eye
irritation is noted at the'same time as the max. concentration of
nitrogen dioxide. The chamber data have shown that the initial
concentrations of the 2 principal reactant contaminants,
hydrocarbons, oxides of nitrogen, and the relationship between
them, must be considered in studying the production of eye
irritation from photochemical smog. To determine how the initial
reactant concentrations affect the degree of eye irritation which
can be produced, the available data from several experimental
studies were analyzed.ft
C. Atmospheric Interaction 205
-------
01587
G.J. Doyle
MODEL AEROSOLS FOB ATMOSPHERIC SMOG. Stanford Research
Inst., South Pasadena, Calif., Southern California. 1961.
18pp.
One model reaction"for formation of aerosol in the atmosphere
requires the presence of sulfur dioxide at fractions of a part
per million in phbtoxidizing mixtures of olefin and nitrogen
oxide at part per million concentrations. An experimental study
of this type of reaction and the results to date are described,
with particular .emphasis on 2-methyl-2-butene as the olefin.ft
01602
E.A. Schuck
THE NATURE OF EYE IRRITANTS IS SMOG. Stanford Research
Inst., south Pasadena, South Pasadena, Southern California
Labs. 1961. 8 pp.
Three ppm of individual hydrocarbons were mixed in pure air along
with 1 ppm of nitric oxide or nitrogen dioxide. During the
subsequent two hour irradiation with near-ultraviolet light the
mixture was monitored with a long-path infrared spectrophotometer.
The major products formed by photooxidizing many individual
hydrocarbons were readily identified and their concentrations
measured. In general, it was found that most olefins react
rapidly and generate irritation while saturated hydrocarbons
are relatively unreactive and do not result in irritating
mixtures. In the absence of specific Knowledge of the types and
concentrations of the components of smog-producing
atmospheres, control of olefins rather than oxides of nitrogen
appears to be the more practical approach to control of eye
irritation. The effect of control measures on eye irritation
will be a function of several factors. Some of these factors
are: the olefin-to-oxides of nitrogen concentration ratio; the
type of olefin or olefin mixture involved, and the length
of irradiation time and intensity of sunlight. To the extent
that these auto exhaust mixtures are typical, it is concluded
that ethylene arid propylene are the most important precursors of
eye irritation in such mixtures.#t
01649
C. H. Nicol and J. G. Calvert
RELATIONS BETWEEN PHOTODECOHPOSITION MODES AND MOLECULAR STRUCTURE
IN THE SERIES'OF CARBONYL COMPOUNDS, N- C3H7COR. Preprint.
(Presented in part at the Gordon Conference on Organic
Photochemistry, Tilton, N.H., July 1965.)
The vapor phase photolysis of a series of carbonyl compounds of
general structure n-C3H7COH was studied at 3130 A as a
function of temperature and pressure. The R group was varied
in the series, H, CH3, C2H5, n-C3H7, iso-C3H7, n-CHH9,
206 HYDROCARBONS AND AIR POLLUTION
-------
iso-C4H9, sec-C4H9, tert-C4H9, in order to evaluate the
effect of structure upon the individual primary photodissociative
processes and the relationship between these processes. Quantum
yields of carbon monoxide and ethylene products were used as
neasures of the type I (n-C3H7 COB + h mu yields n-C3H7CO
+ E and n-C3H7 + COE) and type II (n-C3H7COB + h mu
yields C2HU » CH2=C (OH)E primary photodissociative modes
in the ketones. A number of correlations were noted between the
structural features and the efficiency of the Type II
rearrangement. One striking effect was the relation between phi
II and the extent of alkyl substitution on the alpha-carbon atom
of the E group. An empirical rule was formulated which relates
molecular structure and the phi II values for the n-propyl
ketones. (Author abstract)##
01650
B. E. Saltzraan , A. I. Coleman, and C. A. demons
HALOGENATED COMPOUNDS AS GASEOUS BETEOBOLOGICAL TEACEBS:
STABILITY AND ULTHASENSITIVE ANALYSIS BY GAS CHEOMATOGRAPHY.
Anal. Chem. 38, 753-8, May 1966.
Tracer compounds added to moving air masses are useful for
demonstrating the transfer of pollutants from one local area or
city to another. A study of gaseous compounds resulted in the
selection of three suitable materials: sulfur hexafluoride,
bromotrifluoromethane, and octafluorocyclobutane. These materials
are non-toxic, are rare in the atmosphere, and can be readily
dispersed from weighed tanks containing them in liguid form under
pressure. An appropriate mixture can be employed if necessary to
reduce possible errors caused by interfering emissions, and the
components in air can be determined with high sensitivity in a
single 10—minute run. An ultrasensitive gas chromatographic
procedure with an electron-capture detector was developed
which utilized carefully purified carrier gas and optimized
columns, detectors, and operating parameters. Sensitivity of
10 to the minus five power ppm was achieved for sulfur hexafluoride
without concentration of the sample. Convenient procedures for
sampling and calibration were established. Eeactivities
of these materials with ordinary atmospheric pollutants such
as automobile exhaust, hydrogen sulfide, nitrogen dioxide, ozone,
and sulfur dioxide were studied at various humidities, both with
and without irradiation equivalent to sunlight. Good stability
was indicated. Losses by washout due to rainfall appeared to be
negligible. These techniques should be very useful both for
tracing local emissions and for long—range meteorological studies
of movement of air masses. (Author abstract)##
01761
T. Kato
GAS CHBOMATOGSAPHY OF SMALL AMOUNTS OF HYDBOCARBONS IH THE
ATMOSPHERE. Nenryo Kyokaishi (J. Fuel Soc. Japan,
Tokyo) 45, (470) 406-13, June 1966.
Gas chromatographic analysis in practical air pollution research
was studied. Low temperature trapping and adsorption were most
important. In each method, sampling, concentration, G.C.
analysis and examples of the results were described. In the
C. Atmospheric Interaction 207
-------
former, sample air was introduced into a vacuum glass bottle,
which was evacuated through a concentration tube filled with
adsorbent and cooled with liquid oxygen'to -183 C, then trapped
pollutants were transferred to G.C. sampling tube and
analyzed. For total analysis of air sample, sample air was
introduced into the adsorption tube filled with charcoal, then
adsorbed pollutants were desorbed by heating to 350 C,
transferred to a G.C. sampling tube and chromatographed.
(Author summary)#f
01825
S. L. Kopczynski
PHOTO-OXIDATION OF ALKYLBENZENE-NITROGEN DIOXIDE MIXTURES IN
AIR. Intern. J. Air Water Pollution. 8, 107-20, 196«.
Measurements of the relative reaction rates of various
alkylbenzenes in photo-oxidative reactions with N02 in the air
are reported. The reaction rates are compared with the relative
basicities of the compounds. A partial analysis of the gas
phase and condensed phase products is also reported. It appears
that as much as 50 per cent of the reacted carbon atoms may be
contained in the condensed phase. The several irradiation and
analytical technigues employed are compared. The
photo-oxidation reactions of olefins and alkylbenzenes are
compared. Free radical chains appear to play a more important
role in the photo-oxidation reaction rates of certain alkyl-
benzenes than in the reaction rates of olefins. Hyperconjugative
interaction of the methyl groups with the aromatic ring is
proposed as a possible explanation of the order of reactivity of
various isomers of the methylsubstituted benzenes. (Author
abstract)##
01828
A. P. Altshuller, G. C. Ortman, B. E. Saltzman, and
R. E. Neligan
CONTINOODS MONITORING OF METHANE AND OTHER HYDROCARBONS IN
URBAN. J. Air Pollution Control Assoc. 16, (2) 87-91,
Feb. 1966.
Continuous measurements of total hydrocarbons (and other organic
substances) and of methane were made in Cincinnati and Los
Angeles for three-month periods. Some of the measurements' were
made during episodes of photochemical air pollution. Two
instruments, one for measurement of total hydrocarbons and the
other for methane, were operated in parallel. Both incorporated
flame ionization detectors having greater sensitivity than
commercial flame ionization instruments. The flame ionization
analysis for methane was made specific by use of an adsorbent
carbon column preceding the analyzer to retain all organic
substances except methane. Subtracting the methane concentration
values from those for total hydrocarbons gave nomethane
hydrocarbon concentrations. The data showed diurnal patterns of
concentrations of methane and nonmethane hydrocarbon's in the
atmosphere. Average hourly values for methane were
strikingly similar in Los Angeles and in Cincinnati (2.6 and
2,4 ppm, respectively); those for nonmethane hydrocarbons were four
208 HYDROCARBONS AND AIR POLLUTION
-------
times as high in Los Angeles (3.0 and 0.8 ppm, respectively).
A bimodal frequency distribution pattern of the concentrations
suggested that atmospheric ventilation was either good or poor,
with less than a random amount of time in intermediate stages.
The width of the methane frequency distribution peak was about
half the width of that for nonmethane hydrocarbons, indicating i
different and more constant source for the former. (Author
abstract)*#
01984
A. P. Altshuller and I. R. Cohen
STRUCTURAL EFFECTS ON THE RATE OF NITROGEN DIOXIDE FORHATION IN
THE PHOTO-OXIDATION OF ORGANIC COMPOUND-NITRIC OXIDE MIXTURES IN
AIR. Intern. J. Air Water Pollution, 7, 787-97, 1963.
The rapid conversion of nitric oxide to nitrogen dioxide occurs
in the presence of certain organic species and of ultraviolet
radiation below 4000 A. The reaction is an important and
critical step in the over-all reactions of organic compound-nitric
oxide photochemical systems. These systems in turn are an
important part of the reaction complex associated with the
photochemically initiated type of air pollution. The eye
irritation and plant damage effects found in photo-chemical "smog"
have been simulated by the irradiation of certain
hydrocarbon-nitrogen oxide systems (Leighton, 1961). Until
recently the available experimental data on the photochemically
initiated conversion of nitric oxide to nitrogen dioxide has been
restricted almost entirely to work on olefinic hydrocarbons
including isobutene, trans-2-butene, and 1,3-butadiene
(Leighton, 1961; Tuesday, 1961). Recently, preliminary work has
been reported on other organic species including the aromatic
hydrocarbons (Altshuller et al. 1962a). It was shown that a
number of dimethyl and trimethylbenzenes participate in this
reaction about as effectively as do the 1-alkenes and appreciably
more rapidly than tehylene. In the present work this study is
extended to additional aromatic hydrocarbons, aldehydes, ketones,
paraffinic hydrocarbons, and alcohols. Analyses for oxidant
concentrations have been made on some of the systems studied.
Some data have been obtained on the formation of aliphatic
aldehydes in the reactions of aromatic hydrocarbon-nitric oxide
systems, (Author abstract)##
02359
S.L. Kopczynski A.P. Altshuller
PHOTOCHEHICAL REACTIONS OF HYDROCARBONS WITH SULFUR DIOXIDE.
Intern. J. Air Hater Pollution, 6, 133-135, 1962
Gas mixtures of S02 and hydrocarbons n-butane, isobutane,
neopentane, 3-methyl-1-butene irradiated by either a mercury
arc or sunlamp, produced appreciable quantities of condensate
on the walls of the experimental flasks. A carbonyl band
was present at 5.7 microns. In several experiments with
isobutane as the hydrocarbon, a strong band at 5.7 microns was
observed along with other IR bands assigned to the acetone
molecule. A set of 3 strong bands in the 9.5 to 10 micron
region characteristic of methanol was observed also. At 1 ma
partial pressure of S02 and n-butane or isobutane, a slight fill
C. Atmospheric Interaction 209
-------
of condensate could be observed when the Hg arc was used, but
not when the sunlamp orovided the UV radiation. Acetone and
methanol were indicated by spectral data on the more dilute
mixtures. ,At concentrations of 0,05 to 0.1 mm, no film could
be detected from S02 and isobutane or 1-pentene mixtures
irradiated by sunlamp; with the Hg lamp only weak IB bands
could be obtained after 20 hours. Evidence indicates that
photooxidation of S02 in the presence of saturated hydrocarbon
at concentrations found in the atmosphere does not
significantly contribute to formation of aerosols in air
pollution situations in comparison with aerosol results
from other reactions involving S02 in combination with NO and
olefins.*f
02352
J.J. Bufalini A.P. Altshuller
SYNERGISTIC EFFECTS IN THE PHOTOOXIDATION OF MIXED
HYDROCARBONS;. Environ. Sci. Technol. 1, (2) 133-8, Feb.
1967.
Since there is considerable disagreement in the published -values
for rate constants for olefin-ratomic oxygen and olefin-ozone
reactions, the reality of the so-called excess rate has been
questioned. If the excess rate is not real, then the rate
of oxidation of a given olefin should depend only on light
intensity and N02 concentration. If a second olefin of
different reactivity is added to a given olefin, then no effect
other than the influence of different 0-atom and ozone
concentrations should .be observed on the given olefin and
the hypothesis that the principal mode' of disappearance of
olefins is due to 0-atom .and ozone reactions is correct. As a
test of this hypothesis, 1-butene was irradiated-at three light
intensities with N02, both alone and in the 'presence of trans-2-
butene and 1,3,5-trimethylbenzene separately.' Synergistic
effects were observed that could not be explained by 0-atom
and ozone reacrions alone. (Author abstract)#f
02U76
E. R. Stephens.
REACTIONS OF OXYGEN ATOMS AND OZONE IN AIR POLLDTION. Intern.
J. Air Water Pollution 10, 649-63, Oct. L1966 (Presented at
the Symposium on Photochemical Aspects of Air Pollution,
Cincinnati, Ohio, April 1965.)
' - i- .
The reactions of free oxygen atoms and ozone as they apply to air
pollution and the factors which govern' the oxygen atom and ozone
concentrations are reviewed. The role played by reactions of
oxygen atoms with oxides of nitrogen is discussed as it affects the
determination,ot light intensity by photolysis of nitrogen dioxide.
The realtionship of these inorganic reactions to the attack on
hydrocarbon molecules is discussed along with the various attempts
which have been made to account for the rate of disappearance of
hydrocarobon in terms of its reactions with oxygen atoms and ozone.
Since most of these attempts have indicated that these two
reactions fall short of accounting for the observed rate of-
reaction, it has been suggested that f ree jradical attack may play a
210 HYDROCARBONS AND AIR POLLUTION
-------
role. Some difficulties with this concept are pointed out.
Experiments on the reaction of olefins with ozone have produced
discordant results and are discussed. (Author abstract modified)*
02777
A. P. Altshuller, I. R. Cohen, and T. C. Purcell
PHOTOOXIDATION OF HYDROCARBONS IN THE PRESENCE OF ALIPHATIC
ALDEHYDES. Science 156 (3777), 937-9, (Hay 19, 1967). 1966.
A new group of gas-phase reactions has been shown to contribute
to the photooxidation of hydrocarbons. The photooxidation of
aliphatic aldehydes in the part-per-million range at wavelengths
below 31400 A produces intermediates that react with olefinic and
aromatic hydrocarbons. The reactions have been investigated with
laboratory ultraviolet radiation sources and solar radiation.
Although the reaction rates are slower than those
associated with the corresponding nitrogen oxide induced
photooxidations, the rates are significant in terms of the ti«e
scale of interest in urban atmospheric reactions. These results
may cause modifications of current considerations of whether
control of nitrogen oxides will effectively reduce photochemical
air pollution. (Author abstract)##
0306H
Cadle, R. D. and J. B. Powers
SOME ASPECTS OF ATMOSPHERIC CHEHICAI REACTIONS OF ATOMIC OXYGEN.
Tellus (Dppsala) , 18 (2): 176-186, 1966. UK refs.
Some features of atmospheric atomic oxygen chemistry that have
received little attention, that need to be re-evaluated in the
light of recent data, that have been studied in the author's
laboratory, or that encompass some combination of these three are
discussed. Newly-calculated values for the concentrations of
excited atomic oxygen below 100 km are so low that it is unlikely
that its reactions contribute appreciably to the concentration of
any atmospheric component in that region with the possible
exception of excited molecular oxygen. Reactions of ground state
atomic oxygen may constitute a sink for methane and a source of
sulfate in this atmospheric region. Many chemionization reactions
probably occur in the atmosphere, and three possible types are
considered in detail. (Author abstract)*#
03381
M. Neiberger, "Chairman."
THE DISPERSION AND DEPOSITION OF AIR POLLUTANTS OVER CITIES.
(Air Over Cities Sjrmp., Cincinnati, Ohio, 1961.) pp. 155-71.
HEW A 62-5
In setting limits for the control of pollution sources in
industrial and urban complexes, limits must not be established
solely on the basis of individual stacks and plants; the basic
concept must be the area-source strength, in terms of total
emissions per square mile, since the emissions from separate
C. Atmospheric Interaction 2V\
-------
stacks and plants are additive as the air moves across them
toward residential and commercial communities. The
dispersion of pollutants from vehicle exhaust along congested
streets and roads deserves attention. Such questions as the
influence of heat from motor and the motion of the vehicles need
examination. Studies of dispersion have generally assumed
flat uniform terrain and wind conditions in which the direction
is steady and the average speed is high compared to turbulent
fluctuations. Studies must be performed on the dispersion of
pollutants over an irregular somplex of buildings and under the
influence of wind conditions in which the average speed is low and
the magnitude of windspeeds in fluctuations is as great or greater.
(Author summary)#f
03673
Bainbridge, A. E. and Leroy E. Heidt
MEASUREMENTS OF METHANE IN THE TBOPOSPHEKE AND LOWER
STRATOSPHERE. Tellus (Uppsala), 18 (2):221-224, 1966. 18 refs.
Two profiles of air samples have been collected over southern
U.S.A. (30 deg N lat.) between ground level and 23 km and
analysed for methane. The results show, with increasing altitude,
a mixing ratio nearly constant to the tropopause and decreasing
rapidly in the lower stratosphere. The results suggest that the
trophsphere is the major region of destruction of methane.
(Authors' summary)ft
03858
A. P. Altshuller, S. L. Kopczynski, W. A. Lonneman,
T. I. Becker, B. Slater
t
CHEMICAL ASPECTS OF THE PHOTOOXIDATION OF THE PROPYLEtJE—
NITBOGEN OXIDE SYSTEH. Environ. Sci. Technol., .1 (11):899-914,
Nov. 1967. 29 refs.
Although it is not possible to fully represent all of the
diverse effects associated with photochemical air pollution
by studies of a single hydrocarbon, propylene was chosen as a
representative reactive hydrocarbon. The propylene-nitrogen
oxide or propylene nitrogen oxide-sulfur dioxide system when
irradiated reacts readily to produce oxidant, formaldehyde,
acetaldehyde, carbon monoxide, peroxyacetyl nitrate (PAN),
and methyl nitrate, along with light scattering, and causes ozone
and PAN-type plant damage and eye irritation. Thus, all of
the major "smog" manifestations are reproducible, but not
necessarily at the intensities experienced in the ambient
atmosphere. The chemical and physical measurements of the
photooxidation of propylene-nitrogen oxide or of propylene
nitrogen oxide-sulfur dioxide over a range of reactant
concentrations, at several light intensity levels, and under
static or dynamic flow conditions are reported. Biological
indicator measurement s will be reported in another paper.
(Authors' abstract, modified)##
212 HYDROCARBONS AND AIR POLLUTION
-------
03875
D. E. London
RBQOISBHENTS FOR SAFE DISCHARGE OF HYDROCARBONS TO ATMOSPHERE,
Proc. »a. Petrol. lust.. Sect. III. 43, 418-33, 1963.
(Presented at the 28th Hidyear Meeting, Aaerican Petroleum
last. Division of Sefining, Philadelphia, Pa., Hay 15, 1963.)
Current knowledge, opinion, and service experience relative to the
disposal of released hydrocarbons, is assembled with emphasis on
atnospheric discharge. Potential hazards to personnel and
equipaeat associated with the release of hydrocarbon vapor to the
atmosphere include: 1, ignition of outflow, either imaediate or
delayed; 2, explosive release of energy from delayed ignition; 3,
flaae radiation; 4, condensation of vapor; 5, noise; and, 6,
pollution. The present state of knowledge relative to these
hazards is discussed. This leads directly to an appreciation of
aspects where general knowledge, experience data, or fundamentals
are inadequate or totally lacking. The individual subjects
requiring attention are suaaarized. (Author abstract modified) **
OU245
N, A, Krylova
COLORIHETRIC AHD SPECTROPHOTOHETBIC DETERMINATION OF
PBENI1URBTHYI.ANE IN FACTORY AIB. Hyg. Sanit. 31, (8) 250-5,
Aug. 1966. Russ. (Tr.)
CFSTI: TT-51 160/7-9
Phenylurethylane solution boiled with an alkali hydrolyzes to
aniline and sodium acetate. Thus, the deteraination of
phenylurethylane can be based on the determination of aniline. In
the present work the diazotizing reaction of aniline was used and
followed by the reaction of the diazo coapound with alpha-
naphthylethylenediaaine. Colorinetric analysis was
recoaaended for separate investigations of the two substances,
phenylurethylane and aniline, when present together,
Spectrophotoeetric deteraination of phenylurethylane in samples
was also recoaaended. This aethod is non-specific as aniline
interferes by yielding an absorption aaximuis in the saae range.**
F. D. Krivoruchko
DETE8BINATIOS OF AERIAL COSCSHTRAXIOH OF DECOHPOSITIOS A8D
OXIDATIOB PRODOCTS OF CERTAIN ORGAKQALOaiHOH COHPOUHDS (TEA,
BEAC. 2IBA, ASD DIBAC). (Opredelenie prodaktov
raslozheaiya i okisleniya v vozdukhe nekotorykh
alyuainiiorganicheskikh soedinenii (TEA, DEAKhr TIB& i DIB—
AKh,) Hyg. Sanit. 31, (8J 256-9, Aag, 1966. Suss. (Tr,)
CFSTI: TT 66-51160/7-9
In connection with srtudies of working conditions in the
aanufactare of triethylalnainua {JEAJ, diethylaluainan chloride
(DBAC), triist>butylalaainua (TIBA) and diisobutylalaainua
chloride (DIBAC) it was necessary to determine health hazards in
C. Atroosphstjic Iniwactioa
-------
the factory air. Determination in air of substances formed by the
decomposition and oxidation of TEA, DEAC, TIBA and DIBAC
formed the purpose of the present work. Organoaluminum conpounds
in sealed glass ampules were used. Investigations were performed
in 100 1 chambers with a fan for uniform distribution of the
decomposition products from organoalunimum compounds. The
ampules with samples were broken with a special rod. The
breaking of an ampule was followed by the formation of a white
aerosol in the chamber (obviously, aluminum oxide) which persisted
for 1.5-2.5 hr and then was slowly deposited on the chamber walls.
Air samples were taken from the chamber at different time
intervals (from 2 min to 3.5 hr) . ' Aluminum oxide aerosols were
sampled on an ashless filter paper of "Blue Band" grade in a
Plexiglas cartridge. Samples for other toxic substances were
taken by menas of absorbers, placing filter paper in front of the
absorber -in order to exclude aluminum oxide. Investigations
showed that the processes liberated aluminum oxide aerosol,
isobutylene, lower and higher'alcohols, aldehydes, carbon monoxide
and hydrogen. -Moreover, the decomposition and oxidation of
DIBAC yielded hydrochloric acid aerosols while the decomposition
and oxidation of DEAC yielded ethyl Chloride.#f
OU933
Niemeyer, L. E. and R. A. McCormick
SOHE RESULTS OF (lOLTIPLE-TRACER DIFFDSION EXPERIMENTS AT
CINCINNATI- J. Air Pollution control Assoc., 18 (6):403-405,
June 1968. ' 7 refs. (Presented at the 60th Annual Meeting,
Air Pollution Control Association, Cleveland, Ohio, June•
11-16, 1967. Paper 67-86.)
A number of diffusion experiments during .near-neutral stability
conditions are described which utilize the simultaneous
dissemination of up to three gaseous and one particulate tracer
material. The gases are sulfur hexafluoride (SF6),
octafluorocyclobutane (CUF8), and bromotrifluoromethane
(CBrF3) . The fourth tracer was a particulate, zinc-cadmium
sulfide (ZnCdS), referred-to as FP. The magnitude and
sources of "non-meteorological" errors are analyzed with' respect
to a single experiment using but one tracer. The relation of
observed ground-level'concentrations out to distances of the
order 125 km from the source to those estimated by the
extrapolation of shorter-range experimental results is also
discussed. The magnitude of nonmeteorological errors in diffusion
experiments is shown to be as high as plus or minus 50%. The
primary causes for these non-meteorological errors lie in the
analytical techniques, the loss of particulate tracer" material,
sampling errors, and uncertainties in source strength.
Nevertheless, a limited number of long-range tracer experiments
demonstrate that both the'SF1 and FP tracer techniques can be,
used to obtain quantitative1 diffusion data over ranges (greater
than 100 km) for which precise knowledge is almost non-existent.t*
OU988
H. D. Cadle H. S. Johnston
CHEMICAL REACTIONS IN-LOS ANGELES SMOG. Proc. Natl. Air
Pollution .Symp., 2nd, Pasadena, Calif., 1952. pp. 28-3«.
214 HYDROCARBONS AND AIR POLLUTION
-------
Cheaical reactions in smog are either reactions between two
or more man-introduced contaminants or between an impurity
and the natural components of the atmosphere. This paper
discusses (1) certain well-known reactions which must certainly
occur, (2) experiments to determine the nature of other reactions
expected to occur under conditions which exist in the Los
Angeles atmosphere, and (3) speculations about some reactions
which may occur. Several investigators have discussed
certain types of reactions which possibly occur in smog.
Haagen-smit has suggested that reaction products of olefins with
ozone and oxides of•nitrogen in the presence of sunlight are
responsible for some of the unpleasant properties of smog.
Johnstone has discussed the oxidation of sulfur dioxide to sulfur
trioxide in the atmosphere, which would result in' the
formation of a mist of sulfuric acid. Blacet has proposed several
photochemical reactions which could contribute to the ozone
content of smog; in particular, he considered photoactivation
and photolysis of nitrogen dioxide, sulfur dioxide, and
aldehydes. ##
05575
G. P. Larson, J. E. Taylor, and W. J. Hamming
STUDIES OF POLLUTION LEVELS IN RELATION TO AIR MOVEMENT IN THE
LOS ANGELES ATMOSPHERE. Proc. Natl. Air Pollution Symp.,
3rd, Pasadena, Calif., 1955. pp. 33-1*2.
Sanples were collected in dustfall jars from a large number of
stations in the Los Angeles Basin. The results are plotted in
tons per square mile for S02, .salt, total dustfall, and water
insoluble solids. The results of a nitrogen dioxide survey are
also plotted showing surface trajectories for air, cross sections,
and area distribution. .Subsequent to these studies, 50.wind
stations were established throughout ,the basin making it possible
to demonstrate the effects .of two separate source areas on
adjoining areas. To determine the variations that could occur
during smoggy periods when one source area might influence the
other, the variations in air flow trajectory were.studied. CO,
nitrogen oxides, and hydrocarbons were measured hourly at several
locations in both areas. The oxidation of hydrocarbons to produce
eye irritation was also studied. These investigations illustrated
the importance of relating the air movement to the sources of
pollution, in order ,to anticipate influences that may be effected
in the surrounding areas. #f
05533
lltshuller, A. P., S. L. Kopczynski, W. Lonneman, and
D. Wilson
PHOTOCHEMICAL REACTIVITIES OF EXHAUSTS FROM 1966 MODEL
HOTOHOBILES EQUIPPED TO REDUCE HYDROCARBON EMISSIONS. J. Air
Pollution Control Assoc. , 17 (11) :734-737, Nov. 1967.
(Presented at the 60th Annual Meeting, Air Pollution Control
Jssociation, Cleveland, Ohio, June 11-16, 1967, Paper 67-6.)
In the summer of 1966, some automobiles from the Cincinnati phase
of the GSA study were used'in an irradiation chamber study to
evaluate the photochemical air 'pollution potential of
C. Atmospheric Interaction 215
-------
representative models of equipped and unequipped automobiles.
Only one set of automobiles, the unequipped Chevelles, produced
exhaust capable under irradiation of forming significant levels of
oxidant and PAN. Neither the equipped Chevelles nor any of the
Fords or Plymouths, whether equipped or unequipped, produced
exhaust having the characteristics necessary to form oxidant or
PAN upon irradiation. The eye irradiation level reported by the
panel upon irradiation of exhaust from unequipped Chevelles was
much higher than that produced by the irradiated exhausts fron any
of the other types of automobiles. Overall, there does appear to
be some small improvement with respect to eye irritation in
comparing equipped automobiles with unequipped automobiles. To a
large extent, the improvement in the air.pollution potential of
exhausts from equipped Chevelles compared to the unequipped
Chevelles can be attributed to the reduction in the hydrocarbon to
nitrogen oxide ratio. The irradiated exhaust from equipped
Chevelles, except for aldehyde levels, is about the sane in
photochemical air pollution potential as are the exhausts fron
unequipped Fords and Plymouths. Such irradiation chamber
measurements are related to exhaust reactivities. Hydrocarbon
reactivities can be obtained by direct measurement of reactive and
nonreactive hydrocarbons in the automotive emissions.##
05817
E. R- Stephens
THE REACTIONS OF AUTO EXHAUST IN SUNLIGHT. Preprint.
(Presented at a Session of the Conf. Air Pollution Research
on "Atmospheric Reactions of Constituents of Motor Vehicle
Exhaust," Los Angeles, Calif., Dec. 5, 1961.)
When auto exhaust is 'diluted with air and exposed to sunlight
chemical changes take place which-lead to a variety of noxious
products. Among these are eye irritants, plant toxicants, and
aerosols. These effects can also be observed when dilute
nistures of hydrocarbons, nitrogen oxides, and sulfur dioxide with
air are irradiated. A number of the noxious products have been
identified. Ozone and a new "series of compounds called the
peroxyacyl nitrate's (PAN) are the principal plant toxicants
formed by this reaction. The various members of the PAN family
are powerful eye irritants as are the formaldehyde and acrolein
produced in this oxidation reaction. The formation of products
such'as PAN and alkyl ni'trate indicates the presence'of organic
free radicals since these compounds most probably arise through the
reactions of the appropriate radicals with nitrogen dioxide. The
corresponding reactions with nitric oxide probably lead to its
oxidation to nitrogen dioxide, a phenomena which is observed and
which is required to account for the formation of ozone.
(Author abstract)*t
05818
E. R. Stephens, W. E. Scott, P. L.^Hanst,• and H. C.
Doerr
RECENT DEVELOPHENTS IN THE STDDY OF THE ORGANIC CHEMISTRY OF THE
ATHOSPHERE. Preprint. (Presented at a Session on Smoke and
Fumes, 21st Midyear Meeting, ((American Petroleum Inst.,
Division of Refining,^Montreal, Canada)), May 16, 1956.)
216 HYDROCARBONS AND AIR POLLUTION
-------
ft long-path IB cell, with which it is possible to detect many
compounds in the air at concentrations in the parts-per million
range, is being used to study reactions of air pollutants. Field
studies of the Los Angeles smog by other investigators have
shown that photochemical reactions caused by sunlight play an
important role in its development. In the laboratory it has been
demonstrated that 03 is formed when mixtures of N02 and an
organic compound in air are irradiated with artificial sunlight.
This paper presents the results of further studies on this and
other reactions of air-pollution chemistry. IE analysis of the
products of the photochemical reaction between N02 and an organic
compound frequently reveals, in addition to bands of known
compounds, several unidentified absorption bands which apparently
belong to a single compound produced in significant guantity.
Although this compound is unstable, moderately pure samples of it
can be condensed if the reaction products are drawn through a cold
trap. Physical and chemical properties of this condensate,
referred to as compound X, are consistent with the belief that it
is an acyl-nitrogen compound, but its structure is not
unequivocally determined. The importance of compound X in an
explanation of the chemistry of the atmosphere is stressed. 03 is
formed when compound X is irradiated, with or without added
gasoline. 03 formation is slower with added gasoline, perhaps
because the olefins present in the gasoline react with some of the
03. 03 is also formed when nbutyl nitrite is photolyzed in 02.
The rate of formation of 03 was only slightly changed when S02
was present in an irradiated mixture of olefin and N02. Since
the S02 disappeared very slowly, it was concluded that neither
the 03, the free radicals, nor any peroxides which are formed will
oxidize S02 to S03 at a significant rate. (Author abstract
modified) f# '
06013
M. Neiburger
METEOROLOGICAL ASPECTS OF OXIDATION TYPE AIR POLLUTION. (In:
The Rossby Memorial Volume.) California Univ., Los
Angeles, Dept. of Meteorology. 1959. pp. 158-69.
The replacement of coal by petroleum products as an energy source,
instead of eliminating air pollution, has led to a new type of air
pollution characterized by the presence of oxidizing substances,
chiefly ozone, and the occurrence of eye irritation, damage to
vegetation, and reduction to visibility. It has been shown that
photochemical reactions involving hydrocarbons and nitrogen dioxide
in concentrations of a few parts per million can produce all these
manifestations. The photochemical reactions require the
combination of (1) sources of reagents, (2) conditions which
prevent their dispersal, and (3) adequate solar radiation. The
tremendous concentrations of automobile traffic, the exhaust froa
which is estimated to contain 7 percent of the hydrocarbons put
into the fuel tank, in all metropolitan centers in the U.S.
constitute sources which are at least as large as industrial
sources (refineries). However, only on the subtropical west
coasts of continents do the meteorological conditions for
accumulation of pollutants, namely persistent light winds and
temperature inversions, occur consistently together with adequate
solar radiation. The outstanding example of this combination is
Los Angeles, California. Studies of the relationship of air
trajectories to the smog manifestations in Los Angeles are
C. Atmospheric Interaction 217
-------
presented. These studies demonstrate the contribution of
automobile exhaust as a principal source. (Author'.s abstract) M
06235
Goetz, A. Stoeber, W. and T, Kallai
SYNERGISTIC PPOPEKTIES OF AEROSOLS (FINAL, PBOGPESS KEPT. JAN. 20,
1961-Nov. 15, 1961) California Inst, of Tech., Pasadena,
U9 pp. Nov. 15, 1961.,
The general subject of this Report is the interaction of air-borne
participates with gaseous trace components of the atmosphere which
leads to their accumulation upon these nuclei and causes what is
commonly called "aerosol formation". An understanding of these
processes is important because this accumulation of irritating
substances may produce their synergistic intensivation, and the
growth of these particulates increases their capacity for diffuse
light scattering and causes the well-known visibility restriction
by smog-like aerosols. The studies reported center on the physical
aspects of aerosol formation, particularly on those resulting froa
photochemical reactions between N02 and olefinic hydrocarbons.
Instrumentation and methods, especially developed for the synthetic
production of such aerocolloid systems, are described in detail —
as well as the procedures resulting in the guantative size and Bass
distribution of such aerosols. Experiments of exploratory nature
are discussed which demonstrate that su ch reaction products form
temporary condensates on artifically introduced particulates
whenever present during photoactivation.
06«82
J. R. Hicks
IMPROVING VISIBILITY DURING PERIODS OF SOPEBCOOLED FOG. Army
Cold Regions Research and Engineering Lab., Hanover, N.H.
(Rept. No. 181.) (Dec. 1966). KO pp.
CFSTI, DDC: AD 6U8 «8H
Six tests of dispersal systems using propane were conducted in
Hanover, New Hampshire during winter 1964-65 and a like number
in Greenland during summer 1965 mainly on supercooled fogs and in
a few instances when air temperatures were within the lower 2
meters at or slightly above freezing. Propane was introduced into
the fog,as a liquid aerosol to induce spontaneous nucleation either
by cooling or by. clathrate reaction which may be important in fog
modification. The tests show that liquid propane will.improve
visibility in fogs, is safe to use, and no standby time is needed.
The system may be permanently installed with,either radio or
manually controlled valve units, and is expensive, a cost of $20/hr
estimated to keep an airport approach zone clear of fog. Details
of the individual tests conducted are given. The dispensing
apparatus, flammability tests, and the theory of formation, growth,
and precipitation of ice crystals, thermal reaction, and the
clathrate concept are discussed.<(Author summary)#f
*18 HYDROCARBONS AND AIR POLLUTION
-------
06632
A. Goetz and S. Pueschel
BASIC MECHANISMS OF PHOTOCHEMICAL AEROSOL FORMATION. Atmos.
Environ. 1, 287-306 (1967).
A photochemical reactor was applied to studies of the effects of
sulfur dioxide humidity, and order of mixing of reactants on the
photochemical production of aerosol from 1-octene and nitrogen
dioxide in air. The effects of all three parameters are complex
but explainable from a few reasonable assumptions, the most
important of vhich is probably that initial contact between the
aerosol nuclei and the more polar reactants has a governing effect
on the nature of the product. The experimental results presented
are obviously still lacking in sufficient detail for formulation
of an adequate description of the complex reaction patterns which
lead to the formation of photochemical aerosols in the presence of
S02 under various humidity conditions. Nevertheless, the data
definitely indicate that the presence of stable particulates is
a dominant factor, not only as centers of accumulant formation,
but also as loci for the concentration of reactant gas molecules
(H20, NOx, S02) in their immediate environment. The
subsequent photoactivation will thus be more efficient at these
centers than in the free volume between them. The existence of
such localized statistical "order states" appears to be the most
likely interpretation for the effect of the contact sequence order
between reactants and particles.#t
06994
S. Hillman, G. Pressman, P. Harneck
OZ.ONOSPHERIC MODIFICATION BY MISSILE EXHAUST. Geophysics
Corp. of America, Bedford, Mass. (GCA Technical Eept.
No. 62-14-G. Scientific Kept. No. 9-) 65 pp. (Dec. 1962).
A possible consequence of the increased launching of large
rocket missiles is the large-scale local or worldwide
modification of the atmosphere, in particular the occurrence of
perturbations that might disturb the existing equilibria by
causing chain, cyclic, or catalytic processes. This report
considers these possible missile exhaust chemically induced
changes in the ozonosphere, the lower reactive portion of the
atmosphere. The possibility of chain, cyclic or catalytic
processes initiated by one of the components in a rocket's
exhaust trail that might cause appreciable changes in the
composition of the atmosphere is studied. Chain, cyclic, and
catalytic type processes are of greatest interest since
destruction (or creation) of ozone on the basis of 1 molecule
of ozone per molecule of initiating material would require
immense amounts of material released into the ataosphere. In
particular, possible reactions that occur when large
quantities of OH or H radicals are uniformly released into the
atmosphere at a height of 30 kms from hydrocarbon - lox
systems are considered. Suggestions for experimental work are
made in order that some of the preliminary estimates nay be
rendered less tentative. The results obtained indicated that
large scale perturbations of the ozonosphere are possible under
certain circumstances.#t
C. Atmospheric Interaction 2V9
-------
07257
Khan, A. U., J. 8. Pitts, Jr., and E. B. Smith
SINGLET OXYGEN IN THE ENVIRONMENTAL SCIENCES: THE ROLE OF
SINGLET MOLECULAR OXYGEN IN THE PRODUCTION OF PHOTOCHEMICAL AIR
POLLDTION. ((Environ. Sci. Technol.)), 1 (8):656-657, Aug.
1967. 14 ref.
CFSTI; DDC 675 969
A new mechanism is proposed to explain the rapid conversion of NO
into No 2 with a concurrent disappearance of hydrocarbons and
appearance of oxidants in photochemical air pollution. Singlet
oxygen generated by triplet energy transfer from strongly
absorbing polynuclear aromatic hydrocarbons to normal oxygen
produces excited singlet molecular oxygen which attacks olefins to
give unstable peroxides. A mechanistic chain is set up involving
free radicals generated by decomposition of these peroxides. &
solution of differential equations relating to the proposed
mechanism yields a set of rate-time curves for NO-N02-03 which
have the same general characteristics as those observed in actual
smoggy atmospheres. .The presence of singlet oxygen in urban
atmospheres has potentially great implications in the
environmental sciences. (Authors' abstract)##
07518
Yantovskii, S. A., I. Yu. Sidorina, and M. V. Chernyak
CONDITIONS OF SAFE OXIDATION OF TOLUENE BY ATMOSPHERIC OXYGEN.
Text in Russian. Neftekhimiya, 6 (1):105-111, 1966. 22 refs.
Engl. transl. Intern. Chem. Eng., 7 (1):144-1U9, Jan. 1967.
The maximum permissible amount of oxygen and the limiting
temperature to assure safe conditions for the liguid-phase
oxidation of toluene at pressures from 1 to 20 atmospheres was
determined. In order to assure safe conditions for the
liquid-phase oxidation of toluene on an industrial scale it is
necessary to maintain minimum oxygen,concentration after the
reactor at about 6%.. In order to maintain a constant safe
concentration of the toluene + air mixture in the reactor, in
which the amount of oxygen can be brought up to 21%, it is
necessary to maintain the temperature above the limiting
temperature. At 10 atm. the temperature of the reactor should not
be less than 130 deg. This value is 35-45 deg below the oxidation
temperature of toluene, which is recommended for the optinuB
conditions.t#
09U30
Liberti, Arnaldo and Giuseppe Devitofrancesco
EVALUATION OF SULPHUR COMPOUNDS IN ATMOSPHERIC DUST. In:
Air Pollution. Proceedings of the Symposium on the
Physico-chemical Transormation of Sulphur Compounds in the
Atmosphere and the Formation of Acid Smogs. Organisation for
Economic Co-operation and Development, Paris Directorate for
Scientific Affairs, Paper 6, Dec. 1967, p. 17-51.
Z20 HYDROCARBONS AND AIR POLLUTION
-------
Extensive research on the physical constitution and chemical
composition of atmospheric dust and physico-chemical transformation
of sulphur compounds is discussed. Surface area was determined
for dust collected in various Italian cities by using a,gas
adsorption technique. The surface area was found to be;about
6,2 sq. m./g. Volatile compounds were analysed by infrared
spectroscopy. C02, CO, CH4, NH3, N20, nitro-compounds,
and ethylene were detected. Sulphur content of atmospheric
dust was determined by combustion and the sulphate by extraction
with dilute mineral acid. No detectable amount of sulphur
dioxide and of free acidity was found.##
10018
Fensterstock, Jack C. and Robert K. Fankhauser
THANKSGIVING 1966 AIR POLLUTION EPISODE IN THE EASTERN DNITED
STATES. Public Health Serivce, Durham, N.C., National Cen-
ter for Air Pollution Control, Publication N/. AP-45, 45p,
July 1968, 12 refs.
The Thanksgiving 1966 Air Pollution Episode in the Eastern United
States is documented in terms of daily meteorology and ambient air
quality. Analysis of the available air quality data indicates that
the Air Pollution Potential Forecast Program (APFP) of the Public
Health Service and Weather Bureau did forecast the stagnation.
Heteorological data for selected cities were based on the diurnal
average tenperature, cloud cover, afternoon mixing depths, average
wind speed through mixing depth, ventilation, resultant wind
direction and the average surface wind speed. Air quality
measurements on the gaseous pollutants sulfur dioxide, oxides of
nitrogen, hydrocarbon and carbon monoxide were made daily. Suspende
and settling particulate of solids and liquids were also measured
diurnally. The high level of air pollution in the eastern U. S.
during the period Nov. 24 through 30, 1966, created adverse health
effects. Researchers in New York City found an increase in the death
rate of approximately 24 deaths per day during the period.
11004
Schmidt, F. H.
HETEOROLOGICAL ASPECTS OF ATHOSPHERIC POLLUTION AND ATMOSPHERIC
CHEHISTRY. Atmos. Environ., 2(4):423-426, July 1968.
Discussions are made in this report on the following topics:
network of stations for measuring background pollution; sampling
techniques from the meteorological point of view; meteorological
factors influencing the dispersion of atmospheric pollution;
boundary layer observations; special pollutants; forecasting
pollution problems.##
11052
R, 0. Weedfall, B. Linsky
A MESOCLIHATOLOGICAL CLASSIFICATION SYSTEH FOR AIR POLLUTION
ENGINEERS. Preprint, West Virginia Univ., Morgantown,
Dept. of Civil Engineering, 59p., 1968. 21 refs. (Presented
C. Atmospheric Interaction 221
-------
at the 61st Annual Meeting, Air Pollution Control
Association, St. Paul, Binn., June 23-27, 1968, Paper 68-53.)
A method of deriving 3 air pollution potential indexes based on
selected climatic data and meso-climate topographic factors has
been defeloped, through not yet adequately field tested, for use
by engineers in choosing between alternate factory sites.
Three indexes, one for general air pollution, one for
photoreactive air pollutants, and one for fog-reactive air
pollutants, the latter two based on the first one plus sunshine
and humidity fa'ctors respectively, are presented. These indexes
vary with locations, not with air pollutants or time. Weaknesses
and possible uses of the various stagnation indexes are discussed.
(Authors' abstract, modified)*#
11225
Hilst, Glenn E.
AN AIR POLLUTION MODEL OF CONNECTICUT. Preprint, Travelers
Research Center, Inc., Hartford, Conn., 33p., 1967.
(Presented at the IBM Scientific Computing Symposium,
Yorktown, Hgts, N. Y., Oct. 24, 1967.)
' V v
A working air pollution simulation model for the -State of
Connecticut is presented. The model is capable of simulating
air pollution concentration patterns for conservative pollutants
within the State of an hour-by-hour basis, given the tine and
space variability of the sources of 'that'pollutant within the
State, the flux of that 'pollutant across the State border (also a
time and space variable), and the time and space variability of
atmospheric flow and diffusion patterns within the State.
Reduced to its bare essentials, -the problem of predicting air
pollution concentrations in any arbitrary volume of the atmosphere
requires specification of the following factors: (1) The
immediate past trajectory of that volume of air - where has it
been? (2) The emissions of pollutant at each locality over which
the air has passed during the time of passage - how much
pollution has been injected into the volume? (3) The lateral and
vertical mixing of pollutants between this volume and adjacent
volumes-how much has each incremental input of pollutant been
diluted with air or other pollutants during its time of flight?
(4) The loss or alteration of the pollutant by chemical reaction,
deposition, sorption processes-how much of each incremental input
of pollutant -has been altered or lost during its time of flight?
The Connecticut model structures 'the first three of these
factors.##
111*79
Gusev, M. I. and R. S. Gil'denskiol'd, B. K. Baikov,
and E. V. Elfimova
DETERMINATIONS OF THE COMBINED EFFECT OF TOXIC SUBSTANCES IN
PREDICTIONS OF ATMOSPHERIC POLLUTION. ((Ob uchete summarnogo
deistviya tokischeskikh veshchestv pri prognozirovanii
zagryazneniya vozdushmogo basseina.)) Hyg. Sanit. (English
translation of: Gigiena i Sanit.), 33(4-6):88-80, April-June
1968, ((17)) refs.
CFSTI: TT 68-50449/2
222 HYDROCARBONS AND AIR POLLUTION
-------
Several investigations of the combined effect of several
pollutants present simultaneously in the atmosphere have been
recently made. :The results are listed. Trie data provide
convincing proof that as a rule the combined effect of toxic
substances in the atmosphere at the levels of liminal and
subliminal concentrations are in accordance with the principle
of simple summation. Data from many specialized institutes and
organizations suggest that in most cases calculations of the
expected atmospheric pollution are based on the maximum permissible
concentrations established for individual pollutants, so that the
results of mathematical determinations are compared only against
such standards. There is a definite gap between theory and
practice in the establishemnt of standards for atmospheric
pollutants and the application of its recommendations. It is a
matter of common knowledge that the implementation of the necessary
hygienic measures at an operating enterprise is undoubtedly more
complex and difficult than the prevention of marked air pollution
at the planning stage. 511 these considerations point to the
necessity for the planner to take account of the complex effects
on man of any combination of industrial pollutants discharged into
the atmosphere. The results of comprehensive investigations
of the reflex effects produced by combinations of substances and
the largely uniform findings of such investigations make it
possible to recommend, with a high degree of reliability, that for
practical predictive purposes the approved formula for calculations
of combined effects should be extended to all combinations of
substances present in discharges from a specific industrial
enterprise or a complex of enterprises.##
11019
Altshuller, A. P.
COMPOSITION AND REACTIONS OF POLLUTANTS IN COMMUNITY ATMOSPHERES.
Bull. Horld Health Organ. (Geneva), HO (4):616-623, 1969. 26
refs.
Data are presented showing the composition of gaseous and
particulate substances in community atmospheres, based on
measurements in various cities in the United States. Many of the
pollutants react further, usually to produce substances as
undesirable as the original ones, or more so; most of these
reactions involve thermal oxidation or photooxidation. Because
of the importance of considering air pollution on a regional
or even continental scale, a general framework of residence
times of pollutants is postulated: up to several days under
adverse conditions in many regions, but less than 2U hours
across large urban areas under more usual conditions of wind
speed and movements of weather fronts. Pollutants and other
atmospheric substances are categorized as either reactants-
those substances emitted directly into the atmosphere from
combustion, industrial, and biosphere processes; or products
such as nitrogen dioxide and sulfates. Some substances may fall
into both groupings. Data are given on rates of various
reactions, and the nature of the products is described. In
general, the measurements showed 1% to 15S conversions of
gaseous to particulate species on a long-term basis; rates
of conversion of nitrogen dioxide to nitrate were consistently
lower than those of sulfur dioxide to sulfate. Recent work on
particle size distributions of various metallic and non-metallic
ions in particulates in 0. S. cities is reviewed, with data
C. Atmospheric Interaction 223
-------
given in terms of mass median diameters. It is pointed out
that the ,biosphere is a source of, as well as a sink for,
pollutants, and that Durban levels of methane or nitrous oxide,
for example, reflect to a considerable extent biosphere, rather
than urban, emissions. Reactions originating in biosphere '
processes may contribute significantly to regional pollution,
particularly during periods of stagnation. The need for increased
emphasis on atmospheric investigations, as opposed to laboratory
work, and for improved sensitivity and specificity in monitoring
and sampling is discussed.
15308
Bockian, A. H., Frank Bonamassa, Herbert Faigin, and Herman
Pinsky
USE OF THE INTEGRATING NEPHELOMETER TO MEASURE AEROSOL FORMATION
FROM HYDROCARBONS. Preprint, California Air Resources Board,
Los Angeles, 9p., 1969. (Presented at the Am. Chem. Soc.,
158th Natl. Beet., New York, 1969.)
A recently-designed integrating nephelometer was used in
environmental chamber experiments to measure light scattering
resulting from the irradiation of different hydrocarbons in the
presence of nitric oxide at ppm levels. In some of the
experiments, 2 ml of gasoline were used; in others, several
individual alkene and aromatic components of gasoline, in
concentrations of 2 ppm each, were irradiated separately in the
presence of O.U ppm nitric oxide for about 5 hrs. Six ppn of
some alkanes found in gasoline were also allowed to react
individually with Q.U ppm NO. Several other experiments were
performed in which the hydrocarbon was allowed to react with
ozone in the dark. Agreement in the amount of light scattering
between duplicate runs was excellent. In several cases, large
amounts of aerosol were produced while the net oxidant
concentrations were at a fairly low level. It was shown that
some short-chain olefins, which may be very reactive in producing
oxidant and eye irritation, produced little or no aerosol; in
contrast, many paraffins which were found to be non-reactive
in eye irritation studies produced aerosol. A great many aerosol
producers contain seven or more carbon atoms and do not seem
to be restricted to any class of hydrocarbon; a possible
synergistic action between a short-chain high oxidant producer
and a large molecule which produces aerosol remains to be
investigated. The agreement between nephelometer readings
and visual measurements of visibility was excellent.
15712
WHERE DOES,IT ALL GO. Stanford Res. Inst. J., 23:«-8, Dec. 1968.
The Environmental Research Department of Stanford Research
Institute undertook a global study of the atmosphere. The world
and it's surrounding atmosphere were considered as a complete
system. Estimates were made of the amount of sulfur compounds,
nitrogen compounds, .organic compounds, and inorganic carbon
compounds discharged to the air by automobiles, home furnaces,
or power plants. Calculations were made of .the amount of the
material in the atmosphere. By comparing the two figures it was
possible to estimate how effectively nature removes pollutants
from the atmosphere. Included in the atmospheric balance was the
£24 HYDROCARBONS AND AIR POLLUTION
-------
amount of material contributed by nature since there are natural
sources for a wide variety of gaseous materials and particles
which are classed as air pollutants when they are emitted by man's
activities,
15729
Kozyrev, B. P. and V. A, Bazhenov
THE ROLE OF N20, CH4 AND CO IN ATMOSPHERIC ABSORPTION IN THE
INFRARED. (Sol* malykh atmosfernykh primesey v pogloshchenii
infrakrasnoy radiatsii). Text in Russian. Fix- Atm. i Okeana
(Moscow) , 5(7) :738-744, 1969. 8 refs.
The transparency of minor atmospheric impurities is interpreted
in the form of a function of the mass of absorbing gas divided by
the equivalent mass of gas needed for 50% absorption at a given
wavelength. This function fits available data with a scatter of
not more than 8X. When talcing into account, the non-uniformity
of the atmosphere by the effective mass method, the selection of
the fitting parameter (n) may lead to significant error in
calculating transparency (T). If the average radiation absorption
(A) at the center of the nitrous oxide methane and carbon
monoxide and bands varies from 10-9056, then (n) may be selected
so that the maximum absolute error in calculating transmission
will not exceed plus or minus 14S. Taking into account the
variability of (n) with the mass of the gas and the pressure
reduces the error in calculating the transparency of minor
components to plus or minus 5-7X. Calculating the transparency
of various air masses in the centers of N20, CHt and CO
absorption bands indicates the significant role of minor
atmospheric components in the attenuation of infrared radiation.
C. Atmospheric Interaction 225
-------
D. MEASUREMENT METHODS
00011
B. Sawicki, T. W. Stanley, and H. Johnson
DIRECT SPECTROPHOTOFLUOROBETBIC ANALYSIS OF AKOHATIC COMPOUNDS ON
THIN-LAYER CHROBATOGRAMS. BicEOChem. J. , 8 (3) :257-28l», Sept.
196D.
& simple aethod has been introduced by means of which
fluorescence spectra can be obtained directly from a thin-layer
chromatogran. The usefulness and sensitivity of the method have
been demonstrated for a wide variety of polycyclic compounds.
Some of the spectral differences between the dry and wet spots
have been found to be useful analytically. The ease of
applicability of the method has been proved through the
characterization of the spots obtained from the thin-layer
chromatogran of a coal-tar-pitch basic fraction.
Benzo(h)guinoline, nethylbenzo(h)guinoline,
dimethyl(or ethyl)benzo(h)quinoline, benz(c)acridine, and
nethylbenz(c) acridine have been identified in the sample.
(Author)*!
00036
T.A, Bellar, M.F. Brown, J.E. Sigsby, Jr.
DETERMINATION OF ATBOSPHBRIC POLLUTANTS IN THE PART-PER-BILLION
RANGE BY GAS CHROHATOGRAPHY; A SIMPLE TRAPPING SYSTEB FOR USE
SITH FLAHE IONIZATION DETECTORS). Anal. Chen., Tol. 35:192U-
1927, Nov. 1963.
A simple procedure is described for the determination of
atmospheric pollutants at concentrations as low as 0.1 p.p.b.
Hydrocarbons in the part-per-billion range -in 100cc. gas
samples can easily be determined. A simple trapping system
provides for high collection efficiencies over a wide range of
flow rates. Most samples can be handled by this system in less
than 10 minutes. This collection system is used in
combination with analysis by flame ionization gas
chromatography. Data are shown for analyses for atmospheric
olefins and paraffins derived from automobile exhaust. The
general utility of the method is evaluated and described.
(Author) **
00051
J. S. Nader E. C. Tsivoclou (Co-Chairmen)
SYBPOSIDH - ENVIRONMENTAL MEASUREMENTS - VALID DATA AND LOGICAL
INTERPRETATION. Public Health Service.
227
-------
Cincinnati, Ohio, Div. of Air Pollution and Div. of Water
Supply and Pollution Control. July 1964. 332 pp.
GPO: 81«-105-12, HEW: 999-AP-15
This collection of papers on air and water environaental
measurements contains material pertaining to the data
acquisition fields of air pollution. The systems operated
by the Los Angeles County Air Pollution Control District
and the U.S. Public Health Swrvice (Continuous Air
Monitoring Program) are reviewed. Other articles connected
with air and air pollution information include those on data
acquisition systems for fields of meteorology,- physiology, and
data interpretation.#*
00060
F.J. Woods, M.E. Umstead, J.E. Johnson
A STUDY OF THE IONIZATION PRODUCED BY THE CATALYTIC COMBUSTION
OF HYDROCARBONS. NAVAL RESEARCH LAB., Washington, D.C.
(NRL Hept. 6316.) Oct. 15, 1965. 15 pp.
CFSTI.DDC: AD 62301U
lonization produced during the catalytic combustion of
hydrocarbons has been studied for its usefulness in applications
such as chromatographic detection. Hhen'a Pt filament is heated
above 500 C in an atmosphere containing the hydrocarbon, the
formation of ions takes place during oxidation of the'compound.
The number of ions produced by the hydrocarbons is an
exceedingly small fraction of the number of c atoms oxidized and
varies widely depending upon the molecular structure of the
hydrocarbon and the catalyst temperature. Branched hydrocarbons
produce greater ionization than straight-chain compounds,
although the ease of oxidation is opposite. • H and CO burned
in the combustion cell exhibit no ionization current, even when
completely oxidized. Because of the marked effect of
molecular structure on ionization and 'the response of the .
method to low concentrations of hydrocarbons in air, the
procedure may find future use as a specific detector in gas
chromatography. (Author)#f
00068
M.W. Korth
DYNAMIC IRRADIATION CHAMBER TESTS OF AUTOMOTIVE EXHAUST.
Public Health Service, Cincinnati, Ohio, Division of Air
Pollution, PHS-999-AP-5. Nov. 1«963, 59p.
A dynamic irradiation chamber facility was designed and built for
investigations of irradiated auto exhaust under conditions of
continuous mixing. The facility consists of a programmed
chassis dynamometer, an exhaust dilution system, a dilution-air
purification system, two irradiation chambers, and various exposure
facilities. Three variables were considered in .this first series
of tests: (1) initial exhaust concentration (approximately 13 pp«
carbon and 35 ppm carbon), (2) average irradiation time (85 and
120 minutes), and (3). fuel composition (1<»* and 23% olef ins) . , The
effects of varying these test parameters .were determined by use of
228 HYDROCARBONS AND AIR POLLUTION
-------
appropriate test criteria including NO2 formation rate, oxidant
production, total hydrocarbon losses and reaction of specific
species, aldehyde production, plant damage, and bacteria kill.
Of the three variables studies, the exhaust concentration at the
start of irradiation appeared to produce the most significant
effects. Fuel composition had a lesser influence on some of the
test criteria; vdry little difference was noted in the effects
produced at the two average irradiation times. (Author)##
00092
B. Drexler M. Barchas
CHEHO-ELECTHICAL SENSING DEVICE. Airkem, Inc., New Tork
City, June 1961, 1«2p.
CFSTI, DDC: AD 262502
This report describes an investigation of the feasibility of
utilizing gas adsorption phenomena for the identification and
quantitative determination of various gaseous materials. A
discussion is presented of the factors influencing the
performance of the various components of an experimental gas
analyzer based on the measurement of characteristic adsorption
energies. Reasons are given for the attempted use of this
principle in such an instrument together with a theoretical
discussion of the basis for concluding the instrument to be
non-feasible in practice within the limitations of the original
specifications., A review of material
obtained from available literature sources as well as
informa
-------
0011«
E. Sawicki, T. W. Stanley, W. C. Elbert, J. Meeker
and S. McPherson
COMPARISON OF METHODS FOE THE DETERMINATION OF BENZO(A)PYRENE
IN PARTICULATES FROM URBAN ATMOSPHERES AND AIR POLLUTION SOURCE
EFFLUENTS. Atmospheric Environ. (London) 1, (2) 131-45, Bar.
1967.
Fourteen methods for the determination of benzo(a)pyrene in air
and in other complicated mixtures are compared. Many of the
methods are introduced in this paper and all have been applied to
the determination of benzo(a)pyrene in airborne particulates. The
precision and accuracy.of the methods, the man-hours of actual
work, and the time to complete an analysis are compared. Specific
recommendations are given for methods by means of which a high
order of selectivity, a maximum amount of information, a
considerably reduced analysis time, or a low cost of analytical
operation are possible. (Author)##
00122
D. L. Klosterman and J. E. Sigsby, Jr.
APPLICATION OF SUBTRACTIVE TECHNIQUES TO THE ANALYSIS OF
AUTOMOTIVE EXHAUST. Environ. Sci. Technol. 1, 309-111 (Apr.
1967), (Presented before the Division o£ Hater, Air, and
Waste Chemistry, American Chemical Society, Atlantic City,
N.J., Sept. 12-17, 1965.)
A simple system has been developed for chemical class analysis of
hydrocarbons found in automotive exhaust. The technique should
prove useful for evaluating the contributions of automotive
emissions to photochemical air pollution. A system of scrubbers
permits the sample to be analyzed for paraffins, olefins and
acetylenes, and aroaatics. Benzene may be determined with either
the paraffinic or aromatic hydrocarbons. The system may be used
with existing standard hydrocarbon analyzers without requiring
their modification. '(Author abstract)##
00141
A. Zdrojewski, L. Dubois, and J. L. Monkman
INSTRUMENTATION FOR AIR POLLUTION MONITORING. Preprint.
(Presented at the Annual Symposium AID Division, Instrument
Society of-America, Houston, Tex., Hay 11-13, 1966.)
The design of instruments for the continuous measurement of air
pollution is discussed. Particular reference is made to two
instruments, a carbon monoxide analyzer and a total hydrocarbon
analyzer. (Author)*#
230 HYDROCARBONS AND AIR POLLUTION
-------
001«2
R. G. Hinners, J. K. Burkart, and G. L. Contner
ANIMAL EXPOSURE CHAMBERS IN AIH POLLUTION STUDIES. Preprint.
1966.
Recent developments in animal exposure chambers and their use in
studying the biological effects of air pollution are described.
The various atmospheres studied include irradiated and
non-irradiated auto exhaust atmospheres, oxides of sulfur, and
oxides of nitrogen. (Author)*#
001<»6
E. Sawicki and J. Pfaff
ANALYSIS OF COMPOUNDS CONTAINING THE P-NITROANILINE PHOSPHOR AND
ANALOGOUS GROUPS BY PHOSPHORIHETRY AND BY HOOMrTEHPERATURE AND
LOS TEMPERATURE FLUOHIMETRY. Preprint. Microchem. J. 12, (1)
7-25, Mar. 1967.
Since aromatic nitro compounds usually give poor absorption
spectra and do not fluoresce, and since the nitrophenylhydrazines
are useful colorimetric reagents for analysis of a wide variety of
compounds, the phosphorimetric 'properties and the room—temperature
and low-temperature fluorimetric properties of these types of
compounds were investigated. Results showed that
4-nitrophenylhydrazine could be a valuable reagent for the analysis
of aromatic carbonyl compounds present in auto exhaust fumes and
that low-temperature fluorimetric trace analysis is a tool well
worth exploiting. Most of the aliphatic aldehyde and ketone
1-nitrophenylhydrazones are nonfluorescent but strongly
phosphorescent, whereas many of the aromatic aldehyde and ketone
U-nitrophenylhydrazones are nonphosphosescent but strongly
fluorescent in solvents of low dielectric 'constant and are' highly
fluorescent in all types of solvents at liquid-nitrogen
temperatures. Examples are given, of compounds that are
neither fluorescent at room temperature nor phosphorescent but are
intensely'fluorescent at liquid-nitrogen temperature.
Phosphorimetry and low-temperature and room-temperature
fluorimetry are three powerful complementary tools, much more
valuable when used;together, in trace analytical research than
when used singly. (Author)**
00155
Sweeney, M. Patrick and Miles L. Brubacher
EXHAUST HYDROCARBONS MEASUREMENT FOR TUNEUP DIAGNOSIS? In:
Vehicle Emissions, Part II, SAE Progress in Technology
Series Vol. 12, New York, Society of Automotive Engineers,
Inc., 1966, p. 307-316. 5 refs. (Presented at the SAE
Automotive Engineering Congress, Detroit, Mich., Jan.
10-1H, 1966.)
With an activated control program in California and its imminent
prospect nationwide, recently attention h'as been focused on
simplifying exhaust hydrocarbon measurement for7 potential use as a
D. Measurement Methods 231
-------
tuneup garage diagnostic tool. Work has been underway to evaluate
new instrumentation and procedures for hydrocarbon measurement
suitable for field use. It is concluded that: (1) With a
"one minute" cycle, measured emissions seem to correlate adequately
with the California procedure; (2) There are prototype
instruments which are inherently much less susceptible to
environment of use; and (3) For engine diagnostic purposes, the
principal uses of hydrocarbon measurements would be: (a) an
initial check (almost any engine malfunction raises hydrocarbons,
if low, engine does not need tuneup work); and (b) recheck after
tuneup (an increase in hydrocarbons indicates a tuneup oversight
or error, and the car would then be checked further). (Authors'
abstract) #t
00188
G. A. Cleeves, T. J. Lemmons, and C. A. demons
A LOW-LEVEL AIS SAMPLING AND METEOROLOGICAL SOUNDING SYSTEH.
J. Air Pollution Control Assoc. 16, («) 207-11, Apr. 1966.
A captive-balloon borne radio transmitting device measuring
temperature and humidity at desired levels in the lower
thousand feet of the atmosphere over a city is described. A
companion device which captures a sample of air at a desired
altitude and a method of later determining trace gas concentrations
in the sample is presented. Temperature, humidity, and methane
concentrations in air samples taken above Cincinnati were
determined and are presented as examples of the system's
capabilities. (Author)#t
00203
E. Sawicki, T. W. Stanley, and W. C. Elbert
COHPAEISON OF FLOOPIHETBIC METHODS OF ASSAY FOR BENZ(C)ACRIDINE
AND BENZO(H)QUINOLINE IN DREAD ATMOSPHERES AND AIR POLLUTION
SOURCE EFFLUENTS. J. Chromatog., Vol. 26:72-78. 1967.
Five methods for the estimation of benz(c)acridine in urban
particulate samples are compared, as are three methods for
benzo(h)guinoline. The methods involving thin-layer
chromatography followed by some form of fluorimetry are compared
with the column chromatographic absorptiometric procedure for aza
compounds. Through the quick estimation of benz(c)acridine, the
analyst should be able to determine the presence and amount of the
polynuclear aza heterocyclic compounds in urban atmospheres and
other appropriate samples. (Authors' abstract)#f
0021«
T. R. Hauser and D. W. Bradley
THE SPECIFIC SPECTROPHOTCBETRIC DETERMINATION OF OZONE IN THE
ATMOSPHERE USING 1,2-DI-(U-PYRIDYL)ETHYLENE. Anal.
Chem. 38, 1529-32, Oct. 1966.
232 HYDROCARBONS AND AIR POLLUTION
-------
A new method for the sampling and analysis of ozone in the
atmosphere is described. Atmospheric ozone is collected in a
solution of 1,2-di- (4-pyridyl) ethylene in glacial acetic acid.
The olllected ozone reacts with the 1,2-di(4-pyridyl) ethylene to
form an ozonide that undergoes cleavage to yield
pyridine-4-aldehyde for which a simple spectrophotometric
determination was developed. The relationship between the
micrograms of pyridine-4-aldehyde generated per microgram of ozone
sampled has been determined, so that pyridine-4-aldehyde may be
used for calibration. Various other oxidizing or reducing
substances do not interfere with the method, at least not in the
concentrations in which they are found in the atmosphere. The
method offers good sensitivity, reproducibility, and excellent
stability for delayed analysis after sampling. (Authors'
abstract) #t
00224
H. Shepherd, S. H. Bock, R. Howard, and J. Stormes
ISOLATION, IDENTIFICATION, AND ESTIMATION OF GASEOUS POLLUTANTS
OF AIR. Anal. Chem. 23 (10) :1431-1440, Oct. 1951.
Previous attempts to concentrate air pollutants in a cold trap
and analyze the concentrates by mass spectrometer have had
disappointing results. A new method by which the air of Los
Angeles County has been examined combines the isolation of
gaseous pollutants on a filter at liquid oxygen temperatures,
separation of the isolated frozen concentrate by isothermal
distillation or sublimation at low temperatures and pressures, and
identification and estimation of distillates by the mass
spectrometer. The method is capable of determining as littla as
0.0001 ppm of some pollutants from a 100-liter sample of air; with
larger samples, 0.000001 ppm of some substances can be
determined. The gaseous phase of the Los Angeles smog was found
to be of the order of 0.5 ppm of the air. About 60 chemcial
compounds or families of compounds were identified or tentatively
identified, and the amounts of some of these were determined. It
was shown that the gaseous phase of the smog was primarily a
mixture of hydrocarbons, and of hydrocarbons combined with 0, H,
and C1, These hydrocarbons, principally the unsaturated ones,
when oxidized with 03 and N02 in the presence of UV light,
produce substances which constitute a large proportion of the smog
concentrates. These oxidation products cause eye and respiratory
irritations such as are produced by the real smog, and smell like
spectra of the smog concentrates may eventually indicate the
presence of other irritants. The new method may be applied to
special problems in air pollution over large areas or inside
industrial plants. (Authors' abstract)##
00230
D.F. Bender, E. Sawicki, R.M. Wilson, Jr.
CHAHACTERIZATION OF CARBAZOLE AND POLYNUCLEAR CABBAZOLES IN UHBAN
AIR AND IN AIE POLLUTED BY COAL TAR PITCH FUMES BY THIN-LAYER
CHROMATOGBAPHY AND SPECTROPHOTOFLUOHCMETRY. Intern. J. Air
Hater Pollution, (London) Vol. 8, 633-643, 1964. (Presented
at the Air Pollution Symposium, Chicago, 111., Aug-Sept,,
1964.)
D. Measurement Methods 233
-------
The presence of carbazole in urban air samples and of polynuclear
carbazoles in certain source samples is shown for the first time.
Carbazole is found in the benzene soluble particulate and in
the aromatic fraction of the benzene-soluble particulate from urban
air. Certain source samples contain 11H-benzo(a)carbazole and
8H-benzo(c)carbazole in addition to carbazole. The already
known presence of these polynuclear carbazoles and of
5H-benzo (b)carbazole in coal tar pitch samples can be
demonstrated readily with thin-layer chromatography and
spectrophotofluorometry in alkaline N,N-dimethylformamide. The
characterization procedure consists of tw,o thin-layer
chromatographic separations followed by running the fluorescence
emission and excitation spectra of the extract of the appropriate
spots in neutral and alkaline K,N-dimethylformamide.
Samples containing carbazole include the composite benzene-soluble
particulate from the air of 150 United States communities, the
aromatic fraction of the benzene-soluble particulate from the air
of a city, air polluted by coal tar pitch tarring operations, and
a coal tar pitch sample. (Author) ##
0026U
B, H. wade, J. H. Boss and H. K. Benedict
A METHOD FOB THE DETECTION AND ISOLATION OF TBACES OF OBGANIC
FLOOBINE COMPOUNDS IN PLANTS. (FINAL HEPT.) Stanford
Research Inst., South Pasadena, Calif., Southern California
Labs. Apr. 1963. 20 pp.
A method for the detection and isolation of submicrogram
guantities of organic fluorine compounds from plant materials in
the presence of much larger amounts of inorganic fluoride is
presented. The procedure consists first of a rapid screening step
for use with large numbers of vegetable samples and extracts and,
second, of a chromatographic step to isolate and characterize any
fluoro-organics found. These methods are developed in light of
specific chemical characteristics of organic fluorine compounds as
a general class. A modification of Soep's guantitative submicro
fluoride analytical method is presented as applicable to these
isolation methods. Microgram guantities of organic fluorine
compounds were found in the plant materials investigated but at a
level too low for isolation and identification. (Authors'
abstract) *#
00275
J. R. Dewhurst and C. G. Holbrook
A TEST FOB THE SOOTING PROPENSITY OF TOWN GAS. Inst. Gas
Eng. J. (London) 6, (6) 387-tOO, June 1966.
A new test is described in which the sooting propensity of town
gas may be assessed as a Sooting Number. Laboratory tests and
district experience have been used to define the maximum Sooting
Number that is acceptable for British appliances adjusted for
G4 gas. When the appliances are adjusted for other groups, the
test burner is similarly adjusted so that the same Sooting Nunber
limit is obtained. A simple method has been developed for
calculating the Sooting Number of a gas from its composition.
(Authors' summary)ft
234 HYDROCARBONS AND AlR POLLUTION
-------
00277
E. S. Spindt
COMPUTER ANALYSIS OF THE CALIFORNIA CYCLE. J. Air Pollution
Control Assoc., 17 (3):166-167, Bar. 1967. (Presented at the
59th Annual Meeting, Air Pollution Control Association, San
Francisco, Calif,, June 20-24, 1966, Paper 66-72.)
The State of California, through its Motor Vehicle Pollution
Control Board, has specified a characteristic driving cycle to be
used to evaluate the exhaust gas emissions of a motor vehicle.
The standard method of analysis may take several hours to
complete. While there are a number of short cuts that have been
used, most of these are suspect if "correct" data are to be
obtained. If one uses a data logger, then improvement of the
analytical capability will permit more extensive data analyses.
The California cycle requires measurement of only C02, CO,
and hydrocarbons by means of nondispersive infrared analyzers. By
adding an oxygen analyzer, data on air/fuel ratio can be calculated
for each driving condition. The system selected consists of a
coupler, scanner, digital voltmeter, recorder, and manual entry
keyboard. The driver starts the car and the logger is started
before the first acceleration. Data are recorded to the end of
the run. The bag sample data (total exhaust gas collection) and
final zero and span data are each recorded with their preceding
manual entry code in a similar manner. (Author's abstract) ##
00293
E, C. Tabor and G. V. Smith
NATURE OF THE BENZENE-SOLUBLE FRACTION OF AIR PAHTICULATE
MATTES. Preprint. (Presented at the 59th Annual Meeting,
Air Pollution Control Association, San Francisco, Calif.,
June 20-24, 1966, Paper 66-121.)
Annual composites of the benzene-soluble portion of air
particulate matter were obtained from suspended particulate
samples collected at 78 urban and 32 non-urbzn stations of the
National Air Sampling Network. These samples of
benzene-soluble organics were separated into the following
functional groups of organic compounds: water-soluble, acids,
bases, aliphatic hydrocarbons, aromatic hydrocarbons, and
oxy-neutral compounds. Tables are presented showing the
composition of the individual samples and frequency distributions
of percentage values for the different fractions. Results are
discussed and suggestions made concerning causes of unusual
results. Infrared absorption curves are presented to illustrate
similarities and differences. (Authors1 abstract)##
00328
H. Watanabe and T. Nakadoi
FLUOROPHOTOBETRIC DETERMINATION OF TRACE AMOUNTS OF ATMOSPHERIC
OZONE. J. Air Pollution Control Assoc. 16, (11) 614.7.
Nov. 1966. (Presented at the 59th Annual Meeting, Air
D. Measurement Methods 235
-------
Pollution Control Association, San Francisco, Calif., June
20-2«, 1966.)
This work has initiated in an effort to obtaina better method for
the manual determination of trace amounts of atmospheric ozone.
The method described depends upon the fact that ozone oxidizes
nonfluorescent 9,10-dihydroacridine to fluorescent acridine.
When the ethyl alcohol solution of acridine is acidified by
6N acetic acid, the fluorescence maximum occurs approximately at
182 millimicrons and its intensity is sufficiently strong to be
useful in this analysis. Linear relationships between acridine
concentrations and fluorescence intensities were obtained from
0.1 to 3.5 micrograms per ml. by measurement with a commercial
fluorophotometer. The results indicated that the low
concentrations of experimentally prepared ozone measured by this
method were in good agreement with those obtained by the
phenolphthalin method. This method appeared to be about twice as
sensitive as the phenolphthalin method but it is subject to some
interference from nitrogen dioxide. (Authors' Abstract)##
,00386
E. Sawicki and J. D. Pfaff
QUENCHOPHOSPHOHIMETRIC ANALYSIS FOR CONJUGATED COMPOUNDS.
Mikrochira. Acta (1-2) 322-33, 1966.
A new method of analysis that incorporates many of the reagents
found useful in guenchofluorometry is introduced. Since many
types of non-fluorescent and weakly fluorescent compounds can be
analyzed, guenchophosphorimetry is a complementary tool. This
method of analysis is superior to colorimetry and fluorometry in
simplicity, sensitivity and selectivity for many types of
compounds. Examples of this technigue are given. One striking
example is the determination of p-nitroaniline in the presence of
carbazole, p-hydroxyacetophenone, triphenylamine and tri-phenylene
all of which are usually intensely phosphorescent. New types of
functional group analyses for individual compounds and families of
compounds should be possible with quenchophosphorimetry.
(Author) **
00399
W. C. Elbert and T. W. Stanley
A STUDY OF THE ELUTING POHEB OF SOLVENT SYSTEBS ON THIN LAYERS OF
FLOBISIL. Chemist-Analyst. 54, 68-9, July 1965.
This paper presents the results of investigation of the eluting
power of single solvent systems on thin layers of Florisil with
standards of immediate and future importance in air pollution
studies. B polynuclear aromatic hydrocarbon, aza and imino
-heterocyclic hydrocarbons, an aromatic amine, a guinone, and a
ring-carbonyl compound were selected for the study. Clean glass
plates (20 by 20 cm) were coated with a 500-micron layer of
Florisil from a slurry of 70 ml. of water and 35 g. of substrate,
which had been mixed for 3 min. The coated plates were
activated at 110 C and stored in a desiccator. Chambers
containing the solvent systems were lined on one side with
Whatman No. 1 filter paper and allowed to equilibrate for 16
236 HYDROCARBONS AND AIR POLLUTION
-------
hrs (or over-night) at room temperature. Plates spotted with the
standards were allowed to develop to a height of 15-cm.; spots on
the developed chromatogram were outlined and the movement of the
standards relative to the solvent front was determined by
observation under IJV light. This study showed that the order of
solvents in terms of development on a plate varies with the type
of compound being separated. Because of this phenomenon,
two-dimensional development on a Florisil plate can be useful in
the separation and analysis of organic airborne particulates.##
00426
G, lundeen and R. Livingston
CHEMILDMINESCENCE OF HYDROCARBON OXIDATION. Photochem.
Photobiol. Vol. 4:1085-96, 1965.
CFSTI, DDC: AD 631111
That chemiluminescence accompanies autoxidations and
decompositions of some peroxides has been known for some tine.
Recently mechanisms have beeen proposed to explain such
chemiluminescence. This paper is a report of an experimental
study of the luminescence which accompanies the aatoxidation,
spontaneous and induced by the decomposition of benzoyl peroxide,
of tetralin and amyl benzene. Anthracene, 9,10-diphenyl
anthracene and*9,10-dibromo-anthracene were used as intensifiers of
luminescence. t#
00440
E. Sawicki and H. Johnson
CHARACTERIZATION OF AROMATIC COMPOUNDS BY LOW-TEMPERATURE
FLUORESCENCE AND PHOSPHORESCENCE: APPLICATION TO AIR POLLUTION
STUDIES. Hicrochem. J. 8(1):85-101, Bar. 1964.
Characterization through low-temperature fluorescence and
phosphorescence properties of aromatic molecules under neutral,
acid, and alkaline conditions has been investigated. Compounds
that are fluorescent at room temperature are usually fluorescent at
liquid-nitrogen temperatures. Many polar compounds that are
nonfluorescent at room temperature become strongly fluorescent at
low temperatures. Hany azulene and azo derivatives that are not
fluorescent under neutral conditions give vivid fluorescence under
liquid nitrogen. Many of the investigated compounds have vivid
phosphorescence properties. Hany of tie compounds show
differences in fluorescence and phosphorescence dependent on
whether they are dry or in solution on the paper. Both paper
and thin-layer chromatograms can be examined for goom-temperature
fluorescence, low-temperature fluorescence, and phosphorescence in
neutral, acid, or alkaline media. Examples of the more difficult
thin-layer chromatogram procedure with air pollution samples are
given. An example of an applied paper-chromatographic procedure
is given also.f#
D, Measurement Methods 237
-------
00449
H. Konosu and Y. Kashiko
TECHNICAL ANALYSES BY OPTICAL METHODS (XI) DESIGN OF A
NONDISPERSIVE ULTRAVIOLET GAS ANALYZER AND ITS APPLICATION TO
QUANTITATIVE MEASUREMENT OF TRACES OF TOXIC GASES AND VAPORS IN
AIR.) Tokyo Kogyo Shikensho Hokoku 61 (2) :62-68, Feb. 1966.,
Text in Japanese
Details of a nondispersive ultraviolet gas analyzer, designed to
determine traces of toxic gases and vapors in air, are presented.
The analyzer measures small transmission differences between a
standard gas and the sample gas. The principal parts of the
instrument are an ultraviolet source (hydrogen discharge lamp), a
double-beam optical system, measuring cell of 50 cm length, a
secondary electron photomultiplier detector, and a
measuring meter (ammeter). The sensitivity of detection in ppm
for gas and vapors in 50 cm cell is: S02-3, CS2-28, C6H6-27,
CH3COCH3-32, CH3COC2H5-34, CHC1CC12-13. This
method has a precision to plus or minus 9.OX for the range of
0-100 ppm, to plus or minus 4.0% for 100-1,000 ppm and to plus or
minus 1.5% for 1,000-1,250 ppm S02. The equipment is relatively
simple, and its rapid response permits measurements to be
made in less than 1 minute. (Author summary)
00451
H. Sakabe, H. Matsushita, H. Hayashi, K. Nozaki,
Y. Suzuki
HINERAL COMPONENTS AND 3,4-BESZPYRENE IN AIR POLLUTANTS OF
TOKYO. Ind. Health (Japan) 3 (3-4) :126-139, Dec. 1965.
Minerals and 3,4-benzpyrene in particulate pollutants in winter
air of Tokyo were studied by the methods developed by the authors.
Minerals in air pollutants of Tokyo were quartz, feldspar,
cristobalite, mica and kaolin minerals which were the mineral
assemblage of Kanto loam constituting earth surface of Kanto
plain. The highest'concentration of quartz in .the air during''this
survey was 0.034 mg/cu H and mean concentration of 3,4-
benzpyrene in Tokyo air was 15.1 micrograms/1000 cu H. Data
were discussed in relation to "Toky/-Yokohama asthma" and lung
fibrosis. (Authors' abstract)**
00169
G.D. Jaros, N.R. Parkin, J.G. Mingle, N.B. Paul
THE FATE OF OXIDES OF NITROGBH THROUGH A DIRECT FIAHE AFTEHBUHNEB
IN THE EXHAUST OF A "GASOLINE ENGINE. Preprint. (Presented
at the Second Annual Meeting, Pacific Northwest International
Section, Air Pollution Control Association, Portland Oreg.,
Nov. 5-6, 1964, Paper No. 64-AP-10.)
This paper deals with a study which was made to determine the
concentration of N'oxides before and after a direct-flame
afterburner connected to the exhaust of an internal-combustion
238 HYDROCARBONS AND AIR POLLUTION
-------
engine. The scope of the worK covered in this investigation is
being confined to a single engine and one afterburner. The
laboratory setup consisted of a 6-cylinder overhead camshaft engine
direct-connected to an electric dynamometer. Steel flywheels
mounted on the dynamometer shaft made possible the simulation
of vehicle road operation during acceleration and deceleration.
Operation of the engine was automatically controlled to the
California sevenmode cycle. Analysis of NOx was accomplished
by drawing exhaust gas samples every 2-1/2 sec during the 129 sec
of the 7-raode cycly. NOx determinations were made by an
instrument partially designed and totally built at Oregon State
University. Other constituents of the exhaust gas (CO,
C02 and unburned hydrocarbons) were recorded with continuous,
nondispersive infrared detectors. Polotted profiles of
instantaneous NOx concentration during the 7-mode cycle time
show results before and after the direct-flame
afterburner for both rich and lean mixture operation.##
00479
E. Sawicki, T. W. Stanley, S. McPherson, and M.
Morgan
USE OF GAS-LIQUID AND THIN-LAYER CHROMATOGHAPHY IN
CHARACTERISING AIR POLLUTANTS BY FLUOROMETRY. Talanta Vol.
13:619-629, 1966.
Relatively large amounts of alkylated derivatives of the
polynuclear aromatic hydrocarbons are present in some urban
atmospheres. These compounds are believed to be derived from
industrial sources. Because alkylation of the tetracyclic
aromatic hydrocarbons can confer carcinogenic activity on the
derivatives, the presence of substantial amounts of these alkylated
compounds in the air needs thorough study. The R sub f value and
the retention time, by themselves, are inadequate for '
characterisation of the polynuclear compounds. Gas liquid
chromatography followed by fluorometric examination of the eluent
bands, and mixed-adsorbent two-dimensional thin-layer
chromatography followed by direct fluorometric examination are very
useful in characterising all types of organic compound in the
organic fractions of airborne particulates and effluents from air
pollution sources. (Author Abstract)##
00484
Holaa, B.
SHORT-TERM LUNG CLEARANCE IN RABBITS EXPOSED TO A RADIOACTIVE
BI-DISPERSE (6 AND 3 MICHON) POLYSTYRENE AEROSOL. In:
Inhaled Particles and Vapours II. (Proc. Intern. Symp.
Brit. Occupational Hyg. Soc., Cambridge, 'England, 28 Sept.
-1 Oct. 1965.) C. N. Davies (ed.), London, Pergamon Press,
1967, p. 189-203. 8 refs.
This paper presents a technique for external measurenent which can
be use'd for studying the rate of lung clearance for two
monodisperse aerosols, i.e. a "di-disperse" aerosol simultaneously
in a single animal. Using this technique, the lung clearance of
6 micron and 3 micron polystyrene particles, tagged with Au(198)
D. Measurement Methods 239
-------
and Sc (16) respectively, has been studied in 8 rabbits for 48
hours after exposure. The results show that the clearance rate
is faster for the larger than for the smaller particles. (Author
abstract)ft
OOH92
F. E. Ordoveza and P. W. West
HICRODETEHMINATION OF CAFFEINE USING THE RING OVEH TECHNIQUE.
Anal. Chim. Acta Vol. 30:227-233, 1964.
A rapid and highly selective method for the microdetermination of
caffeine of special interest for.air pollution studies is
presented. With the ring oven technique and with solutions of
acetylacetone in sodium hydroxide and p-dimethylaminobenzaldehyde
in hydrochloric acid, as little as 0.5 microgram caffeine on the
ring can be determined with an average error of 3%. Compounds
containing purine bases which would be likely to give the same
color reaction as caffeine do not interfere. Of the organic air
pollutants which might be collected from the atmosphere during the
sampling for caffeine, benzo(alpha)pyrene and formic acid do not
interfere. Interferences frcm formaldehyde and urea are easily
eliminated. (Authors' summary)ft
00542
T.A. Bellar J.E. Sigsby, Jr.
EVALUATION OF VARIOUS SILICA GELS IN THE GAS CHROMATOGHAPHIC
ANALYSIS OF LIGHT HYDROCARBONS. Environ. Sci. Technol.
1 (3):242-246, Harch 1967. (Presented at American Chemical
Society, Pittsburgh, Pa., Bar. 23-24, 1966.)
The paper describes the separations of light hydrocarbons
obtained with columns packed with the following Davison silica
gels: Types No. 08, 15, 35, 58, 62, 81, 113, and 950.
experimentally these silica gels were classified in 2 groups:
(1) high-activity silica gels with average pore diameter
around 25 angstroms, and (2) medium-activity silica gels
with average pore diameter around 150 angstroms. Light-
hydrocarbon chromatograns characteristic of the 2 groups
are shown. The effects of various polar liquid phases and
water upon the silica gels of 150 angstroms pore diameter
are discussed in detail. A system is described that can
be used for analyzing C1 to C5 paraffins, C2 to C4 olefins,
and acetylene in automotive emissions and in ambient air.
Some of the advantages of using solid adsorbents for such
analysis are also discussed. (Author's abstract)ft
00584
C.A. demons A.P. Altshuller
PLASTIC CONTAINERS FOR SAMPLING AND STORAGE OF ATMOSPHERIC
HYDROCARBONS PRIOR TO GAS CHROMATOGRAPHIC ANALYSIS. J. Air
Pollution Control Assoc. 14, (10) 407-8, Oct. 1964.
240 HYDROCARBONS AND AlR POLLUTION
-------
The results of the present work indicate that Mylar containers
should prove adequate for sampling and long-term storage of C1 to
C5 aliphatic hydrocarbons prior to gas chromatographic analysis.
6ong-term storage of aromatic hydrocarbons in these containers
should be avoided. Containers made of plastic films fabricated
from various fluorinated polymeric materials may prove more
useful for the storage of aromatic hydrocarbons. Difficulties in
storage of atmospheric samples containing higher-molecular-weight
hydrocarbons or polar substances for periods of weeks should not
deter workers from using these containers for short-term storage
of synthetic calibration mixtures or atmospheric samples. Mylar
containers have proved satisfactory for storage of a wide variety
of reactive substances for periods of a few hours to several days.
(Authors' abstract)##
00610
A. P. Altshuller
ATMOSPHERIC ANALYSIS BY GAS CHHOBATOGEAPHY. Preprint. 1966.
A number of the gas chromatographic procedures developed for
atmospheric analysis have received little application. Several
investigators have done atmospheric analysis for hydrocarbons
and peroxyacetyl nitrate directly without concentration.
Monitoring gas chromatographs could be built for obtaining
large quantities of atmospheric analyses. Such equipment has
not yet been fabricated. A related problem is the read-out
of the large number of peaks or areas generated by making
analyses every 10, 15 or 30 min. for 2t hrs. a day. Integration
equipment capable of handling such outputs is available;
such equipment is already in routine use in measuring hydrocarbons
in auto exhaust studies. The application of the electron capture
detector to analysis of low-molecular-weight
halogenated substances, pesticides, and tracer materials in
air has been demonstrated. The capability to measure such
substance sby gas chromatography is excellent. Many future
applications in atmospheric chemistry should make use of such
procedures. (Author abstract)#f
00620
H.D. Conner J.S. Nader
AIR SAMPLING BITH PLASTIC BAGS. Am. Ind. Hyg. AssioC. J.
Vol. 25:291-297, June, 196«.
An inexpensive sampler has been developed whereby air samples
can be collected in plastic bags without pump contamination
and shipped to a laboratory for analysis. Data are presented
to illustrate how well these bags contain (1) sulfur dioxide,
nitrogen dioxide, and ozone in samples collected from
synthetically prepared mixtures, and (2) 'hdrocarbons in samples
collected from an auto .exhaust irradiation chamber. The
inorganic samples were in the concentration range of 0.5 to
1.5 ppm, and the hydrocarbon samples were in the concentration
range of 7 to 20 ppm. The samples were stored for periods of
several days. (Author abstract)##
D. Measurement Methods 241
-------
00623
G.C. Ortman
CONTINUOUS SELECTIVE MONITORING OF HYDROCARBONS:
APPLICATION TO DETERMINATION OF HETHANE. Preprint. 1964.
Described is an instrument system for selective monitoring of
trace hydrocarbons. It is comprised of sample pump, treated
column of adsorbent material, hydrogen flame ionization detector,
electrometer amplifier, and recorder. In operation
a continuous flow of sample air is pumped through the column
to the detector. The column removes unwanted hydrocarbons
whole passing unaltered the one of interest. A protype
field instrument for monitoring atmospheric methane is
detailed and typical results characterizing its operation
reported. Response is linear and independent of the direction
of change of the measured variable. Principles, design
factors, application, and performance of the system are discussed
and experimental data presented. (Author abstract)t#
00624
E. Sawicki, T. «. Stanley, H. C. Elbert
CHARACTERIZATION OF POLYNUCLEAB AZA HETEROCYCLIC
HYDROCARBONS SEPARATED BY COLUMN AND THlN-LAYEB
CHBOMATOGRAPHY FROM AIR POLLUTION SOURCE PARTICULATES. J.
Chromatog. Vol. 18:512-519, 1965.
By column and thin-layer chromatography approximately 200
spots have been obtained in the analysis of various air
pollution sources. With the help of direct spectrophoto-
fluorometric analysis of the spots on the thin-layer
chromatograms 25 aza heterocyclic and 8 polynuclear aromatic
hydrocarbons were characterized according to the present
ring structure. Eleven of the aza heterocyclic hydrocarbons
were identified unequivocally. The following carcinogens have
been found in air pollution source effluents: dibenz-
(a h)acridine and dibenz (a j) acridine- In addition, alkyl
derivatives of benz (a)acridine and benz(c)acridine were
obtained, some of which could be carcinogenic. (Author
summary)*i
.00728
S.S. Epstein K, Bush
A SIMPLE PHOTODYBAMIC ASSAY FOR POLYCYCLIC ATMOSPHERIC
POLLUTANTS. Preprint. (Presented at the 58th Annual
Meeting, Air Pollution Control Association, Toronto, Canada,
June 20-2K, 1965, Paper Bo. 65-111.)
The photodynamic bioassay employed in this study is simple,
rapid, and reproducible. However, the significance of data
acquired with this technique is, at present, not easy to interpret.
It appears that the assay provides an in vivo measure of the
concentration of photosensitizing compounds in atmospheric
242 HYDROCARBONS AND AIR POLLUTION
-------
particulates, and yields results which discriminate between
pollutant fractions from the same source, and between pollutants
from different sources. Whether these differences would
be paralleled in non-composite samples cannot be assessed at
present. The inter-source variations cannot be accounted for
merely by a concomitant difference in the concentration of
atmospheric particulates. Although there appears to be a
general association between the BaP concentration and
photodynamic potency of benzene-soluble extracts, the chemical
data are, at -present, too restricted for more aeaningful
correlations. -Apart from this, while the presence of BaP may
account for the major part of the potency of benzene-
soluble and aromatic fractions, it obviously does not account for
photodynamic potency in oxy-neutral or basic fractions. Both
these fractions are frequently very potent and while largely
chemically undefined, are devoid of BaP. The presumptive
isolation of carcinogenic alkylated benz(c)acridines from basic
fractions probably accounts for their occasional high
potency and should serve to direct biological attention to this
small but, hitherto, largely ignored fraction. (Author's
summary modified)*#
007H7
R.D. Stewart, B.C. Dodd, D.S. Erley, B.B. Holder
DIAGNOSIS OF SOLVENT POISONING. J. Am. Bed. ASSOC.,
193(13):1098-1100, Sept; 27, 1965.
The diagnosis of solvent poisoning or exposure can be rapidly
established by breath analysis. The analytical methods employed
specifically identify the solvent and are sufficiently sensitive
to permit detection hours to weeks.after exposure, depending upon
the amount of solvent absorbed, its rate of metabolism, and its
rate of excretion. Serial breath analyses after a solvent
exposure, allow the construction of an excretion curve which
can then be compared to the excretion curves of humans previously
exposed to known amounts of a given solvent. In this manner
the total body burden or total body burden of total amount
absorbed may be estimated. Based upon the identity of the toxic
agent and the amount present within the body, a reasonable
prognosis can be advanced and appropriate therapy begun. The
breath samples are collected in saran gas bags or glass pipettes
and analyzed directly for their solvent content in a long
path-length gas cell of an infrared spectrometer or in a capo'r
phase chromatograph. (Authors' abstract)##
00765
E. Sawicki, D.F. Bender, T.R. Hauser, R. H. Wilson,
Jr., J.E. Heeker
FIVE NEW METHODS FOB THE SPECTHOPHOTCHETBIC DETERMINATION OF
ALKYLATING AGENTS INCLUDING SOME EXTBEMELY SENSITIVE ADTOCATALYTIC
METHODS. Anal. Chem. 35 (10):1479-86, Sept. 1963.
The presence of alkylating agents in the air and in various air
pollution sources has been demonstrated with the new reagents.
Because of the wide range of toxic effects caused by alkylating
agents, a more thorough investigation of the composition of.the
0. Measurement Methods 243
-------
air in terms of alkylating agents is necessary. Four new
sensitive reagents for the determination of alkylating agents
are introduced. A much more sensitive 4-(4-nitrobenzyl)-pyridine
procedure is described for the determination of the relative
reactivity of over 90 alkylating agents. A new type of
spectrophotometric method for the analysis of organic compounds
involves an autocatalytic reaction for determining alkyl iodides
in trace guantities. For example, in the 4-yrridinecarboxaldehyde
2-benzothiazolylhydrazone procedure for the determination of
1-iodobutane a molar absorptivity of 1,500,000 can be obtained.
The determination limit is about 50 nanograms of 1-iodobutane.
These reagents can be used to determine very low concentrations
of iodine and iodine precursors through an autocatalytic reaction.
For example, in the determination of iodine with 4-
pyridinecarboxaldehyde 2-benzothiazolylhydrazone a molar
absorptivity of 6,000,000 can be obtained. The determination
limit for iodine with this reagent is 15 nanograms. Several new
methods use the new reagents for the detection of acylating
agents. The relative activity of many functional groups is
discussed. (Authors' abstract)t#
00766
J.D, Pfaff E. Sawicki
DIRECT SPECTEOPHOSPHOBIHETRIC ANALYSIS OF ORGANIC COMPOUNDS ON
PAPER AND THIN-LAYER CHROMATOGRAMS. Chemist-Analyst, 54(1):30
-31, 1965.
Author discusses the advantage of phosphorimetric analysis
of organic compounds and concludes that it is a more sensitive and
more selective method of analysis.##
00767
E- Sawicki H. Johnson
THIN-LAYER CHROHATOGRAPHIC CHARACTERIZATION TESTS FOR BASIC
POLYNOCLEAR COMPOUNDS. APPLICATION TO AIR POLLUTION.
Hikrochim. Acta (Vienna), (2-1) 435-50, 1964.
A group of methods for the characterization and differentiation
of various classes of basic aromatic compounds has been described.
Polycyclic hydrocarbons, aromatic carbonyl derivatives, aromatic
ring carbonyl compounds, aza heterocyclic compounds, and polycyclic
aromatic amines show changes in fluorescence color with sulfuric
acid on the thin-layer plate and in solution. The piperonal color
test gave some selective reactions on the thin-layer plates with
various polycyclic aromatic hydrocarbons. A trifluoroacetic
•color test for oxidizable aromatic compounds containing nitrogen
atoms was investigated. Compounds containing carbazole rings
gave positive results. The piperonal test, the trifluoroacetic
acid oxidation test, and the trifluoroacetic acid test for
compounds more basic than the hydrocarbons were applied to the
study of the spots separated through thin-layer chromatography of
organic airborne particulates. Carbazole in amounts greater than
0.03% in an organic air sample could be estimated after thin-layer
chromatography. 8ith the help of thin-layer chromatography
and the trifInoroacetic acid vapor test, organic airborne
244 HYDROCARBONS AND AIR POLLUTION
-------
particulates were f.ound to contain fairly large amounts of
compounds more basic than the polycyclic hydrocarbons. A
spectral procedure for characterizing and differentiating aromatic
hydrocarbons, aromatic carbonyl derivatives, aza heterocyclic
compounds, and aromatic amines has been described. (Author
summary modified)##
00768
D.F. Bender, E. sawicki, R.M. Wilson, Jr.
SPECTROPHOTOMETEIC DETERMINATION OF ALKYLATING AGENTS WITH
t-PICOLINE AND 0-DINITROBENZENE. Analyst, 90 (1075):630-634,
Oct. 1964.
An accurate, sensitive spectrophotometric method has been
developed for determining alkylating agents. The method involves
the alkylation of 4-picoline at 100 c in 2-methoxyethanol, with
subseguent reaction of the 4-picolinium cation with o-
dinitrobenzene in the presence of alkali to produce the chromogen.
With 2-phenylethanol as the solvent, the method is autocatalytic
at 100 C. The variables in the procedures were studied, and
the methods were compared to one another and to methods in
literature. Some preliminary studies of other possible methods
for alkylating agents are discussed. (Authors' abstract)tf
00772
T.A. Bellar, M.L. Bellar, J. E. Sigsby, Jr.
GAS CHROMATOGRAPHIC ANALYSES OF PARAFFINS AND OLEFINS IN COMPLEX
HYDROCARBON MIXTURES: CHEMICAL FHACTIONATION WITH DUAL HIGH-
CAPACITY TUBULAR COLUMNS. Preprint. (Presented at
Pittsburgh Conference on Analytical Chemistry and Applied
Spectroscopy, Pa., Bar. 2-6, 1964.)
Auto exhaust and other complex hydrocarbon samples are analyzed
directly for over 40 paraffins and cycloparaffins and numerous
olefins in 70 minutes. By means of a unigue valving system, a
sample of exhaust is separated into two fractions by a silver
nitrate-ethylene glycol column and each fraction is trapped
individually. The fractions are then analyzed simultaneously on
separate columns, one fraction for paraffins and cycloparaffins
and the other for olefins. The latter fraction also contains
the remaining hydrocarbons of the exhaust sample excepting
aldehydes and acetylenes, which appear to react irreversibly with
the fractionating column. (Authors' abstract)t#
00845
SELECTED METHODS FOR THE MEASUREMENT OF AIR POLLUTANTS.
Public Health Service, Cincinnati, Ohio, Div. of Air
Pollution. Hay 1965. 53 pp.
GPO: 820-519, HEW: 999-AP-11
D. Measurement Methods 245
-------
This manual is an effort to assist in the development of
uniform standard methods of analysis of air pollutants. It makes
available the judgment and knowledge of a large group of chemists
in the Public Health Service. Methods of determining
pollutants of common interest are presented in uniform format by
chemists on the staff of the Division of Air Pollution. The
methods were critically reviewed by the Interbranch Chemical
advisory Committee, which is composed of representatives of the
professional chemical groups in all branches of the Division.
Methods presented are as follows: For determination of sulfur
dioxide, the West and Gaeke and the hydroge.n peroxide methods;
for determination of nitrogen dioxide and nitric oxide, the
Saltzman method; for determination of oxidants, the neutral
bnffered-potassium iodide and the alkaline potassium iodide
methods; for determination of aliphatic aldehydes, the 3-methyl-2
benzothiazolone hydrazone hydrochloride method; for
determination of acrolein, the t-hexylresorcinol method; for
determination of formaldehyde, the chromotropic acid method; for
determination of sulfate in atmospheric suspended particulates,
the turbidimetric barium sulfate method; and for determination
of nitrate in atmospheric suspended particulates, the 2,i» xylenol
method, (Author abstract)#f
00862
R.A. Vomela
GENERATION AND DECAY OF SMALL IONS. SECTION IV: THE CHARGING
AND MOBILITY OF CHAIN AGGREGATE SMOKE PARTICLES (PROGRESS
REPT.). Minnesota Univ., Minneapolis, Dept. of
Mechanical Engineering. (Particle Lab. Publication No. 95.)
June 1, 1966.
Using a modified electrical particle counter, an experimental
study was made of two typical linear aggregate aerosols. These
were an aerosol generated by exploding a fine copper wire with a
high current pulse and one produced by the burning of a mixture
of kerosene and benzene in air. The electric charge acquired
by the particles by diffusion of ions in a pure diffusion charger,
the electrical mobility of the particles, and their size, were
measured and correlated. This information was then used to
calculate the dynamic mobility of the particles and the charge-size
relationship. The charge acquired by spherical methylene blue
dye particles under similar charging conditions was also measured
and compared to the data on chain aggregates.##
00867
E. Sawicki, T.W. Stanley, T.H. Hauser, W. Elbert,
J.L. Noe
SPOT TEST DETECTION AND COLOHIHETEIC DETERMINATION OF AROHATIC
AMINES AND IMINO HETEROAROMATIC COMPOUNDS WITH 3-
METHYL-2-BENZOTHIAZOLONE HYDHAZONE. Anal. Chem. 33 (6): 722-
725. May 1961.
A new analytical method is introduced for the detection and
determination of organic compounds containing the aromatic aline
grouping. Among these compounds are the aromatic primary amines.
246 HYDROCARBONS AND AIR POLLUTION
-------
aralkyl amines, aryl dialkylamines, diarylamines, indoles,
carbazoles, and phenothiazines. In a preliminary survey of this
reaction, limits of identification, wave length maxima, and
molar absorbance values have been given for approximately 100
compounds. Noteworthy were the brilliant intense colors abtained
with aniline, N-alkylanilines, and N,N-dial)cylanilines and
their ring-substituted derivatives. Many carcinogenic amines were
found to be capable of analysis by the colorimetric method. The
colorimetric determination of N,N-dimethylaniline was
studied and found to be extremely sensitive and reproducible.
Beer's Law was obeyed from 4-64 micrograms of N,N-
dimethylaniline/ml of test solution. The shortcomings and
limitations of this procedure are also discussed. In an
alternative procedure modified for use only with the basic
aromatic amines Beer's Law was obeyed from 0.4 to 8 micrograms of
N,N-dimethylaniline/ml of test solution. The absorptivity of
the chronogen obtained from N,N-dimethylaniline was 0.70/
micrograms ml/cm. (Author summary)ft
00868
E. Sawicki J.D. Pfaff
ANALYSIS FOR AROMATIC COMPOUNDS ON PAPER AND THIN-LAYER
CHBOMATOGRAMS BI SPECTROPHOTOPHOSPHOHIMETRY, APPLICATION TO
AIR POLLUTION. Anal. Chim. Acta Vol. 32:521-543, June
1965.
A new technique is introduced in spectrophosphorimetric analysis
by menas of which spectra can be obtained directly on an
adsorbent after chromatography. With this procedure spectra of
the phosphorescent compound, its salts, its reduced or
oxidized forms, or its derivatives can be obtained in all types
of solvents. A large number of examples of this simple technique
are given; detection limits range from 0. 1 nanogram to
microgram amounts. A new system for the circular paper
chromatographic separation of aza heterocyclic hydrocarbons
using aqueous formamide is described. Many of these heterocyclic
compounds can be separated from each other as can the parent
compounds from their alkyl drivatives. Air pollution mixtures
separated by column and paper chromatography are analyzed with
the phosphorimetric technique. Spots obtained on the
paper chromatograms are analyzed directly in the phosphorimeter.
With these techniques benzo (f)quinoline, benzo(h)quinoline,
benz (a)acridine, benz(c)acridine, and hydrocarbons such as
phenanthrene and benzo(e)pyrene are radily characterized.
(Author summary)##
00898
M.P. Chovin M.J. Lebbe
(AN EFFECTIVE WORK INSTRUMENT: THE LABORATORY TRUCK USED BY THE
MUNICIPAL LABORATOHY OF PARIS IN A STUDY OF AIR POLLUTION.)
Un Instrument de Travail Efficace: Le Camion-laboratoire
d'Etude de la Pollution Atmospherique du Laboratoire
Municipal de Paris. Pollut. Atmos. (Paris) 8(29):1-11, Bar.
1966.
D. Measurement Methods 247
-------
A Paris Bunicipal Laboratory truck used for air pollution
studies, principally for automobile emission studies, is described.
This mobile laboratory which was set up in 1961 by the
Technical Services Department of the Prefecture of Police,
helped in a long-term series of studies known as "Operation
Carbon Monoxide". It gave great mobility to these studies,
and because of the relatively small size of the truck, it could
be parked without interfering too much with normal traffic. It
was a Citroen H with a lengthened body and a reinforced
suspension. It was equipped so that the instruments could be
operated wither with batteries or a central supply of
electricity. It was thermally insulated to'protect the
instruments. The roof was reinforced so that meteorological
observations could be made with instruments mounted on top, or the
area could be used for visual observations. Scientific equipment
in the truck consisted of an analyzer for carbon monoxide
(infrared, automatic), a carbon dioxide automatic analyzer, a
Perkin Elmer apparatus for unburned hydrocarbons, as well as a
Wohstoff apparatus, other types of apparatus specific for sulfur
oxides and hydrogen sulfide, equipment for gas phase chromatography
and a pump for a Millipore filter. All equipment was mounted on
special shock absorbers. The cost was about 200,000 francs.ft
00911
E. D. Barber E. Sawicki, and S. P. McPherson
SEPARATION AND IDENTIFICATION OF PHENOLS IN AUTOMOBILE EXHAUST
BY PAPEB AND GAS LIQUID CHBOMATOGRAPHY. Anal. Chen.,
36(5) :2U!42-2«tt5, Dec. 1964.
MEASUREMENT METHODS: Automotive exhausts. Gas chromatography.
Paper chromatography. Phenols
A method is described for the separation and identification of
simple phenols in automobile exhaust by paper and gas liquid
chromatography. Extended data are given on the separations in
Crump's system on Schleicher and Schuell 20UOA and 35 to 10%
silica gel-impregnated 966 papers as well as separations on
dimethylformamide-impregnated papers in dimethylformanide-hexane.
The results of analysis of several samples by paper and gas liquid
chromatography are presented. (Author abstract)i#
00912
D. F. Bender, E. Sawicki, and B. H. Wilson, Jr.
FLUORESCENT DETECTION AND SPECTROPHOTOFLUOROHETRIC
CHARACTERIZATION AND ESTIMATION OF CABBAZOLES AND POLYNUCLEAH
CARBAZOLES SEPARATED BY THIN-LAYEB CHBOMATOGRAPHY. Anal.
Chem., 36(6):1011-1017, May 196«.
A modification of the solvent medium used in a previous method for
carbazole has resulted in considerable stabilization of the
carbazole anion. It has improved the earlier spectrophotonetric,
spectrophotofluorometric, and fluorescent spot test techniques for
carbazoles containing acidic hydrogen on the nitrogen. The
improved spectral methods have been applied to carbazoles of
248 HYDROCARBONS AND AIR POLLUTION
-------
higher molecular weight, including polynuclear carbazoles. The
fluorescent spot test has been applied to htese carbazoles
adsorbed on thin-layer chromatographic substrates. The
absorption and fluorescent spectra in u,N-di-methylformamide and
N,N-dimethylformamide-29% methanolic tetraethylammonium
hydroxide (5 to 1) , the fluorescent color changes, and the
identification limits are reported for carbazoles and polynuclear
carbazoles. A number of thin-layer chromatographic systems are
described, whereby carbazoles can be separated from other types of
compounds and from one another. Commercially pure chrysene is
separated readily by thin-layer chromatography into
5H-benzo(b) carbazole and chrysene. (Author abstract)##
00926
E. Sawicki, H. Johnson, and K. Kosinski
CHROMATOGRAPHIC SEPARATION AND SPECTBAL ANALYSIS OF POLYNUCLEAR
AROMATIC AMINES AND HETEROCYCLIC IMINES. Microchem. J.
Symp. Ser., 10 (1-4):72-102, Jan. 1966. {Presented at the
International Symposium on Microchemical Techniques—1965,
Pennsylvania State Dniv., University Park, Aug. 22-27, 1965.)
Many polynuclear aromatic amines are carcinogenic. Consequently,
methods of separation and analysis for these compounds have been
developed. The separation methods include the use of column and
thin-layer chromatography. Various methods of characterization
for approximately 45 polynuclear aromatic amines and heterocyclic
imines on the thin-layer plate and in solution have been compared.
The absorption and fluorescene spectra of aromatic amines and
their cationic and anionic salts have been discussed. The use of
direct fluorometric examination of thin-layer plates for aromatic
amines was useful in the nanogram to microgram range.
Quenching techniques were shown to make the fluorometric analysis
of aromatic amines and heterocyclic imines much more selective.
(Author summary) ##
00927
E. Sawicki and T. W. Stanley
A SENSITIVE NEW PROCEDURE FOB THE ANALYSIS OF ALIPHATIC,
AROMATIC AND HETEROCYCLIC ALDEHYDES. APPLICATION TO AIB
POLLUTION. Preprint. 1958.
A new sensitive spot test for aliphatic, aromatic and
heterocyclic aldehydes is introduced. Limits of identification
for over 70 aldehydes are recorded. All aldehydes except chloral
and hexadecanal give positive results in the tests. A positive
test is revealed by a blue or a green color with wave length naxima
ranging around 610 to 630 mu. For the determination of total
aldehydes the procedure is at best an estimation. (Author
summary)*#
D. Measurement Methods 249
-------
00928
E. Sawicki
IDENTIFICATION AND DETERMINATION OF UNUSUAL FUNCTIONAL GHOUPS.
Pure Appl. Chea., 10,101-23, 1965. (Presented at a meeting of
International Onion of Pure and Applied Chemistry,
Pennsylvania State Univ.) 1965.
Functional group methods of analysis with sensitivities in the
nanogram to microgram region are described for the following
types of compounds: aromatic compounds more basic than benzene
and with the highest electron density at an unsubstituted aromatic
carbon atom, azulenes with an unsubstituted 1-position, compounds
with a cyclopentadiene CH2 grouping by itself or as part of a
polynuclear ring system, compounds containing a fluoranthenic ring
system, pyrene and its derivatives, pyridine and its derivatives,
polynuclear aza heterocyclic compounds, various types of aromatic
amines, heterocyclic imines, 3-indoly-methylene compounds,
heterocyclic imines containing the -NH-CH2-CH2- grouping,
guinones of various types, p-hydroxystyryl compounds, formic acid
and formates, and acylating agents. In addition,
quenchofluorometric methods and quenching reagents of value in
thin-layer chromatography are considered. (Author summary)##
00931
E. Sawicki, S. P. HcPherson, T. W. Stanley, J.
Meeker, and W. C. Elbert
QUANTITATIVE COMPOSITION OF THE URBAN ATMOSPHEKE IN TEEHS OF
POLYNUCLEAB AZA HETEROCYCLIC COMPOUNDS AND ALIPHATIC AND
POLYNUCLEAH AROMATIC HYDROCARBONS. Intern. J. Air Water
Pollution, Vol. 9:515-524, 1965. (Presented at the Air
Pollution Symposium, 149th American Chemical Society
Meeting, Detroit, Mich. Apr. 4-9, 1966.)
Nineteen polynuclear aza heterocyclic compounds have been found in
the Nashville atmosphere. Of these compounds
dibenz (a,h)acridine, dibenz (a,j)acridine, and possibly some of the
alkylated derivatives of dibenz (a,j)acridine and
benz(c)acridine are known carcinogens. Because of this finding,
a quantitative study has been made of the atmospheres of six large
American cities in terms of polynuclear aza heterocyclic
compounds and polynuclear aromatic hydrocarbons. In addition,
the quantitative composition of a composite sample (consisting of
the yearly accumulation of airborne particulates from over 100
American communities) has been determined in terms of long-chain
aliphatic hydrocarbons, polynuclear aza heterocyclic compounds, and
polynuclear aromatic hydrocarbons. (Author abstract)tt
00934
E. Sawicki, T. W. Stanley, H. C. Elbert, and H. Morgan
COLUMN AND THIN-LAYER CHROMATOGBAPHIC SEPARATION OF POLYNOCLEAH
RING-CARBONYL COMPOUNDS. Talanta, Vol. 12:605-616, 1965.
250 HYDROCARBONS AND AIR POLLUTION
-------
Methods for the separation of polynuclear ring-carbonyl compounds
by alumina column chromatography and alumina and cellulose
thin-layer chromatography are described. A method for the
thin-layer chromatographic separation of acridones and
phenanthridones from other types of polynuclear compound is also
described. Compounds on a thin-layer chromatogram are located
by fluorescence methods employing trifluoracetic acid fumes and
tetra-ethylammonium hydroxide solution. Fluorescence spectra of
these compounds on the thin—layer chromatogram and in solution are
also reported. (Author summary)##
00942
D. F. Adams
IMPROVED SULFUR-REACTING MICROCODLOMETRIC CEIL FOR GAS
CHRCMATOGRAPHY. Anal. Chem., 38(8)1094-1096, July 1966.
(Presented at the Air Pollution Symposium, 150th Meeting,
American Chemical Society, Atlantic City, N.J., Sept.
1965.)
Because of the differences in electron requirements for oxidation
of H2S, S02, mercaptans, and organic sulfides and disulfides,
it is necessary to standardize the titration cell against each type
of compound or calculate the electron eguivalents for each
oxidation reaction for quantitative gas chromatographic analysis.
To increase the sulfur specificity and to eliminate the need for
individual corn-pound calibration, the column effluents may be either
oxidized to S02 or reduced to H2S in a suitable furnace prior
to introduction into the microcoulometric titration cell to obtain
an equivalent response for an equivalent number of sulfur atoms.
The furnace oxidation prior to titration should also destroy any
olefinic compounds which might be present in complex gas
mixtures, be titrated by bromine, and be erroneously reported as
sulfur. Reduction to H2S rather than oxidation to S02 has the
added advantage of providing a four-fold increase in sensitivity
because of the greater electron change required for the bromine
oxidation of H2S. Although the need for individual calibration
for each compound favors the use of a furnace between the
chromatography column and the detector, it complicates the
analytical system and thus may not be suitable for process
control analysis under mill conditions. (Author summary)##
00966
S. S. Epstein
THO SENSITIVE TESTS FOR CARCINOGENS IN THE AIR. J. Air
Pollution Control Assoc. 16, (10)545-6, Oct. 1966. (Presented
at the 59th Annual Meeting, Air Pollution Control
Association, San Francisco, Calif., June 20-25, 1966, Paper
No. 66-19.)
This report describes briefly 2 new bioassays, the photodynanic
and mouse neonate, which have been developed recently as indirect
and direct measures, respectively, of the carcinogenicity of
organic atmospheric pollutants. The photodynamic assay measures
concentrations of photosensitizing polycyclic compounds in organic
extracts of atmospheric particulates, and reflects the ability of
Measurement Methods 251
-------
these compounds to sensitize cells to the otherwise non-toxic
effects of long-wave ultraviolet light. The relevance of this
assay to carcinogenicity depends on the previous demonstration, in
a large series of polycyclic compounds of a strong positive
association between photodynamic toxicity, using the motile ciliate
Paramecium caudatum, and carcinogenicity attributable to
polycyclic compounds. The use of neonatal animals for the
carcinogenicity testing of pure chemicals is well documented.
Neonates have been shown to be highly sensitive to defined
carcinogens, administration of which in very low concentrations,
in general, results in high tumor yields with relatively short
latency periods. The present studies, although primarily
methodological, established the high sensitivity of neonatal nice
to carcinogens extracted from air.t#
00977
R.S. Yunghans W.A. Hunroe
CONTINUOUS MONITORING OF AMBIENT ATMOSPHERES HITH THE
TECHNICON AOTOANALYZER. In: Automation in Analytical
Chemistry, 6pp. (Presented at the Technicon symposium,
"Automation in Analytical Chemistry," New York City, Sept.
8, 1965.)
A variety of air contaminants can be monitored continuously with
Auto/Analyzers. Instrument sensitivity, precision, and
response time are more than adequate. The basic modules are
all interchangeable, the instrument does not become obsolete as
chemical procedures change or are modified, new approaches can be
programmed easily, and the equipment is useful in methods
research. In addition, automatic baseline programing and
restandardization are decidedly advantageous as is the
capability for introducing liquid calibration standards at any
time.##
00998
E. Sawicki, T.H. Stanley, J.D. Pfaff, W.C. Elbert
THI8-LAYER CHROMATOGRAPHIC SEPARATION AND ANALYSIS OF
POLYNOCLEAR AZA HETEROCYCLIC COMPOUNDS. Anal. Chim. Acta,
Vol. 31:359-75, 196U,
Hany thin-layer chromatographic systems can be used for the
general separation of aza heterocyclic compounds from
polynuclear aromatic hydrocarbons. Several can be used for the
separation of the aza compounds from each other. With alumina
as the adsorbent the sterically hindered aza heterocyclic compounds
can be readily separated from the non-hindered aza compounds. The
use of the trifluoro-acetic acid spot test on the thin-layer plate
is discussed. Spectral data for the aza compounds are presented
and discussed. (Author summary)##
252 HYDROCARBONS AND AIR POLLUTION
-------
01023
H. Buchwald
ACTIVATED SILICA GEL AS AN ADSORBENT FOB ATHOSPHERIC
CONTAMINANTS. Occupational Health Rev. (Ottawa) Vol.
17(4} :U-18, 1965.
The use of activated silica gel as an adsorbent for ataospheric
eontaninants is reviewed. The basic principles influencing the
adsorption of substances on silica gel are discussed. The
advantages and disadvantages in the use of silica gel are
highlighted by some studies on the adsorption of such conaon
solvents as acetone, aroaatic hydrocarbons and sone halogenated
hydrocarbons. (author abstract)##
01178
I. H, Killiams
GAS CHROHATOGRAPHIC TECHNIQUES FOE THE IDENTIFICATION OF LOS
CONCENTRATIONS OF ATMOSPHERIC POLLUTANTS . Anal. Chea. 37, (13)
1723-32, Dec. 1965.
Sethods have been developed for collecting low concentrations of
volatile organic compounds froa the atmosphere and gualitatively
analyzing them by gas chronatographic and related techniques.
An inert substrate at -80C is used as a collecting agent while
subtractive techniques, two different types of detectors and
retention times on two columns of differing polarity are used in
identifying the collected compounds. Over thirty organic
coapounds have been identified. These include a large nunber of
paraffins, soae aroaatics, particularly benzene and toluene, some
chlorinated hydrocarbons and on a few occasions ethyl nitrate and
•ethyl disulfide. The pattern of coapounds present has varied
very little over the period studied, though, concentrations have
varied by a factor of twenty or isore. (Author abstract) t*
01205
B, Truitt and J. ». Robinson
RESEARCH ON NEW TECHNIQUES IN ABSORPTION AND EMISSION SPECTSOSCOPI
(QDARTERLt PROGRESS SEPT.). Louisiana State Univ., Baton
Rouge. Jan 25, 1966. 17 pp.
DDC: AD «79-2«1
A demountable hollow cathode was designed and constructed. The
signal was erratic and electrical shorting across the electrodes
took place. The cathode was aodified and tested. The enission
spectra of aluainun, copper, heliua, fused annonium dihydrogen
phosphate and naphthalene has been recorded. The NH4 H2P04
(in heliu«) gave eaission lines characteristic of aluaicua, PO
and NH, Saission from metallic elements in sealed hollow
cathodes can fee greatly intensified with an electron bea>.
Initial experiaents vith nolecules indicate that electrons can be
transported froa one electrode to another without causing
eeission, (Author abstract)**
D. Measurement Meftods 253
-------
01208
E. R. Stephens and F. R. Butleson
ANALYSIS OF THE ATHOSPHERE FOR IIGHT HYDROCARBONS. J. Air
Pollution Control Assoc. 17, (3) 147-53, Bar. 1967.
(Presented at the 59th Annual Meeting, Air Pollution Control
Association, San Francisco, Calif., June 20-25, 1966, Paper
No. 66-108.)
A procedure has been developed for the analysis of trace
quantities of light hydrocarbons in air. A freeze-trap filled
with chromatographic packing was installed in.place of the gas
sample loop of a flame ionization.chromatograph. An air
sample of 0.1 to 0.5 liter volume was-passed through the trap which
was chilled with liquid oxygen. The trap was then brought to ice
temperature and its contents simultaneously swept into the
column. The resulting chromatogram could be used to determine
about twenty-five hydrocarbons through n-hexane. The nininum
detectable concentration was below one ppb for these hydrocarbons.
with such sensitivity it is possible to make useful measurements
even on samples of light air pollution. Air samples from the
Riverside area were'analyzed in this fashion starting in the
summer of 1965. The relative amounts of these hydrocarbons were
then compared with the distribution reported for the various.known
hydrocarbon sources. The attenuation of the more reactive
hydrocarbons by photolysis was also observed.- A system for
irradiating trapped air samples was also constructed. Samples
were collected in five gallon brosilicate bottles which were then
irradiated with ultraviolet radiation and the concentration '
changes followed. (Author abstract)##
01225
E. S. Jacobs
RAPID GAS CHROMATOGHAPHIC DETERMINATION OF C1 TO C10
HYDROCARBONS IN AUTOMOTIVE EXHAUST GAS. Anal. Chen. 38,
(1) U3-8, Jan. 1966. (Presented at the 119th Meeting,
Division of Water, Air and Haste Chemistry, Detroit, Mich.,
Apr. 1965.)
A gas chromatographic procedure is described for the rapid
determination of C1 to C10 hydrocarbons in automotive exhaust
gas. The method features the application of a programmed
temperature run from -55 C. "to plus 1HO C. with a single open
tubuXar column and flame ionization detector. As many as 85 C1
to C10 paraffins, olefins and aromatic hydrocarbons may be
determined within 13 minutes. Automatic integration of the flame
detector signal is used to provide instantaneous quantitative
analysis for as little as 1 ppm (v./v.) of each hydrocarbon.
The equipment and operating conditions of the chromatographic
method are discussed and an analysis of exhaust gas is illustrated.
(Author abstract)*t
Z54 HYDROCARBONS AND AIR POLLUTION
-------
01230
N. L. Soulages
SIMULTANEOUS DETERMINATION OF LEAD ALKYLS AND HALIDE SCAVENGERS IN
GASOLINE BY GAS CHBOBATOGBAPHY HITH FLABE IONIZATION DETECTION .
Anal. Chem. 38. (1) 28-33, Jan. 1966.
A gas chromatographic method with flame ionization detection for
the determination of lead alkyls and scavengers in gasoline is
described. These compounds are separated in a partition column
and hydrogenated using a nickel catalyst, and the resulting methane
and/or ethane is separated from gasoline hydrocarbons on an
absorption column. The equipment employed and its application to
the continuous analysis of leaded gasolines are discussed. The
reliability of results and the lack of interferences are verified
with both laboratory-prepared and commercial samples. (Author
abstract)##
01232
E. Sawicki, T. W. Stanley, and W. C. Elbert
DIRECT FLDOROBETRIC SCANNING OF THIN LAYER CHROHATOGBAHS AND ITS
APPLICATION TO AIR POLLDTION STUDIES . J, Chromatog. 20, 348-53,
1965.
A direct method is presented for automatic fluorometric scanning
of thin-layer chromatograms with much greater selectivity and
sensitivity than has hitherto be<;n possible. By use of the proper
excitation and emission spectral bands, a chromatogram can be
examined for an individual compoind or for a family of compounds.
In addition, quenchofluorometric techniques applied to the
thin-layer plate eliminate many interferences and further improve
the sensitivity.t#
01238
L, DeHaio and B. Corn
GAS CHROMATOGEAPHIC ANALYSIS OF POLYNDCLEAR AROBATIC HYDROCARBONS
WITH PACKED COLUMN (APPLICATION TO AIR POLLDTION STUDIES).
Anal. Chem. 38, (1) 131-3, Jan. 1966.
A method utilizing gas chromatography for the analysis of
polynuclear aromatic hydrocarbons has been suggested for general
use. The method was developed for use in analyzing polycyclic
hydrocarbons associated with particulate matter in the air:
however, it can be used wherever it is required to analyze for
polynuclear aromatic hydrocarbons. The primary advantages of this
method when compared to the methods now used are the ease of
performance and time differential. One man can easily complete
the analysis in two hours after the sample is extracted from the
filter. Previously, several analysts required two days to
complete the procedures.**
D. Measurement Methods 255
-------
01269
F. D. Fleming, B. Dimitriades, and R. W. Hum
PROCEDURES IN SAMPLING AND HANDLING AUTO EXHAUST. J. Air
Both the composition and discharge rate of auto exhausts vary
widely and rapidly as speed and load demands upon the engine are
changed. Moreover, among the combustion products are compounds
that are highly reactive under proper conditions and others that
are readily bound by receptive surfaces or absorbents. Onder
these conditions both the sampling procedure and subsequent sample
handling must be such that (1) the sample that is recovered
contains all or a fixed proportion of each incremental volume of
the total to be represented and (2) the products so sampled are not
allowed either to react with each other or to be lost or diminished
in sample storage or transfer. Experimental research and
development relevant to each requirement have been carried out, and
results are reported and discussed. Two methods have been used
for recovering small-volume samples representative of the total
volume produced during any combination of steady or transient
engine modes. One employs a servo-followup system appropriately
coupled to both the engine air-intake and to the sampling element;
the sampling rate is continuously controlled to bear at all tines a
fixed ratio to the engine air-intake rate. The second method
employs variable dilution, involving addition of diluent gas
necessary to maintain a constant total of (exhaust plus diluent).
If the mixture is sampled at a constant rate, the sample will
contain exhaust appropriately proportioned. Experiments have
shown differences in both hydrocarbon and NOx values determined
for comparable samples obtained by the two methods. The
seriousness of this problem is discussed in relation to the
sampling and sample handling procedures that are used. (Author
abstract)##
01278
K. Grob
GAS CHHOMATOGRAPHY OF CIGABETTE SMOKE, PART III. SEPARATION OF
THE OVERLAP REGION OF GAS AND PARTICULATE PHASE BY CAPILLARY
COLUMNS . J. Gas Chromatog. 3, 52-6, Feb. 1965. (Presented
in part at Tobacco Chemists* Research Conference, Raleigh,
N.C., Oct. 22, 196U.)
Following the investigation of gas phase constituents boiling
within-the range of 20-100C, the section of less volatile
substances with boiling points between 100 and 200C has been
studied. The separation by capillary columns is demonstrated, and
61 substances are indicated as probable gas phase constituents.
The partition of certain substances between gas phase and
particulate phase is shown to be of great importance. Some
influences upon the partition equilibrium, for instance charcoal
filters, are discussed. (Author abstract)##
256 HYDROCARBONS AND AIR POLLUTION
-------
01289
H. Feldstein, S. Balestrieri, and D. A. Levaggi
STUDIES ON THE GAS CHEDHATOGBAPHIC DETERMINATION OF MEBCAPTANS.
J. Air Pollution Control Assoc. 15(5):215-7, May 1965.
(Presented at the Sixth Conference on Methods in Air
Pollution Studies, California Dept. of Public Health,
Berkeley, Calif., Jan. 6-7, 1964.)
A series of partitioning agents were studied to determine their
ability to separate organic sulfur compounds by gas chromatography.
Several columns showed promise, but did not separate organic
sulfur compounds from normally occurring atmospheric hydrocarbons.
Higher concentrations of organic sulfur compounds in stack gases
are separated as metallic salts in a- series of impingers. The
nature of the precipitated sulfur compound can be determined by gas
chromatography after regeneration of the compound by addition of
acid to the metallic precipitate. (Author abstract)##
01302
S.S. Epstein, H. Small, E. sawicki, H.L. Falk
PHOTODYNABIC BIOASSAT OF POLYCYCIIC ATMOSPHERIC POLLUTANTS.
J. Air Pollution Control Assoc., Vol. 15(4) :174-176, April
1965. (Presented at the Sixth Conference on Methods in Air
Pollution Studies, California Dept. of Public Health,
Berkeley, Calif., Jan. 6-7, 1964.)
A photodynamic bioassay which can be conducted on one mgm
amounts of organic atmospheric particulates is described. The
results of a pilot study on pollutants from several American
cities indicate that the assay may provide a rapid, simple and
economical biological index of potential carcinogenic hazard
attributable to polycyclic compounds. The utility of the
assay for this purpose is under further evaluation. (Author
abstract) ##
01304
K.B. Barlage, Jr. F.C. Alley
SAMPLING AND MASS SPECTROMETER ANALYSIS OF REACTION PRODUCTS
FROH THE PHOTOCHEMICAL DECOMPOSITION OF VARIOUS OLEFINS. J.
Air Pollution Control Assoc., 15 (5) :235-238, Hay 1965.
Results of this investigation have shown the sampling technigue
described in this paper to have ptential for mass spectrometer
analysis of trace products from the photochemical decomposition
of olefins. In addition, preliminary results of this
investigation using 1—pentene and 1—hexene as reactants, along
with nitrogen dioxide in air mixtures, have shown the presence
of compounds or ion fragments of compounds with molecular masses
as high as 166 and possibly higher. More work is needed to
determine if these compounds are indeed peroxyacyl nitrites or
nitrates, "compound X," or perhaps some from of a polymer
produced in the photochemical reactions.##
D. Measurement Methods 257
-------
01310
E.A. Boettner F.C. Dallos
ANALYSIS OF AIR AND BREATH FOR CHLORINATED HYDROCARBONS BY
INFRARED AND GAS CHROHATOGRAPHIC TECHNIQUES. Am. Ind. Hyg.
Assoc. J. Vol. 26:289-293, June_1965. (Presented at the
Annual Meeting, American Industrial Hygiene Association,
Philadelphia, Pa., April 28, 1965.)
This paper is a report of an investigation establishing the
sensitivity of gas chromatography and infrared techniques for the
chlorinated aliphatic hydrocarbons listed in the booklet
"Threshold Limit Values for 1963." The gas chromatographic
measurements include those made with the following detection
methods: thermal conductivity, flame ionization, argon
ionization, and electron capture. The infrared work was done
with the aid of scale expansion techniques and multipass cells
up to 40 meters in length. The analytical technique used
and the sensitivities attained in the analysis of air and exhaled
breath are presented. (Author abstract)##
01333
A. Y. Ping, L. R. Clayton, T. E. McEwen, and J. S.
Paydo
THE APPLICATION OF SILICA GEL IN SOURCE TESTING. PART I:
COLLECTION OF SAMPLES. Preprint.- (Presented at the 59th
Annual Meeting, Air Pollution Control Association, San
Francisco, Calif., June 20-25, 1966, Paper No. 66^79.)
The engineering of air pollution'control'deals with testing gas
effluents for air contaminants and their concentrations. In this
endeavor, the Bay Area Air Pollution Control District
has developed and improved a technique of using silica gel
adsorption tubes for determining test data on the organic^compound
emissions from commercial and industrial operations. This.paper
discusses a phase of source testing for such gaseous emissions from
solvent-user operations. General details, involving the sample
probe, sampling train, and pressure drops are included in the
paper. Some typical test data and calculations are also given.
(Author abstract)**
01356
C.W. Louw
THE QUANTITATIVE DETERMINATION OF BENZO(A) PYRENE IN THE AIR OF
SOOTH AFRICAN CITIES. Am. Ind. Hyg. Assoc. J., Vol.
26:520-526, Oct. 1965.
The atmospheres of three South African cities have been
investigated for the presence of polynuclear hydrocarbons.
Standard techniques were improved and applied for
separation of benzo (a)pyrene from other polynuclear hydrocarbons.
Ultraviolet-visible spectrophotometry at the U02 n aicron peak .
was employed for quantitative determination of benzo(a)pyrene.
A correction factor for the interference of benzo(k)fluoranthene
258 HYDROCARBONS AND AIR POLLUTION
-------
at the 402 m micron peak was determined experimentally and
applied to the results. It is believed that this method
is more reliable than those presently used. Some
benzo(a)pyrene concentrations are presented. (Author abstract)ft
01392
C.L. Fraust, E.B. Hermann
CHARCOAL SAHPLING TUBES FOR ORGANIC VAPOB ANALYSIS BY GAS
CHROMATOGRAPHY. Am. Ind. Hyg. Assoc. J., 27(1):68-71,
Feb. 1966.
Variation in efficiency of recovery of organic vapors collected
on activated charcoal and desorbed into carbon disulfide, was
studied with respect to certain parameters of the process.
Chemicals used were methylethyl ketone, toluene,
trichloroethylene, butyl acetate, 2-methylcyclohexanol, and
styrene. Analyses were performed with a gas chromatograph.
The effects of charcoal mesh size, sampling rate, volume
collected, and vapor concentration were considered. Mesh
sizes of carbon granules studied were 10/20, 20/30, 30/10, and
10/50. Also, a special vapro adsorption charcoal, 60/80 mesh
was used. Effects of sampling rate were determined over a 100
ml/min range. From 0.5 to 1.5 liters of sample were collected for
experiments dealing with volume collected. In studying the
effect of carying concentration, a range of 1 TLV to 5 TLV
was employed. (Author abstract)ft
01395
R. Tye, A.W. Horton, I. Eapien
BENZO (A)PYRENE AND OTHER AROMATIC HYDROCARBONS EXTRACTABLE FROM
BITUMINOUS COAL. Am. Ind. Hyg. Assoc. J., Vol. 27:25-28,
Feb. 1966.
Benzo(a)pyrene, benz(a)anthracene, and other polycyclic
aromatic hydrocarbons have been shown to be present in bituminous
coal. Extraction with toluene, chromatography on alumina, the
Diels-Alder reaction, solubility in concentrated sulfuric acid,
and catalytic iodination on alumina were coupled with
ultraviolet spectrophotometry and mass spectrometry to obtain
quantitative estimates of these compounds in the extracts.
(Author abstract)**
01119
A. Turk, J. I. Borrow, S. H. Stoldt, and W. Baecht
ENHANCED DESORPTION OF ATMOSPHERIC SAMPLES FROM ACTIVATED
CARBON . J. Air Pollution Control Assoc. 16 (7):383-385, July
1966. (Preliminary portion of this work was presented before the
Division of Water and Waste Chemistry, 141th Meeting,
American Chemical Society.)
It has been previously shown that the desorption of either a
chemisorbed or a physically adsorbed gas can be enhanced by the
D. Measurement Methods 259
-------
subsequent introduction of a foreign gas. Under conditions in
which desorption recovery of butane from activated carbon was 50
to 65%, subsequent adsorption of CCT* enhanced the recovery of
butane to 100%. Recovery of CC12F2, originally 79%, was
enhanced to 99% by the same method. The method of enhanced
desorption was applied to the recovery of samples from activated
carbons exposed to atmospheres in Chicago, Mew Orleans,
Philadelphia, Washington, B. C,, and Cincinnati. Three
different types of carbons, characterized by different
distributions of pore diameters, were used simultaneously in the
Cincinnati sampling. In general, the enhanced desorption
technique was advantageous in providing analytical information on
adsorbed samples recovered from carbon media. The enhancement
effect is especially marked with hydrocarbon material. The
effects of these structural attributes of the carbon media are
evaluated by detailed consideration of infrared adsorptions.
(Author abstract)#f
01U30
V. B. Huebner, H. G. Eaton, and J. H. Chaudet
A GAS CHROMATOGRAPH FOB THE APOLLO SPACECRAFT (PBELIMINARY
BEPT .) J. Gas Chromatog. , Vol. 4:121-125, April 1966.
Gas chromatographic columns and detectors suitable for monitoring
the atmosphere within a space vehicle are described. Holecular
sieve, liquid coated Teflon, and liquid coated Chromosorb
columns were developed to achieve a high degree of separation and
freedom from adsorption for the most likely atmospheric
contaminants. Miniature cross-section ionization detectors have
been designed to provide better than 10 ppn sensitivity for most of
these contaminants. The chromatographic system has been designed
to operate at a flow rate of only 12 ml/min, thus assuring a long
operational time from a small gas container. (Author summary
modified) ##
01«51
B. J. Prager
DETECTION OF 1,1-DIMETHYLHYDRAZINE BY FRUSTRATED MULTIPLE
INTEBNAL REFLECTION SPECTROSCOPY. Am. Ind. Hyg. ASSOC. J.,
Vol. 27:272-277, June 1966.
The detection of vapors, especially of the missile propellant
fuel, 1,1-dimethylhydrazine, by frustrated multiple internal
relection (FHIR) spectroscopy was studied. This method is most
sensitive to substances with high boiling points; however, it can
be used 'to detect microgram quantities of substances with
relatively low boiling points by coating the FMIR plate with a
thin adsorptive film or by dissolving the samples in a suitable
solvent. (Author abstract)ft
01U61
A. J. Chiantella, W. D. Smith, H. E. Umstead, and J.
E. Johnson
260 HYDROCARBONS AND AIR POLLUTION
-------
AROMATIC HYDROCARBONS IN NUCLEAR SUBMARINE ATMOSPHERES. Am.
Ind. Hyg. Assoc. J., Vol. 27:186-192, Apr. 1966.
in analytical study has been directed to the identification and
determination of individual aromatic hydrocarbons present in
nuclear submarine atmospheres in concentrations of parts per
million or less. Hydrocarbon oil samples were desorbed from
activated carbon which had been exposed in submarine atmospheres.
The aromatic hydrocarbon content of these oils was approximately
25 to 30% of the total. The quantitative distributions of
individual aromatic hydrocarbons found in submarines were
strikingly similar to those of typical petroleum distillates in the
same boiling range. Several commercial products were studied as
possible sources of hydrocarbons in submarine atmospheres.
(Author abstract) *f
01495
A. A. Strong and J. F. Horton
THE INSTRUMENTATION FOR AUTOMATIC MEASUHEMEBT AND RECORDING OF
LABORATORY-PRODUCED AUTOMOBILE EXHAUST. Preprint. 1966.
I A system that automatically measures and records the concentration
of six different gases from twelve animal exposure chambers
supplied with diluted, laboratory-produced automobile exhaust and
i other gases is described. The gases are sequentially fed fron the
animal exposure chambers to the appropriate gas analyzing
instrument. Multipoint recorders connected to the output of the
gas instruments register the concentrations and control the
sequence of the gas measurements. A data acquisition system is
also connected to the output of of the gas instruments to record on
a punched paper tape the time of measurement and the gas
concentration. The data are punched on cards or inserted directly
into a digital computer for analysis. (Author abstract)##
01199
E. E. Campbell and H. M. Ide
AIR SAMPLING AND ANALYSIS HITH MICHOCOLUMNS OF SILICA GEL.
Am. Ind. Hyg. Assoc. J. 27, (<») 323-31, Aug. 1966.
This paper describes a simple microcolumn of silica gel, its
behavior under experimental conditions and its applicability to air
sampling. Data are presented for the ultraviolet spectral
absorbance analysis of selected aromatic hydrocarbons, using a
base line correction for background in-terference. The problems of
direct silica gel elution and ultraviolet spectrophotometry are
discussed, and resolution of the particulate background problem by
base line calculations is shown. The silica gel microcolumn is
proved, simple, practical, and highly efficient for sampling air
contaminants. Although only spectrophotometric analysis of
eluates is reported here, other methods of analyzing the sorbed
contaminant are suggested. (Author abstract)##
D. Measurement Methods 261
-------
01503
L. E. Green, D. K. albert, and H. H. Barber
A SEHI-AUTOMATIC GAS CHROMATOGRAPH FOB DETERMINING N-PARRAFFINS
AND HYDROCARBON TYPES IN GASOLINES. J. Gas Chromatog.,
« (9):319-321, Sept. 1966.
A gas chromatographic method for determining aromatics, saturates,
and olefins in gasolines recently was extended to include
individual C5 to C11 n-paraffins. Three optional analyses with
the instrument are described. To determine the accuracy and
precision of the semi-automatic method, 6 samples were analyzed and
the results compared with those obtained by the FIA method. The
instrument is adaptable to routine use and is applicable to
samples other than gasolines, and has recently been adapted to the
determination of hydrocarbon types in exhaust gases.ft
01560
C. J. Domke, D. J. Lindley, and C. N. Sechrist
HOW TO STUDY EFFECT OF BLOWBY GAS. Hydrocarbon Process
1*5(9) : 303-306, Sept. 1966.
The character and chemical composition of blowby gases were
studied by ducting them from an engine modified with Teflon parts
and fractionating them in a series of traps at 32, -100, and -326
F. The fractions were analyzed by infrared absorption, mass
spectrometry, and gas chromatography. The hydrocarbons portion
of the blowby gas was roughly 50% aromatics, 35% saturates, and
15% olefins. The combined concentration of oxygenated organic
compounds present in the blowby gas was found to be less than
five parts per million. The analytical data showed that changing
air-fuel ratio had little or no effect on the composition of the
hydrocarbons being emitted from the crankcase.tt
01581
E.D. Barber
IDENTIFICATION OF AROMATIC COMPOUNDS AS SIMPLE AZINES BY PAPEH AND
THIN-LAYER CHROHATOGRAPHY. J. Chromatog., Vol. 27:398-406,
1967.
A method is described for the separation of carbonyls as simple
azines by paper and thin-layer chromatography. Schliecher and
Schuell 2040 a gl. papers were used in paper chromatography.
Extensive data are given for separations on papers impregnated
with N,N-dimethylformamide in (1) N,N-dimethylformamide-
cyclphexane; (2) dibutyl ethertetrahydrofuran - N, N-
dimethylformamide; (3) cyclohexane - N,N-dimethylformamide -
carbon tetrachloride; (4) cyclohexane - N,N-dimethylformamide -
ethylacetate - water and (5) decalin - N,N-dimethylformaaide.
Separations were also performed on papers impregnated with
methylformanilide in cyclohexane-formanilide. Thin-layer separ-
ations were performed on silica gel in benzene; ethyl acetate -
hexane; benzene - paraffin - acetic acid-water; dibutyl ether
tetrahydrofuran; dichloromethane; and decalin - dichloromethane -
262 HYDROCARBONS AND AIR POLLUTION
-------
nethanol. An example of the thin-layer separation of an
automobile exhaust sample is given. (Author abstract)##
01592
F.L. Ludwig, D.M. Coulson, E. Robinson, L.A. Cavahagh
SIZE DETERMINATION OF ATMOSPHERIC SULFATE AND ORGANIC
PABTICULATES (-.INTERIM REPT.). Stanford Research Inst.,
Henlo Park, Calif. Dec. 196U. 78 pp.
Methods of determining size distributions of sulfate and
organic aerosols have been developed and tested in the San
Francisco and Los Angeles areas. The methods show promise
of providing size distribution information which could
significantly add to the understanding of some current public
health problems. The heart of the sample collection system is a
Goetz Aerosol Spectrometer, which has been
modified to prevent loss of sample or entrainment of
contaminated air and to allow collection of the particles which
are not deposited in the spectrometer itself. Enough data have
benn collected to prove the feasibility of the methods
developed. Furthermore, these initial data provide a
preliminary estimate of size distributions of the sulfate and
organic aerosols in the tested areas. The Appendix contains
discussions of the calculation of size distribution and effect of
temperature and humidity on sulfuric acid droplet size.##
01593
METHODS OF MEASURING AIB POLLUTION (--REPORT OP THE WORKING PARTY
ON METHODS OF MEASURING AIR POLLUTION AND SURVEY TECHNIQUES).
Organisation and Development, Paris, France, Directorate for
Scientific Affairs. 1965. 9t pp.
Methods for the measurement of the amounts of the following
pollutants in the atmosphere out of doors using relatively
simple and inexpensive apparatus were examined: grit and dust -
particles coarse enough to settle out under their own weight;
suspended matter - particles or droplets fine enough to
remain suspended in the air; sulphur oxides; hydrocarbons; and
fluorine compounds.##
01683
R. Klein, B.E. Rebbert, R. Stair, R.S. Tipson
AIR POLLUTION PROGRAM, NATIONAL BUREAU OF STANDARDS
(QUARTERLY HEPT. OCT.1, 1965 TO DEC. 31, 1965.) National
Bureau of Standards, Washington, D.C., Divisions of
Analytical Chemistry, Metrology, and Physical Chemistry
(Rept. No. 9031). (NBS with PHS Support) 1965.
Progress is reported on: the purification of naphthacene;
anthraguinone derivatives; oxidation products of pyrene; oxidation
products of perylene; photochemical reaction on the solid
particulates anthracene and pyrene; photochemical reactions of
D. Measurement Methods 263
-------
pyrene on Maryland soil; photochemical reactions of pyrene on
silica gel-alumina; photosensitized decomposition of 3-
methylpentanal; surface chemistry; and solar radiation.**
01693
I.R. Cohen T.C. Purcell
SPECTROPHOTOKETRIC DETERMINATION OF HYDROGEN .PEROXIDE WITH 8-
QHINOLINOL. Preprint. 1966.
A method is reported for the spectrophotometric determination of
microgram quantities of hydrogen peroxide. The analytical
procedure makes use of the colored- complex obtained upon
extraction of titanium-hydrogen peroxide mixtures with a 0.1%
solution of 8-guinolinol in chloroform. The method is very
specific and more sensitive than that which uses the color
given by titanium and hydrogen peroxide alone. The optimum • •
procedural conditions were selected with regard for the effect of
temperature, pH, rate of color formation, stability of complex,
and the like. Application of the method for the analysis of vapor
concentrations is also discussed. {Author abstract)**
01696
H. Johnson, E. Sawicki
SPECTRAL CHARACTERIZATION OF NITROARENES AND POLYCYCLIC
ALDEHYDES, KETONES, QUINONES, AND AMINES. Talanta 13, 1361-73,
1966.
Three methods are introduced for the post-chromatographic
spectral characterization of carbonyl and nitro compounds. Most
often, elution from the chromatogram is necessary, but sometimes
fluorescence spectra can be obtained directly from the
chromatogram. The usefulness and sensitivity of the methods have
been demonstrated for a variety of nitroarenes and polycyclic
aldehydes, ketones, quinones, and amines. (Author abstract)**
0171U
W. Kutscher and R. Tomingas
INVESTIGATING SOOT AND ATMOSPHERIC DOST IN THE MANHHEIM AREA.
STAUB (English Transl.) 26, (6) 5-10, June 1966.
The benzpyrene content of different types of soot was determined
quantitatively. Soot from coke firing is practically free from
benzpyrene. Soot from oil firing exhibits considerable variations
in its chemical composition and benzpyrene content. Soot from
hard coal firing has the highest benzpyrene content. In addition,
dust collected in a filter plant at a level of 49 n was also
investigated. The largest part of benzpyrene is bound to the
finest coal particles which penetrate to the deepest alveolar
chambers of the lungs. More than 70% of the dust is comparatively
free from benzpyrene. Finally, a test is carried out to calculate
the amount of dust in air and the amount of benzpyrene to which a
breathing person is exposed. (Author summary)**
264 HYDROCARBONS AND AIR POLLUTION
-------
01720
E. D. Barber and J. P. Lodge, Jr.
PAPER CHROMATOGRAPH1C IDENTIFICATION OF CARBONYL COMPOONDS AS
THEIR 2,4-DINITROPHENYLHYDROZONES IN AUTOMOBILE EXHAUST.
Anal. Cham. 35, 348-50, Bar. 1963.
A method is described for the separation and identification of
carbonyl compounds in automobile exhaust by paper chromatography,
Extended data are given for separations in a modified Heigh
phase as well as for limited separations in DeJonge's system.
Although homologous aldehydes are completely separated, ketones
show higher Rf values than aldehydes of the same carbon number.
The results of analysis of several samples are
presented. (Author abstract)##
01729
E, Sawicki, T. W. Stanley, T. E. Hauser, H. Johnson,
and W. Elbert
CORRELATION OF PIPERONAL TEST VALUES TOR AROHATIC COMPOUNDS WITH
THE ATHOSPHERIC CONCENTRATION OF BENZO (A)PYRENE. Intern.
J. Air Water Pollution 7, 57-70, 1963.
Several general methods for the determination of aromatic
compounds in polluted air are described and compared. Of these
the piperonal test is most thoroughly investigated in respect to
precision, color stability, and general usability. The color
obtained in the procedure is in compliance with Beer's law.
Over the last four years approximately 200 samples of airborne
particulates have been analysed for their piperonal test K
values and their concentrations of benzo(a)pyrene. These two
values show a fair but definite correlation. For some
communities, the correlation is good, for a few it is poor. A
broad range of values is obtained: a sample from Gulf State
Park in Alabama showed a K755 value of 0.009 and a concentration
of 0.076 micrograms of benzo(a)pyrene per 1000 cubic meter of air;
for a london sample the K755 value was 13 and the benzo (a)pyrene
concentration 270 microgram; for an incinerator stack sample the
K755 value was 4900 and the benzo (a)pyrene concentration 19,000
microgram benzpyrene per 1000 cubic meter of gas. The correlation
coefficients between benzo (a)pyrene concentration in micrograms per
1000 cubic millimeter (X), and the piperonal test K755 values
(Y) , were 0.95 and 0.89 for 17H urban and 25 non-urban samples,
respectively. The corresponding formulae are X equal -0.52 plus
19.3Y for urban samples and X egual -0.132 plus 15-3Y for
non-urban samples. The piperonal test.should be of value in
studying combustion processes, the aromatic compound pollution in
various parts of a community, and in evaluating the effluents of
pollution sources. (Author abstract)##
01735
E. Sawicki, T. W. Stanley, W. C. Elbert, and J. D.
Pfaff
D. Measurement Methods 265
-------
APPLICATION OF THIN LAYER CHROHATOGHAPHY TO THE ANALYSIS OF
ATHOSPHERIC POLLUTANTS AND DETERMINATION OF BENZO(A)PYRENE.
Anal. Chem. 36, (3) U97-502, Hat. 1964.
Rb-values, and fluorescent colors have been obtained through
thin-layer chromatography of 20 polynuclear aromatic hydrocarbons
with the following absorbents and developers: . alumina with
pentane: ether (19:1; v./v.); cellulose acetate with
ethanol:toluene:water (17:t:1; v./v.); and cellulosxecellulose with
dimethylformamide:water (1:1, v./v.). Of the three absorbents,
alumina gave the best separation of fluowescent organic compounds
from the organic fractions of.airborne and air pollution source
particulates. The pattern and fluorescent color of the spots of a
thin-layer chromatogram varied with the type of pollution. The
cellulose acetate absorbent system gave best results for the
separation of the benz-pyrene fraction obtained in column
chromatography. The cellulose adsorbent system gave the best
results for the separation of the polynuclear aromatic
hydrocarbons. The greatest range in Hb-values was obtained with
this absorbent. Two methods for the estimation of benzo (a)pyrene
following thin layer chromatography are described. One method
involves ultraviolet analysis at 382 millimicrons, the other
method involves spectrophotofluorometric analysis in sulfuric
acid. (Author abstract)f#
01781
E. Sawicki, T.R. Stanley, J.D. Pfaff, W.C. Elbert
THIN-LAYER CHROMATOGRAPHIC SEPARATION OF BENZO (A)PYRENE AND
BENZO (K)FLOOBANTHENE FROM AIRBORNE PARTICULATES. Chenist-
Analyst 53, 6-8, Jan. 196U.
By column chromatography followed by thin-layer chromatograpy a
better separation was obtained. The latter technic is
relatively simple and rapid and offers the advantage that enough
material can be readily obtained for spectrophotofluorometric
study and, with somewhat more difficulty, for absorption spectral
studies. It has been found that using a cellulose acetate
adsorbent and ethanol-toluene-water as the solvent'benzo (a)pyrene
and benzo(k)fluoranthene can be readily separated from each other
and from other members of the "benzpyrene" fraction. (Author
abstract) *#
0178K
D.F. Adams, R.K. Koppe, B.N. Tuttle
ANALYSIS OF KRAFT-BILL, SULFUR-CONTAINING GASES WITH GLC
IONIZAION. J. Air Pollution Control Assoc. 15, (1) 31-3,
Jan. 1965
The technique includes the use of two chromatographic columns in
series to separate 02, N2,CO,C02, H20, H2S, S02, and
CH3SH. Column 1, containing Triton U5 on Chromosorb,
separates H20, H2S, S02 and CH2SH. Column 2, packed
with Holecular Sieve, separates 02, N2, C02. The
conditions required to obtain adequate sensitivity and
separation are discussed. (Author abstract)tf
266 HYDROCARBONS AND AIR POLLUTION
-------
01795
E. Sawicki, T.W. Stanley, w.C. Elbert
ANALYSIS OF THE URBAN ATMOSPHERE AND AIK POLLUTION SOUBCE
EFFLUENTS FOR PHENALEN-1-ONE AND 7H-BENZ(DE)ANTHRACEN-7-
ONE. Mikrochim. Acta (5-6), 1110-23, 1965.
Through the use of one- and two-demensional thin-layer
chromatography and direct spectrophotofluorometric examination of
thin-layer plates, two members of a new family of compounds have
been found in the atmosphere. Phenalen—1—one and 7
H-Benz (de)anthracen-7-one were identified and determined in
particulates obtained from urban atmospheres and air pollution
source effluents. Scanning techniques and other methods of
analysis were also used in characterization and estimation. Two-
dimensional thin-layer chromatography followed by direct
spectrophotofluorometric analysis appears to be the most promising
chromatographic method for the routine analysis of chemical
compounds in complex mixtures. It approaches colorimetric
analysis in simplicity and speed and surpasses it in sensitivity,
selectivity and the amount of information that can be obtained
from one analysis. (Author summary)##
01798
B.D. Tebbens, J.F. Thomas, H. Hukai
PARTICULATE AIR POLLUTANTS RESULTING FBCM COMBUSTION.
Am. Soc. Testing Hater., Spec. Tech. Publ. 352. (Presented
at the Symposium on Air-Pollution Measurement Methods, Los
Angeles, Calif., Oct. 5, 1962.) pp 3-31, Dec. 1963.
An enormous variety of organic by-products result from both
oxidative degradation of fuels and synthesis of complex molecular
species occurring simultaneously when combustion is incoeplete.
Synthesis is demonstrated by the fact that polynuclear aromatic
hydrocarbons with molecular weights up to 300 may be derived from
incomplete combustion of such a simple fuel as methane. These
hydrocarbons are part of the solid phase of combustion by-products
and may be filtered from gaseous components. Among them are the
arenes naphthalene, anthracene, pyrene, benzo(a)pyrene,
dibenz(a,h) anthracene, and others. Additionally, there exist
relatively non-volatile oxidation derivatives such as alpha- and
beta-naphthol and others. Only a few of the 90 or more
individual chemical entities found in these series have been
postively identified. Sufficient evidence exists from burning
a variety of gaseous, liquid, and solid fuels to state
categorically that it is the process of combustion rather than the
chemical quality of the fuel which leads to synthesis of these
arenes. Fuels studied include natural gas; propane; butane;
1-butene; 1,3-butadiene; ethyne, hexane; 2,2,4 trimethylpentane
cyclohexane; 1-hexene; benzene; toluene; and gasoline, as well as
the miscellaneous celluloses involved in incineration of paper,
wood, tree trimmings, and the like. The same range of aromatic
hydrocarbons has been separated from contaminated air in distressed
urban atmospheres. Investigation of aldehydes produced
by combustion indicated that only formaldehyde decreased with
increasing secondary air when combustion was incomplete. However,
with complete combustion, use of additional secondary air
D. Measurement Methods 267
-------
was accompanied by an increasing quantity of formaldehyde. Thus
using large excesses of secondary air to control smoke may be
inadvisable for air-pollution control. The total amount of
arenes produced depends in part on the incompleteness of the
burning process. While one would assume that the smoking point
of fuels would be an index of relative ease of combustion and of
relative desirability of fuels for urban usage, the possible
production of combustion nuclei is also suggested. Such a
criterion may become significant in choosing fuels suitable for
use in urban environments. (Author summary modified)!*
01802
T.R. Hauser E.L. Cummins
INCREASING SENSITIVITY OF 3-METHYL-2BENZOTHIAZftLONE
HYDROZONE TEST FOR ANALYSIS OF ALIPHATIC ALDEHYDES IN AIR,
Anal. Chem. 36. (3) 679-81, Mar. 1961.
A modification of the (3-methyl-2-benzothizolone hydrazone test)
procedure is described in which the addition of sulfamic acid,
in the oxidizing step of the reaction, gives a solution free of
turbidity and capable of colorimetric analysis without dilution
by acetone. A reduction in the volume of the oxidizing
agent originally added in this step further contributes to the
concentration of the color. Although a comparison of this
procedure with that of Sawicki shows a loss in molar
absorbance, the sensitivity of the method is increased
approximately sixfold. This increased sensitivity easily
permits the analysis of aliphatic aldehydes7 in the parts-per-
billion range in ambient air.## '
01817
E. Sawicki, J.E. Meeker, J. Morgan
COLUMN CHROHATOGRAPHIC SEPARATION OF BASIC.POLYNUCLEAR AROMATIC
COMPOUNDS FROM COMPLEX MIXTURES. J. Chromatog. 17, 252-6,
1965.
A new method for the column chromatographic separation of
basic polycyclic fractions of extremely complicated mixtures is
described. Heterocyclic hydrocarbons sterically hindered at the
aza nitrogen atom are readily separated from non-sterically .
hindered aza compounds. Aza heterocyclic hydrocarbons with the
same amount of steric hindrance are eluted in the order
of their increasing number of fused rings per molecule. The
method has been applied to the separation of the basic
fraction of coal tar pitch. An alkylbenzo(h)quinoline,
benzo (h)guinoline, benzo (f)guinoline, acridine, benz(a)acridine
and benz (c)acridine have been identified. In addition,
approximately 100 unknown compounds were believed to be present
in the fractions. The evidence for this conclusion was derived
from the absorption spectra. (Author summary)*f • .
268 HYDROCARBONS AND AIR POLLUTION
-------
01823
G.C. Ortman
HONITORING HETHANE IN ATMOSPHERE WITH A FLAME IONIZATION
DETECTOR. Anal. Chem. 38, 64«-6, Apr. 1966.
Complex analytical problems are involved in the study of the
reactants and products of atmospheric photochemical reactions.
One such problem is the determination of atmospheric hydrocarbons
levels and the relation of these to emissions of hydrocarbons from
vehicles and other sources. The greatest interest is in those
hydrocarbons that participate in photochemical reactions.
Hhile methane is innocuous and while it does not participate
in photoinitiated reactions, it does constitute a major portion
(about 65%) of the total hydrocarbons present in air and nearly
all of the nonreactive fraction. A rough correlation may thus be
seen to exist between "reactive hydrocarbons" and "total
hydrocarbons less methane." Pending the development of a type-
specific method for determing ractive hydrocarbons directly, it
has been found that a compound-specific method for methane has
real value. The system for methane measurement operates by
passing a sample air stream through a solid adsorbent which
has been stripped of all hydrocarbons and then saturated with
6 to 10 p.p.m. of methane in air. The effluent from a column
of air less all hydrocarbons except methane passes into a flane
ionization analyzer. (Author abstract)**
01826
H. C. Elbert, and T. W. Stanley
THE FLUORESCENCE-QUENCHING EFFECT IN THIN-LAYER CHROMATOGRAPHY OF
POLYNUCLEAR AROMATIC HYDROCARBONS AND THEIR AZA ANALOGS.
J. Chromatog. 17, 120-6, 19&5.
Fluorescence quenching effects were studied with volatile
quencher in the developer, with a relatively non-volatile quencher
after development. On the basis of quenching effects the aromatic
compounds can be divided for analytical purposes into
non-fluoranthenic aromatic, fluoranthenic and aza hydrocarbons.
The latter group can be further subdivided. Two systems for
the separation of polycyclic aza hydrocarbons elute according to
the size of the ring system and the amount of steric hindrance at a
ring nitrogen atom. Pyrenoline can be characterized by the
specific violet color it forms on the plate. The various methods
show promise for use in air pollution studies. (Author summary)*#
0183T
L. C. Broering, Jr.
AN EVALUATION OF TECHNIQUES FOR MEASURING AIR-FUEL RATIO.
Preprint. (Presented at the Annual Meeting, Society of
Automotive Engineers, Detroit, Mich., Jan. 10-11, 1965.)
Four methods for determining air-fuel ratio by exhaust analysis
are compared. The methods selected for study are all potentially
useful with analyses of integrated samples obtained in road tests
D. Measurement Methods 269
-------
or exhaust samples generated in the laboratory. A V-8 engine
mounted on an engine dynamometer was used to generate exhaust,
from which the air-fuel ratios were determined simultaneously by
the various methods. The air-fuel ratio of the mixture delivered
to the engine was determined by measuring directly the quantities
of air and fuel supplied. This value was compared to those
obtained by the four exhaust analysis techniques. Comparisons
were made during normal operation and during conditions of
deliberate cylinder misfire to simulate the most adverse
combustion condition encountered on the road. (Author abstract)!*
01832
C. A. demons and A. P. Altshuller
RESPONSES OP ELECTRON-CAPTURE DETECTOR TO HALOGENATED SUBSTANCES.
Anal. Chem. 38, (1) 133-6, Jan. 1966. (Presented before the
Division of Water, Air, and Waste Chemistry, T»8th Meeting,
American Chemical Society, Chicago, 111., Sept. 196U.)
Authors' investigation of the respones of the electron-capture
detector to halogenated hydrocarbons revealed that the responses
varied over about seven orders of magnitude. Low responses are
shown by saturated and vinyl-type fluorinated hydrocarbons
including those containing one chlorine atom. Compounds with the
chlorine atom attached to a vinyl carbon gave lower responses than
the corresponding saturated compounds. Attachment of the chlorine
to an allyl carbon atom resulted in greater sensitivity than that
obtained for the corresponding saturated compound. The
response characteristics of the fluorinated cyclobutane ring
closely resembled those of compounds with allyl CF3 groups.
The completely fluorinated benzene derivative, C6F6, gave a
high response. As reported previously, the response decreased in
the order I greater than Br greater than Cl greater than F
and also increased markedly with increase in the number of Cl,
Br, or I atoms in the molecule. One iodine atom in a molecule
caused about the same response in the same range as two bromine
atoms or three chlorine atoms. Responses in molecules of
different structures containing the same number of halogen atoms
varied by one to two orders of magnitude.*#
01871
CONTINUOUS AIR MONITORING PROGRAM IN WASHINGTON, D.C.
(1962-1963). Public Health Service, Cincinnati, Ohio, Div.
OF AIR POLLUTION. SEPT. 1966. 222 PP.
HEW: 999-AP-23; GPO: 827-23U-15
This report presents the results of the operation of the
Public Health Service Continuous Air Monitoring Program
(CAMP) in Washington, D.C., during 1962 land 1963. Data on
atmospheric levels of sulfur dioxide, oxides of nitrogen, total
oxidants, total hydrocarbons, and carbon monoxide are sumnarized,
analyzed, and discussed. The data are tabulated as hourly, daily,
and monthly mean concentrations; background information about
Washington and a description of the instrumentation used
are included. (Author abstract)**
270 HYDROCARBONS AND AIR POLLUTION
-------
01876
Schuette, F. J.
PLASTIC BAGS FOE COLLECTION OF GAS SAMPLES. California Dept.
of Public Health, Berkeley, Div. of Labs., AIHL-19, 8p.,
Dec. 1965. Also: Atmos. Environ., 1 (U) :51 5-5 19 , July 1967.
((12)) refs.
Criteria for judging what kind of film is likely to be most
suitable for a given application are delineated. Information
concerning supply sources of needed materials is provided.##
01922
E. Sawicki, R.A. Carnes, B. Schumacher
SPECTROPHOTOFLOORIHETRIC DETERMINATION OF 3-CARBON
FRAGMENTS AND THEIR PRECURSORS HITH ANTHRONE. APPLICATION TO
AIR POLLUTION. Bikrochim. Acta, No. 5 929-935, 1967.
5 refs.
Two modifications of an anthrone procedure for the
characterization and determination of -CH-CO-CHO and -CH-CHO
compounds and their precursors are described. Two main types of
fluorescence spectra are obtained. The procedure for analysis of
-CH-CO-CHO precursors works well for the aldopentoses; by
comparison, aldo and ketohexoses react poorly. Hater-soluble
fractions of airborne particulates were analyzed by the anthrone
procedure. At least three families of compounds were found: two
give fluorogens, of which one is a -CH-CO-CHO precursor, and
a third gives chromogen (s) absorbing at 423 and 540 microns.
(Authors' abstract) *#
01926
T. Bellar, J. E. Sigsby, C. A. demons, and A. P.
Altshuller
DIRECT APPLICATION OF GAS CHEOBATOGRAPHY TO ATMOSPHERIC
POLLUTANTS. Annal. Chem. 348 (7) 763-58 June 1962.
The use of a flame ionization detector permits direct
determination of hydrocarbons at concentrations found in the
atmosphere. Prior concentration of samples in a cold trap is not
necessary. Hith the system described, the investigators were
able to detect the lower molecular weight hydrocarbons found in
automotive emissions in controlled irradiation studies. Ease of
operation, high sensitivity, and reproducibility are advantages of
the technique. Concentrations as low as 0.001 p.p.m. may be
detected in air samples. The experimental parameters required to
obtain these results are evaluated. Instrumental modifications
required for several applications are discussed, with emphasis upon
development of a reliable system with which the hydrocarbons at
atmospheric concentrations can be determined routinely. (Author
abstract) ##
D. Measurement Methods 271
-------
019 7 3
E, Sawicki, H. Johnson, and T. H. Stanley
THE DETERMINATION OF NITBATE OR NITRATE PLUS NITRITE WITH
AHINOPYRENE: APPLICATION TO AIB POLLUTION. Anal. Chen.
35, 1934-6, Nov. 1963.
A new procedure is introduced for the determination of nitrate or
nitrate plus nitrite. The two ions can be determined together.
since they produce similar spectra and Beer's law curves. These
ions can be determined in the presence of up to 50 equivalents of
bisulfite. The new nitrate procedure, which utilizes
1-aminopyrene, is compared with the 2,4-xylenol, 2,6-xylenol,
phenol-2,4-disulfonic acid, brucine, and chromotropic acid
procedures. With the use of sulfamic acid, nitrate can be
determined in the presence of 6 micrograms of nitrite ions. The
advantages of the 1-aminopyrene procedure are that it is simple
and direct and more sensitive than any method found in the
literature. Amounts ranging from 0.04 (A eguals 0.1) to 1.6
micrograms of nitrate nitrogen per milliliter of aqueous solution
can be determined. The 1-aminopyrene procedure has been applied
to the determination of soluble nitrates in airborne particulates.
Nitrogen dioxide could be determined as nitrate plus nitrite with
the new method. The procedure introduced for the determination of
nitrate with 1-aminopyrene will be compared with these literature
methods. (Author summary modified)##
01979
A. P. Altshuller
GAS CHROMATOGHAPHY IN AIR POLLUTION STUDIES. J. Gas
Chromatog. 1, (7) 6-20, July 1963.
Gas chromatography as a powerful tool in the determination of the
chemical composition of trace constituents in sources of pollution
and in the atmosphere is reviewed. Topics covered include!
Calibration Methods; Subtraction Techniques; Detectors
(Thermal-Conductivity Detectors; Infrared C02 Detectors;
Electron-Impact lonization Detectors; Argon Type
lonization Detectors; Flame lonization Detectors; Flame
lonization Analyzers; Electron Capture Detectors); Column
Selection; Identification and Quantitative Analysis;
Atmospheric Analysis; Synthetic Atmosphere Analysis; Auto
Exhaust Analysis; Blowby Emission Analysis; Diesel Exhaust
Analysis; Incinerator Effluent Analysis.##
01991
V. Goppers and H. J;-Paulus
HACROMOLECULAR'COMPOUNDS ISOLATED'FROH AIRBORNE PARTICLES BY
ELECTHOPHORESIS AND PAPER CHROHATOGRAPHY. Am. Ind. Hyg.
Assoc. J. 23, 181-5, June 1962'.
Paper chromatography and electrbphoresis are used to isolate
microquantities of two biologically significant compounds, "A"
and "B," from samples of airborne particles. Electrophoretic
272 HYDROCARBONS AND AIR POLLUTION
-------
and chromatographic patterns are presented and discussed. A new
rapid electrophoresis method is described which requires only two
hours for separating a complicate'd mixture of aglycones.
(Author abstract) ft
E. Sawicki, T. W. Stanley, and J. Pfaff
A COMPARATIVE STUDY OF VARIOUS METHODS FOE THE DETECTION OF
FORMALDEHYDE. Chemist-Analyst 51, 9-11, Mar. 1962.
Identification limits for formaldehyde in various tests are
discussed. Tests involving the reaction of CH20 in H2S04
with chromotropic acid, J—acid, phenyl J-acid and
2-hydroxycarbazole may be considered together since a polynuclear
xanthylium dye is formed in all cases. The last reagent is the
least selective; the first 3 are highly selective but react with
CH20-releasing compounds in warm H2SO<*. Heat is
unnecessary with J-acid and phenyl J-acid for good results.
Thus,, most compounds that only release CH20 in heated H2SO'*
do not interfere in these 2 tests. The J-acid test may be
conducted spectrophotofluorometrically, allowing 1 part of
CH20 to be detected in 2 x 10 to the 8th power parts of test
solution. Acrolein can be differentiated from CH20 by emission
spectra. Three N2H4 reagents give positive results with
aliphatic aldehydes; with 2-hydrazinobenzothiazole the test is
more sensitive for CH20 than for other aliphatic aldehydes. The
2-nitro-1,3-indandione test is very sensitive, especially when
conducted spectrophotofluorometrically. The pure trimethine dye
formed in the 1-ethyl-guinaldinium iodide test has a molar
absorptivity of about 210,000 liters/mole cm'. A similar
selectivity was found with 1-ethyl-U-picolinium iodide as the
reagent.t#
01995
E. Sawicki, T. H. Stanley, J. Pfaff, and A. D'Amico
COMPARISON OF FIFTY-TWO SPECTBOPHOTOHETHIC METHODS FOR THE
DETERMINATION OF NITRITE. Talanta 10, 641-55, 1963.
This paper can be considered as a concise, source of
spectrophotometric methods for the determination of nitrite.
Fifty-two methods, of which about 36 are new, are compared with
respect to molar absorptivity, selectivity, sensitivity,
simplicity, colour stability, and conformity to Beer's law. A
new type of spectrophotometric procedure-autocatalytic in
principle-is introduced; a molar absorptivity of 620,000 is
obtained. Over 20 new methods have been shown to give higher
molar absorptivities with nitrite than any of the Griess type of
reagents. Consequently they are worthy of further investigation
in respect of their application to the analysis of nitrites and
nitrite precursors. (Author summary)##
D. Measurement Methods 273
-------
01997
E. Sawicki and T. W. Stanley
DETECTION AND COLORIKETRIC DETERMINATION OF POLYNITRO AROMATIC
COMPOUNDS. Anal. Chim. Acta 23, 551-6, 1960.
A sensitive new spot test for polynitro aromatic compounds is
introduced. In most cases a blue to green color is obtained using
fluorene (or some other polynuclear cyclopentadiene derivative)
as the reagent. A colorimetric procedure for the analysis of o-
and p-dinitro compounds is also presented. (Author summary)##
01998
T. W. Stanley
DETECTION OF POLYNUCLEAR DIARYL KETONES: APPLICATION TO AIR
POLLUTION. Chemist-Analyst U9, «I8 and 56, June 1960. '
In air pollution research, the problem exists of assigning the
strong carbonyl bands present in the infrared spectra of airborne
This has prompted the development of new tests for specific
classes of carbonyl compounds. This paper introduces a new method
for the detection of diary1 ketones, ArCOAr'., With the
exception of 2-benzoylthiophene, which gives a green color the
test is fairly selective for diaryl ketones having an equivalent of
three or more aromatic rings. It involves reaction of the ketone
with methylmagnesium bromide and subsequent solution in
trifluoroacetic acid giving red to blue colors of the diarylmethane
dye (ArC(CH3) Ar1)• (plus). "The colors formed are stable and
show no fading eve'n after four hours. Aliphatic, alicyclic, and
aralkyl ketones do not give colors distinguishable from the
yellow color of the blank.ft
01999
E. Sawicki and 8. R. Miller
DETECTION OF PYRENE, BENZO (A)PYRENE, AND OTHER POLYNUCLEAB
HYDROCARBONS. Anal. Chem. 30, (1) 109-10, Jan. 1958.
A new color test has been developed for the detection of
polynuclear compounds. A brilliant dark blue color was obtained
with pyrene and benzo(a)pyrene. Some eight compounds gave
red to violet colors. About 15 other hydrocarbons gave an.
essentially negative reaction. (Author abstract)t#
02048
E. Hunigen, N. Jaskulla, and K. Wettig
(THE REDUCTION OF CARCINOGENIC CONTAMINANTS IN EXHAUST GASES OF
PETROL ENGINES THROUGH FUEL ADDITIVES AND CHOICE OF LUBRICANTS.)
Die Herabsetzung Krebsfordernder Schadstoffe in
Ottomotoren-Abgasen Durch Kraftstoffzusat ze Und
Schmierstoffauswahl. Proc. (Part I) Intern. Clean Air
Cong., London, 1966. (Paper VI/12). pp. 191-3.
274
HYDROCARBONS AND AIR POLLUTION
-------
Data so far published about the content of 3,4 benzpyrene in the
exhaust gases of petrol engines vary greatly. A measurement
stand was set up to carry out routine tests on GDR Bade engines,
and a quantitative analysis method worked out by the Berlin
Institute for Hygiene employed thereby. Numerous
measurements indicate that hitherto publications do not permit an
objective evaluation of various types of engines. The reason
seems to be the considerable degree to which the measurement value
of 3,4 benzpyrene depends on the temperature at which the sample
is taken from the exhaust gas. Results indicate: the lower
the temperature at which the sample is taken the more hyperbolic
the increase of the 3,4 benzpyrene content. Hence, comparing the
amount of benzpyrene will only be meaningful as long as this is
done under clearly defined and identical test conditions-as long
as the pertinent causes remain unproven. Investigations of the
effect exercised by fuel additives and lubricants which were
carried out after the samples had been taken at comparable
temperatures indicate that the latter make the 3,4 benzpyrene
content practically disappear in the exhaust gases of two-stroke
petrol engines, whereas this effect is only exercised at the
beginning if the amount of lubricating oil is reduced, and is
hardly exercised at all if the ratio is lower than 1:40. However,
the hygienic evidence presented by the 3,4 benzpyrene measurements
will remain unclear as long as the ways for and means of
separating the substance from the carrier particles have not been
found, and as long as this is only dene by particulates with a
magnitude of 100-5,000 nm. Further work should be done in this
direction and for the purpose of laying down a MIK value.tt
02077
E. Sawicki R. Barry
NEB COLOUR TESTS FOR THE LARGER POLYNUCLEAR AROHATIC
HYDROCARBONS. Talanta 2, (2) 128-34, March 1959.
An investigation of the reaction of the aromatic aldehyde-
phosphorus pentachloride reagents with polynuclear aromatic
hydrocarbons has shown that a number of aldehydes can be
substituted for piperonal in this spectral test but only two were
specific for the more basic aromatic compounds. The 9-
anthraldehyde reagent gives intense bands in the 800-900
millimicron spectral region with the larger hydrocarbons. The 3-
nitro-4 diaethylaminobenzaldehyde reagent reacts readily
procedure is ideal for the analysis of peri-condensed aromatic
hydrocarbons. It was found that
trifluoracetic anhydride could be substituted for phosphorus
pentachloride in the test reagent, but no particular advantage was
incurred by this substitution. (Author abstract)#t
02078
E. Sawicki, T.W. Stanley, W, Elbert
HEW METHOD FOR THE SPECTROPHOTOHETRIC DETERHINATIOH AND
CHARACTERIZATION OF H,N-DIALKYLANILINES, DIPHESYLAHINES AND
CAHBAZOLES DSING 5-NITROISATIN. Hikrochim. Acta 3, 1961.
N,B-Dialkylanilines react with 5-nitroisatin chloride to give
a blue-green chromogen with a chharcteristic absorption spectrua.
D. Measurement Methods 275
-------
Aniline and N-alkylanilines give an essentially negative test.
Determination of N,N-dialkylanilines and diphenylamine and
carbazole derivatives is possible. (Author summary)#t
02079
E. Sawicki W. Elbert
NEW METHODS OF DETECTION OF GIYOXAL. Talanta 5, 63-5, 1960.
In the new colour and fluorescent tests for glyoxal introduced
in this paper it was found that a solution of the reactants on
filter paper could be heated with one-inch wide jet of steam
without any serious loss of solvent or acid. By this technique
the reagents 1:2-dianilinoethane, 2:3-diaminonaphthalene
and 2-aminothiophenol gave blue, green and blue stains
respectively, with corresponding identification limits of 0.1,0.2
and 0.05 microgram of glyoxal. With 2-hydrazinobenzothiazole a
golden-yellow fluorescence and an identification limit of 0.008
microgram of glyoxal was obtained. On the other hand, 0.1
microgram 2-aminothiophenol, 1 microgram,2:3-diaminonaphthalene,
and 1 microgram 1:2-dianilinoethane could be detected with glyoxal
as the reagent. (Author summary)i#
02080
E. Sawicki, T.B. Staley, J. Pfaff, J. Ferguson
NEW METHODS FOB THE SPOT TEST DETECTION AND
SPECTBOPHOTOHETHIC DETERMINATION OF FORMIC ACID. Anal.
Chem. 1962. pp. 62-9.
This paper describes the development of sensitive and selective
methods for the detection and determination of formic acid. The
following spot tests are discussed: J-acid spot test; HBT (2-
hydrazinobenzothiazole) spot test; HBTH (3-methyl-2-
benzothiazolone hydrazone hydrochloride) spot test; I-alkyl-
guinaldinium spot tests. The optimum selectivity and
sensitivity was obtained with I-methylguinaldinium toluene-p-
sulfonate; no interference was caused by ketones, aldehydes, and
other acids. The other reagents are more sensitive, but extremely
sensitive for formaldehyde. The J-acid spot test is the
simplest and gives a brilliant yellow fluorescence.
In spectrophotometric procedures, water was found' to have a
drastic effect on the intensity obtained, but high intensities
were obtained with the amount necessary for the solution
of formate salt. Yield of chromogens in quantitative methods
with diverse guinaldinium and lepidinium salts ranged from about
7 to 43% and the sensitivity might well be improved. A decrease
in the dilution factor (final vol. test solution vol.) would
improve'the sensitivities.##
02081
E. Sawicki W.C. Elbert
NEW SPECIFIC ANALYTICAL PROCEDURES FOR THE DETECTION AND
CHARACTERIZATION 6F 1,4-NAPHTHOQUINONES. Anal. Chim.
Acta 23, 205-8, 1960.
276 HYDROCARBONS AND AIR POLLUTION
-------
A new sensitive and Lspecific color test for 1,4-naphthoguinones
is introduced. With the reagent, o-aminothiophenol, a red color
is obtained in neutral solution on paper. 1,4-Naphthoguinones
containing electron-donor groups in the 2-position give a
negative reaction. With additional spectrophotometric
studies the guinones giving a positive test can be
differentiated. A new specific fluorescence test for 2-
hydroxy-1,4-naphthoquinone has also been developed. Reaction
with o-phenylenediamine on paper and then treatment with alkali
gives a brilliant rose-red fluorescence. (Author summary)##
02083
E. Sawicki W. Elbert
A SIMPLE SPECIFIC TEST FOR INNER-RING 0-QUINONES. Anal.
Chim. Acta 22, 448-51, 1960.
A simple specific test for inner-ring o-guinones is
introduced. The test consists of the reaction of the
guinone with 3,4-dinethoxyaniline in hot acetic acid
to give dye (s) absorbing near 600 mu. Spot test and
colorimetric modification of the test are described. Other types
of guinones and' ketonic compounds give negative results.
The spectra of the o-guinones in sulfuric acid are also presented.
With the new method, fairly specific tests are now available for
(a) inner-ring p-guinones, (b) inner-ring o-guinones, and (c)
terminal reing o- and p-guinones. (Author summary)*f
02084
E. Sawicki, T.R. Hauser, F.T. Fox
SPECTROPHOTOMETRIC DETERHINATION CF ALIPHATIC ALDEHYDE, 2,4-
DINITROPHENYLHYDRAZONES WITH 3-HETHYL-2-BENZOTHIAZOLINONE
HYDHAZONE. Anal. Chim, Acta 26, 229-34, 1962.
A sensitive new spectrophotometric procedure is described for
the analysis of aliaphatic aldehyde 2,4-dinitrophenylhydrazones.
The chromogens formed in the procedure absorb at 668 mu and are
approximately three times as intense at this band as the
starting aldehyde derivatives are in neutral and alkaline solvent
at their wavelength maxima. With further improvement the
procedure is capable of even greater sensitivity. Other
aliphatic aldehyde derivatives also should be analyzable by this
procedure,- but 2,4-dinitrophenylnydrazones of ketones do not react.
(Author summary)##
02085
E. Sawicki, T.W. Stanley, H. Elbert
SPECTROPHOTOHETRIC DETERMINATION OF AZOLENE WITH ELECTROPHILIC
REAGENTS. Proc. Intern. Symp. Microchemical Technigues
2, 633-42, 1961.
In a study of the. composition of the atmosphere in terms of
polycyclic aromatic hydrocarbons, analytical .methods for various
classes of these compounds have been recently developed. A study
D. Measurement Methods 277
-------
is presented of ten different spectrophotometric methods for the
microdetermination of azulene. Seven of these methods are new,
and two have been reported on recently. In most cases,
electrophilic reagents are chosen that form intensely colored
cationic chromogens with azulene. The new reagents are U-
azobenzenediazonium fluoroborate, indole-3-carboxaldehyde,
flavyliun perchlorate, xanthen-9-ol, l-anthraquinonediazonium
chloride, N,N-dimethyl-4-nitrosoaniline, and 5-nitroisatin
chloride. The results with these reagents are compared with
those obtained previously with N,N-dimethyl-U-aminobenzaldehyde,
3-methyl-2-benzothiazolone hydrazone, and 2-hydr,azinobenzothiazole.
In these diverse methods molar absorptivities are obtained ranging
from 12,000 to 100,000. Optimum conditions for reactivity,
sensitivity, selectivity, and stability are also discussed.
(Author abstract)#i
02086
E. Sawicki, T.B. Hauser, S. HcPherson
SPECTROPHOTOHETBIC DETERMINATION OF FORMALDEHYDE AND
FORMALDEHYDE-RELEASING COMPOUNDS WITH CHROHOTROPIC ACID, 6-
AMINO-1-NAPHTHOI-3-SULFONIC ACID (J ACID), AND 6-ANILINO-1-
NAPHTHOL-3-SDLFONIC ACID (PHENYL 0 ACID). Anal. Chem. 3U,
(11) 1160-U, Oct. 1962. (Presented before the Division of
Water and Waste Chemistry, 1t2nd Meeting, American Chemical
Society, Atlantic City, N.J., Sept. 1962.)
Three highly selective procedures for the determination of
formaldehyde and formaldehyde - releasing compounds are
introduced. In all cases xanthylium cationic or dicatonic dyes
are formed. Rhe procedures have sensitivities approximately two
and one-half times that of the chromotropic acid method.
A sensitive thermochromic blue spot test for formaldehyde with
6-amino-1-naphthol - 3 - sulfonic acid is described, and nine
different methods for the determination of formaldehyde are
compared. The interference of formaldehyde-releasing compounds
is discussed. (Author abstract)##
02087
E. Sawicki, T.W. Stanley, S. McPherson
SPECTROPHOTOMETRIC DETERMINATION OF 1,U-NAPHTHOQOINONE AND ITS
, 2,3-DICHLORO DERIVATIVE. Chemist-Analyst 50, 103-4, Dec.!
1961.
Some new color and fluorescent spot tests for the detection
and characterization of 1,4-naphthoquinones have been
reported. In the present paper, one of these test is extended to
the selective and sensitive spectrophotometric determination of
1,4-naphthoguinone and its 2,3-dichloro derivative employing
o-aminobenzenethiol as the chromogenic agent. As described
previously, the color-forming reaction involves the
formation of a hydroxybenzophenothiazine salt. For both 1,4-
naphthoguinone and its 2,3-dichloro derivative. Beer's law is
obeyed at 790 and 495 millimicrons over a concentration range
of 1 to 27 micrograms per ml. of final solution. The
molar absorptivities developed in the procedure at these two
278 HYDROCARBONS AND AIR POLLUTION
-------
wavelengths by both compounds are respectively, 15,000 and 16,000
liters per mole cm. Various substituted 1/4-naphthoquinones, such
as the 2-hydroxy and 2-methyl derivative, give entirely different
spectra with bands only 1/4 of the intensity of only 1/20 to 1/50
of the intensity of the 1-4 naphthoquinone. At 790 millimicron,
their absorbance is negligible. The non-interference of many
other types of compounds in the spectrophotometric procedure can
be anticapated from the qualitative findings described
previously.t#
02088
E. Sawicki, T-H. Hauser
SPOT TEST DETECTION AND COLOBIHETRIC DETERMINATION OF
ALIPHATIC ALDEHYDES WITH 2-HYDHOZINOBENZOTHIAZOLE: APPLICATION
TO AIR POLLUTION. Anal. Chem. 32, (11) 1434-6, Oct. 1960.
(Presented before the Air Pollution Symposium, Division of
Water and Baste Chemistry, 138th Meeting, American
Chemical Society, New York City, Sept. 1960.)
A versatile new procedure for the detection and determination
of aliphatic aldehydes is introduced. all modifications
of the new procedure have an especially high order of
sensitivity for formaldehyde. On the spot plate 0.01 microgran
of formaldehyde, 0.3 microgram of acetaldehyde, and 0.3 microgfam
of propionaldehyde can be detected; on paper 0.05 microgram of
formaldehyde, 1 microgram of acetaldehyde, and 1 microgram of
propionaldehyde can be detected. With proper standards, the
amount of formaldehyde can be estimated. A tube containing silica
gel impregnated with 2-hydrazinobenzothiazole solution can be used
to detect or estimate formaldehyde in the air or in auto exhaust
gases. A new colorimetric method for the determination of
formaldehyde has also been evaluated. It is reproducible and
sensitive, and can be applied to the determination of formaldehyde
in the air. In all these modifications an easily visible
brilliant blue color is obrainable. (Author abstract)f#
02089
E. Sawicki, J.L. Noe, F.T. Fox
SPOT TEST DETECTION AND COLOHIMETHIC DETERMINATION OF ANILINE,
NAPHTHYLAMINE AND ANTHHABINE DERIVATIVES WITH 4-AZOBENZENE-
DIAZONIUM FLUOBORATE. Talanta 8, 257-64, 1961.
Some new sensitive procedures are introduced for the
detection and and determination of anline, alph and beta
naphthylamines, and alph and beta-anthramines, as.well as their N-
alkyl and N,H-dialkyl derivatives. The chromogens are
(p-phenylazophenylazo)-aniline, -naphthylamine and -anthramine
dyes. For example with N,N-dimethylaniline, the blue di-cation
of N,N-dimethyl-p-(phenlazophenylazo)aniline is formed. '
The absorptivity of N,N-dimethylaniline obtained in the
colorimetric procedure is 0.823 microgram/ml/cm. In the
analysis for N,N-dimethylaniline, Beer's Law was obeyed from
0.1 to at least 3.6 microgram per ml of.final solution. Because
of the widely differing rates of reaction, naphthylamine or
anthramine derivatives can be determined in the presence of
primary and secondary amines. Spot tests for aniline.
0. Measurement Methods 279
-------
napthylamine and anthramine derivatives are described, but
their sensitivity does not compare with the sensitivities obtained
in the colorimetric procedure. (Author summary)##
02090
E. Sawicki, T.R. Mauser, T.W. Stanley, W. Elbert,
F.T. Fox
SPOT TEST DETECTION AND SPECTBOPHOTOMETRIC CHARACTERIZATION AND
DETERMINATION OF CARBAZOLES, AZO DYES, STILBENES, AND SCHIFF
BASES. APPLICATION OF 3-BETHYl-2-BENZOTHIAZOLONE
HYDRAZONE, P-NITROSOPHENOL, AND F-LUOROMETRIC METHODS TO THE
DETERMINATION OF CARBAZOLE IN AIR. Anal. Chem. 33, (11)
1574-9, Oct. 1961. (Presented before the Divisions of
Analytical and Hater and Waste Chemistry, 140th Meeting,
American Chemical Society, Chicago, 111., Sept. 1961.)
Two new spectrophotometric methods for the determination of
carbazole are introduced. Beer's law was obeyed from 4 to more
than 90 micrograms of carbazole in the 3-methyl-2-benzothiazolone
hydrazone and p-nitrosophenol procedures. Both methods can .be
used for the estimation of carbazole in the benzene extracts of
airborne particulates. Two new spot tests for carbazole are also
introduced. With the p-nitrosophenol test, 0.4 nicrograms of
carbazole can be detected. In strongly alkaline solution 0.2
micrograms of carbazole can be detected through the brilliant
blue fluorescence of the anion. Carbazole can be .characterized
and estimated in the benzene extract ,,of airborne
particulates by the p—nitrosophenol spot test and
spectrophotometric procedure, by the 3-methyl-2-
benzothiazolone hydrazone (MBTH) spectrophotometric
procedure, and by the excitation and emission spectra of the
material in pentane, dimethyl-formamide, and alkaline dimethyl-
formamide. The detection and determination of approximately
50 azo dyes and a smaller group of stilbene and Schiff base
derivatives using 3-methyl-2-benzothiazolone are also described.
(Author abstract)##
02091
E..Sawicki, T.W. Stanley, W. Elbert
SPOT TEST DETECTION AND SPECTROPHOTCMETRIC DETERMINATION OF
AZULENE COMPOUNDS WITH 2-HYDRAZINOBENZOTHIAZOLE OB 3-
METHYL 2-BENZOTHIAZOLONE HYDRAZONE. Microchem. J. 5, (2)
225-32, 1961.
Two sensitive new methods are introduced for the spot test
detection and spectrophotometric microdetermination of azulene
and its compounds. With 3-methyl-2-benzothiazolone hydrazone,
0.05 microgram of azulene .can be detected. (Author summary)#1
280 HYDROCARBONS AND AIR POLLUTION
-------
02092
E. Sawicki, T.W. Stanley, W.C. Elbert
SPOT TEST DETECTION AND SPECTROPHOTOMETEIC DETERMINATION OF
AZULENE DERIVATIVES WITH H-DIMETHYLAHINOBENZALDEHYDE. Anal.
Chen. 33, (9) 1183-5, Aug. 1961.
The detection and determination of .azulenes with tt-
dimethylaminobenz-aldehyde have been investigated. One
micrograra of azulene; .'guaiazulene, of 2,1,6-trimethylazulene can
be detected onca spot plate. These azulene compounds can be
determined spectrophotometrically at 620 or 642 micrograms (for
guaiazulene). Their molar absorptivities range around 90,000.
The chromogenes formed in the^procedure obey Beer's law from
0.1 to i» micrograms of azulene compound-per ml. of final
solution. Spectrophotometrically it was possible to detect 1 part
of the azulene compound in 5 million parts of test solution.
(Author abstract)##
02094
E. Sawicki, T.W.,Stanley, W.C., Elbert
SPOT TEST AND SPECTROPHOTOHETRIC DETERMINATION OF NITRITES AND
AROMATIC NITROSAHINES WITH BENZALDEHYDE 2-BENZOTHIAZOLYHYDHAZONE
AND P-PHENYLAZOANILINE. Mikrochim. Acta 6, 891-8, 1961.
Nitrous acid is reacted with p-phenylazoaniline to give the
diazonium salt which then combines with benzaldehyde 2- ,
benzothiazolyhydrazone to give a formazan. Addition of alkali
gives an intensely blue'anion. (Author summary)f#
02095
E. Sawicki W. Elbert
THERHOCHHOMIC DETECTION OF POL YNUCLEAR-1 COMPOUNDS CONTAINING
THE FLDOR2NIC HETHYLENE GROUP. Chemist-Analyst U8, 68-9,
Sept. 1959
A large number of aromatic hydrocarbons and their
derivatives contain the 6,5,6-fused, aromatic ring system of
fluorene. A simple, sensitive, and specific test for this
ring system would be of value in air pollution studies and in
organic analysis generally. Sprinzak found that fluorene reacts
in a strongly alkaline, pyridine medium with oxygen to yield
fluorenone. Sawicki and co-workers found that fluorenone and
structurally related ketones give a thermochromic reaction
in dimethylformamide containing sodium borohydride involving
reduction to the fluorenol and its anion. The new color
test for the fluorene moiety is based on a combination of
these observations. The fluorene derivative in
dimethylformamide made alkaline with tetraethylammonium hydroxide
forms a carbanion which is readily.oxidized by shaking with air
to the fluorenone,'and the latter is reduced by potassium
borohydride at the boiling point to the highly colored fluorenol
anion. On cooling and ahaking, the less highly colored fluorenone
is regenerated.##
D. Measurement Methods 281
-------
02096
E. Sawicki, T.W. Stanley, T. R. Hauser
A THERBOCHROMIC TEST FOR POLYCYCLIC P-QUINONES. Anal. Chem.
30, (12) 2005-6, Dec. 1958.
Many compounds containing a polyclyclic quinone structure show a
reversible thermochromic reaction in reducing media. This test
is useful for unsubstituted polycyclic q-quinones, such as
9,10-anthraquinone, 5,12-naphthacenedione, 6, 13-pentacenedionei
7,12-benzo(alpha)anthracenedione, and naphtho (2,3-alpha)pyrene-7.12
-dione - e.g., boiling a pink dimethyl-formamide solution of 5,12-
naphthacenedione in the presence of potassium borohydride gave
a dark blue solution, which upon cooling became pink again. This
color change can be repeated at least a dozen times. The color
reaction has been applied to air particulate matter in that the
presence of polycyclic quinone-like compounds has been demonstrated
in the aromatic fraction. (Author abstract)##
02097
E. Sawicki, T.R. Hauser, T.W. Stanley, H. Elbert
THE 3-METHYL-2-BENZOTHIAZOLONE HYDRAZONE TEST. SENSITIVE
HEW METHODS FOR THE DETECTION, SAPID ESTIMATION, AND
DETERMINATION OF A1IPHATIC ALDEHYDES. Anal. Chem. 33, (1)
93-6, Jan. 1961.
Sensitive new analytical methods for water-soluble aliphatic
aldehydes have been introduced. Versatile spot plate, paper,
silica gel, and colorimetric modifications of the procedure are
of value in the detection, estimation, and determination of these
aldehydes. In the test procedure an intensely brilliant blue
cationic dye is formed. Particularly advantageous is the
simple sensitive silica gel procedure for the detection or
estimation of aldehydes. The color of the dye obtained in the
colorimetric procedure for formaldehyde is much more intense than
any of the colors obtained for formaldehyde with well known
procedures. In the determination of formaldehyde. Beer's law
was obeyed from 5 to at least 125 micrograms per 100 ml. of
solution. The silica gel and colorimetric methods can be
applied to the analysis of auto exhaust fumes and polluted air.
Two simple methods for the synthesis of the reagent, 3-
methyl-2-benzothiazolone hydrazone, are described. (Author
abstract)#t
02098
4.P. Altshuller L.J. Leng
APPLICATION OF THE 3-METHYL-2-BENZOTHIAZOLONE HYDRAZONE
METHOD FOR ATMOSPHERIC ANALYSIS OF ALIPHATIC ALDEHYDES. Anal.
Chem. 35, (10) 15U1-2, Sept. 1963.
Presented in this study are results of work on fontrolled
synthetic atmospheres which provide data on collection efficiencies
and reproducibility and which give further indications of the
£82 HYDROCARBONS AND AIR POLLUTION
-------
accuracy of the method. Analyses also were made for
formaldehyde and acrolein, and results are compared with
those for total aliphatic aldehydes.i#
02121
H. D. Babina.
DETERMINATION OF CHLOROPRENE IN AIR. J. Anal. Chem. USSR
(English Transl.) 20, (11) 1300-2, Nov. 1965.
Chloroprene was sampled by absorption on silica gel treated to
free it of chlorine ions at a through-put rate of 0.5-1 liters/min.
The chlorprene was.then desorbed by the passage of hot air into
absorption flasks containing glacial acetic acid. Chloroprene was
determined photometrically by coupling with p-nitrophenyl-
diazonium. Error in this determination was plus and minus 20S.M
02130
R. Eberaneberhorst
(ENGINE COMBUSTION AND ITS EXHAUST GAS PRODUCTS AS A PROBLEM OF
HIGH INCIDENCE). Die Motorische Verbrennung und ihre
Abgasprodukte als Haufigkeitsproblem. ATZ
(Automobiltechnische Zeitschrift) (Stuttgart) 68 (8):263-268,
Aug. 1966.
The increasing incidence,of gasoline engines necessitates reducing
the air pollutants from exhaust gas by i*0» within the next 10
years. The influence of engine operation on the emission of
carbon monoxide, hydrocarbons and.nitrogen oxides is described,
e.g., in high gear, while changing gears and speeds (7-mode
California test), and in neutral. Limiting values for emissions
dependent on motor size and normal usage are suggested. Methods
to reduce exhaust gas pollutants included fuel injection systems to
replace carburetors and controlled turbulence techniques.t#
02135
E. S. Gronsberg
(COLORIMETRIC DETERMINATION OF VINYL CHLORIDE IN THE AIR.)
Kolorimetricheskoe Opredelenie Khloristogo Vinila v
Vozdukhe. Khim Prom (Moscow) (7) 30-1, 1966.
The method described in this paper is based on the ability of
ethylenic hydrocarbons to be oxidized by permanganate to glycol,
which on further oxidation with periodic acid yields formaldehyde.
The formaldehyde is then determined colorimetrically by reaction
with chromotropic acid. The air to be analyzed was passed over
activated charcoal; the charcoal was then extracted with a. 1:1
mixture of glacial acetic acid and ethyl alcohol. The data
indicate that vinyl chloride in air can be detected accurately in
quantities as low as 0.5 mg/liter. Methyl alcohol will
interfere with the reaction and must be removed by passage through
water and CaC12 before the vinyl chloride is absorbed on
charcoal. Ethylene also interferes with the determination.f#
Measurement Methods 283
-------
02157
A. P. Altshuller, T. A. Beilar, and C. A. demons.
CONCENTRATION OF HYDROCARBON ON SILICA GEL PEIOR TO GAS
CHHOHATOGRAPHIC ANALYSIS. Am. Ind. Hyg. Assoc. J. 23,
Apr. 1962. pp. 164-6.
In the determination of substances in various atmospheres by gas
chromatography the sample often must be concentrated prior to
analysis. Silica gel at dry ice-acetone temperatures has been
found to be a satisfactory adsorbant for concentration of
hydrocarbon and sulfur containing compounds. In the present work
recovery efficiencies are obtained for a number* of four and five
carbon paraffins and olefins. Isomerization reactions of olefins
of silica gel at elevated temperature were investigated. Losses
of very light hydrocarbons are discussed. Reproducibilities are
given for the analyses of several three, four and five carbon
hydrocarbons existing at concentrations between 0.005 and 0.2 ppm
in synthetic smogs. (Author abstract)ttt
02158
A. P. Altshuller, L. J. Lage, and S. F. Sleva.
DETERMINATION OF OLEFINS IN COMBUSTION GASES AND IN THE
ATMOSPHERE. Am. Ind. Hyg. Assoc. J. 23, 289-95, Aug.
1962.
Four-carbon and higher molecular weight olefins can be
quantitatively determined in the gas phase by reaction with
p-dimethylaminobenzaldehyde in concentrated sulfuric acid, heating
at 100 C, and measurement of the absorbance at 500 millimicrons.
The absorptivities are such that less than 0.1 ppm of gaseous
olefins can be determined. Interference by formaldehyde is
appreciable. Excess amounts of aromatic hydrocarbons and phenols
interfere somewhat in the procedure. Simple methods for removing
possible interferences in gas mixtures are discussed. The
method has been applied to the analysis of automobile exhaust and
diluted irradiated exhaust mixtures. (Author abstract)f#
02159
A. P. Altshuller and C. A. Clemens.
GAS CHROHATOGRAPHIC ANALYSIS OF AHOBATIC HYDROCARBONS AT
ATMOSPHERIC CONCENTRATIONS USING FLAME IONIZATION DETECTION.
ANAL. CHEM. 3«, (t) U66-72, APR. 1961. (PHESENTED.BEFORE THE
Division of Water and waste Chemistry,t110th fleeting,
American Chemical Society, Chicago, 111., Sept. 1961.)
In the present investigation, methods were developed for
preparing and transferring to the chromatograph vapor state
aromatic hydrocarbon in air-mixtures in the 0.05 to 5-p.p.m. range.
Quantitative analysis of automobile exhaust for six- to 10- or 11-
carbon aromatic hydrocarbons-in the 1-to 10-p.p.m. range has been
demonstrated. Quantitative analyses of synthetic photochemical
"snog" have been made on mixtures containing individual
aromatic hydrocarbons-in the 0.05- to 1-p.p.m. 'range. The
284 HYDROCARBONS AND AIR POLLUTION
-------
accuracy attained is sufficient to permit measurement of changes in
aromatic hydrocarbon concentration during irradiation with solar
type light sources. These measurements' provide evidence that
many aromatic hydrocarbons should photooxidize to an appreciable
extent in photochemical "smog" reactions in urban atmospheres.
(Author abstract) ##
02161
A. P. Altshuller and S. F. Sleva.
SPECTBOPHOTOMETBIC DETERMINATION OF OLEFINS. Anal. Chem. 33,
(10) TH3-20, Sept. 1961.
Four-carbon'and'higher molecular weight olefins can be determined
guantitatively in the'gas and liquid phases by reaction with
p-dimethylaminobenzaldehyde in"concentrated^sulfuric acid, under
appropriate'conditions, and measurement of'the absorbance at 500
millimicrons. With gaseous olefins, the absorptivities are such
that 0.1 p;p.m. or-less-can be determined. Interference by
formaldehyde;and excess aromatic hydrocarbons and phenols is
appreciable, and simple methods for their removal and discussed.
The"method has been applied to the analysis of automobile
exhaust and diluted irradiated exhaust mixtures. Liquid olefins
have been studied under somewhat different reaction conditions;
consequently, the positions, shapes, and intensities of the
absorption bands differ somewhat. Although the work on liquid
olefins was not as extensive as in the investigation of olefin
gases, the results should have applicability in the identification
and analysis of small quantities of liquid olefins. (Author
abstract)*#
02162
A. P. Altshuller and S. F. Sleva.
VAPOE PHASE DETERHI8ATION OF OLEFINS BI A COULOHETRIC
METHOD. Anal. Chem. (Presented before the Division of
Uater and Waste Chemistry^ 1<*0th Meeting, American-Chemical
Society, Chicago, 111., Sept. 1961.) 34, (3) 418-22, Bar.
1962
An instrument based on a bromocoulometric method has been
evaluated for analysis of olefins at concentrations between 20 and
1000 p.p.m. - The instrument has 'been calibrated for its vapor
phase response to a number of olefins, including ethylene,
propylene, propadiene, 1-butene, trans-2-butene, cis-2-butene,
isobutylene, 1,3-butadiene, 1-pentene, and 2-methyl-2-butene.
The possible interferencfe of a number of substances, including
sulfur dioxide, nitric oxide, nitrogen dioxide, hydrogen sulfide,
n-butyl sulfide, acrolein, phenol, and m-cresol, has been
investigated. Sulfur dioxide, hydrogen sulfide, nitrogen dioxide,
and acrolein react appreaciably with the brominating solution.
Nitrogen dioxide lowers the response to olefins. ^Severe
interference is experienced when the nitrogen dioxide concentration
equals or exceeds that, of olefins. Even when the olefins are
present in excess, the interference by nitrogen dioxide is
sufficient to necessitate removal of most of the latter. In
analyses of samples in containers, direct determination of these
vapor phase interference effects may"be'complicated further by gas
D. Measurement Methods 285
-------
phase reactions of olefin and nitrogen dioxide, and perhaps by
reactions within container walls. With this olefin instrument,
diluted automobile exhaust and a variety of synthetic mixtures have
been analyzed. Results have compared favorably with those
obtained by the colorimetric dimethylaminobenzaldehyde method.
(Author abstract)tt
02188
D. Bersis, and E. Vassiliou.
A CHEBILOMINESCENCE HETHOD FOR DETERMINING OZONE. Analyst
(Cambridge) 91, (1085) U99-505, Aug. 1966.
A method for determining ozine is described which is characterized
by the direct recording and automatic determination of ozone within
a wide range of concentrations. The development of the method is
based on the use of a chemiluminescent solution that is stable and
shows a linear relationship between the light emitted and the
ozone concentration. The electronic instrumentation used is
simple. Other methods of ozone analysis based on this principle
met difficulty, owing to the direct oxidation of the ,
chemiluminescent compound. The present method involves the use of
gallic acid as an ozone acceptor, and rhodamine B which remains
unchanged during the measurement as a photon emitter.
Observations made with an oscillograph of the light emitted by
single bubbles of ozonized air passing through the
chemiluminescent solution gave valuable information about the
response time of the system. (Author abstract modified)#f
02205
J.W. Thomas, K.H. Knuth
PATTERNS OF AEROSOL PARTICLES SETTLING IN STREAMLINE FLOW IN A
STRAIGHT HORIZONTAL TUBE. Intern. J. Air Water
Pollution 10, (9) 569-72, Sept. 1966.
The theory of particles settling in streamline flow in a
horizontal tube previously published has been expanded to take
into account the influence of the sampling filter in changing the
flow lines. Experiments with a 1.305 micron diameter monodisperse
polystyrene latex aerosol have shown excellent agreement with the
expanded theory. This modification of theory makes possible
a new method of determining the settling velocity and density of
a monodisperse aerosol. (Author abstract)f#
02226
E. Sawicki, F.T. Fox, W. Elbert, T.R. Hauser, J.
Keeker
POLYNUCLEAR AROMATIC HYDROCARBON COBPOSITION OF AIB POLLUTED
BY COAL-TAB PITCH FOMES. Am. Ind. Hyg. Assoc. J. 23, U82-6,
Dec. 1962.
Coal-tar-pitch pollution can be characterized by the large
amounts of anthracene, phenanthrene, pyrene and carbazole present
286 HYDROCARBONS AND AIR POLLUTION
-------
in collected airborne particulates. Carbazole has not yet
been found in pollution due to incomplete solid fuel combustion
products or auto exhaust fumes. Coal-tar-pitch pollution is
characterized by much higher P/BaP/BghiP, and BaP/Cor
ratios when compared to other types of pollution. The large
amounts of polynuclear hydrocarbons (and especially benzo (a)pyrene)
often present in coal-tar-pitch polluted air indicate the
necessity of a thorough study of this problem as it affects lung
cancer. *#
02227
E. Sawicki, E. Elbert, T.W. Stanley, T.R. Hauser,
F.T. Fox
SEPARATION AND CHARACTERIZATION OF POLYNUCIEAR AROMATIC
HYDROCARBONS IN URBAN AIR-BORNE PARTICULATES. Annal. Chem.
32, (7) 810-6, June 1960.
A simplfied procedure is described for the characterization of
polynuclear hydrocarbons in air-borne particulates. The method
involves one pass through a chromatographic column and subsequent
ultraviolet, visible, and fluorescence studies on the fractions
thus obtained. The final step then involves a destructive method
of analysis e.g., spectral analysis in sulfuric acid-or a color
test. The ultravioletvisible absorption spectra of analogous
fractions obtained from different communities are closely similar.
In the air-borne particulates of some 100 communities pyrene,
fluoranthene, benzo (a)fluorene and/or benzo (b)fluorene,
chrysene, benzo—(a) anthracene, benzo (a) pyrene, benzo (e) pyrene,
benzo(k)fluoranthene, perylene, benzo(g,h,i)perylene,
anthanthrene, and coronene are found consistently.t#
02233
R.L. Stenburg, D.J. Von Lehmden, B.P.'Hangebrauck
SAMPLE COLLECTION TECHNIQUES FOR COMBUSTION SOURCES -
BENZOPYRENE DETERMINATION. Am. Ind. Hyg. Assoc. J. 22, («)
271-5, Aug. 1961, (Presented at the 22nd Annual Meeting,
American Industrial Hygiene Association, Detroit, Mich.,
Apr. 1961.)
In evaluating combustion processes for their contribution of
benzo(a)pyrene and other potential carcinogens to the atmosphere,
the materials of interest may be lost during sampling unless the
collection temperature is controlled. Cooling of the gases
under both wet and dry conditions has been tried. This study
demonstrates that collection of benzo(a)-pyrene from high
temperature gas streams can be effectively accomplished by
filtration after cooling the gas stream to or near ambient
temperatures. A series of water bubblers and condensate traps
immersed in an ice-water bath, followed by a high efficiency filter
proved to be a satisfactory technique. (Author abstract)ft
D. Measurement Methods 287
-------
022«8
P. DiMattei P. Melchiorri
EFFECTS OF ORGANOPHOSPHORUS ESTERS ON THE CILIARY MOVEMENT AND
THEIR DSE FOB THE DETEFTION OF TRACES OF ORGANOPHOSPHOHUS.
COMPOUNDS. Arch. Intern. Pharmacodyn. 153, (2) 339-U5,
Feb. 1965
A correlation was found between the acetylcholinesterase activity
and the ciliary movement in cultures of ciliated epithelium
cells. DEP (disopropylfluophosphate) and paraoxon, added to the
culture medium at concentration levels of 0.00001M and 0.0001M
respectively, inhibited the acetylcholinesterase activity and
increased the ciliary movements. Concentrations of 0.0001B of
DEP and 0.001M paraoxon slowed the ciliary movements.
DFP and paraoxon at concentrations which slightly inhibited
the acetylcholinesterase activity increased the stimulatory effect
of acetylcholine on the motility of ciliated cells. This effect
may be used for the detection of very small quantities of
organophosphorus compounds. (Author summary)#f
02323
J.P. Flesch, C.H. Norris, A.E-, Nugent, Jr.
CALIBRATING PARTICIPATE AIR SAMPLERS WITH MONODISPERSEAEBOSOLS:
APPLICATION TO THE ANDERSEN CASCADE IMPACTOR. Am. Ind.,Hyg.
Assoc. J., p. 507-516, Nov.-Dec. 1967.. 10 refs. (Presented
at the American Industrial Hygiene Conference, Pittsburgh,
Pa., Hay 16-20, 1966.
Monodisperse aerosols of methylene blue dye generated via at
spinning disk and polystyrene latex aerosols generated via
atomization have been applied in calibrating a multi-stage cascade
impactor, the Andersen Sampler Model 0203. Previous
calibrations of impactors relied almost exclusively upon
the size-count method of analysis of test aerosols, usually
polydisperse, retained at the deposition sites to determine
their collection characteristics. Many difficulties encountered*
with this method are obviated by using nearly monodisperse
aerosols for calibration. Collection efficiency characteristics
of the Andersen Sampler are computed directly from mass retained
at the deposition sites, since concurrent size distribution
information on each aerosol generated indicates that values for
number and mass median diameter are nearly equal.
Experimental methods of generation, sampling, mass determination,
and aerosol evaluation are presented with representative data.
Collection efficiency curves obtained for the various stages of
the Andersen Sampler are given with computed values of effective
stage cutoff diameters for aerodynamically equivalent unit*
density spheres. Results are compared with those of previous
experimenters. (Authors' abstract)t#
02336
C. A. Parker and W. T. Rees.
DETERMINATION OF 3:H-BENZPYRENE IN THE ATMOSPHERE OF A
SUBMARINE. Admiralty Materials Lab., Poole, England,
288 HYDROCARBONS AND AIR POLLUTION
-------
General Chemistry Div. (A.M.L. Heport A/68 (M)) Mar.
1966. PP. 9.
DDC AD 186121 -
A direct method has been devised for the determination of the
carcinogenic 3,1-benzopyrene in the cyclohexane extracts of the
particulate matter collected from submarine atmosphres. The "
method depends on the measurement of the characteristic guasi-line
emission spectrum shown by 3,t-benzopyrene when its solution in a
mixture of cyclohexane and n-octane is frozen at liquid nitrogen
temperature. Concentrations of benzopyrene less than 10 to the
-9th power/ml of solution can be reliably identified without
separation. The maximum amount found in the present trials
corresponded to the concentration of 3,U benzopyrene produced by
the dispersion of the smoke from one cigarette in 70 cubic metres
of air. (Author summary)f#
023H9
A. P. Altshuller.
NEEDS FOR NEW INSTRUMENTATION FOR MONITORING THE ATMOSPHERE FOR
ORGANIC GASES AND VAPORS. Proc. Instr. Soc. Am. Natl.
Analysis Instr. Symp., Charleston, W. Va., April 30-May 2,
1962. pp. 239-U3.
The importance of high sensitivity and specificity in
atmospheric monitoring instruments cannot be too strongly
emphasized. For almost all organic analysis of urban atmospheres,
instruments must be capable of detection at concentrations of 0.01
ppm or lower. Substances are present which can interfere in
almost all concerivable analytical procedures for determining
either a class of substances or an individual substance.
Processes for removing the interferences or methods of correcting
for them should be an integral part of the instrument development
work. The detection methods suggested in this discussion involve
either electrometric sensors or the ionization sensors used in gas
chromatography. Alone or in combination with a chromatographic
column, such detectors also have satisfactory specificities. •
These sensors offer considerable opportunity for tfce development
of compact equipment. The range of possible application of these
instruments covers many of the classes of organic substances of
present interest in air pollution. {Author summary modified)ft
02354
K.F. Chrisman K.E. Foster
CALIBRATION OF AUTOMATIC ANALYZERS IN fr .CONTINUOUS AIR MONITORING
PROGRAM. Preprint (Presented at the"56th Annual Meeting,
Air Pollution Control Association, Detroit, Michigan, June
9-13, 1963.)
The need for uniformity of instrument calibration among the
several stations' of the Continuous Air Monitoring Program
of the U.S. Public Health Service has prompted the development
of a compretensive program of instrument calibration. The
program relies heavily, upon static and dynamic checks performed
by the station' operators. The frequency of these checks varies
with each'specific instrument; but, in all cases, the checks
D. Measurement Methods 289
-------
are frequent enough to insure the continued accuracy of the
recorded data. The routine checks are substantiated and
supplemented by dynamic calibrations performed at all stations
by the headquarters staff. The dilution board method
for the preparation of standard gas mixtures has been adapted
to the requirements of compactness and portability, and has been
used successfully in this work. In a conscientious effort to
insure and maintain the accuracy of the data produced by the
program, further refinements in the method will be made and more
suitable new.methods will be adopted as they are developed.
(Author's summary)**
02358
L.B. Graiff
A RAPID-RESPONSE TOTAL EXHAUST HYDROCARBON DETECTOR. Preprint.
(Presented before the Division of Water, Air, and Waste
Chemistry, American Chemical Society, Detroit, Hich., Apr.
5, 1965.)
This paper discusses the development and use of a rapid response
automotive exhaust hydrocarbon detector based on the hydrogen flame
ionization principle. This instrument is ideally suited for
monitoring the total exhaust hydrocarbon content of cycling engines
The rapid response exhaust hydrocarbon detector has been used
to measure the hydrocarbon emission from a number of cars operated
on a chassis dynamometer according to the HVPCB test procedure.
i typical exhaust hydrocarbon emission pattern obtained from a
car with a carburetted engine during one of the seven-mode
warmup cycles is.included, from which it is seen that the
individual operating modes are well defined. A car with an
inlet-port fuel-injection system was found to give a different
emission pattern during deceleration from a carburetted car, as
illustrated. The fairly positive fuel cut-off with the fuel-
injection car during the early stages of deceleration is clearly
indicated. The rapid response hydrocarbon detector can be used
for purposes other than hydrocarbon emission from automotive
engines. For example, the unit has been used to monitor the
gases leaving a liguid-air trap in order to design an efficient
hydrocarbon trap. The device can probably be used to monitor
gas-turbine exhaust for unburned fuel.##
02378
B. Smith, A. H. Rose, and R. Kruse.
AH AUTO-EXHAUST PROPORTIONAL SAMPLER. INTERN, J. AIR WATER
Pollution (Presented at the 56th Annual Meeting, Jir
Pollution Control Association, Detroit, Mich., June 9-13,
1963.) 8, H27-HO, Sept. 196H.
The development of an instrument to obtain a proportional sample
of auto exhaust gas is described. The proportional sampler is a
servo device, which controls the flow of exhaust gas in the
sampling line to maintain"it at a fixed percentage of the
carburetor air flowrate. The flow-rates in carburetor and
sample line are measured continuously by means of laminar-flow
elements and associated pressure-difference transducers. The
proportional sampler is used in a vehicle on the road to provide a
,290 HYDROCARBONS AND AIR POLLUTION
-------
representative sample of exhaust gas, which is then analyzed to
obtained mole-fraction measurements of various air contaminants in
the vehicle exhaust. The total volume of air entering the
carburetor is also measured. The values for total air volume
entering the carburetor and mole fraction of contaminants are used
to calculate the emission rates in pounds of each air contaminant
emitted per vehicle mile traveled. (Author abstract)##
02i»06
A.E. Barrington
INSTANTEOOS MONITORING OF MOLTICOMPONENT EXPIRED GASES. GCA
Corp., Bedford, Mass. (Hept. CR-619.) Dec. 1966. 17 pp.
CFSTI, NASA
Because of the urgent requirements of the manned space
flight program, the prototype gas analyzers described below were
developed specifically for aerospace applications. Their design
thus inevitably was subject to restrictions of weight, volume and
power consumption. Nevertheless, their operational
performance has been most encouraging. The sensing element of the
gas analyzer is called a mass spectrometer whose concept
utilizes two basic physical phenomena: first, gaseous atoms and
molecules can readily be charged electrically; second, there is a
selective effect by electric and magnetic forces on such
charged particles which depends on the atomic or molecular
mass. A complete sampling and sensing system for 12
constituent gases, utilizing a magnetic deflection mass
spectrometer is shown. It is designed to monitor H2, CO,
CHI», NH3, H20, N2, COH, 02, H2S, HC, C02 AND COOH. IT
includes i» sample inlet capillaries, a calibration sample, a
liguid nitrogen chilled sorption pump and an electronic ion
pump.ft
02«15
C.W. Louw
ATMOSPHERIC POLLUTANTS AND THEIR ANALYSIS (SPECIAL BEPOBT
SMOG 2). Council for Scientific and Industrial
Research, Pretoria, (South Africa). Air Pollution
Research Group 1966. 60 pp.
In view of the recently passed Act on Air Pollution
(No. <»5 of 1965) in South Africa and the anticipated increase
in interest and analytical activity in this field, it was felt
that the need existed for an up-to-date survey of air pollutants
and their analysis. A review report was conseguently prepared and
is presented here. Aspects such as the types, sources and
occurrence, concentrations and methods of analysis of the various
pollutants are discussed. Also, recommendations are made with
regard to the selection of suitable analytical methods.
(Author abstract)**
D. Measurement Methods 291
-------
02U33
K. T. Whitby and B. A. Vonela
EVALUATION OF OPTICAL PABTICLE COONTERS (PROGRESS REPT.)
Minnesota Dniv., Minneapolis, Dept. -of Mechanical Engineering
(Particle Lab. Publication Ho. 86) 89 pp.. Bay 1965
Bonodisperse polystyrene, India ink, and dioctyl pthalate
aerosols have been used to evaluate the Royco, Southern Research
Institute and prototype Bausch and Lomb optical counters. The
cumulative particle size distributions measured by the counters
on the monodisperse aerosols have been compared to the accurately-
determined microscope size distributions. The size ranges of the
monodisperse aerosols used so are: 0.365 to 1.3 microns for
polystyrene latex (PSL), 1 to 6 microns for polystyrene ' (PS),
1 to 10 microns for India ink (I.I.), and 1 to 5 microns for
dioctal pthalate (DOP). These aerosols have been used to
evaluate two characteristics of the counters: the ratio of the
median size measured by the counter to that measured by the
microscope' (C/M), and the ability of the counter to resolve-a
monodisperse aerosol as'measured by the geometric standard
deviation (og). Analysis of the standard deviation data shows
that the resolving power of all three counters is close to the
theoretical value for DOP and PSL aerosols larger than 1
micron, but is less than the theoretical value for the PS and
I.I. aerosols larger than 1 micron as evidenced by an increase
in standard deviation from about-1.3 at 1 micron to over 1.8 at
10 micron. The resolving power also decreases for PSL smaller
than 1 micron. Analysis of the C/M data for PS and DOP
shows that the counters respond alike to PS and DOP, that the
absolute calibration of all three counters is good between 1 and
1.5 microns, but these show significant variations for both larger
and smaller aerosols.- The C/M ratios of the counters for I.I.
varied from 0.2 to 0.5-and showed,significant shape effects for
aerosols larger than 5 microns. (Author summary modified)##
02439
A. V. Demidov, L. A. Bokh'ov, and B. S. Levine (Tr.)
RAPID BETHODS FOR THE DETERMINATION dF HARMFUL GASES AND VAPORS
IS THE AIH. Vol. 10 of O.S.S'.R. Literature on Air
Pollution and Related occupational Diseases. Hedgiz, Moscow,
Russia. (Technical Transl. No. TT 6'6-11767.) 1962-. pp.
11i».
Volume' 10 of the survey series "U.S.S.R. Literature on Air
Pollution and Related Occupational Diseases" is a translation
of A. V. Demidov's and L. A. Bolhov's book "Rapid Methods
for the Determination of Harmful Gases and Vapors in the Air"
(Yekbpehhlie Metoubi Oiipeuejiehnr B B Boeuyxe Bpeuhlir N
lopooopaehlix Bewectb), published by Bedgiz of Moscow in 1962.
The greater part of the outlined p'roeediires have been developed by
D.S.S.R. analytical chemists, while some were taken from *
literature of other' countries. The collection of tests appears to
be intended primarily for the detection of dangerous gaseous and*
v'aporo>us air' pollutants in indoor working premises. For each
harmful gas or vapor qualitative as well as closely approximate
quantitative procedures are given to make possible the early
292 HYDROCARBONS AND AIR POLLUTION
-------
determination of dangerous harmful gas and vapor concentration in
the air of working premises and to forestall the occurrence of
serious accidents. The volume was intended to meet the needs
of smaller laboratories and of field industrial laboratory
workers.**
02460L
F.G. Sherrell J.A. Baltz
A TRACE CONTAMINANT ANALYSIS TEST ON AIE SAMPLES. ARO Inc.,
Tullahoma, Tenn. (Bept. AEDC-TR-66-42) pp. 84, Mar. 1966
CFSTI, DDC AD U78886 I
A test in which wet air samples were analyzed for trace
contaminants was conducted at the Arnold Engineering
Development Center for the DSAF School of Aerospace
Medicine. Sample processing and analysis techniques used
during the test are described. The sample processing
technique provided a way to transfer the 77K condensables in each
sample to a trap of small volume. This trap was designed to
allow removal of small portions of both the sample vapor and the
liquid for mass spectrometric and chromatographic analyses.
The chromatographic and mass spectrometric instrumentation
calibrations, and data reduction procedures are described.
The basic test results are presented and discussed. Observations
are made concerning the utility,of the procedures used:## ;
02500
A. B, Calongne and J.' P. Borris
NEW TECHNIQUES FOB TESTING TBACE HYDROCARBON CONTAHINATION OF
GASES. Preprint. (Presented at the Fourth Annual Technical
Meeting and Exhibit, American Association for Contamination
Control, Miami Beach, Fla., May 25-28, 1965.)
This paper presents techniques for the analysis of total and
nonvolatile .hydrocarbons. Terminology used to define hydrocarbon
limits in specifications include: (1) Total hydrocarbon content,
(2) Condensable hydrocarbon content, (3) Oil content, and (4)
Nonvolatile residue content. There are basically four methods of
analysis which are used ;for the detection of,low hydrocarbon
concentrations. "These methods are as follows: (1) Gas •»
scrubber - infrared spectrophotometry. (2) Flame ionization. (3)
Gas chromatography. (U) Gas cell - infrared
spectrophotometry.##
02538
(CHEMICAL AND PHYSICAL CHARACTERIZATION OF POLLUTED ENVIRONBENTS,
INHALED OR INGESTED, AND OF ACOUSTICAL "NUISANCES.")
Caracterisation chimique et physique des milieux pollues, inhales
ou ingeres et des "nuisances" acoustiques. In: Les pollution
et "nuisances" d'origine industrielle et urbaine. Tone 1.
Leur prevention et les problemes scientifiques et techniques
gu'elle pose en France, pages 27-32. Premijer Binistre
Delegation generale a la recherche scientifi'que et technique.
0. Measurement Methods 293
-------
In discussing the methodology of measuring and evaluating the
degree of pollution, the following are considered: infra-red,
emission, and mass spectrometers; x-ray and electron diffraction;
gravimetric, volumetric, and colorimetric methods; optic and
electronic microscopes, and spectometry for acoustic absorption.
In the section on the inhalation milieu, are discussed the
composition of the natural atmospheric air and of the air polluted
by cities (particles, gases and vapors, and smog); diffusion of
pollutants in the atmosphere; chemical reactions in the
atmosphere; international standardization of current methods and
measurements (deposited material, fumes, sulfur dioxide, and
hydrocarbons); cartiography; and principal concerns of research.
Discussed in this same section (chapter 2) are pollution of food
and water, and problems of noise.tf
02544
I. A. Pinigina
COLORIMETRIC DETERMINATION OF ALCOHOL VAPOR IN AIR. (O
kolorimetricheskom operedelenii parov spirta v vozdukhe.) Hyg.
Sanit. 31, (1) 58-60, Jan. 1966.
CFSTI: TT66-51160/1-3
The reaction of alcohols with black vanadium-hydroxyguinoline
which produces a vivid orange color was modified by using sodium
hydroxide to destroy any excess vanadium-hydroxyquinoline. The
need of using xylene is thus eliminated. Benzene was substituted
for xyelen in the preparation of the scale. The air sample is
adsorbed on sorbent-activated charcoal. These modifications
increase the sensitivity from 0.01 to 0.002 mg.##
02559
B.E. Seleznev I.A. Chernichenko
SPECTROPHOTOMETRIC DETERMINATION OF THE CONCENTRATION OF
CHLORTETRACYCLINE IN THE AIR. Opredelenie kormovogo
khlortetatsiklina v atmosfernom vozdukhe spektrofotometricheskim
metodom.) Hyg. Sanit. 31, (3) 346-8, Mar. 1966.
CFSTI: TT66-51160/1-3
The possibility of using spectrophotometry for the quantitative
determination of chlortetracycline in the air was studied. Among
the solvents investigated, the most suitable was 0.1 N, HC1
solution, since this produced the highest optical density in the
ultraviolet. The method is fairly sensitive (0,01 micrograms/ml)
but nonspecific, interference being encountered from other
organic componds which absorb similar wavelenghts.##
02581
K. wettig
MODIFIED METHOD OF DETERMINING 3 ,4-BENZPYRENE IN THE
ATMOSPHERE. (Modifitsirovannyi metod opredeleniya
3,4-benzpirena v atmosfernom vozdukhe.) Hyg. Sanit. 29, (6)
66-8, June 196U.
CFSTI: TT65-50023/6
294 HYDROCARBONS AND AIR POLLUTION
-------
For the purpose of determining 3, if-benzpyrene absorbed on dust
particles in the atmosphere, benzene extraction is used in the
majority of cases. The extract is subjected to chromatographic
fractionation on columns; the fractions containing 3,4-benzpyrene
are evaporated, and the residue is dissolved in cyclohexane.
Benzpyrene is determined from absorption spectra in the
ultraviolet region or by fluorescence spectra. The Grimmer
method described by author is characterized, when the work is
properly performed, by a high degree of sensitivity (0.5-1
microgram of benzpyrene/ml), by a loss of material averaging
10-15%, and by reproducibility of the results. The polycyclic
aromatic hydrocarbons interfering with quantitative evaluation of
the benzpyrene spectrum (1,12-benzperylene, benzofluoranthen) are
particularly well separated. The determination of 3,4-benzpyrene
by the method described takes 1 1/2 - 2 days.tf
02595
I. M. Al'shits, T. A. Anikina, E. A. Babenkova, and N.
H. Grad
DETERHINATION OF STYRENE AND COMENE HYDBOPEROXIDE IN THE AIR
WHEN THEY ARE PRESENT TOGETHER. (Opredelenie v vozdukhe
stirola i giperiza pri ikh sovmestnom prisutstvii.) Hyg. Sanit.
29, (9) 64-7, Sept. 1964.
CFSTI: TT65-50023/9
Of the known methods of determining styrene in air in the presence
of cumene hydroperoxide the simplest and most
specific is the Ivanov method, based on colorinetry of yellow
products of styrene transformation by concentrated sulfuric acid.
Of the known methods of determining cumene hydroperoxide in air in
the presence of styrene the most sensitive and specific is the
Alekseeva method, based on colorimetry of pink combinstion
products of phenol and diazotized p-nitroaniine, obtained from
the decomposition of cumene hydroperoxide by the action of
concentrated sulfuric acid. Both methods are sufficiently
sensitive and specific for the analysis of the air of room
containing mixtures.of styrene and cumene hydroperoxide.*t.
02601
V. I. Vashkov, A. P. Volkova, V. H. Tsetlin, and E.
Y. Yankovskii
DETERMINATION OP THE TOXICITY OF PBOPELLANTS USED IN AEROSOL
TANKS. (Opredelenie toksichnosti propellentov, ispol'zuemykh
v aerozol'nykh ballanokh.) Hyg. Sanit. 29, (10) 74-9, Oct. 1964
CFSTI: TT 65-50023/10
Jn azeotropic mixture of 60 percent tetrafluormonochlorethane
(Freon 124) and 10 percent octafluorcyclobutane (Freon C 318}
was studied as a propellent for pesticide cylinders. Judging by
the elasticity of the saturated vapors and the chemical stability,
this mixture resembles that of Freons 11 and 12. The azeotropic
mixture of Freons 124 and C 318 with concentrations used for
practical purposes is non-toxic for warmblooded animals. A
slight irritation of the mucous membranes of the eyes may occur if
the concentration is exceeded 20-30 times, i.e., up to 10-15
g/cu. The mixture with the concentration of 15 g/m and over
produced a slight narcotic effect. (Author abstract)##
.. D. Measurement Methods 295
-------
02607
P. A. Korotkov, N. N. Serzhantova, Y. P. Tsyashchenko,
and N. Y. Yanysheva
DETERMINATION OF SMALL CONCENTBATIONS OF
1,2,5,6-DIBENZANTHRACENE. (Opredelenie malykh kontsentratsii
1,2,5,6-dibenzantratzena.) Hyg. Sanit. 29, (12) 59-6U, Dec.
196U.
CFSTI: TT 65-50023/12
A sensitive and accurate method is suggested for the analysis of
1,2,5,6-dibenzanthracene. A detailed study of the
luminescence of 1,2,5,6-dibenzanthracene in various crystalline
matrices at the temperature of liquid oxygen was made. Of the
solvents investigated, hexane was found to be the only solvent
which gave a characteristic luminescence spectrum consisting of
sufficiently narrow lines and bands at the temperature of liquid
oxygen. In all other solvents, the bands were wide and anorphic
and the corresponding wavelengths were impossible to determine
with the accuracy required for the purpose of analysis.t*
02657
G. Schonauer
PARTICLE SIZE ANALYSIS OF PABAFFIN AEROSOLS BY ELECTROS
HICEOSCOPY. Staub (English Translation) 25, (U) 2i»-8, Apr.
1965.
CFSTI TT 66-510«0/«
A method of determination of particle-size distribution of
paraffin aerosol is described which enables spherical particles
which are unstable in the electron microscope to be measured with
an error below plus or minus 5*. The particles are precipitated
in a thermal precipitator and, in order to maintain the spherical
shape, are vapour treated with strong cooling. The shadows of the
spheres are photographed and measured electron-microscopically.
(Author summary)##
02685
H.O. Hettche
THE MEASUREMENT OF POLYCYCLIC AECHATICS IN THE ATMOSPHERE.
Staub (English Translation) 25, (9) 11-U, Sept. 1965.
CFSTI TT 66-510UO/9
Methods for collecting, separating and measuring aromatic
polycyclic hydrocarbons in air are described. Investigations have
shown that concentrations of 13 aromatics contained in dust
corresponded, in a medium-size town, large town and industrial
town of Nordrhine-Westphalia, to 1:1.5:2.5. In the industrial
town the content of anthracene and phenanthrene was
comparatively higher, and in the medium-size town the content of
coronene as a result of special emission sources.#t
296 HYDROCARBONS AND AIR POLLUTION
-------
02747
H. J. Jacumin and L. A. Ripperton
FURTHER EFFECTS OF TEMPERATURE AND PRESSURE ON PHOTOCHEMICAL
OXIDANT PRODUCTION. J. Air Pollution Control Assoc. 14,
(3) 96-7, Mar. 196i». (Presented at the 56th Annual Meeting,
Air Pollution Control Association, Detroit, Mich., June
9-13, 1963, Paper No. 63-101.)
Oxidant production was observed for a photochemical reactant
system N02 plus hexene-1 over a pressure range of 6UO to 860 mm
Hg at temperatures of It, 25, and 35 C. An apparent inhibition
took place around 711 mm at all temperatures. From a low at -714
oxidants values rose to a secondary peak at 700 mm and then
dropped with decreasing pressure. The significance of these
results is discussed. (Author abstract)##
02785
H. H. Linnell and W. E. Scott
DIESEL EXHAUST ANALYSIS (PRELIMINARY RESULTS). Arch.
Environ. Health 5, 616-25, Dec. 1962.
Interest in the emissions from the exhaust of diesel engines on
the road is rising mainly because interest in possible sources of
air pollution has been steadily increasing. However, the
problems of sampling and analysis of diesel exhaust have not been
solved yet. This paper outlines of the techniques being used and
some being evaluated for the first time for exhaust analysis.
Many analytical problems remain to be solved. Some results are
presented which are considered preliminary.##
02786
R. H. Linnell and H. E. Scott
DIESEL EXHAUST COMPOSITION AND ODOR STUDIES. J. iir Pollution
Control Assoc. 12, (11) 10-5, Nov. 1962.
Some of the techniques being used and evaluated for exhaust
analysis are outlined. Results except for sone qualitative and
tentative findings are shown in tables 1-8. Most values are
averages of 2 or 3 determinations. These determinations were made
on new samples taken at different times, with intervals of
several weeks elapsing in some cases. Particulate matter
information in table 1 indicates organic compounds adsorption.
This is of interest in eye irritation and odor work since
aldehydes may be present on particulate matter in higher
concentrations than are present in the gas phase. The CC14
extracts of particulate matter show infrared bands characteristic
of hydrocarbons, olefins, aldehydes, and carbonyl. Comparison of
hydrocarbon measurements, formaldehyde and acrolein, and
miscellaneous compounds are discussed. 26 references.##
D. Measurement Methods 297
-------
02795
E. Sawicki, T. W. Stanley, W, c. Elbert, and J. D.
Phaff
APPLICATION OF THIN-LAYER CHROMATOGRAPHY TO THE ANALYSIS OF
ATBOSPHEHIC POLLUTANTS. Simplified Analysis for
Benzo (a)pyrene. Preprint. (Presented at the 152nd Meeting,
American Chemical Society, New York City, Sept. 13, 1966.)
RB values and fluorescent colors have been obtained through
thin-layer chromatography of 20 polynuclear aromatic hydrocarbons
with the following absorbents and developers: alumina with
pentane:ether (19/1;v/v), cellulose acetate with
ethanol:toluene:water (17/t/f»; v/v) and cellulose with
dimethylformamide:water (1/1, v/v). Of the three absorbents
alumina gave the best separation of fluorescent organic compounds
from the organic fractions of airborne and air pollution source
particulates. The pattern and fluorescent color of the spots of a
thin-layer chromatogram varied with the type of pollution. In
samples from communities with different types of pollution
different types of patterns were obtained. The different
fractions obtained from organic airborne particulates - e.g.
aliphatic, aromatic neutral oxygenated, basic, acidic, and
water-soluble fractions - exhibited entirely different patterns.
The cellulose acetate absorbent system gave best results for the
separation of the benzpyrene fraction obtained in column
chromatography. The cellulose absorbent system gave the best
results for the separation of the polynuclear aromatic
hydrocarbons. The greatest range in RB values was obtained with
this absorbent. Two methods for the estimation of benzo (a)pyrene
following thin-layer chronatography are described. One method
involves ultraviolet analysis at 382 microgram; the other method
involves spectrophotofluororaetric analysis in sulfuric acid.
(Author summary)t#
02796
Sawicki, E., R. Schumacher, and C. R. Engel
COMPARISON OF MBTH AND OTHER METHODS FOB THE DETERMINATION OF
SUGARS AND OTHER ((ALPHA))-GLYCOLIC DERIVATIVES. APPLICATION
TO AIR POLLUTION. Microchem. J., 12 (3) :377-395, Sept. 1967.
15 refs.
Methods for the determination of aldoses, ketoses, and other
alpha-glycolic compounds are described. The various methods are
compared through their use in the determination of ribose.
These methods include the direct and oxidative MBTH, and the
azulene, J-acid, orcinol, and pyrogallol procedures. The
oxidative MBTH procedure introduced in this paper is especially
sensitive for the determination of alpha-glycolic compounds as
shown by the high molar absorptivities (=approx. 100,000)
obtained for ethylene glycol, glycerol, and other polyols.
Airborne particulates obtained from various cities contain a
substantial amount of water-soluble alpha-glycolic compounds.
In addition, a variety of dust samples have been found to contain
a large quantity of water-soluble alpha-glycolic compounds and
lesser amounts of adsorbed aliphatic aldehydes. Chromatographic
media were found'to be contaminated with these chemicals.
(Author abstract)**
298 HYDROCARBONS AND AIR POLLUTION
-------
02797
E. Sawicki, H. Elbert, T. W. Stanley, T. R. Hauser,
and F. T. Fox
THE DETECTION AND DETERHINATION OF POLYNUCLEAR HYDROCARBONS IN
URBAN AIRBORNE PARTICIPATES. I. THE BENZOPYRENE FRACTION.
Intern. J. Air Pollution 2, 273-82, Bar. 1960.
A new simple procedure for the determination of benzo(a)pyrene in
complex mixtures is introduced. A comparison of the concentration
of benzo(a)pyrene in the air of nine cities for the month of
November, 1958, is given. Evidence is presented for ..the
identification of each hydrocarbon found in the benzopyrene
fraction. The relative concentration of benzo(a)pyrene,
benzo(e)pyrene, benzo (k)fluoranthene and perylene in the nine
cities is approximately constant. (Author abstract)##
02798
E. Sawicki, J. Noe, and T. W. Stanley
A NEW TEST FOR THE DETECTION OF ARALKYL AND DIAIKYL KETONES
CONTAINING THE OC-CH2-GROUPING. Preprint. 1960.
A new simple color test for dialkyl and aralkyl ketones containing
the structure, B-CO-CH2-, is introduced. Limits of
identification for some 50 ketones are recorded. A positive test
is revealed by a blue and occasionally a violet color with wave
length maxima ranging from 560-590 millimicrons. The advantages
and the shortcomings of the test are discussed. (Author
summary)#t
02799
E. Sawicki and J. L. Noe
A SENSITIVE NEW HETHOD FOR THE DETERfllNATION OF NITRITES AND
NITROGEN DIOXIDE WITH U-ABINOAZOBENZENE-1-NAPHTHYLAHINE.
Anal. Chim. Acta 25, 166-9, 1961.
A sensitive method for the determination of nitrites is
introduced. The method should also be applicable to the
determination of nitrogen dioxide. The test consists of the
reaction of 4-aminoazobenzene and 1-naphthylamine with nitrous
acid to form the blue dication of
i»-(p-phenylazophenylazo)-1-naphthylamine. Beer's Law was
obeyed from 0.5 to over 15 micrograms of nitrite ion per 15 nl of
final solution. Spectrophotometrically it is possible to detect
part of nitrite ion in 60 million parts of solution. (Author
summary)#t
0. Measurement Methods 299
-------
02801
E. Sawicki, T. H. Stanley, and 3. Noe
SIMPLE SENSITIVE TEST FOR COMPOUNDS CONTAINING THE CYCLOPENTADIEHE
CH2 GROUPING. APPLICATION TO AIR POLLUTION. Anal. Chem.
32, 816-7, June 1960.
The reaction of 1,2-dinitrobenzene, 1,1-dinitrobenzene and
1 ,<*-dinitronaphthalene in alkaline solution with compounds
containing the cyclopentadiene CH2 group results in a stable blue
to green color with long w'ave length maxima ranging from 600 to
750 millimicrons. The wave length maxima and identification
limits obtained from the reaction of 1,2-dinitrobenzene with over
100 fluorene derivatives have been tabulated. In a neutral
aromatic traction this test appears to be specific for the
cyclopentadiene CH2- grouping. The presence of fluorene and
benzo(a)-and/or benzo(b)-fluorene in airborne particulates has been
confirmed with the help of the test procedure. (Author summary)#*
02803
E. Sawicki and T. R. Hauser
SPECTROPHOTOMETHIC DETERMINATION OF «-AMINOAZOBENZENES,
U-AHINOSTILBENES, SCHIFF BASES, AND ANALOGOUS COMPOUNDS HITH
3-HETHYL-2-BENZOTHIAZOLONE HYDRAZCNE. ' Preprint. 1961
3-Methyl-2-benzothiazolone hydrazone is shown to be a powerful and
versatile electrophilic reagent which can be used for the spectral
detection and determination of strongly nucleophilic molecules
containing a carbon atom of high electron density. The
determination of approximately 50 azo dyes and a smaller group of
stilbene and Schiff base derivatives by a new' procedure for these
compounds is described. U-amino-, U-alkylamino, and U-dialkylaaino
derivatives of azobenzene can be readily analyzed. The
determination of N,N-dialkyl-U- aminoazobenzene was thoroughly
investigated. Beer's law was obeyed from 1 to more than 70
micrograms of compound per 10 ml of final solution. The color was
stable for approximately 1/2 hour. The molar absorptivity for
N,N-dimethyl-U-aminoazobenzene was 70,000.
N,N-Dimethyl-p-aminostilbene reacted readily in the procedure;
it had a molar absorptivity of 119,000. The procedure should
prove of value in the detection and determination of two types of
carcinogens, the aminoazobenzenes and the aminostilbenes. (Author
summary modified)##
02805
E. Sawicki, T. R. Hauser, and T. W. Stanley
ULTRAVIOLET, VISIBLE, AND FLUORESCENCE SPECTKAL ANALYSIS OF
POLYNUCLEAR HYDROCARBONS. Intern. J. Air Pollution 2,
253-72, Mar. 1960. (Presented at the 136th National Air
Pollution Symposium, American Chemical Society, Atlantic
City, N.J., Sept. 1959.)
A novel.approach to the analysis of polynuclear hydrocarbons in
mixtures is introduced. On the basis of this approach a new
300 HYDROCARBONS AND AIR POLLUTION
-------
simple, sensitive, and specific test for benzo(a)pyrene was
developed. In a mixture of 50 compounds containing benzene,
naphthalene, anthracene, phenanthrene, benzx
naphthalene, anthracene, phenanthrene,-behz(a)anthracene,
benzo(c)phenanthrene, chyrsene, pyrene, benzo (5)fluoranthene,
benzo (e)pyrene, perylene, benzo (g,h,i)perylene, anthanthrene, and
coronene, benzo (a)pyrene can be identified unequivocally. The'
TJV visible, activation, and fluorescene spectra in pentane of a
large number of polynuclear hydrocarbons are presented. The
fluorescene intensities of the different hydrocarbons are compared.
Some, like anthanthrene and perylene, have an extremely high
intensity, which simplifies their detection in a mixture. The
sensitivity of the fluorcmetric methods are of the order of
millimicrograms per milliliter, or parts per billion. From a
comparison of the activation spectra in pentane and sulfuric acid
of different hydrocarbons, it can be ascertained whether a given
hydrocarbon can be determined in the presence of hydrocarbons of
somewhat similar structure. In many instances it is possible to
obtain the pure fluorescence spectrum of an aromatic hydrocarbon by
determining the spectrum of the mixture at an appropriate
activation wavelength maximum of the aromatic hydrocarbon. Thus
benzo (e)pyrene can be determined in the presence of benzo (a)pyrene
and vice versa. Perylene or anthanthrene can be detected readily
in a complicated mixture .of some 25 analogous hydrocarbons.
Naptho (2,3-a)pyrene can be detected in a mixture of 50 polynuclear
hydrocarbons. Bany other possibilities are apparent from an
examination of the activation spectra of the hydrocarbons. The
quenching effect of a fairly high concentration of miscellaneous
compounds in a mixture as'it affects fluorometric analysis for
some particular hydrocarbons is also discussed. (Author abstract)
028«3
E. Sawicki and H. Johnson
NEW METHOD FOE THE PHOTOBETBIC DETERBINATION OF PRIBARY ABINES.
Chemist-Analyst 55, 101-3, Oct. 1966.
A highly selective and sensitive method for.the photometric
determination of primary amines, including amino acids and
aliphatic and aromatic amines has been devised based on the
reaction of the asine with succinaldehyde formed in situ, from
2,5-dimethoxytetrahydrofuran, and then reaction of the
N-substituted pyrrole formed with p- (dimethylamino)
benzaldehyde (Procedure A) or wi,th p-(dimethylamino)
cinnamaldehyde (Procedure B). Amides, pyrimidine and purine
amines, and secondary and tertiary amines do not undergo the
reactions and do not interfere.t*
02848
Jackson, M. W.
ANALYSIS FOR EXHAUST GAS HYDROCARBONS - NONDISPERSIVE INFRARED
VERDS FLABE-IONIZATION.. J. Air Pollution Control Assoc. '
(Presented at the Instrument Society of America, New York ;-
City, Oct. 1962.) 11 (12):697-702, Dec. 1966.
D. Measurement Methods 301
-------
An investigation has been made of the suitability of a
nondispersive infrared analyzer and two flame-ionization analyzers
for measuring the total hydrocarbon concentrations of automobile
exhaust gas. The investigation consisted of measuring relative
responses of various hydrocarbons, checking for possible exhaust
gas interferences and finally comparing exhaust hydrocarbon
concentrations indicated by the flame-ionization analyzer to those
indicated by the infrared analyzer. The infrared analyzer has
high relative.responses for parraffins and low responses for
olefins, acetylenes, and aromatics. Also, the infrared indicated
hydrocarbon concentrations must be corrected for exhaust water
vapor interference.##
0285U
K. Marcali A.L. Linch
PERFLUOHOISOBUTYLENE AND HEXAFLOOROPROPENE DETERMINATION IN AIR.
Am. Ind. Hyg. Assoc. J. 27, (
-------
consequent uncertainty as to whether other ingredients have been
deliberately added or whether the discrepancy is due to variations
between different manufacturers' specifications for what is
nominally the same solvent. The main purpose of this report is
to list a number of fingerprint chromatograms for such solvents and
in some cases to consider the variations between products from
different sources. A second purpose is to outline methods for
specific separations e.g. of aliphatic and aromatic solvents.##
02886L
H. Konosu and Y. Mashiko
DESIGN OF A NON-DISPEHSIVE ULTRAVIOLET GAS ANALYZER AND ITS
APPLICATION TO QUANTITATIVE MEASDBEMENT OF TBACES OF TOXIC GASES
AND VAPORS IN AIR. (Hibunsangata Shigaisen Gasu Bunsekikei
no Shisaku oyobi Sono Yugai Gasu.Joki Bensekie no.) Kogyo
Kagaku Zasshi 68, 1868-72, 1965. {O.N.I. Translation 2127)
DDC AD «82365
A non-dispersive UV gas analyzer for measuring the concentration
of toxic gases and vapors in the air is reported. This analyzer
is a device which measures simultaneously the differences in the
UV absorption of a standard gas and a test gas over the total
range of wave lengths. The optical source employs a hydrogen
discharge tube and the optical system is a complex optical path
system. The gas cell is 50 cm long and a secondary electron
multiplier is used as an optical receiver tube. This analyzer
was used to measure 6 types of samples and to compile detection
lines. Values for the sample and detection limits (ppm) were 3
for sulfur dioxide, 28 for carbon disulfide, 27 for benzene, 32
for acetone, 3t for methyl ethyl ketone, 13 for trichloroethylene.
The relative error below 100 ppm for sulfur dioxide was plus or
minus 9.0% plus or minus 4,0% for 100-1000 ppn, and 1.5% for
1000-1250 ppn. This method can be used for 1-min. measurements,
for the measurement of toxic gases and vapors in working
environments, and for'determining lower explosive limits.'
(Author abstract modified)##
02963
H. W. Schlipkoter
THE INJURIOUS EFFECTS OF ATMOSPHERIC DUSTS. Staub English
Transl.) 25, (10) 2-11, Oct. 1965.
CFSTT: TT66-51040/10 Q
Increasing industrialization, growing population, traffic density
and closeness of industrial areas and residential districts
necessitate the continuous measurement, analysis and control of
air pollutants. Each method must be selected critically.
Proposals are made for a suitable dust measuring method. The
effect of air pollutants on breathing and, in particular,
their influence on the purifying action of the lungs must be
considered first of all. Bore attention must be paid to dust as
a carrier and catalyst, to soot with its cytotoxic effects and to
polycyclic aromatic compounds. Instructions for controlling air
pollution should take into account the protection of sick persons.
(Author summary)t#
D. Measurement Methods 303
-------
03010
H. Devorkin, H.L. Chass, A.P. Fudurich, C.V. Ranter
SOURCE TESTING HANDAL. Los Angeles County Air Pollution
Control District, Calif. 181 pp., Nov. 1965
Specialized methods and techniques for the curtailment
of contaminants being released into the atmosphere, developed in
the laboratory and in the field are described in this manual.
These methods are concerned primarily with the measurement of
emissions from stationary sources, and in general, with little
or no modification, these methods can also be used for testing
vehicles or other moving sources'. Information obtained
form source tests is invaluable as a guide in selecting
appropriate control equipment and improving the design
of future installations to minimize the discharge of air
contaminants. Following topics are discussed: Planning a
source test; Determination of gas flow rate; Collection and
analysis of particulate matter, and of gaseous constituents;
Odor measurement; Source test report. The appendixes deal
with rules and regulations, conversion factors and constants, and
auxiliary field sampling equipment.f#
03059
A. P. Altshuller and I. R. Cohen.
APPLICATION OF DIFFUSION CELLS TO THE PRODUCTION OF KNOHN
CONCENTRATIONS OF GASEOUS HYDROCARBONS. Anal. Chem. 32, (7)
802-10, June 1960 V
Diffusion coefficients have been determined for a number of
hydrocarbons, including 2-methyl-1, 3-butadiene, hexane,
1-hexene, heptane, 1-octene, decane, benzene, and toluene.
Diffusion coefficients at a number of temperatures have been
determined tor hexane, 1—hexene, heptane, 1-octene, decane, and
benzene. The effect of turbulence at the end of the diffusion
tube, resulting from the rapid flow of carrier gas over the top of
the tube, has been investigated as a function of gas flow rate,
temperature, diffusion tube diameter, and tube length. These
results, with related data in the literature, should aid in
defining the experimental limits within which a diffusion tube
apparatus may be operated so that calculated values of diffusion
rate can be used, if one experimental value of the diffusion
coefficient is available for the liquid compound of interest.
(Author abstract)##
03080
E. Sawicki
THE SEPARATION AND ANALYSIS OF POLYNUCLEAR ABOHATIC HYDROCARBONS
PRESENT IN THE HUHAN ENVIRONHENT. Chem. Anal. (Warsaw)
53, 2«-6, 28-30, 56-62, 88-91, 196«
The steadily increasing rate of lung cancer has stimulated
efforts to analyze the polynuclear hydrocarbons which are
304 HYDROCARBONS AND AIR POLLUTION
-------
a group of carcinogens with which human beings come into contact
with in varying degrees. Because the polycyclic hydrocarbons are
present usually in very low concentrations together with thousands
of other types of compounds, separation is an essential part of
their determination. Methods used to accomplish this
separation include: sublimation, distillation, solid-liquid
extraction, liquid-liquid extraction, column
chromatography, paper chrcmatography, thin-layer
chromatography, gas chromatography. These methods are reviewed
along with analysis procedures involving absorption spectra,
fluorescence spectra and phosphorescent spectra. Two hundred
and forty references are included.##
03081
E. Sawicki, T.E. Hauser, S. McPherson
SPOT TEST DETECTION AND SPECTBOPHOTOMETSIC DETERMINATION OF
COMPOUNDS CONTAINING THE P-HYDROXYSTYRYL GROUP: 3-METHYL-2-
BENZOTHIAZOLINONE HYDRAZONE PROCEDURE. Chem. Anal. (Warsaw)
50, 68-9, Sept. 1961
In the present study the reagent was applied to the detection
and determination of compounds containing the p-hydroxystyryl or p-
alkoxystyryl grouping. The test is highly selective for
phenols containing a p-vinyl group (and their ethers) as compared
to phenols (and ethers) without a vinyl group. It is possible
that phenols with an o- or m-vinyl group will react as phenols to
give a red-orange color. A p-hydroxy compound having a
allyl group, i.e., where a methylene group is placed between
the ethylenic double bond and the benzene ring, gives practically
no reaction. Eugenol and safrol show this phenomenon and the
slight reactions observed are probably due to impurities such as
isoeugenol and isosafrole. The spot test procedure was
tried with several derivatives of p-hydroxystyrene which gave
a reaction in the spectrophotometric procedure. The
identification limits ranged from about 0.1 to 0.7 microgram.
Phenol and polycyclic phenols gave negative results.ft
03096
N.A. Lyshxow
A RAPID AND SENSITIVE COLORIMETRIC REAGENT FOR NITROGEN DIOXIDE
IN AIR. J. Air Pollution Control Assoc. 15, (10)
«81-"», Oct. 1965 (Presented at the 58th Annual Meeting, Air
Pollution Control Association, Toronto, Canada, June 20-21*,
1965)
High speed instrumentation requires a colorimetric reagent
capable of detecting traces of nitrogen dioxide with little
delay for color development. Rate of color development
and sensitivity of Griess-type reagent have been improved by
adding a promoter (R-salt) and optimizing the concentrations of
diazotizing and coupling reagents. Field tests show that the new
instrument -reagent combination can resolve short-duration peaks in
NOi concentrations of 5 to 10 pphm. (Author abstract)##
D. Measurement Methods 305
-------
03103
J. Harkins S.H. Nicksic
STUDIES ON THE BOLE OF SULFUR DIOXIDE IN VISIBILITY REDUCTION.
J. Air Pollution Control Assoc. 15, (5) 218-21, May 1965.
Highly sensitive radiotracer techniques were used to see if the
sulfuric acid mist from sulfur dioxide oxidation allows the
incorporation of organic matter. Tagged organic compounds were
irradiated with and without sulfur dioxide. When the aerosol
was filtered off, no radioactivity was found on the filter paper
showing the absence of organic matter and the lack of sulfur
dioxide synergism. (Author abstract)##
03112
E.R. Stephens M.A. Price
A SEARCH FOR SOME NITRO-OLEFINS IN POLLUTED AIR. J. Air
Pollution Control Assoc. 15, (7) 320-2, July 1965.
An electron capture chromatographic method of detecting nitro—
ethylene and 1-nitro-1 propene was developed and applied to ambient
air samples, photolyzed propene/nitrogen dioxide mixtures and
auto exhaust. No trace of either compound was found in
ambient air or in the photolyzed mixtures. The detection limit
was estimated to be 1 ppb. A single sample of auto exhaust showed
several small peaks which, if attributed to nitro-olefin,
would amount to insignificant traces. (Author abstract)ft
03185
D. L. Venezky and H. B. Moniz.
HETHOD FOR ON-SITE DETERMINATION OF RESIDUAL ADSORPTIVE CAPACITY
OF CHARCOALS USED IN CLOSED ENVIRONMENTAL SYSTEM. Naval
Research Laboratory, Washington, D.C. (NRL Bemorandum
Rept. 1710). Aug. 31, 1966. 21 pp.
CFSTI, DDC AD 6391H5
The relationship between the moisture content of adsorbent-type
charcoals and their residual adsorptive capacity for organic
compounds was studied. Investigation of fourteen charcoal
samples from submarine main-carbon filters has shown that the
moisture content of the charcoals correlates with the organic
loading previously determined by a steam desorption method. A
simple apparatus for determining the moisture content of a charcoal
sample was devised, in which continuously recirculated air in a
closed-loop system transfers water from a charcoal sample to a
desiccant. The moisture content of the charcoal is determined by
weighing the sample and desiccant tubes before and after water
transfer. The on-site determination of the residual
adsorptive capacity of main-filter charcoals is suggested by the
low cost of the closed-loop apparatus and the simplicity of the
method. For a monitoring procedure, a reference charcoal sample,
prepackaged for handling ease, could be exposed to submarine
atmospheres, thus avoiding the removal of samples froa the
main-filter bed. Rather than a fixed exposure period, the
306 HYDROCARBONS AND AIR POLLUTION
-------
remaining adsorptive capacity of the charcoal would determine the
time for replacement. Safety is enhanced, since heavy organic
loading of the charcoal brought about by unusual circumstances
could be rapidly detected. Since 70% of the charcoal samples
which were investigated had more than half of their adsorptive
capacity remaining, substantial savings should result. Sone
charcoals meeting the requirements of specification flIL-C-17605ft
are anomalous with respect to water content; this behavior is being
investigated. (Author abstract)#t
03253
Sawicki, E. and R. A. Carnes
SPECTROPHOTOFLUORIHETRIC DETERMINATION OF ALDEHYDES WITH DIHEDONE
AND OTHER REAGENTS. Hikrochim. Acta (Vienna , No. 1:148-159,
1968. 16 refs.
Two new reagents, dimedone and 1,3-cyclohexanedione, are
introduced for the fluorimetric determination of aliphatic
aldehydes. Six fluorimetric methods for the determination of
formaldehyde and other aldehydes are compared. Of the selective
methods for the determination of formaldehyde the J-acid
procedure is recommended when a high order of sensitivity is
necessary, the 2,4-pentanedione method when a high order of
selectivity is desirable. The dimedone procedures are recommended
when it is necessary to analyze for aldehydes other than
formaldehyde. However, the dimedone procedures are the most
sensitive for the determination of formaldehyde and can be used
for this purpose where conditions are appropriate and maximal
sensitivity is necessary. These various procedures should also
be useful in the analysis of various types of aldehyde
precursors.*#
03234
R. S. Tipson, A. Cohen, and A. J, Fatiadi
AIR POLLUTION STUDIES. National Bureau of Standards,
Washington, D.C. (NBS Technical Note 405) 1-28, 1966
The oxidation of polycyclic aromatic hydrocarbons is described.
Results are reported for the oxidation of naphthalene, anthracene,
phenthrene, pyrene, and perylene with a variety of oxidants.
Oxidation products are identified where possible. The results
obtained with periodic acid as an oxidant are particularly
noteworthy. Studies of photooxidation of the polycyclic
hydrocarbons on silica gel, alumina, soil, and air-borne
particulate matter have revealed, for each hydrocarbon, products
that may arise in contaminated air under smog conditions.
(Author abstract)t#
03267
H. F. Sweeney and J. N. Pattison
A NEW AUTOHOBILE EXHAUST ANALYTICAL TRAIN. ProC. Tech.
Meeting Rest Coast Section, Air Pollution Control Assoc.,
3rd, Bonterey, Calif., 1963. 93-105 pp.
D. Measurement Methods 307
-------
Data has been developed to permit the recommendation of the
dilution technique with a hexane detector to minimize zero shift
problems. It is suggested that the hexane detector nay be
operated at a span of about 3000 ppm, with dilution ratio of 3 to
1. It is recommended that the flow through the instruaents be in
parallel. It is concluded that the propylene detector gives
results relative to hexane which are in the direction expected for
variations between high and low emitting modes and vehicles.**
03291
S. Balestrieri, and M. Feldstein
THE DETECTION AND ESTIMATION OF PABT PER BILLION CONCENTRATIONS OF
HYDROCARBONS. Preprint. (Presented at the Sixth
Conference on Methods in Air Pollution Studies, California
Dept. of Public Health, Berkeley, Calif., Jan. 6-7, 1964.)
A liquid nitrogen freeze-out step has been added to the gas
chromatographic analysis of hydrocarbons using a flame ionization
detector. Concentrations in the low ppb range of C2 and higher
hydrocarbons can accurately be determined. Contaminant
concentrations of these compounds have been measured in nitrogen,
helium and hydrogen cylinders. (Author summary)##
03354L
J. H. Sullivan, D. H. Robertson, and C. Herritt, Jr.
THE DETERMINATION OF THE VOLATILE COMPONENTS OF FOODSTOFFS. III.
COFFEE ABOMA. Quartermaster Research and Engineering
Center, Natick, Mass., Pioneering Research Division.
(Research Report Analytical Chemistry Series No. 12.)
(Presented before the Division of Agricultural and Food
Chemistry, 135th National Meeting, American Chemical Society,
Boston, Mass., Apr. 1959.) Sept. 30, 1959. 16 pp.
CFSTI DDC 636331
Mass spectrometric analysis has led to the identification of
several components of coffee aroma. The volatile compounds from
ground roasted coffee are collected by distillation under high
vacuum "at room temperature into a receiver at liquid nitrogen
temperature. Direct fractionation of a "center cut" on the mass
spectrometer and subsequent analysis has shown the presence of aore
than twenty compounds. Among the compounds identified are furans,
aldehydes, esters, alcohols, nitriles and sulfur compounds. The
techniques which have been used offer the following advantages:
(1) The method of collection by vacuum distillation in a closed
system is superior to other methods of collection.
(2) A minimum of sample handling reduces greatly any loss of
material. (3) Direct analysis on the spectrometer permits a
complete qualitative analysis in a rapid, efficient manner and also
provides for the extension to quantitative analysis, if desired.
(Author abstract)**
308 HYDROCARBONS AND AIR POLLUTION
-------
03369
S. Hantzsch and K. E. Prescher
ANALYZING AMINE TRACES IN ATMOSPHERIC AIR. STAUB (English
Transl.) (Duesseldorf) 26, (8) 28-32, Aug. 1966.
A report on the concentration of primary aliphatic amines in air
is given. Absorption tests on low concentration of amines in air
were carried out in diluted hydrochloric acid, using wash bottles
and impingers. Material losses during the concentration of
absorption solutions were also evaluated. Practical experience in
extracting primary aliphatic Cl to C6 amines with auylactic
ester is reported. Reaction of primary amines with ninhydrine was
used for photometric amine determination. (Author summary)##
03125
S. B, Smith and R. J. Grant.
A NON-SELECTIVE COLLECTOR FOR SAMPLING GASEOUS AIR POLLUTANTS
FINAL KEPT,) Pittsburgh Coke and Chemical Co.,
Research and Development Dept. Dec. 15, 1958. 63 pp.
Tests of the retentive power of various adsorbents indicated
activated carbon is superior to silica gel and molecular sieves for
the non-selective collection of air pollutant gases. When dry ice
is used as a refrigerant on a carbon column it is possible to
collect methane and all gases of lower volatility in a sample of
reasonable size. Certain oxidizing gases such as No, NO2 and
03 appear to react with activated carbon and must be considered
separately. Columns of various sizes were tested over a wide
range of gas concentrations and a column containing 55 grams of
Pittsburgh HDL activated carbon chosen to sample 20 liters of
air for light contaminants. ft smaller column for operation at
room temperature containing 1.5 grams of the same carbon may be
used ahead of the refrigerated column to collect C4 and higher
compounds from 100 liters of air. A field collector kit was
designed which affords a preliminary filtration and drying of the
air sample, positive displacement measurement of the sample volume,
continuous flow measurement and mechanical pumping of the air
sample. A helium flushing system for the refrigerated collector
is also provided to remove the bulk of air adsorbed from the
sample. Prototype columns were tested satisfactorily for
retention under exaggerated test conditions on selected hydrocarbon
vapors. A few recovery runs indicated that good recovery can be
confidently expected after further experimental development of
recovery techniques. (Author summary)##
03430
E. S. Watson.
SPECTROPHOTOHETRIC AND CHROBATOGEAPHIC METHOD OF MONITORING
SPACECRAFT ATMOSPHERES. Perkin-Elmer Corp., Norwalk,
Conn., Electro-Optical Div. 24 pp., Jan. 1964.
The basic principles of spectrophotometry and its application to
spacecraft atmosphere monitoring, using a miniaturized C02 sensor
0. Measurement Methods 309
-------
are described. Also included is a brief summary of the elements
of gas chromatography and a comparison of spectrophotometric and
gas chromatographic techniques that indicates the way they
complement each other for space instrumentation. ft
03HH8
A. P. Altshuller and A. F. Wartburg-
PRESSURE-BROADENING EFFECTS ON INFRARED PEAK INTENSITIES OF
HYDKOCARBONS. Appl. Spectry. 15, (2) 67-9, 1961.
The pressure-broadening effects of one atmosphere of air or of
carbon dioxide on various infrared bands of hydrocarbons have been
investigated. Large pressure-broadening effects are shown by
ethylene at 10.52 microns and acetylene at 3.1 and 13.7 microns,
moderate effects by acetylene at 7.4 microns and propylene at 10.95
microns, and small effects by 1-butene at 10.85 microns,
trans- 2-butene at 10.375 microns, and benzene at 9.50 microns.
The variation of absorbance at several of the infrared absorption
maxima of ethylene and acetylene was investigated using varying
partial pressures of air or carbon dioxide at fixed partial
pressures of the 2 hydrocarbons. (Author abstract) ##
Farmer, J. R. and J. D. Williams
INTERSTATE AIR POLLUTION STUDY PHASE II PROJECT REPORT. III.
AIR QUALITY MEASUREMENTS. Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution
Control, 182p., Dec. 1966. 71 refs.
The development of an effective air resource management program
begins with the determination of what pollutants are in the air,
the quantity of each, and where they originate. The aerometric
network was designed and operated to determine the nature and
extent of air pollution in the Metropolitan St. Louis area.
Once the air pollution problem is defined, the emission inventory
and the opinion surveys can be used in connection with air
quality criteria to set the air quality goals. Then the
aerometric network will be used to monitor the air to insure the
goals are attained. The salient portions of this report are the
tabular data on particulates, gaseous pollutants, and material
deterioration. f I
03H85
H. 0. D. Low and S. Coleman
THE MEASUREMENT OF INFRARED EMISSION SPECTRA USING MULTIPLE-SCAU
INTEBFEBOMETRY. Preprint. 196U
A multiple-scan interference spectrometer is described, as are
exploratory experiments on the application of the instrument to
observe low-temperature emission spectra from solid surfaces. The
instrument is highly sensitive and could be used for transmission,
reflection, and emission spectroscopy, especially in situations
where the signals obtained are weak. (Author abstract)ft
310 HYDROCARBONS AND AIR POLLUTION
-------
03520
B. I. Larsen
PARAMETEBS OF AEROMETRIC MEASOEEMENTS FOE AIE POLiaTION
EESEAHCH. Am. Ind. Hyg. Assoc. J. 22, (2) 97-101, Apr.
1961.
A brief description of a continuous gas sampling network is
presented in which a number of air pollutants is to be measured in
six United States cities beginning about mid 1961. Parameters
are presented of aerometric measurements from a two year study of
sulfur dioxide in Louisville, Kentucky, to be related to health
and other effects. Six eguations are developed to depict the
frequency, duration, and air pollution dosage. (Author
abstract) ##
03523
E. Sawicki
ORGANIC SPECTROPHOTOHETRIC ANALYSIS - EEVIEW. Becord Chem.
Progr. (Kresge-Hooker Sci, Lib.) 22, (U) 249-80, 1961.
This paper is not a critical evaluation of procedures in the
literature; it is essentially a review of our recent work. The
detection and determination of trace amounts of chemicals in the
human environment has become one of the prime factors in the
necessary attempt to understand and control all aspects of this
environment. The chemical composition of the atmosphere is one
phase of this problem which is being probed by various methods of
trace analysis. These analytical methods are generally applicable
to the analysis for microgram or nanogram guantities of organic
compounds in extremely complicated mixtures. A knowledge of
collection techniques, separation procedures, organic synthetic
chemistry, and absorption and fluorescence spectrophotometry
(as applied to the ultraviolet, visible, and infrared regions of
the spectrum) is invaluable in the origination and application of
such methods.#t
03527
R. 0. HcCaldin
EVALUATING AIR POLLUTION PROBLEMS (ACCEPTABLE EQUIPMENT AND
PROCEDURES). Arch. Environ. Health 2, 228-33, Mar. 1961.
Some of the more common equipment used in making environmental
air quality determination, such as Hi-Volume Samplers, Filter
Tape Samplers, Gas Samplers, and simplified monitoring
techniques, are discussed. Hi-Volume Samplers are frequently
used to measure suspended particulate which may consist of smoke,
dust, or other solids small enough to remain air-borne for long
periods. This includes particulates under 100 microns in dian,
and, for the most part, those less than 1 micron in diam. Fiber
glass filters commonly used with this sampler collect
practically all particulates down to 0.3 micron in diam.
The sampler itself consists of a vacuum cleaner motor with
mounting to accomodate an 8-in by 10-in filter. Filter Tape
0. Measurement Methods 311
-------
Samplers are commonly used in the field studies and
usually are equipped with a diaphragm pump to draw air through at
a rate of about 7 liters/min. Various automatic instruments are
used for the continous collection"and recording of gaseous
pollutants. However, various manual or semimanually operated
bubbler collection trains have been used in the majority of
gaseous measurements. Simplified monitoring techniques are
discussed in conjunction with dustfall sulfation rates, H2S,
corrosion and fluoride sampling.##
03537
T. R. Mauser, D. W. Bradley
EFFECT OF INTERFERING SUBSTANCES AND PROLONGED SAMPLING ON
THE 1,2-DI-(«-PYRIDYL)ETHYLENE METHOD FOR DETERMINATION OF
OZONE IN AIR. Anal. Chem. , 39 (10) : 1181-1186, Aug. 1967. U
refs. (Presented at the Division of Water, Air, and Waste
Chemistry, 153rd Meeting, ACS, Miami Beach, Fla., April
1967.)
A new method for the sampling and analysis of ozone in the
atmosphere involves the collection of atmospheric ozone in a
solution of 1,2-di-(4-pyridyl)ethylene (PE) in glacial acetic
acid, reaction of the ozone with the PE via the
ozonolysis reaction to form pyridine-t-aldehyde, and
colorimetric analysis of the resultant pyridine-U-aldehyde using
a modification of the 3-methyl-2-benzothiazolone hydrazone
method. This paper describes the effect of two additional
analytical parameters on the PE method. These parameters,
namely the effedt of possible interfering substances present
in the atmosphere and the effect of prolonged sampling time on
final analysis, are very important when any analytical procedure
is applied to the field analysis of atmospheric contaminants. The
results demonstrate that the method can be used for 2U-hr. sampling
simply by increasing the volume of absorbing solution since there
is no loss of collected ozone from the absorbing solution during
a 2<* hr. sampling period due to a possible aeration effect.**
03542L
L. Heckner, F. R. Taylor, W. E. Scott, H. J. Wimette
DIESEL EXHAUST COMPOSITION, ODOR AND EYE IRRITATION
(PROGRESS BEPORT MAY 1, 1962 TO FEB 15, 1963. Preprint 1963.
Further work with the two-cycle 6-cylinder V-type diesel engine
is reported which which covers solid and liquid particulate
emissions at various operating conditions, odor intensity and eye
irritation observations by a human panel at three operating
conditions, analyses of the particulate for polycyclic aromatic
hydrocarbons and further analyses of the gaseous emissions by
long-path infrared and colorimetric techniques. A number of
polycyclic arolnatic hydrocarbons, including benzo(a)pyrene and
several other compounds with reported positive biological activity,
have been detected in diesel exhaust by fluorescence
spectroscopy. The concentrations of most polycyclics were
highest from 1/2 load to 7/8 load with a sharp decrease from 7/8
load to full load. The benzo(a)pyrene concentrations found in
diesel exhaust (0.6 to 7.U micrograms per cubic meter) were
312 HYDROCARBONS AND AIR POLLUTION
-------
lower than the 8.5 micrograms per cubic meter recently
reported for automobile exhaust, but the diesel produced more
benzo (a) pyrene (0.15 to 1.3 milligrams) per gallon of fuel than
the automobile (0.27 milligrams). Fluorescence analyses of new
and used lubricating oil and the rate of oil consumption indicate
that the contribution of the oil to the exhaust particulate of
this engine is negligible. Values for the emissions of nitrogen
dioxide have been revised downward as a result of using an
improved sampling technique which minimizes the oxidation of
nitric oxide to nitrogen dioxide. Of the three engine operating
modes studied, the odor intensities and eye irritation observed by
the human panel were lowest at the 1200 RPM-1/4 load condition.
It is believed at this time that the eye irritation from the
exhaust can be accounted for by the formaldehyde and acrolein
found in the exhaust. There is no clear-cut correlation,
however, between the concentrations of these aldehydes and the
odor differences observed. ##
B- E. Saltzman N. Gilbert
MICRODETERMINATION OF OZONE IN SMOG MIXTURES (NITROGEN DIOXIDE
EQUIVALENT METHOD). Am. Ind. Hyg. Assoc. J. 20, 379-86,
Oct. 1959.
A new method has been presented for conveniently and
specifically' determining low concentrations of ozone in polluted
air, even in the presence of large amounts of other commonly
occurring oxidizing or reducing gases. Ozone was
stoichiometrically converted to (and determined as) nitrogen
dioxide, by addition of controlled amounts of gaseous nitric
oxide to the sample air stream and allowing a short reaction
flow time. Better than 95S conversion was obtained in a
convenient apparatus which was developed, when 1 p.p.m. excess
nitric oxide and forty seconds reaction time were used. In the
short time allowed, oxidation of nitric oxide by air and organic
oxidant was negligible. Results for pure ozone were in good
agreement with those of an iodide reagent. For synthetic smog
oxidant mixtures (generated by the ozone reaction with
1-hexene) the method appeared specific for ozone, whereas the
iodide reagent also responded to organic oxidants. (Thus the
mixture could be differentiated into two oxidant components by
simultaneous application of the two methods.) Reducing gases such
as sulfur dioxide and hydrogen sulfide did not appreciably
interfere even in one hundred to one ratio to ozone. The method
should make possible interesting new data for polluted air. It
should be readily adaptable to automatic recording of ozone
in smog without interference from associated pollutants. (Author
summary) if
03569
A. J. Andreatch and R. Feinland.
CONTINUODS TRACE HYDROCARBON ANALYSIS BY FLAME IONIZATION.
Anal. Chem. 32, (8) 1021-K, July 1960. (Presented at the
Pittsburgh Conference on Analytical Chemistry and
Applied Spectroscopy, Pittsburgh, Pa., Feb. 1960.)
0. Measurement Methods 313
-------
An inexpensive, rugged, and portable flame ionization detector has
been designed for the continuous analysis of trace amounts of
hydrocarbons. The detector is insensitive to inorganic gases but
responds to hydrocarbons in proportion to the carbon atom content.
A detectable limit of 1 p.p.b. of hexane is obtainable. As an
automotive exhaust analyzer, the unit can first measure total
unburned hydrocarbons, and then by introducing an 8-inch silica gel
column, the unit can determine methane, ethane, ethylene,
acetylene, and propylene. (Author abstract)ft
03592
S. T. Cuffe
AIR POLLUTANTS FROM POWER PLANTS (TECHNIQUES FOR EVALUATING
AIR POLLUTANTS). Arch. Environ. Health 6, 422-7,
Mar. 1963. (Presented at the 27th Annual Meeting, Industrial
Hygiene Foundation, Pittsburgh, Pa., Oct. 24-25, 1962.)
The objective of the study is to evaluate the emissions of oxides
of nitrogen, oxides of sulfur, polynuclear hydrocarbons, total
hydrocarbons, total solids, formaldehyde, organic acids, and common
metals in the gases emitted from various types of coal—burning
power plants which may be useful in establishing the range of
atmospheric emissions under various conditions of operation.
Determination of the efficiencies of control equipment is also
essential for the long-range objective of reducing total air
pollution. This paper describes the sampling and analytical
techniques used in evaluating the several types of emissions under
study.t*
03679
A, P. Altshuller and I. R. Cohen
SPECTROPHOTOMETRIC METHODS FOR OLEFINS (COLOHIMETRIC
DETERMINATION OF CONJUGATED DIOLEFINS). Anal. Chem. 32, (13)
1843-8, Dec. 1960. (Presented at the Division of Hater,
Sewage, and Sanitation Chemistry, Symposium on Air Pollution,
136th Meeting, American Chemical Society, Atlantic City N.
J., Sept. 1959.)
In a new colorimetric method conjugated diolefins are coupled with
2-methoxyethanol-phosphoric acid solvent medium. Isoprene-type
diolefins couple to form products with strong absorption near 490
millimicrons, while butadiene couples to form a product with a
maximum near 405 millimicrons. The intensities of these maxima
are linearly related to concentration between at least 0.3 and 30
millimicrons per ml. for isoprene-type diolefins and 20 and 200
microgram per ml. for 1,3-butadiene. A 2- to 4-hour reaction
period is necessary to obtain optimum intensities. Ho
appreciable interference occurs from paraffinic, acetylenic, simple
aromatic, and most other types of olefinic hydrocarbons. Some
aldehydes, ketones, and phenols interfere moderately. Isoprene
has been efficiently collected and determined from dilute
isoprene-air mixtures, and in several liguid mixtures containing
various other hydrocarbon components, including 1,3-pentadiene,
unconjugated diolefins, and various types of mono-olefins.
(Author abstract)**
314 HYDROCARBONS AND AIR POLLUTION
-------
03680
A. P. Altshuller, D. L. Miller, and S. F. Sleva
DETERMINATION OF FORMALDEHYDE IN GAS MIXTURES BY THE
CHROHOTBOPIC ACID METHOD. Anal. Chem. 33, (4) 622-5, Apr.
1961. (Presented before the Division of Water and Waste
Chemistry, 138th Meeting, American Chemical Society, New
York City, Sept. 1960.)
The modification of the chromotropic acid method for formaldehyde
proposed by West and Sen has been investigated. With only minor
variations, the present study confirms the previous findings of
reagent concentrations, color stability of the product, and the
stability of the reagent solution. A much more detailed
investigation of the possible interference of olefins, alcohols,
aldehydes and ketones, aromatic hydrocarbons, phenols, and of
nitrogen dioxide has been made. Nitrogen dioxide, most aldehydes
and ketones, and straight-chain alcohols do not interfere
significantly. The interference of olefins and aromatic
hydrocarbons can be largely eliminated by the use of appropriate
sampling conditions. (Author abstract)#f
03684
A. P. Altshuller and I. R- Cohen
DETERMINATION OF PRIMARY NITBOPARAFFINS BY THE NITRODS ACID
REACTION. Anal. Chem. 32, (7) 881, June 1960.
Nitrous acid reactions with primary nitroparaffins,
dinitroparaffins, and a variety of nitroalcohols are reported. To
an aqueous solution of a. sample containing a nitroalkane, about 0.1
gm of KOH was added to ensure solution; 0.25 gm of KN02 and
0.6 ml of 18N H2S04 were added; the solution was shaken with
10 ml of diethyl ether and the layers were separated. The
aqueous layer was transferred to the absorption cell.
Absorbance at 330 millimicrons was read 5 min after mixing. The
final alkaline aqueous extract of 1-nitropropane has an absorption
band at 330 millimicrons due to the formation of sodium
propylinitrolate. The reaction of HN02 with nitroparaffins
gives solutions with red-orange or red-brown colors of low
intensity, resulting from far weaker absorption in the visible
spectrum than that found at 330 millimicrons. The blue color
resulting from the reaction of HN02 with secondary nitroparaffins
is also of low intensity and the visible absorption observed is not
usable for determinations in the microgram range. Interferences
were determined for a number of other aliphatic nitro compounds.
Primary amines as well as large amounts of secondary amines will
interfere with the analysis of the primary nitroparaffins.t#
03727
A. P. Altshuller, S. F. Sleva, A. F. Wartburg
SPECTROPHOTOHETHIC DETERMINATION OF OLEFINS IN COUCENTBATED
SD1FURIC ACID. Anal. Chem. 32, (8) 946-54, July 1960.
(Presented before the Division of Water, Sewage, and
D. Measurement Methods 315
-------
Sanitation Chemistry, Symposium on Air Pollution, 136th
Meeting, American Chemical Society, Atlantic City, N.J. ,
Sept. 1959.)
A new spectrophotometric method for the determination of small
quantities of olefins is based on the absorbance produced in the
300 to 310 millimicron range from their reaction with
concentrated sulfuric acid. The procedure is insensitive' to
ethylene under all conditions studied and to propylene
concentrations below 1500 p.p.m. Propyl and higher molecular
weight alcohols react to form absorbing products at 300
millimicron. Some higher molecular weight aldehydes, nitrogen
dioxide, and sulfur dioxide interfere moderately. The method has
been applied to the analysis of a number of two component liquid
mixtures and to gas mixtures containing butrenes, 1-hexene, or 1-
hexene-benzene in air. The experimental evidence favors
carbonium ions as the absorbing species. (Author abstract)ft
03732
P. Drone J. E. Smith
ANALYSIS OF CHLORINATED HYDROCARBONS WITH THE GAS CHROHATOGEAPH.
Am. Ind. Hyg. Assoc. J. 22, (1) 36-41, Feb. 1961.
(Presented at the 21st Annual Meeting, American Industrial
Hygiene Association, Rochester, N.Y., Apr. 25-28, 1960.)
The gualitative and quantitative behavior of eleven chlorinated
hydrocarbons on the gas chromatograph was investigated for
possible application to the analysis of their vapors in air.
Relative retention volumes and quantitative standardization
curves are given. Methods for the sampling and measurement of
chlorinated hydrocarbons in air are described. (Author abstract)f#
03773
J. May
ODOR THRESHOLDS OF SOLVENTS FOR ASSESSMENT OF SOLVENT ODORS IB THE
AIR. STAUB (English Transl.) 26, (9) 34-8, Sept. 1966.
Ger (Tr.)
Detection limits of thirty seven (37) solvents were investigated
to determine their odor thresholds. Quantitative analyses of
vapor concentrations of the solvent mixtures were carried out using
gas chromatography. Directives for the limitation of solvent
vapor emissions are proposed.t#
03828
Pustinger, John V.
ANALYTICAL TECHNIQUES FOR IDENTIFICATION OF GAS-OFF PRODDCTS
FROH CABIN MATERIALS. In: Proceedings of the Conference on
Atmospheric Contamination in Confined Spaces: 30 March - 1
April 1965, Aerospace Medical Research Lab., (6570th)
Wright-Patterson AFB, Ohio, bScontract AF 33 (657)-11305,
Proj. 6302, AMRL-TR-65-230, p. 276-295, Nov. 1965.
CFSTI, DDC: AD 629622
316 HYDROCARBONS AND AIR POLLUTION
-------
A program was initiated to identify the gas-off products from a
variety of candidate space craft materials and to estimate the
concentration and gas-off rates of these potential space
contaminants. Eventually 50 materials will be tested and
approximately 1000 analyses will be performed. A listing of
general types is presented. Some standard procedures for
establishing minimum detection levels are needed. The simple
methods of weight loss from thermal degradation or olfactory
sensing, as used in the Mercury program, will not suffice. As
shown in this study, the highly sensitive detection system of gas
chromatography and the specific identification possible with
supporting mass spectrometry and infrared absorption
spectrophotometry fulfill most criteria. The technigues employed
in this program were developed for application to survey a wide
range of materials. In each material system, more optimum
instrument conditions, particularly gas chromatography operation,
could be established. It is felt that with improved gas
chromatography technigues, considerably lower detection levels can
be established. The biggest problems in standardization of
methods are sample preparation and handling. There are many
variables, e.g., freshness of sample, surface area, mixing, curing,
sample uniformity and changes in proprietary mixes, which can
influence the nature and degree of gas-off products. Early
results indicate that standardization of methods for gas
chromatography and mass spectrometry can best be accomplished for
individual sample types, e.g., silicone polymers, rather than a
single comprehensive approach. Each system produces different
gas-off products, which reguire different analyses. Also, the
most significant data can be obtained when the materials are
evaluated in the approximate form for final use.tt
03829
Saunders, Raymond A.
ATMOSPHERIC CONTAMINATION IN SEALAB I. In: Proceedings of the
Conference on Atmospheric Contamination in Confined Spaces:
30 Harch - 1 April 1965, Aerospace Medical Besearch Lab.,
(6570th) Bright-Patterson AFB, Ohio, Contract
AF 33(657)-11305, Proj. 6302, AMHL-TR-65-230, p. 296-305,
Bov. 1965.
CFSTI, DDC: AD 629622
The Man-in-Seas Program has several important goals, one of
which is to make possible the free movement of scuba divers for
extended periods of time at depths up to 1000 feet. Present
practical dives are limited to a few hundred feet for useful work
periods measured only in minutes. More importantly, hours of time
nay be required after such dives to return the divers safely to the
surface. Techniques now being investigatred by the Navy,
however, are designed to permit divers to work at depths of
hundreds of feet for 6 to 8 hours a day, day after day, without the
necessity for intervening returns to the surface. Such long dives
will permit exploration of large areas of the undersea
continental shelf, areas which abound'inmineral and food riches.
Diving explorations of this magnitude are made possible by
eliminating the long decompression periods required for returning
divers to the surface. This is accomplished by providing the
divers with undersea living accomodations which they may enter or
leave at will. After working in the open sea the divers have only
to re-enter their undersea home to rest and refresh themselves.
They will be able to live comfortably inthese quarters for months
D. Measurement Methods 317
-------
at a time, secure from their hostile outer environment. The first
0. S. Navy open sea tests of these new concepts were made in the
summer of 1964 at Argus Island, a Texas Tower off the coast of
Bermuda. The divers' submerged living quarters was called
SEALAB I. A description of the facility is presented and
methods of analyzing contaminants are discussed. Deference is
made to nuclear submarine atmospheres and methods for studying
atmospheric contaminants are discussed.#i
03866
J. R. Farmer J. D. Williams
INTERSTATE AIR POLLUTION STDDY: PHASE II PROJECT REPORT. III.
AIR QUALITY MEASUREMENTS. Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution Control.
Dec. 1966. 190 pp.
The development of an effective air resource management
program begins with identification of the pollutants in the
air, and determination of the quantity and origin of each type.
The air quality measurement program was designed and operated
to make these determinations in the Metropolitan St. Louis
area. Once the physical aspects of the air pollution problem
are defined, air-pollution-effect data and criteria as well as
opinion surveys can be used to set the air quality goals.
From this base, with use of the pollutants emission inventory
the air resource management emission control plan can be
designed. At this stage the air quality measurement program
is used to monitor the air quality to assure that the goals are
attained. In addition ot its use in the air resource management
program, this report provides a reasonably complete list of air
quality data in a form that will assist research and
program personnel in developing activities and attaining progran
objectives. A population distribution map of the study area is
provided to allow comparison between distribution of population,
pollutants, and sampling measurement networks.t*
0392«
V. A. Tret'yakova
THE DETERMINATION OF H,H•DIPHENYLMETHANE DUSOCYANATE IN AIR
UNDEK EXPERIMENTAL CONDITIONS. Hyg. Sanit. 31, (U-6) 73-5,
Apr.-June 1966. Rr. (Tr.)
.CFSTI, TT 66-51160/U-6
Two methods are suggested for the photometric determination of
«»,U-diphenylmethane dusocyanate (DMD). The first method of
determination is based on the reaction of DMD with aromatic
amines and nitrites for which the sensitivity is 1 microgram in 4.2
ml and the determination error is plus or minus 7%. The second
method of determination is based on the reduction of DMD with
N02 ion. In this case the sensitivity is 20 micrograms/5.5 nl
for photometric deterination with an FMS-56 instrument, with a
mean error of plus or minus H%; the sensitivity for photometric
determinations by the standard series method is 2 microgram/5.5 il,
with an error of plus or minus 10S. DMD vapor is absorbed by
acetone when the air is drawn through two absorbing vessels with
porous partitions cooled by ice, at a rate of up to 30 1/hr.M
318 HYDROCARBONS AND AIR POLLUTION
-------
03929
E. G. Kachmar
DETERMINATION OF DIBETHYLAMINOAZOBENZENE IN AIR. Hyg. Sanit.
31, (4-6) 234-5, Apr.-June 1966. Russ (Tr.)
CFSTI, TT 66-51160/4-6
Dimethylarainoazobenzene is a basic azo dye and is used for
staining ethyl liquid (antiknock). During the manufacture
of this compound, its aerosol pollutes the air of the factory
shops. Therefore it was necessary to devise a method for its
determination in air. The reaction proposed by Selina for the
investigation of another azo compound, viz. o-
aminoazotoluene was utilized. The method is based on the
reaction of azo compounds with acids, with the formation of colored
solution. It was found that the highest sensitivity
(0.2 microgram) was achieved by adding 0.2 ml of 15% HC1
solution to 2 ml of alcohol solution of dimethylaminoazobenzene.#t
03937
0. G. Neronskii
PHOTOELECTROCOLORIMETRIC DETERMINATION OF HIGHER ALIPHATIC AHINES
IN AIH. Hyg. Sanit. 31, (4-6) 381-3, Apr.-June 1966.
Russ. (Tr.)
CFSTI, TT 66-51160/4-6
The present method was developed for the investigation
of air with respect to enrichment of potassium salts in which
the flotation agent is represented by aliphatic amines (C16-C20)
in the hydrochloride form which are markedly toxic. There is
no established maximum permissible concentration for higher
aliphatic amines in factories and in the atmospheric air.
The method is based on studies of amines in aqueous
solutions. The determination is based on the reactions
of amines with methyl orange at a pH of 3.0-4.0, forming a
yellow compound which is readily soluble in organic solvents
(dichloroethane, chloroform). The sensitivity is 1
microgram in the analytical volume in the case of
octadecylamine. Ammonia does not interfere. The accuracy
of the method (99.8-100%) practically corresponds to the accuracy
of the instrument in the interval of 5 to 100 micrograms.
Addition of 25 micrograms of a mixture of KC1 plus NaC1
in the ratio in which they are present in potassium concentrate
does not affect the sensitivity and the accuracy of the
determination. The method was used in studies of air
pollution by amines at the ore-dressing factory of the
1st Soligorsk Potassium Works. Amines were discovered in
all air samples, in concentrations of 0.001 to 2.09 mg/cu n.#t
03938
G. I, Benzina
SPECTBOPHOTOMETPIC DETERMINATION OF FURFURAL IN AIR. Hyg.
Sanit. 31, (4-6) 383-5, Apr.-June 1966. Huss. (Tr.)
CFSTI, TT 66-51160/4-6
D. Measurement Methods 319
-------
The use of modern construction mate*rials involves the danger
of liberation of toxic substances into the air of the living
rooms. A laboratory investigation of samples of chipboard which
were subsequently treated with FA monomer (mixture of
furfural and acetone) was made. In addition to be
chemical methods (AleKseeva) for the determination of
furfural concentrations in air, adsorption spectroscopy
in the ultraviolet spectrum region was used. The *
spectrophotometric measurements resulted in the determination
of the absorption maximum for furfural and produced its
spectral pattern. According to the findings, the
determination of furfural can be performed within a period of
20 min to 5 days from the moment of the taking of air
samples. The air is drawn through a V-shaped absorption vessel
containing 5 ml ethanol at a rate of 0.5 1/m for 20 to 30 min.
The spectral patterns of formaldehyde in ethanol containing
0.1 and 0.01 mg/m1 were demonstrated. Formaldehyde did not
interfere with the determination of furfural. Acetone likewise
causes no interference. Interference is caused by the'presence
of phenol. However, the absorption maximum of phenol is
considerably higher and the method described can be used
for the investigation of furfural in the presence of
formaldehyde and acetone and in the absence of phenol.tf
039«0
A. S. Filatova, A. I. Kuz'minykh, F. D. Vedernikova,
N. S. Solomennikova
DETERMINATION OF 3,U-BENZPYRENE LIBERATED BY SUBLIMATION OF
ANODE MATERIAL IN ELECTROLYTIC SHOPS OF ALUMINUM PLANTS.
Hyg. Sanit. 31, (1-6) 381-4, Apr.-June 1966. Russ. (Tr.)
CFSTI, TT 66-51160/U-6
An investigation of the group of neutral multinuclear cyclic
hydrocarbons with the intention of subsequent isolation and
quantitative determination of 3,i*-benzpyrene which is the most
actively carcinogenic hydrocarbon was undertaken. Samples
at the electrolytic shop of an aluminium plant of dust from the
anode, from the inlet connector of the cell, from the anode
pin and from the "fog" evolving from under the pins as well as
at the position occupied by the operator were taken. Air was
drawn at a rate of 20 1/rain through a filter made of the
FPP-15 fabric fixed on a steel funnel, taking.larger
volumes of air in order to concentrate'the small quantities of
3,1-benzpyrene assumed to be present. Since the carrier
of carcinogenic substances is represented by tarry substances,
the dust samples were extracted in a Soxhlet apparatus and
quantitative determinations were made of the yield of tarry
substances. Nonfluorescent benzene was used as the solvent.
From the complex mixture of tarry substances by 3,U-benzpyrene
was isolated by partition paper chromatography and
fluorescence. The contents of 3,4-benzpyrene in the air
samples taken in the electrolytic shop of an aluminum plant
were as follows: 0.0137 to 0.022 1 micrograms/1 at the
worksite, 0.0361 to 0.2250 micrograms/1 during the removal
of the pins and 0.0519 to 1.3200 micrograms/1 in the "fog"
issuing from under the anode pins.*#
320 HYDROCARBONS AND AIR POLLUTION
-------
03949
H. Jeltes
ABSORPTION OF POLAR SUBSTANCES ON THE SOLID SUPPORT OF COLUMN
PACKING IN GAS-LIQUID CHROHATOGRAPHIC ANALYSIS OF AIR
CONTAMINANTS. J. Chromatog. 24, (2) 402-3, Oct. 1966.
The phenomenon of the adsorption of polar substances on the
solid support of nonpolar columns may be used in the
qualitative analysis of air contaminants. When this analysis
is performed on both polar and nonpolar packed columns very
probably polar substances will not be detected on nonpolar
packed columns.##
03955
N. Carugno and S. Rossi
EVALUATION OF POLYNUCLEAR HYDROCARBONS IN CIGARETTE SMOKE BY GLASS
CAPILLARY COLUMNS. J. Gas Chromatog. 5, (2) 103-6, Feb.
1967.
The detection and identification of polycyclic hydrocarbons in
cigarette smoke, airborne particles, and petroleum waxes by gas
chromatography with flame ionization detector or electron capture
detector is reported. The use of capillary columns affords the
opportunity of separating a large number of polynuclear
hydrocarbons from complex mixtures. A large number of cigarettes
were used for the gas chromatographic analyses. Solutions with
polynuclear hydrocarbons in high concentrations were used, as
samples introduced in capillary columns must be small for good
resolution of the peaks.#f
03965
H. J. Boldue and R. K. Severs
A MODIFIED TOTAL COMBUSTION ANALYZER FOR USE IN SOURCE TESTING
AIR POLLUTION. Air Eng. 7, (8) 26-9, Aug. 1965.
(Presented before the Division of Water, Air, and Waste
Chemistry, 149th National Meeting, American Chemical
Society, Detroit, Bich., Apr. 4-9, 1965.)
The development of a Total Combustion Analyzer (TCA) for
portable, on-site sampling and analysis of combustion gases for
hydrocarbon, carbon monoxide, and carbon dioxide concentrations is
described. The TCA was tested in comparison with the Flame
Ionization Analyzer and Detector at three industrial sources.
The data collected show the TCA unit to be reliable, accurate
and capable of on-site use.*#
D. Measurement Methods 321
-------
03967
R. S. Braman
FLAHE EMISSION AND DUAL FLAME EMISSION-FLAME IONIZATION DETECTORS
FOR GAS CHRCMATOGRAPHY. Anal. Chem. 38, (6) 734-U2, .Hay 1966.
A hydrogen-air flame emission detector was constructed employing
interference filters and standard gas chromatography
instrumentation. Instrumentation variables were studied.
Detection sensitivity was in the microgram range, wavelength
dependent and generally greatest for heteroatom - containing
compounds. The study of emission response at 589, 515, and 415
millimicrons indicates that the emission intensity attributed to
C2 or CH molecules in the flame plasma are dependent upon the
structure of the chromatographed compounds. The design and
operation of a dual flame emission-flame ionization (FE/FI)
detector for gas chromatography is also described. The influence
of structure on response ratios was studied on a chlorinated
methane series of compounds, an aromatic series of compounds, and a
three-carbon series of compounds. The influence of structure on
response ratios was demonstrated thus eestablishing the potential
use of the dual detector in qualitative identification of peaks.
(Author abstract)**
03971
R. G. Confer and R. S. Brief
MYLAR BAGS USED TO COLLECT AIR SAMPLES IN THE FIELD FOR LABORATORY
ANALYSIS. Air Eng. 7, (10) 34-6, 1965.
Mylar plastic bags, as a means of sample collection, were studied
to determine bag conditioning effects and decay rates at accepted
threshold limit concentrations and to establish a method of
sampling. Industrial solvents were of particular interest in the
study. It was determined that bag conditioning is necessary to
insure that sampled air represents workroom air contaminant
concentrations. Samplers collected remained at or above 90% of
the initial airborne concentration for several days for some
materials.#i
03977
D. J. McEwen
AUTOMOBILE EXHAUST HYDROCARBON ANALYSIS BY GAS CHROHATOGRAPHY.
Anal. Chem. 38, (8) 1047-53, July 1966.
A new gas chromatographic method has been developed to analyze
the complete range of hydrocarbons in both raw and highly
diluted automobile exhaust gas. A commercial gas chromatograph
was modified to include a separate oven for thermostating a
gas sampling valve and a flow - switching valve, a subtracter
322 HYDROCARBONS AND AIR POLLUTION
-------
column for removing the unsaturated hydrocarbons, and an
adsorption column in dual arrangement with a capillary column.
Sampling of exhaust gas and hydrocarbon calibration mixtures was
investigated. The capabilities of the method are demonstrated
with examples of analyses of exhaust gas from different engine
operating modes.##
03991
G. G. Esposito M. H. Swann
DETEBSINATION OF AROHATIC CONTENT OF HYDROCARBON PAINT SOLVENTS BY
GAS CHROHATOGBAPHY. J. PAINT TECHNOL. 38, («98) 377-80,
July 1966.
The solvency characteristics of petroleum thinners for alkyd
resins can be related to the amount of aromatic hydrocarbons
present. Many other synthetic resins require thinners of high
aromatic content and there is a need for a rapid, accurate
analytical method that can be used for quality control. A
procedure is described for the determination of aromatic
solvents in petroleum thinners by gas-liquid chromatography
(GLC) using a highly selective partitioning liquid. (Author
abstract)#*
ouom
D. Bondia
(ON THE VOLATILITY OF POLYCYCLIC HYDROCARBONS.) SUB LA
VOLATILITE DBS HYDROCAHBUBES POLYCYCLIQUES . Intern. J. Air
Water Pollution 9, (3) 113-21, Bar. 1965. Fr.
Despite the high boiling point of hydrocarbons, certain
polycyclics volatilize rapidly due to air currents with little
change in ordinary-temperature. It is probable that such
products are disseminated from industrial establishments where
solid fuel (charcoal) is used. In air pollution sampling, the
concentration of particulate polycyclic compounds is estimated by
collection of suspended matter on glass or paper filters. This
method introduces errors into the results because of evaporation,
especially for those compounds which have particularly low Belting
points. Particle size, volume and temperature of the air flowing
through the factors during sampling should be considered as
important parameters in this type of sampling. Oxidation of
samples during storage is also a possibility to consider.**
0«029
E. Sawicki, C. B. Engel, and W. C. Elbert
CHROMATOGRAPHIC LOCATION AND COLOHIHETBIC DETEBHINATION OF
HEHCAPTANS, PBOLINES AND FREE RADICAL PRECURSORS . Talanta,
Vol. 1«, p. 1169-1178, 1967. 19 refs.
0. Measurement Methods 323
-------
A new reagent is introduced for the colorimetric determination of
free radical precursors, such as cysteine, proline, hydroxyproline,
the phenoxazine family, and mercaptans. 7,7,8,8-
Tetracyanoguinodimethan (TCNQ) is also useful in the location
and characterization on paper or thin-layer chromatograms of
proline, hydroxyproline, cysteine, polynuclear compounds,
mercaptans, thiocarbonyl amides, and thiosemicarbazones. In
addition, amino acid derivatives, such as the N-
(phenylthiocarbamyl) amino acids and the 3-phenylthiohydantoins,
can be located and characterized on chromatograms. TCNQ has been
applied to the location and characterization of atmospheric
proline, carbazole, and 11 H-benzo (a)carbazole. For
characterization purposes absorption spectra were obtained directly
from glass-fiber, paper, or thin-layer chromatograms from about
300 to 900 millimicron. (authors' abstract)f#
03966
H- J. Boldue, R. K. severes, and G. L. Brewer
TEST PROCEDURES FOR EVALUATION OF INDUSTRIAL FUME CONVERTERS
(SAMPLING AND ANALYTICAL TECHNIQUES REVIEHED FOR) . Air Eng.
8, (2) 20-3, Feb. 1966. (Presented at the 58th Annual Meeting,
Air Pollution Control Association, Toronto, Canada, June
20-21, 1965.)
The purpose for development of the source testing outline was to
permit systematic evaluation of air pollution control equipment
on gaseous organic fume streams. Data were obtained to fulfill
the following objectives of the source outline: (1) Determination
of combustible emission and conversion .efficiency. (2)
Determination of particulate matter emissions. (3)
Identification of specific emissions by laboratory analyses. (4)
Determination of the odor concentration of the effluent stream in
conjunction with these objectives of source test measurements, the
outlined program was to include: (5) A method to check
credibility of sampling and analyses. (6) A technigue for future
monitoring of the control equipment performance. Source tests
were conducted on catalytic fume converter units located on a
metal-coating oven, a varnish-cooking kettle, a phthalic anhydride
plant and a wire-coating oven. Sampling procedures, analytical
technigues and developed equipment are discussed. The results of
each of the evaluations of the catalytic fume converters are
presented.f#
0<»0.«9
R. A. Duffee, E. J. Schulz, and E. W. Ungar
DISTURBING FACTORS IN PARTICULATF SAMPLING. Preprint.
(Presented at the Third Conference on Applied Meteorology,
Santa Barbara, Calif., Apr. 5-8, 1960.)
The study reported in this paper, which was carried out in .the
course of developing a tracer technique for industrial emissions,
324 HYDROCARBONS AND AIR POLLUTION
-------
was designed to measure the magnitude of the errors resulting from
anisokinetic sampling in the atmosphere and the effects of
deposition on the filter. Uranine dye, axfluorescent pigment, was
utilized as the sample particulate in all the experimental studies.
A 10% water-uranine solution was prepared and sprayed from two
pneumatic nozzles, with liquid and-atomizing air,pressures of
HO psig. The-water evaporated guickly, leaving dry uranine
particles with mass median diameters of,6 and 12 microns as
measured by a cascade impactor. Sample analysis consisted of
dissolving the dry sample in 20 ml of.distilled water and reading
the fluorescence on a fluorescent meter. These studies indicate
that, for particles with Stokes.diameters greater than 10 microns,
the error in mass concentration resulting from neglect of
deposition may be a factor of two.. For particles with Stokes
diameters less than 10 microns, this error appears negligible.
The effect of variations in sampling velocity on sample
concentration, for the range of sampling velocities used in these
runs, indicates that a; sixfold.increase in sampling velocity
results in a doubling of the sample concentration. However, in
one case,.a ninefold increase in sampling velocity resulted in only
a 15% increase in sample concentration, and, in another instance,
a sixfold;increase in sampling velocity resulted in an increase in
the sample concentration by a factor of four. . The results of
these studies serve only to identify some of the potential errors,
and their relative magnitudes, involved in the sampling of
atmospheric particulates. Differences in the results of the
wind-tunnel and atmospheric tests indicate the difficulties
involved in measuring true mass concentration in the atmosphere.
Perhaps of more importance is the fact that these results point
out the dangers inherent in'using a measure^of one-physical
property, such as mass concentration, to predict another, such as
deposition rates, in a turbulent atmosphere.#f
0«053
D. Rondia
TESTS TO ESTABLISH ADEQUATE CRITERIA FOR THE HARHFOLNESS OF
ATMOSPHERIC POLLUTANTSiAND,SUGGESTIONS-FOR A^CAMPAIGN'TO COHBAT
AIR POLLUTION. Essais de.Mise-au Point d'um Critere
Adequate de Novivitetdes. Polluants Atmospheriques et
Suggestions sur une-Campagne-de Lutte Centre la Pollution.
Preprint. (Presented attthe Inter-Regional Symposium on
Criteria for Air Quality and Methods of Measurement, Geneva,
Switzerland, Aug. ,6-12,,1963.)
i . ' ^
In establishing the health hazards of polluted air the measurement
of reflection,and lightitransmission of smoke samples is inadequate
for two reasons. The first is technological and is due to the
insufficient validity of the methods used; the second is biological
and is due to the lack of relation between the toxicity of the
smokes which contaminate air and their weight as obtained by the
sampling. A fluorometric approach to this problem was
investigated and it was found that in.the particular industrial
area in which the study was made there are seasonal factors that
would have to be taken into consideration, particularly during the
summer, in order to establish a reliable system for pollution
measurement. Air pollution programs should establish priorities
in their approach to the general problem, giving first priority to
toxic contaminants, after which-the-disagreeable pollutants from a
psychological or economic standpoint could be dealt with.ft
0. Measurement Methods 325
-------
04061
M. V. Alekseeva, N. A. Krylova, and V. A. Khrustaleva
SPECTROPHOTOMETRIC DETERMINATION OF EENZENE, ISOPROPYLBEUZENE,
AND ALPHA-METHYLSTYROL IN THE AIE. Gigiena i Sanit. 28, (1)
31-6, Jan. 1963. Buss. (Tr.) (Translated by B. S, Levine
in U.S.S.R. Literature on Air Pollution and Related
Occupational Diseases, Vol. 12.)
The following two problems were investigated: (1) determination
of small amounts of benzene, isopropylbenzene and
alpha-dethylstyrol in the air, and (2) selection of a solvent
medium for the collection of samples of the above substances, which
might make possible the gaantitative determination of the
substances. In this connection the spectrophotometric method
is based on the determination of the optical density of the
investigated substance in solution at wave length corresponding to
its maximum absorption. An essential requisite of this method is
that the investigated substance must behave in the selected
solution in accordance with Beer's law. Ethanol was finally
selected as the solvent in the study here described using
spectrophotometer SF-l.ft
04085
P. A. Krotkov, N. N. Serzhantova, and V. B. Timofeev
A PHOTOELECTROHETRIC METHOD FOR THE DETERMINATION OF LOH 3, 4-
BENZPYHENE CONCENTRATIONS. Gigiena i Sanit. 28, (5) 47-9,
May 1963. Russ. (Tr.) (Translated by B. S. Levine in
U.S.S.R. Literature on Air Pollution and Related
Occupational Diseases, Vol. 12.)
The report published by P. P. Dikun in 1961 contains a
quantitative spectrophotometric method for the determination of
low 3, 4-benzpyrene concentrations. The sensitivity of the method
makes possible the determination of 10 to the minus 8th power
micron of 3,4-benzpyrene in 1 ml of solution. The
quantitative analytical procedure previously recommended by the
same author which was based on fluorescent 3,4-benzpyrene spectra
at low temperatures and on the use of a photometer as described
by F. Heigart in 1934; V. K. Prokof'ev, 1951; by that
procedure 1,12-benzperylene was used as the inside standard.
The spectra were recorded photographically. The present
authors increase the method sensitivity and rapidity by recording
spectral intensities photoelectrically.##
04086
G. S. Salyamon'
COLORIMETRIC METHOD FOR TOTAL ALKYL AMINES DETERMINATION.
Gigiena i Sanit. 28, (5) 50-3, Hay 1963. Russ. (Tr.)
(Translated by B. S. Levine in D.S.S.R. Literature on Air
Pollution and Related Occupational Diseases, Vol. 12,)
326 HYDROCARBONS AND AIR POLLUTION
-------
The following reagents are used in determining amines in the air:
1) Ammonia-free distilled water; remove ammonia and acid by
boiling the distilled water for 1-1/2 to 2 hours; keep in a bottle
with a stopper through which insert an absorber tube containing
activated charcoal and ascarite; store so as to prevent contact
with air containing ammonia or acid vapor; 2) 0,1% solution of
0-nitrophenol prepared at 40-50 degrees with intermittent stirring
; 3) Nessler-Folin solution, prepared from potassium iodide,
iodine, mercury, and alkali, as described by D. T. You in 1935;
4) Standard 0.1 millimolar (0.1 micro mole/ml) solutions of
aliphatic amine and ammonia, prepared by hundredfold dilution of
0.01 M stock solutions, using ammonia-free water; check by
titrating 100 ml of the 0.01 M amine solution with a standard
0.1N HC1 solution using methyl red as the indicator; 5)
ascarite granular 2-4 mm in diameter. Concentrations of amines
in the air was computed on the basis of total bases minus ammonia
concentration. The value of H/1000, in the case of methyl amine
is 0.031; for dimethyl or ethyl amine it is 0.045, and for
triethyl amine, 0.101. The method is accurate to 0.02 micro mole
in the colorimetrically analyzed volume; for methyl amines and
ethyl amine it corresponds to about 1 gamma, for di- and tri-
ethylamine 2 gamma, and for ammonia 0.4 gamma per sample volume.
The method was applied in practice and yielded satisfactory
results in determining content of aliphatic amines in the air of
working premises and in experimental animal exposure chambers.##
04099
B. I. Poletaev
COLOBIMETRIC HETHOD FOR THE DETERMINATION OF
HONOISOPBOPHYDIPHENYL IN THE AIR. Gigiena i Sanit. 28, (8)
40-1, Aug. 1963. Russ. (Tr.) (Translated by B. S. Levine
in U.S.S.R. Literature on Air Pollution and Related
Occupational Diseases, Vol. 12.)
The purpose is to report on attempts to develop a method for the
determination of MIPD (Monoisopropyldiphenyl) in the air of
working premises. This author used the method based on the
colorimetric determination of HIPD by the Yanovskii
reaction. Air samples were collected by the aspiration method
using the Polezhaev microabsorber which contained 1 ml of a nitro
mixture consisting of 10 g of ammonium nitrate in 100 ml of
sulfuric acid of 1.82-1.84 sp. gr.; the air was aspirated through
this medium at the rate of 0.2-0.4 li/min. Where the
concentration of HIPD is suspected to be high, air samples can
be collected by the vacuum method into special containers of
100-200 ml capacity. Two ml of the nitro mixture is added to the
air sample containing vessel, and let stand for 1 hour
periodically washing the walls of the sample container with the
nitro mixture. The minimal amount of HIPD determined by the
acetone-alkaline medium extraction was 3 microns in colorimetric
volume, and by the ether extraction in acid medium, the minimum
was 2 microns. In the presence of other aromatic substances, the
method is nonspecific.tt
D. Measurement Methods 327
-------
04102
R. V. Lindval and I. V. Yerraakova
ACETYLENE DETERMINATION IN THE AIR BY INFRARED SPECTHOSCOPY.
Gigiena i Sanit. 28, (9) 51-4, Sept. 1963. Russ. (Tr.)
(Translated by B. S. Levine in D.S.S.E. Literature on
Air Pollution and Related Occupational Diseases, Vol. 12.)
CFSTI: TT 66 61429
Acetylene vapor is present in the air of working premises in the
production of calcium carbide, in the air of acetylene stations
and of plants which use acetylene in their production processes.
No maximal permissible concentration of acetylene vapor in the
air has as yet been established. A colorimetric method for the
determination of acetylene in the air was previously developed.
Determination of very low concentrations of acetylene vapor in .the
air by this method required the collection of large volume air •
samples, which.is time consuming. In addition different samples
are characterized.by different color shades which makes precise
determination at times difficult, if not impossible. By the
method described it is possible to determine minute quantities of
acetylene in the air with the aid of infrared microscopy. Data
presented show that the colorimetric method yielded some-what loner
results than the spectral method, A method was described for the
quantitative determination of low acetylene concentrations in the
air; it was developed on the basis of infrared spectrophotometry
and is sufficiently sensitive to determine acetylene vapor in the
air within the limits of 0.002-0.5% by volume.##
04143
T. Iritani and Y. Morishita
QUANTITATIVE DETERMINATION OF BENZENE TOLUENE, AND XYLENE IN
SOLVENT AND IN AIR BY GAS-CHROMATOGRAPHY. Japan. J. Ind.
Health (Tokyo) 2, '(6) 56-67, June 1960. Jap.
The minimum determinable concentration of benzene, toluene, and
xylene in solvents was found with gas chromatography to be 0.1S
and the error was within 0.5S of the value determined. The
quantitative determination of benzene, toluene, and xylene in air
using colorinetry after'separation by gas chromatography showed
gross error and is of no;practical use, because the vapors
condensed near the outlet. When the air was supplied to the gas
chromatograph without preparation, the minimum determinable
value was about 75ppm for 10 ml of air, but 75ppm is too high, to
be a desirable minimum value. To concentrate the air then, 1
liter' of air was passed at the rate of-100 ml/min through a small
column filled with 1 g of solid support (DOP)" and cooled by dry
ice; when the gases are attached to the inlet' of the gas
chromatograph and heated to 130 degrees C, a satisfactory gas
chromatogram is obtained. When the vapor determination is made
in air, the adequate column temperature is 100 degrees C instead
of 125 degrees-C (as with the analysis with solvents), since at
125 degrees C the vapors are not separated sufficiently from
steam. In order to prevent disturbance by steam, phosphorus
pentoxide must be put around the concentration column during
air-sampling. Silica gel and a molecular sieve are inadequate as
desiccating agents since they absorb benzene, toluene, and xylene
328 HYDROCARBONS AND AIR POLLUTION
-------
as well as steam. This method proved reliable when air samples
containing known quantities of the vapors were analyzed. The
minimum determinable concentration by this method using 1 liter of
air is approximately 2ppm for benzene, Ippm for toluene, and lOppm
for xylene, and these are equivalent to about 0.003mV (4mm) in
the peak height of gas chrcmatograms. Measurements can be taken
in the field if the samples are taken into concentration columns
with phosphorus pentoxide columns and tightly corked. (Author
summary modified)##
01199
H. Konosu
DETERMINATION OF ORGANIC SUBSTANCE VAPOR-AIR MIXTURES BY A
NON-DISPERSIVE ULTRAVIOLET GAS ANALYZER. Gov. Chem. Ind.
Res. Inst., Tokyo 62, (1) 25-33, Jan. 1967. Jap.
Vapors from organic substances used in chemical processes may have
hazardous levels of toxicity or explosibility. A nondispersive
ultraviolet gas analyzer, a device for determining the
concentration of an ultraviolet-absorbing component in a
nonabsorbing mixture of gases, has been developed and applied to
toxic or explosive gases. The samples were HCOOCH3,
HCOOC2H5, CH3COOCH3, CH3COOC2H5, CH3CH2Br,
(C2H5)2NH, and CH3CH2CH2CH2NH2. The concentrations
of the gases in air were determined from calibration curves
plotted as absorbance vs. volS. The analyzer could operate over
a wide concentration range from 6 ppm for (C2H5)2NH to 6 vol%
for HCOOCH3. The coefficients of variation of analysis (per
cent transmission) were 0.023 and 0.016X for the concentration
levels of 137 ppm and 2.74 vol% HCOOCH2H5, respectively. Time
required for an individual determination was 1 rain or less.
(Author summary)##
04206
Y. Matsumura and F. Soda
GAS CHROMATOGRAPHIC ANALYSIS OF ATMOSPHERIC POLLUTANTS IN
INDUSTRIES. Bull. Natl. Inst. Ind. Health (Kawasaki,
Japan) 4, ««»-51, 1960.
A description is given of the sampling efficiency of six kinds of
sampling bottles used for absorbing organic vapors where the
sampling solution is analyzed quantitatively by gas chromatography.
Toluene was used as the sampling solvent and benzene as the
organic vapor. A sampling solution was fed into the chromatograph
and the benzene and toluene peaks recorded. Benzene sampling
efficiencies were then determined and various factors affecting
efficiency discussed. It was found that bottles having the best
efficiencies are long midget impingers with glass beads at the
bottoms. The results of field measurements of nethanol, ethyl
acetate, benzene, and xylene in a dyeing factory are presented.*!
D. Measurement Methods 329
-------
01210T
HETHODS OF MEASDRING AIR POLLDTION. HEASUBEHENT OF HYDROCARBONS.
(PAKT 5.) Bisura deli Idrocarburi (Parte 5). Fumi
Polveri (Milan) 6, (12) 333-6, Dec. 1966. It.
Polycyclic hydrocarbons, present in the air as an integral part of
the material in suspension, and volatile hydrocarbons present in
the gaseous state, were investigated as pollutants. Polycyclic
hydrocarbons can cause cancer. Work on the "anthracene index"
and the "method of quinine sulfate" made it possible to define a
simple index of the tar material, -whether this index could or
could not be related to the concentration of individual
polycyclic hydrocarbons. Good results for determining the smoke
content of tars are possible if contamination by other pollutants,
such as lubricating oil, is avoided. The "method of quinine
sulfate" can be correlated with the daily measurements of
smoke/302 being carried out in various locations. Volatile
hydrocarbon pollutants are becoming more prevalent in large cities
due to automotive emissions. The principle of the index of the
quinine sulfate method is described using fluorometric measurements
on the sample and on a reference.##
0<4219
BENZENE: TOLUENE AND XYLENE: STYRENE (METHODS FOR THE
DETECTION OF TOXIC SUBSTANCES IS AIR). Binistry of Labour,
London, England. (Booklet No. U.) 1966. 12pp.
This booklet is one of a series describing chemical methods
involving color changes to be used to give a rapid indication of
the atmospheric hazard where the primary object is not extreme
accuracy. For benzene in the presence of toluene, xylene, and
styrene, the toluene and xylene are removed by absorption in a
solution of selenous acid in sulfuric acid. The benzene
is then determined from the color produced in concentrated
sulfuric acid containing paraformaldehyde which is compared with
a range of color standards. Toluene, xylene, and ethyl benzene
up to 300 ppm and styrene up to 170 ppm do not interfere.
Toluene and xylene are determined by comparing the yellow
color produced with a sulfuric acid solution of potassium iodate
with a range of standard colors. Styrene and ethyl benzene react
like toluene and xylene. For styrene, the color with
concentrated sulfuric acid is compared with a range of standard
colors. Vinyl styrene reacts like styrene. Acetone (500 ppm)
and ethyl methyl ketone (200 ppm) reduce the color produced by
100 ppm of styrene by 2036 and 10% respectively.ft
E. P. Aigina and I. B. Bints
DETERBINATION OF LOW 3, U-BENZPYRENE CONCENTRATIONS BY BEANS
OF THE SHPOL'SKII EFFECT. (K voprosu o kolichestvennom
330
HYDROCARBONS AND AIR POLLUTION
-------
opredelenii malykh , kontsentratsii 3, 4-benzpirena s pomoshch'yu
effekta Shpol'skogo.) Hyg. Sanit. 31, (8) 264-7-, Aug. 1966.
Russ. (Tr.)
CFSTI: TT 66-51160/7-9
The use of quasilinear fluorescence spectra for the
quantitative determination of 3,4-benzpyrene is said to increase
the sensitivity by 2 or 3 orders of magnitude in comparison to the
spectrophotometric method. The known procedures suffer from
several disadvantages. The purpose of the present work was the
development of a better procedure. A new procedure was devised
for the quantitative determination of 3,4-benzpyrene without an
internal standard, by using the mercury line of wavelength 390.6
nm (3906 A) as the reference line, and the advantage of using
this line was demonstrated. The range of determinable
concentrations lies between 0.002 and 0.05 microgram/ml. The
relative standard deviation for a single analysis is 26*. A
cruder qualitative determination of 3,4-benzpyrene is also possible
for lower concentrations of this substance. The new procedure
ensures a higher sensitivity than Dikun's procedure (approximately
by one order of magnitude) and moreover is considerably simpler,
more readily available, and less labor consuming. A procedure
was devised for a quantitative determination of 1, 12-benzperylene
in the concentration range of 0.02-2 microgram/ml. The relative
standard deviation is 36%.##
04254
M. T. Tsupikov, and" A. I. Grigorenko
RAPID METHODS FOR THE DETERMINATION OF TERTIARY >ATTY ALCOHOLS,
LOWER KETONES AND XYLENES IN AIR. ((Bystrye metody opredeleniya
tretichnykh zhirnykh spirtov, nizshikh ketonov i ksilolov v
vozdukhe.)) Hyg. Sanit.' 31 (9) :418-421, Aug. 1966. Russ. (Tr.)
CFSTI: TT 66-51160/7-9
The method for determination of tertiary fatty alcohols and
lower ketones is based on adsorption of vapors of these substances
on silica gel, followed by acid-thermal condensation with vanillin
to obtain colored reaction products. The reaction consists of an
acid-thermal condensation on silica gel of vanillin as a reagent
with active methylene alkyls that are directly bound with the
C-OH group'in tertiary alcohols or with the CO group in ,
ketones. The intermediate reactions produce unsaturated hydroxy
ketones or alcohols resembling curcumins in their chemical
structure; these,substances are converted to .dyes of a complex
composition by the acid-thermal factor. The procedure is as
follows: A thin short length of rubber tubing is attached to the
syringe of the air-sampling device. The,narrow end of the tube
with silica .gel (which is open at both ends) is connected to the
air-sampling device and a measured volume of air is pumped
through. The tube is disconnected, 4 or 5 drops of the solution
of vanillin-sulfuric acid are introduced and the tube is shaken
until the silica gel is completely impregnated. The silica gel
layer is then heated in a flame. On cooling, the length of the
colored silica gel layer is measured. A blank test is perforned
in parallel, without the pumping through of air. The
concentration of substances in the measured volume of air passed
through the siliva gel is found by means of a graph, in which the
D. Measurement Methods 331
-------
length of the colored silica gel layer is marked on the x-axis
(in millimeters), while the concentrations (milligrams) are marked
on the y-axis. The concentration is converted to milligrams per
liter by means of the formula: X=a-1000/b, where X is the
concentration of the substance in question (mg/1), a is the
concentration of the substance in the volume of air passed
through the tube (mg), and b is the volume of air (ml). The
method for determination of commercial xylene is based on the
production of red-colored anils by the reaction of xylenes with
urotropinsulfuric acid on silica gel.##
04255
H. S. Bykhovskaya and P. N. Makedonskaya
DETERMINATION OF ALIPHATIC AMINES IN AIR. ((K metodike
opredeleniya alifaticheskikh aminov v vozdukhe.)) Hyg. Sanit. 31,
(9) «2.1-«25, Aug. 1966. Buss. (Tr.)
CFSTI: T 66-55160/7-9
In studies of the primary aliphatic amines, optimum conditions
were studied for their determination with ninhydrin,
potassium 1, 2-naphthoguinone-U-sulfonate and p-nitro-
phenyldiazonium. The best reproducibility was achieved in
an agueous-pyridine solution with the addition of a little
ascorbic acid. The reaction product imparts a blue-violet color
to the solution, as distinguished from the control solution which
displays a pinkish-violet color. The maximum light absorption of
the solution occurs at the wavelength of 575 OA. The
sensitivity is 1 microgram in the volume analyzed. In the
concentration range of 1 to 10 micrograms there is a linear
relationship between the optical density and the amine
concentration in solution. No interference is caused by
secondary and tertiary aliphatic amines or by aromatic amines.
Any ammonia interferes with the determination, because its
presence in the sample to the extent of 1 microgram colors the
solution an intense blue-violet. The most selective
reaction for the determination of secondary amines is based on the
formation of copper dialkyldithiocarbamate. Where an air sample
is taken in ethanol, and 0.1 ml of 15% alcohol solution of
CS2, 0.1 ml of 0.1% alcohol solution of copper acetate and 0.1
ml alcohol solution of NH3 are added to the 2-ml sample. The
addition of each reagent is followed by mixing of the solution.
After 10 min. the intensity of the colored sample is compared
against the standard scales, or else the optical density of the
solution is measured in a cell. A method for the determination
of-trimethylamine in air using a citric acid solution in acetic
anhydride wa-s developed. Reactions with citric acid and acetic
anhydride as well as those with phosphotungstic or phosphomolybdic
acids-may also be applied to studies of several tertiary amines,
no interference being caused by secondary and (other) tertiary
amines.t#
OU262
J. D. Adams, J. P. Conkle, W. E. Babson, J. T.
Watson, P. H. Wolf, and B. E. Welch
332 HYDROCARBONS AND AIR POLLUTION
-------
STUDY OF HAN DURING A 56-DAY EXPOSURE TO AN OXGEN-HELIUM
ATMOSPHERE AT 258 BH. HG TOTAL PRESSDRE. II. MAJOR AND
MINOR ATMOSPHERIC COMPONENTS. Aerospace Med. 37,(6) 556-8,
June 1966.
CFSTI: AD 6IH819, DDC
The atmosphere to which four human volunteers were exposed for
56 days during a study designed to describe the effects of oxygen-
helium on man was analyzed for major and minor constituents. The
partial pressure of the major constitutents, oxygen (175.2 plus
or minus 2.U mm. Hg) and helium (73.9 plus or minus 2.3 mm. Hg),
remained within the established experimental parameters.
Sixty-eitht minor constituents were detected. The concentration
of these compounds remained below a level thought to cause a
physiologic effect. The instrumental methods employed" were
sufficient for a comprehensive anaylsis of the synthetic
atmosphere. (Author abstract)##
0«318
A. J. Hocker, W. 0. Yates, P. M. May, and M. P.
Sweeney
CERTIFICATION OF AUTOMOTIVE EXHAUST EMISSION LABORATORIES BY CROSS
CHECKS OF THE ANALYTICAL INSTRUMENTS, Instr. SOC. Am.,
Conf. Preprint. 1965.
Implementation of the California law on auto exhaust emissions
required the active participation of laboratory facilities of the
industry in determining emission levels of their products. The
law authorizes the certification of laboratories. This paper
discusses the methods used by the State of California at its
official laboratory in testing automotive exhaust emissions and the
technigues employed and results cf typical cross check
pre-certification tests which were conducted to insure that the
California motorist will receive 1966 model automobiles that
comply with the legal standards. As a result of such work,
fourteen private industrial laboratories have been so certified.
These companies include six American automobile manufacturers.
Similarly equipped and instrumented laboratories in various
locations can duplicate the results obtained by another facility:
Similar instruments if exposed to the same concentration of
contaminants will yield the same results. The technical
community has demonstrated the ability to evaluate exhaust
emissions in different test laboratories with the same results.lt
0«328
E. Sawicki, M. Guyer, and C. R. Engel
PAPER AND THIN-LAYER ELECTROPHOEETIC SEPARATIONS OF POLYNUCLEAH
AZA HETEHOCYCLIC COMPOUNDS. Preprint. 1967.
A large number of polynuclear aza heterocyclic compounds have
been separated by paper and thin-layer electrophoresis. The
pherograms were scanned fluorinetrically. Many of the separated
D. Measurement Methods 333
-------
compounds were capable of being characterized and assayed by the
scanning procedure. Analysis by fluorimetric scanning of the
pherograms was much more selective when the appropriate excitation
and emission wavelengths were used. Samples of urban airborne
particulate can be separated and analyzed with the help of paper
or thin-layer electrophoresis. (Author abstract)i#
OU329
T. W. Stanley, H, J. Morgan, and J. E. Meeker
THIN-LAYER CHEOKATOGBAPHIC SEPARATION AND SPECTROPHOTOMETEIC
DETERMINATION OF BENZO(A)PYRENE IN ORGANIC EXTRACTS OF
AIR-BORNE PARTICIPATES. Preprint. 1967.
A modification of a recently reported procedure by Sawicki, et
al, for thin-layer separation and spectrophotometric determination
of benzo(a) pyrene is reported. Modified procedures are
discussed and compared with other methods, and the data obtained by
different technicians are reported. Procedures involved the
spotting of a 0.5-to-5-mg aliguot of a dichloromethane solution
of organic residue of air participates from the bottom of a
thin-layer plate. A 2-microgram aliguot of a dichloromethane .
solution of pure benzo (a)pyrene was added to the same plate.
Plates were placed in a .development chamber and the solvent was
allowed to travel 15 cm from the origin. The developed
chromatogram was observed under a 3600 A light source and the
fluorescent area of.the pure,standard and corresponding area of the
sample were scored with a stylus. The amount., of benzo (a) pyrene
in the sample was determined at 375,382 and 390 micrograms on a
Beckman'DU spectrophotometer. The thin-layer chromatograms
exhibited 1U distinctively different.fluorescent bands similar
in spectral characteristics to class-fractions emergent fron an
alumina column separation. Advantages included: (1) the
separation of crude organic extracts required less than 1 hour,
and the speed of separation did not,affect resolution; (2)
benzo (ghi) perylene, which absorbs at 382 millimicron and would
constitute a major interference, was contained in a narrow yellow
fluorescent band well separated from the benzo (a)pyrene fraction;
(3) benzo(k)fluoranthene and several unknown compounds were found
in a blue fluorescent band separating the benzo(a)pyrene and
"benzo (ghi)perylene fractions; (U) samples ranging from 0.5 to 5
milligrams could be resolved on a 250-micron film of the absorbent
with no observed changes in the chrcmatogram; (5) variations in
Hf values above 0.5 did not prevent determination of the '
benzo(a)pyrene present in the sample; (6) over-activated plates
that gave poor separations could be returned to normal in several
hours by storage in a vacuum desiccator adjusted to t5% RH with
freshly prepared agueous H2SOU. The more experienced
technician analyzed samples ranging from 0.31 to 3.26 mg; when all
results were used the mean benzo (a)pyrene concentration per gram
extract was 516 microgram and the relative standard deviation was
plus or minus 7%. The investigation-showed also that
benzo (e)pyrene could be determined in the same fractions eluted
for the determination of benzo (a)pyrene.*#i >
334 HYDROCARBONS AND AIR POLLUTION
-------
01U40
E. I. Smith, Jr., and H. E. Moran, Jr.
PORTABLE DETECTOR FOR MIXED HYDRAZINES PROPEILANT JOEL VAPORS
AT LOW CONCENTRATION. Naval Research Lab., Washington,
D.C., Engineering Research Branch. (NHL Memorandum Rept.
1602.) Apr. 1965. 15 pp.
DDC, AD 614821
Paradimethylaminobenzaldehyde (DMABA) was examined as a color
forming agent for the colorimetric determination of mixed
hydrazines propellant fuel vapor in air. Contaminated air was
drawn through a filter paper disc which had been moistened with
DMABA solution. The reaction between the fuel vapor and
the indicator until the yellow color matched an arbitrarily
selected standard yellow color. The volume of air required to
produce the standard color was related to the concentration of
fuel vapor in the air over the range of 0.5 to 10 ppm.
Several gases which might be found in the air at least
occasionally were examined for interference with the
fuel vapor test. Ammonia at 50 ppm did not interfere, but higher
concentrations either decreased the indicator sensitivity or
completely inhibited color formation. Sulfur dioxide at 500 ppm
did not interfere with the test; higher concentrations did
interfere. Carbon dioxide at concentrations up to 50,000 ppm (5X)
did not affect the test. Chlorine at 2 and 5 ppm reduced the
sensitivity of the test indicator. Fifty ppm and higher
concentrations of chlorine formed brown or green colors with the
indicator, thus interfering with the fuel vapor test. (Author
abstract) tf
04484
S. P. Zhdanov, A. V. Kiselev, Ya. I. Yashin
OSE OF COARSE POROUS GLASS IN GAS-ADSORPTION CHROHATOGRAPHY FOR
THE SEPARATION OF LIQUID HYDROCARBONS. Neftekhimiya
(Fussia) 3, (3) 417-24, 1963. Russ. (Tr.)
DDC, AD 630970
The possibility of using coarse prous glass for the separation
of normal alkanes and aromatic hydrocarbons with boiling
temperatures up to 150 degrees by the method of gas-adsorption
chromatography was investigated. The dependence of the
effectiveness of the coarse prous glass column on the linear
speed of the gas-carrier indicated the possible use of such
columns at great linear speeds. From the chromatograns taken
at various temperatures, the adsorption heats of a series of
hydrocarbons on the hydroxylated surface of silicon were
determined. The adsorption heats of normal alkanes and
normal alkyl benzenes increase linearly with the increase in
the number of carbon atoms in the molecule. The adsorption heat
of ethylene is greater than that of benzene, and that of alkyl
benzene is greater than that of the corresponding n-alkanes because
of the specific interaction, primarily of the electron bonds
with the hydroxyl groups of the surface. The values determined
from the chromatograms of heat adsorption were close to those
obtained calorimetrically.#t
Measurement Methods 335
-------
01*541
M. Feldstein and S. Balestrieri
THE DETECTION AND ESTIMATION OF PART PER BILLION CONCENTRATIONS
OF HYDROCARBONS. J. Air Pollution Control Assoc. 15, (K)
177-8, Apr. 1965.
The addition of a freeze-out step in liquid nitrogen prior to
analysis by gas chromatography with flame ionization detection
permits the accurate determination of C2 and higher hydrocarbons
in the part per billion (ppb) range. The procedure involves
passage of an accurately measured volume of approximately one
liter of gas sample through a freeze-out trap immersed in liquid
nitrogen. After flushing with a measured volume of He to
remove trapped N2 and 02, the hydrocarbons are flushed into the
gas chromatograph analytical column by immersing the trap in a
beaker of hot water. Concentrations of C2 and higher
hydrocarbons have been measured in commercial cylinders of N2,
He and H2. Using a 150 ml sample of gas, recovery of ppb
concentrations is 95 to 100%. (Author abstract modified)##
04547
A. Turk, J. I. Morrow, B. E. Kaplan
OLEFIN ISOMEBIZATION IN ADSORPTIVE SAMPLING ON ACTIVATED CARBON,
Anal. Chem. 34, (4) 561-U, Apr. 1962. (Presented before the
Division of Hater and Waste Chemistry, 140th Meeting,
American Chemical Society, Chicago, 111., Sept. 1961.)
To assess the validity of adsorptive sampling of atmospheres
for gases and vapors, it is necessary to determine the degree to
which the sample is altered prior to analysis. 2n sampling
atmospheres for olefinic vapors, the known proclivity of some
structures to undergo double bond or skeletal rearrangement
and the importance of the molecular location of the double bond
in determining the degree to which the olefin may act as a smog
precursor, make the study of isomerization important.
In this investigation, bimethallyl, biallyl, and 1-hexene were
selected for study of olefin isomerization in adsorption and
desorptive with activated carbon. Bimethallyl, which is
particularly labile to isomerization to conjugated dienes,
produces 5 to A 5% rearranged products. Biallyl, which is
generally more resistant to change, yields 1 to 2% rearrangement.
The mono-olefin, 1-hexene, gives no detectable change. It is
concluded that most gasoline-range hydrocarbons can be sampled on
carbon and recovered for analysis without serious double bond
migration or skeletal rearrangement. New designs for
desorption apparatus are described. (Author abstract)##
336 HYDROCARBONS AND AIR POLLUTION
-------
04596
R. Smith
PROGRAM DEVELOPMENT THROUGH APPLYING MEASUREMENTS AND
MONITORING KNOW-HOW. Proc. Natl. Conf. Air Pollution,
Washington, D.C., 1962. pp. 233-45. 1963.
Author directs our attention to the problem of appropriate air
quality. Many large communities are able to deal with the direct
nuisance problem in which there is a specific individual source of
pollution and some rather direct social or economic effects on
adjacent inhabited areas. While such programs eliminate many
source of complaint, they seldom provide a community with an
overall air quality of a desirable nature. Although this problem
is complex and knowledge is imperfect, author discusses simple
guidelines through which reasonable long-range objectives can be
delineated. Such objectives are capable of periodic evaluation
as knowledge and techniques improve.#t
04631
J. Tighe, R. B. Engdahl, and E- J. Center
DIRECT INFRARED SPECTRAL ANALYSIS OF CONTAMINANTS IN THE
ATMOSPHERE (A PRELIMINARY STUDY). Preprint. 1953.
A preliminary study of the application of infrared spectral
analysis to the direct examination of the atmosphere for
contaminants has been made. A Beckman IR-2 infrared
spectrometer and auxiliary equipment have been assembled and
infrared-absorption spectra obtained for compounds in the air in
the concentration range of 0.2 to 25 ppm (vol/vol). This range
is of interest in air—pollution work. Improvement of the
equipment should lower the minimum detectable concentration by a
factor of at least five. The work indicates that a commercial
infrared spectrometer, together with simple and inexpensive
auxiliary equipment, may be made mobile to permit direct spectral
atmospheric analyses in the field.##
04635
W. F. Serat, F. E. Budinger, and P. K. Mueller
TOXICITY EVALUATION OF AIE POLLUTANTS BY.USE OF LUMINESCENT
BACTERIA. Atmos. Environ. (London) 1, (1) 21-32, Jan.
1967. (Presented at the Seventh Confreence of Methods in Air
Pollution Studies, Los Angeles, Calif., Jan. 25-26, 1965.)
Cells of a species of luminescent bacteria were treated with d
gas stream containing products formed by the photochemical
oxidation of cis-2-butene and NO. Luminescence and viability
decreased with the time of irradiation of reactants. The rate of
luminescence decrease was dependent on the ratio of the initial
concentrations of cis-2-butene and NO with a ratio of giving the
most rapid loss. Known photochemical oxidation products, ozone.
D. Measurement Methods 337
-------
N02, formaldehyde, acetaldehyde, and PAN were examined
individually. Aldehydes did not appear to contribute to the
decrease in luminescence but ozone and PAN did. Although N02
alone up to 0.5 ppm produced no decrease, it may contribute to the
luminescence loss in the total irradiation mixture. The total
oxidant concentration produced upon irradiation gave luminescence
decreases which were matched by comparable concentrations of pure
ozone. However, this does not imply that luminescence losses
caused by photochemical oxidants are due only to ozone. A
possible mechanism of the toxic effect and the interpretation of
this bioassay in relation to other organisms are briefly discussed.
(Author abstract)##
04648
Y. Matsumura
THE ADSORPTION PROPERTIES OF ACTIVE CARBON. II. PRELIMINARY
STODY ON ADSORPTION OF VARIOUS ORGANIC VAPORS ON ACTIVE CARBON BY
GAS CHROHATOGRAPHY. Ind. Health (Japan) 3, 121-5, Dec.
1965.
Gas chromatography was used to observe the retention times of
thirteen organic vapors on active carbon. The compounds were
n-alcohols of Cu-C4, n-paraffins of C5-C6, acetone, methyl
ethyl ketone, diethyl ketone, ethyl acetate, cyclohexane, benzene,
and carbon tetrachloride. The active carbon was a commercial
activated wood charcoal produced for gas mask canisters. The
retention times of the organic vapors depended upon the temperature
of the column in accordance with Arrhenius1 equation in the range
of 60-250 C. In the homologous series of n-alcohols and ketones,
the logarithmic retention times were in linear relation with their
boiling points respectively at each temperature of 150, 200, and
250 C. Retention time of each compound was extrapolated to 60
C. by Arrhenius1 relation to obtain their relative retention
times to compare with that of carbon tetrachloride at that
temperature. (Author summary modified)##
04667
H. K. Sharma, D. R. McLean, J. Bardwell
AN APPARATUS FOR THE ANALYSIS OF COMBUSTION PRODUCTS OBTAINED
DURING THE OXIDATION OF HYDROCARBONS. Indian J. Technol.
(India) 3, (7) 206-8, July 1965.
A gas chromatographic apparatus with several improved features,
permitting the analysis of conplex mixtures of combustion products
obtained during the oxidation of hydrocarbons is described. The
improved features are (1) a sampling device that avoids the use of
stopcock grease and permits operation at elevated temperatures
and pressures; (2) six-way valves that facilitate sample injection;
and (3) a dual-column gas chromatograph permitting separation
of compounds with widely varying boiling points. The products
obtained by the low temperature (284 C.) oxidation of propane and
butane have been analysed using this apparatus. Although the
338 HYDROCARBONS AND AlR POLLUTION
-------
gas chromatographic method is particularly appropriate for most
types of combustion products, it is less satisfactory for certain
highly reactive products, namely hydrogen peroxide,
formaldehyde and organic acids. The presence of formaldehyde
in the combustion gases has a detrimental effect on the gas
chromatographic analysis for certain other compounds, notably
methanol. (Author abstract modified)##
0«716
S. L. Sachdev, J. W. Robinson, and P. W. West
EFFECT OF MIXED ORGANIC SOLVENTS ON ATOMIC ABSORPTION
SPECTROPHOTOMETRY OF HEFRACTORY METALS. Anal. Chio. Acta
37, 156-63, 1967.
The effect of various organic solvents on the absorption signal of
vanadium in fuel—rich oxy-acetylene flames and nitrous
oxide-acetylene flames was investigated. The absorption of the
3183.9 A line of V was greatly enhanced by the use of various
mixed organic solvents when fed to oxy-acetylene flames. In
general, the solvents' effect was in the following order:
Propanol-2 greater than ethanol which was greater than methanol.
Results showed that absorption was maximum in highly reducing
flames and increased as the concentration of organic solvent
increased. Maximum absorption was observed when the solution
contained more than 70% of the respective solvents. In the case
of nitrous oxide-acetylene flame, the addition of diethylene glycol
(about 8% in the final solution), and similar compounds, to the
aqueous solution of V increased the absorption by about 50%.*f
047U2
H. Sakamoto and T. Kozima
RELIABILITY OF MEASUREMENT OF EVAPORATED BENZENE HOMOLOGOE
CONCENTRATIONS HITH THE BENZENE-DETECTION TDBE. Japan J.
Ind. Health (Tokyo) 3, (8) 419-21, Aug. 1961. Jap,
A study was made of the reliability of measurement with the
benzene detection tube, widely used to measure the amount of
benzene and its homologues in the air of workshops. The richer
the benzene concentration in the air, the larger the probable error
of the mean of obtained values, whereas the coefficient of
variation of obtained values is at a minimum when a benzene
detection tube is used. The same results were obtained in cases
of toluene and its mixture with benzene in the air of workshops.
Ihen the benzene-like mist in the workshop air which evaporated
from sprayed paint was examined, the values obtained with the
benzene-detection tubes showed half of the values obtained by the
sulfuric acid-formalin method. (Author summary modified)ft
D. Measurement Methods 339
-------
01772
M. Alperstein and R. L. Bradow
COMBUSTION GAS SAHPLING VALVE. Hev. Sci. Instr, 36, (7)
1028-31, July 1965.
A valve suitable for extracting a sample of high temperature,
high pressure gases and introducing this sample into a low
pressure regime has been developed and successfully operated for
two years. Slow combustion reaction studies in a normally-fired
spark-ignition engine are being accomplished with the aid of this
gas sampling valve located in the combustion chamber end-gas region
The valve exhibits excellent sealing, achieves choked flow
conditions, and permits sampling times on the order of 1 msec.
The construction, operation, and monitoring of this gas sampling
valve are described. (Author abstract)##
OU796
J. E. Sigsby, Jr., L. J. Lage, T. Bellar, and H. L.
Eisele
CHEHICAL METHODOLOGY IN AUTO EXHAOST STUDIES. Preprint.
(Presented at the 54th Annual Meeting, Air Pollution Control
Association, New York City, June 11-15, 1961.)
A major auto exhaust research project reguires extensive chemical
analytical support. Such compounds as NO, N02, acrolein, and
the individual hydrocarbons and such classes of compounds as
olefins and oxidants are determined routinely. Sampling
schedules and conditions are important in the over-all program.
This paper describes the specific analyses and the general
laboratory program that provide the greatest amount of
significant chemical information. The procedures discussed
include 18 spectroscopy, wet chemical analysis and gas
chromatography. Wet chemical analyses are made for N02, NO,
four-carbon and higher olefins, acrolein, and formaldehyde. All
samples for wet chemical analysis are taken with bubblers. A
Beckman Spectrophotometer, Model DU, is used to determine
absorbance. For hydrocarbon analysis the gas chromatograph used
is a modified three-stage instrument. The first and second stages
are operated in series, using thermal conductivity detectors and
helium carrier gas. The third stage operates separately with a
flame ionization detector and a silica gel column to determine the
higher hydrocarbons. The first two stages are used in
conjunction with a double trapping system to determine four-carbon
and higher materials. -The utilization of this array of testing
methods and equipment requires careful planning, if each experiaent
is to yield maximum information. On one occasion 50 samples were
analyzed in a 4-hour period; this is more than one sample every
five minutes, and is typical of the quantity of data that »ay be
obtained if necessary. Normally, the reproducibility of the
chemical results is better than 10%.#*
340 HYDROCARBONS AND AIR POLLUTION
-------
04825
H. Halanchuk
CONTINOODS AUTOMATIC DETERMINATION OF SULFUB DIOXIDE IN THE
PRESENCE OF AUTO ENGINE EXHAUST. Am. Ind. Hyg. Assoc. J.
28, 76-82, Feb. 1967.
An instrument normally used for measuring nitrogen oxides was
found suitable for the continuous automatic monitoring of sulfur
dioxide under conditions that exist in animal exposure chambers.
This was accomplished by substituting a ferric-phenanthroline
solution for the Saltzman reagent that is required for nitrogen
oxides in such an instrument. The arrangement has the,advantage
of being specific for S02 determination under conditions
similar to those mentioned above. The conductimetric-detector
instrument employing water for the absorption medium has severe
limitations in accurately determining 302 in the complex
engine exhaust composite. The conductimetric instrument using
hydrogen peroxide has fewer limitations. Typical of colorimetric
methods involving an absorption step and a color-developing
period, this instrument has a 20- to 30- minute delay in response.
Modification of the equipment to suit the analytical method
should result in'faster response, greater sensitivity, and
wider range. For example, thermostating the absorption section
for operation at a higher temperature, such as the 50 C would
yield greater sensitivity. A lesser coil and sample cell
volume would produce a faster response.*#
04839
R. K. Stevens and R. E. Painton
APPLICATION OF A HOT WIRE IONIZATIOS DETECTOR TO AUTOMOTIVE
EXHAUST GAS ANALYSIS. Micro Tek Instruments Corp., Baton
Rouge, La. Mar 17, 1967. 26 pp.
The objective was to investigate the application of a catalytic
combustion ionization detector to the determination of
hydrocarbons in automotive exhaust. The catalytic element is a
coiled platinum hot wire of the general type used in conventional
catalytic combustion detector cells in which thermal effects are
measured. In the present device the effect measured is the ion
current resulting from charged radicals formed during the process
of catalytic combustion. A major feature of this technique for
auto exhaust gas analysis is its complete selectivity to C2+
hydrocarbons in the presence of CO, H2, CHU, C02, air and
H20. The effect of operating parameters on selectivity to
different types of hydrocarbons was examined, results are
compared to those obtained with the Flame Ionization Detector,
and typical results on actual auto exhaust'samples are reported.
The CCID (Catalytic Combustion Ionization Detector) can be
a critical component in a composite "black box" analyzer to be used
for field surveillance of automobile exhaust with regard to
emission of hydrocarbons and carbon monoxide. (Author summary
modified)##
!D. Measurement Methods 341
-------
04857
G. Dimitriades
DETERMINATION OF NITROGEN OXIDES IN AUTO EXHAUST. J. Air
Pollution Control Assoc. 17, (U) 238-43, Apr. 1967.
A new procedure for determining nitrogen oxides in automobile
exhaust has been developed. The new procedure was included in a
Bureau of Mines comparative study that aimed at evaluating
various widely used methods for determing NOx in auto exhaust.
The methods included in the evaluation study follow: (1) Static
oxidation in tank (ST method). The method involves oxidation
of NO in residence with 02 in a stainless steel tank. (2)
Bureau of Mines method (BM method). The method involves
application of the ST procedure in exhaust samples from which
the gydrocarbons have been revoced by combustion over catalyst.
(3) Chevron Research method (CE method), as described in the
literature. (4) Phenoldisulfonic acid method (PDS method), as
described in the literature. The principal objective of this
study was to generate experiemental evidence which would lead to
defining an optimum procedure for converting NO, present in
exhaust gas, into N02; this conversion is desired so that the
total of NO + N02 can be determined quantitatively in the form
of N02. In pursuing this objective, the procedures prescribed
by the foregoing methods were comparatively tested. The results
indicated that all four methods are subject to error, the extent
of which depends on the conditions employed. The-BH method was
superior from the standpoint of accuracy because it was less
affected by interferences due to hydrocarbon-N02 reactions.
(Author abstract)*#
04880
B. C. Newbury
THE USE OF THE CORRELATION SPECTROMETER IN THE STUDY AND CONTROL
OF AIR POLLUTION. Preprint. (Presented at the Air'and-Water
Pollution Conference, Sacramento, Calif., Feb. 2-3, 1967.)
The Barringer Correlation Spectrometer is a highly specific
instrument offering great advantages in pollutant monitoring: (1)
It is a physical measurement and does not require frequent renewal
of reagent solutions; (2) It can operate through a wide range of
temperature: it does not require constant temperature enclosures,
or even protection from freezing: (3) It requires no pumps or
valves. The passive model requires power.only for the 4
electronics and remote operation using solar cells if possible;
and (4) The basic instrument is suitable for a large number of
compounds, reducing drastically, the spare parts and expertise
required, in comparison with the usual range of unrelated.
instruments. The Barringer Tape Sampler is a modular sampler
of improved design and with a very flexible timing control unit.
The sequential sampler module will be additive for extended
sampling schedules.f#
342 HYDROCARBONS AND AIR POLLUTION
-------
04881
A. E. Barringer
NEW INSTRUMENTATION AND TECHNIQUES FOE POLLUTION MONITORING.
Preprint. (Presented at the Air and Water Pollution
Conference, Sacramento, Calif., Feb. 2-3, 1967.)
Correlation spectrometers utilize an internal memory of the
spectrum which it is desired to detect. Real time correlation is
carried out against the spectrum of the incoming radiation. The
first of these devices uses a conventional grating spectrometer.
A photographic replica of the spectrum of the gas being detected
is installed in the position normally occupied by the slit of a
dispersive spectrometer. A spectrometer is used to make the
replica mask, by exposure through a cell of the gas, matching
exactly the dispersion and aberration characteristics of the
spectrometer. The unknown spectra of the incident light is caused
to vibrate across the correlation mask, by using a refractor plate
oscillating in a rotary fashion to displace the entrance slit
image from side to side. Phase locked detection of the output of
the photo-multiplier is carried out in synchronism with the
oscillations of the refractor plate. Integration of the
synchronous detection can be made over a period varying from a
fraction of a second to several seconds. A telescope may be
incorporated in the instrument. Alternative means may be employed
for oscillating the slit image such as a high stability tuning fork
and dual refractor plate assembly. An instrument of this type has
been programed for sulfur dioxide detection. It is capable of
detecting concentrations as low as ten parts per billion over a
one hundred meter pathlength. It is highly specific for sulfur
dioxide having an excellent immunity ot interferences. Operation
is in the ultraviolet region between 2,900 and 3,150 Angstroms
where there is sufficient solar spectral radiant flux penetrating
the atmosphere to enable the eguipment to function passively
using natural daylight. An automatic gain control
system operates on the average DC value of the photomultiplier
output. The AC signal under these conditions is directly
proportional to the percentage modulation caused by sulfur
dioxide.ft
04895
R. N. Thompson, C. A. Nau, and C. H. Lawrence
IDENTIFICATION OF VEHICLE TIRE EUBBER IN ROADWAY DOST. Am.
Ind. Hyg. Assoc. J. 27, (6) 488-95, Dec. 1966.
A technique combining pyrolysis and chromatography for the
detection of vehicle tire abrasion products in roadway dust is
described. Samples of elastomers used in tire formulations were
volatilized and separated by gas-liquid chromatography to provide
characteristic chromatograms. These identifying patterns appeared
consistently in the chromatpgraphic separations of the pyrolyzates
of compounded tire rubber and various roadway dusts. To confirm
the technique, two chromatographic procedures were used for the
identification of specific components of the thermal degradation
products of raw elastomers, compounded rubbers, and roadway dusts.
(Author abstract) ##
D. Measurement Methods 343
-------
01930
Mauser, T. R.
THE DETEHMINATION OF POLYNOCLEAR AROMATIC HYDBOCARBONS IK 4IB
PARTICULATE MATTER. Preprint. ((Public Health Service,
Cincinnati, Ohio, Div. of Air Pollution,)) ((19))p., 1965. 12
refs.
The determination of the polynuclear aromatic hydrocarbon content
of air particulate matter is described. Air particulate samples
are collected on glass fiber filters using a high volume air
sampler. The samples are then extracted with benzene in a
Soxhlet extractor to obtain a benzene soluble fraction of air
particulate matter which is normally referred to as the "organic
fraction." This organic fraction is then further separated into
approximately 30 to 40 sub-fractions by means of column
chromatography of alumina using increasing amounts of diethyl ether
in pentane as the eluent. Each of the sub-fractions is dried,
dissolved in pentane, and spectrophotometrically analyzed for
polynuclear aromatic hydrocarbon content. The polynuclear
aromatic hydrocarbons that can be effectively separated and
analyzed by this technique if they are present in a particular air
sample are anthracene, phenanthrene, fluoranthene, pyrene,
benz (a)anthracene, chrysene, benzo (a)pyrene, benzo(e)pyrene,
perylene, benzo (g,h,i)perylene, anthanthrene, and coronene.
Reference is made to review articles which discuss other
techniques for the analysis of polynuclear aromatic hydrocarbons,
particularly in urban air and from coal tar pitch.t#
OH931
R. J. Charlson, H. Horvath, and R. F. Pueschel
THE DIRECT MEASUREMENT OF ATMOSPHERIC LIGHT SCATTERING COEFFICIENT
FOB STUDIES OF VISIBILITY AND AIR POLLUTION. Atmospheric
Environ. 1 («) , U69-78 (July 1967)
The integrating nephelometer of Beuttel and Brewer has been
modified for studies of air pollution. The instrument, which is
'simple, stable, and inexpensive to construct, has been operated
continuously for several months. Interpretation of the data is
simplified by use of a theoretical approach which indicates that
the measured light scattering coefficient is proportional to the
mass of suspended particulates for well-aged atmospheric
aerosols. (Author abstract)ft
OK960
S. W. NicKsic and R. E. Rostenbach
INSTRUMENTATION FOR OLEFIN ANALYSIS AT AMBIENT CONCENTRATIONS.
J. Air Pollution Control Assoc. 11, (9) i|17-20, Sept. 1961.
(Presented at the 5Hth Annual Meeting, Air Pollution Control
Association, New Yrolc City, June 11-15, 1961.)
344 HYDROCARBONS AND AIR POLLUTION
-------
This paper describes a brominaticn and cculometric system and the
instruments developed to measure olefins in automobile exhaust
and in the atmosphere. The concentration of olefins in automobile
exhaust considered here is over 100 ppm while that in the
atmosphere is usually less than 1 ppm. The method is based on the
observation that the olefins, excluding ethylene, can be
quantitatively brominated by passing a gas sample through a
solution of appropriate composition. The method is based also on
the principles of coulometric titration. The system differs from
the conventional coulometric practice in the bromination is
carried out before coulometry. The excess of bromine to do this
is about 0.00002 moles per liter. In this system, the gas
sample is passed through the sensing solution and the time is
measured to generate the bromine absorbed by the sample. The two
Olefin Analysers developed - one for atmospheric use and one for
auto exhaust analysis are self-contained portable instruments for
automatic, continuous olefin analysis of a gas sample or stream.
These were designed for operation with a recorder modified
slightly for this purpose.##
0«973
P. L. Bagill
TECHNIQUES EMPLOYED IN THE ANALYSIS OF LOS ANGELES SBOG. ProC.
Natl. Air Pollution Symp., 1st, Pasadena, Calif., 1949.
pp. 61-8.
An analysis of smog was undertaken with the major objectives being
the determination of the materials responsible for the reduction of
visibility and those responsible for eye irritation. The
instruments and methods used for collecting particulate and gaseous
matter from the atmosphere are described. A new method for
semi-quantitative analysis of samples by proton bombardment is
explained. A tabular summary of the components of Los Angeles
smog is provided. The effects of particulate matter on visibility
are described and a simulation experiment is mentioned which shows
eye irritation to be the result of the synergistic effect of
several substances.##
050«2
J. E. Johnson, Chiantella, A. J., W. D. Smith, and H.
E. Umstead
NUCLEAR SUBMARINE ATHOSPHERES. PART 3. ABOMATIC HYDROCARBON
CONTENT. Naval Research Lab., Washington, D. C.,
Chemistry Div. (NHL Rept. 6131.) Aug. 2H, 1964. 32 pp.
A detailed analytical study has been directed to the
identification and determination bf the amounts of aromatic
hydrocarbons present in nuclear submarine atmospheres. Many
individua,! aromatic hydrocarbons have been identified and their
occurrence in a number of nuclear submarines has been established.
The hydrocarbon oil samples were desorbed from activated carbon
which had been exposed in nuclear submarine atmospheres. The
0. Measurement Methods 345
-------
aromatic hydrocarbon content of these oils was found to be
approximately 25 to 30 percent of the total. The quantitative
distribution of individual aromatic hydrocarbons was very similar
from submarine to submarine with this distribution strikingly
similar to that of typical petroleum distillates in the same
boiling range. (Author abstract)##
05056L
50561
R. A. Stuart
APPLICATION OF GAS-LIQUID CHROHATOGEAPHY FOE DETERMINATION OF
TRACE HYDROCARBONS IN AIR AND COMPRESSED BREATHING GASES.
Naval Research Establishment, Dartmouth, Nova Scotia,
Canada, Defense Research Board. Bar. 1963. 10 pp.
(NRE Rept. No. 63/3.)
A method for gas-liquid partition chromatographic analysis of the
hydrocarbons commonly found in petroleum vapors is described. The
relative retention times of some hydrocarbons are listed and
preliminary evidence of their distribution in gasoline vapors is
given. Modifications which allow the use of conventional gas
chromatographic apparatus for the detection of these hydrocarbons
at or below 1 p.p.m., and the technique as it can be applied to the
determination of such contaminants in compressed breathing gases
are discussed. (Author abstract)f#
0508«
K. Rothwell,* and J. K. Hhitehead
COMPLEX FORMATION, ISOLATION, AND CARCINOGENICITY OF POLYCYCLIC
AROMATIC HYDROCARBONS. Nature 213, (5078)' 797, Feb. 1967.
Methods for the isolation of polycyclic aromatic hydrocarbons
which are based on partition, adsorption or complex formation used
singly or in combination, are reviewed. A new electrophoretic
method and its possible relationship to carcinogenic activity is
considered. Using curtain paper electrophoresis with platinum
electrodes in troughs at the top and bottom of the paper,
complexes of polycyclic aromatic hydrocarbons with both caffeine
and 1:3:7:9-Tetramethryiuric acid (TMU) have been found to
migrate readily. Complexes were formed before spotting on the
paper; the solvent was a solution of 2 g purine in 90 ml. water-10
ml. ethanol-2 ml. ammonia and the potential and>current,were
30-35 V/cm and 3-1 m.amp/cm. The ,twenty-f iveicomplexes of
polycyclic aromatic hydrocarbons examined all migrated as
discrete spots which completely left the baseline. Using the
same method, it was later shown that these^polycyclic aromatic
hydrocarbons could be separated.from twelve times their own
volume of 'Vaseline1. In large, scale applications of,the:.method,
as much as 1 g,of,hydrocarbon mixtures containing polycyclic
aromatic hydrocarbons has been adsorbed on 80-100 g silica and
the residue packed into a column 38 mm in diameter. By. applying a
potential of 1,200-1,500 V to the coluan and slowly elating with
346 HYDROCARBONS AND AIR POLLUTION
-------
The solvent already mentioned, almost all the species which could
be detebted by electron capture during gas-liquid
chromatography have been separated from the bulk of the mixture
"hich remained on the column. Furthermore, in experiments in
which radioactively labelled polycyclic aromatic hydrocarbons were
incorporated in the hydrocarbon mixture, 97-98 per cent of the
labelled polycyclic aromatic hydrocarbons were isolated. The
exact experimental details of the method, which is now being used
«ith most encouraging results to examine the condensate of
cigarette smoke, are to be published subsequently.##
05092
H. G. Zigler, and W. F. Phillips
A THIN-LAYER CHROHATOGRAPHY METHOD FOR ESTIMATION OF
cHLOROPHENOLS. Environ. Sci. Technol. 1, (1) 65-7, Jan. 1967.
A highly sensitive, rapid, and selective thin-layer
chromatographic method is used for the determination of
m-chlorophenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol,
2,4,6-trichlorophenol and pentachlorophenol in a raw and treated
water. The two-directional thin-layer chromatographic technique
employs two supplementary reagents, aminoantipyrine and silver
nitrate, both of which provide independent sensitivities of less
than 1 p.p.b. The technique has been applied to surface waters
before and after treatment and should be useful to investigators
studying the effects of water treatments. Concentrations of 0.1
microgram per liter or more can be determined using 1-liter samples
and the silver nitrate reagent. Confirmation of 0.5 microgram
per liter or more can be readily achieved with the
U—aminoantipyrine reagent, again using 1 liter as the sample size.
The use of two separate chromogenic reagents, one of which
responds to phenols and the other to the halogen, in conjunction
with thin-layer chromatography, provides a very high degree of
specificity. The method is rapid, offers good recovery and
reproducibility, and has been found satisfactory for all samples of
waters encountered.ft
05135
J. E- Sigsby, Jr.
DISCUSSION ON GAS CHROMATOGHAPHY - MEASURING EXHAUST HYDROCARBONS
DOWN TO PARTS PER BILLION BY L. J. PAPA. Preprint. (Presented
at the Bid-Year Meeting, Society for Automotive Engineers,
Chicago, 111., May 18, 1967.)
A critical discussion of the subject paper is presented. The
subtractive technique, when applied to simple instrumentation,
may yield considerable information on internal composition
without producing vast masses of data. Schemes for the detailed
analysis of gas chromatograph data usually involve summing either
by compound type or by a reactivity scheme, which partially
negates the value of the detailed analysis. The system described
for the total gas chromatographic analysis of automotive exhaust
appears to be one of the most workable systems so far presented.
D. Measurement Methods 347
-------
It results in a single data output which might lead to significant
dollar savings in data reduction. The use of plastics at any
point, in any sampling procedure, should be evaluated. It is not
desirable to use polyethylene or saran for calibration, daily
standards, or any other application in which
higher-molecular-weight hydrocarbons may be involved. A column
of mixture Porapak Q and F separates most of the hydrocarbons,
but does not afford a separation of propane and propylene. The
use of silica gel for such a column, with or without support
modification, might well afford a complete separation.
Information on any technique, ether than an initial ice trap, for
removing the water would be appreciated. Host techniques
interfere with detailed analysis by removing many specific
hydrocarbons. Differences have been noticed between static and
dynamic sampling systems. If one samples dynamically through a
system that is maintained at reasonably constant flow, equilibrium
is reached rather quickly and there is no apparent increase in
response with increased flow time. The only apparent necessity
is to allow for complete flushing of all sample lines, for
approximately 10 times the volume. Valve leakage may be
corrected by lapping both the rotor and the base of two surface
valves carefully. Only valves of Teflon and stainless steel
should be used. Changes in composition of exhaust have been found
in various classes of hydrocarbons. These differences are
quantitative rather than gualitative. The overall gas
chromatographic pattern of the fuel closely resembles that of
the exhaust. Quantitatively, however, variations as large as
20 or 30 per cent from predicted concentrations may occur.##
05136
Sawicki, E. and R. A. Carnes
FLOORIMETRIC ASSAY FOR ALPHA-GLYCOLIC COMPOUNDS AND OTHER ALDEHYDE
PRECURSORS . Bicrochim. Acta, Bo. 3:602-607, 1968. 2 refs.
Three reagents and a variety of fluorimetric methods are
introduced for the assay of alpha-glycolic compounds, polar
olefinic compounds, and olefins. The procedures are based on the
controlled oxidation of these compounds to aldehydes and analysis
of the aldehydes with J-acid, 2,4-pentanedione, or dimedon.
Host of the methods show reasonable sensitivity and accuracy and
should be capable of use in air pollution studies.
Recommendations are made for their use. Results confirm the
presence of large amounts of alpha-glycolic compounds in aqueous
extracts of urban airborne particulates. (Authors' abstract)ft
05170
F. G. Rounds, and H. W. Pearsall
DIESEL EXHAUST ODOR (ITS EVALUATION AND RELATION TO EXHAUST GAS
COHPOSITION. Vehicle Emissions (Selected SA.E Papers) 6, 45-
69, 196U. (Presented at the National Diesel Engine Reeting, .
Society of Automotive Engineers, Chicago, 111., Nov. 1-2,
1956, Paper No. 863.)
343 HYDROCARBONS AND AIR POLLUTION
-------
Techniques, based on panel estimates, were developed for
evaluating the odor and irritation intensities of undiluted Diesel
engine exhaust gases or of various dilutions of these gases in air.
Along with the estimates, chemical analyses were made to determine
the concentrations of total aldehydes, formaldehyde, and oxides of
nitrogen. Statistically significant correlations were found
between odor or irritation intensity estimates and the analytical
data, but these correlations were too weak to permit accurate
prediction of odor or irritation from chemical analyses. The
effects of some engine variables on Diesel odor were studied.
Possible means of reducing Diesel odor are discussed. Limited
studies indicated that engine load has a pronounced effect on
exhaust odor and irritation intensity. Engine make, engine speed,
engine condition, fuel type and lubricating oil type had
comparatively little effect.f#
05191
A. H. Barringer
DEVELOPMENTS TOWARDS THE REMOTE SENSING OF VAPOURS AS AN AIRBORNE
AND SPACE EXPLORATION TOOL . Proc. Symp. Remote Sensing
Environ., 3rd, Ann Arbor, Mich., 1964. pp. 279-92. Feb. 1965
The remote sensing of geochemical parameters is investigated.
The techniques under study and development are concerned with
sensing the dispersion of volatile components of orebodies or
their oxidation products in the surface soils and in the air above.
The elements and compounds of interest include mercury, iodine
and sulphur dioxide in connection with metal bearing deposits,
and hydrocarbon gases and iodine in association with oil fields.
(Author abstract) ##
05210
A. A. Belyakov
DETERMINATION OF CARBON TETHACHIORIDE IN AIR. Zavodsk. Lab.
(Moscow) 23, (2) 161-2, 1957. Russ. (Tr.)
Determination of carbon tetrachloride and chloroform by
colorimetric analysis is discussed. The method involves
application of the condensation reaction between
2,4-dinitrochlorobenzene and pyridine to form pyridinium chloride
which is converted by hydrolysis to glutaconic aldehyde and
2,
-------
05257
F. E. Saalfeld
MASS SPECTBCMETRIC DETERMINATION OF THE ALIPHATIC AND AROMATIC
CONTENT OF A HYDROCARBON MIXTURE . Naval Research Lab.,
Washington, D.C., Chemistry Division. (NRL Rept. No. 6178.)
Nov. 12, 1961. 8 pp.
A simplified mass spectrometric technique has been devised for
determining the aromatic content in hydrocarbon mixtures of: the
type that have been recovered from adsorptive carbon samplers
exposed in the atmospheres of nuclear submarines. The method is
based on the summation of ion currents at mass-to-charge ratios'
(m/e) of 27, 28, 29, 41, 43, and 57 for aliphatic hydrocarbons and
aromatic hydrocarbons. The mass spectrometric results agree
reasonably well with Fluorescence Indiator Adsorption analyses
of the same samples. While, due primarily to cost and operational
complexity, no available mass spectrometers are suitable for
shipboard operation, future developments in the field of mass
spectromctry should be carefully observed for advances that make
such use possible. (Author abstract)
05263
P. G. Jeffery, and P. J. Kipping'
GAS CHROMATOGRAPHY FOR THE ANALYSIS OF EXHAUST GASES. Proc.
Inst. Mech. Engrs., London, Engl., 1966. 180 (3G), 95-100
(1966) .
The traditional methods for the analysis of vehicle exhaust gases
have never been entirely satisfactory. The recent development of
gas analysis by gas chromatographic methods offers considerable
improvement in accuracy, precision, and also in time required.
Difficulties still arise for certain constituents, notably sulphur
dioxide and oxides of nitrogen, for which chemical methods of
analysis are still preferred. The chromatographic analysis of the
hydrocarbon fraction and the remaining inorganic fraction of
exhaust gases, where this is reguired, is now a routine operation,
calling for niether expert chromatographic'knowledge, nor
exceptional skill in manipulation. A typical gas chromatograph
may be considered as comprising a number of simple building
blocks, including a carrier gas flow system, a sample inlet
mechanism, a chromatographic material for component resolution, a
detector for those components of interest, and a display
mechanism. Some form of electrical control is reguired; this
may amount to little more than'a Wheatstone bridge network, or
may be a high guality linear amplifier and associated voltage-
decade supply for the more sophisticated ionization detectors.
Each of these building units is considered in detail, and the
errors that can arise in the course of making an analysis of an
exhaust gas are noted. The possibility of gross errors arising
from defective equipment is also considered.**
350 HYDROCARBONS AND AIR POLLUTION
-------
05299
B. Katz
STANDARDIZATION OF METHODS OF MEASUREMENT OF AIR QUALITY IN
HEHBER COUNTRIES . Preprint. (1963)
Measurement methods for dust fall, suspended particulates,
sulfur dioxide, sulfur trioxide, sulfuric acid, nitrogen
oxides, ozone or oxidants, and hydrocarbons are reviewed.
Standardization of techniques and methods of reporting data is a
prerequisite for international exchange of information and for
further co-operative research in order to establish a sound basis
for the control of air pollution.
05319
Engel, C. R., and E. Sawicki
A SUPERIOR THIN-LAYER CHROMATOGRAPHIC PROCEDURE FOR THE SEPARATION
OF AZA ARENES AND ITS APPLICATION TO AIR POLLUTION. J. Chromatog.,
Vol. 31, p. 109-119, 1967. 8 refs.
A thin-layer-chromatographic method for separation of polynuclear
aza heterocyclic compounds with silica gel is presented which is
superior to previously reported paper and thin-layer
chromatographic methods. Many of the groups of compounds had run
together in previous separation methods. This procedure has been
applied to the separation of various basic fractions of interest in
air pollution studies. Ben (c)acridine, benzo (h)guinoline,
acridine, benz(a)acridine, and phenanthridine can be separated and
identified in these samples with the help of two-dimensional thin-
layer chromatography on silica gel-cellulose (2:1), In addition, a
column chromatographic separation of a basic fraction of coal-tar
pitch, with silica gel as the adsorbent, was investigated, and the
amounts of benz(c)acridine and benz(a) acridine were estimated.
Evidence obtained from the absorption spectra indicates the
presence of a large number of unknown and previously identified
compounds in the fractions. The various silica gel methods are
recommended for use in air pollution studies. (Authors' abstract)
05322
MONITORING OF CONTAMINANTS. THE FIRST STEP IN AIR POLLUTION
CONTROL. Instrument Development Co., Reston, Va. Feb. 1, 1967. 27
pp.
This paper was prepared in order to contribute to the better
understanding of the need for air contaminant monitoring. Included
are explanatory remarks on the Clean Air Act of 1963, some
histroical considerations on air pollution, lists of sources
pollutants, and specifications on air pollution monitoring
equipment currently offered by the Instrument Development Company.
D. Measurement Methods 351
-------
05339
Stebar, R. F., M. J. Cianciolo, F. M. Ward, and D. A.
Brownson
DIGITAL DATA ACQUISITION AND COMPUTER DATA REDUCTION FOR THE
CALIFORNIA EXHAUST FMISSION TEST. In: Vehicle Emissions,
Part II, SAE Progri ,3 in Technology Series, Vol. 12,
Society of Automotive Engineers, Inc., N.Y. 1966, p. 3U2-351.
(Presented at the SAE Mid-Year Meeting, Detroit, Mich.,
June 6-10, 1966.)
The tedious, time consuming task of hand reducing data from the
California exhaust emission test has been alleviated through the
use of digital data acquisition equipment and a digital computer.
Analog signals from exhaust gas analyzers and an engine speed
transducer are converted to digital measurements which are
recorded on tape and submitted to a digital computer for data
analysis and computation of results. In the data analysis, the
computer identifies the required driving modes from engine speed
changes, taking into account the sample delay time. "Reported"
composite emissions determined by the automatic data reduction
method agree within 5% with results determined by careful hand
analysis of analog strip chart recordings. The results determined
by the automatic data reduction system are more consistent and
accurate because of human errors prevalent in hand analysis have
been eliminated, and because nonlinear analyzer response is
accounted for. With the automatic system, data reduction time has
been decreased from about U hr per test to less than
3 minutes. (Authors' abstract)##
05376
Khrustalev, V. A.
DETECTION OF. PHENOL IN THE ATMOSPHERE WITH U-AMINOANTI-
PYKENE. Gigiena i Sanit. 10, «2-5 (1962). Russ. (Tr.)
In the detection of phenol by the use of U-A.A.P. (U-
aminoantipyrene), it was established that dimethyl p-cresol,
acetophenone, alpha-methyl-styrene, diethyl ether, isopropyl
alcohol, hydroperoxide of isopropyl benzene, benzene, dimethyl
phenylcarbinyl; ethyl- and butyl-benzine do not interfere. In the
detection of phenol with diazotized p-nitroaniline, presence of
dimethyl p-cresol interferes to the extent of 0.7 microgram which
attests to the expediency of the use of the U-A.A.P. and not of the
diazotized p-nitroaniline. The absorption of phenol from air can
be achieved by liquid media or sold sorbent. The use of 0.05 M
solution of sodium borate, of which 3 or 6 ml. should be put into a
V-shaped absorber with a No. 1 porous membrane is recommended for
liquid media. It is possible to carry out the liquid media
absorption of phenol at a speed of 5 L/min. Silica gel in
suspension was used as the solid absorbent. Absorption rates for
complete absorption here were 5-10 L/min. The use of ethyl alcohol
effected complete extraction of the phenol from the silica gel in
15 min. Results of these studies are presented in diagram. The
rose color of the sample in the 0.1 percent aqueous i»-A.A.P.
solution was compared with the standard curve.
352 HYDROCARBONS AND AIR POLLUTION
-------
05383
Krilov, N. A.
DETERMINATION OF ETHYLENE OXIDE IN THE ATMOSPHERE. Gigiyena i
Sanit. 10, 48, 1961. Huss. (Tr.)
A colorimetric method was developed for the estimation of ethylene
oxide in the atmosphere, based on the hydration of ethylene oxide
to the ethylene glycol and its subsequent oxidation by periodic
acid or potassium periodate to formaldehyde and the determination
of the latter with chromotropic acid. The sensitivity of the
method is 0.000 5 gnu in 5 ml. It is recommended that ethylene
oxide be sampled in 6 ml. of HO percent H2S04 contained in a U-
shaped absorber with a No. 1 porous membrane at a speed of 0.5 1/
min. (Author conclusions modified)
05401*
E. J. Levy and D. G. Paul
THE APPLICATION OP CONTROLLED PARTIAL GAS PHASE THEPBOLYTIC
DISSOCIATION TO THE IDENTIFICATION OF GAS CHROMATOGRAPHIC
EFFLUENTS. J. Gas Chromatog. 5 (3) 136-45, Mar. 1967.
A technique has been developed for gas chromatographic effluent
identification. In the application of this technique, the peak
selected for identification is transferred in a continuous flow
system, from the primary gas chromatographic unit, through a
tubular quartz pryolysis reactor, and then through a second gas
chromatograph for identification of the pyrolysis products. The
pyrolysis patterns obtained are characteristic of the parent
compound, independent of sample size and constant for the standard
pyrolysis condition. Under these standard conditions, the
pyrolysis product distribution may be treated in a manner analogous
to the mass spectral ion distribution reported as a percentage of
total ionization. The pyrolysis product distribution obtained
using hexadecane as a test compound agreed very closely with the
distribution predicted by the modified Rice free radical
mechanism for thermal dissociation. (Authors' abstract, modified)
05456
Roschig, M. and Matschiner, H
INVERSE POLAROGRAPHIC DETERMINATIONS OF TRACES OF LEAD IN HIXTUBES
OF TECHNICAL HYDROCARBONS. Inverspolarographische Bestimnung von
Bleispuren in Technischen Kohlenwasser-Stoffgemischen. Chem. Tech.
(Berlin) 19 (2) : 103-104, Feb. 1967. Ger.
A method is described in which lead in benzene in concentrations of
1 to 100 ppb can be determined. After reducing the tetraethyl lead
with bromine, the lead is extracted with 0.1N HN03 and determined
in an inverse polarographic cell. The threshold of detection of
0.8 ppb of lead depends on the purity of the reagents used. The
method is fast, requiring about 45 min, with a standard deviation
of plus or minus 7 percent.
D. Measurement Methods 353
-------
05U61
Y. Suzurki and H. Matsushita
THIN LAYER CHROMATOGHAPHIC SEPARATION OF POLYNUCLEAR HYDROCARBONS
ON THE PLATE COHPOSED OF TWO ADSORBENT LAYERS. . Ind. Health,
(Japan) «, (3) 109-17, Oct. 1966.
In thin layer chromatography, the band widith of a sample
applied to a plate is one of the most important factors affecting
the efficiency of separation of a sample. A new method is
described to narrow and to separte adequately a band of a
mixture of polynuclear hydrocarbons applied to a chromatoplate
composed of two adsorbent layers by means of a chromatocharger.
One layer of of the chromatoplate is used to narrow a band
of sample applied to a plate and the other is used to
separate the narrow band into several bands corresponding
to each hydrocarbon. A successful separation of polynuclear
hydrocarbons is obtainable by thin layer chromatography
using 26% acetylated cellulose-aluminum oxide G plate, silica
gel WOELM-cellulose plate, and aluminum oxide G-cellulose
plate. By using this method, a mixture of several.hydrocarbons in
10 ml of dilute solution can easily be separated into the
separate hydrocarbons without further concentration. (Author
summary, modified)##
05501
G. J. Cleary
NATURE OF POLYNDCLEAR AROMATIC HYDROCARBONS IN AIB PARTICIPATES
(A REPORT OF SOME OBSERVATIONS IN THE SYDNEY AREA).
Proc. Clean Air Conf., Univ. New South Wales Vol. 1,
1«p. 1962, Paper 2.
Procedures are described for the separation and
characterisation of polynuclear hydrocarbons in air borne
particulates and related samples. The basic method involves
chromatographic separation using activated alumina columns
considerably longer than usually encountered. This factor,
coupled with careful elution, enables quite good separation
to be achieved in the column itself. Ultraviolet spectral
analysis is then used as a means of characterising the samples
whilst mixed fractions and trace quantities, after concentration,
may be rechromatographed on acetylated paper. Among the
compounds identified or characterised were acenaphtene,
phenanthrene, anthracene, pyrene, fluoranthene, 1,2
benzfluorene and 2,3 benzfluorene, chrysene, 9,10
benzpenanthrene, 3,« benzpyrene and 1,2 benzpyrene, 2,3
benzfluoranthene, 1,12 benzpherylene, anthanthrene and
coronene. (Author abstract)##
354 HYDROCARBONS AND AIR POLLUTION
-------
05502
M. Katz J. L. Monkman
THE ORGANIC FEACTION OF PARTICOLATE POLLUTION, INCLUDING
POLYCYCLIC HYDROCARBONS. Proc. Clean Air Conf., Univ.
New south Wales, Vol. 1, 25p. , 1962, Paper 3.
Seasonal variation in content of organic material in urban
atmospheres shows the anticipated high winter low summer
trend. The constitution of the extremely complex organic
media besides differing with source, depends upon possible
photochemical, catalytic oxidation and polymerisation
reactions in the atmosphere. Solid fuel burning equipment is the
most prolific source of aromatic polycyclic hydrocarbons.
Suggestions have been made for utilising the concentration
ratios 3,4 benzpyrene/coronene and 3,4 benzpyrene/1, 12
benzperylene as indicative of pollution from coal burning
plant or autombile exhaust, however, extensive tunnel tests
have shown that the contribution of'efficiently operated
internal combustion engines is less than expected. It should be
stressed that the separation and determination of polycyclic
constituents is a complex and delicate investigation and
cannot be considered routine research. There "is still a need for
complete classification of aromatics and other hydrocarbons,
phenols, quinones, nitrogen derivatives and other organics.
Moreover, new and quicker methods of biological
appraisal of potentially cancerous air contaminants are long
overdue. (Author-abstract)l#
05536
Broering, L. C. Jr., Werner, W. J. , Rose, A. H. Jr.
AUTOMOTIVE MASS EMISSION ANALYSIS BY A VARIABLE DILUTION
TECHNIQUE. Preprint. (Presented at the 60th Annual Meeting, Air
Pollution Control Association, Cleveland, Ohio, June 11-16, 1967,
Paper 67-200.)
The objective of this.study was to develop an improved nethod for
measuring engine exhaust, to be used,both for compliance,testing
and for .the design and/development,'of new engine-emission-controls.
The variable dilution^sampling .technique was chosen for the system.
The operation of this systemincludes collection and simultaneous
dilution of the total-exhaust volume with a variable volume of
dilution air, such that the total mass flow rate of exhaust gas
plus diluent air .is constant for a given unit of vehicle operation.
Measurement of contaminant concentration in the exhaust-diluent air
mixture provides direct measurement.of the mass of contaminants
discharged per unit operation of the vehicle. For continuous mode
mass emission measurements, samples are withdrawn continuously
after the sample pump. Carbon monoxide, carbon dioxide,
hydrocarbons, and oxides of nitrogen are measured by the standard
exhaust measurement techniques. The practical capabilities of the
variable dilution system to measure auto exhaust emissions during
cyclic operation, were evaluated by comparing the mass-emission
levels indicated by this system to those obtained with the
proportional sampler. Toe determine the response characteristics
of the system under continuous sanpling conditions, known
0. Measurement Methods 355
-------
quantities of butane were injected at the inlet of the sampling
system, and the regponse of the hydrocarbon (NDIB) instrument was
recorded. The redponse time of the total system, including that
attributable to the analytical instruments, compared favorably to
that obtained with the instrument train specified in both the
current Federal and the California Exhaust Emission Standard
Procedures. In summary, the variable dilution sampling technique
possesses 2 distinct advantages over present emission testing
procedures: (1) The technique is simple, practical, and accurate
for the direct measurement of vehicle-exhaust mass emissions. (2)
The rapid and highly sensitive response characteristics of the
system to changes in mode mass-emission levels establish its
usefulness as a design and development tool.
05561
R. D. Stewart and D. S. Erley
DETECTION OF VOLATILE ORGANIC COMPOUNDS AND TOXIC GASES IN HOHANS
BY RAPID INFRARED TECHNIQUES. Progr. Chem. Toxicol. 2, 183-
220 (1965).
Advances in infrared analytical techniques and sampling
accessories have permitted the development of methods for
detecting toxic gases and volatile organic compounds in the
expired breath, blood, urine, and tissues. Inherent in these
infrared techniques are the desired specificity, sensitivity,
speed, and simplicity. Infrared analysis of the expired breath
may be used effectively to detect the following groups of
compounds: (1) the halogenated hydrocarbons, such as carbon
tetrachloride, trichloroethylene, and methylene chloride; (2) the
alcohols, such as methanol, ethanol, and isopropanol; (3) the
ethers and aldehydes, such as ethyl ether and paraldehyde; (1) the
ketones, such as acetone and methylethyl ketone; (5) gases such as
carbon monoxide, carbon dioxide, and ammonia. Infrared
techniques for the determination of carbon monoxide in the
exhaled breath are faster and more sensitive than the standard
carboxyhemoglobin determination. Solvent extractions of body
fluids may be analyzed by infrared for the following groups of
compounds: (1) the halogenated hydrocarbons; (2) the alcohols;
(3) the ethers and aldehydes; and (U) the ketones. infrared
analysis of body fluid extracts has proved valuable in the fields
of toxicology, industrial and forensic medicine, and pharmacology.
The infrared identification of any compound ultimately depends on
the comparison of its spectrum with that of a standard of known
purity. While it is true that the spectrum itself will often
reveal m.uch information about the functional groups present,
specific identification and quantitative analysis always require
comparison with a standard spectrum. It is essential, therefore,
to have a reference file of the spectra of pure materials, and sone
means for reaching this file efficiently.##
05572
Scott, W. E. and E. R. Stephens
A SCIENTIFIC APPROACH TO THE PROBLEM. Proc. Symp. Cleaner
Air Urban Areas, Philadelphia, Pa., pp. 24-35 (1956)
356 HYDROCARBONS AND AIR POLLUTION
-------
Chemical reactions that take place in a polluted atmosphere
produce substances that lend smog its eye-irritating,
crop-damaging, visibility-lo¥ering characteristics. The authors
relate how, in an effort to identify these reactions and
substances, the staff devised the long-path (up to 500 meters)
infrared absorption cell. They describe the construction of the
cell, and how it is used to detect and "fingerprint" the products
of photochemical reactions, both in synthetic and in actual smog.
Early work with this new tool was pointed to explaining the
characteristic high ozone concentrations of smog, and proceeded
from Dr. Haagen-Smit's evidence that nitrogen dioxide reacted
with organic compounds in air to produce ozone. They trace the
nitrogen dioxide studies that finally led to discovery of Compound
X (peroxyacyl nitrite) , believed to be the "missing link" in
the process of ozone formation in snog. Gasolines and auto"
exhaust as sources of organic pollutants that take part in N02
reactions are discussed. They relate their plans for further
studies with the infrared cell, and the possibility of applying
Los Angeles smog research to other afflicted cities. It may
appear that the work reported here is concerned solely with the
Los Angeles problem. This is partly true because there air
pollution problems in some cities which involve pollutants and
weather conditions entirely different from those of Los Angeles.
On the other hand, however, many large cities do have pollution
sources of the same kind as LOS Angeles: power plants,
refineries and other industry, incinerators, automobiles, etc.
The results of studies of reactions of pollutants from these
sources are valid regardless of the city. Heather conditions and
topography in the Los Angeles area are such that the products of
reactions in the atmosphere frequently accumulate and result in
damage and irritation. While conditions for the accumulation of
these products occur less freguently in other cities, nevertheless
they do occur and the resulting smog is objectionable and costly
With an inversion and no wind, we have a good trap for pollutants
from these sources, and as good a chance of having smog as Los
Angeles. Plant damage is reported in areas surrounding most
large cities of the world. Los Angeles studies show that there
are other pollutants besides coal smoke and S02 that may be
objectionable, especially in and around large cities.##
05578
H. W. Patton and J. S. Lewis
FRACTIONATION AND ANALYSIS OF A MICRO SCALE BY GAS
CHHOBATOGRAPHY. Proc. Natl. Air Pollution Symp., 3rd,
Pasadena, Calif., 1955 pp. 74-9.
The work reported in this paper concerned a study of the
usefulness of gas chromatography for the separation, isolation, and
identification of the components of a complex mixture. Automobile
exhaust gas was chosen as the source of samples because of its
ready availability and its importance in air pollution studies.
The objective was not to obtain a complete analysis but to
discover some of the potentialities of the method alone and in
combination with other methods.tt
D. Measurement Methods 357
-------
05583
B. R. Austin
AN EXPERIMENTAL INSTRUMENT FOE THE CONTINUOUS HEASUBEMENT OF THE
CONCENTRATION OF OLEFINS IN AIR. Proc. Natl. Air Pollution
Symp., 3rd Pasadena, Calif., 131-5 (1955).
The principles of electrolytic generation of bromine and reaction
of this reagent in the gas phase at high temperature in a contact
bed with olefin have been studied and proved practical as the basis
for a continuous record of the concentration of olefins in the
atmosphere and in such sources of emission as exhaust gases. An
experimental model of a recording instrument of this kind has been
developed and successfully operated with manual control of sample
gas. Work is in progress to complete the instrument development
and carry out field tests.#f
05605
Boubel, B. W. and L. A. Ripperton
BENZO (A)PYRENE PRODUCTION DURING CONTROLLED COMBUSTION. J.
Air Pollution Control Assoc. 13 (11) :553-557, Nov. 1963.
(Presented at the 56th Annual Meeting, Aic Pollution Control
Association, Detroit, Mich., June 9-13, 1963.)
A statistical experimental design was initiated to determine if
the quantitative production of benzo (a)pyrene during combustion
could be related to some of the variables of the combustion
process. Four fuels of different molecular structure, but the
same carbon number, were chosen. These were benzene, cyclohexane,
hexene-1, and hexane. Three air-fuel ratios were selected: the
richest and leanest practical mixtures plus one intermediate.
The combustion was investigated with and without the effects of
flame quenching by a cooled surface in the combustio'n chamber.
Choice of these levels of variables led to the establishment of a
rogram containing 72 treatments (4 fuels x 3 energy levels x 3
A/F ratios x 2 cooling levels = 72 runs). The apparatus was
constructed around a surplus truck preheater. This heater was a
gasoline-burning type equipped with electric ignition, a forced
draft combustion air system, and a vaporizing pot-type burner.
"Sample analysis was carried out spectrophotometrically utilizing
the variable reference technique of Jones, Clark and Harrow.
The results confirm previous work by others who have shown
measurable benzo (a)pyrene production during incomplete combustion.
The statistical method of this experimental design was very
efficient for indicating the significant differences of the
variables and magnitude of these differences. The curvlinear
regression equations can be used in any future work with this
system to predict the mean value of benzo(a)pyrene
produced by any combination of the variables used in this
experiment. The fact that the benzo (a)pyrene can be minimized for
any one fuel used in the apparatus is highly significant. The
procedures used in this study can be applied to any combustion
process to determine the effects of the system parameters on the
quantity of benzo(a)pyrene produced, and can be adapted for use in
field studies and utilized to predict the quantity of this
carcinogen emitted by each of the many sources contributing to
its atmospheric concentration.##
358 HYDROCARBONS AlilD AIR POLLUTION
-------
05617
Morris, R, A. and R. L. Chapman
FLAME IONIZATION HYDROCARBON ANALYZER. J. Air Pollution
Control Assoc., 11 (10) :467-469, Oct. 1961. (Presented at
the 54th Annual Meeting, Air Pollution Control Association,
New York City, June 11-15, 1961.)
The empirical basis for the flame ionization method is the
observation that while the flame of pure hydrogen contains an
almost negligible number of ions, the addition of even traces of
organic compounds produces a large amount of ionization. In
practice, the sample to be analyzed is mixed with a hydrogen fuel
and passed through a small jet. Air is supplied in the annular
space around the jet to support combustion. Any hydrocarbon
carried into the flame results in the formation of ions which are
accelerated to a collector electrode by an electric field set up
between the jet and electrode. The generated ion current is
proportional to the rate the hydrocarbon molecules are introduced
into the flame. If flow rates are held constant, the ion current
is proportional to hydrocarbon concentration. It has been found
empirically that the ion current produced in the hydrogen flame
is proportional to the heat of partial combustion of the sample
(to C02 and H20). Therefore, it is possible to construct a
table showing the approximate relative contribution which carbon
atoms in aliphatic, aromatic, olefinic, acetylenic, and carbonyl
molecules will make on the observed signal. Such a table is
included. The hydrocarbon analyzer is ideally suited to
instrumentation for auto exhaust inspection. In general, it can
be used to determine the presence of total hydrocarbons in inert or
inorganic gases such as He, A, N2, H2, and air.
Determinations of carbon content in concentrations from 0.1 ppn to
2558 are possible with excellent discrimination against water, CO,
C02, and other inorganic gases. The instrument gives equivalent
sensitivity for various hydrocarbons, thus it is not selective for
mixtures of organic compounds.fi
05831
B. Feldstein
STDDIES ON THE ANALYSIS OF HYDROCARBONS FROM INCINERATOR
EFFLUENTS WITH A FLAME IONIZATION DETECTOR. (J. Air
Pollution Control Assoc.) 12, (3) 139-41, Bar. 1962.
(Presented at the 54th Annual Meeting, Air Pollution
Control Association, New York City, June 11-15, 1961.)
Flame ionization units capable of detecting small concentrations
of hydrocarbons make use of the principle that when a hydrocarbon
is introduced into a hydrogen flame, electron concentrations are
formed and can be measured. The thermionic work function for
carbon is 4.35 electron volts which, apparently, is low enough
for electron emission at hydrogen flame temperatures. The
response of the instrument is proportional to the number of carbon
atoms in the compound being burned; that is, hexane will give
six times the response of methane. The instrument can thus be
considered as a carbon counter. Apparatus and equipment
included a Carad flame ionization analyzer and detector.
D. Measurement Methods 359
-------
recorder, a Carad gas sampling unit, and stainless steel
collecting tanks. A 30 ml sample of effluent was injected and
yielded a reading proportional to the total hydrocarbon content
of the sample. A second 30 ml sample was then injected with the
silica tube in line. Response due to methane, ethane, ethylene,
and acetylene was then noted on the recorder as these gases
separated on the silica column. The difference between the total
hydrocarbon reading and the methane reading is proportional to the
C2-C6 hydrocarbons present in the sample. The same samples were
also analyzed by gas chromatography- By converting the results
obtained with each method to similar units, direct comparison
may be made. For the series of effluents analyzed, agreement
between the two methods is excellent. The flame ionization method
ulk adsorption properties of particle and surface. Adhesion of
provides a more rapid procedure for the analysis and may be
considered as a comparable method for the analysis of C2 and
higher hydrocarbons.ft
05836
H. F. Clark
EVALUATION OF MICROBIOLOGICAL SYSTEMS FOE ESTIMATING AIR
POLLUTING SDBSTANCES. Preprint. (1957).
The procedure used in the evaluation of microbiological systems
for estimating air polluting substances consisted of: (1) Placing
an indicator organism on a membrane filter strip in a logarithmic
increasing concentration; (2) Exposing the bacterial indicator on
the surface of the strip to a synthetic aerosol (irradiated
automobile exhaust) at a flow rate for the aerosol of 5/min with
the strip moving 7.8 mm/mm; (3) cultivation of the remaining
viable bacteria on the strip after aerosol exposure by
incubation on an appropriate medium at 35C for 18-20 hrs; and (1)
Comparison of the bacterial colony density on the exposed strip
with suitable control strips to estimate the growth inhibiting
property of the aerosol under examination. A recently isolated
E. coli. was used as an indicator. The procedure appears to have
valuable application in the study and comparison of exhaust before
and after irradiation. The concentrations of hydrocarbons in so»e
of the experimental tests were in the range of those which might
occur on a street during heavy motor vehicular traffic. The test
procedure has sufficient merit to justify further development work
on methodology, interpretation and application.#f
05837
E. W. Cieplinski and L. S. Ettre
A NEW SIMPLIFIED DETECTOR FOR THE ANLAYSIS OF ORGANIC
IMPURITIES IN ATMOSPHERE AND EXHAUST GASES. Preprint.
(Presented at the Joint Symposium on Air Pollution
Instrumentation, Instrument Society of America and Air
Pollution Control Association, New York City, June 12-13,
1961.)
360 HYDROCARBONS AND AIR POLLUTION
-------
The Model 223 Flame lonization Analyzer is a'117-volt, 60-cps,
line-operated instrument. It measures 10 1/4 inches on a side and
veighs about 25 pounds. A meter located on the front of the
instrument indicates the organic vapor concentration of the
sauple. Since different classes of organic compounds give a
different detector response, the meter indication for a given
saiple must be interpreted on the bases of instrument calibration
uith an appropriate test gas. Output connections are provided for
asing the instrument with a standard 0-5 or 0-10 millivolt,
potentiometer recorder. Hydrogen, air, test gas, and zero gas
supplies are necessary for operation. Filters containing 5-A
Bolecular Sieve mus should be used to remove any small impurities
present in the air and hydrogen. The test gas contains a known
concentration, in the same order of magnitude as the sample, to
periit the proper calibration of the panel meter. The'zero gas is
the same as the background gas of the sample and is usually only
necessary when the higher sensitivity ranges are being used. The
gas is used to check and eliminate any effect the background gas
nay have on the flame detector operating parameters. The
instrument will continuously monitor organic impurities in the
atmosphere and exhaust gases.. The unit is transportable, line-
operated, and is very stable. Samples may be introduced in the
range of 35-75 millimeters of mercury pressure when external
regulation is used and between 0.4-9.5 liters per minute when the
instrument's back pressure regulator is used. The linearity of
response for the detecting system has been shown to be very good
over a wide range of concentrations ##
05848
R. Goldstein and J. H. Elliott
EXPERIMENTAL PROGRAM FOR THE CONTROL OF ORGANIC EMISSIONS FROM
PROTECTIVE COATING OPERATIONS (INTERIM REPT. NO. 5.
DEVELOPMENT OF SAMPLING AND ANALYTICAL METHODS.) Los Angeles
County Air Pollution Control District, Calif. Bar. 1960.
H pp.
Analytical methods have been developed for the determination of
low concentrations of solvent vapors emitted from protective
coating operations. Organic compounds are detected and
determined as C02 in a nondispersive infrared C02 analyzer
after combustion. A chromatographic apparatus has been
constructed to be used in conjunction with the combustion-infrared
C02 analyzer to determine low concentrations of organic vapors as
C02 in the presence of background concentrations of C02 as high
as six %. The development of a chromatographic procedure for the
coiplete separation and guantitative determination of individua-1
compounds in an effluent containing solvent vapors is in progress.
(Author abstract) ft
05863
I. S. Ettre
IMPLICATION OF GAS CHROMATOGRAPHIC METHODS FOR AIR POLLUTION
STDDIES. J. Air Pollution Control Assoc.
D. Measurement Methods 36]
-------
11 (1), 3U-Q3 (Jan. 1961). (Presented at the 53rd Annual
Meeting, Air Pollution Control Association, Cincinnati,
Ohio, May 22-26, 1960.)
The modifications of conventional gas chromatography apparatus are
described which allows the use of gas chromatography in air
pollution studies. The newest developments of supersensitive
chromatography are described with special respect to their
importance in trace analysis. The construction, and operation of
a new instrument based on the flame ionization principles is
detailed. (Author summary)##
05951
Alekseeva, N. V.
METHODS FOR THE DETERMINATION OF ATMOSPHERIC POLLUTANTS. (In:
Limits of allowable concentrations of atmospheric pollutants. Book
6.) U.S.S.R. Literature on Air Pollution and Related Occupational
Diseases, Vol. 9. pp. 107-33. (1962). Russ. (Tr.)
Development in the synthesis of high molecular compounds resulted
in the production and utilization of many new organic substances by
the USSR national industries. Plants producing these substances
and their intermediate products discharge into the air gases,
vapors and by-products as surrounding atmospheric air pollutants
the detection and quantitative determination of which require
special and highly sensitive analytical methods. Methods are
described for the detection of acetic acid esters, acetates, dinyl,
isopropylbenzene, furfurol, ethylene oxide, monobasic carbonaceous
acids, methylmetacrylate, dimethylformamide, and isopropylbenzene
hydroperoxide. An index of allowable concentration limits for
harmful substances in atmospheric air of inhabited areas is •
appended.
05952
Ryazanov, V. A.
A SUMMARY OF 1961 STUDIES IN THE FIELD OF LIMITS OF ALLOWABLE
CONCENTRATIONS OF ATMOSPHERIC AIR POLLUTANTS. (In: Limits of
allowable concentrations of atmospheric pollutants. Book 7.)
U.S.S.R..Literature on Air Pollution and Related Occupational
Diseases, Vol. 9, pp. -138-i»1, (1963). Huss. (Tr.)
The Committee for the Sanitary Protection of Atmospheric Air
approved limits of allowable concentrations in the air for the
following new substances: furfurol, dimethylfornamide and styrol.
Furfurol is a heterocyclic aldehyde which is a good solvent for
many organic substances used in the preparation of some plastics
and a selective solvent for the purification of crude oil
lubricants. The threshold of aldehyde odor perception in most
sensitive persons was established at 1 mg/cu m. It was determined
that 0.05 mg/cu m of furfurol constituted the subthreshold
concentration in all the tests employed. Therefore, 0.05 mg/cu a
of furfurol was accepted as the maxiaal single allowable
362 HYDROCARBONS AND AIR POLLUTION
-------
concentration. Styrol is a benzene homologue with one double bond
at its side chain. The maximal single allowable concentration of
styrol in the atmospheric air was suggested as 0.003 mg/cu m.
Dimethylformamide is a colorless liquid having a nauseating herring
odor; it is used as a polyacrylnitryl solvent in the synthetic
fiber industry known as orlon and nitron. It was recommended that
0.03 mg/cu m be adopted as the limit of allowable single and 21
hour concentration of dimethylformamide vapor in the air, since it ;
proved to be the subthreshold concentration in relation to all the
test indexes. The limit of allowable phenol concentration in
atmospheric air was set at 0.01 mg/cu m. Hats were exposed to the
inhalation of nitrogen dioxide 6 hours daily for :16« days at
different dose levels. No maximum allowable .concentration was
agreed upon.
05959
Alekseeva, M. V. Tkachev, P. G,
METHODS FOB THE DETERMINATION OF SOME ORGANIC ATMOSPHERIC AID
POLLUTANTS. (In: Limits of allowable concentrations 'of '
atmospheric pollutants. Book 7.) O.S.S.R. Literature on Air
Pollution and Related Occupational Diseases, Vol. 9. pp. 203-12.
(1963) . Huss. (Tr.)
Methods are described for the determination of aniline, xylol, n-
butyvinyl ester and dimethylterephthalate in the atmosphere.
Standard color scales are also included for the quantitative
determination of xylol, n-butylvinyl ester and
dimethylterephthalate (DMTPH). A method for the determination of
phenol with H-aminoantipyrine is described and standard color
scales for the quantitative determinations are included.
05981
Cantuti, V.}G. P. Cartoni, A. Liberti, and A. G. Torri
IMPROVED EVALUATION OF POLYNUCLEAR HYDROCARBONS IN ATMOSPHERIC DOST
BY GAS CHBOMATOGRAPHY. J. Chromatog. 17, (1) 60-5, Jan. 1965.
In the investigation of the application of gas chromatography to
the determination of polynuclear hydrocarbons in airborne particles
new liquid phases were evaluated and programmed temperature
chromatography was used. An electron capture detector was used for
the determination of polynuclear hydrocarbons. Its relative
response was compared with results obtained with a hydrogen flaae
ionization detector. It is shown in one of the chronatograms of an
atmospheric dust sample that the response of the electron capture
is very different from that of the flame and at the same time shows
nany other unknown compounds as large peaks that are not detected
by the flame detector because of being present in too small an
amount.
D. Measurement Methods 363
-------
06008
D. J. Morgan and G. Duxbury
THE DETEBHINATION OF CHLORINATED HYDBOCABBONS IN THE ATMOSPHERE BY
ACTIVATION ANALYSIS. Ann. Occupational Hyg. (London)
8 (3):253-256, July 1965.
The maximum allowable concentration for continuous exposure to
trichlorethylene varies by a factor of teh depending on the country
in which it is used; in this country it is variously quoted as 100
ppm or 200 ppm but recent studies (Morgan, 196t) have suggested
that these values may be too high. A limited experimental
programme using neutron irradiation was undertaken to examine its
potentialities and to demonstrate its utility in the field of
industrial hygiene. The air samples are drawn through charcoal,
which is then irradiated in a thermal neutron flux, where C1-38
is formed; this then decays with a half-life of 37 min, emitting
gamma-radiation of energies 1:60 and 2:15 MeV. The amount of
C1-38 is then determined by spectrometry. A series of
measurements was carried out in a well-ventilated room in which a
degreasing tank was situated. Concentrations less than 10 ppm of
trichlorethylene were generally found in the room air during
the day, a sampler operated at a height of 5 ft above ground level,
near the side of the tank, indicated a concentration of about 20
ppm averaged over the whole day.tt
06021
W. Stanilewicz and E. Mirowska
(THE USEFULNESS OF THE NEPHELOBETRIC METHOD FOB BENZENE AND OIL
DETERMINATION IN THE AIP. (Przydatnosc metody
nefelometrycznej do oznaczania benzyny i nafty w powietrzu.) (Med.
Pracy (Lodz) 16 (3), 223-9 (1965). Pol.
Nephelometric methods for the determination of benzene and oil
concentrarion in air were investigated. Detection methods,
standard scale range, the effect of the addition of water on
turbidity, and the durability of oil and benzene solution in
glacial acetic acid were studied. The method of Zapolsky and
Vorochobina and that of Pieregud are not considered suitable for
the determination of benzene concentrations in air because the
resultant values are too low.##
06025
A. L. Linch, R. B. Davis, B. F. Stalzer, and W. F.
Anzilotti
STUDIES OF ANALYTICAL METHODS FOB LEAD-IN-AIB DETERMINATION AND
OSE HITH AN IMPBOVED SELF-POWERED PORTABLE SAMPLEB. Am. Ind.
Hyg. Assoc. J. 25(1):81-93 (Feb. 196U). (Presented at the
364 HYDROCARBONS AND AIR POLLUTION
-------
Annual, fleeting, American Industrial Hygiene Association,
Cincinnati, Ohio, May 10, 1963.)
The portable "Uni-Jet" Lead-in Sir Analyzer was revised to
provide constant rate collection of tetraethyl (TEL) and
tetramethyl lead (TML). Reliable results from monitoring leaded
gasoline storage tanks, cleaning and decontamination procedures,
were obtained by drawing a two-cubic foot sample during twenty
ninutes through methanolic iodine. The aspirating unit powered
by nonflammable "Freon-12" has been used widely in fire and
explosion hazard areas. (Authors' abstract)##
06050
D. F. Adams
OZONE ANALYSIS WITH THE MINI-ADAK II. J. Air Pollution
Control Assoc. 13, (2) 88-90, Feb. 1963. (Presented at the
55th Annual Heeting, Air Pollution Control Association,•
Chicago, 111., May 20-24, 1962.)
The suitability of sodium diphenylaminesulfonate (NaDS),
potassium iodide, and phenolphthalein reagents for ozone analysis
in a multipurpose, automatic analyzer such as the Mini-Adak II
was investigated. The oxidation potential for NaDS is more
negative than that for iodine and, therefore, NaDS is believed
less susceptible to oxidative interference as a colorimetric
reagent. The reagents were prepared along with a mixture of
ozone and oxides of nitrogen. The test atmosphere was drawn
through a single manifold and thence to two midget impingers in
parallel, one containing 10 ml of the neutral KI reagent and the
other 10 ml of either the NaDS or phenolphthalin reagent. A
second series of comparisons was made between a midget inpinger
containing neutral KI and the Mini-Adak II utilizing the
NaDS or phenolphthalin reagent. Based on the literature and
the work herein reported, either the phenolphthalin^or NaDS
reagents can be used in the Mini-Adak for ozone analysis.
Selection of the reagent to be used should be based upon an
evaluation of the possible interferences which may be present with
ozone in the atmosphere and the relative sensitivities (molar
absorbancy) of the two reagents. Either reagent shows only
one-fourth as much response to N02 neutral KI and is therefore
superior to KI in this respect. Based on the laboratory study,
the phenolphthalin reagent appears somewhat preferable for use in
the Mini-Adak. This selection is tentatively made upon the
basis of the greater sensitivity (molar absorbancy) of the
phenolphthaline which permits the use of a lower Hini-Adak
sensitivity range with its attendent reduction in electronic
background noise.ft
06052
J. L. Jones, B. A. Schuck, H. W. Eldridge, N. Endow,
F. W. Cranz
BEASUREMENT OF ADTOMOBILE EXHAUST GAS HYDKOCARBONS. J. Air
Pollution Control bSassoc. 13, (2) 73-7, Feb. 1963. -- (Presented
D. Measurement Methods 365
-------
at the 1UOth' National Meeting, American Chemical Society,
Chicago, 111., Sept. 3-8, 1961.)
The purpose of the study was to compare hydrocarbon analyses
obtained with a non-dispersive infrared analyzer and those
obtained by other instruments. Automobile exhaust was examined
with a dispersive IR analyzer, with a flame ionization .
hydrocarbon detector, and gas chromatographs. As a part of this
study, the methods of handling automobile exhaust gases were also
examined. Dispersive IB analyses were performed using a
Perkin-Elmer Model 21 spectrophotometer equipped with 40-meter
gas cells and a scale expander. The nondispersive IR
hydrocarbon analyzer essentially measures the saturated hydrocarbon
fraction of the total hydrocarbon concentration in exhaust. Since
the ratio of saturated to unsaturated components in exhaust is not
constant, the hydrocarbon concentrations obtained with this
instrument are not necessarily proportionate of the total
hydrocarbon concentration in the exhaust. Specifically, this
instrument is insensitive to certain short-chain unsaturated
aliphatic hydrocarbons which are the principal reactants in
photochemical smog. Thus, this instrument could indicate that
an exhaust was relatively free of hydrocarbons when in reality it
contained high concentrations of smog precursors. The flame
ionization hydrocarbon detector, the IB spectrophotometer, and
the gas chromatograph can measure most of the hydrocarbon
components in exhaust. Using the flame ionization hydrocarbon
detector in conjunction with the n-hexane-sensitized nondispersive
infrared analyzer prevents erroneous conclusions concerning
hydrocarbon concentrations. If the flame ionization hydrocarbon
detector measures the total hydrocarbon concentration in the
exhaust and the nondispersive infrared instrument measures
saturated hydrocarbons, then the difference between the
concentrations will provide a rough measure of the unsaturated
hydrocarbons (plus methane) in an exhaust. In analyses of exhaust
gas hydrocarbons, the method of direct 5:1 dilution of the hot
exhaust gas with nitrogen gas, followed by parallel analysis with
the nondispersive IK and flame ionization instruments, is
suggested in preference to the method utilizing condensate traps,
or heated exhaust sampling.ft
06065
V. Levin, B. W. Nippoldt, and R. L. Hebertus
SPECTROPHOTOMETRIC DETERMINATION OF PRIMARY AROBATIC AHINES HITH
THIOTRITHIAZYL CHLORIDE (APPLICATION TO DETERfllNATION OF
TOLONE-2, H-DIISOCYANATE IN AIR). Anal. Chem. (O.S.)
39(6) : 581-58«, May 1967.
Highly colored intermediates form during the reactions of
thiotrithiazyl chloride with some primary aromatic amines. The
nolar absorptivities range from about 21,500 liters/mole cm for the
red product from'm-phenylenediamine to about 300 liters/mole CB for
the green product from aniline. Rapid color development is
achieved at room temperature either by direct combination of solid
thiotrithiazyl chloride with a solution of the amine in
methanol-chloroform, or by percolating the amine solution over a
bed of thiotrithyiazyl chloride mixed with dry sand. Although .the
colored species generally decompose within a few minutes, linear
.366 HYDROCARBONS AND AIR POLLUTION
-------
calibration'curves are readily obtained by controlling reaction
conditions. These observations have been applied to the
determination of airborne toluene-2,4-diisocyanate at
concentrations as low as 0.01 ppm by volume. (Author abstracts)tt
06070
H. H. Bockind
INFRARED ANALYSIS OF HULTICOHPONENT GAS MIXTURES. Anal. Chen).
39, (6) 567-8U,~May 1967. (Presented at the 153rd National'
Heeting, American Chemical Society, Miami Beach, Fla., Apr.
9-1U, 1967.)
A new-method for the infrared analysis of multicomponent gas
mixtures which involves a condensed phase" sampling technique
employing commercially available cryogenic equipment is described.
Only a few micromoles of material are required for positive
qualitative identification of most chemical species; hence, the
method is sensitive and suitable for impurity analysis. The
technique is very general in its applicability.; Structurally
similar molecules are readily differentiated, and molecules
differing only in isotopic content may sometimes be distinguished.
Molecules are characterized by a small number of well defined ,
frequencies. The method permits analyses to be executed rapidly.
and is capable of creditable quantitative results. Herein
spectral analyses are demonstrated for a series of 13'C(1)
C(U) hydrocarbons. '(Author abstracts)i#
06112
Tada, 0.
HEASOREMENT OF AIB POLLUTANTS. Bunseki Kagaku (Japan Analyst)
(Tokyo) pp. 110R-7R. 1966. Jap.
Important papers published in Japan Analyst in 1964 and 1965 are
summarized. The subject is limited to measurement methods.of air
pollutants known to be toxic to health. Pollutants from stacks and
automobile exhausts are covered, including many cyclic
hydrocarbons, aldehydes, sulfur oxides, nitrogen oxides, ozone,
carbon monoxide, carbon dioxide, fluorine compounds, hydrogen
sulfide, lead compounds, and offensive odors. Various sampling
methods are described, especially using filtering .with glass wool
filters, electric dust collectors, gas absorbers, and portable
samplers containing silica gel. The pollutants can be measured by
electroconductivity methods, colorimetric measurement recorder, gas
chromatographic analysis, electron capturing detector, and hydrogen
ion detector. The papers summarized do not include those dealing,
with industrial or occupational environment or nining.
06135
Clemo, G. R.
SOHE CONSTITUENTS OF CITY SHORE. Tetrahedron 23, (5) 2389-93, Hay
1967.
D. Measurement Methods 367
-------
An interest in the complementary action of cigarette smoke and the
neutral constituents of city smoke prompted this study of the
isolation and identification of the aromatic jydrocarbons collected
on cotton filters through which air had been drawn for 10-12 weeks.
Chromatography on an alumina column of the neutral portion of the
atmospheric soot which had been eluted from the cotton filters with
a light petroleum gave a nuber of nitrogen-free hydrocarbons from
which the crystalline 1,3,5-trinitrobenzene complexes were
prepared. Identification was based on infrared, ultraviolet, and
mass spectrometry as well as on the melting points. Pyrene, 3-
methylpyrene, 1,2-benzpyrene, triphenylene, chrysene, 1,12-
benzperylene, and picene were isolated and identified.
The 3,t-benzpyrene was identified, but not the
non-aromatics which formed the bulk of the neutral portion.
Mass spectrometry showed that the most volatile fraction of the
light petroleum extract contained a series of 10 compounds with
molecular weights from which a.base, C13H15N, has been isolated.
06200
Stanley, Thomas W. James E. Meeker, and Hyrna J. Morgan
EXTRACTION OF OBGANICS FROM AIRBORNE PARTICULATES: EFFECTS OF
VARIOUS SOLVENTS AND CONDITIONS ON THE RECOVERY OF BENZO (A) PYHENE,
BEN(C) ACRIDINE, AND 7H-BENZ (DE)ANTHBACEN-7-ONE. Environ.
Sci.Technol., 1 (11) :927-931, Nov. 1967. 20 refs. (Presented at the
153rd National American Chemical Society Meeting, Miami, Fla.,
April 9-1U, 1967.)
Recently developed spectrophotometric and spectrophotofluorimetric
methods of analysis for several known carcinogens were applied in
studies of extraction efficiencies of solvent systems used to
obtain the organic tractions of airborne participates. Some of the
solvents investigated were pentane, benzene, cyclohexane, acetone,
diethyl ether, methylene chloride, and benezene: diethylamine (U:1,
V/V). Weights of organic extracts from known weights of carefully
composited air particulates ranged from 20 to 1300 mg. Variations
of time, temperature, and method of extraction affect total weights
of organic extracts and concentrations. In the analysis of equal
weights of air particulates enriches with pure benzo(a)pyrene,
benz(c)acridine, and 7H-benz (de)anthracen-7-one the percentages of
these compounds extracted ranged from 50 to 100, 15 to 100, and 40
to 80, respectively. On the basis of these data extraction
efficiency studies are reguired for the proper selection of
solvents used to define the organic extracts of airborne
particulates. (Author's abstract)
06203
K. T. Hhitby, and B. Y. H. Liu
GENERATION OF COUNTABLE PULSES BY HIGH CONCENTRATIONS OF
SUBCOUNTABLE SIZED PARTICLES IN THE SENSING VOLUME OF OPTICAL
PARTICLE COUNTERS. (IN: EVALUATION OF OPTICAL PARTICLE
COUNTERS-FINAL REPORT.) Minnesota Univ., Minneapolis,
Particle Technology Lab. (Particle Laboratory Publ. No.
110.) 25p., June 1967.
368 HYDROCARBONS AND AIR POLLUTION
-------
It is shown by analysis and has been confirmed by experiment that
large numbers of sub-countable particles in the sensing zone of
single particle optical counters generate spurious counts in the
counting range of the instrument. A statistical theory has been
developed which is capable of predicting the size distribution and
number of the spurious pulses from the concentration and -particle
size of the sub-countable aerosol. The theory has been extended
to atmospheric aerosols obeying the distribution law dN/dDp =
O.H1 phi D/t and it is shown that the-many sub-countable particles
present in atmospheric aerosols can account for the false mode
often observed when single particle optical counters are used to
size concentrated urban aerosols. it -is also shown that the
numerous sub-countable residue particles present in the atomized
poly-styrene latex aerosols can generate spurious .pulses in the
lower channels, thereby affecting the accuracy of this
calibration method.##
06231
A. Goetz and 0. Preining •
THE AEROSOL SPECTROMETER AND ITS APPLICATION TO NUCLEAR
CONDENSATION STUDIES. ((National Academy of Sciences-
National Research Council, Washington, DC)) Publ. 746.
(1960) pp. 164-82.
The Aerosol Spectrometer (A.S.) separates quantitatively
air-borne particles in the diameter range 3 microns to 0.03 micron
from the atmosphere in the form of a size-spectrum, i.e. a
continuous band-shaped deposit. The position of a particle
thereon is indicative of its "Stokes1 diameter" while'it was
air-borne, and .independent of physical etc.. changes incurred after
its separation from the suspending air. This size classified
separation results from the exposure of a laminar, continuous air
flow to a large centrifugal field (up to 26,000 g), the flow rates
vary between 3.3 and 7.4 lit/min. The size - (and mass-)
distribution of the aerosol is derived from the topical variation
of the deposit density along the spectrum. A brief description
of the instruments and the mathematical basis of the analytical
procedure is presented, as well as its application to a "model"
aerosol of polystyrene latex. From the size definition in terms
of the Stokes diameter a.-relationship between the locus of
deposition of dry and hydrated hygroscopic nuclei is derived and
subsequently supported experimentally for NaCl aerosols. The
A.S. has been applied to the analysis of natural and artificial
aerosols in the submicron range. The artificial generation and
conditioning of NaCl aerosols and the so resulting size
distribution is described. Traces of organic vapors during
hydration and dehydration prevent or delay the equilibrium of the
nucleus when the humidity of its gaseous environment is altered.
(Author summary)#f
06284
R. Buscaglia and S. Wallack
FEASIBILITY STUDY OF A MULTIPURPOSE INFBABED PROPELLAtiT
DETECTOR. (Patterson Hoos Research Division, Leesona
D. Measurement Methods 369
-------
Corp., Jamaica, N.Y.) (ASD Technical Rept. No. 61-382.)
(Aug. 1961) . 22 pp.
This investigation was concerned with determining the
feasibility of developing open-path narrow absorption infrared
(NAIR) instrumentation capable of detecting and measuring
very low atmospheric concentrations of various toxic propellant
vapors. In the course of this program a novel measurement
system was conceived, and a laboratory prototype of this system
was designed and fabricated. Because of the unique spectral
response characteristics of the NAIR detector, it was
possible to combine in this one instrument the desirable features
of both single and double beam instrumentation. The system
was applicable to ethylene oxide, unsymmetrical dimethyl-hydrazine,
dinitrogen tetroxide and hydrazine. Tests performed with this
prototype instrument demonstrated system feasibility.
The measurement sensitivity was, in all cases, within one order
of magnitude of that required; in most cases it was
substantially better than this. Sensitivity to ethylene oxide
exceeded the specified requirements. In addition to
demonstrating feasibility and determining sensitivity, these
tests also indicated several simple modifications which
would substantially reduce noise and thereby improve
sensitivity. (Authors* abstract)##
06301L
MECHANISMS OF AIB POLLUTION REACTIONS. - (Section VIII of
Air Pollution Research Progress Report for Quarter Ended
December 31, 1966.) Bureau of Mine's, Pittsburgh, Pa.,
Coal Research Center, 1966, pp. BM/69-BM/76.
The NOx-sensitized photooxidation of 2-methyl-1-butene was
investigated. Yields with regard to the reaction production
formaldehyde, methyl ethyl ketone, PAN, PPN, nitrates and
CO were determined. The study of the NOx-sensitized
photooxidation of tagged ethylene in the presence of other
hydrocarbons was terminated. Results indicated that (u) the
photochemical reactivity of ethylene in mixture with other
hydrocarbons varies with change in the mixture composition, and
.(2) the variation is unpredictable at the present time. (Author
summary)*t
06328L
J. D. Mocker
ANALYSIS OF COMBUSTION PHODOCTS WITH GAS CHROMATOGRAPHY
APPARATUS (A MASTER'S THESIS). (1963). 63 pp. (For the
degree of Master of Science, Arizona Univ., Tucson.)
DDC: AD «102«0
The purpose of this study was to develop techniques for applying
principles of gas chromatography to the analysis of fuel gases and
combustion products. By effective calibration of the gas
chronatography apparatus, unknown samples of combustion products
370 HYDROCARBONS AND AIR POLLUTION
-------
and fuel gases were analyzed both quantitatively and qualitatively.
The procedure employed was to use known mixtures of pure gases and
to record on an electronic recorder the response of the gas
chromatography apparatus. Six different gases were used in the
calibrating mixtures: H2, 02, N2, CH4, C02 and CO.
Techniques, procedures and methods were established to identify
the composition of unknown samples by the application and
principles of gas chromatography. (Author abstract)##
06380
Dubois, L., A. Zdrojewski, C. Baker, and J. L. Honkman
SOME IMPROVEMENTS IN THE DETERMINATION OF BENZO(A)PYHENE IN
AIR SAMPLES. J. Air Pollution Control Assoc.,
17(12):818-821, Dec. 1967. 10 refs. (Presented at the 60th
Annual Meeting, Air Pollution Control Assoc., Cleveland,
Ohio, June 11-16, 1967.)
As benzo (a) pyrene (BaP) and benzo(k)fluoranthene (Bk) both
fluoresce strongly and it is possible to make accurate measurement
of BaP in the presence of BkF in an unchromatographed air
sample extract using fluorescence, this measuring technique served
as the basis of the research discussed here. In this method
benzene was first used as the extracting solvent, the colusns being
processed in a fume hood on account of its well known toxicity.
As more experience was gained it was found that toluene could also
be used with satisfactory results and benzene was abandoned as an
eluting agent. Both benzene and toluene, with their aromatic
structure, would be quite unsuitable eliting agents if subsequent
measurements were to be made by ultraviolet absorption. Since in
this method fluorescence is used, the aromatic structure is
irrelevant. The essential condition is that the toluene used be
free from fluorescing impurities. The method is simple and
direct, and probably demands somewhat less skill and experience
than older methods. It is worth mentioning that the calculations
of the final values require an appreciable percentage of the total
analytical time. The use of a programmed bench top computer
reduces this calculation time for 20 samples from 5 hoars to 5
minutes.##
06U33
Singh, T., R. F. Sawyer, E. S, Starkman, and L. S.
Caretto
RAPID CONTINUOUS DETERMINATION OF NITRIC OXIDE CONCENTRATION IN
EXHAOST GASES. J. Air Pollution Control Assoc.,
18(2):102-105, Feb. 1968. 8 refs, (Presented at the 60th
Annual Meeting, Air Pollution control-Association,
Cleveland, Ohio, June 11-16, 1967, Paper 67-151.)
A continuous sampling, continuous analysis method for measuring
nitric oxide was demonstrated. Bapid oxidation of nitric oxide to
nitrogen dioxide is obtained through ozonation. Nitrogen dioxide
concentrations are determined by means of an ultra-violet
absorption technique. Nitric oxide concentrations between 100 and
5000 ppm have been measured and response times of about 20 sec
D. Measurement Methods
-------
obtained. The presence of unburned hydrocarbons in the exhaust
sample has an adverse effect on the results of this technique vhich
requires either the removal of hydrocarbons or adjustment of ozone
concentration. (Authors' abstract, modified)f#
06U35
Smith, D. S., B. F. Sawyer, and E. S. Starkman
OXIDES OF NITROGEN FROM GAS TURBINES. J. Air Pollution
Control Assoc., 18(1):30-35, Jan. 1968. 6 refs. (Presented at
the 60th Annual Meeting, Air Pollution Control Association,
Cleveland, Ohio, June 11-16, 1967.)
Experimental and theoretical studies were made to provide
information on nitrogen oxide concentrations produced by gas
turbine engines. Nitric oxide concentrations of from 100 to 350
ppm, adjusted to stoichiometric conditions, were measured in
aircraft turbojet engines. Concentrations of less than 50 ppm,
similarly adjusted, were measured in a 60 hp industrial gas
turbine. Concentrations of about 100 ppm, also adjusted, were
measured in a laboratory combustor of a design similar to gas
turbine combustors. Carbon monoxide and unhurried hydrocarbon
concentrations also were determined. Comparison with predicted
equilibrium concentrations shows strong departures from
equilibrium. (Authors' abstract)##
06«45
K, T. Whitby
RECENT AEROSOL RESEARCH - UNIVERSITY OF MINNESOTA. Preprint.
(Presented at the 60th Annual Meeting, Air Pollution Control
Associztion, Cleveland, Ohio, June 11-16, 1967, Paper No.
67-103.)
Polystyrene aerosols produced by an improved generator (described
in study) have been studied with respect to the electrostatic
charge on the polystyrene particles and the size distribution and
charge on the residue aerosols resulting from the evaporation of
the non polystyrene containing droplets. The median number of
unit charges and standard deviation g of the charge distribution
found on the plus and (-) particle is summarized. The PSL
charges found are great enough to have a serious effect in many
experimental applications. Diffusion and field charging studies
.of micron and submicron aerosols at pressure from atmospheric to 1
torr have been made. A new diffusion charging theory based on an
improved kinetic model has been developed. The final equation
which is identical in form to the White diffusion charging
eguatio'n has been shown by experiment to be satisfactory for
Knudsen numbers from 0 to 1 and by calculation to be satisfactory
for large-r Knudsen numbers. Work on an improved field
charging theory for Knudsen numbers on the order of 1 is in
progress. Considerable data has been obtained and an improved
theory has been developed. A two stage electrostatic aerosol
sampler of accurate sampling of micron and subnicron size aerosols
372 HYDROCARBONS AND AIR POLLUTION
-------
onto any flat collecting surface of an area up to 50 sg. cm has
been developed. The concentration and size distribution of
particles from 0.001 to 3 microns in radius dispersed in the urban
atmosphere was measured with a continuous-sampling sizing system
composed of a nuclei counter, an electrical particle counter, and
an optical counter. Atmospheric aerosol size distribution
measurements made by previous investigators were reviewed and
compared with the new information.##
06471
H. H. G. Wyeth and G. W. Timmins
DETECTION AND MEASUREMENT OF INFLAMMABLE VAPOURS IN AIRCRAFT.
Ministry of Aviation, Farnborough Hants, England, Royal
Aircraft Establishment. (Hept. No. 65191.) (Sept. 1965). 74
pp.
DDC: AD477 232
A study is made of the feasibility of detecting and measuring
concentrations of inflammable vapour within compartments of
aircraft in flight. The basic requirements are outlined. A
review is made of properties of inflammable vapours that might be
exploited. Mention is made of some existing instruments and
techniques, and their limitations for the present purpose are
discussed. Especial emphasis is given to techniques of catalytic
combustion and ionization which with further development are
thought likely to be suitable. (Author summary)
06504L
J. M. Beebe and E. L. Dorsey
A FLUORESCENT DYE TRACER AS A MEANS FOR DETERMINING PHYSICAL
DECAY RATES OF AEROSOLS. Army Biological Warfare Labs.,
Fort Detrick, Frederic, Md. (Aug. 1958). 21 pp. (BWL
Technical Memorandum 8-4.)
The use of fluorescein as a dye tracer for the determination of
the physical decay rates of aerosols was investigated. Two types
of chambers were used for most of the preliminary experiments: a
20-liter horizontal irradiation .chamber, and a 1500 -liter, 6 foot
diameter toroid which can be revolved at speeds of from 0.27 rpm on
up, for periods up to 24 hrs or more. Small chamber clouds were
generated by a Vaponefrin Nebulizer Clouds in the toroid were
generated by a modifed DCTL atomizer. The spray medium in all
cases was beef heart infusion. Two methods of sampling were
employed. The small chamber samples were collected on
Hillipore Filters. Samples from the toroid were collected in
standard 2.5 1/min impingers, containing 10 ml of glass-distilled
water. Fluorometric analyses of the above dye solutions were
made with a Light Scattering Microphotometer. A standard
curve, showing the relationship between a known dye concentration
and photomultiplier reading, was established with the particular
dye lot to be used. A separate curve must be developed for each
dye, or dye lot, and/or for each solvent in which samples are to be
collected, since some impinger fluids contain materials that will
0. Measurement Methods 373
-------
fluoresce. Whenever possible samples were collected in
glass-distilled water, or on MF filters and then dissolved out
established for a particular dye lot and solvent it was but a
matter of a few minutes to determine the dye content of a series
of samples. The method is simple and can be performed rapidly
with a high degree of precision, sensitivity and reproducibility.*t
06624
B. A. Saunders
ANALYSIS OF THE SPACECRAFT ATMOSPHERE. Naval Research Lab.,
Washington, D. C. , Chemistry Div. (NRL Rept. No. 5816.)
(Oct. 23, 1962) . 21 pp.
DDC: AD 288 255
A study has been made of the nature of the contaminants introduced
into the cabin atmosphere of a Project Mercury space capsule,
external to the pressure suit, by the deliberately induced
malfunction and overheating of certain parts of the capsule
equipment during simulated flight. The contaminants were
collected and concentrated by an adsorption-desorption cycle
employing activated charcoal as the adsorbing medium. An
analytical gas chromatograph was used to resolve the components of
the contaminant mixture, which were then recovered individually
from the effluent stream of the chromatograph and identified by
means of their infrared spectra. Thirty-five components were
detected in this atmosphere, 26 of which were identified.
Approximate minimum concentrations have been indicated for the
latter. The contaminant mixture comprised aliphatic and aromatic
hydrocarbons, chlorinated hydrocarbons, and aliphatic alcohols,
esters, and ketones. Some of the contaminants were present in
sufficient concentration that they could possibly reduce the
effectiveness or efficiency of an exposed pilot. (Author
abstract) #*
06634
K. Wettig
ESSAY ON THE PROBLEMATICS CONCERNING THE DETERMINATION OF
BENZPYRENE IN ATMOSPHERIC AIR. Neoplasma 14 (2), 181-4 (1967).
A proposal of method of hydrocarbon determination, which takes
into consideration the problems of interpretation, is discussed.
The majority of toxic substances in atmospheric air is present in
the same form in which they take effect in vivo. The degree of
concentration of a given, injurious substance, is in most cases a
measure for the endangerment of the health of human beings. Quite
different, however, is the cancerogenic effect of polycyclic
hydrocarbons in the air. The conclusions drawn from the
atmospheric content of cancerogenic hydrocarbons with regard to the
endangerment of health of human beings depends solely in the
assumption, that the total content of hydrocarbons stands in
correlation with the active hydrocarbons. Owing to the
diversities of the possibilities which govern the formation of
"active" hydrocarbons, such a correlation is naturally very
questionable. A better approximation may be attained by using a
274 HYDROCARBONS AND AIR POLLUTION
-------
method consisting of the following steps in succession: The
splitting-up of an aspirated sample .of dust into its components
according to the diameter of the separate particles; The portional
extraction of the particles having a diameter of 100 to 5000
micrograms with a simulated body-liquor for.a period of time
corresponding to the time of retention of the dust particles in
the human lung; and Review of the cancerogenic activity of the-
extract. The usual.determination of the content of hydrocarbons
in atmospheric air cannot be replaced but merely supplemented by
procedures tor the determination of'their.active components, as the
knowledge of the total amount of the various hydrocarbons permits
conclusions to be drawn with regard to their origin, this being of
great importance for the removal or abatement of emissions.ft
06661
E. G. Kachmar
DETERMINATION OF BENZENE TOLUENE ANE XYLENE SIMULTANEOUSLY
PRESENT IN THE AIR . U.S.S.R. Literature on Air Pollution
and Related Occupational Diseases, Vol. 7, 1i»3-7, 1962.
(Gigiena, i Sanit.) 258 (5) 58-62, 1960. Translated from
Russian.
CFSTI: 62711103
The new methods in this presentation were based on the formation
of azo-coopounds. Benzene was nitrified with a 10% nitration
mixture to the dinitro form, which was then reduced with metallic
zinc, diazotized in the presence of concentrated hydrochloric acid
by a 1% solution of sodium nitrate, and combined with
m-phenylenediamine. The resulting azo-comppund is of a yellow-
brown color. The sensivity of,this reaction is 0.005 mg in the
volume used for colorimetry.- A series of experiments were
performed with.known amounts,of benzene determined on a parallel
basis, by, the azo-compound formation and,the Yanoyskii reactions.
Control-tests showed that the-presence of an'egual amount of
toluene and of an' equivalent 60S amount of xylene, did not
interfere with the determination. The toluene determination
method consisted in the reduction of trinitrotoluene and the
combination of the reduced products with diazotized sulfanilic
acid. The sensitivity of the reaction was 0.01 mg of toluene in
the colorimetric volume. Additional control tests showed that the
presence of an equal concentration of sylene and of half the
equivalent volume of benzene did not interfere with, the
determination. No suitable basis found for the development of a
method for xylene determination in the presence of toluene; for
this reason; xylene w.as separated from benzene and toluene. The
following studies were made; 1) conditions of benzene, toluene and
xylene absorption on silicagel; 2) conditions of desorption such as
effects of temperature and air' volume passed through the silicagel
in order to displace the benzene, toluene and sylene. On the
basis of results obtained conditions for the separation of xylene
from benzene and toluene are recommended.##
0., Measurement Methods 375
-------
06662
P. P. Dikun
QUATITATIVE DETERMINATION OF LOW 3, 4-BENZPYRENE CONCENTRATIONS
WITH FINE STRUCTURE FLUORESCENT SPECTRUM . U.S.S.B.
Literature on Air Pollution and Related Occupational
Diseases, Vol. 7, 153-69, 1962. (Vopr. Onkol.) 7, (7) U2-53,
1961. Translated from Russian.
CFSTI: 62-11103
A new method is described for the determination of lower 3,
t-benzpyrene concentration than with any previous tests. This
method combines the principle of spectrofluorometry with the
fine structure spectral fluorescence phenomenon described by E.
V.- Shpol'skii. Quantitative determination is based on ratio
between 3,U-benzpyrene and 1,12—benzoperilene absorption intensity
lines. By the fine structure spectral fluorescent method,
determinations can be made of 0.05 - 0.10 gamma or less of 3, i»-
benzpyrene per sample with a high degree of accuracy. Average
deviation of 15 control tests was only + or — 855. Deviations ex-
ceeding 10% occurred in 3 of the 15 control tests, and none ex-
06682
D. N. Sunderman, J. E. Howes, and H. S. Tosenberg
THE DEVELOPMENT OF AN IMPROVED METHOD OF SAMPLING AND ANALYSIS
FOR ATMOSPHERIC IODINE . (Battelle Memorial Inst., Columbus,
Ohio.) (July 22, 1965). 20 pp. (Rept. No. BMI-X-10137.)
The feasibility was studied of an iodine sampler which will be
somewhat analogous to a gas-liquid chromatographic column
although the separation of the iodine species will not employ the
chromatographic principle. The system will consist of a column
of sodium bisulfite particles or sodium bisulfite on a solid
matrix such as Chromasorb, coated with*a viscous organic solvent.
A glass-fiber filter will precede the column to remove particulate
iodine from the sample stream. In operation, the elemental iodine
and organic iodine compound will be absorbed and retained by
dissolution in the organic film on the particles. The elemental
iodine will diffuse to the interface between the liquid and solid
phase, react with the solid phase to form the iodide, and thus be
separated from the organic iodide. Gaseous inorganic iodine
compounds are expected to be absorbed on the surface of the .organic
film or pass through the column unaffected. Following the
sampling period, water would be passed through the column to elute
any water soluble iodine compounds, organic iodides would be
recovered by dissolution of the organic phase with a solvent, and
the sodium bisulfite particles would be recovered to obtain the
reacted, elemental iodine. Reaction studies between the various
forms of iodine, dodecane, and NaHS03 indicate that the
proposed io'dine sampling technique is feasible. Elemental iodine
and methyl iodide will dissolve in the stationary liquid phase.
Methyl iodide will remain in stationary liquid, while the
elemental iodine will be reduced to the iodide by solid NaHS03,
the solid support material. The experiments show that both at
2tt C and 100 C the extraction efficiencies for elemental iodine
are better than 9i» per cent after 15 minutes contact times. The
376 HYDROCARBONS AND AIR POLLUTION
-------
extraction of iodine in the solid NaHS03 should occur rapidly,
therefore, reaction with the organic phase will not be significant.
The experiments also show that no apparent reactions occur between
the methyl iodide and the reducing phase1,' When iodine was
extracted front a mixture of methyl iodide, iodine, and dodecane,
isotopic exchange occurred between the iodine and methyl iodide.
When Nal and HI solutions were contacted with dodecane, I-
in solution did not react with dodecane.f#
06699
C. F. Ellis, R. F. Kendall, and B. H. Eccleston
IDENTIFICATION OF SOME OXYGENATES IN AUTOMOBILE EXHAUSTS BY
COMBINED GAS LIQUID CHROMATOGRAPHY AND INFRARED TECHNIQUES.
Jnal. Chem. 37 (4) 511-6 (Apr. 1965).
A method for identifying certain oxygenates in automobile
exhausts by gas liguid- chromatography with confirmation by
infrared spectra is described. The oxygenates were separated from
exhaust gases by scrubbing with a 1% solution of NaHS03,
Then, oxygenates which eluted ahead of water were separated from
the solution iji a preparatory column. The carbonyls indicated in
the chromatograms were derived from the thermal decomposition of
the bisulfite complexes of these compounds in the
chromatographic column. The eluted oxygenates were collected in a
cold trapping needle and charged to an analytical GLC unit
employing thermal conductivity detection. A chromatogram was thus
obtained, and the individual components indicated in the sample
were collected in separate plastic bags and transferred to a
10-meter infrared cell for confirmation of the GLC IDENTIFICA-
tions., Acetaldehyde, propionaldehyde, isobutyraldehyde, n-
butyraldehyde, acetone, methyl ethyl ketone, methanol, and ethanol
were present. Acrolein cannot be detected by this method. After
identification of the oxygenates present, GLC analyses
employing flame detection were made directly upon the scrubber
solutions and also on preparatory column effluents.ft
06702
Pagnotto, L. D. and L. M. Lieberman
ORINARY HIPPORIC ACID EXCRETION AS AN INDEX OF TOLUENE EXPOSURE.
Am. Ind. "Hyg. Assoc. J., 28(2):129-134, Harch-April 1967.
20 refs. (Presented at the 27th Annual Meeting, American
Industrial Hygiene Assoc., Pittsburgh, Pa., May 1966.)
A simple procedure is described for the analysis of hippuric acid
in urine. The sample is extracted with an isopropyl,
alcohol-diethyl ether mixture, and the hippuric acid is measured in
the extractant by ultraviolet spectrophotometry. The excretion of
hippuric acid in urine as a metabolic product of toluene was
studied in relation to its usefulness in industrial exposures
to toluene. Good correlation of hippuric acid content of
end-of-shift samples and toluene exposure was found in studies
performed in leather-finishing and rubber-coating plants. The
0. Measurement Methods* 377
-------
hippuric acid test was also found to be useful in measuring the
adequacy of cartridge-type respirators in tank painting vork.
Air-urine correlation, although not complete, suggests that
exposures to 200 ppm (HAC) of toluene would produce a urinary
hippuric acid content of about 7.0 gin/liter or 5.0 gm/gm of
creatinine in samples collected at the end of the work shift.**
06858
A. Richardson, J. Robinson, E. Bush, 'and J. H. Davies
DETERMINATION OF DIELDFIN (HEOD) IN BLOOD. Arch. Environ.
Health 14 (5), 703-8 (Hay 1967).
Two methods for the determination of HEOD (1,2,3,1,10,10,
hexachloro-6, 7 epoxy-1, i*,i»a, 5,6,7, 8,8a-octahydro-1, •» endo,
exo-5, 8-dimenthanonaphthalene (Dieldrin) in blood were
assessed. The procedure using acetone as an extraction
solvent gives reproducible results and is rapid. The precision
of the extraction procedure, as reassured by the coefficient
of variation, is of the order of 6%. The accuracy, assessed
by comparison with the destructive hydrolysis technique, does not
appear to differ significantly from 100%. Evidence has been
obtained that the concentration of HEOD in the blood of the
same person can vary in random manner from time to time, and the
coefficient of variation for samples of blood collected at differ-
ent times from the same person is about 25%. The aceton extraction
procedure is nondestructive and should therefore be applicable
to the determination of the organochlorine insecticides,
particularly those which are unstable to alkalies and their
metabolites.*#
06876
F. H. lagoshnaya and N. A. Zhuravleva
DETERMINATION OF FREON-22 IN AIB. (Kolichestvennoe
opredelenie freona-22 v vozdukhe.) Hyg. Sanit. (Gigiena i
Sanit.) 30 (6), 366-71 (June 1965). Huss. (Tr.)
The colorimetric and manometric methods for the determination of
Freon-22 in the air were described. The colorimetric method is
applicable for freon-22 concentrations in the air ranging from 0.5
to 0.00006% and the analytical time is approximately five minutes.
The manometric method makes possible the determination of freon-22
in the air for concentrations ranging from 0.5 to 15 vol. % and the
analytical time is 10 to 15 minutes.##
06893
Belyakov, A. A., and V. G. Smirnova
DETERHINATIOH OF FDHFUROL IN THE AIH. ((Opredelenie furfurola
378 HYDROCARBONS AND AIR POLLUTION
-------
vozdukhe.)) Hyg. Sanit, (Fifiena i Sanit.) 30 (3):390-391,
Mar. 1965.. Translated from Russian.
CFSTI: , TT 66-51033
Methods based on color reaction with aniline have been proposed
for determining furfurol vapors in the air of industrial premises.
The reaction results in the formation of dianilide of
oxyglutaconic aldehyde, belonging to the class of polymethine dyes.
A common defect of these methods is the instability of dyed
solutions, which is reflected in the reproducibility of the
results. Using the above-mentioned reaction, the authors were
able to find the conditions for a more reliable determination of
furfurol in the air. They used 98% of icy acetic acid as the
absorbent solution and solvent. An aniline concentration within
the limits of 50-70 mg per ml of acetic acid is perferable. In
this case the dying of the solutions reaches the maximum in 15
minutes and is preserved unchanged for the next 45 minutes.
Furfurol vapors are well absorbed by acetic acid. To determine,
for instance, the maximum permissible concentration of furfurol
(0.01 mg/1), it suffices to pass not more than 25 ml of air
through an absorbing instrument with 2 ml of acetic acid. The
air humidity is apparently little detained by the icy acetic acid.
Thus, the sucking of up to 10 1 of air through the absorbing
instrument with 2 ml of acetic acid containing 0.5-5 ug of furfurol
is not reflected in the results of the determination.##
0689«
Razumov, V. A., and T. K. Aidarov
A FAST METHOD FOR DETERMINING LEAD IN THE AIR. ( (Oskorennyi
netod opredeleniya svintsa v vozdukhe.)) Hyg. Sanit. (Gigiena
i Sanit.), 30(3):392-39U, Mar. 1965. Translated from Russian.
CFSTI: 66-51033
In a number of cases there is a need for rapid and accurate
determination of the lead aerosol content in the air. The usual
chemical and physicochemical methods applied for this purpose are
rather lengthy and labor-consuming. The most advantageous is
color reaction on paper"without any previous working of the ground.
The fullest response to all requirements is afforded' by the color
reaction with tetrahydroxy-p-benzoquinone. Here a legible scale
is obtained for microgram parts of lead on paper, the pink coloring
lasts for up to six months, and the reagent solution itself is
stable for up to 4- months. Antimony, bismuth, zinc, copper, iron,
arsenic, chromium and calcium, also cadmium (in equal
concentrations with lead) do not interfere with determination.
The air sample was taken out with an aspirator plant at a rate of
3 1/min onto filter paper (blue band). When the lead content is
within the normal limits, 10-15 1 of air have to be taken. A
disk of paper 17 mm in diameter was placed in a plexiglas holder of
the proper dimensions, and a drop (0.05 ml) of reagent was applied
to the filter in the holder; after it had dried, samples were
taken, and then a drop (0.05 ml) of buffer solution was applied.
The pink coloring appeared at once. Then the filter was taken
out of^the holder and was placed on clean filter paper (with the
coloring upward) to dry. After a few seconds, the coloring was
compared with the scale on the paper obtained by the analogous
sethod-for certain lead concentrations. The sensitivity of the
D. Measurement Methods 379
-------
method was 0.015 ug in the drop (0.05 ml). For more reliable
results, it is better to make two parallel (in the worst case,
successive) determinations. The duration of one determination is
not more than seven minutes, if the air contains lead in more than
the normal amount.##
06902
B. V. Gorskaya
A NEW PHOTOCOLOBIMETBIC METHOD FOB THE DETEBMINATION OF
NAPHTHALENE IN AIR. (Novyi fotokolorimetricheskii metod
opredeleniya maftalina v vozdukhe.) (Hyg. Sanit). (Gigiena i
Sanit.) 30 (11), 243-4 (Nov. 1965 Buss. (Tr.)
A photocolorimetric method for routine analysis of naphthalene
is described. The method was tested under industrial conditions
by determining the naphthalene in the air of the naphthalene shop
of the Rutchenkovskii coke-chemical plant. Interference by
phenols was prevented by trapping them first in an absorber
containing 0.1 N alkali which was placed in front of the
absorber for the naphthalene. The determination was carried
out by two methods, with a nitrating mixture and with
alloxantin. There was good agreement between the results.#t
06903
I. A. Pinigina
THE SEPARATION AND DETEBHINATION OF ALIPHATIC ALCOHOLS IN AIB BY
PAPER CHROHATOGRAPHY. (Razdelenie i kolichestvennoe
opredelenie alifaticheskikh spirtov v vozdukhe s pomoshch'yu
khromatografii na bumage.) Hyg. Sanit. (Gigiena i Sanit.)
30 (11), 244-9 (Nov. 1965). Buss. (Tr.)
Separate determination of aliphatic alcohols (C1-C10) that
simultaneously pollute the air in factories manufacturing
synthetic alcohols was accomplished by paper chromatography.
Volatile compounds can be determined by paper chromatography after
their conversion to nonvolatile compounds. The alcohols are
converted to the benzoates. The derivatives of alcohols C1-C6
arranged themselves on the chromatogram in the order of
increasing number of carbon atoms. The derivatives of alcohols
C7-C10 arranged themselves on the chromatogram in the
descending order of the number of their carbon atoms. The
alcohols can be quantitatively determined by chromatographic
separation, by means of the intensity of the color of the spots
formed by their eluates. In the case of alcohols C1-C6, the
color is eluted and the optical density of the elute measured with
an SF-4 spectrophotometer or a photocolorimeter.
Quantitative determination of the alcohols .C7-C-10 was
performed visually by comparing the color intensities of the
sample spots with those of reference spots made with standard
solutions.f #
380 HYDROCARBONS AND AIR POLLUTION
-------
06955
R. N. Inscoe
PHOTOCHEMICAL CHANGES IN THIN LAYER CHROBATOGBABS OF POLYCYCLIC,
AROMATIC HYDEOCAEBONS. Anal. Chem. 36, 2505-6 (Dec. 1964).
The change in spot color due to photochemical changes of thin
layer chromatograms in the identification of polycyclic aromatic
hydrocarbons was discussed. The changes were observed on spots of
15 representative hydrocarbons following exposure to ultraviolet
light. The absorbents used were silica gel G, aluminum oxide G,
cellulose powder, and acetylated cellulose (21S). After the
initial exposure to ultraviolet light, the changes take place even
•hen the plates are kept in the dark. Similar, but slower,
changes also occur on plates kept in ordinary roomlight, without
exposure to other ultraviolet illumination. The changes are
accelerated by continuous irradiation, either by long-wavelength
ultraviolet light or by light of 253.7 millimicron. The nature of
the developing solvent appears to have little effect on the colors
observed. The presence of solvent often accelerates the changes
in the spots. This effect is particularly noticeable with
chlorinated solvents.##
07061
». E. Whitman and A. E. Johnston
SAMPLING AND ANALYSIS OF AROBATIC HYDROCAEBON VAPORS IN AIR: A
GAS-LIQUID CHFOHATOGHAPHIC METHOD. Am. Ind. Hyg. ASSOC. J.
25 (5) , «64-9 (Oct. 196U) .
The sampling and analysis of air for mixtures of benzene, toluene
and xylene vapors are described. The application of a molecular
sieve prefilter to remove water vapor and a silica gel adsorption
tube for the collection of the hydrocarbon was investigated. The
development of a method for the extraction of aromatic hydrocarbons
from silica gel and their subseguent estimation by gas
chromatography is reported. The method is sufficiently sensitive
to permit accurate measurement at 10% of the MAC level.
(Authors' abstract) ##
07097
L. H. Piette, J. H. Sharp, T. Kuwana, and J. N.
Pitts, Jr.
PARAMAGNETIC RESONANCE OF SOBE BENZOPHENONE DERIVATIVES IN THEIR
PHOSPHORESCENT STATE. J. Chem. Phys. , 36 {11} , 309U-5 (June
1, 1962) .
Paramagnetic resonance absorption of the triplet or phosphorescent
state in several para-substituted derivatives of benzophenone was
observed. The phosphorescent states are formed during uv
irradiation of the compounds in rigid solutions at liquid-nitrogen
temperatures. Solutions of 4-aminobenzophenone,
D. Measurement Methods 381
-------
4-diraethylaminobenzophenone, 4,4', bis- (dimethylami.no)benzophenone,
and i»-phenylbenzophenone were irradiated at 77 deg K.
Paramagnetic resonance absorption was observed for all the above
compounds at a magnetic field of about 1500 gauss, (g equals 4).
In addition to paramagnetic resonance absorption at g equals 4,
the irradiated solid solutions show strong phosphorescence. This
phosphorescence decays exponentially with a mean lifetime of 0.41
plus or minus 0.04 sec and agrees favorably with the decay of the
paramagnetic resonance absorption signal when the light is cut "off.
Mean phosphorescent lifetimes of the other'compounds range from
0.2 to 0.4 sec and are being correlated with the decay of their
EPR signals at g equals 4.##
07104
HcEwen, D. J.
IMPROVED SAMPLING VALVE FOR GAS CHROBATOGHAPHY. J.
Chromatog., Vol. 9, p. 266-269, Oct. 1962.
For the gas chromatographic analysis of engine exhaust and air for
trace amounts of hydrocarbons, a gas sampling valve with the
following features was required: (I) no detectable gas leaks,
(2) no contamination or adsorption of the sample, (3) past
switching speed for instantaneous sample injection, (4)
interchangeable sample volumes with the smallest about 0.1 ml, and
(5) good sampling precision. A four-way solenoid valve for use
with industrial gas chromatographs leaked seriously, but otherwise
showed promise of meeting the above requirements. A method for
making the valve gastight and an example of the use of the valve
in the analysis of highly diluted hydrocarbon mixtures are
discussed. In the disassembled valve the stainless steel part is
separated from the brass base by a Teflon diaphragm, which opens
and closes the valve ports by means of air pressure. The J
surfaces separated by the diaphragm bore the marks (mainly long
scratches) of the grinding operation in the manufacture of the
valve. It was found that the valve could be made gastight with
Teflon diaphragms by polishing both surfaces to a mirror-like p
finish. The smallest sample that has been measured with the *
valve is 86 ul. The precision of the valve has not been
extensively investigated; however, the average deviation of,peak
heights for repeat analyses of dilute hydrocarbon mixtures is"
usually better than plus or minus O.SX.tt
07146
Gronsberg, E. Sh.
DETERMINATION OF VINYL CHLOBIDE IN THE AIR. D.S.S.R.
Literature-on Air Pollution and Related Occupational
Diseases, Vol. 1:148-150, Jan. 1960. (Also published in
Gigiena i Sanit., No. 11:43-44, 1954,) Translated from
Russian.
CFSTI: TT 60-21049
The procedure described is based on bromination in chloroform
solution with a bromine solution in a 1:1 Mixture of glacial acetic
382 HYDROCARBONS AND AIR POLLUTION
-------
acid and chloroform. The method is sensitive to 0.10 mg of vinyl
chloride per test., The absorption of vinyl chloride from air is
accomplished by -aspirating the tested air through chloroform kept
at -10 to -15 deg., at the rate of 10 - 12 liters per hour. This
method is specific in the presence of methanol and dichlorethane.
Observing the additional steps and precuations indicated obviates
the interference of ethylene and of chlorine.**
07150
Dzedzichek, V. P. and A. V. Demidov
APPARATUS FOB THE DETERMINATION OF CARBON MONOXIDE AND CARBON
DIOXIDE IN THE AIR AND OF GASEODS COMPONENTS OF LIQUID FUEL.
U.S.S.B. Literature on Air Pollution and Related
Occupational Diseases, Vol. 1:168-177, Jan. 1960. (Also
published in Lab. Delo 3(
-------
07156
Senderikhina, D. P.
DETERMINATION OF PARAFFIN AND CERESIN AEROSOLS IN THE AIB OF
INDUSTRIAL PLANTS. U.S.S.P. Literature on Air Pollution
and Related Occupational Diseases, Vol. 1:206-207, Jan. 1960.
(Also published in Gigiena i Sanit., 23(8):77-78, 1958.)
Translated from Russian
CFSTI: TT 60-21049
For quantitative determination of petroleum paraffin vapor its
differential characteristics of dissolving readily in ether and
with difficulty in ethanol were utilized. The ethanol is added to
the ether-dissolved petroleum paraffin and cooled to 0 deg which
causes the paraffin to separate from solution as an emulsion whose
turbidity 'varies directly with the quantity of the dissolved
paraffin. The standard solution to be used in the turbimetric
comparator is prepared from a weighed amount of petroleum paraffins
in ethyl ether, usually 1 mg per ml. Quantitative analysis of
synthetic cerecin is done gravimetrically by aspirating through
a glass filter No. 2 at the rate of 0.2 lit./min. using ether
as the absorber. The absorbed cerecin is removed from the glass
filter plate by dissolving it in hot gasoline; the latter is driven
off by evaporation in a preweighed porcelain dish over a waterbath.
After the gasoline has been evaporated the dish is cooled for
20 - 30 minutes in a desiccator and weighed on an analytical
balance.##
07285
Khrustaleva, V. A.
DIFFERENTIAL DETERMINATION OF ORGANIC AND INORGANIC LEAD IN THE
AIR OF GARAGES. Text in Russian. Gigiena i Sanit. No.
9:i»8-U9, 1952. Engl. transl. by B. S. Levine, O.S.S.R. Lit.
on Air Pollut. 6 Relat. Occup. Dis., Vol. 2, p, 8-10,
Harch 1960.
GFSTI TT60-21188
Air samples tor the determination of inorganic compounds should be
collected by aspirating 300 - 500 li of air through absorbent
cotton at a rate of 10 li/min. With reference to tetraethyl lead
it "may be stated that, owing to the presence of carbon monoxide and
vapors of hydrocarbons in the air, and the nonspecificity of the
method, its determination in the form of intact molecules is not
feasible. It is necessary first to destroy the molecules and to
proceed with the determination of free lead. For this purpose
tetraethyl lead is absorbed from the air into alcohol at a rate not
exceeding 1 li/min, i.e. , 60 li per hour; at a higher rate
evaporation of t'he alcohol-dissolved tetraethyl lead will take
place. By the method used in this study metallic lead
determinations could be made reliably .with 0.002 - 0.005 mg as the
lower limit. For the collection of tetraethyl lead air samples
the use of conventional equipment "is proposed, such as a suction
dust collector, a high velocity flowmet'er, corrugated tubes as
adapters for cotton filters to retain metallic lead, and Petri
384 HYDROCARBONS AND AIR POLLUTION
-------
tubes-containing 10 ml of alcohol for the absorption of the
tetraethyl lead. By the proposed method of air sampling it was
possible to aspirate within one hour and a half up to 1 cu. m. of
air and to accumulate a quantity of tetraethyl lead sufficient for
a percise determination.##
07298
Dikun, P. P.
THE DETERMINATION OF 3,U-BENZPYRENE IN PRODUCTS OCCURRING IN
THE HANUFACTURE OF SYNTHETIC LIQUID FUEL. Text in Russian.
Vopr. Onkol., Vol. t, p. 289-291, 1958. H refs. Engl.
transl. by B. S. Levine, U.S.S.R. Lit. on Sir Pollut. 6
Relat. Occup. Dis., Vol. 2, p. 122-125, March 1960.
CFSTI TT60-21188
The results of fluorescent-spectral analyses of a series of the
primary, intermediate, and final products in the O.S.S.H.
manufacture of synthetic liquid fuels by the hydrogenation method
are presented. The analytical.procedure was as follows: One
gram of the test material was dissolved in 15 - 20 ml of petrolic
ether. Highly viscous products, such as coal paste, petroleum
residue, etc., not easily soluble in petrolic ether were first
dissolved in 2 - 3 ml of benzene, and then diluted with a
specified volume of petrolic ether, which was accompanied by the
formation of a heavy precipitate, the latter was removed with
the aid of a Buchner funnel filter. The filtrate was passed
through a column of aluminum oxide; the adsorbed substances were
eluted with a mixture of petrolic ether and benzene. The passing
of the substances through the column was followed with the aid of a
luminescent light. The fluorescent spectra of the
chromatographically partitioned fractions were photographed for
permanent recording of the presence of carcinogenic substances.
From the concentration of 3,4-benzpyrene found in the
partitioned fraction the total content of 3,<»-benzpyrene in the
product was-calculated. The method employed was designed for the
detection of 3,U-benzpyrene as the representative carcinogenic
factor of polynuclear aromatic hydrocarbons. Results of
investigations by this method fully agree with theoretical
assumptions that 3,1-benzpyrene and probably the other
carcinogenic substances of this type were not newly formed during
the production of synthetic liquid fuel, but were destroyed, if
originally contained in the primary material. It must be borne in
mind that these conclusions apply only to the 3,4-benzpyrene
types of carcinogenic substances; the results of this investigation
do not exclude the possibility of the formation of carcinogenic
substances of different chemical structures.##
07335
H. Tanimura
AN APPLICATION OF GAS CHBOMATOGRAPHY TO THE ANALYSIS OF SOLVENT
VAPOURS IN THE INDUSTRIAL AIR. REPT. 1. Text in
Japanese. Japan J. Ind. Health (Tokyo), 7(9):7-16, Sept.
1965. 7 refs.
0. Measurement Methods 385
-------
The determination of solvent vapours by means of gas
chromatography is discussed. Industrial air is sampled and a
survey is made on the method of quantitative determination
of aromatic hydrocarbons and others in the solvent. The best
result is obtained with gas chromatography under the following
conditions. Stationary phase: 2% sgualane/diasolid M (i»0-60
mesh) 2 m packed column. Column temperature: 80 degrees C-100
degrees C. Sample inlet temperature: 80 degrees C-100 degrees
C. Sample inlet temperature: 80 degrees C-100 degrees C.
Carrier gas: Nitrogen. Gas flow rate: 20-30 ml/min. Detector:
Hydrogen flame ionization detector. After performing gas
chromatography with gas, the detector response peak is measured.
An then the concentration of the sampled gas is determined by
reading the value of the response peak against the standard
calibration curve of its equivalent gas.##
07373
Hettche, 0. and H. Von Becker
HETHOD FOR THE GRAVIMETRIC TRACE ANALYSIS OF HYDROCARBON VAPORS.
((Verfahren zur gravimetrischen Spurenanalyse der Dampfe
von Kohlenwasserstoffen.)) Text in German. Stadtehygiene
(Uelzen/Hamburg), 16(3):64-68, Mar. 1965. 10 refs.
A survey of maximum allowable concentrations for various
hydrocarbons suggests that it is desirable to develop a simple
non-selective analytical method to determine quantitatively
hydrocarbons down to concentrations of the order of magnitude of 1
ppm. The method described in detail is based on the adsorption of
hydrocarbons on activated carbon. A 500-liter plastic sack is
used to sample the air. The fabrication of the sack is described.
With a membrane pump the gas is taken from the bag, metered, and
passed through two drying bottles filled with sulfuric acid.
For aromatic compounds, the sulfuric acid must be replaced by
CaC12, P205 or Hg(C104)2. Then the gas passes through two
0-shaped tubes with activated carbon. The tubes are weighed
before and after the air passage. Height differences of the
second tube are used to correct the weighing of the first tube.
The method was tested with n-hexane, benzene, carbon tetra-
chloride, ethyl acetate, trichloroethylene, diethyl ether, chloro-
form, tetrachloroethane; and butane. On the average, about 65% of
the theoretical amount could be detected. Butane and carbon
disulfide give large errors. Results from tests performed in the
laboratory and in an underground garage are presented in four
tables. Typical concentrations of the test substances were 10 to
70 mg/cu. m.
07375
S. Horiguchi, K. Shinagawa, T. Dtsunomiya, K.
lyoda', N. Tanaka
ATMOSPHERIC DETERMINATIONS OF CHLORINATED HYDROCARBONS, ESPECIALLY
THE DETERMINATION OF 1,1,1-THICHLOROETHANE. Text in
Japanese. Japan J. Ind. Health (Tokyo), 7(5):25-28, May
1965. 5 refs.
386 HYDROCARBONS AND AIR POLLUTION
-------
The determination of chlorinated hydrocarbons in air,
particularly that of 1,1,1-trichloroethane in air was
examined. Vapor of 1,1,1-trichloroethane is collected by
adsorption on silica gel in U-tubes. Extraction of the
vapor from silica gel is made by isopropyl alcohol at 52 C,
followed by filtration. Hydrolysis of the filtrate is made
at 52 C by dissolving some pellets of potassium hydroxide.
The solution is then neutralized with 5% acetic acid and 1 ml of
5* potassium chromate is added as an indicator, determination is
made for hydrolyzed chlorine ion by titration with 0.1N silver
nitrate.##
07386
H. Konosn
DETERMINATION OF ORGANIC SOLVENT VAPOR-AIH MIXTURES BY A
NON-DISPERSIVE ULTRAVIOLET GAS ANALYZER AND EXAMINATION OF
PRECISION. Text in Japanese. Tokyo Kogyo Shikensho Hokoku
(Rept. Govt. Chem. Ind, Fes. Inst. Tokyo) (Tokyo), 62(7):
257-265, July 1967, 11 refs.
A convenient and rapid procedure for determining the organic
solvent vapors in air has been studied which permits determination
by direct ultraviolet photometric absorbance measurements.
The higher boiling point samples were vaporized in a newly
designed, electrically heated evaporator. The organic
solvent capor can then be admitted to the sample gas cell until
its pressure eguals atmospheric pressure. Precision and
accuracy of the determination by the analyzer were
examined statistically. Toluene ethylbenzene, chlorobenzene,
aniline, cyclohexanone, pyridine, nitromethane, nitroethane,
tetrachloroethylene, and furfuryl alcohol were detected in the
following minimum concentrations: 4, 3, 13, 1, 65, i»t, 17, 1
and 1 ppm, respectively. There was a linear relationship between
the absorbance and the concentration in the chlorobenze, aniline,
cyclohexanone, pyridine, nitromethane, and nitroethane.
Maximun allowable concentration value (75 ppm) of chlorobenzene
can be determined, whereby a 95% confidence interval extends from
60 ppm to 90 ppm. Considerably less than the maximum allowable
concentration of many organic solvents can be detected by the
analyzer. (Author's summary, modified)**
07UOO
Shabad, L. 11.
STUDIES IN THE D.S.S.R. ON THE DISTRIBUTION, CIRCULATION
AND FATE OF CARCINOGENIC HYDROCARBONS IN THE HUHAN ENVIRONMENT AND
THE HOLE OF THEIR DEPOSITION IN TISSUES IN CARCINOGENESIS: A
REVIEW. Cancer Res. 27 (6):1132-1137, June 1967. UO refs.
(Presented in part at the 9th Int. Cancer Congr., Tokyo,
Japan, Oct. 1966.)
By the use of quantitative spectrofluorescent assay of such
carcinogenic hydrocarbons as benzo(a)pyrene (BP), it is possible
to follow the carcinogenic hydrocarbons at different stages of
their distribution and circulation in animal organisas and in
hu»an environment. The carcinogens circulate fron one product to
D. 'Measurement Methods 397
-------
another, and from industrial and transport exhausts into the air.
The exhausts from factories, heating systems, and combustion
engines fall on soil, appear in water, accumulate or disappear,
pass from nutrient medium into microorganisms, and contaminate
fodder and even human food. The action of some soil bacteria in
transforming and destroying BP not only throws light on the fate
of this material in the soil, but indicates the possibility of
biological purification of the human environment from
carcinogenic hydrocarbons. Modern accurate methods of hydrocarbon
determination (for BP the limit is 0.000001 mg/ml) show new ways
to cancer prevention.##
07U03
Syczewska, K., Z. Kartyniak, and B Glowiak
INTERFEROMETRIC MEASUREMENT METHODS OF AIR POLLUTION.
((Interferometryczna Zanieczyszczen.)) Text in Polish.
Ochrona Pracy (Warsaw), 22(2): 16-19, Feb. 1967. t| re'fs.
Experiments confirming the suitability of the interferoaetric
method for analyzing all known and unknown gaseous substances of
atmospheric air were made. The basis of the method is the
refraction of light by gases measured in an interferometer. This
consists of two enclosed parallel tubes with the following
arrangement: monochromatic light source, slit, collimator, lens,
diaphragm, cuvette, movable compensator, telescopic lens
arrangement for observing the field of view, and a rotating drum
for manual adjustment of the compensator. By this method, a wide
range of concentrations of all chemical substances can be
measured in several seconds. A schematic of the instrument, a
discussion of the calculations, and a report of an experiment to
determine the cyclohexane concentration in air are given. At
present, the method is still limited to the analysis of binary
mixtures.##
07«27
G. E. Moore, H. S. Thomas, J. L. Monkman
THE ROUTINE DETERMINATION OF POLY.CYCLIC HYDROCARBONS IN
AIRBORNE POLLUTANTS. J. Chromatog., 26 (2) :«56-l»6U, 1968.
9 refs.
A method for the analysis of polycyclic hydrocarbons found
in polluted air and tobacco tars is described in detail.
The chromatography of polycyclic hydrocarbons involves
compromises including the activity of the alumina,' the depth
of the adsorbent, and the amount of the ether, or other.
polar solvent used. Ultraviolet spectroscopy as a monitoring
technique is _not sufficiently "sensitive. This lack of
sensitivity may be the reason that column losses have been
reported. Fluorescence as a monitoring technique is much
more sensitive and must be used when benzo(a)pyrena is being
measured, since the benzo(k)fluoranthene present in the
venzo(a)pyrene fractions causes serious interference with.
measurements made at the.characteristic benzo (a)pyrene peak at
ca. «02nm.t*
388 HYDROCARBONS AND AIR POLLUTION
-------
07K32
M. Selucky, J. Novak, J. Jana-k
THE USE OF THE CHROMATOGRAPHIC EQUILIBRATION PROCEDURE FOB AIR
POLLUTION STUDIES. DETEBMINATION OF MINUTE AMOUNTS OF BENZENE,
CHLOROBENZENE, AND NITROBENZENE IN AIR. J. Chromatog., 28(2):
285-292, 1967. 13 refs.
The equilibration technique was used for the determination of
benzene in the presence of nitrobenzene and chlorobenzene. The
applicability of the chronatographic equilibration technique
for air pollution control was verified for the systems
benzene-chlorobenzene, benzene-nitrobenzene, and for a ternary
mixture of the three compounds. For field assays, invaluable
advantages of the method used are: (1) Water does not interfere
with the determinations when non-polar phase is used for the
concentration-tube packing. (2) The extent to which
individual components are trapped is proportional to their
partition coefficients, i.e. usually inversely proportional to
their volatility. Thus, the least volatile compounds that are
present in the atmosphere usually at lowest concentrations, are
most efficiently accumulated. (3) During sampling, care need
not be taken of the exact volume drawn through the concentration
not be taken of the exact volume drawn through the concentration
tube, thus eliminating' the use of clumsy-to-operate sampling
devices. (4) The sampling procedure is very versatile and
extremely simple, thus rendering the method suitable for field
practive. Also the transport of the pocket-size tubular samples
is convienient. (5) The overall time necessary to prepare and
analyse samples of benzene in the presence of chloro- or
nitrobenzene is about 30 to to min. as compared with standard
procedures, where a complete analysis takes several hours. The
equilibration method is therefore of considerable advantage in
studying micro-climatic conditions and momentary surges of
exhalates.##
07i»35
A. Zdrojewski, A. L. DuBois, G. E. Moore, R. S.
Thomas, J. L. Monkman
COLUMN CHROMATOGRAPHY AND SPECTROSCOPY IN THE ANALYSIS OF
AIRBORNE POLYCYCLICS. J.Chromatog., 28 (2):317-325. 1967. 16 refs
Analytical difficulties encountered during the separation
(column chromatography) and measurement (spectrophotometric and
fluorimetric) of polynuclear compounds are discussed. A
glass tube 1.0 cm I.D. and HO.0 cm long is fitted with a teflon
plug stopcock. The column is filled to a depth of 12 cm with a
slurry of the deactivated alumina in cyclohexane. For
ultraviolet absorption a Bausch E tomb spectrophotometer
and a Cary 14 recording spectrophotoueter were used. For
fluorimetric measurements a modified Aminco-Bowman
spectrophotometer was used,. The use of fluorescence is
mandatory in the measurement of polycyclic hydrocarbons in air
samples. Without its use, the analyst would be seriously
handicapped with regard to sensitivity. There seems to be no
evidence for losses on the chromatographic column and
D. Measurement Methods 389
-------
accordingly no need to correct for such losses. It is
possible that apparent losses may be due to interference from the
background. The background may be due to overloading of the
column or to incomplete separation of a mixture of
hydrocarbons having a common structure. These hydrocarbons are
likely to be of the two to three ring type. Overloading of the
column and incomplete separation are different affects, but the
influence on the chromatogram will be the same.#t
07561
Jacobs, Horris B., M. H. Braverman, and Seymour
Hochheiser
CONTINUOUS DETERMINATION OF CARBON MONOXIDE AMD HYDROCARBONS IN
AIR BY A MODIFIED INFRARED ANALYZER. J. Air Pollution
Control Assoc., 9 (2):110-11*, Aug. 1959. 5 refs.
The estimation of hydrocarbons and carbon monoxide in small
amounts in the ambient air was achieved by modification of the
nondispersive type of infrared gas analyzer. Essentially the
analyzer consists of an infrared source, a sample and comparison
cell, a beam combiner and filter cell, a detector cell, an
amplifier and a recorder. The sensitivity of the instrument can
be increased by increasing the length of the sample and comparison
cells, and by increasing the pressure of the sample gas. Hater
vapor has an absorption throughout the infrared region and is
therefore an interference in the analysis of carbon monoxide and
hydrocarbons. By saturating the incoming air stream with water
vapor and adjustment of the controls the concentration of water
vapor is constant and can be wliminated as a source of error. The
daily variation of hexane and carbon monoxide during a typical day
of high pollution in New York City is illustrated. The
sensitivity of this instrument was increased sufficiently so that
it could be used for the direct measurement of carbon monoxide in
the ranges of 0 to 20 ppm and 0 to 50 ppm and of hydrocarbons such
as hexane in the ranges of 0 to 5 ppm and 0 to 10 ppm.ft
07575
Hanita, H. D. and G. Kh. Ripp
SPECTHOPHOTOBETRIC DETERMINATION OF LOW ATMOSPHERIC CONCENTRATIONS
IN THE PRESENCE OF OTHER PRODUCTS LIBERATED DURING THE
MANUFACTURE OF SYNTHETIC RUBBER. (Spektrofotometricheskii
metod opredeleniya malykh kontsentratsii divinila v atmosfernon
vozdukhe v prisutstvii drugikh produktov proizvodstva
sinteticheskogo kauchuka.) Text in Russian. Gigiena i Sanit.,
30(8), Aug. 1965. 1 ref. Engl. transl. by Israel Program for
Scientific Translations, Hyg. Sanit., 30(8) :231-23U, Aug.
'1965.
CFSTI: TT66-51033/3
The spectrophotometric method for the determination of DV
(1,3 butadiene) was tested under field conditions in the
atmosphere around the factory manufacturing synthetic rubber SK.
The naximuB DV concentrations were 6.12 to 0.5 mg/cu. m. at
390 HYDROCARBONS AND AIR POLLUTION
-------
distances of 50 to 2000 m, respectively, from the source of
pollution in the summer season, and 3.8 to 0.1 mg/cu. m. at the
same distances in the autumn-winter season. Thus, the
spectrophotometric determination of DV in the atnosphere in the
presence of alpha-methylstyrene, isopropylbenzene, butane, and
butylenes is based on measurements of the optical density of the
isooctane solution of the mixture of wavelengths 224 and 2U5
millimicron in quartz cell with 1 equal 1 cm with an SFU
spectrophotometer. DV concentration in the solution is
calculated from the provided formula. The sensitivity is 0.125
microgram/ml, the accuracy is within plus or minus 2.6%.**
07578
Krylova, N. A.
THE S.PECTROPHOTOHETRIC DETERMINATION OF DIMETHYLPHENfLCARBINOL AND
DIMETHYL-PHENYL-P-CRESOL IN AIR. (Spektrofotometricheskoe
opredielenie dimethilfenilkarbinola i dimetilfenilparakrezola v
vozdukhe.) Text in Russian. Gigiena i Sanit., 30(9), Sept.
1965. 2 refs. Engl. transl. by Israel Program for Scientific
Translations, Hyg. Sanit., 30 (9):375-379, Sept. 1965.
CFSTI: TT66-51033/3
The spectral characteristic of DHPC (dimethylphenylcarbinol) in
the ultraviolet region was studied. The solvent was ethanol.
The instrument was an FE-4 spectrophotometer. The calibration
graph was checked against several synthetic samples prepared in the
laboratory. The mean error lay within plus or minus 3.6%.
Consequently, the calibration graph can be used for the
determination of DMPpC (dimethylphenyl-p-cresol) in solutions.
The sensitivity is 0.5 microgram/ml. The degree of conformity of
DMPpC solutions to Beer's Law was studied and a calibration
graph in the region of 279-280 millimicrons was constructed. The
sensitivity at lambda equaling 279 millimicrons was 2
micrograms/ml. DHPC and DBPpC can best be absorbed by
drawing air, at a rate of 0.5 1/min, through three Zaitsev
absorption vessels connected in series, each of which is filled
with 5 ml ethyl alcohol and cooled with ice. Op to 90S DHPC and
Dmp pC is retained by the first absorber, and up to 10% in the
second. The next step was concerned with the possibility of
determining DMPC and DMPpC separately when present together.
This mixture was analyzed by means of a modificiation of
Vierordt's method, in which one component absorbs light at a
wavelength at which the other is not detected. At lambda equaling
225 millimicrons, DHPpC solutions have an intense absorption
whereas DHPC solutions have an insignificant absorption up to a
concentration of 10 micrograms/ml, without producing any
appreciable deviations. At lambda equaling 210 millimicrons both
substances absorb intensely. The effects of phenol and acetone
on the determination of DMPC and DHPpC were verified.
Phenol interferes with the determination of the substances in
question because of its considerable light absorption in the
region 210-225 millimicrons. Acetone hardly interferes with the
determination because even solutions containing 10 nicrograms/al of
acetone cause only a slight degree of deviation (of the order of
0.015 to 0.02) in the regions used in the determination.**
D. Measurement Methods 391
-------
07627
Sturgis, B. H., W. F. Biller, J. w. Bozelc, and S. B.
Smith
THE APPLICATION OF CONTINUOUS INFEARED INSTRUMENTS TO THE ANALYSIS
OF EXHAUST GAS. In: Vehicle Emissions, SAE Tech,
Progress Series, Vol. 6, Society of Automotive Engineers,
New York, 1961, 81-93. (Presented at the Annual Meeting,
Society of Automotive Engineers, Jan. 1958.)
The Infrared Analyzer, applicable to analysis of the hydrocarbon
component of exhaust gases, and the Exhaust Gas Analyzer which
analyzes exhaust gas simultaneously are described for hydrocarbons,
carbon monoxide, and carbon dioxide. The installation,
calibration, and operation of these instruments and their use for
the analysis of exhaust gases are discussed. Extensive use of
continuous methods of analysis outlined here has made possible
large scale field surveys of vehicle exhaust gases as well as
studies of the effect of engine variables on exhaust gas
composition. (Authors' abstract, modified)##
07628
"Hum, R. H., K. J. Hughes, and J. 0. Chase
APPLICATION OF GAS CHBOHATOGRAPHY TO ANALYSIS OF EXHAUST GAS. In:
Vehicle Emissions, SAE Tech. Progress Series, Vol. 6, Society of
Automotive Engineers, New York, 1964, 91-101, (Presented at the
Annual Meeting, Society of Automotive Engineers, Jan. 1958.)
Information providing historical reference to work and findings in
the early stages of development of gas-liquid chromatography (GLC)
techniques for separation of the hydrocarbons emitted in auto
exhaust gas are reported. Both equipment and techniques are
suitable for separation of the major portion of the hydrocarbon
component of exhaust gas condensate into separate fractions with
identification and quantitative measurement of each fraction. In
general, however, determinations are limited to C7 or lighter
hydrocarbons and do not include, or where included do not
differentiate, the oxygenated products of combustion. In the
procedure described, about 500 ml of raw exhaust gas are required
for the determinations to be made. Information is given on the
technique of analysis, exhaust gas sampling and transfer
procedures, and on the identification of fractions separated by the
GLC technique.
07692
Ixfeld, H. and M. Buck
A METHOD FOB DETERMINING THE TOTAL AMOUNT OF COMBUSTIBLE ORGANIC
SUBSTANCES IN BASTE GASES. ((Eine Methode zur Bestinmung der
Gesamtmenge verbrennbarer organischer Substanzen in Abgasen.)) Text
in German. Brennstoff-Chem. (Essen), 47 (3) :79-83, March 1966. 2
refs.
•392 HYDROCARBONS AND AIR POLLUTION
-------
The gas sample is passed through a snail tube filled with silica
gel on which organic compounds from the gas are absorbed, with the
exception of C02. These compounds are then desorbed by heating and
oxidizing on platinum wool. In order to remove sulfur oxides and
halogen compounds which are also absorbed, the gas is passed
through silver wool which by chemo-sorption eliminates these
compounds. Subsequently the gas passes through a gas washing
bottle with Ba(OH)2 solution where the C02 formed by combustion is
absorbed. Its amount is determined by titration with oxalic acid.
The applicable range of concentrations suitable for this method is
20 to 400 mg C/cu Mm, with 3% relative standard deviation. The
laboratory procedure is described in detail, and calibration values
are listed. The results of tests on 17 substances are also
reported.
07706
Feldstein, H., S. Balestrieri, and D. A. Levaggi
THE USE OF SILICA GEL IN SOURCE TESTING. Am. Ind. Hyg. Assoc. J.,
28(«):381-385, July-Aug. 1967. 9 refs.
This is a study of the adsorption of a large group of solvent
vapors upon silica gel and their subsequent quantitative
desorption. Esters, ketones, aromatic and aliphatic hydrocarbons,
and halogenated, hydrocarbons were among those studied. Except for
certain low-molecular-weight hydrocarbons, the silica gel was
extremely efficient for adsorbing organic solvents. In general,
dimethylsulfoxide proved ideal for elution of adsorbed materials
and for subseguent analysis by gas chromatography. It could not be
used for hydrocarbon solvent mixtures or for higher boiling
solvents. In these cases, carbon disulfide, alone or with water,
was used for desorption. (Authors' summary)
077«3
Bender, D. F.
THIN-LAYER' CHROBATOGRAPHIC SEPARATION AND
SPECTROPHOTOFLDOROMETRIC IDENTIFICATION AND ESTIHATION OF
DIBENZO (A,E)PYRENE. Environ. Sci. Technol., 2(o):20U^206,
March 1968. 10 refs.
Only two hexacyclic aromatic hydrocarbons containing the pyrene
nucleus have been found in urban airborne p'articulate matter.
An investigation of the application of thin-layer chroaatography
and spectrophotofluorometry to the identification of additional
hexacyclic aromatic hydrocarbons containing the pyrene nucleus was
undertaken to determine whether these compounds are indeed present
in urban atmospheres before proceeding to quantitative analysis for
them. Further experiments were conducted to produce a method of
estimating the amount of dibenzo (a,e) pyrene in urban airborne
particulate matter. Two-dimensional thin-layer chromatography was
used in exploratory research to find out whether any dibenzopyrenes
could be found in the air. The general patterns were not very
reproducible. Dibenzo (a,e)pyrene, placed on the plate and
D. Measurement Methods 393
-------
developed one-dimensionally, gave a higher Bf value than was
obtained with the same system in the two-dimensional procedure.
The identity of the components of each fluorescent area was
investigated by collecting the fluorescent area and extracting.
The fluorescence spectra obtained for the various fluorescent
areas in a composite particulate sample taken in Birmingham,
Alabama provide evidence for the presence of
dibenzo (a,e)pyrene in urban airborne particulate matter. With a
method using two one-dimensional separations and fluorescence
spectra, the amount of dibenzo (a,e)pyrene in the Alabama composite
was found to be approximately 100 micrograms per gram of
benzene-soluble. The concentration of benzo(a)pyrene in
Birmingham was approximately 1900 micrograms per gram of
benzene-soluble and in Atlanta, approximately 730 micrograms per
gram of benzene-soluble.##
077U9
Ives, N, F. and Laura Giuffrida
INVESTIGATION OF THERMIONIC DETECTOR RESPONSE FOR THE GAS
CHROHATOGRAPHY OF P, N, As,AND C1 ORGANIC COMPOUNDS. J. ASSOC.
Offie. Anal. Chemists, 50(1): 1-4, Feb. 1967. 8 refs. (Presented at
the 8th Annual Meeting, Association of official Analytical
Chemists, Washington, D.C., Oct. 10-13, 1966.)
Investigations were conducted to determine the degree of
specificity and enhanced response of the thermionic detector (TD),
using alkali metal salts.The test compounds included the triphenyl
derivatives of group V (a) elements. Because of special interest in
nitrogen response, several types of nitrogen compounds were
included. The effects of varying jet diameter, carrier gas, and
other operating parameters were also studied. Thermionic response
to grooup V (a) elements in organic compounds was found to depend on
the salt cation used in the TD. The magnitude of response was
similar for different salts of the same cation. Increased response
for phosphorus was 10,000 fold or better, for nitrogen about 100
fold, and for arsenic about 30 fold. With an unknown response,
phosphorus can be distinguished from nitrogen or arsenic by compar-
ing the thermionic and conventional flame responses.The detection
of nitrogen in organic compounds was not affected adversely by us-
ing nitrogen as a carrier gas. With certain size flame jets, a
significant increase in thermionic response can be obtained by
substituting helium for nitrogen as the carrier gas. Detector
stability was best with potassium salts and was better with
rubidium than with cesium salts; KC1 was preferred for phosphorus
compounds and RbC1 for nitrogen compounds.
07807
Altshuller, A. P.
APPLICATION OF REACTIVITY CONCEPTS TO EMISSIONS FROH DEVICE
EQUIPPED AND UNEQUIPPED AUTOMOBILES. Preprint, Public Health
Service, Cincinnati, Ohio, National Center for Air Pollution
Control, ((18))p., ((1967)). 12 refs.
394 HYDROCARBONS AND AIR POLLUTION
-------
Various manifestations of atmospheric photochemical reactions can
be associated with the relative ability of various hydrocarbons to
participate in these reactions. The ratings derived from such
nanifestations have been used to develop a number of hydrocarbon
reactivity scales. These scales are utilized in evaluating the
effectiveness of automotive exhaust control devices. The
effectiveness of the devices as computed from reactivity scales is
compared with total hydrocarbon measurements.
07830
Popov, V. ft.
THE PRESENCE OF OXIDANTS IN THE ATMOSPHERE OF CERTAIN TOWNS IN
THE O.S.S.R. ((Prisultstvie oksidantov v atmosfernom vozdukhe
nekotorykh gorodov SSSR.)) Text in Russian. Engl. transl.
Hyg. Sanit., 31(1-3): 3-8, Jan.-Barch 1966.
Oxidants in the air of certain towns of the Soviet Onion were
neasured by the phenolphthalein method. The standard color
scale was a mixture of an alcoholic-aqueous solution (3:2) of
phenolphthalein and 1% borax solution. The maximum concentration
of oxidants on the highways of Moscow and Baku on sunny days was
as high as 0.1 mg/cu m, and on cloudy days did not exceed 0.03
ig/cu a. A study of this type of pollutants in Baku
revealed their presence in the area of oil refineries at
concentrations within 0.15 mg/cu m. On the other hand, the
laximum value of oxidants in the vicinity of Batumi oil refinery
was considerably lower (0.04 mg/cu m).##
07838
Dimitriades, Basil
BETHODOLOGY IN AIR POLLUTION STUDIES USING IRBADIATION CHAMBERS. J.
Jir Pollution Control Assoc., 17 (7):H60-U66, July 1967. 12 refs.
Experimentation in large irradiation chambers has been useful in
providing insightt,into the chemistry of the photochemical smog
formation problem. Initial efforts to reproduce the atmoshperic
phenomena artifically at controllable scale were successful in that
gross atmospheric smog symptoms were observed in irradiation
chambers. However, as the experimentation and evidence produced
nere becoming more elaborate, the guestion arose as to how much one
could rely on cheiaical data in understanding and interpreting
atmospheric phenomena. The question becomes highly pertinent in
view of the difference in ,concentration levels between atmosphere
and chamber work. This issue was discussed during recent Amercian
Chemical Society meetings, and the conclusions from presnetations
and discussions were as follows: (1) There is qualitative
agreement between chamber data and atmospheric data wherever
comparison is feasible. (2) There is need for more precise chamber
work at concentration levels more nearly equal to those in the
atmosphere. Experimentation in chambers under typical atmospheric
conditions presents some special problems associated with the
chamber design and chemical analysis. Chamber methodology has been
the focus of considerable research effort, and it appears to be an
inportant factor affecting further progress in air pollution
research. This paper describes methods and techniques used at the
Bartlesville Petroleum Research Center. (Author's abstract)
D. Measurement Methods 395
-------
07850
Walsh, J. T. and D. H. Rosie
STUDIES OF THE GAS DENSITY CELL. J. Gas Chromatog.,
5(5):232-2«0, May 1967. 9 refs.
The gas density cell as a gas chronatographic detector possesses
the unique possibility of providing both quantitative and
molecular weight information. Studies are reported in regard to
optimum operational parameters for maximum cell response and upon
the accuracy of quantitative and molecular weight measurements.
The magnitude of cell response was found to be a function of (1)
the value of reference and measuring gas flow rates, (2) the
physical properties of the reference gas, and (3) the density
change produced in the reference gas by sample vapor. Accuracies
of 1-2% for per cent weight and 3-4% for molecular weights-were
obtained on a large variety of compound types over reasonably wide
concentration and molecular weight ranges; An equation was
developed,which accounts for the variables upon which cell response
is dependent and which permits comparison to other type detectors.
(Authors' abstract)##
07878
Engel, C. S. and E. Sawicki
AZULENE PROCEDURE FOR CHHOHATOGRAPHIC ANALYSIS OF AHOMATIC AND
HETEROCYCLIC ALDEHYDES, CARBOHYDRATES, AND OTHER ALDEHYDE
PRECURSORS. Preprint, Public Health Service, Cincinnati,
Ohio, National Center for Air Pollution Control, ((27))p:,
( (1967)). 9 refs.
A new. location method for many types of conjugated aldehydes and
their precursors is introduced. Because -the compounds of interest
are neither fluorescent nor colored, they are difficult to
locate once they are separated. This method, with azulene as the
reagent, is compared with a number of other location methods.
Evidence is presented for the location of aromatic 'aldehydes,
furfural derivatives, sugars, dinitrophenylhydrazones, and
azines on paper and silica gel plates with azulene. This location
procedure was applied to the identification of
5-hydroxymethylfurforal in extracts of effluents from a
coffee-roasting plant. Techniques described in this paper have
been developed for eventual application to analyses of airborne
particulate. (Authors' abstract, modified)##
07885
R. J. Lewis, R. Smith, P. Baker
AN ANALYSIS OF INSTRUMENT DOWNTIME FOR A LARGE AIR MONITORING
NETWORK. Preprint. Public Health Service, Cincinnati,
Ohio, National Center for Air Pollution Control, (12)p.,
1967. (Presented at the 60th Annual Meeting, Air Pollution
Control Association., Cleveland, Ohio, June 12-16, '1967.)
396 HYDROCARBONS AND AIR POLLUTION
-------
There is a prevalence of ^opinion encouraged by company sales
representatives that currently available continous air
monitoring equipment is truly continuous and automatic.
The vord automatic as applied to present air monitoring
instruments is defined by a detailed analysis of the type of
instrument failures which can be expected. The experience is
drawn from the operating reports and records of the Continuous
Air Monitoring Project (CAHP). Failure of the instrument
system can come about for many reasons, and is defined by the
loss of anticipated valid data output. Three major causes for
loss of data are instrument failure, personnel failure, and supply
support failure. It is concluded that successful network
operation of continuous air monitoring equipment demands careful
design of support functions and personnel selection. A
continual reanalysis (of operating efficiency and upgrading- of
personnel training is mandatory. (Authors' abstract,
uodified) ##
078871
McCabe,.J. E.
J TRACE CONTAMINANT ANALYSIS TEST ON AIR SAMPLES - PHASE II Arnold
Engineering Development Center, Aro^ Inc.'Arnold Air Force
Station, Tenn., Contract-AF 40 (600)-1200, -.AEDC-TB-67-19,
93p., Feb.:1967.
DDC: AD 807i>85
Oetails of transferring and concentrating contaminants from 150-cc
stainless steel cryogenic traps to small volume glass traps more
suitable to trace analysis are given. A description of the gas
chromatographic equipment used in -the analysis are given. A
description of the gas chromatographic equipment used in the
analysis, and the analysis procedures used, 'are presented. The
chromatographic instrumentation, calibrations, and data
assimilation procedures are described. Basic test results and
observations concerning the utility of procedures used, along with
comparative discussions of various aspects of Phase 2'compared with
Phase T, 'are noted. (Author's abstract, modified) :
07898
Hyant, E. E., M. K. Scott, A..F. Fentiman, and B, H.
Poirier
IMPROVED DETECTION AND IDENTIFICATION OF INCAPACITATING AND
LETHAL AGENTS. Battelle Memorial Inst., Columbus, Ohio,
Contract DA-18-035-AMC-379 (A), Ptoj. IC622401A102,
BM1-6, 17p., Jan. 1967. 13 refs. DDC: AD 814888
The search for specific, sensitive, and direct methods for
functional groups or moieties. vasjcontinned. The synthesis of
reagents for the detection of lethal-agents (organophosphorus-type
agent) was emphasized. , Materials that are capable of undergoing
the second-order Beckman reactions that lead to detectable
fragments were emphasized. Particular attention was directed to
oximes that would produce triaryl methane dyes or aliphatic
D. Measurement Methods 397
-------
mercaptans. Thus, through the high tinctorial strength of
triaryl methane dyes, or the highly odoriferous nature of certain
mercaptans, detection systems with enhanced sensitivity might be
realized.**
07908
Zdrojewski, A., L. Dubois, G. E. Moore, E. Thomas,
and J. L. Honkman
FLUORESCENCE SPECTROSCOPY IN THE ANALYSIS OF AIR SAMPLES. Am.
Chem. Soc., Div. Water, Air, Waste Chem., Preprint,
6(1):«0-UU, 1966. (Presented at the American Chemical
•Society, Division of Water, Air, and Waste Chemistry,
Pittsburgh, Pa., March 1966.)
Column separations and ultraviolet measurements are accepted as
almost the only procedure available for the analytical
determination of polycyclic aromatic hydrocarbons in air
samples. The air sample extract is passed through an alumina
column and each fraction is scanned in the ultraviolet. All the
fractions containing a compound detected by ultraviolet
measurements are combined and a quantitative determination is made
on the composite. Two analytical difficulties encountered in the
use of this technique are one, low recoveries of some of the
polycyclic hydrocarbons and two, the "background". To elucidate
these two problems, ultraviolet absorption and fluorescence
techniques were used separately and in conjunction. Each of the
following possibilities for low recovery of polycyclics was
investigated. 1. Lack of sensitivity of the technique.
2. Irreversible adsorption. 3. Tailing. H. Incomplete
separation. The minimum of limiting concentration required to get
a measurable response was determined and is shown in a table.
From results of column chromatography combined with ultraviolet
and fluorescent measurements it was concluded that: the
adsorption is reversible, and that tailing, for all practical
purposes, is negligible. When working with standards only,
recovery is not a problem. The results obtained by fluorescence
measurements on air samples indicate that the spectrum of the so
called background is identical to the spectrum of an air sample
extract. Moreover, a curve of background fluorescence against
the elution volume has the shape of a typical decay curve. It
seems therefore that overloading of the column by a high
concentration of unknowns is a possible explanation of the
back ground.#*
07981
Green, A. E. S., D. T. Williams, H. S. Sholtes, and J. Cowling,
Jr.
THE MIDDLE ULTRAVIOLET AND AIR POLLUTION. In: A. E. S. Green, ed.,
The Hiddle Ultraviolet:' Its Science and Technology, New York, John
Wiley 6 Sons, 1966, Chapt. 8, p. 158-16*. 32 refs.
Currently in the air pollution field a great effort is underway to
find and develop more specific aethods of measuring contaminants.
398 HYDROCARBONS AND AIR POLLUTION
-------
It appears that ultraviolet spectroscopy would be an important tool
in measuring these trace species. The important pollutants such as
nitrogen dioxide, sulfur dioxide, and ozone all have strong
absorption coefficients in the ultraviolet, as do many of the other
lesser pollutants and the products of the photochemical reactions
which play such a large role in smog formation. Both chemical and
spectroscopic methods have their advantages and disadvantages.
Perhaps the greatest importance in utilizing ultraviolet
spectroscopy is that a program which complements the chemical
program could be obtained. The two programs working together
should indeed contribute significantly to the body of knowledge
which is necessary to solve the air pollution problem.
08066
Bohlers, Henry C.
RECOMMENDED PBOCEDDRES FOB MEASURING ODOBOUS CONTAMINANTS IN THE
FIELD. J. Air Pollution Control Assoc., 17(9):609-613, Sept. 1967.
15 refs.
Although the perception of odorous contaminants cannot be precisely
described, certain basic facts about human olfaction are known.
Bith known facts or principles, it is possible to investigate
odorous contaminants for air pollution control purposes. Odor
remains, however, a very intangible commodity. Odorous contaminant
investigations must be tailored to the individual problem or
locality. Consequently, the methods described were designed for
individuals who have working knowledge of either odor or air
pollution problems. Background references are available for
workers who are not familiar with either field. Generalized facts
concerning odors as well as subjective and objective methods for
ueasuring odorous contaminants in the field are described. The use
of specific portions of the method depends upon each individual
investigation. (Author|s summary, modified)
08077
Johnson, F. A.
DETECTION OF LOW LEVELS OF TETRAFLUOROH5TDBAZINE IN AIR. Rohm and
Haas Co., Huntsville, Ala., Redstone Research Labs., Contract
DAAHOI-67-C-0655, S-137, 19p. , June 1967.
DDC: AD 8159«0
Tetrafluorohydrazine was converted to fluoride ion by nitrogen
dioxide and water. The fluoride ion was detected continuously by a
commercial fluoride ion electrode. A 30-mV change in electrode
potential was obtained for one part per million of N2FU in the air.
various factors affecting sensitivity, stability, and speed of the
detection system were considered. (Author|s abstract)
D. Measurement Methods 399
-------
08079
Keenan, Robert G.
CHEMICAL ASPECTS Of ENVIRONMENTAL HEALTH. Occupational Health
Rev.Ottawa, 18(1):3-8, 1966. 39 refs.
Modern methods of physical and chemical analysis, as applied to
biological materials, atmospheric samples containing gaseous or
particulate contaminants, industrial process materials,
intermediates, and finished products 'are discussed briefly. A
discussion of the uses to be made of such analytical data
includes: (1) the "normal" concentrations of certain metallic
elements in body tissues and fluides; (2) the need to compare these
concentrations with those developed analytically on samples fron
exposed subjects; (3) the comparison of atmospheric concentrations
of contaminating" substances found in the working environment with
the A.C.G.I.H. Threshold Limit Values; (<*) the analysis of
industrial process materials, settled dusts, and finished products
to help in assessing the total exposure of the worker to chemical
elements. (Author)s abstract, modified)
08083
Hercer, W. B.
CALIBRATION OF COULTER COUNTERS FOR PARTICLES ABOUT 1 MICRON IN
DIAHETER. Rev. Sci. Instru. , 37 (11) ;:1515-1520, Nov. 1966.
A linear relationship between particle volume and instrument
response is confirmed for particles between 0.75 and 2.5 cubic
microns, but this relationship may-not hold for smaller particles.
The implicit assumption of neglible surface conductance in
derivations of this relationship is found acceptable for
polystyrene spheres about 1 micron "in diameter. A potential source
of error in calibration is identical and allowed for. A
relationship is developed between observed count and true count
which allows coincident passage correction to be based on all
available experimental points. The critical volume is found
experimentally to be a function of particle volume. (AuthorIs
abstract)
08132
M. I. Poletayev
COLORIMETRIC DETERMINATION OF SMALL QUANTITIES OF'STTRENE IN
THE AIR. In: Survey of U.S.S.R. Literature on Air
Pollution and Related occupational Diseases. Translated
from Russian by B. S. Levine. National Bureau of
Standards, Washington, D. C., Inst. for Applied Tech.,
Vol. 3, p. 1U-16, May 1960.
CFSTI: TT 60-21U75
The determination of small quantities of styrene is based
on its nitration property and is made photocolorimetrically.
400 HYDROCARBONS AND AIR POLLUTION
-------
An experimental attempt was made to absorb styrene directly
into the nitrating mixture. Absorption was made from a special
bottle, the air of which was saturated with styrene vapor, by
aspirating the test air through two absorbers connected in
succession. Nitrated styrene vapor acquired a yellow color; the
nitrated product was completely retained' in the first absorber
even when the air was aspirated at a rate of 1 1/min. To
prevent the yellow color f om fading it was necessary to change
the medium as follows: after styrene vapors; were absorbed from
the air the content of the absorber was diluted with 3 ml of
distilled water and neutralized by a 25% ammonia solution until
litmus paper showed an alkaline reaction. Final colors were
compared with colors yielded by standard styrene solutions in
carbon tetrachloride.ft
08136
Senderkhina, D. F.
DETERMINATION OF CHLORINATED HYDROCARBONS IN THE AIR BI THE
METHOD OF WICRO-COHBDSTION. In: Survey Of D.S.S.R.
Literature on Air Pollution and Related Occupational
Diseases, Translated from Russian by B. S. Levine.
National Bureau of Standards, Washington, D. C., Inst. for
Applied Tech., Vol. 3, p. 23-27, May 1960.
CFSTI: TT 60-21485
The method described is based on the quantitative oxidation of
chlorinated hydrocarbon vapor in a combustion chamber
equipped with a platinum coil heated to redness. The combustion
products are then passed through an absorber solution and the
ionic chlorine determined nephelometrically. With an
appropriately prepared standard scale accurate determinations
can be made in solutions containing 0.001 mg of chlorine in 1 ml.
Control tests were made with ethylene chloride, chloroform,
carbon tetrachloride and trichlore.thylene. A portable
apparatus for the determination of chlorinated hydrocarbons in the
air by the micro-combustion method was constructed. The
micro-combustion method described proved to be accurate for the
determination of thousandths of a milligram of chlorine within 30
to 140 minutes. A new micro-absorber is described which assures
complete absorption of products of hydrocarbon combustion. Air
samples are aspirated into gas pipettes filled with a saturated
solution of sodium sulfate or into vacuum gas
pipettes.It
08171
Formicheva, N. I. and P. A. Bel'nikova
RAPID DETERMINATION OF SHALL QUANTITIES OF DIMETHYLANILINE IN THE
AIR. Gigiena i Sanit. , No. 5:<»9-52, 1952. Translated
from Russian by B. S,. Levine, U.S.S.R. Literature on Air
Pollution and Related Occupational Diseases, Vol. U, p. 1-5,
Aug. 1960. CFSTI: TT 60-21913
CFSTI: TT 60-21913
0. Measurement Methods 401
-------
A rapid colorimetric method is described for the determination of
small quantities of dimethylaniline in the air, based on the
formation of a yellow colored paranitrosobasic salt. The air
aspiration and the colorimetric estimation with the aid of an
artificial scale requires approximately 15 to 20 minutes; the
dimethylaniline content per 1 ml of the air must be within 0.001
0.01 mg. The method is simple, requires no complex equipment
and is suitable for dimethylaniline determination in the air of
industrial premises at concentrations in the order of hundredths
and thousandths of a millegram per liter. ACMti
08226
Likina, B. T. and G. L. Barodina
LINEAR-COLOBIHETRIC METHOD FOR THE DETERMINATION OF CARBON DIOXIDE
IN AIR. Gigiena i Sanit., 24(8):30-32, 1959. « refs. Translated
from Russian by B. S. Levine, U.S.S.R. Literature on Air Pollution
and Related Occupational Diseases, Vol. 5, p. 212-215, Jan. 1961.
CFSTI: TT 61-11149
A linear-colorimetric method for the determination of carbon
dioxide in sewage system air is described. The advantages of this
method over those used by the sanitary chemists are speed of the
analysis and the ease with which it can be used under field
conditions even at low air temperature, since the determining
chemical reactions depends upon a solid absorber. Hydrazine-
hydrate-N2HU. H20 is a good carbon dioxide absorber and it
combines with basic fuchsin in solution to form an unstable
colorless solution, the original fuchsin color is restored in
proportion to the carbon dioxide concentration in the air. Best
results are obtained with 125 ml of the C02-containing ait. This
volume of air can be passed through the indicator tube for the
-determination of C02 concentrations ranging between 0.5 and 9.0
percent. Results of experiments indicate that unsaturated
hydrocarbons, gasoline vapor and small amounts of hydrogen sulfide
affected neither the height nor the color in the indicators;
however, when the concentration of hydrogen salfide was 0.3 mg/li
or more the color of the solumn faded almost completely. However,
the maximum content on the hydrogen sulfide in the air of the
sewage system never exceeded 0.007 mg/li.
08257
Baum, Fritz, Inge Reichardt, and Wolfgang Steinbach
SIMPLE MEASURING ARRANGEMENT FOR RECORDING HYDROCARBON CONTENT.
Staub (English translation), 27 (6):16-19, June 1967. 11 refs.
CFSTI: TT 67-51«08/6 (HC$2.00)
A method for using a batch-sampling gas-chromatograph with
flameionization detector to record continuously the presence of
hydrocarbons is described. Use of this measuring device is
illustrated by several examples. Hydrocarbons are thermally
ionized in a hydrogen flame in the flame-ionization detector.
Flue gases of an oil stove with vaporization burner, flue gases of
a Bedium-size waste incinerator, and automobile exhaust were
402 HYDROCARBONS AND AIR POLLUTION
-------
•easured. The hydrocarbon content of the flue gas of an oil
stove only exceeded that of the air in the laboratory above a
combustion rate of 0.5 kg of oil per hour. With decreasing
chimney draft the hydrocarbon content of the flue gases rose
sharply, being accompanied by an increase of the Bacharach soot
number. When the chimney draft was throttled to 0.1 mm W.G. at
the maximum combustion rate, the concentration of hydrocarbons
rose to 350 times the value of normal operation. The combustion
phases in a medium size waste incinerator can be directly observed
with the measuring device. Total hydrocarbon concentration in the
exhaust of an automobile at various operating conditions is
presented. In neutral, a slight increase in hydrocarbon
concentration was recorded. During acceleration in neutral the
concentration dropped immediately. The concentration varied when
the position of the accelerator was changed. On a 1HS grade,
finally, the concentration dropped briefly and then rose
considerably.#*
08270
(!. F. Fracchia, F. J. Schuette, P. K. Mueller
A METHOD FOB SAMPLING AND DETERMINATION OF ORGANIC CABBONYL
COMPOUNDS IN AUTOMOBILE EXHADST. Environ. Sci. Technol.,
1 (11):915-922, Nov. 1967. 2« refs. (Presented at the
Division of Water, Air, and Waste Chemistry, 152nd Meeting,
ACS, New York, N. Y. , Sept. 1966.)
Automobile exhaust was sampled at 1 liter per minute through a
water trap and two bubblers in series. The bubblers contained
aqueous acidified 2,4-dinitrophenylhydrazine. The carbonyl
compounds in the water trap were precipitated with the hydrazine
reagent. The hydrazones in the trap and in the bubblers were
collected by filtration and extraction, dissolved in carbon
disulfide, and analyzed by gas chromatography using a flame
ionization detector. The water trap contained mostly
formaldehyde. All aldehydes were quantitatively trapped in the
first bubbler, and the ketones were determined from the hydrazones
in the second bubbler. The role of potential interferences
has been evaluated. Sampling efficiencies and analytical
errors have been established for several compounds. Alkyl and
aromatic carbonyl compounds obtained from selected automobiles
under several operating modes are compared. More sensitive
methods are needed for analyzing carbonyl compounds in air, but a
methodology is now available for studying combustion sources.
(Authors' abstract) #t
08285
B. Briegleb
GASCHBOMATOGRAPH COLUMN CIRCUIT FOB ANALYSIS OF GASES IN CLOSED
SYSTEMS FOB BIOLOGICAL AND BIOMEDICAL INVESTIGATIONS.
((Gaschromatographische Kolonnenschaltung fur die Analyse der
Gase in geschlossenen Systemen fur biologische und
biomedizinische Untersuchungen.)) Text in German. Deutsche
D. Measurement Methods 403
-------
Versuchsanstalt fuer Luft- und Haumfahrt, Munich, Germany,
DLR-FB-66-60. 12p., Sept. 1966. « refs.
DDC: AD 803715
A variable gaschromatographic column circuit is described for
measuring oxygen, nitrogen, carbon dioxide, carbon monoxide,
helium, and argon gases as well as the lower hydrocarbons in a
single run. Diagrams of the circuit in a specially developed
Beckman gaschromatograph column and a chromatogram of an
analysis are provided.##
08290
Vander Kolk, Alvin L.
SAMPLING AND ANALYSIS OF ORGANIC SOLVENT EMISSIONS. Am. Ind. Hyg.
Assoc. J., p. 588-589, Nov.-Dec. 1967.
Stack emissions were evaluated for air pollution purposes by using
both Mylar bag sampling and gas washing bottles contaning normal
hexane and orthoxylene. Analysis was done by gas chromatography.
Agreement between the two sampling techniques was good, and each
method has its advantages and disadvantages. (Author)s abstract)
0829U
Boettner, E. A. and Benjamin Heiss
AN ANALYTICAL SYSTEM FOB IDENTIFYING THE VOLATILE PYROLISIS
PRODUCTS OF PLASTICS.
Am. Ind. Hyg. Assoc. J., p. 535-540, Nov.-Dec. 1967. 1 ref.
(Presented at the American Industrial Hygiene Association
Meeting, Houston, Texas, 1965.) .
Techniques are described for determining the identity and toxicity
of the pyrolysis products of plastics. Differential thermal
analysis (DTA) and thermogravimetric analysis (TGA) determine the
temperature at which the plastic melts, the temperature at which it
goes through physical and/or chemical change (oxidation or
reduction),, and the temperature at which it undergoes weight
losses. The identity and quantity of the combustion products are
determined with a controlled .combustion furnace, utilizing the
temperature information obtained by DTA and TGA. The combustion
products emitted by the furnace are separated by gas
chromatographic techniques and analyzed by infrared absorption,
ultraviolet absorption, other gas chromatographic techniques, and
mass sectroscopy. The results obtained utilizing polyvinyl chloride
are described. (Authors! abstract)
08296.
Valori, P. C. Melchiorri, A. Grella, and G. Alimenti
VOLATIZATION AND DECOMPOSITION OF AROMATIC POLYCYCLIC HYDHOCARBOHS
DURING THE USUAL PROCEDURE FOR THE CONCENTRATIONS OF EXTRACTS OF
404 HYDROCARBONS AND AIR POLLUTION
-------
ATMOSPHERIC DUST. ((Sulla volatilizzazione e la decomposizione
degli idrocarburi policiclici aromatic! nel corso degli abituali
procedimenti per la concentrazione degli estratti di pulviscolo
atmosferico.)) Text in Italian. Nuovi Ann. Igine Microbiol.
(Home), 17 (4) : 311-324, 1966. 37 refs.
Research is described on a series of commercially available
hydrocarbons which are found in polluted air (naphthalene,
acenaphthalene, fluorene, phenanthrene, anthracene, 9,10-
dihydroanthracene, pyrene, fluoranthene, chrysene, 1,2-
benzanthracene, naphthacene, perylene, 3,4-benzopyrene, 1,12-
benzoperylene, anthanthrene, 1,2,5.,6-benzanthracene, and coronene).
The sample hydrocarbons were evaporated at medium heat (hot water
bath at 90-95 deg Co.), or dried with a jet of filtered air, or
with a jet of nitrogen; samples were either evaporated to dryness
or to a liquid volume of 2 ml. The per cent loss for all three
techniques is tabulated. The highest proportion of sample loss (up
to 100 percent) is generally encountered when dry heat is used to
evaporate to dryness. The per cent loss varies with the individual
hydrocarbon, and is generally correlated with volatility. Other
modes of sample loss are discussed: decomposition, reaction with
other chemicals, oxidation, and ultraviolet photodeconposition. The
data are discussed with reference to experimentation with air—borne
carcinogens. These data were to be used in the development of a
procedure for the analysis of polluted air.
08316
Louis, Rudolf
PROTON MAGNETIC RESONANCE ANALYSIS OF
GASOLINES. ((Protonenresonanzanalyse von Motorenbenzinen.))
Text in German. Erdoel Kohle (Hamburg), 19(1):281-287, April
1966. 4 refs.
Gasolines exhibit typical proton magnetic resonance spectra.
Their qualitative and quantitative interpretation is discussed in
detail for 19 super and regular gasolines, covering characteristic
hydrocarbon gtoups as well as single components and additives.
Thus, far-reaching conclusions about composition and quality of
gasolines are possible with a minimal expenditure of time. The
range of application of this method is shown b.y a comparison with
CH-,FIA-, infrared- and gas chromatographic analyses.
08321
Stefanescu, A. and L. Stanescu
THE DEGREE OF DANGER CAUSED BY THE INFLUENCE OF AKOHATIC
POLYNDCLEAR HYDROCARBONS DURING THE MANUFACTURING PROCESS OF
CARBON BLACK. I. THE DANGER OF ANTHRACENE AND THE DETERMINATION
OF THE ANTHRACENE CONTENT OF THE AIR. ((Der Gefahrdungsgrad
unter Einwirkung der aromatischen polynuklearen
Kohlenwasserstoffe beim Fabrikationsprozess von Russ. I. pie
Gefahrdung durch Anthrazen und die Bestimmung des
Anthrazengehaltes der Luft.)) Text in German. Z. Ges.
Hyg. Ihre Grenzgebiete (Berlin), 12 (3):182-189, 1966.
D. Measurement Methods 465
-------
The toxic effect of anthracene was strongest in workers who
handle crude anthracene, while the ones who worked with refined
anthracene showed very few detrimental effects. The skin cancer
noted in anthracene workers is most likely caused through contact
of the skin with the polynuclear hydrocarbons which are impurities
in anthracene oil. The maximum allowable concentration of
anthracene recommended by the American Conference of
Governmental Industrial Hygienists is 0.1 mg./cu m of air. A
new method for the determination of anthracene in air during the
production of carbon black is described. The hydrocarbons were
absorbed on active carbon and desorbed using benzene vapor and
oxygen-free nitrogen. The desorption apparatus is illustrated.
The amount of anthracene obtained was determined by gas-fluid
repartitioning chromatography. The chromatograms illustrated show
that besides anthracene, several lighter and heavier unidentified
components were obtained, most likely higher condensed polynuclear
hydrocarbons. The degree of danger caused by anthracene to
workers in the manufacture of carbon black is tabulated, showing
the variations caused by different work places, work time, and
concentrations of the toxic substance.f*
08354
Brink, D. L., and J. F. Thomas, and D. L. Feuerstein
MALODOROUS PRODUCTS FROM THE COMBUSTION OF KRAFT BLACK LIQUOR.
II. ANALYTICAL ASPECTS. TAPPI, 50 (6) :276-285, June 1967.
25 refs. (Presented at the 51st Annual Meeting of the
Technical Association of the Pulp and Paper Industry, New
York, N. Y., Feb. 21-24, 1966.)
Gaseous and liquid products isolated by pyrolysis of kraft black
liquor, were analyzed qualitatively and quantitatively using
gas-liquid chromatography with detection by flame ionization.
More than 60 compounds were detected in the pyrolysis liquid and
at least 32 of these were present in the pyrolysis gas. Using the
microcoulometric titration system, hydrogen sulfide, methyl
mercaptan, dimethyl sulfide, dimethyl disulfide, and at least 19
unidentified sulfur-containing components were detected in the
pyrolysis products; 7 of the major components were determined
quantitatively. Using cochromatography and the methods of
detection noted, the identities of methyl mercaptan, dimethyl
sulfide, and dimethyl disulfide were verified and tentative
identifications of several other sulfur-containing products were
also made. Hydrogen, oxygen, nitrogen, methane, carbon monoxide,
ethane, carbon dioxide, and acetylene were resolved and
determined quantitatively. Hydrogen sulfide, methyl mercaptan,
and five unidentified components were also qualitatively detected.
Sulfur present in pyrolysis residues was determined using a wet
oxidation procedure. A powerful analytical method has been
developed for detailed study of the effects of recovery furnace
operation on such emissions and it should prove to be a valuable
aid to industry. With adequate development, pyrolysis carried
out independently of gaseous, liquid, and solid products could
provide an answer to complete odor control; in addition, isolation
of organic by-products may be feasible. AAM##
406 HYDROCARBONS AND AIR POLLUTION
-------
08356
Cave, G. C. B.
THE COLLECTION AND ANALYSIS OF ODOROUS GASES FROM KRAFT PULP
HILLS. PAET II: A LABORATORY STODY OF THE COLLECTION OF
POLLUTANTS FOR ANALYSIS. TAPPI, 46(1):5-11, Jan. 1963. 5
refs.
An experimental study was made of the performance of traps, in
collecting kraft-mill pollutants from an air stream. The traps
were in a mixture of dry-ice and acetone. Some traps in the train
were empty; others contained ethylbenzene as a solvent. A
convenient experimental method is described for artificially
producing a polluted air stream, and for evaluating the
performances of traps. The distribution was found of hydrogen
sulfide, sulfur dioxide, methyl mercaptan, dimethyl sulfide, and
dimethyl disulfide among the traps of the train. The effect of
flow-rate, volume of solvent, and trap design on trap performance
was measured. The effect of varying the degree of air turbulence
in an empty cold trap was studied. It was confirmed that cold
ethylbenzene is a satisfactory solvent for all the pollutants
except hydrogen sulfide. For this latter pollutant, an aqueous
solution of cadmium was used to trap it. A study was included on
the losses of the pollutants that might occur on extended
storage of their ethylbenzene solutions. Apparatus and a
procedure are described for the concentration of the original
ethylbenzene solution of pollutants, to improve the sensitivity of
the method. (Author's abstract)##
08357
Cave, G. C. B.
THE COLLECTION AND ANALYSIS OF ODOROUS GASES FROM KRAFT POLP
BILLS. PART III: THE ANALYSIS OF COLLECTED POLLUTANTS BY
GAS CHROHATOGRAPHY. TAPPI, «6 (1):11-1«, Jan. 1963. H refs.
The qualitative and quantitative analysis of kraft-mill
pollutants in ethylbenzene by using gas chromatography is
discussed. Columns of tri-m-cresyl phosphate and of Carbotrax
15tO are proposed for use at 35 and 85 C. These columns permit
the resolution of all known kraft-mill pollutants. Techniques are
described for qualitative analysis. They include the two-column
method, and graphs prepared by this method are presented for
homologous series of mercaptans, Ketones, esters, and normal
alcohols. It is emphasized that the unequivocal identification of
an unknown pollutant is rarely possible by gas chromatography
alone. Quantitative analysis is also described, including the
preparation of standard solutions ,and the presentation of prepared
calibration curves. These curves were straight lines. The use
of an ultrasensitive detector, the ionization chamber, is briefly
discussed. (Author's abstract)#f
D. Measurement Methods 407
-------
08433
B. B. Tupeeva
THE DETERMINATION OF METHOXONE IN AIR. ((Metody opredeleniya
metoksona v vozdukhe.)) Hyg. Sanit. (English translation of:
Gigiena i Sanit.), 32 (4-6):72-76, April-June 1967. 4 refs.
CFSTI: TT 67-51409/2
The optimum conditions were established for the determination
of rcethoxone by the method of wet combustion 'with a mixture
of sulfuric acid and potassium dichromate, followed by
iodometric determination of the liberated chlorine. The
sensitivity was found to be 0.080 mg methoxone in the
analytical volume. A sensitive method was devised for the
determination of methoxone based on its hydrolysis with
concentrated sulfuric acid, with -the liberation of formaldehyde,
followed by the photometric deter-mination of the latter with
chromotropic acid. The sensitivity was found to be 0.010 mg in
the analytical volume. The hydrolysis of methoxone with
concentrated sulfuric acid in the presence of
chromotropic acid provides a more sensitive and accurate method
for the determination of this substance.i#
08446
L. I. Gavrilova
METHODS FOP THE DETERMINATION OF SODIUM AND BOTYL 2,4-
DICHLOROPHEN-OXYACETATES IN AIR. (Hetody opredeleniya natrievoi
soli i buty-lovogo efira 2,4-dikhlorfenoksiuksusnoi kisloty v
vozdukhe.) Hyg. Sanit. (English translation of: Gigiena i
Sanit.), 32 (4-6):394-396, April-June, 1967. 4 refs.
CFSTI: TT 67-51409/2
Different colorimetric methods for the determination of
different preparations of 2,«-D in air were tested in order
to determine which was most suitable for routine sanitary work.
The 2,U-D herbicides are used in agriculture in the form of
liquid aerosols and dust, while under actual working conditions
they are present as dust. They should therefore be sampled on
FPP-15 filters placed in metal cartridges, by means of
electrical aspirators. It is recommended that the air for
sampling 2,4-D herbicides be drawn up at a rate of 10 1/min.
This was tested under working conditions and found to be the
optimum rate.**
08471
Tuhi, Kennosuke
STUDIES ON THE CHEMICAL ESTIMATION METHOD OF INDUSTRIAL
ENVIRONMENT. II. DETERMINATION OF TRICHLOROETHYLENE, CHLOROFORM
AND BENZYLCHLORIDE BY THE PYRIDINE-FORMALIN METHOD. Text in
Japanese. Japan. J. Hyg. (Tokyo), Vol. 21, p. 407-409,
Feb. 1967. 12 refs.
408 HYDROCARBONS AND AIR POLLUTION
-------
A simple method for the determination of trichloroethylene,
chloroform and benzyl chloride was developed, utilizing
formaldehyde to stabilize the color developed by the reaction of
pyridine and halogen compounds (Fuziwara reaction). An air
sample was passed through 5 ml. of pyridine-formaldehyde solution
(9:1 ratio), and the solution mixed with 1 ml. of sodium hydroxide
solution; amounts of halogen compound were determinted
spectrophotometrically. The method is both sensitive and
specific. 1.5 gamma of trichloroethylene, 2.5 gamma of
chloroform and 1.0 gamma of benzyl chloride were measured in 5 ml,
of sampling solution.#*
08490
Kol'lcovski, Peter
A NEB COLOR REACTION FOE VAPOES OF CERTAIN AROMATIC
HYDROCARBONS. ((0 novoi tsvetnoi reaktsii parov nekotorykh
aromaticheskikh uglevodorodov.)) Text in Russian. Zh. Analit.
Khim. (Moscow), Vol. 22, p. U56-458, 1967. 9 refs.
A new color reaction has been found for benzene, toluene and
xylene vapors using a solution of cesium disulfate in fuming
sulfuric acid supported on silica gel. Linear-colorimetric
methods have been developed on the basis of this reaction for
determining benzene, toluene and xylene vapors in the air of
industrial establishments.**
08519
Smith, Walter D.
THE NRL TOTAL HYDROCARBON ANALYZER. In:A.L. Alexander and
V.H. Piatt, Status of Chemical Research in Atmosphere Puri-
fication and Control on Nuclear-Powered Submarines (Fifth
Annual Progress Report), Naval Research Lab., Washington,
D.C.,NRL-6U91, p. 18-22,Jan. 11, 1967. 7 refs.
CFSTI, DDC: AD 6U8505
Sampling of atmospheric gases on submarines for later analysis in
the laboratory has always been a problem. The judicious choice of
equipment and techniques is paramount in obtaining a
representative sample that will not change during storage and
transit. The NRL Total Hydrocarbon Analyzer fulfills a need for a
method of analysis which can be used aboard ship to determine the
total hydrocarbon concentration. The instrumentation and procedure
of operation for this analyzer are described. The use of the
instrument has been made more practical by devising a scheme for
purifying the ships* air to make it suitable for use as an air
supply for the detector. Other applications of this analyzer are
mentioned.
08589
Kunte, Helga
CARCINOGENIC SUBSTANCES IN WATER AND SOIL. XVIII. THE
DETERMINATION OF POLYCYCLIC, AROMATIC HYDROCARBONS USING COMBINED
D. Measurement Methods 409
-------
THIN-LAYER CHROHATOGRAPHY AND FLUORESCENCE MEASUREBENT. (Kanzero
anzerogene Substanzen in Wasser und Boden. XVIII. Die
gene Substanzen in,Hasser und Boden. XVIII. Die mittels Misch
Dunnschichtchromatogtaphie und Fluoreszenzmessung.) Text in
German. Arch Hyg. Bakteriol. (Munich), 151 (3-4):193-201, Aug
1967. 25 refs.
A method is described for the separation of polycyclic,aromatic
hydrocarbons from extracts of water, soil, and dust by two-
dimensional mixed thin-layer chromatography and their quantitative
determination by fluorescence measurement. The behavior of these
compounds is described: pyrene, fluoranthene, 1,2-benzanthracene,
3,4-benzpyrene, 3,4-benzfluoranthrene, 10, 11-benzfluoranthrene,
11,12-benzfluoranthrene, perylene, indeno(1,2,3-cd) pyrene, and
1,12-benzperylene. These hydrocarbons are detected at
concentrations of 0.05-1.0 micro./ml. at wavelengths from 400 to
650 milli microns. This study was limited by the use of 365 milli
microns as the standard wavelength. Limitations, such as reduced
intensity, possible errors, and correction factors are discussed.
The simplicity, speed, and sensitivity of the method recommend it.
08592
Luft, K. F., G. Kesseler, and K. H. Zoner
NON-DISPERSIVE INFRARED GAS ANALYSIS WITH THE ONOR APPARATDS.
(Nichtdispersive Oltrarot-Gasanalyse mit deir ONOR.) Text in
German. Chen. Ingr. Tech. (Weinheim) , 39(16):937-915, Aug.
1967, 7 refs.
A single or double ray appartus can be used for nondispersive
infrared gas analysis. The new one-ray apparatus is schematically
illustrated and its measurement principles and technical
performance are described. Measurement sensitivity and interference
effects are discussed, taking into consideration the underlying
physical principles. The UNOR apparatus is illustrated and its
technical applications are outlines. This method permits
sensitive, continuous readings of pollutants in the atmosphere, the
determination of single components in stack, exhaust and waste
gases, as well as the determination of synthetic gas components.
08643
Dubois, L., A. Zdrojewski, and J. L. Honkman.
HEASOREMENT OF BENZO(a)PYPENE, BENZO(k)FLUORANTHENE AND
BENZO(g,h,i)PERYLENE BY ULTRAVIOLET SPECTROSCOPY. Bikrochim. Acta,
No. 5:831-842, 1967. 8 refs. (Presented at the Congress on
Occupational Medicine, Budapest, Hungary, Sept. 1966.)
Published ultraviolet data for BaP in air may be grossly in
error, particularly those published before
1960. It is not possible to measure Bap in air
samples with accuracy, using the 401 nm peak,
unless BaP is present alone (no BkF). The BaP detection limit
measurable at 401 nin by ultraviolet is too high. The horizontal
measurement technique produces results of greater accuracy than the
base line technique. Better analytical values for BaP are obtained
410 HYDROCARBONS AND AIR POLLUTION
-------
if, instead of using the peak at 401 nm, the 388 nm peak is used.
BkF can be precisely measured using the 307 nm peak and a
horizontal drawn at 314 nm. The technique for determining
benzo( (a) ) pyrene, benzo{(k))fluoranthene, and
benzo((g,h,i))perylene respectively in microgram amounts by UV
absorption measurements is described. The feasibility of using
this technique to analyze air samples has been investigated.
086««
Dubois, L., A. Zdrojewski, and J. L. Honkman.
COHPARISON OF THREE METHODS FOR TRACE ANALYSIS OF POLYCYCLICS.
Bikrochim. Acta (Vienna), No. 5:903-911, 1967. 16 refs.
(Presented at the Anachem Conference, Detroit, Hich., Oct.
11, 1966.)
Several analytical techniques for the determination of polycyclic
aromatic hydrocarbons in air have been evaluated. Two solvents,
benzene and cyclohexane, were compared for effectiveness in the
preliminary preparation of the air sample. To identify and measure
the polycyclics, the techniques of ultraviolet absorption and
fluorescence were used. Air sample extracts were analyzed with and
without prior chromatographic separation. A rapid chromatographic
procedure using benzene as elutant was employed for th e first
time. The extract aliguot or eluate fraction was chromatographed
on fully activated alumina using benzene as the eluting solvent.
BaP and BkF are eluted from such a column in 30 minutes or less in
a total eluate volume of perhaps 50 ml and the two hydrocarbons are
determined by fluorescence emission. Work in progress suggests
that benzene may be replaced in this application by the less toxic
toluene. By any method used the BkF values found were in good
agreement. The agreement between the various BaP 'values was poor,
suggesting not all were of equal validity. The highest, and also
least accurate, BaP values seem to be associated with the use of
benzene as extractant, or ultraviolet absorption as a measuring
technique. (Authors* abstract)
08681
Chapman, Robert L.
AM INSPECTION METHOD FOR AOTOHOBILE HYDROCARBON EHISSION.
J. Air Pollution Control Assoc., 10 (6) :«63-U64, Dec. 1960.
5 refs. (Presented at the 53rd Annual Meeting, Air Pollution
Control Assoc., Cincinnati, Ohio, Hay 22-26, 1960.)
There has been a need for a simple, inexpensive and extremely
sensitive method for the discriminate detection of hydrocarbons in
auto exhaust, that may be used by the law enforcing agencies. The
use of the flame ionization detection method to fill this need, is
discussed. The operation possibilities and limitations of this
method are discussed.
D. Measurement Methods 411
-------
08762
Katz, Morris
GUIDE TO THE SELECTION,OF METHODS FOB MEASURING AIR POLLUTANTS.
Preprint. World Health Organization, Geneva (Switzerland),
WHO/AP/67.29, 115p., 1963. 2refs.
The contents of this review are: main purposes of air pollution
investigations, units for expression of result?, atmospheric
sampling, selection of sampling procedure and apparatus, gas
analysis methods, automatic sampling and monitoring instruments,
recent advances in instrumentation for gas analysis, analysis of
polycyclic aromatic hydrocarbons and carcinogenic air pollution,
and indicators and other rapid methods for identification or
measurement of air pollutants.t#
08838
Hoover, Gary M., Charles E. Hathaway, and Dudley Williams
INFRARED ABSORPTION BY OVERLAPPING .BANDS OF ATMOSPHERIC GASES.
Appl. Opt., 6 (3):U81-U87, March 1967. 9 refs.
The spectral transmission of carbon monoxide, nitrous oxide, and
mixtures of the two has been studied in the 2200 per cm 'region,
where overlapping absorption bands occur. With spectral slit
widths sufficiently large to include several absorption lines, it
was found that the observed spectral transmittance of a mixture is
equal to the product of the transmittances of the components
measured separately, provided that sufficient nitrogen is added to
give the same total pressure for all samples. This result was
also obtained for overlapping bands of nitrous oxide and methane in
the 1300 per cm region. The present work confirms earlier studies
of overlapping bands of C02 and water vapor. An investigation
of the possible breakdown of the multiplicative property of
transmission for narrow spectral slit widths was inconclusive.
(Authors' abstract, modified)**
08848
Vander Kolk,- Alvin L.
SAMPLING AND ANALYSIS OF ORGANIC SOLVENT EMISSIONS. An. Ind.
Hyg. Assoc.'J,, 28 (6) :588-589, Nov.-Dec. 1967.
Stack emissions were evaluated for air pollution purposes by using
both Mylar bag sampling and gas washing bottles containing
normal hexane and orthoxylene. Analysis was done by gas
chromatography. Agreement between the two sampling techniques was
good, and each method has its advantages and disadvantages.**
412 HYDROCARBONS AND AIR POLLUTION
-------
08889
Dubois, I. and J. L. Monkman
THE ANALYSIS OF ilEBOENE POLLUTANTS. In: Pollution and Our
Environment: Conference Background Papers. Vol. 3, Montreal,
Canadian council of Resource Ministers, Paper D25-3, p. 1-20, 1967.
23 refs. (Presented at the National Conference, Canadian
Council of Resource Ministers, Montreal, Oct. 31-Nov. <», 1966.)
Available from the Canadian Council of Resource Ministers,
620 Dorchester Boulevard West, Montreal, Canada, $10.00 per
volume.
Some specific problems in the sampling and analysis of pollutants
are discussed illustrating some discrepancies in data already
obtained. The analysis of H2S and BaP are emphasized to indicate
that some data may be unreliable. Conclusions dravn from the
discussion indicate that measuring technigues and sampling methods
should be considered as an integrated whole. To avoid possible
conflict, the use of direct reading recording instruments is
preferred to batch sampling devices and methods. If the instrument
or batch sampling method does not produce accurate results, efforts
to measure a particular pollutant should be abaondoned until a
satisfactory method has been developed. •. Much is being said about
the setting of standards and criteria. If methods do not exist
which can determine with accuracy the limit chosen, it is better to
avoid, at least temporarily, the setting of a limit. All factors
must be considered, including current data on toxicity and current
ability to measure before deciding on a standard or limit. Data
are not an end in itself but merely an intermediate from which
conclusions and correlations may be drawn. It is better to spend
some effort and money in the development of .a better measurement
technique than to continue to use methods which are known to be
unsatisfactory.
09111
Chapman, Robert L.
THE ROLE OF OPTICS IN AIR POLL0TION MONITORING. Opt. Spectra,
1(3):15-18, 1967.
Optical instrumentation and analysis technigues commonly used in
air pollution monitoring are described. Beginning with a
definitive description of major-air pollutants and their causes,
the article traces the development and use of optical instruments
for this purpose from the "beginning" more than two decades ago to
present. Comprehensive descriptions of instruments and technigues
currently in use and a brief discussion of developments that would
still further enhance the value of optical instrumentation in this
application are presented.f#
09223
Kohler, H. and H. J. Eichoff
A RAPID METHOD FOR THE DETERMINATION IN ATMOSPHERIC DUST. ((«EINE
Schnellnethode zur Bestimmung von mehrkernigen, aromatischen
D. Measurement Methods 413
-------
Kohlennasserstoffen in Luftstaub.)) Text in Gernan Z. Anal. Che«.
(Berlin), 232 (6):401-409, Nov. 24, 1967 5 refs.
The dust is sampled onto a cellulose asbestos filter and is
extracted with benzene in a soxhlet apparatus. The polycyclic
hydrocarbons are then isolated from the extract, using 2-
dimensional thin-layer chromatography on aluminum oxide-cellulose
acetate. The eluted spots are analyzed by fluorospectroscopy,
usually at normal temperature in solution or, in special cases, at
lower temperatures in a solid state. About 70 percent of the
polycyclic aromatic hydrocarbons originally contained in the dust
are detected, as determined by a test with labelled 3,H-benzpyrene.
The apparatus used is diagramed. (Authors summary, modified)
09231}
Kartinelli, Giorgio
THE CONTINUOUS CONTROL OF AIR POLLUTION WITH
INDUSTRIAL ANALYSERS. ((II controllo continue dell inguinamento
atmosferico con analizzatori industrial!.)) Text in Italian.
Termotecnia (Bilan), 21 (10):558-565, Oct. 1967.
For protection against air pollution from increased vehicular
traffic, urbanization, and industry, Italy established a law on air
pollution control in August 1966. Some provisions of the law are
cited. A monitoring system for continuous measurements of air
samples involves wind direction, registration of concentrations,
determination of pollutants, and the emitter. Better results could
be obtained from a network of monitoring stations at various
cities, and a plan is proposed for their establishment and
operation, where continuous measurement would also be made of air
temperature and humidity, concentrations of S02, H2S, N02, C02,CO,
and hydrocarbons. Photographs showing equipment and apparatus for
the stations are reporduced. A schematic diagram depicts the
picoflux apparatus for S02 measurements; an electrical cell for
measuring H2S is also shown. The UHAS infrared analyzer is used to
measure C02. Analyses for CO, hydrocarbons and dust are discussed,
along with the equipment for air pollution monitoring in Frankfurt,
Germany.
09333
Lial W. Brewer, (ed.)
ANALYTICAL PROCEDURES FOR THE ENVIRONMENTAL HEALTH
LABORATORY. Sandia Corp., Albuquerque, N. Hex.,
Industrial Hygiene Lab., SC-M-3044, 147 p., Feb.
1968. 13 refs.
This is a manual compiled of thirty-nine analytical procedures
used by an industrial hygiene laboratory. The procedures for
the following substances in air are included: The Determinaton
of Acetone, Acid and Alkali Contaminants; Benzene,
Toluene, and Other Aromatics; Beryllium (Spectrographic
Method); Beryllium (Borin Method); Cadmium; Chromic Acid,
Chronates, and Dichromates; Formaldehyde; Lead; Methanol;
414 HYDROCARBONS AND AIR POLLUTION
-------
Nitrogen Dioxide; Oil Mist; Ozone (Colorimetric Method);
Ozone (Titration Method; Phosgene; Silica (Colorimetric
Method); Sulfur Dioxide; Thallium; and Zinc.tfi
093«2
Papa, Louis J.
GAS CHROMATOGRAPHY-MEASURING EXHAUST HYDBOCAEBONS DOWN TO PARTS
PER BILLION. Preprint, Society of Automotive Engineers,
20p., 1967. 26 refs. (Presented at the Mid-Year Meeting,
Chicago, 111., Hay 15-19, 1967, Paper 670U94.)
Several methods for determining hydrocarbons in automotive
exhaust are presented and discussed. These include:
nondispersive infrared, ultraviolet, flame-ionization detection,
and gas chromatography. A gas chromatographic method is
presented for determining individual hydrocarbon components in
automotive exhaust. The minimum detectable concentration of
each hydrocarbon is one part per billion (ppb) volume/volume.
The method has thus far detected over two hundred hydrocarbons
of all classes, i.e., paraffins, olefins, and aromatics, in
exhaust. The total analysis time is 25 to 30 minutes. A
technigue for collecting the exhaust sample in small plastic
bags is described along with a brief study on the selection of
suitable bag material. Technigue for sampling, calibration, and
standardization are also discussed. Applications of the method
are presented along with a discussion of the results. (Author's
abstract) ##
093U3
Pearsall, H. W.
BEASDHING THE TOTAL HYDROCARBONS IN DIESEL EXHADST. Preprint,
Society of Automotive Engineers, 11p., 1967. 19 refs.
(Presented at the Automotive Engineering Congress,
Detroit, Mich., Jan. 9-13, 1967, Paper 670089.)
In order to simulate diesel exhaust of known composition,
veighed amounts of various high-boiling hydrocarbons were
evaporated into a stream of hea'ted air. These mixtures were
sampled continuously and the hydrocarbon contents measured with a
heated flame ionization detector (FID). The evaporator unit
and FID were operated at various temperatures and 375 F was
optimum as regards percentage of input material accounted for
(85-100%, for paraffins through C16), fast response, and
repeatability. The FID was then used at various temperature
total hydrocarbons in exhaust from a 1-cyl diesel engine.
Again 375 F was optimum for obtaining maximum apparent
hydrocarbon concentration, fast response, and repeatability.
Finally, FID measurements were obtained at 375 F on exhaust
from the engine at various operating conditions, to assess the
effects of operating variables on hydrocarbons. Increasing
compression ratio'and temperatures of the inlet air and crankcase
oil were effective ways of lowering hydrocarbons. Some
principles for valid sampling and measurement of diesel exhaust
hydrocarbons are discussed. (Author's abstract)##
D. Measurement Methods 415
-------
093U8
Westveer, J. A.
COREELATION OF EXHAUST EMISSION TEST FACILITIES. Preprint,
Society of Automotive Engineers, 8p., 1967. i» refs. (Pre-
sented at the Automotive Engineering Congress, Detroit, Hich.,
Jan. 9-13, 1967, Paper 670165.)
Current legally specified test procedures for measuring hydro-
carbon and carbon monoxice concentrations in vehicle exhaust gases
contain intrinsic test variables which significantly affect test
results. These variables constantly hamper efforts to correlate
test data generated at one or more exhaust emission test
facilities. Some of the more prominent test variables such as
vehicle repeatability, test driver repeatability, instability of
calibrating gases and changing ambient test conditions and the
success of various measures which were undertaken to reduce or
eliminate the influence of some the variables on test repeatabiltiy
and facility correlation are described. It is recommended that
one of the facilities be designated as a control facility which
would be responsible for establishing and maintaining a set of
primary gas.concentrations. Particular attention should be
placed on the driving patterns of the test drivers, as deviations
from the prescribed patterns alter test results. Standardization
of the analytical instruments improved correlation. Particular
emphasis should be placed on matching and reducing the sizes of the
internal cavities, such as water traps, filters, and common
manifolds, etc. The size of sample cells should be standardized
especially in the hydrocarbon sample train as the hexane to pro-
pane response varies with the sample cell length. The infrared
analytical instruments should be located in an area relatively
free of harsh drafts as the abrupt temperature changes may cause
the instrument calibrations to change momentarily. The analyzers
should be mounted in a console or cabinet type enclosure to re-
duce the possibility of rapid temperature changes within the ana-
lyzer case. Vehicle exhaust emissions are affected by barometric
pressure changes. The existing ambient barometric pressure should
be recorded for each test and appropriate correction factors
applied to the test results to compensate for barometric pressure
differences. Circulating a test vehicle among facilities for
correlation purposes has remained a standard practice within the
industry because it is presently the best known method for obtain-
ing comparative emission data. The development of devices and of
procedures which will eliminate the major variables will signifi-
cantly simplify the present correlation problems.
09365
Hill, R. L. and J. M. Sonley
A FOUR CHANNEL CHROMATOGRAPH FOR RAPID GAS ANALYSES. Lab.
Pract., 1-7(1) :55-59, Jan. 1968.
A multiple column chromatograph is described which quickly and
accurately analyzes gas samples for hydrogen, oxygen, nitrogen,
carbon monoxide, carbon dioxide and hydrocarbons. The total time
for an analysis is just under six minutes. Operator fatigue is
reduced to a minimum and electronic integrators enhance the
1,16 HYDROCARBONS AND AIR POLLUTION
-------
accuracy. The cost of the equipment (3,250 pounds) is
justified by the large number of samples. Apparatus specifically
described include; the sampling system, detectors, the electrical
system, and oven units. The operation and calibration of the
equipment are briefly discussed.**
09369
Wilson, H. N. and G. M. Duff
INDUSTRIAL GAS ANALYSIS: A LITERATURE REVIEW. Analyst,
92(1101):723-758, Dec. 1967. 712 refs.
Analytical methods are reviewed for: permanent and inorganic
gases; analysis of liquefied or pure gases; fuel gases; flue gases;.
motor exhaust gases; analysis of micro samples; and atmospheric
pollutants. The years from 195R to about mid-1966 were covered.
In no branch of analysis is the sving towards physical methods
more marked than in gas analysis. There have been no important
developments of the conventional methods during the last ten years;
the chief advances have been the application of galvanic methods to
"trace" of certain gases, and gas chromatography. The rapid
spread of the electrogalvanic methods for the "on-streaa"
determination of traces is also most significant. The other most
noticeable feature is the vast and increasing attention being paid
to atmospheric pollutants of all kinds, particularly sulphur
dioxide, sulphuric acid and hydrocarbons.##
09388
Talori, P. and A. Grella
CHROMATOGHAPHIC SEPARATION OF POLYCYCLIC AROMATIC HYDROCARBONS.
A METHOD FOR CONCENTRATION AND PRELIMINARY PURIFICATION OF EX-
TRACTS FROH SAMPLES OF ATMOSPHERIC DUST. (Separazione cromato*
grafica degli idrocarburi policiclici aromatici. Hetodo per la
concentrazione e la preliminare purificazone degli estratti di
campioni di pulviscola atmosferico.) Text in Italian. Nuovi
Ann. 'Igiene Microbiol. (Home), 17 (5):351-382, Sept.-Oct.
1966. 35 refs.
Different techniques in chromatographic separation are discussed;
they generally yield different results. Another method is de-
scribed which involves: a) the concentration of polycyclic con-
stituents by absorption on alumina; b) the purification of extracts
from tars and colored materials; and c) a preliminary separation of
polycyclic aromatic hydrocarbons into two large fractions. The
differences between levels of hydrocarbons determined by classical
method and by this new one are considerable, for example, ,0.98 and
3.72 micrograms/100 cu m air for phenanthrene respectively, and
5.UO and 13.56 for 1 f 12-benzperylene. This method can be easily.
adapted for analyses of more complex materials and represents a
"small preparative analysis" in the gas chromatography of poly-
nuclear compounds.
D. Measurement Methods 417
-------
09U32
Dubois, L., T. Teichman, R. S. Thomas, and J. L.
Monkman '
SDLPHOR COMPOUNDS IN URBAN AIR. In: Air Pollution.
Proceedings of the Symposium on the Physico-chemical
Transformation of Sulphur Compounds in the Atmosphere and the
Formation of Acid Snogs. Organisation for Economic
Co-operation and Development, Paris, Directorate for
Scientific Affairs, Paper 8, Dec. 1967, p. 63-73. 6 refs.
Three sampling stations were set up using glass fiber filters.
All filters were carefully washed to reduce the relevant blank
levels as much as possible. Measurements were made of dust
loading, lead, polycyclics and sulphate. Using hot aqueous
extraction, sulphate blank values were determined on a larger group
of glass fiber filters. Sulphate blanks on organic filter media
are much lower than for the glass fiber type. Suitably low blanks
have only been achieved for polycyclic, lead and sulphate blanks.
Results currently being obtained for sulphate in air are shown in
histograms. The effect of wind direction has been applied to the
results. There seems to be a rough correlation between the three
stations. Peaks tend to occur on weekends. Dust and sulphate
air loadings are given in tables. Values are summarized for three
months, with some average values for the same months obtained
10 years previously in the same city at another location one mile
distant. Glass fiber sheet appears to be quite unsuitable for the
measurement o± sulphate or sulphuric acid in air since it is
analytically unsound to try to measure sulphate if the total
sulphate blank is as large, or larger, than the quantity being
measured.*f
09515
California State Dept. of Public Health, Berkeley, Air and
Industrial Hygiene Lab.
A GUIDE TO OPERATION OF ATMOSPHERIC ANALYZERS. SDPH-2-tO,,
1«p., Bay 1966.
Methods for both manual and continuous automatic sampling and
analysis of the common air pollutants are described. Experiments
are described for the measurement of sulfur dioxide using the
West method. Total oxidant content of the atmosphere is
analyzed using the Neutral Buffered Potassium Iodide Method,
C1 through C5 atmospheric hydrocarbons are monitored and
analyzed. Guides to the operation of atmospheric analyzers are
reviewed-t#
09574
Sanders, W. N. and J. B. Maynard
CAPILLARY GAS CHROMATOGRAPHIC METHOD FOB DETERMINING THE C3-C12
HYDROCARBONS IN FULL-HANGE MOTOR GASOLINES. Anal. Chem. (D.
S.), «0(3):527-535, March 1968. 13 refs.
418 HYDROCARBONS AND AIR POLLUTION
-------
A capillary gas-liquid chromatographic method has been developed to
determine the individual C3 - C12 hydrocarbons in full-range motor
gasolines. The analyses are conducted on a 200-foot squalane
capillary column in less than 2 hours. Approximately 2UO
chromatographic peaks are observed in the analysis of an average
gasoline; 180 of them (amounting to 96-99 percent wt of the'sample)
have been specifically identified. The column temperature and
column inlet pressure are both programmed to obtain resolution of
close-boiling hydrocarbons. standard deviations and the 95 percent
confidence limits are given for the quantitative repeatability and
reproducibility of the method. Chromatographic peak
identifications and the detailed quantitative composition of
typical premium and regular-grade gasolines are presented, as well
as the detailed composition of the American Petroleum Institute
Prototype Feul No. 1 -Premium Leaded Reference. Changes that can be
made in the temperature and pressure programs to obtain resolution
of specific groups of hydrocarbons are discussed. With
modifications of present sampling procedures, the method could
easily be applied to analysis of the individual hydrocarbons found
in automotive exhaust gases. (Authors' abstract, modified)
09597
Engle, Carole and Eugene Sawicki
RAPID ITLC FLUORIMETBIC METHODS FOR THE ASSAY OF PHENALEN-1-
ONE AND 7H-BENZ(DE)ANTHRACEN-7-ONE IN POLLDTED URBAN ATBOSPHEBES.
Preprint. Public Health Service, Cincinnati, Ohio, National Center
for Air Pollution Control, ((23))p., Feb. 1968. 4 refs.
Through the use of glass-fiber paper impregnated with silica gel
(called instant thin-layer chromatography, or ITLC), the rapid
determination of phenalen-1-one (PO) and 7H-benz (de)anthracen-7-one
(BO) is facilitated. One method is introduced for the specific
determination of PO, and one method for the determination of both
PO and BO at the same time. Both methods are superior to previous
sensitivity. In addition, they give reasonable accuracy and
precision. samples from urban atmospheres and air pollution source
eff=iemts can be analyzed rapidly for PO and BO by these methods.
Analysis of one sample of organic extracts would take less than 1/2
hour; analysis of a dozen samples would take less than 2 hours.
For those laboratories without instrumentation the amount of PO and
BO can be estimated by eye after separation; eight analyses for
either compound can be accomplished in about 20 minutes. (Authors'
abstract)
09734
De Schmertzing, Hannibal, Sol S. Nelson, and Harold G.
Eaton
CRYOGENICALLY TRAPPED TRACE CONTAMINANTS ANALYZED BY IONIZING
GAS CHROMATOGRAPHY. Helpar,Inc.,Inc..Falls Church, Va.,
Contract AF 41 (609)-2958, Task 793002, SAM-TR-6H-68, 15p.,
Aug. 1967.
CFSTI, DDC: AD 662330
D. Measurement Methods 419
-------
The concentrations of microcontaminants in a sealed environmental
system were determined quantitatively. The separation and
identification of the cryogenically trapped trace contaminants were
accomplished with liquid gas chrcmatography using a flame
ionization detector. Thirty-nine sets of samples were taken during
a manned simulator run; 29 sets from a similar run; one sample set
from a trapping efficiency run. The compounds contained in the
sample cylinders were identified by their time of elution from a
column and the amount measured with the aid of peak areas. The
response characteristics of the chromatograph were calculated from
responses obtained with standard mixtures. (Authors' abstract)
modified)
09738
Berner, Axel and Hemma Reichelt
THE ROTATING-SLIT AEROSOL SPECTROHETEB (ROSL-SPECTHOBETEH):
PHOTOTYPE. In: Aerosol Research at the First Physics In-
stitute. Vienna Univ., Austria, p. 1-18, Jan. 1968. 3 refs.
A new aerosol centrifuge is described. Particle-size spectra
resembling those of the conifuge are produced; their selectivity,
however, is considerably better. Aerosols produced by nebulizing
monodispersed Latex suspensions are analyzed by the centrifuge.
The different locations and are completely separated. (Authors1
abstract)
09888
Flesch, Jerome P.
CALIBRATION STUDIES OF A NEW SUB-MICRON AEROSOL SIZE CLASSIFIER.
Preprint, Public Health Service, Cincinnati, Ohio, National Center
for Air Pollution Control, 17p., 1967. 12 refs. (Presented at the
153rd Meeting, American Chemical Society, Miami Beach, Florida,
April 10-1U, 1967.)
The size-fractionating characteristics of a new aerosol classifier
operating in the size range 0.015 to 0.5 micron were investigated
with homogenous aerosols of zinc ammonium sulfate, polystyrene
latex spheres, and solium chloride cubes. Size analyses were
carried out by electron microscopy. Characteristic deposition
curves were nearly identical in the small-particle collection zone
and agreed with data for methylene blue spheres. For the zone
above 0.2 micron the curves differed significantly, probably
because of charging differences of the various aerosols.
Preliminary application of the classifier to ambient air sampling
has yielded size distribution data for lead in urban Cincinnati.
(Author's abstract, modified)
1003
-------
Aerospace Sciences Div., SC-RR-68-162, 20p., April 1968.
28 refs. (Presented at the "Symposium on Applications of Mass
Spectrometry to Gas Phase Reactions," 155th National Meeting
of the American Chemical Society, Division of Water, Air, and
Haste Chemistry, San Francisco, Calif., April t, 1968, Paper
55),
CFSTI: TID «500 (51ST ED.)
The techniques of flash photolysis and time-resolved mass
spectrometry have been combined for the study of fast gas phase
reactions. The apparatus provides an incident ultraviolet
light flux of 1.0 x 10 to the 18th power quanta per cm2 per flash
and a spectrometer sensitivity of 5 x 10 to the minus 8 power mole
per liter. Time resolution is 1.U micron sec. at successi-ve 50
microns sec intervals. The following chemical systems have been
investigated: 1) nitrogen dioxide sensitized reaction between
hydrogen and oxygen; 2) decomposition of nitromethane; 3)
termolecular recombination of iodine atoms in the presence of
nitric oxide; and U) reaction of excited iodine (2P1/2) atoms with
methyl iodide. The most promising development for pollution
studies seems to be the use of nitrogen dioxide as a
sensitizer and primary reactant. It should be possible to
explore the reaction kinetics of nitrogen dioxide as a sensitizer
and primary reactant. It should be possible to explore the
reaction kinetics of nitroge dioxide and various hydrocarbons with
this technique. The mass spectrometer sensitivity limit of 1 part
per 100,000 will .not permit, however, reproducing the dilution
factor normally experienced in the actual atmospheric environment
(approximate range 0.01 to 1 part per 10 to the 6th power).**
10089
Kol'kovski, P.
INDICATOR METHOD FOR DETERMINATION OF XYLENE VAPOB IN THE AIR.
(Indikatoren metod za opredelyane na ksilolovi pari v'v v'zdukha.)
Text in Bulgarian. Khim. Ind. (Sofia), 39(2): 76-78, 1967. 11 ref
An indicator method based on a color reaction was developed for
determining the xylene concentration in the atmosphere. The
indicator is prepared by treating 0.3-O.U ma. silicate with 0.5 l./g
of a 25 solution of Ce(S04) 2. «H20 in concentrated sulfuric acid, A
mm. long glass tube 0.4 mm. in diameter is filled with the
indicator and is then standardized for xylene concentrations of 0 to
0.5 mg./1. by passing 500 1. air through the tube, or for
concentrations from 0 to 25 og./l. by passing 100 1. air through
the tube. The distance over which the color change from orange to
blue occurs is then recorded as a function of zylene concentration.
The method has a sensitivity of 0.01 mg./l. and an accuracy of 205.
It can be used in the presence of aliphatic hydrocarbons but not in
the presence of toluene, benzene, or benzene derivatives.
10238
Arutyunov, Yu. I. and Z. I. Geller
THE ACCURACY OF CHROMATOGRAPHIC ANALYSIS OF FLUB GiSES WHEN
USING THEHHOCATALYTIC DETECTORS. Thermal Ehg. (English
D. Measurement Methods 421
-------
translation of: Teploenergetika) 1U (10):9U-97, April 1368 7
ref s.
Thermocatalytic detectors, used to analyze flue gases, operate on
the principle of measuring the heat of combustion of the eluted
components in the carrier gas flow. Platinum wires, incorporated
into an unbalanced Hheatstone bridge, are measured for their
changed resistances during catalytic combustion with the eluted
gases. The theoretical basis for the relationship between input
voltage and measured resistances is explored. On combustion of
the eluted component by the wire, an additional amount of heat
is liberated, raising the temperature of the wire's surface a
discrete amount. In experimental verification of the derived
relationships, a KhT-4 chromatograph was used for
automatic analysis of minute constitutent of combustibles in boiler
stack gases. A low-temperature detector of catalytic combustion
was employed. Theoretical and experimental values for
temperature of the heated wire and for internal current, depending
on the variations in supply voltage, differ by not more than plus
or minus 10-15%.**
10242
Dimitriades, B.
METHODS FOR DETERMINING NITROGEN OXIDES IN AUTOMOTIVE EXHAUSTS.
Bureau of Mines, Washington, D. C., El 7133, 29pp., Hay
1968. 10 refs.
Five direct and indirect methods for determining nitrogen oxides
in automotive exhausts have been evaluated from the standpoint of
accuracy and applicability in current exhaust studies. These
methods are: static oxidation in tank. Bureau of Bines method.
Chevron Research method, phenoldisulfonic acid method, and direct
measurenent of NO. Results showed that methods requiring
conversion of nitric oxide to nitrogen dioxide as a part of the
analytical procedure are subject to errors introduced by the
instability of N02. The extent of some of these errors has
been determined, and procedures have been developed to minimize
undesirable influences. On the basis of the results obtained fron
this study, recommendations are made regarding procedures for batch
type or continuous measurement of nitrogen oxides in exhaust
streams.**
10489
Bufalini, J. J.
GAS PHASE TITRATION OF ATMOSPHERIC OZONE. Preprint, Public
Health Service, Cininnati, Ohio, National Center for Air
Pollution Control (8)p., April 1968. 9 refs.
Ozone can be selectively removed from a gas stream containing a
variety of oxidants. Oxidant analysers can be made specific for
ozone by incorporating a small gas reaction chamber on the
instrument. Possible interferences from hydrogen peroxide, n-butyl
hydroperoxide, peroxyacetyl nitrate, nitrogen dioxide, and peracetic
acid are discussed. (Author's abstract)
422 HYDROCARBONS AND AIR POLLUTION
-------
10668
Dubois, K., C. J. Baker, A. Zdrojenski, and J. L.
Honkman
CORRELATION OF THE BLACKNESS INDEX OF HI-VOL AIR SAMPLES HITH THE
POLYCYCLIC HYDSOCAEBON CONCENTRATIONS. Preprint, Department of
National Health and Welfare, Ottawa, (Ontario), Occupational
Health Div., ((24))p., 1968. (Presented at the 61st Annual
Meeting of the Air Pollution Control Association, St. Paul,
Minn., June 23-27, 1968, Paper 68-124.)
The darkness of a soiling index sample being due to products of
combustion it would be interesting to find out if a relation could
be established the blackness index or the dark colored fraction of
the sample, and the polycyclic hydrocarbon concentration. Having
deduced such a relation one could use this blackness index to
indirectly measure the polycyclics in air samples. The time
involved in measuring the blackness (a few seconds for a sample)
is insignificant as compared to two days required for a complete
determination of polycyclics in an air sample. The relation
between the blackness index and the concentration of
benzo((k))flouranthene (BkF) and conseguentley of polycyclics,
vary from one station to the other. Each relation is
characteristic of a given station. Preliminary results indicate
that the curve are different from one city to the other although
the difference from one station to the next or from one month to
the next is more important in some cases. The relationship
between the blackness index and the concentration of BkF or
polycyclic is different from one month to the next. ?or a given
blackness index, the concentration of BkF is lower in summer
than in winter, and for a given amount of particulate natter, the
concentration of BkF is also lower in summer. It then follows
that the dark material is different, from summer to winter. The
blackness index seems to be a poor indicator of the polycyclic
concentration in air samples and it would be unwise to use it to
lake such measurement unless a standard curve for a given city has
been prepared.##
10672
Hersch, Paul A.
CONTROLLED ADDITION OF EXPERIMENTAL POLLUTANTS TO AIP. Gould-
National Batteries, Inc., Minneapolis, Minn., 24p., 1968. 21 cefs.
(Presented at the 61st Annual Meeting of the Air Pollution
Control Association, St. Paul,Minn., June 1968, Paper 68-
153.)
Experience with, and extensions of less known techniques of
providing an air stream with a steady and adjustable level of a
gaseous impurity are described. Leaving aside those means that
enploy moving solid parts, the paper discusses devices using liquid
pistons, mikro-flow through channels, diffusion across channels and
barriers, stream splitters for attenuation, and methods based on
evaporation, electrolysis, chemical conversion, and irradiation.
(Author s abstract, modified)
D. Measurement Methods 423
-------
10755
Jager, J.
UTILIZATION OF QUASILINEAR FLUORESCENCE SPECTRA IN ANALYSIS OF
POLYNUCLEAR AROMATIC HYDROCARBON. AtmoS. Envirpn.,
2(3):293-29U, May 1968.
The utilization of quasilinear fluorescence spectra in the
analysis of polynuclear aromatic hydrocarbons is proposed.
Quasilinear fluorescence spectra of many polynuclear hydrocarbons,
but also enable them to be determined directly in mixtures with
satisfactory accuracy, provided some specific conditions are
strictly adhered to. The method of obtaining the quasilinear
fluorescence spectra is breifly described. (Author's abstract)**
10767
Smith, Charles G., Carl A. Nau, and Charles H. Lawrence
SEPARATION AND IDENTIFICATION OF POLYCYCLIC HYDROCARBONS IN HUBBEB
DUST. Am. Ind. Hyg. Assoc. , J. 29 (3) :242-2i»7, Hay-June
1968.
A spectrophotometric technique is described for determining the
presence of polycyclic aromatic hydrocarbons in furnace black,
vehicular tire rubber, and lung tissue, utilizing benzene and
immiscible solvent system extraction followed by thin-layer
chromatography on cellulose with N,N-dimethylformamide as
developer. By use of this procedure, furnace black and new and aged
vehicular tire rubber are found to contain 3,1-benzyprene, 1,2-
benzyprene, fluoranthene, and pyrene in quantities which are not
diminished by processing, aging, or wear. In a further application
of the procedure it was established that commercial furnace black
and furnace black deposited in the lungs of monkeys are similar in
that both contain adsorbed 1,2-benzyprene, pyrene, and possibly
fluoranthene, and two unidentified fluorescent compounds. They are
dissimilar in that the furnace black from monkey lungs contains no
coronene or 3,4-benzyprene. (Authors' abstract)
10772
Yamamoto, Robert K., and Barren A. Cook
DETERMINATION OF ETHYL BENZENE AND STYRENE IN AIR BY ULTRAVIOLET
SPECTROPHOTOHETBY. Am. Ind. Hyg. Assoc. J. , 29 (3) :238-2«1 ,
May-June 1968.
In .the production of styrene, it is important to be able to
determine ethyl benzene and styrene in the presence of each other
as an indication of sources of dispersion of vapors from the closed
reaction system. The air is drawn at a fixed rate through a
fritted -glass bubbler containing spectro-grade isooctane. The
absorption of ultraviolet light at wavelengths of 268 mu for the
ethyl benzene and 291 mu for the styrene is used as a measure for
the amounts of these compounds collected from the air. This method
has the advantages of sampling over a wide range of concentrations,
of specificity, and of facility in both field and laboratory
phases. (Authors abstract)
424 HYDROCARBONS AND AIR POLLUTION
-------
109U6
Arito, H., R. Soda, and H. Matsushita
GAS CHROMATOGRAPHIC DETERMINATION OF POLYNUCLEAR HYDROCARBONS
IN PARTICDLATE AIR POLLUTANTS. Ind. Health, 5,(3-U):243-259,
Dec. 1967.
An attempt to simplify procedure for analysis of polynuclear
hydrocarbons in participates in town air was carried
out. Vacuum sublimation method was employed to extract organic
materials from the particulates instead of the method with a
Soxhlet apparatus. The sublimate was dissolved in small amount
of benzene and the solution was submitted to direct gas
chromatographic analysis by utilizing a flame ionization
detector or an electron capture detector. It was proved that
further purification of the sublimate by partition was unnecessary
in this method. Seven polynuclear hydrocarbons including
benzo(a)pyrene were determined on the collected
particulates from the air by this method. (Author's abstract)**
10960
Chapman, R. L.
AIB POLLUTION CONTBOL SYSTEMS. Instr. Control Systems,
41(8):79-82, Aug. 1968.
The methods for measuring the major air pollutants are reviewed
briefly. Some of the problems involved in calibration of
instruments are discussed.##
10964
H. J. Davis
GAS CHHOMATOGHAPHIC DETERMINATION OF BENZO{A)PIRENE IN
CIGARETTE SHORE. Anal. Chem., 40 (10):1583-1585, August 1968.
An analytical method which is shorter and more versatile than the
fluorometric method for the determination of benzo (a)pyrene in
cigarette smoke is described. Gas chromatography with an electron
capture detector is found to measure as little as 1 ng of BaP
with satisfactory precision. The electron capture detector is
basically an ionization detector utilizing a helium glow
discharge as the electron source capable of operation at
tenperatures up to 400 degrees C.**
11030
Hanst, Philip L. and John A. Horreal
DETECTION AND MEASUREMENT OF AIH POLLUTANTS BY ABSORPTION OF
INFRARED LASER RADIATION. Preprint, 27p., 1968. (Presented
D. Measurement Methods 485
-------
at the 61st Annual Meeting, Air Pollution Control
Association, St. Paul, Binn., June 23-27, 1968, Paper
68-91.)
A technique of detecting gaseous air pollutants by means of
absorption of laser radiation is under development at the NASA
Electronics Besearch Center. The iodine infrared laser and the
carbon dioxide infrared laser are forced to emit spectral lines
which fall on the infrared absorption bands of atmospheric
pollutants. The attenuation of a laser line when passed 'through
an air sample is the measure of the pollutant concentration.
The narrow spectral width of the laser emission permits
sensitive detection, minimizes interference between pollutants, and
allows penetration of atmospheric water bands. The collimation
and high power outputs available from lasers permit transmission
of the radiation over long straight paths through the atmosphere
and over long folded paths in multiple-pass absorption cells. A
sample of absorbing gas placed within the laser cavity forces the
emission of the selected wavelengths. With a one-half kilometer
path to a retro-reflector and back, it is predicted that the
following concentrations of air pollutants will be detected by
means of the indicated laser lines: carbon monoxide at 2 parts per
million in air (ppm), using the 10.53 micron carbon dioxide line;
sulfur dioxide at 1.5 ppm, using the 9.08 micron carbon dioxide
line; and ozone at 0.15 ppm, using the 9.52 micron carbon dioxide
line. It seems feasible to extend the technique to other
pollutants such as nitrogen dioxide, methane, butane, and peroxy
acetyl nitrate. Continuing effort is being devoted to development
and construction of the laser transmitting and receiving equipment.
Field testing is planned for the near future.##
11061
H. W. Theones, W. Guse
LATEST STATE OF DEVELOPMENT OF INSTRUMENTS FOR THE CONTINOOUS
MONITORING OF GAS EMISSIONS. Staub (English translation),
28(3):53-63, March 1968. 17 refs.
CFSTI: TT 68-50»«8/3
For the measureoet of gaseous emissions, testing methods using
chemical analysis are used for emission control based on random
sampling while automatic gas analyzers are employed for
continuous concentration control. The different types of
measuring instruments, their possibilities and limitations are
explained, and difficulties occcurring during gas cleaning
are considered. Practical experience is available which has been
gained in many years during the operation of gas cleaning
installations and of analysers for continous measurement of
sulphur dioxide present in flue gas. (Authors' summary)#*
11068
C. R. Engel
DIRECT SPECTROPHOTOFLUORIHETHIC ANALYSIS OF COMPOUNDS ON
PAPER AND THIN-LAYER CHROMATOGRAMS AND PHEHOGHAMS.
Preprint, Public Service, Cincinnati, Ohio
426 HYDROCARBONS AND AlR POLLUTION
-------
National Air Pollution Control Administration, ((1))P-,
((1968)) 12 refs.
Direct spectrophotofluorimetric analyses can be coupled with paper
or thin-layer electrophoresis, and paper or thin-layer
chromatography. It is simple and offers many advantages.
Neither time nor compound is lost in extraction or elation. A
thin-layer or paper chromatographic or electrophoretic spot can
be examined immediately after separation. Since no expensive
cells are needed, there are no breakage costs. Characterization
is enhanced through the use of quenchofluorimetric techniques.
Thus, direct spectrophotofluorimetric techniques. Thus direct
spectrophotofluorimetric analysis has great potential in trace
characterization and trace quantitative analysis of complex
lixtures. It approaches colorimetric analysis in simplicity and
speed and surpasses it in sensitivity, and the amount of
information that can be obtained from one analysis. (Author's
abstract, modified) #*
11091
Sawicki, E.
BICHOESTIMATION OF BENZO(a)PYRENE IN AIKBORNE PARTICOLATES
AND AIR POLLUTION SODR7E EFFLUENTS. Preprint, Public Health
Service, Cincinnati, Ohio, National Center for Air
Pollution Control, ((8))p., ((1967?)) 4 refs.
The partlculate collected from the urban atmosphere is
extracted with an organic solvent and then separated alongside
pure benzo (a)pyrene (BaP) with alumina thin-layer chromatography.
The unknown and standard spots are eluted, their solutions are
evaporated, and the residues are dissolved in concentrated
sulfuric acid. Readings of standard and test spot solutions are
taken at F 470/540 with the spectrophotofluorimeter or with a
filter fluorimeter containing a primary filter peaking at 160
millimicrons and a secondary filter peaking at 565 millimicrons.ft
11093
Stanley, Thomas H.
SPECTROPHOTOBETHIC DETERMINATION OF BENZO(a)PYRENE IN
AIRBORNE PARTICOLATES. Preprint, Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution
Control, ((8)) p., 1968. 5 refs.
Airborne particulates collected from polluted atmospheres on
glass-fiber filters are extracted exhaustively with an organic
solvent. These extracts are carefully reduced to tarry residues
through evaporation and then separated on thin-layers of
activated alumina. The fluorescent area of pure benzo(a)pyrene
and a corresponding area of the sample are removed from the TLC
plate and eluted. Solutions of the pure compound and the unknown
are spectrophotometricaliy measured between 4000 and 2400
angstroms. Wavelengths 3900, 3820, and 3750 angstroms are used to
determine the amount of benzo(a)pyrene present in the sample.*!
D. Measurement Methods *27
-------
11164
field, Frank H. and Walter E. Halpin
DETERMINATION OF HALOGENATED AND AROMATIC HYDROCARBONS IN AIB BY
CHARCOAL TUBE AND GAS CHROMATOGRAPHY. Am. Ind.. Hyg. ASSOC.
J., 29 (4) :390-396, July-Aug. 1968.
The preparation and use of a simple charcoal tube is described for
the collection of air samples for the determination of several
commonly encountered halogenated and aromatic hydrocarbons of
industrial hygiene significance. A rapid and efficient desorption
procedure is employed. Specific parameters are presented for
quantitative determination by gas chromatography. The method
provides an easily applicable technique with the advantages of
minimum field sampling equipment; and rapid, specific, accurate and
economical determinations at atmospheric con-centrations ranging
from a few ppm to several times the Threshold Limit Value.
(Authors' abstract)
11165
Rossano, August T. and Hal B. H. Cooper
SAMPLING AND ANALYSIS. Chem. Eng., 75 (22) : 142-146, Oct. 14,
1968.
Knowledge of the types and rates of emissions from a source or
group of sources is fundamental to appraising an air pollution
problem. Three factors are critical,in source testing and analysis:
measuring gas properties.-in.the duct, withdrawing representative
samples, and accurate analysis.
11218
Stanley, Thomas W., Myrna J. Morgan, and James E. Meeker
APPLICATION OF ITLC AND FLtJOHOMETRY TO THE ESTIMATION OF
7H-BENZ(de)ANTHRACEN-7-ONE AND PHENALEN-1-ONE IN ORGANIC
EXTRACTS OF AIRBORNE PARTICULATES FROM 3-HOUR SEQUENTIAL AIR
SAMPLES. Preprint, Public Health Service, Cincinnati,
Ohio, National Air Pollution Control Administration,
((14)) p., Aug. 1968'. ((5)) refs. (Presented at the 156th'
Annual Meeting, American" Chemical Society, Division of
Water, Air, and Waste Chemistry, Atlantic City, N.J.,
Sept. 1968.)
Instant thin-layer chromatography (TILC) was performed by use of
glass-fiber paper inpregnated with silica gel to separate
7H-benz(de)anthracen-7-one and phenalen-1-one found in acetone
extracts" of airborne particulates from 3-hour sequential air
sanples. Only 15 minutes was required to separate 0.2 to 1.25 sg.
of the crude extract with pentanetether, 19:1 v/v. Compounds to
be assayed were located on the chromatogram by use of relative
Rf values and changes in fluorescence colors in an acidic
environment under long-wavelength ultraviolet light. Direct
fluoroietric measurement and scanning at F-418/550 and F 409/490
428 HYDROCARBONS AND AIR POLLUTION
-------
Indicated concentrations ranging from 2 to 47 microgram/1000 cu n
of air for 7H-benz(de)anthracen-7-one and from 0.3 to 17
licrogram/1000 cu m for phenalen-1-one. For
7H-benz(de)anthracen-7-one the precision of the method calculated
as relative standard deviation was plus or minus 3.6% with a
detection limit at 5 nanograms. For phenalen-1-one, precision
las plus or minus 1.6% with a detection limit at 2 nanograms.
Ihe method was applied in analysis of 3-hour sequential air
samples taken with Hi-Vol samplers over two 2t-hours periods
during January 1968. (Authors' abstract)!*
11237
J. C. Chipman, A. J. Rocker, and John chao
HEASURING AND EVALUATING AUTOMOBILE EXHAUST HYDROCARBON
EMISSIONS BY INTERRELATED TECHNIQUES. Preprint,
California Air Resources Lab., Los Angeles, ((19)) p., 1968.
10 refs. (Presented at the 61st Annual Meeting, American
Institute of Chemical Engineers, Symposium on Research and
Development in Automotive Air Pollution Control, Los
Angeles, Calif., Dec. 1-5, 1968, Paper 53-E.)
The smog forming potential of exhaust gas from a 216 car survey
•as determined. This potential is defined in terms of reactivity
units. Exhaust hydrocarbon emissions were measured by
nondispersive infrared, ultraviolet and flame ionization analyzers.
The measurements of these analyzers were correlated with the
reactivity -of the exhaust gas. The results show that each
analyzer is capable of delineating the smog potential of gasoline
powered vehicles. Hydrocarbon emissions were also correlated
uith engine classes. The emission level differences for
concentration are larger than those obtained on a reactivity or
Bass rate basis. (Authors' summary)**
11270
O'Keeffe, Andrew E.
PROGRESS REPORT: PEHHEATION STANDARDS FOR TRACE GAS ANALYSIS.
Preprint, Public Health Service, Cincinnati, Ohio,
National Center for Air Pollution Control, ((6))p., ((1966)).
1 ref. ' (Presented at the 152nd Meeting, ACS, Division of
Rater, Air and Waste Chemistry, New York, N. Y., Sept.
11, 1966.)
A microbottle for dispensing liguefiable gases at rates lower
than can be attained by an original method has proved useful.
The several steps of its construction and filling, are largely
self-explanatory. The glass envelope is drawn down to a size
that will not permit passage of the spherical bead; the
coefficients of expansion of bead and envelope should not differ
widely. For dispensing liguefiable gases incompatible with
FEP Teflon a similar microbottle having a tetrafluoroethylene
(TFE Teflon) barrier has proved suitable. For dispensing
fixed gases a microbottle similar to that described above, but Bade
of metal, is connected directly to a cylinder of gas. A Bourdon
gauge assures that this "infinite" gas source has not been
D. Measurement Methods 429
-------
accidentally exhausted. This verion is incapable of providing a
gravimetrically calibrated primary standard; indirect calibration
will usually be necessary. Substitution of thin-wall TFE
Teflon tubing for the FEP tube of the original device adapts it
for dispensing substances whose properties are such as to limit
their permeation rates at undersirably low values. This
modification has extended the range of usefulness of permeation
tubes, operating at room temperature, to include compounds as
large as cumene.tf
11U76
Andreeshcheva, u. G.
THE EFFECTS OF CERTAIN AROMATIC HYDROCARBONS IN THE AIB.
((0 sanitarno-toksikologicheskoi otsenke nekotorykh
aromaticheskikh uglevodorodov v atmosfernom vozdukhe.)) Hyg.
Sanit. (English translation of: Gigiena i Sanit.),
33(«-6):13-17, April-June 1968. ((10})'refs.
CFSTI: TT 68-50«l»9/2
A spectrophotometric method of determining meta-nitrochlorbenzol
(HNCB) , and 3,4-dichloraniline (3,'l-DCA) in the air is
elaborated. The findings point to a definite relation of the
threshold values of smell to the changes in the chemica'l structure
of the substance due to introduction of nitro-amino- and chlorine
groups into the benzol ring. The action of chlorine products on
the light sensitivity of eyes becomes stronger as additional
chlorine groups, besides the nitro- and amino- groups, are being
introduced into the benzol ring.**
11«85
Kaznina, N. I.
DETERMINATION OF STYRENE IN AIR BY PAPER CHROMATOGRAPHY.
((Opredelenie stirola v vozdukhe s pomoshch'yu bumazhnoi
khromatografii.)) Hyg. Sanit. (English translation of:
Gigiena i Sanit.). 33 (U-6):215-217, April-June 1968. ((2))
refs.
CFSTI: TT 68-50UU9/2
A chromatographic method was developed for the determination of
styrene in air, based on the reaction of styrene with mercury
acetate in an e'thanol medium. The minimum amount of styrene which
can be so determined is 0.5 microgram. Quantitative determination
of styrene is based on the color intensity of spots developed on
the paper by reaction with diphenylcarbazide.lt
11486
Petrova, B. S. and 0. N. Shevkun
HYGIENIC ASSESSMENT OF ODOR OF NONBET4IIIC BUILDING HATERIALS.
((K voprosn o gigienicheskoi otsenke nemetallicheskikh
stroitel'nykh materialov po ikh zapakhu.)) Hyg. Sanit.
430 HYDROCARBONS AND AIR POLLUTION
-------
(English translation of: Gigiena i Sanit.), 33 (4-6):218-220,
April-June 1968. ((2)) refs.
CFSTI: TT 68-50449/2
Testers were first studied to ensure that they have a normal
olfactory threshold (as described below). The testers then
evaluated the odor of the building material under test (Vozhzhova
and Denisenko). The odor of several coatings and other materials
»as tested. A varnish coating based on styrene with epoxy ester
was tested for its odor 8 months after its application to the
substrate. In the testing of a special adhesive with a
phenolformaldehyde base, an olfactory sensation was produced by
0.6-0.8 ml air; i.e., it produced a "moderate odor". Every
naterial tested by this method (taking into account the specified
conditions of its envisaged use) may be categorized in terms of its
odor. The method makes it possible to appraise the odor of new
articles and materials at moderate cost and with simple equipment.!
111*96
Dmitriev, H. T., N. A. Kitrosskii, and V. A. Popov
FLAME-IONIZATION CHHOHATOGRAPHY FOR DETERMINATION OF ORGANIC
HATTER IN AIR. ((0 termoionizatsionnom khromatograficheskom
veshchestv v atmosfernom vozdukhe.)) Hyg. Sanit. (English
translation of: Gigiena i Sanit.), 33 (4-6):350-356, April-June
1968. ((«)) refs.
CFSTI: TT 68-50449/2
Flame-ionization chromatography performed with serially
manufactured gas chromatographs is .discussed in detail. This
method is useful where large ranges of substances manufactured by
the chemical industry makes it very difficult to devise and apply
specific colorimetric techniques for the determination of organic
atmospheric pollutants. A technique for the determination of
tetrahydrofuran in air on a chromatograph, according to the
standard methods is presented. Flame-ionization chromatography
possesses important operational advantages. The normal air
components, including water vapor, do not produce background noise,
so that all the peaks are formed by organic pollutants. The
chromatographs are insensitive to vibrations, temperature
variations, changes in air pressure and wind velocity, and are
practically free from inertia. Small variations in the flow
rates of hydrogen and nitrogen are likewise immaterial.
Tlame-ionization instruments may be used in mobile units and in
expeditions. Flame-ionization chromatography may be recommended
as a universal method 'for the determination of atmospheric
pollutants of organic origin.#t
1U98
Aigina, E. P., G. S. Lopukhova, and S. S. Khikmatullaeva
SPECTROPHOTOMETHIC DETERMINATION OF THIOPHENE IN AIR.
((Opredelenie tiofena v vozdukhe 'spekrofotometricheskin metodon.))
Hyg. Sanit. (English translation of: Gigiena i Sanit.),
33(4-6) :409-411, April-June 1968. ((!)) refs.
CFSTI: TT 68-50449/2
D. Measurement Methods 431
-------
The spectral characteristic of thiophene in the wavelength range
220 - 250 millimicron, using ethanol, methanol, heptane, hexane
and octane as the solvents was studied. Measurements of the
optical densities of methanol solutions of thiophene with
concentrations up to 15 micrograms/ml at lambda = 231 millimicrons
showed these solutions to obey the Lambert-Beer law. Therefore
the concentration of thiophene in the solution can be determined
from the optical density using,a calibration graph, or calculating
from an equation. For determinations of thiophene in air in the
presence of benzene, another variant was elaborated making use of
Vierordt's method. This "method makes it possible to determine
concentrations of each of the components of a binary mixture from
the optical density of solution. The spectral characteristics of
methanol solutions of benzene and thiophene are shown. Thus, two
variants of the spectrophotometric method are proposed for the
determination of thiophene in air. The first variant, proposed
for hygienic experiments, is based on measuring the absorption of
0V radiation by the methanol solution of thiophene at lambda =
231 millimicrons. Its sensitivity is 0.5 micrograms per 1 ml
solution. Benzene in concentrations of up to 20 micrograms/ml
does not interfere with the determination. The second variant,
proposed for determination of thiophene in air in the presence of
benzene, is based on measurements of absorption of UV radiation
by a thiophene — benzene mixture in methanol at 231 and 254.6
millimicrons. The thiophene concentration in the solution is
calculated from an equation. This variant is used in the presence
of benzene concentrations exceeding 20 micrograms in 1 ml methanol.
115KO
Yeich, B. A.
A METHOD FOR DETECTING LOW CONCENTRATIONS OF AIRBORNE GASEOUS
CONTAMINANTS. Western Electric Co., Reading, Pa.,
p. 219-229, ((1968)).
CFSTI: N68-29312
A condensation nuclei counter, with suitable converters, may be
used to monitor concentrations of sulfur dioxide and certain
hydrocarbons. Problems encountered and items of value discovered
in using this equipment are discussed. The counter is not
actually a counter, but a photometer which measures the forward
scattered light in a dark-field optical system. The instrument is
unique because it enables monitoring of particles in the
submicroscopic range of 0.001 micron to 0.1 micron. The intensity
of the scattered light is read by a photomultiplier tube. The
meter is divided into linear steps of 300, 1,000, 3,000, 10,000 and
100,000 nuclei per cc exponential steps of 1,000,000 and 10,000,000
and, thereby permitting a response time of only two seconds fro«
intake to readout of a sample. The nuclei counter and sulfur
dioxide converter are extremely useful for detecting ainute
guantities of sulfur dioxide in the ambient air. They are
sensitive and reliable, as can be verified by our two years of
almost constant monitoring. The value as a quantitative
instrument is limited because of a lack of ease in checking
operation and the narrow range of contamination measured on the
linear scales and the limitations of readout and sensitivity on the
exponential scales. The simplicity of operation far outweights
the faults of readout in the investigative area.##
432 HYDROCARBONS AND AIR POLLUTION
-------
11554
Bricteux, J., 8. Fasotte, and P. Ledent
A METHOD FOE SAMPLING AND DETERMINING HEAVY HYDROCARBONS IN
COMBUSTION FUMES. (Mise au point d'une methode de prelevement
et de dosage des hydrocarbures lourds dans les funees de
combustion.) Text in French. Ann. Mines Belg. n (3):309-331,
March, 1968. 16 refs.
A method has been devised for sampling and measuring heavy
hydrocarbons in combustion smokes. The sampling technique is
based on the adsorption of the hydrocarbons on a short adsorbent
column placed within the chimney itself. The smokes can be
drawn up through the sampling tube in less than one minute with
the help of a rubber syringe. In order to measure the
hydrocarbons collected, the sampling tube is inserted in a
carrier gas circuit which also includes a flame ionization
detector. The tube is brought up to a high temperature in a
mobile oven. The hydrocarbons are desorbed and carried by the
carrier gas towards the dector; there is no separation of the
hydrocarbons and the response appears in the form of a single
peak on the recording paper. It is possible to desorb
hydrocarbons having a boiling point above 500 degrees C without
inducing cracking phenomena. The output, which depends on the
boiling temperatures of the sampled hydrocarbons, is excellent and
can be still farther improved if, prior to the sampling, the tube
is refrigerated. A quantity of 10-6g anthracene produces a peak
allowing accurate guantitative determination of the compound.
The method also makes possible to perform a detailed analysis of
the sample and determine the individual concentrations of the
various components. For this purpose, a chromatographic
column must be inserted into the carrier gas, between the sampling
tube and the detector. Several examples of the determination of
total and individual concentrations in various synthetic gas
mixtures, combusion smokes, cigarette smoke, automobile exhaust,
are presented. The possibility of applying the method to the
measurement of benzo (a) pyrene is being-considered. Another
method for assessing the sample by methanol elution followed by a
spectrophotometric examination is also described, ft
11558
Delaunois, C.
ANALYSIS OF SMALL GAS SAMPLES BY MEANS OF GAS CHROMATOGRAPHY.
(Analyse par chromatographie en phase gazeuse, de faibles
volumes de gaz.) Text in French. Ann. Bines Belg.
n(5) :6««-6i»8, 1968. 7 refs.
In various fields of research, it frequently occurs that
guantitative analyses of gas cannot be made by chromatography, if
the gas is present in small quantities, as the standard methods of
injection cannot be used. This problem was solved during research
concerning the cracking of phenols in a micro-autoclave, when less
than one milliliter of gas is produced. A gas-drainage device,
under mercury, was devised, whereby .the volume of gas could be
measured under atmospheric pressure. An original system for the
circulation of mercury, and a method for analysing H2, CH», N2,
C02, C2H«, C2H6, on a column of activated charcoal kept
permanently at a temperature of 150 degrees.C, were developed.fi
D. Measurement Methods 433
-------
11559
Delaunois, C. and B. Bettens
ANALYSIS BY GAS CHROMATOGHAPHY OF PHENOLIC AND ABOHATIC COMPOUNDS
OBTAINED FROH THERMAL CRACKING OF PHENOLS. (Analyse par
chromatographie gazeuse des constituants phenoligues et
aromatigues issus du craguage thermigue dcs phenols.) Text in
French. Ann. Mines Belg., n (5):633-641, May 1968. 7 refs.
A capillary column of 100 m loaded with propylene glycol was used
to separate thirty-six components obtained during the thermal
cracking of phenols. In addition to the separation of several
aromatic hydrocarbons, it was possible, following previous
etherification with hexamethyl disilazane, to separate the isomers
of cresols and xylenols. A flame ionization detector was used to
determine guantitatively the various components studied to
approx. 0.1% in weight. The use of a Perkin Elmer D 2U
integrator, contributed greatly to the reproducibility of the
results, and reduced the time of analysis.##
11567
Hood, L. V. S., and J. D. Kineforder
THIN-LAYER SEPARATION AND LOW-TEMPERATURE LUMINESCENCE
MEASUREMENT OF MIXTURES OF CARCINOGENS. Text in English.
Anal. Chim. Acta, «2 (2) : 199-205, Aug. 1968. 16 refs.
Low-temperature fluorescence and phosphorescence characteristics
of a number of polynuclear aromatic hydrocarbons are reported.
Complex mixtures of hydrocarbons were studied to determine the
selectivity of low-temperature luminescence measurement.
Low-temperature fluorimetry is applied to measure several
hydrocarbon carcinogens after ethanolic extraction from thin-layer
chromatograms. The method described permits determination of 0.1
micrograms of most of the potent carcinogens (such as pyrenes,
anthracenes, perylenes, tryphenylenes, etc.). The results
suggest that the method may be well suited for environmental
studies of hydrocarbon pollution.t#
1157«
Lahmann, Erdwin
STUDIES ON AIR POLLUTANTS. I. ANALYTICAL METHODS. ((Die
Untersuchung von Luftverunreinigungen. I. Analysenmethoden.))
Text in German. Bundesgesundheitsblatt, (10):115-150, May
12, 1967. 71 refs.
This detailed review of the apparatus and technigues used for air
pollution measurements deals with both sampling and analytical
methods. A distinction is made between empirical or discontinuous
and continuous methods of sampling and it is pointed out that only
the latter can yield readily interpretable results. In connection
with gas sampling technigues, the value of an impinger for
increasing the rate of dissolution of gaseous pollutants is
discussed. Methods are then described for the quantitative
434 HYDROCARBONS AND AIR POLLUTION
-------
determination of S02, SO3, N02, NO, CO, H2S, HF,
and NH3, and brief mention is made of the techniques of gas
chromatography and flame jonization detection for traces of
organic compounds. The two principal techniques for estimating
the total particulate content of the air are dust-fall and
dust-concentration determinations. The latter which depends on
photoelectric measurement of the particle density after filtration
is more difficult to perform, but more interesting from the health
point of view.##
12001
Jacobs, E. S.
GAS CHROMATOGRAPHIC DETERMINATION OF HYDROCARBONS IN AUTOMOBILE
EXHAUST. In: Report on CHC Symposium on Exhayst Gas
Analysis. Coordinating Research Council, Inc., >ew York,
N.Y., Group on Composition of Exhaust Gas, C8C-RN-40U,
pp. 3«-38, Sept. 21-22, 1965.
The principle proposed for gas chromatographic determination of
hydrocarbons in automobile exhaust and gasoline is based on the
use of a wide range temperature program with an open tubular column
and a flame ionization detector. Automatic integration of the
flame detector signal provides peak area values for determining the
concentration of each component. All exhaust gas samples for gas
chromatographic analysis are collected in 3 cubic feet coated
Hylar plastic bags. The hydrocarbon concentration of exhaust
samples decreased 3-5% after standing for one hoar in these bags.
Typically, gas chromatographic analysis showed that the decrease
was due primarily to the loss of the more reactive components.
The use of the 0.01 in ID column provides the separation and
determination for as little as 1 ppm mole carbon of each component
from C1 through C10 within 13 minutes. At present, an 0.02 in.
ID open tubular column is being used to provide analysis for as
little as 0.1 ppm carbon for each component. The conditions for
use of the 0.02 in. 1D column are the same as for the 0.01 in.
1D column except for the final column temperature. The
separation of hydrocarbons on the larger bore column is quite
adequate for quantitative as well as qualitative analysis. The
C1 and C2 hydrocarbons are determined on a short packed column of
silica gel with a flame ionization unit. The chromatographic
conditions are given. An average exhaust chromatogram contains
80-100 measurable peaks while a fuel chromatogram may contain
120-160 measurable peaks. At present, all components are
identified by comparison to retention- times obtained with
standards. This technique was found to yield fast and efficient
information for the individual hydrocarbon components found in
exhaust and gasoline. Determination o'f the individual
components allows application of specific reactivity factors to the
individual components, so that a smog potential for fuel as veil
as exhaust may be ascertained.ft
12002
Harklns, John
BROMOCOULOHETRIC 01EFIN ANALYSIS. In:. Report on CRC
Symposium on Exhaust Gas Analysis. Coordinating Research
D. Measurement Methods 435
-------
Council, Inc., New York, N. Y., Group on Composition of
Exhaust Gases, CRC-RN-UOK, pp. 41-43, Sept. 21-22, 1965.
The bromocoulometric method is based on the /observation that
olefins, excluding ethylene, can be quantitatively brominated by
passing a gas sample through a solution of appropriate composition.
Briefly, the sample is passed through the sensing solution and the
tine to generate the bromine absorbed by the sample is measured
amperometrically, that is, by noting the current flowing through
the solution when a constant potential of 220 or 230 mv is applied
to the electrodes. With the exception of ethylene the
bromocoulometric method appears to do an excellent job in
measuring olefins in exhaust gases. Work completed several years
ago indicated that ethylene could be obtained by changing the
solvent in the cell.ft
12072
Grupinski, Leonhard
MEASURING THE CONCENTRATIONS OF ORGANIC SUBSTANCE IN WASTE GASES
BY ABSORPTION AND INFRARED SPECTROMETRY. Staub (English
trnaslation), 28 (8):28030, Aug. 1968, U refs,
CFSTI: TT 68-501H18/8
A method is described for determination of organic substances in
waste gases. 10 liters of waste gas, passed through three was
bottles connected in series, are sufficient for detecting 25mg of
organic substances in 1 cu m of waste gas by means of an infrared
spectroscope. Perchloroethylene is suitable to be used as the
absorbent. The efficiency of washing may be determined with
sufficient accuracy by separate determinations carried out in the
three gas washing bottles. The method permits direct samples to
be taken from waste gas lines at intervals of 10 - 15 minutes.
(Author's summary, modified)ft
12086
Chakraborty, B. B. and R. long
THE FORMATION OF SOOT AND POLYCYCLIC AROMATIC HYDROCARBONS IN
DIFFUSION FLAHES. PART THREE. EFFECT OF ADDITIONS OF OXYGEN
TO ETHYLENE AND ETHANE RESPECTIVELY AS FUELS. Combustion
Flame, 12 (5) :"»69-«76, Oct. 1968. 15 refs.
The amounts of chloroform-soluble material, polycyclic
aromatic hydrocarbons (PCAH), and carbonaceous residue in the dry
soot recovered from ethylene-air and ethane-air diffusion flames,
respectively, have been determined and the effects on these of
increasing additions of oxygen to the fuel have been investigated.
With ethylene, the amounts of dry soot, chloroform-soluble
material, PCAH and carbonaceous residue (CR) all increase to
maxima and then decrease. With ethane, the amounts of dry soot
and CR increase to maxima and then decline whereas the
chloroform-soluble material and PCAH decrease steadily with
increase in oxygen/ethane molar ratio in the fuel stream. The
PCAH adsorbed on the soot particles leaving the flame have been
analysed by programmed temperature gas chromatography. Pyrene
predominates in the mixture but the carcinogen 3,4-benzopyrene is
436 HYDROCARBONS AND Al R POLLUTION
-------
present in smaller amounts. Increasing the addition of oxygen
to the fuel stream is shown to lead to higher temperatures in the
pyrolysis zone and an attempt has been made to account
qualitatively for the above results on the basis of the effects on
pyrolysis o± the fuel and on the oxidation of the products leaving
the tip of a diffusion flame. ft "qualitative model" for the
formation of PCAH andi"carbon" has been proposed tentatively on
the basis of recent results from this laboratory and elsewhere.
(Author's Abstract) #.*
12663
N. G. McTaggart, C. A. Miller, B. Pearce
QUANTITATIVE HYDROCARBON GAS ANALYSES DSING ALUMINA-PACKED
GLASS CAPILLARY COLUMNS. J. Inst. Petrol., 54 (538) :265-277,
Oct. 1968. 11 Pefs.
The experimental conditions necessary to obtain
quantitative hydrocarbon gas analysis by gas chromatography
using alumina-packed glass capillary columns (o.ol inch id) and
flame ionization detection are described. These conditions
include the method of reducing the activity of the alumina and the
procedure for maintaining a high and constant column
performance. The deviation of detector'response from true
weight proportionality and the need to apply determined correction
factors are shown. The quantitative results of a number of
analyses of blends of saturated and unsaturated hydrocarbon gases
are presented and statistically assessed repeatability figures are
given. Analysis times are about a half of that required when
using the conventional (3/16 inch id) columns. Inorganic
gases, if'present, must, however, be determined by other
means.. chromatograms are shown to illustrate the application of
these columns to the quantitative analysis of saturated and
unsaturated hydrocarbon refinery gas streams, and also to
natural gas samples. (Author's Summary)##
12579
Bovee, H. H. and P. A, Breysse
STUDY OF AIR QUALITY AND CONTAMINANT ANALYSIS FOR WORK UNDER
COMPRESSED AIK. Am. Ind. Hyg. Assoc. J.
29(5):432-438, Sept.-Oct. 1968. 6 refs.
The quality of air in a tunnel being constructed under pressures
varying from 0 to 30 psig was monitored'for a period of 24
months. Except for an electrical fire and an oxygen deficiency
incident, the tunneling was completed without hazardous levels of
air'contaminants being encountered. The"compressor facilities and
sampling and analytical procedures are described. (Authors'
abstract)*#
12668
R, R. Forsey
A DUAL-COLUMN GAS CHROMATOGRAPHIC METHOD FOE THE ANLAYSIS OF
LIGHT GASES. J. Gas Chromatog., 6 (11) :555-556, Nov. 1968
D. Measurement Methods 437
-------
Although many separation methods for H2, N2, 02, C02, CO,
CKH, C2H6, and H20 mixtures using gas chromatography have
been described in the literature, all have had certain limitations.
A system which combines a molecular sieve and a polyaromatic'
polymer-bead column has.the advantage of elating 02 before N2
and resolving C02 and J20, all at ambient or higher
temperatures. The column temperature was programmed at 12 degrees
C/min. from 30 degrees to 150 degrees C after the CO emerged
from the molecular sieve column to speed the elution of water
and higher molecular weight hydrocarbons from the polyaromatic
polymer-bead column. Higher molecular weight hydrocarbons,
amines, chlorinated and nitrated hydrocarbons may be analyzed by
this method because the column can be programmed as high in '•
temperature as 290 degrees C to speed the elution of these
compounds.#f
12887
Ludwig, C. B., B. Bartle, and M. Griggs
STUDY OF AIF POLLUTANT DETECTION BY REMOTE SENSORS. General
Dynamics Corp., San Diego, Calif., (122)p., July 1969. 12<» refs.
The feasibility of detecting the major air pollutants by earth-
oriented, satellite-borne sensors is investigated. The major
pollutants considered are carbon monoxide, sulfur dioxide, ozone,
ammonia, nitrogen dioxide, typical hydrocarbons, and peroxyacetyl
nitrate (PAN). The spectral region considered extends from the
ultraviolet to the microwave region. Considerations of the number
of species accessible to optical detection, the matter of day
and night detection, and of specificity indicate that the infrared
region extending from 3.5 microns to 13 microns is the most useful
one. A discussion of the pollutant species, their occurrence,
formation, chemistry, concentration levels, and distribution
profiles through the atmosphere is given. The problems of
detection in the 0V and visible regions, in relation to aerosol and
molecular scattering, are discussed. Calculations of signal
changes expected for an ideal Rayleigh atmosphere are presented.
Some considerations of aerosol (particulate) pollution detection
are discussed. Then, the radiative transfer of the thermal
emission of the earth and atmosphere under the influence of
meteorological conditions is investigated. Signal changes arising
from the difference in radiation levels due to clean and polluted
atmospheres are calculated and found to be usually more than 1%.
A performance evaluation of eight different spectroscopic
instruments for the remote detection of pollutants is made. These
include radiometers, grating spectrometers, Fourier-transform
interferometer-spectrometers, three instruments based on optical
correlation methods, microwave radiometers, and one active
system—a satellite—based laser^ Two instruments, which are
based on optical correlation methods (matched filter and selective
chopper), have the greatest potential for near-future application.
(Authors' abstract modified)
13028
Bernert, Jurgen
A METHOD FOR DETERMINATION OF THE TOTAL AMOUNT OF COMBUSTIBLE
ORGANIC SUBSTANCES IN WASTE GASES HITH HIGH HATEB VAPOR
438 HYDROCARBONS AND AIR POLLUTION
-------
CONTENT. (Eine Hethode zur Bestimmung der Gesantmenge
verbrennbarer organischer Substanzen in Abgasen mit hohen
Wasserdampfgehalten). Text in German. Wasser Luf t Betrieb,
13(6):215-216, June 1969. 5 refs.
The method for determination of the total amount of combustible
organic substances in waste gases described in two previous
papers by J. Bernert and H. Engsfeld becomes inaccurate in cases
when the waste gases have a high moisture content or are even
saturated with water vapor. This drawback is corrected by a
new sampling aspirator in which the waste-gas sample is cooled to
remove the moisture by condensation. In this manner, the sample
is separated into an aqueous phase and a gaseous phase. The
determination of the total C concentration in the latter can now
be carried out with high precision by the original method, while-
the composition of the condensate can be determined in several
different ways. The method of Egli-Shar, which involves the
determination of dissolved organically bound carbon in waste
water, is believed to be best suited
for this type of investigation.
13050
Budzak, Paul M.
SAFETY AND VENTILATION. Mining Engineering, 21 (2): 110-1 11, Feb.
1969.
Coal mine gas explosions may be due to an accumulation of
undetected methane, a flammable gaseous hydrocarbon. A new
methane monitoring system is being developed and tested by
industrial and government agencies. This system is designed as an
integral part of permissible face equipment and would
automatically cut off power to the mining machines when the
percentage of methane reached a concentration of 2% or more for
a period of 3 sec. The monitor's electrical system is completely
isolated from the mine's power circuit, and the warning lights
of the monitor are visible to everyone in the vicinity of the
unit. The monitor offers greater protection from methane gas
liberated from the coal seam.
1315«
Tada, Osamu
ON THE METHODS OF EVALUATING, THE EXPOSURE TO TOXIC SUBSTANCES BY
ANALYZING THE METABOLITES IN THE BODY. (Tainai taisha sanbutsu ni
yoru yugaibutsu bakuro hyokaho). Text in Japanese. Rodo Kagaku
(J. Sci. Labour, Tokyo), «5 («):171-183, 1969. 177 refs.
Under certain conditions, the amount of toxic substance absorbed
by workers exposed to toxic air contaminants cannot be predicted
from air analysis data. If the concentration of metabolites in
tissue or excreta is proportional to that of the toxic substance
in the air, the degree of adverse exposure may be evaluated by
analyzing samples of expired air, blood, urine, or hair, with
reference to atmospheric threshold limit values. Tests for
assessing the level of exposure to carbon monoxide, mercuric
vapor, inorganic lead, and chlorinated hydrocarbons are
D. Measurement Methods 439
-------
discussed. Of the various methods developed for determining the
carboxyhemoglobin level in the blood of workers exposed to
carbon monoxide, the 20-second breath holding method is the most
practical and convenient. If the determination is carefully made,
the urinary excretion of mercury can be used as an indicator of
exposure to mercuric vapor. The absorption of lead varies
according to whether it is absorbed as fume or dust. Therefore,
the degree of exposure should be evaluated by analyses of lead
in urine or blood during repeated exposure. The storage of lead
in the body can be determined by the increase in urinary
excretion of lead following the administration of calcium
ethylenediaminetetraacetate. The determination of urinary
excretion of alkaline-pyridine reactants is tentatively suggested
as an indicator of exposure to chlorinated hydrocarbons.
(Author abstract modified)
13543
Brunauer, Stephen and Paul H. Emmett
THE USE OF LOW TEMPERATURE VAN DER WAALS ADSORPTION ISOTHERMS
IN DETERMINING THE SURFACE AHEAS OF VARIOUS ADSORBENTS. J. Am,
Chem. Soc., Vol. 59, p. 2682-2689, Dec. 1937. 12 refs.,
low temperature van der Waals adsorption isotherms of various
gases have been determined on a variety of adsorbents. Argon
and nitrogen were determined at -195.8 C; argon, nitrogen,
carbon monoxide and oxygen at -183 C; carbon dioxide at -78 C;
and butane and sulfur dioxide at 0 C. A number of different
adsorbents were used, including copper catalysts, nickel,
silica gel samples, and activated carbon. All the adsorbents
except carbon gave S-shaped isotherms. The values for the
surface area evaluated from the different isotherms for the
same adsorbent were consistent with each other.
13779
Thompson, C. J., H. J. Coleman, C. C. ward, and H. T. Ball
DESULFURIZATION AS METHOD OF IDENTIFYING SULFUR COHPOUNDS.
Anal. Chem., 32 (3) :12«-U30, March 1960. 11 refs.
A desulfurization technique is described for pure sulfur
compounds and gas-liquid chromatography fractions of less than
0.0002 ml of sulfur compound concentrates from crude oils. The
apparatus consists of an aluminum reaction tube packed with
catalyst, a furnace for heating the reaction tube to the
desired temperature, a motor-driven syringe for charging
relatively large quantities of pure compounds, and the necessary
adapters, valves, and connectors for handling very small trapped
samples from the GLC column. Samples are passed through the
apparatus at a temperature of 150 to 200 C, and the hydrocarbons
produced upon desulfurization are collected and identified by
gas-liquid chromatography. By analyzing the hydrocarbons
produced, it is possible to determine the exact sulfur compounds
found in the crude oil fractions. Data are presented showing
the desulfurization of typical members of the sulfur compound
classes: alkane and cycloalkane thiols, alkane and cyclic
sulfides, thiophenes, and benzothiophenes.
440 HYDROCARBONS AND AIR POLLUTION
-------
13805
Chaigneau, H., L. Giry, and L. P. Ricard
ANALYTICAL INVESTIGATION OF SOME TYPES OF SOOT, USING MASS
SPECTRCMETRY. (Etude analytigue de quelques suies par
spectrometrie de masse). Text in French. Chim. Anal. (Paris),
51 (4) : 187-195, April 1969. 9 refs.
Application of mass spectrometry to soot obtained from the
combustion of fuel in a boiler furnace, from the combustion
of motor fuel, and from chimney deposits caused by the burning
of firewood revealed that carbonaceous deposits comprise ,
complex mixtures containing numerous organic substances. Of
the 71 organic bodies identified, 34 were hydrocarbons and these
included a number of condensed-nucleus polycyclic compounds and
aromatic hydrocarbons. Among the main compounds were
derivatives of naphthalene, pyrene, perylene, acenaphthalene,
and diphenyl. other compounds identified were acridines, phenols,
and quinones. The data obtained show that the composition of soot
varies according to the origin of the fuel and the method of
combustion. Soot from wood contains more hydrocarbons than
soot from fuel oils or even motor fuels, but soot from fuel
oil contains only hydrocarbons. Quinones, phenols and their
ethers, acetic acid, and benzaldehyde are found only in soot
from wood.
13971*
flrose, H.
DETERHINATION OF HYDROCARBON CONTENT OF THE AIR BY GAS
CHROMATOGRAPHY. (Bestimnung des Kohlenwasserstoffgehaltes der
Luft mit Hilfe der Gaschromatographie). Text in German. Z.
Meteorol., 20 (1-6):60-67, 1968. 9 refs.
A flame ionization detector installed at the outlet of an
appropriate gas chromatographic column permits direct
measurements for quantitative and qualitative analysis of
atmospheric hydrocarbons up to 0.1 ppm. Traces two orders of
magnitude smaller must be analyzed in concentrated form. The
physical-chemical fundamentals of gas chromatography are briefly
summarized, as is the function of the detector. An experimental
apparatus which shows the stated sensitivities is described.
(Author abstract modified)
13989
Oblaender, K. and D. Kraeft
DETOXICATION OF AUTOMOTIVE EXHAUST GASES - MEASURING METHODS AND
TEST CYCLES. (Abgasreinigung an Kraftfahrzeugen -
Messverfghren und Testzyklen). Text in German. ATZ
(Automobiltechnische Zeitschrift) (Stuttgart), 71 (4) : 117-124,
1969. 24 refs.
0. Measurement Methods 441
-------
Detoxification of automotive exhaust gases raises not only motor
engineering problems but also measurement engineering problems.
The various methods for measurement of CO based on heat
conductivity, on heat evolution and an infrared absorption are
discussed and compared. The disadvantages of hydrocarbon
measurements in the hexane range and of the flame ionization
method are pointed out. Also discussed are the measurement of
nitric oxide and the existing and planned multi-stage test
cycles. A brief discussion of the possibilities of lowering the
exhaust gas emission by motor modifications, the effects of
traffic, and the fuel composition is included.
Leonardos, Gregory, David A. Kendall, and Nancy J. Barnard
ODOE THRESHOLD DETERMINATIONS OF 53 ODOEANT CHEMICALS. Preprint,
Air Pollution Control Assoc. , Pittsburgh, 23p., 1968. 1 refs.
(Presented at the 61st Annual Meeting of the Air Pollution Control
Assoc.., St. Paul, Minn., June 23-27, 1968, Paper 68-13.)
Recognition odor thresholds for 53 commercially important
chemicals were determined in the laboratory by an expert panel of
four members. By standardizing the method of sample presentation
and minimizing extraneous sensory interference, the concentrations
determined as producing the minimum identifiable odor response
provided consistent and internally comparable data for one
parameter of odor. The odorants were presented to the panel in a
static air system utilizing a low-odor background air as the
dilution medium. The odor threshold was defined as the first
concentration at which all panel members were able to recognize
the odor. Aspects of human odor detection and of the concept of
the odor threshold are discussed. The thresholds determined for
each odorant in terms of parts per million by volume are
presented. The minimum threshold observed was with trimethyl
amine at 0.00021 ppm. As a group, compounds with sulfur had the
lowest thresholds of the compounds tested. It was noted that
carbon disulfide, sulfur dichloride, and sulfur dioxide affect
the other chemical senses (taste and feel) as well. The
presence of unsaturation in an odorant chemical was not found to
be associated with low threshold concentrations, and it is
observed that extended generalizations pertaining to the odor
threshold based on similar chemical structures cannot easily be
made. With reference to benzenoid-type materials, substitution
on the benzene ring reduced the odor threshold by as much as a
thousandfold depending on the nature of the group added, and in
general produced a wide variation in thresholds. Three
chemicals, toluene, styrene, and tolylene diisocyanate were
purified by a gas-liguid chromatography to note the effect of
chemical purity on the odor threshold; differences from
thresholds determined from starting materials seemed slight, if
any.
1U125
Matsushita, Hidetsuru, Yasutomo Suzuki, and Hiroyuki Sakabe
A SPECTROFLDOROMETRICAL METHOD FOR DETERMINATION OF 3,U-
BENZPYRENE IN BENZENE SOLUTION CONTAMINATED KITH 3,«-
442 HYDROCARBONS AND AIR POLLUTION
-------
8ENZFLUORANTHENE OR 3,«-BENZFIOORANTHENE AND 1,2-BENZPYRENB.
Ind. Health, (Japan), vol. 3:107-120, 1965. 11 refs.
I spectrofluorometric method is proposed which consists of removing
oxygen dissolved in a test solution, measurement of fluorescence,
and determination by a narrow base line method as outlined by
Coninins. By this method, 3,4-benzopyrene can be determined
accurately even in a solution containing 3,U-benzopyrene,
3,U-benzofluoranthene and 1,2-benzopyrene in a concentration ratio
of 1:100:100.- This method has an advantage over the ordinary peak
lethod in that it eliminates interference of the contaminants
which may be attributed to the following facts. Fluorescence
intensities of the contaminants change in an approximately linear
Banner over the narrow range of wavelength near 405 millimicrons
and removing the oxygen makes the characteristic peak of 3,4-
benzopyrene distinct at 405 millimicrons. However, the narrowing
of wavelength range has some limit, as it results in a decrease
in peak height and drop in sensitivity. The base line which
connects the two points 25-30A distant from the 405 millimicron
peak on either side is assumed to be most suitable for the
determination of 3,4-benzopyrene in the benzene solutions
contaminated with impurities. selection of a excitation source
seems to be an important factor to minimize interference of
contaminants, although in this case only 366 millimicron mercury
light was used. If the exciting light is so selected that it is
absorbed strongly by 3,4-benzopyrene and weakly by contaminants,
the present method will be also useful for the determination of
3,4-benzopyrene in a solution contaminated with various other
polynuclear hydrocarbons.
14173
Sharkey, A. G., Jr., J. L. Shultz, T. Kessler, and R. A. Friedel
DETERMINING ORGANIC CONTAMINANTS IN AIR AND WATER. Res./Dev.,
20(9):30-32, Sept. 1969. 14 refs.
In this limited investigation of organic contaminants in airborne
particulate matter and .treated sewage, the potential of the high-
resolution mass spectrometer for expanding the knowledge of
pollutants in air and water supplies is demonstrated. A major
advantage of this type of instrumentation is that the elemental
compositions of a wide variety of components can be determined on
essentially total samples. Information concerning alkyl
derivatives, such as carbon number distribution data obtainable by
mass spectrometry, could be of prime importance in studies of
carcinogenic pollutants. A limitation is that particular
isomers cannot be determined. Combined gas chromatographic-mass
spectrometric techniques, particularly with the use of high-
resolution mass spectrometry in this combination, will increase
the usefulness of the method for studies of organic pollutants.
Data are presented on ten typical airborne pollutants to
illustrate the applicability of the high-resolution technique to
detect and determine the elemental composition of polynuclear
species in atmospheric particulate matter. Additional data are
given to illustrate the ability of the instrument to detect
organic compounds having the same nominal molecular weight but
different precise mass resulting from the presence of heteroatons.
(Author conclusions modified)
D. Measurement Methods 443
-------
14301
Wallcave, Lawrence
GAS CHROMATOGBAPHIC ANALYSIS OF POLYCYCLIC AROMATIC
HYDROCARBONS IN SOOT SAMPLES. Environ. Sci. Technol., 3(10):
948, Oct. 1969. 3 refs.
An unknown pyrene derivative was isolated from soot by Long and
Chakraborty in 1967. An apparently identical compound
isolated by this author from a coal tar pitch is presumed to
be cyclopenta (c,d)pyrene (or acepyrene) . The absorption
spectrum of this substance has the seemingly characteristic peaks
found by Long and Chakraborty at 378 and 358 millimicrons.
Its molecular weight is 228, and its mass spectrum possesses
peaks at m/e values greater than 228. Cyclopenta (c,d)pyrene is
the only compound of reasonable structure that can have a
molecular weight of 228 as well as the absorption spectrum and
chromatographic behavior of an alkyl pyrene derivative. It is
by no means a trace element. Five to 10 micrograms were
isolated from 5 mg of coal tar pitch, indicating a concentration
of 0.1%.
14428
Hadzija, Olga
ABSOEBENTS IN MICROANALYSIS. IV. ADSOBPTION PROPERTIES OF
SILICA GEL IN SIMULTANEOUS DETERMINATION OF CARBON, HYDROGEN,
AND IODINE OR CARBON, HYDROGEN AND SULPHUR. Mikrochim. Acta
(Vienna), no. 5:1114-1116, 1969. 2 refs.
A simple gravimetric method is described for simultaneous
microanalytical determination of carbon and hydrogen together
with sulfur, bromine, or iodine, in non-nitrogenous compounds.
Commercial silica gel is used as the external absorbent for
sulfur dioxide and halogens at room temperature. Under these
conditions, sulfur dioxide does not oxidize to sulfur trioxide.
The increase in weight of the silica gel tube corresponds to
sulfur dioxide formed from which the percentage of sulfur can be
calculated. One silica gel layer can be used for 4-5 analyses,
provided that the first analysis is that of a sulfur-containing
compound. The method does not work for nitrogen-containing
compounds.
14430
Benes, Milos, Milada Halechova, Jiri Halecha, and Jaroslav
Myslivecek
ANALYSIS OF GASEOUS MIXTURES CONTAINING CARBON MONOXIDE, CARBON
DIOXIDE, HYDROGEN, METHANE, NITROGEN AND OXYGEN. (Deleni smesi
kyslicniku uhelnateho, kyslichniku uhliciteho, vodiku, methanu,
dusiku a kysliku plynovou chromatografii). Text in Czech.
Chem. listy, 63 (6) :703-709, 1969. 13 refs.
The title compounds are found in combustion products, in chemical
plants, and in all cases where the burning of fuel is not fully
444 HYDROCARBONS AND AIR POLLUTION
-------
accomplished. The use of gas chromatography for measurement
gives more precise and rapid results than all other known methods.
Analysis of incompletely burned methane uses helium as carrier
gas and thermal conductivity and combustion detectors are used
for determinations. Gases are separated on a molecular sieve 5A
and Synachrome. Individual gaseous mixtures are recorded at
laximal sensitivity, in accordance with possible percentage
content of individual components in the sample. From empirical
results it is evident that the greatest accuracy is achieved for
carbon dioxide and methane and the least for nitrogen.
1I4U70
Steger, Eberhard and Hermann Kahl
THE ANALYSIS OF GASEOUS AIR CONTAHINATIONS BY INFRARED
SPECTPOSCOPY. (Die ultrarotspektroskopische Analyse
gasfoermiger Luttverunreinigungen). Text in German. Chem.
Tech. (Berlin), 21 (8):U83-U88, Aug. 1969. U3 refs.
The detection thresholds of infrared spectrometry were determined
for diethylether, carbon tetrachloride, benzene, acetone,
nethanol, carbon dioxide, sulfur dioxide, hydrogen sulfide,
propane, and acetylene in the gaseous state. The recorded
spectra were analyzed by the method of Wright. In all analyses
of the gases, such influences as pressure and interference by
other compounds must be taken into account. It is important to
use the same pressure for the measurement and the calibration.
Interfering substances, particularly H20, were eliminated by use
of the drying agent calcium chloride. Study of mutual
interference showed that only methanol was slightly influenced
by diethylether. The error calculation method for evaluation
Has used when the average value was determined from at least
five measurements. The detection thresholds found for the
substances measured are listed. It is concluded that infrared
spectrometry can be used for gas analyses in the concentration
range of the threshold limit value for eight hours (with the
exception of H2S). It is not good enough, however, for
concentrations in the range of maximum allowable values in the
atmosphere."
W76
Ixfeld, H.
BETHOD FOR DETERHINING ORGANIC SUBSTANCES IN WASTE G&SES.
(Verfahren zur Erfassung organischer Substanzen in Abgasen).
Text in German. Brennstoff-Chem. (Essen), 50(6):186-189, June
1969. U refs.
The method of Ixfeld and Buck for guantitative determination of
organic substances in waste gases (with the exception of the
hydrocarbons C1-C1) can be improved if the samples are carefully
taken and prepared. This improvement is illustrated by the
example of waste gases from a lacguer-drying stove. The waste
gases from these stoves are usually cleaned in catalytic after-
burners. The partially clean gases contain much higher fractions
of C02 (50 to 100 g/cu m) and water vapor (20 to 50 g/cu m) than
the uncleaned waste gases. These high concentrations may have a
0. Measurement Methods 445
-------
considerable influence on hydrocarbon analysis by the Ixfeld and
Buck method. To determine the magnitude of this influence, C02
and synthetic air were nixed in a 1:1 ratio and freed of
combustible organic substances. The gas mixture, cooled to room
temperature and saturated with water vapor, was passed for 10 min
through a silica gel tube. The tube was tightly sealed
afterwards and left to rest for periods of up to 24 hrs. After
that it was flushed for 5 Bin with nitrogen and desorbed. The
desorbed C02 quantity was proportional to the length of time
the silica gel tube rested. The optimum resting period between
the two flushings was H hrs. After this period, further reduction
of the remaining C02 content was found to be negligible. The
nitrogen flushings did not influence analysis of the adsorbed
organic substances. Similar experiments were conducted to
determine the influence of H20. So-called MN silica gel was used
as the adsorbent and hexane as the organic component with synthetic
air. The measurement errors increased with water content.
Lowering of the gas throughput in the same sampling time brought
no improvement. Aerosols can be better sampled if glass fiber
filters are inserted ahead of the silica gel tube.
1H525
Innes, W. B.
SELECTIVE COMBUSTION ANALYSIS AND APPLICATION TO AUTO EXHAUST.
Franklin Inst. Research Labs., Philadelphia, Pa., Materials
Science and Engineering Dept. and Public Health Service, Durham,
N. C., National Air Pollution Control Administration, Proc. First
Natl. Symp. on Heterogeneous Catalysis for Control of Air
Pollution, Philadelphia, Pa., Nov. 1968, p. 363-382. U refs.
The application of a vanadia catalyst to hydrocarbon analysis is
discussed. The combination of hydrocarbon-carbon monoxide
analysis involves a second parallel reactor with a Hopcalite
catalyst. Air with constant moisture content passes through a
temperature-controlled preheater and catalyst bed at a constant
flow rate, and the gas sample is added to the air stream in a
small quantity. A review of California data indicated that the
idle mode was reasonably good for predicting pass/fail
hydrocarbon emission levels and that it could be correlated with
cyclic values on a statistical basis. About 300 cars were tested
at local service stations, car washes, and dealerships'which were
believed to be representative of the Los Angeles basin car
population. About 200 cars were also tested in car clinics. The
results suggested that over half the emissions can be attributed
to the high emitters (greater than 1000 ppm), most of which are
believed to have defective ignition 'systems. The effect of
routine tuneup by tuneup specialists on emissions was also
studied. The results, in line with other studies, suggest that
cars with reasonably low emissions are not helped and emissions
may even increase, and that the average degree of improvement
from a professional tuneup is proportional to how much the levels
exceed that of a car in good shape. - Together with the
distribution data, they suggest that an effective, che'ck and
correct program could lower emissions by as much as 50%.
446 HYDROCARBONS AND AIR POLLUTION
-------
1IJ607
Skala, H., F. G. Padrta, and P. C. Samson
DIESEL ENGINE POLLUTANTS. PART I. IDENTIFICATION. Franklin Inst.
Research Labs., Philadelphia, Pa., Materials Science and
Engineering Dept. and Public Health service, Durham, N. C.,
National Air Pollution Control Administration, Proc. First Natl.
Symp. on Heterogeneous Catalysis for Control of Air Pollution,
Philadelphia, Pa., Nov. 1968, p. 209-220.
High molecular weight organic constituents of diesel exhaust
other than unburned diesel fuel were identified. Samples were
collected by the use of a thermal gradient trap from a slip
stream off the total exhaust effluent. The organic pollutants
were partitioned out with n-hexane. A portion of the diesel
odor concentrate was subjected to additiona'l separation over
silica gel. Identification of the components was made by mass
spectrometry. The pollutants were found to be partially
oxidized components of the diesel fuel over its full molecular
weight range. Five different classes of oxygenated hydrocarbons
were found: aldehydes and ketones, carboxylic acids, alcohols,
phenols, and nitrophenols. These yielded a total of over
tOO observable species. Aldehydes and ketone derivatives of
paraffins, cycloparaffins, olefins, and aromatics were observed.
In the aromatic series, benzaldehyde, indanohe, cinnamaldehyde,
indenone, naphthaldehyde", acenaphthenone, and fluorenone and
their higher homologues were found. The aromatic carbonyl
compounds were the predominant species. The vital role of the
aromatic oxygenates in
-------
oxide. A standard solution of pure 3,4-benzpyrene is added to
the specimen so that after the dilution, the limit of 0.15
raicrograms/ml is not exceeded. To keep error lower than 8%,
absorption of the solution should never be higher than 0.017 for
1 cc of solution at 3650 A, The other sources of measurement
error are high concentration, unsteady current in the source
of radiation, error in freezing the dilution, and error of
dilution.
1H662
Dikun, P. P.
DETECTION OF POLYCYCLIC AROMATIC HYDROCARBONS IN POLLUTED
ATMOSPHERE AND OF OTHER POLLUTANTS BY MEANS OF QUASILINEAB
FLUORESCENCE SPECTRA. (Obnaruzheniye politsiklicheskikh
aromaticheskikh uglevodorodov v zagryazneniyakh atmosfernogo
vozdukha i drugikh ob'yektakh s pomosch'yu kvazilineychatykh
spektrov fluorestsentsii). Text in Russian. Zh. Prkl. Spektrii,
6 (2) :202-209, Febs 1967., 19 refs.
Contaminants present in urban atmospheres were investigated
by column and thin-layer chromatography and by spectral
analysis of guasilinear fluorescence spectra. Nine substances,
including three compounds possessing very high carcinogenic
activity, were detected in contaminated atmospheres. Polycyclic
aromatic hydrocarbon data obtained from the present
investigation were compared with earlier data. Structural
formulae of the compounds found in the polluted atmosphere are
given. Tables give numerical information extrapolated from
data obtained by means of fluorescence spectroscopy.
1U722
STUDY OF THE CONTINUOUS DETERMINATION OF ORGANIC SUBSTANCES WITH
FLAME IONIZATION DETECTORS. (Beitrag zur kontinuierlichen
Summenbestimmung organischer Substanzen mit
Flammenionisationsdetektoren). Text in German. Hasser Luft
Betrieb, 12(2):68-69, 1968. 8 refs.
Two hydrocarbon analyzers were used for continuous determination
of gaseous organic substances in the air. They were set up
in a busy street of Berlin and calibrated with 4.6 and 16.5 ppm
methane in synthetic air. The recordings were evaluated by
planimetry and half-hourly averages were computed. From these,
the daily averages were computed for a total of 20 measurement
days. From the daily averages for a concentration range of
2.0 to 7.3 ppm methane, a standard deviation of 0.46 ppm was
obtained. The results showed that the flame ionization
detector can be used for such measurements if it is carefully
calibrated and serviced.
1U773
Starshov, I. M. and G. Ya. Ivanova
DETECTION OF TRACE QUANTITIES OF DICHLOBOETHANE IS AIR.
(Opcedeleniye mikrokolichestva dikhloretana v vozdukhe). Text
448 HYDROCARBONS AND AIR POLLUTION
-------
in Russian. Gigiena i Sanit., no. 7:5«-55, 1969. <* refs.
Chromatographic detection of dichloroethane using a DIP-1
chromatograph is described. Analysis takes four minutes
and is sensitive to a concentration of 0.005 g
dichloroethane per liter of air. This equipment is suitable
for single determination or for continuous monitoring.
Preparation and calibration of the column is described.
11839
Freedman, R. W., H. W. Lang, and B. Jacobson
GAS CHROMATOGRAPHIC ANALYSES OF THE PRINCIPAL CONSTITUENTS
OF BINE ATMOSPHERES. Bureau of Bines, Washington, D. C.,
RI 7180, 13p., Sept. 1968. 7 refs.
CFSTI: PB 183 373
A gas Chromatographic method for the rapid and accurate
determination of oxygen, nitrogen, carbon dioxide, and if present,
carbon monoxide, in mine air was developed. This method
replaces presently used gas-reaction types such as the Haldane or
Orsat analysis, offering advantages of precision, accuracy,
speed, and convenience, j The gas Chromatographic system can
detect 02, N2, CH4, and C02 in a sample of air in concentrations
ranging from 0.01 to 100%. Precision and accuracy are
attainable over most of the range with a coefficient of variation
of plus or minus 1%. Chromatographic analysis is complete
within about 7 minutes of sample injection. If carbon monoxide
is present in excess of 0.01%, it can be deter rained as a peak
separating about 3 minutes later. The sample is introduced
by a gas sampling valve and is split into two analytical columns.
Column 1 separates oxygen, nitrogen, and methane, and, if
indicated, carbon monoxide. The methane peak appears in about
6 minutes, and the carbon monoxide peak appears in about 10
minutes. Column 2 effects the separation of carbon dioxide from
composite gases in about 2 minutes- Concentrations of the
gases are quantitatively determined by comparing the
integrated peak areas with the areas of standard gas peaks under
similar conditions.
15171
Yamate, Noburu
BANDAL METHODS AND AUTOMATIC CONTINUOUS INSTRUHENTS FOR
MEASUREMENT OF GASEOOS AIP POLLUTANTS. (Gasujo taiki osenshitsu
no sokutei to sono sokuteikiki). Text in Japanese. Kogai to
Taisaku (J. Pollution Control), 5 (10):785-796, Oct. 1969. 36
refs.
In order to prevent air pollution, measurement of pollutant
concentrations must be continuously performed. In this report,
both continuous monitoring and manual analyses of typical air
pollutants are reviewed. Numerous methods are tabulated and most
of them are explained, with particular attention to continuous
methods and apparatus. Sulfides are measured manually by
colorimetric'analysis with rosaniline or barium molybdate, by the
D. Measurement Methods 449
-------
lead per oxide method, or by test paper methods. Sulfides are
also measured continuously by means of solution conductance
(Thomas autometer) or by optical absorption with rosaniline or
with iodine-starch. Carbon monoxide is measured manually Kith
palladium sulfate and ammonium molybdate, by gas chromatography,
or by the hopcalite method. It is measured continuously by
infrared or ultraviolet absorption of reduced mercuric oxide.
nitrides are measured manually by the Saltzman or the Jacobs
method, or with ortho-tolidine sulfate. Hydrogen sulfide is
measured manually by reethylene blue and continuously by a
colorimetric filter paper method. Hydrocarbons are measured
manually by gas chromatography and continuously by flame
ionization detectors. Formaldehyde is measured manually by
colorimetric analysis with a chrcmotropic acid or with
acetylacetone, or by the MBTH method. Ozone is measured manually
by the phenolphthalein or the potassium iodide method and
continuously by coulometric titration or by optical absorption
with potassium iodide. Fluorides are measured manually by
colorimetric analysis with thorium neothron(?) or lanthanum
alizarin complex and continuously by filter paper fluorescence.
Actual Tokyo data on changes in the concentrations of carbon
monoxide, nitric oxide, and nitrogen dioxide are tabulated.
15200
King, W. H., Jr.
THE CONTINUOUS MEASUREMENT OF HYDROGEN, METHAHE, AND HYDROCARBONS
IN THE ATMOSPHERE. Preprint, American Chemical Society,
Washington, D. C., 20p., 1969. 3 refs. Presented at the
American Chemical Society, 158th National Meeting, New York, Sept.
8-12, 1969.
Photochemically inert methane accounts for 90% of atmospheric
hydrocarbons, and its large signal interferes with the flame
ionization detection of active smog-producing hydrocarbons. To
overcome this problem in hydrocarbon monitoring, automatic systems
were developed which use a flame ionization detector or water
sorption detector in conjunction with a selective catalytic
combustor. The programmed combustor unit, consisting of a guartz
tube containing a platinum wire coil, takes advantage of methane's
inertness to analyze for it in the presence of hydrocarbons. The
combustor can be utilized in three ways, each of which was
evaluated for several months in the laboratory and in the field.
One method involves the selective combustor and a flame ionization
detector. An automatic zero level, methane, and total hydrocarbons
are recorded by this method. In the second method, hydrocarbons
are dried, combusted, and converted to water and carbon dioxide.
The water is detected by a sorption detector. Hydrogen, olefins,
paraffins, and methane are recorded. The third method is analogous
to the second, except that carbon dioxide is determined, rather
than water. The second method is preferred since no extra gases
are required, calibration is simple, and equipment is portable and
battery-operated. With this technique, 1.6 ppm methane, 1.5 ppm
paraffins, and 1.9 ppm olefins and other reactive hydrocarbons have
been recorded. However, it is expected that air monitoring
stations with flame units will prefer the first method. The water
sorption technique should gain acceptance if hydrocarbon monitoring
becomes important.
450 HYDROCARBONS AND AIR POLLUTION
-------
15277
Institut National de 1"Industrie Charbonniere, Liege, Belgium
DESIGN OF A HETHOD OF SAMPLING AND MEASURING HEAVY HY.DEOCABBON
CONCENTRATIONS IN COMBUSTION FUMES. (Hise au point d'une
nethode de prelevement et de dosage des hydrocarbures lourds
dans les fumees de combustion). Text in French. Bull. Tech.
Houille et Derives, no. 36, 15p., March 1968.
A method was devised for sampling and measuring heavy hydrocarbons
in combustion smokes. The sampling technique is based on the
adsorption of the hydrocarbons on a short adsorbent column placed
within the chimney itself. The smokes can be drawn up through
the sampling tube in less than one minute with the help of a
rubber syringe of the 'Propipette' type. To measure the
hydrocarbons collected, the sampling tube is inserted in a
carrier gas circuit which also includes a flame ionization
detector. The tube is brought to a high temperature in a mobile
oven. The hydrocarbons are desorbed and carried by the carrier
gas towards the detector; there is no separation of the
hydrocarbons, and the response appears in the form of a single
peak on the recording paper. It is possible to desorb
hydrocarbons with a boiling point above 500 C, and it has been
demonstrated that no cracking occurs. The drainage output, which
depends on the boiling temperatures of the sampled hydrocarbons,
is excellent and can be still further improved if, prior to the
sampling, the tube is cooled to the temperature of the dry ice.
With regard to sensitivity, it was demonstrated that, in the case
of anthracene, quantities equal to 0-000001 g produced a peak
the area of which allowed a precise measurement to be made.
The method also makes it possible to carry out a detailed
analysis of the sample and determine the individual
concentrations of the various components. For this purpose,
a chromatographic column must be inserted into the carrier gas
between the sampling tube and the detector. Several examples
of the determination of total and individual concentrations
are given in various fields: synthetic mixtures, combustion
smokes, cigarette smokes, and automobile exhaust gas. The
possibility of applying the method to the measurement of
benzo(a)pyrene is being considered. In variation, a secondmethod
of assessing the sample by methanol elution followed by a
spectrophotometric examination is described.
15337
Stanley, Thomas W., Myrna J. Morgan, and James E. Meeker
HAPID ESTIMATION OF 7H-BENZ(DE)ANTHEACEN-7-ONE AND PHENALEN-1-ONE
IN ORGANIC EXTRACTS OF AIRBORNE PARTICULATES FROH 3-HOUR
SEQUENTIAL AIR SAMPLES. Environ. Sci. Technol., 3 (11) :1198-1200,
Nov. 1969. 5 refs. (Presented at the Div. of Hater, iir, and
Baste Chemistry, American Chemical Society, 156th Annual
Heeting, Atlantic City, N. J. , Sept. 1968.)
Thin-layer chromatography using glass-fiber paper impregnated with
silica gel was used to separate 7H-benz(de)anthracen-7-one and
phenalen-1-one found in acetone extracts of airborne particulates
from 3-hr sequential air samples. Only 15 min was required to
separate 0.2-1.25 mg of the crude extract with 19:1 pentane-ether.
D. Measurement Methods 451
-------
Direct fluoremetric measurement and scanning at ? 418/550 and
F 1*09/190 indicated concentrations ranging from 2 to 48
micrograms/1000 cu m of air for 7H-benz(de)anthracen-7-one and from
0,3 to 17 for phenalen-1-one. For 7H-benz(de)anthracen-7-one, the
precision of the method calculated as relative standard deviation
was approximately 3.2%, with a detection limit at 5 nanograms.
for phenalen-1-one, the precision was approximately 1.0%, with a
detection limit at 2 nanograms. The method was applied in analysis
of 3-hr sequential air samples taken with Hi-Vol samplers over two
24-hr periods during January 1968 in polluted urban atmospheres.
In the absence of detailed meteorological and land-use data, no
meaningful conclusions can be drawn to explain changes in
concentrations of these compounds during the 24-hr periods
investigated. At the same site used for this investigation, a
different diurnal distribution pattern was observed for four
polynuclear aromatic hydrocarbons. However, the distribution
patterns were consistent with peak concentrations occurring from
6-9 a.m. and from 3-6 p.m. The direct spectrophotofluorcmetric
procedure reported in this paper and similar procedures show
potential for application to more comprehensive air pollution
studies.
15354
Wilson, K. W., G. J. Doyle, D. A. Hansen, and R. D. Englert
PHOTOCHEHICAL REACTIVITY OF TRICHLOROETHYLENE AND OTHER
SOLVENTS. Am. Chem. Soc. Div. Org. Coatings Plastics Chem.
Preprints, 29(2):445-449, 1969. 6 refs. (Presented at the
158th Beeting of the Am. Chem. Soc., Div. Organic Coatings and
Plastics Chemistry, New York, Sept. 1969.)
A special smog chamber was built to study the slowly reacting
solvents which, in the presence of nitrogen oxides, form smog
much more slowly than do automobile exhausts. The chamber has
Pyrex panels vith an access wall of cast aluminum. The aluminum
wall incorporates eye ports for measurement of eye irritation,
an access hole for the optics of a miltireflection infrared
cell, and sampling ports through which gas is removed for wet
chemical analysis. An air purification system for the chamber
removes contaminants by catalytic combustion over platinum
at 5-8 atm and 500 to 600 C and cools the purified air to below
327 C and about 1 atm. Performance of the chamber was validated
by charging it with test hydrocarbons, e.g., ethylene, cyclohexane,
tricholoroethylene, xylenes, and paraffins at 1, 4, or 8 ppm
and nitric oxide at 0.25, 1, or 2 ppm. The photooxidation
experiments show that the rate of photochemical smog formation
decreases as the hydrocarbon:nitric oxide ratio decreases
and that eye irritation is caused primarily by formaldehyde.
As judged by its rate of disappearance, trichloroethylene is
less reactive than ethylene. Trends observed with changing
concentrations of trichloroethylene also suggest that average
atmospheric concentrations of trichloroethylene would produce
no eye irritation or other measurable smog symptoms.
15355
Luis, P., C. U. Carducci, and A. Sa
DETECTION OF FLUORINE ON THE NANOGRAB SCALE; INORGANIC AND OBGANIC
452 HYDROCARBONS AND AIR POLLUTION
-------
FLUORINE COMPOUNDS. Mikrochira. Acta (Vienna), no. 4:870-881,
1969. 6 refs.
Simple techniques are described for detecting fluorine on the
nanogram scale. They are based on the evolution of hydrofluoric
acid as revealed by an alizarin-3-methylamine-N,N'-diacetic
acid-cerium(III) complex reagent and the use of a Pyrex
capillary siliconized to prevent the glass from retaining
hydrofluoric acid at ordinary temperatures. The methods are
suitable for the detection of fluoride in waters, minerals,
salts, and organic compounds including complex pharmaceutical
preparations and plastics. Even 150 pg of fluorine can be
revealed in a 1:500,000 solution of the reagent.
15400
EXTENDED TESTING OF THE METHANE IONIZATION DETECTOR. (FINAL
BEPORT) . Contract AT(30-1)-3717, Melpar, Inc., Falls Church,
Va. Sept. NYO-3717-1, 21p., Dec. 1968.
A sensitive automatic detector was developed for monitoring the
t-iilding of methane in coal mines and detecting the gas before
it reaches the lower explosive limit. The detector uses a
cross-section ionization detector as the basic transducer. Each
transducer cell contains two foil electrodes and each electrode
contains titanium tritide. A preliminary series of mine tests
resulted in improved electronic-circuitry waterproofing,
conversion to a single—point ground system to prevent ground loop
problems, addition of a heater to prevent condensation of
moisture within the detector, and pneumatic balancing of the gas
transport system. A reference air system was added to improve
the units's response to small or slow changes in methane
concentration. Cross-talk and pickup problems were eliminated
when retested and operated continuously for 48 hours, the
unit gave no false positive indications of methane concentration.
Unfortunately, the probe or the probe line could be damaged
by large chunks of falling coal. It is though that this
difficulties can be ameliorated by using flexible armored hose
instead of stainless steel tubing in the sampling line. The
detector has good sensitivity and high selectivity, low noise
level and drift rate, and simple maintenance requirements.
15484
Lang, Helen W., W. E. O'Neill, B. A. Coulehan, and R. H. Freedman
CONTINUOUS MONITORING OF DIESEL EXHAUST GAS FOR CARBOK DIOXIDE,
CAEBON MONOXIDE, OXYGEN, METHANE, AND NITROGEN OXIDES. Bureau
of Mines, Washington, D. C., RI 7241, 14p., March 1969. 9 refs.
CFSTI: PB 183386
A monitoring system was applied to provide rapid, continuous
analyses of diesel exhaust gas. Commercially available
continuous analyzers with strip chart readout were employed for
nitric oxide, carbon dioxide, methane, carbon monoxide, and
oxygen. All five continuous analyzers performed satisfactorily
during the preliminary testing and were used-successfully during
D. Measurement Methods 453
-------
several actual diesel approval tests. The results were checked
by two independent analytical methods: gas volumetric and
gas chromatographic analyses. It was shown that the use of
nondispersive infrared analyzers is a generally accepted
technique for on-stream analysis of carbon dioxide, carbon
monoxide, and methane gases. Polarographic analyzers worked
well for on-stream analysis of oxygen. Mass spectrometry wa.s
used to determine the nitric oxide content. Strip chart
recorders provided permanent records of all concentration changes
during the course of the approval tests. It was believed that
the use of analyzers would speed up the diesel approval testing
procedure.
15529
Johnson, J. E., M. E. Omstead, and W. D. Smith
NUCLEAR SUBMARINE ATMOSPHERES. PART 2. DEVELOPMENT OF A TOTAL
HYDROCARBON ANALYZER. (Interim Report). Naval Research Lab.,
Washington, D. C., Chemistry Div., NRL Problems C08-30,R05-2UB,
C08-33, Projects SF-013-08-03-4092-U095, UW-OU1, SP-89H22,
NRL 606«, 5p., Jan. 30, 196«. 12 refs.
CFSTI: AD H311U1
An instrument was developed for the shipboard monitoring of total
hydrocarbons in nuclear submarine atmospheres. In addition to
total hydrocarbons, the instrument also measures methane and
Freon-12 and, with a slight modification in operating procedure,
Freon-11. The system is based on a chromatograph technique
coupled with a highly sensitive flame ionization detector. An
air sample is injected into a chromatographic column and
chromatographed in the usual manner until the methane and Freon-
12 peaks emerge. At this point, the flow of carrier gas is
reversed and the higher hydrocarbons are backflushed from the
column through the detector as a single peak. The area under the
backflushed peak provides a measure of the total atmospheric
hydrocarbon content. The instrument was successfully tested at
sea, with hydrocarbons detected within a few minutes. The
analyzer is relatively insensitive to interference by water, C02,
and other organic gases.
15511
Turk, Amos, Jack I. Morrow, Stephen H. Stoldt, and Warren Baecht
ENHANCED DESORPTION OF ATMOSPHERIC SAMPLES FROM ACTIVATED CABBON.
Preprint, City Coll-, New York, Dept. of Chemistry, 13p., (1963?),
7 refs.
Enhanced desorption techniques as compared with normal desorption
provide significantly more information on the presence of
contaminants in air, especially hydrocarbon materials, thus
enabling sufficiently specific descriptions of individual
atmospheres to afford valuable characterizations. The feasibility
of enhanced desorption was first tested on butane and CC12F2 using
carbon tetrachloride as the displacing vapor. The enhancement
of butane desorption ranged between 35* and 41%. The CC12F2
desorption was also enhanced but to a lesser degree, possible
due to the lesser difference in molecular weights between CC1<*
454 HYDROCARBONS AND AIR POLLUTION
-------
and CC12F2 than between CC14 and butane. The percentage desorption
of CC12F2, with or without CC14, decreased in successive runs,
accompanied by the formation of an insoluble white polymer that
probably caused some pore blockage on the carbon surface.
Preliminary tests on atmospheric samples using activated carbon
(wherein carbon tetrachloride was allowed to adsorb into the
carbon in vacuo and was then chromatographed) showed in increased
response. Infrared spectra obtained from carbon samples exposed
to air at gas sampling stations showed the following: 2360 and
2310 reciprocal cm peaks were probably C02; the broad 2080
reciprocal cm peak was indicative of CO; the 2940, 2920, and
2860 reciprocal cm bands were due to CH2 and CH3 group
absorptions. Carbons of greater surface area per unit weight
have a greater adsorption capacity and will adsorb more rapidly
than carbons of more limited area. Charcoal with the smaller
pore diameter has adsorbate molecules with a lower vapor
pressure; diffusion through the narrower pores is more
difficult.
15708
Hoffmann, Dietrich, Yoshito Masuda, and Ernest L. Hynder
A-NAPHTHYLAHINE AND B-NAPHTHYIAHINE IN CIGARETTE SHORE. Nature,
221 (5177) :254-256, Jan 18, 1969. 8 refs.
Epideroiological data suggest an association between cigarette
smoking and urinary bladder cancer in men. Identification in
cigarette smoke was made of A-naphthylamine and B-naphthylamine,
which are known experimental bladder carcinogens. For the
quantitative analysis, A and B-naphthylamines labelled with 14C
were used as internal standards. Samples isolated
chromatographically were subsequently identified by mass
spectrometry.
15730
Tubina, A. Ya. and L. V. Mel'nikova
METHODS OF DETERMINATION OF NITHOMETH1NE AND NITROETHANE IN THE
AIR PRODUCTION INSTALLATIONS. (Metody opredeleniya nitrometana
i nitroetana v vozdukhe proizvodstvennykh pomeshcheniy). Text in
Russian. Gigiena Truda i Prof. Zabolevaniya, vol. 6:49-50, 1969.
A polarographic method for detecting nitromethane and
nitroethane and a colorimetric method for detecting
nitromethane in air are described. The polarographic method
adequately detects 0.2 micrograms of nitromethane and 0.25
micrograms of nitroethane per milliliter of water. The
colorimetric method is capable of detecting 0.2 micrograms of
nitromethane in 2 milliliters of solution. A 0.2 liter air
sample is thus adequate for detecting concentrations of these
components at levels 3-15 times below permissible values.
15749
Ludwicka, Antonina
THE PROJECT OF NORMALIZED METHOD FOH DETERMINATION OF VAPORS OF
D. Measurement Methods 455
-------
BENZYL CHLORIDE IN AIR. (Projekt 2ncrmalizovanej metody
oznaczania par chlorku benzylu w powietrzu). Text in Polish.
«ed. Pracy (Warsaw), 20 (U) : U25-U29, 1969.
THO standardized methods for the determination of benzyl chloride
vapor in air were discussed which use nitration or pyridine. The
nitration process consisted of nitrating benzyl chloride to form
2,4-dinitrobenzyl chloride. Methyl ethyl ketone was added to
extract 2,1-dinitrobenzyl chloride. Potassium hydroxide was then
added and the resulting violet color determined the concentration.
The reaction of warmed pyridine and sodium hydroxide or benzyl
chloride resulted in a yellow-orange solution which also determined
the concentration. The analysis for both methods was 1 mg/cu m or
5 mg/cu m, depending upon the amount of air sampled.
15763
Candeli, A. and G. Morozzi
THE PROBLEM OF THE CARCINOGENICITY OF ATMOSPHERIC POLLUTANTS. III.
THE RADIOACTIVE TRACER TECHNIQUE FOR THE QUANTITATIVE
DETERMINATION OF APOMATIC POLYCYCLIC HYDROCARBONS. (II problema
della cancerogenicita dell"aria inquinata: III. Tecnica dei
traccianti radioattivi per la determinazione quantitative degli
idrocarburi aromatici policiclici). Text in Italian. Giorn.
Igiene Med. Prevent. (Genoa), 10(1):3-15, 1969. 20 refs.
A tracer technique using H 3- labeled 3,U-benzopyrene was
employed to determine the extent of 3,U-benzopyrene loss during
analytical procedures such as column chromatography followed by
paper chromatography. The H 3-labeled benzopyrene was added to a ,
solution of pure aromatic polynuclear hydrocarbons as an internal
standard. The amount of H 3-labeled benzopyrene was determined at
the beginning and end of the analysis by a liquid scintillation
couting technique. The experimental results showed that the
recovery percentage of tritiated 3,W-benzopyrene corresponds to
the recovery percentage of the ncn-tritiated 3,U-benzopyrene.
The tracer technique was also satisfactory with other polynuclear
compounds. The loss of the polynuclear compounds was about SOS
after column chromatography and 50% after paper chromatoqraphy.
The analysis of the particulate matter of gasoline engine exhaust
gases showed a loss of the tritiated compound which was similar to
that r.evealed on mixtures of pure aromatic polynuclear compounds.
(Author summary modified)
15802
Hollis, 0. L.
SEPARATION OF GASEOUS MIXTURES USING POROUS POLYABOHATIC POLYHER
BEADS. Anal. Chen. (U. S.), 38 (2) :309-316, Feb. 1966. 5 refs.
(Presented at Advances in Gas Chromatography, Third
International Symposium, Houston, Texas, Oct. 1965.)
Outstanding separations of volatile compounds were achieved with
columns of polyaromatic polymer beads synthesized by suspension
with a diluent to give a highly porous structure. Notable sharp,
symmetrical peaks, and low retention volumes were found for
water, alcohols, and glycols. These polymer packings have
456 HYDROCARBONS AND AIR POLLUTION
-------
partition properties of a highly extended liquid surface
without the problems of support polarity, liquid-phase
volatility, or freezing point which hamper gas-liquid
chromatography. The porous polymers can be synthesized from
monomers such as styrene, tertiary-butylstyrene, and
ethylvinylbenzene with divinylbenzene as crosslinker.
Applications of porous gel polymer columns range from the analysis
of oxides of nitrogen to the determination of diethylene glycol
in dipropylene glycol. The analysis of trace quantities of
water in a variety of materials is greatly facilitated because
water is eluted very rapidly with good peak shape from the
columns.4 The columns are also useful where the adsorptive
properties of the stationary phase contributes to tailing or
skewing of the peak from materials such as carbon dioxide and
acetylene on gas-solid chromatographic systems and water on most
gas-liguid chromatographic systems. (Author abstract modified)
15898
Friedrichs, Karl-Heinz and Arthur Brockhaus
MEASUREMENTS OF PAPTICULATE AIR POLLUTANTS WITH TWO FILTER
APPARATUS OF DIFFERENT UPPER SEPARATION LIMITS. (Messung
partikelfoermiger Luftverunreinigungen mitzwei Filtergeraeten
unterschiedlicher oberer Abscheidegrenze). Text in German. Staub,
Reinhaltunq Luft, 29 (11) -.467-470, Nov. 1969. 3 refs.
Filters for the preliminary separation of coarse particles by the
forces of gravity and inertia were used in the atmosphere. The
separation of the aerosol into two portions permitted aerosol
size to be compared at different measuring points. Chemical
analysis showed a considerable difference between the composition
of the fine and coarse particles. Hydrocarbons and 3,4-
benzopyrene were found in the fine aerosol. (Author summary
modified)
15904
Braman, Robert S.
EMISSION-TYPE DISCHARGE STUDY OF SOME AIR POLLUTANT COMPOUNDS.
Preprint, American Chemical Society, Washington, D. C., Div. of
Hater and Waste Chemistry, 16p., 1969. 3 refs. (Presented at
the American Chemical Society, 158th National Meeting, Division
of Hater, Air, Waste Chemistry, New York, Sept. 8-12, 1969.)
The applicability of a four-channel DC discharge system to gas
chromatographic analysis of air pollutants was investigated in
laboratory analyses of automobile exhaust and other gas mixtures.
Air pollutants studied included carbon monoxide, sulfur dioxide,
nitrogen oxides, and carbonyl sulfide. Alkanes, alcohols, and
other compounds were also investigated for comparison purposes.
The four major wavelengths observed were 5165 C2; 4312 CH; 4216
CN; and 6562 H. The detector gave good response patterns suitable
for qualitative identification of gases and pollutants and was
particularly useful in confirming the identity of air peaks,
hydrogen, CO, hydrocarbons, and C02. Limits of detection air in
the ppm range. The limits need improvement if sub-ppm
D. Measurement Methods 457
-------
concentrations are to be directly analyzed and detected in air.
Data presented in the form of tables include wavelength and
band/line spectra of analyzed compounds, response data, and
emission ratios for a series of alcohols.
15909
Tsuda, Mitsushige, Shigekazu Hatano, and Ikuji Mizuta
CONTINUOUS SAMPLING OF AUTOMOBILE EXHAUST GAS AND ADJUSTMENT OF
STANDARD GASES, Mitsubishi Heavy Industries, Ltd., Tech. Rev.,
6(3):40-«6, Sept. 1969. K refs.
Among the problems involved in analyzing automobile exhaust are
the technigues to be used in ccntinous exhaust gas sampling and
in handling the standard gas to be used for calibration of the
analytical equipment. Cooling and dehumidifying of exhaust gas
is of particular importance in continous sampling. The cooling
temperature must be maintained below <41 F. Selection of materials
for the gas channel of an analyzer and the prevention of
hydrocarbon adhesion to filter surfaces are of particular
importance in minimizing measurement errors. To increase the
responsiveness of the analyzer, the volume of gas passage inside
the channel must be as snail as possible and the flow of sampled
gas as large as possible. Continous measurement of total
hydrocarbons in exhaust gas is possible by combining a continuous
sampling channel with a flame ionization detector. The measuring
range of such an analyzer is 100 to about 42,000 ppm methane and
15 to about 7000 ppm n-hexane. Required concentrations of the
standard gas can be correctly determined by combustion methods for
hydrocarbons and by the Orsat method for CO-C02-02 mixed gas.
Standard gas whose concentration is guaranteed by the above
methods should be used in calibrating an analyzer. (Author
conclusions modified)
15969
Hukherii, Anil K., T. Erdman, N. M. Trieff, and K. L. Gabriel
EVALUATION OF THE ADSORPTION PROPERTIES OF MOLECULAR SIEVE 569
COATED WITH 10% WT/WT TRITON X100. Preprint, Drexel Inst. of
Technology, Philadelphia, Pa., Dept. of Chemistry and Drexel Inst.
of Technology, Philadelphia, Pa. , Environmental Engineering and
Science Program, lip., 1968. 1 ref.
*
The usefulness'of molecular sieve 569 coated with 10* Triton x-100
as a dessicant for removing moisture from a gas stream was
established in experiments which showed that water had no effect
on the elution of benzaldehyde, 'pentyl acetate, n-butyl alcohol,
or hexane at 50 C in a gas chromatographic column. In experiments
with an uncoated sieve, hexane was retained by the column at 50 C.
At 100 and 200 C no desorption was observed. When the coated
sieve system is run for 30 min at 2.5 1/min flow rate, quantitative
recovery for hexane and butanol is about 100%; for petyl acetate,
85%; for benzaldehyde, 70%. When the system is run longer than
30 min, all recoveries approach 100%. Recommended procedures
for regenerating the^coated sieve are given. Use of the coated
molecular sieve for collection of organic components present in
air are discussed.
458 HYDROCARBONS AND AIR POLLUTION
-------
15977
Heszina, A. J.
QUANTITATIVE DETERMINATION OF CARCINOGENIC HYDROCARBONS THROUGH
FLUORESCENT SPECTROPHOTOMETRY. (Carcinogen szenhidrogenek
mennyisegi meghatarozasa fluorescens szinkepelemzessel). Text in
Hungarian. Egezsegtudomany, 11 (2):131-135, 1967. 4 refs.
The aromatic hydrocarbon content of air samples amounts to 1-100
ppm of the solutions prepared for spectrophotometric analysis. If
the solutions are not purified by chromatography, the results of
the spectrophotometry will be rather uncertain. The method
reported here combines chromatographic purification of the
solution at room temperature with spectrophotometry at -196 C.
Liquid nitrogen is used for cooling because of this low temperature
the spectrograph shows very sharp lines. The low temperature
aeasurement is very fast and provides advance information on
whether time-consuming deep-cooling is warranted. The
chromatographic purification process uses an aluminum trioxide
column.
16016
Marsh, K. J.
THE MEASUREMENT OF AIR POLLUTATION AROUND OIL REFINERIES'. British
Petroleum Co., Middlesex, England, Rept. of the'Working Group
-.'Stack Height and Atmospheric Dispersion', Concawe, The Hague,
Netherlands, 15p., Jan. 1968. 13 refs.
Principles of air pollution measurements are summarized to guide
oil refineries in planning emission measurements and analyzing
emission data. Pollutants considered are sulfur dioxide, hydrogen
sulfide, mercaptans, smoke, solids such as grit and acid smuts,
nitrogen oxides, hydrocarbons, ozone, and other oxidants. The
advantages of using new commercial instruments for continous or
consecutive measurements;at fixed sites are contrasted with
discontinuous methods using discrete samples. To determine the
long-term pollution pattern around a refinery, data must be
accumulated for a number of years and cumulative frequency curves
derived for various concentrations of a pollutant at each
measuring point. Such a curve can be used to determine the
'dosage' at each point and the damage caused by pollution. The
effect of wind direction on pollution measurements must also be
determined. To do this, measurements at each point are grouped
according to the principle wind directions, a cumulative
frequency curve is derived for each group, and concentrations
obtained from the curve are plotted on vector diagrams similar
to wind roses. These vector diagrams will tell whether changes
in frequency.distribution of pollutants are due to refinery
operations or variations in weather.
16132
Saitoh, Takeshi, Takamichi Hiramatsu, Tatsuyuki Takahashi,
Yasunori Takemoto, and Akira Ochiai
INFLUENCE OF ENGINE VARIABLES ON EXHAUST EfllSSIONS FROM AUTOMOBILE
D. Measurement Methods 459
-------
ENGINE DUBING ACCELERATION. Bull. Sci. Eng. Res. Lab. (Tokyo),
no. i»5:70-82. 1969. 1 ref.
A method was developed to test transient performance of automobile
engines on an engine test bench equipped with an inertia wheel and
a dynamometer controlled by an analogue computer. The air-
controlled disc brake and the clutch actuator were incorporated in
this acceleration equipment to simulate the start of the vehicle.
Accuracy and reproducibility of the equipment and method were
satisfactory. The influence of engine variables on the
concentrations of CO and hydrocarbon in the engine exhaust was
studied with this acceleration simulator. The CO and HC
concentrations during acceleration were the same as the exhaust
composition of the steady running engine. is a consequence,
exhaust compositions during acceleration could be estimated from
those in the steady state.
16170
Scherber, F. I. and J. H. Stoudenmire
A MOBILE TEST STATION FOR HOTOR VEHICLE EXHAUST. Bendix Tech.
J., 2(3):9U-100, Autumn 1969. 1* refs.
The design of a fully integrated mobile test station was
described with emphasis on test-cycle criteria and instrumentation
techniques. Key components and functions performed in the test
facility include nondispersive infrared spectrometers for carbon
monoxide, carbon dioxide, and hydrocarbon analyses, variable-flow,
fixed-dilution, or variable-dilution sampling, a chassis
dynamometer for engine loading, and integrated circuits on
printed-circuit cards for sensor signal conditioning. Also
included are reed switches driven by the program clock for
sensor scanning, a keyboard for manual inputs, and the best
available diagnostic sensors for engine diagnosis. One of the
most important factors governing selection of a suitable testing
cycle is the time restriction imposed; no more than five minutes
may elapse between drive-on and drive-off with hard copy test
data. A procedure under consideration is a high-speed
conditioning cycle.followed by a medium speed surveillance cycle,
the total test time being 155 seconds. Exhaust emission levels
must be capable of direct correlation with Federal standards in
order that a meaningful pass or fail status can be readily
assigned to each vehicle tested. A number of approaches to the
automation of vehicle-exhaust gas analysis were proposed which
call on a variety of techniques, among them analog, digital, and
hybrid schemes which vary in complexity with the intended
application. Visual aids in the test vehicle and on the mobile
laboratory control panel will permit both the vehicle driver and
the dynamometer operator to monitor the test-cycle modes. The
gas levels measured for each mode of the test cycle will be
automatically recorded on punched cards for immediate computation
of concentration and mass-per-mile values. The Friez Data Center
will be used to interface the analog outputs of the analyzers
with the punched card terminal equipment. The modular concept
utilized in the design of the Friez Data Center permits its
adaptation to a wide variety of systems configurations. All
functional circuits are contained on plug-in printed-circuit
cards which can be selected on the basis of the characteristics
required to provide any specified over-all system performance.
460 HYDROCARBONS AND AIR POLLUTION
-------
16211
Bernert, Juergen and Reiner Engsfeld
EXPERIENCES WITH A MODIFIED METHOD FOE DETERMINATION OF THE TOTAL
AHOUNT OF COMBUSTIBLE ORGANIC SUBSTANCES IN WASTE GASES.
(Erfahrungen mit einer modifizierten Methode zur Bestimmung der
Gesarotmenge verbrennbarer organischer Substanzen in Abgasen).
Text in German. Wasser, Luft Betrieb, 12 (7) :«22-i»25, July 1968.
6 refs.
A plant manufacturing glass fiber insulating panels, a brake
lining manufacturing plant, a wire manufacturing plant, and two
chicken manure drying stations are discussed with'respect to how
they determine organic substances in waste gas. In the first
three plants, vapors from solvents and phenols and their cracking
products were analyzed. In the first case, 3 silica gel probes
were used since it was not known how the method would respond to
mineral oils. However, hydrocarbons could be detected at all
measurements. With larger volumes drawn through the probes within
an equal period of time, a higher loading of probe 2 was observed.
This may be explained by the fact that of the water vapor/oil
mixture, the former shows greater affinity to the silica gel than
the latter, which impairs the oil mist adsorption. The result of
30 measurements in the second plant showed that the carbon
concentration in the uncleaned gas experienced a maximum at each
temperature increase which subsided until the next temperature
increase. The carbon concentration of the cleaned gas is almost
independent of time, which indicates that the afterburning system
has an efficiency of more than 90*. Generally it can be said for
all measurements in all three types of plants that no major
difficulties were encountered. Quantitative adsorption was
achieved in almost all cases in the first section of the first
silica gel probe. The result of measurements in the chicken
manure drying plants showed that the initially present mercaptans
appeared in none of the analyses, which indicates that they are
oxidized to sulfates. It was further found that these gases
contain further organic emission components which can presently
not yet be identified (presumably fatty acids and their
derivatives).
16277
Hill, Du W. and H. A. Newell
THE VARIATION WITH POLARIZING VOLTAGE OF THE RESPONSE TO METHANE,
CARBON DIOXIDE AND NITROUS OXIDE, OF A MACHO-ARGON IONIZATION
DETECTOR FOR GAS CHROMATOGPAPHY. J. Chromatog., vol. 32:737-739,
1968. 15 refs.
Response curves with unexpected characteristics were obtained for
methane, carbon dioxide, and nitrous oxide during an investigation
of the physical processes governing the operation of a macro-argon
ionization detector. A previously recorded response vs polarizing
voltage for an argon detector to various concentrations of propane
is contrasted with the obtained response vs polarizing voltage of
an argon detector to various concentrations of methane. The
former is the commonly recorded response to organic vapors with
ionization potentials less than the energy of the argon netastable
atom. The methane curve illustrates a reversal of sign with
D. Measurement Methods 461
-------
voltage increase. This variation could explain previous,
contradictory observations at unquoted field strengths. At low
applied voltages, the positive responses for methane, carbon
dioxide, and nitrous oxide are reported to have similar form, with
carbon dioxide having nearly twice the response of methane and
nitrous oxide. The negative response observed at the high voltage
region was approximately identical for all three vapors. At 30 V,
when the response of each gas was at a maximum, the response of
carbon dioxide coincided with that of propane. The results are in
contrast' to predictions that responses to methane, carbon dioxide,
and nitrous oxide would not occur, since the ionization potentials
of the substances are higher than the argon metastable level. It
is suggested that the positive1 responses are due to lower
recombination coefficients resulting from a lowering of primary
electron temperature by inelastic collisions with added gas
molecules.
16361
Kessler, H. L.
QUALITY CONTROL ASPECTS OF CHRYSLER'S CLEANER AIR SYSTEM.
Preprint, American Society for Quality Control, Milwaukee, His.,
11p., 1968. (Presented at the Conference American Society of
Quality Control, 22nd Annual Technical, Philadelphia, Pa., 1968.)
(Also: Automotive Industries, 141 (7) :7<4-97, Oct. 1, '1969.)
The quality control procedures of Chrysler's program to comply with
Federal limits on allowable concentrations of certain automobile
emissions is described. The basic equipment for the testing
comprises tanks of 'purging and calibration gas, a non-dispersive
infrared analyzer with recorders, dynamometer instruments and
driver's aid, a sunk test console, and digital computer and
typewriter. Personnel required to operate the test facility
are two driver-mechanics, a quality control engineer, and an
analyzer-operator. A complete test consists of three cycles,
the first being a 'dummy' run to ensure proper engine
conditioning; each cycle in turn consists of ten operating
conditions, or nodes, which require 137 seconds to complete. A
vehicle fails the test if the emission level exceeds 275 ppm
hydrocarbons and/or 1.5X carbon monoxide content; or if spark
timing, idle rpm, distributor vacuum and/or idle CO content exceed
the specified limits. Rechecks and adjustments are made on any
vehicle which fails; if it does not then pass re-testing, the
carburetor and/or distributor are replaced. An important aspect of
the quality control program is the series of controls exercised
at the plants that supply auto components; these controls are
particularly carefully applied to suppliers of carburetors and
distributors and at engine-building plants.
16363
Vizioz, J. -P. and W. Leuckel
METHODS AND INSTRUMENTS UTILIZED AT THE F.R.I.F. EXPERIMENTAL
STATION FOR THE MEASUREMENT OF DIFFUSION'FLAHES. (Methodes et
instruments utilises a la Station Experimentale de la F. B. I. F.
pour des mesures dans les flammes de diffusion). Text in French.
Riv. Combust., 23 (9):«27-«37, Sept. 1969. « refs. (Presented at
462
HYDROCARBONS AND AIR POLLUTION
-------
the Conference 'I Problem! della Combustione - Bruciatori1 de
1'Associazione Termotecnica Italiana, Milan, June 18-19, 1969.)
The investigation of turbulent diffusion flames is a highly
complicated field ot work, calling for a large number of
experimental data. For this purpose, two square section
experimental furnaces were built: one 6.5 m long and 2 m wide; the
other, 10 m long and 1.5 m wide. The instruments used offered
extremely quick measurement readings, were compact, and highly
heat and corrosion resistant. Temperature was measured along the
furnace walls and on the gases of combustion. To measure
velocities, a Prandtl tube, parallel with the flame axis, was
employed. To analyze the combustion products sampled at various
points of the flame, the expedient was adopted of cooling them
quickly to arrest the chemical combustion reactions.
Chromatography was used to analyze H2, C02, 02, N2, CHU, CO.
Hydrocarbon levels were also assayed considered as C2, C3, and C4.
To determine unburned solids, a sample of gas was filtered under
isokinetic conditions. (Author summary modified)
16398
Noyes, Claudia Margaret
STUDIES OF THE DETEBMINATION AND REACTIONS OF SULFUR DIOXIDE AS AN
AIR CONTAMINANT. Colorado Univ., Boulder, Thesis (Ph. D.), Ann
Arbor, Mich., Univ. Microfilms, Inc., 1966, 56p. 38 refs.
Analytical methods for sulfur dioxide determination, including
colorimetric and conductrometric methods, were evaluated, and the
reactions of sulfur dioxide with hydrocarbons and nitrogen oxides
at high dilution in air were studied. Radioactive 5(35)02 was used
as a tracer to follow S02 in the gas phase and after its absorption
in the sampling solution. The West-Gaeke colorimetric method gave
slightly less color but better reproducibility and sample stability
than the Helwig-Gordon method. Liquid scintillation counting
showed that the dilute hydrogen peroxide-sulfuric acid solution
used for absorbing S02 in the Thomas conductometric method was also
less sensitive and less reproducible than the West-Gaeke
colorimetric method. It was emphasized that the use of bubblers
in series is not necessarily a reliable method for measuring
absorbing efficiencies of solutions for gases. None of the
mixtures showed any measurable amount of reaction of S02 in dry or
moist air in the dark during residence times as long as three
weeks. Since there was a reaction of S02 in an irradiated mixture
containing both NO2 and hexene in dry air but none with either N02
or hexene alone, it seemed probable that S02 reacts with a product
of the hexene-N02 photolysis. There was no appreciable S02
reaction in an irradiated mixture with benzene alone or in the
presence of N02. All products of the S02 reactions were absorbed,
since both color and counts were low in the gaseous aliquots
taken from flasks immediately after irradiation. Hhether the
S02 is oxidized or held'in some form not detectable by colorimetric
analysis is not known. It is definite that those reaction products
which do not react as S02 in the colorimetric determination do not
remain in the gaseous phase. (Author abstract modified)
D. Measurement Methods 463
-------
16507
Wolstenholme, E. F.
METHANE DETECTION. Colliery Guardian (London), 217 (1) :U7-51,
Jan. 1969. 5 refs.
A recording methanometer and a specially designed recording air-
flowraeter were used to obtain continuous measurements of the total
guantity of firedamp emitted from a longwall coalface. The
sources and variations in total firedamp emission from a production
longwall unit were also analyzed. Results showed it was possible
to split the readings of firedamp emission into different trends
and to correlate the results to coalface activities. Firedamp
emissions from coal cutting operations were shown to be reasonably
constant, whereas emissions from adjacent strata were found to be
cumulative with time. The complex nature of the variations
measured emphasize the inadequacies of spot measuring techniques.
The results indicated numerous ways in which research into firedamp
emission could be extended utilizing continuously measuring
instruments. It was shown possible to continuously record the
variations in air guantity circulating a unit and the variations in
firedamp content of that air. By recording the variations in a
number of units in a mine district and also recording the
variations in pressure across the units, it would be possible to
relate changes in firedamp emission to absolute values of coalface
resistance. A set of instruments on the main return from the
district could be used as a check on the total variations. The
recording airflow meters were found to be reliable research
instruments although requiring regular maintenance. The main
hazard to their performance was the presence of dust which resulted
in a loss of sensitivity. Regular laboratory checks, however,
indicated that this did not affect the calibration. Definition
of the normal sources variations, and magnitude of firedamp
emission by the methods described, could prove an invaluable aid
in increasing the confidence with which abnormal trends can be
identified and analyzed.
16616
Hiam, Leon and Saul Chaikin
DEVELOPMENT OF A SIMPLE ADTO EXHAUST ANALYZER. (FINAL REPORT.)
Stanford Research Inst., Menlc Park, Calif., Contract PH
B6-66-60, SRI Proj. FMU-5859, 18p., Aug. 1966. 23 refs.
The feasibility of applying a heated filament combustible gas
detector for separately analyzing the total hydrocarbons and
carbon monoxide in auto exhaust gases was determined. The first
phase was a detailed study of the filament temperatures required
for oxidation of selected hydrocarbons and CO on a platinum
filament. Additional work was conducted on the effect of 02 and
hydrocarbon concentration on the oxidation initiation temperature;
the interacting effects in simple gas mixtures were studied. The
data showed that the required analyses could not be made on the
basis of the platinum filament temperature. Rhodium, iridium,
palladium, palladium-silver, and palladium-gold alloys, oxidized
nickel, gold, and oxidized cobalt were tested in a search for
materials which might show greater selectivity in catalyzing
oxidation of hydrocarbons and CO. None of these materials were
464 HYDROCARBONS AND AIR POLLUTION
-------
found to make the required analyses feasible on the basis of
filament operating temperature. Two procedures were evaluated for
making a preliminary separation before analysis with a heated
filament. Hopcalite catalyst was used to remove the CO from the
gas sample by selective oxidation. Problems associated with the
adsorption of hydrocarbons on Hopcalite made the procedure of
doubtful use. silica gel was used to selectively remove
hydrocarbons from the gas sample so that an analysis for CO could
be made on the heated filament. The complications it introduced
were such that the basic simplicity of the combustible gas
detector was lost. Since the separate analyses for hydrocarbons
and carbon monoxide did not seem feasible, an effort was made to
construct a detector that would measure total combustibles minus
hydrogen and the lower aliphatic hydrocarbons. The procedure
utilized a platinum wire 'preburner* whose function was to'
selectively combust hydrogen. This procedure did not succeed
because carbon monoxide was found to inhibit the selective
combustion of hydrogen over platinum at low temperatures. It was
concluded that the combustible gas detector does not show any
great potential for auto exhaust analysis. (Author summary
nodified)
16620
Freedman, R. w. and H. H. Lang
A COMPARISON OF INFRARED AND GAS CHROHATOGHAPHIC METHODS FOR
DETERMINATION OF METHANE IN MINE AIR. Bureau of Mines,
Hashington, D. C., RI-7179, Up., Sept. 1968.
CFSTI: PB 182672
The gas chromatographic method was compared with the infrared
method used for confirmatory determination of methane in mine air.
In terms of speed, convenience, and precision, the gas
chromatographic method was far superior to the infrared method.
The comparable infrared analysis required almost a full day per
sample; the gas chromatographic analysis could be performed in
10 min, including sample injection and calculation. Replicate
analyses were unnecessary. Only one or two standards had to be
run per day because of the lack of drift and the high degree of
precision. A coefficient of variation of less than 1* was
attainable. Separation of methane from other hydrocarbons was
complete with the use of molecular sieve columns under proper
experimental conditions. This provided the specificity for
methane that is essential. The amount of sample required for the
chromatograph was only 10 ml compared with 100 ml or more for the
infrared cell. The need for such a small quantity indicated the
possibility of taking mine-air samples in syringes. This would
save space, weight, time of sampling, and time of injection into
the instrument, and would avoid the use of mercury for gas
transfer. (Author conclusions modified)
16701
Bell, J. H., Sue Ireland, and A. W. Spears
IDENTIFICATION OF AROMATIC KETONES IN CIGARETTE SMOKE CONDENSATE.
inal. Chen., 41 (2) :310-313, Feb. 1969. W refs.
D. Measurement Methods 465
-------
Because of the complexity of cigarette smoke, extensive
fractionation was necessary to isolate and identify minor
components. The separation techniques involved solvent partition,
column, paper, and gas chromatography. The gas chrooatographic
system allowed the collection of smoke constituents for
subsequent analysis by ultraviolet and infrared spectroscopy and
mass spectrometry. From the study of one subtraction which
represents 0.08% of the original weight of the condensate,
fluoren-9-one, the four methylfluoren-9-ones and seven other
alkylated fluoren-9-ones were identified. (Author's Abstract)
466 HYDROCARBONS AND AIR POLLUTION
-------
E. CONTROL METHODS
00003
S 306. A Bill to Amend the Clean Air Act to
Bequire Standards for Controlling the Emission of Pollutants
from Gasoline-Powered or Diesel-Powered Vehicles, to
Establish a Federal Air Pollution Control Laboratory and for
Other Purposes. 89th Congress (1st Session) Senate
Committee on Public Works. Special Subcommittee on Air and
Sater Pollution. April 9, 1965. 308 pp.
This document contains Government reports, statements Bade by
Government officials and industrial representatives, and
communications to Senator Muslcie. The following topics are
discussed: (1) photochemical smog; (2) effects of air
pollution; (3) vehicle use trends; (4) recognition by state
governments; (5) exhaust and crankcase emission control; (6)
fuel evaporator loss control; (7) fuels; and (8) diesels. Also
included are reports on causes and control of automotive emissions,
by J.B. Caplan; and descriptions of visits to General
Hotors Research "Laboratories, ford Motor Co. Vehicle
Emissions Testing Laboratory, American Motors Corp.
(Air-guard system for exhaust control), and to Chrysler Corp.
Laboratories {Clean air package components).#t
00015
L. J. E, Hofer, J. F. Shultz, and J. J. Feenan
EFFECT OF LEAD DEPOSITS ON ACTIVITY OF AUTOMOTIVE EXHADST
CATALYSTS. Bureau of Bines, Washington, D.C. (Report of
Investigations 6243.) 1963, 26p.
This study, part of a broad program of research in air pollution
related to minerals, was conducted to determine the nature and
extent of the poisoning of catalysts when used to remove certain
air pollutants from exhaust gases. The poisoning examined in this
investigation occurs when leaded gasoline is used as a. fuel for
aatomotive engines. The smog in the Los Angeles area is
attributed to the effect of radiant energy on the mixture of
hydrocarbons and nitrogen oxides found in the atmosphere there.
To prevent the escape of these hydrocarbons into the atmosphere
catalvtic mufflers have been proposed. In principle, these are
simple and nonmechanical, consisting of a vessel charged with a
catalyst capable of destroying the exhaust hydrocarbons by
catalyzing their oxidation. However, these catalysts are severely
affected by the particulate matter, mainly in the form of lead
sulfate, lead oxysulfate, and lead chlorobromide, contained in the
exhaust gas. Deposition of lead on the catalyst restricts
catalytic activity. After 20,000 miles of operation, the
temperature necessary to achieve 50% conversion of isopentane in a
mixture of 0.2% isopentane, 2% CO and 4% oxygen, and the
467
-------
balance N at 10,000 hourly space velocity has risen from <»00 to
500 C. even with a catalyst taken from the exit portion of the
catalyst bed. The rest of the catalyst was more severely
affected. It would appear that operation for 20,000 miles is
near the limit for a catalyst.f#
00057
R.D. Kopa
PNEUMATIC FUEL ATOMIZATION AS APPLIED TO AUTOMOBILE AIR
POLLUTION CONTROL. California Univ., Los Angeles, Dept.
of Engineering.(Rept. No. 63-61.) Dec. 1963. 19p.
CFSTI, DDC: AD 601025
The principle of pneumatic fuel atomization as applied to,,,.
internal combustion engine carburetion was conceived during
research activity concerned with exhaust gas recycling and its
effects on engine performance. The goal was to find a
solution to thre engine "power surging" problem, a phenomenon
resulting from exhaust gas recycling as a method of nitrogen oxide
control. The test results were obtained during the operation of
an engine equipped alternatively with a factory standard
carburetor or with a fuel atomization device. The earlier
developed exhaust gas recycling devices installed on engines
eguipped with standard carburetors were extensively road tested.
They proved to operate trouble-free for test periods extended
over 30,000 miles of driving. Nitrogen oxides reduction averaged
80% and the specific fuel consumption remained substantially
unchanged. The fuel atomization device eliminates the "power
surging" noticeable with the earlier recycling device, and since it
combines the exhaust gas recycling with fuel-air mixture
homogeneation, an additional benefit, namely, substantial reduction
of unburned hydrocarbons and of carbon monoxide is obtainable.
More research work, however, is needed in order to gain a
conclusive picture about the full potential of pneumatic fuel
atomization as a method of automotive air pollution control.f#
00087
A.F. Bush, R.A. Glater, J. Dyer, G. Richards
THE EFFECTS OF ENGINE EXHAUST ON THE ATMOSPHERE WHEN AUTOMOBILES
ARE EQUIPPED WITH AFTERBURNERS. California Univ., LOS
Angeles> Dept. of Engineering. (Sept. 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 at1 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 trst 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
nitrogen: Fumigations showed that, in all instances of
elevated formaldehyde measurements, eye irritation resulted.##
468 HYDROCARBONS AND AIR POLLUTION
-------
00097
L.L. Winkstrom K Nobe
CATALYTIC DECOMPOSITION OF NITROGEN DIOXIDE. California'
Univ., Los Angeles, Dept. of Engineering. (Beport 63-19.)
Apr. 1963. 40 pp.
CFSTI, DDC: AD 406834
Reactions of the oxides of nitrogen are of considerable interest
in current air pollution research. The investigation reported in
this paper is the study of the complete dissociation of N02 in
nitrogen and in air with CuO-Alumina (1:1) and Ce02-Alumina
(1:1) catalysts. The initial concentration of" the N02 was
varied within the range 720-2200 ppm. The reaction was studied in
a steady-state isothermal flow reactor with the temperature varied
in the range 304 - 520 C at gas space velocities (STP) ranging
from 1,400 to 11,200/hr. It was observed that the kinetic data
were best represented by the' rate expression, r=ap / (1 plus bp) .
At low temperatures and high flow rates the rate reduced to a
zero order reaction. Below 480 C the CuO had a higher
catalytic activity than the Ce02. Above 480 C, however, the
Ce02 had a higher activity. It was observed that there was
considerable decomposition of N02 even in excess air with CuO
catalysts. Since it had been reportd previously that CuO »
catalysts were guite satisgactory for hydrocarbon oxidation, the
results of this investigation indicate that both hydrocarbons and
oxides of nitrogen may be simultaneously eliminated to a
considerable degree with CuO catalysts. (Author)ft
00103
P. Gustafson and S. H. Smith, Jr.
REMOVAL OF ORGANIC CONTAMINANTS FROM AIR .BY TYPE 13X MOLECULAR
SIEVE. Naval Research Lab, Washington, D.C. (NRL Rept.
5560.) Dec. 6, 1960. 20 pp
CFSTI: AD 248512
The adsorption of low concentrations of n-decane, methane,
benzene, toluene, xylene, pyridine, aniline, and nitrobenzene on
type 13X Linde molecular sieve has been studied at influent
concentrations of from 5 to over 100 ppm and superficial linear
velocities (velocities if no sieve were present to reduce the cross
section) of up to 3000 cm/minute. The breakthrough weight
capacity at a flow rate of 2500 cm/minute for a representative
aliphatic compound (n-decane) was 10 wt-% of the sieve and for a
mononuclear aromatic (benzene) was 0.35 wt-% at 25C. Decreasing
the flow rate of the aromatic to 500 cm/minute increased the
breakthrough capacity to 2.1%. Regeneration conditions were also
studied. Water vapor readily displaces organic adsorbates (except
high boiling polar compounds) at room temperature. Therefore,
molcular sieve with coadsorbed water may be reactivated by passing
dry air at 200 to 325C in the same direction of gas flow as that
used during the adsorption cycle. The coadsorbed water will
displace the sorbed organic compounds as it moves down the column,
whereas the organic materials would be pyrolyzed in place if the
water were not there. (Authors' abstract)#t
E. Control Methods 469
-------
00257
A. G. Sandomirsky, D. n. Benforado, L. D. Grames, and
C. E. Pauletta
FUME CONTROL IN RUBBER PROCESSING BY DIRECT-FLAME INCINERATION.
J. Air Pollution Control Assoc., 16 (12) :673-676, Dec. 1966
(Presented at the 59th Annual Meeting, Air Pollution Control
Association, San Francisco, Calif., Paper 66-55, June 24,
1966.)
The application of direct-flame incineration to successfully
eliminate a smoke-oil-mist and odor problem in the manufacture of
rubber-base rug underlay is presented. The investigation of
various air pollution control processes leading to the development
and adoption of the direct flame incineration system is covered.
The rug underlay curing process incorporating the direct-flame
incineration system with primary heat recovery is described.
Besults and discussion of a source test to determine the
effectiveness of direct-flame incineration in this application are
included. (Authors' abstract)##
00269
V. H. Luther, K. Lohner, H. Muller, and W. Zander
POSSIBILITIES OF DECONTAHIN ATOG EXHAUST GASES OF OTTO ENGINES.
Moglichkeiten einer Entgiftung der Abgase von Ottomotoren.
Erdoel Kohle (Hamburg) 18 (12) :96f*-972, Dec. 1965. Text in
German.
The composition of motor exhaust gases is discussed.
Measuring methods and the possibility of decontamination before,
in, and behind the combustion chamber are described in detail.
Fundamental principles of the Cleaner Air Package, crankcase
blowby control devices, after-burner with spark ignition, and the
Man-Air-Ox system are given. The state of the art of catalytic
combustion is summarized and it is shown that the combination of
other after-burrier systems with small catalyst units are worthy of
further development.f#
00373
SUBMARINE ATMOSPHERE HABITABILITY DATA BOOK (REVISION-1).
Navy Dept., Washington, D. C., Bureau of Ships
(NAVSHIPS 250-6<*9-1). Sept. 1962. 198 pp.
This publication brings together scattered information and
references to more detailed information on chemical principles,
experimental results, and operating experience concerned with
maintenance of atmospheric habitability in nuclear-powered
submarines. Habitability is defined as control of chemical
aspects of the atmosphere to meet the requirements of equipment
and personnel. Recommended methods for removal of carbon
dioxide, carbon monoxide, hydrocarbons, aerosols, and odors
are discussed. Basic operation of an electrostatic precipitator
is described. Details- are given on the continuous air monitoring
system required to insure safe operation of the submarine.##
470 HYDROCARBONS AND AIR POLLUTION
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00538
J. Schulte
SEALED ENVIRONMENTS IN DELATION TO HEALTH AND DISEASE. J.
Inst- Heating Ventilating Engrs. (London), Vol. 2<*:79-87,
June 1966.
The general health aspects of life in a sealed environment are
related primarily to habitability and atmospheric control. The
control of the atmosphere involves : (a) some means to provide the
continual addition of oxygen in sufficient quantity to support life
and preserve health, and (b) methods to effect the continuous
removal of carbon dioxide, carbon monoxide, and other
atmospheric contaminants to prevent them from gradually increasing
to concentrations which could produce illness. A number of the
atmospheric constituents are discussed in detail in regard to
their source, effects upon health, and methods of control. The
need for control of temperature and humidity and for protection
from radiation has also been included in the discussion. These
needs and methods for controlling the atmospheric constituents,
temperature, humidity, and radiation exposure in a sealed
environment have been projected to the future space vehicle.tt
00562
E. Hunigen and W. Prietsch
THE ELIMINATION OF NOXIODS SUBSTANCES FROM INTERNAL COMBUSTION
ENGINES. Probleme und Losungswege der Schadstoffbeseitigung
bei Verbrennungsmotoren. Technik (Berlin), 21 (6):377-383, June
1966.
Control of air pollution from internal combustion engine is
reviewed. A table is given of maximum permissible concentrations
of various components of exhaust gases for both Germanics, the
USSR, and USA. The review emphasizes methods of measurement
of various pollutants.##
00583
D.E- Cooper, H.E. Griswold, R.M. Lewis, R. W.
Stokeld
IMPROVED DESORPTION HOUTE TO NORMAL PARAFFINS. Chem. Eng.
Prog. 62 (4) :69-74, April 1966.
In the over-all process economics, desorption of the n-paraffins
from the molecular sieve is the most important step of the
Tecaco selective finishing process. There are basically five
vapor phase technigues for desorbing n-paraffins from molecular
sieves: (1) thermal swing, (2) pressure swing, (3) sweeping with
a nonadsorbable material, (U) desorbing with a material which is
more strongly absorbed than the product n-paraffins, and (5)
desorbing with an adsorbable material which is less strongly
absorbed than the product n-paraffins. The desorption procedure
used in the TSF process combines most of the better features of
several of these desorption techniques and avoids most of
E. Control Methods 471
-------
the disadvantageous aspects of each. The process basically
employs vapor phase, displacement desorption using an adsorbable
desorbing medium which is less strongly adsorbed by the sieve than
the product n-paraffins. The advantages of the TSF desorption
procedure over other methods of n-paraffin desorption are
numerous, especially when processing kerosine or gas oil range
materials. The most significant advantage is that n-paraffin
desorption rates are maximized within economically feasible
operating limits. Desorption rates are maximized by
optimization of key operating variables including temperature,
pressure, desorbing medium material, degree of desorption per
cycle, and desorbing medium flow rate. Integration of this
desorption technigue with the other steps of the cycle results
in a process which is relatively simple from an operational
standpoint and which is capable of efficiently producing high
purity n-paraffins from a variety of feedstocks.##
00587
J.A. Brink, Jr., W.F. Burggrabe, I.E. Greenwell
MIST REMOVAL FRCH COMPRESSED GASES. Chem. Eng. Progr.,
62(«):60-66, April 1966.
Fiber mist eliminators have been successfully used to purify
gases and solve difficult air pollution problems involving:
methanol synthesis gas, sulfonation and chlorination process
gases, nitric acid process gases, chlorine, and compressed air.
Extensive research and development work resulted in the
development of fiber mist eliminators for the collection of
submicron mist particles. The first plant-scale installations
were made for the control of air pollution from sulfuric and
phosphoric acid plants. After full-scale units had been proven
highly efficient on stack gases containing submicron
particles, further research was undertaken to develop fiber
mist eliminators which would be most economical for the
collection of particles which are predominantly 1 to 20 microns
in diameter. The installation of fiber mist eliminators within
various processes to purify gases was started after several
difficult air pollution problems had been solved. The widespread
application of fiber units to chlorine plants was reported
in detail, but the applications to many other processes has not
been reported previously. It should be noted that mists are
present in many chemical processes at pressures ranging up to
5,500 Ib./sq. in. gauge. The temperatures at whcih mists are
present are usually moderate since many mists vaporize at higher
temperatures.#t
00936
Freeman, J. H., Jr. and R. C. Stahman
VEHICLE PERFORMANCE AND EXHAUST EMISSION, CARBURETION VERSOS
TIMED FDEL INJECTION. In: Vehicle Emissions, Part II,
SAE Progress in Technology Series, Vol. 12, Society of
Automotive Engineers, Inc., New York, 1966, p. 32-59. 5 refs.
(Presented at the SAE National Fuels and Lubricants Meeting,
Tulsa, Okla., Nov.. 2-i», 1965.)
472 HYDROCARBONS AND AIR POLLUTION
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Vehicle performance and engine efficiency are evaluated from the
point of view of carburetion versus gasoline injection. The
author discusses measurement of combustion efficiency;
maldistribution and fuel precipitation effects; how to determine
maldistribution, heat rejection mixture strength and timing
effects; exhaust gas composition and vehicle performance in road
service; and octane reguirement effects. (Authors' abstract)#f
01197
L. Ruhnke, E. Will, and P. Pederson
ELECTROHYDRODYNAMIC REHOVA1 OF KICRCOBGANISMS FROM HYDROCARBON
FUELS (FINAL KEPT. JUNE 25, 1963 - NOV. 20, 1965). Litton
Systems, Inc., Minneapolis, Minn., Applied Science Div
(ASD 2905). Nov. 20, 1965. 139 pp.
CFSTI.DDC: AD 630 889
The feasibility of removing microorganisms and other
particulates from hydrocarbon fuels by electrostatic precipitation
was studied. Theoretic investigations describe the physics of
electrohydrodynamic precipitation and essential parameters
influencing collection efficiency. Measurements of fuel
characteristics and filter parameters have been made which led to
the development of an electrohydrodynamic filter. Particulates
and a liquid are unipolarly charged in a corona edge ionizer and
then are flushed into a precipitation tube in which particulates
are moved by Coulomb forces into porous non-conducting walls.
A 10-gpm model showed filter efficiencies of at least 85 percent
by number of particles larger than 1 micron diameter. The basic
advantages of the method investigated are the low pressure drop
over the filter element and the small size of the unit. (Author
abstract)##
01351
H.O, Engel C.D. Calnan
RESIN DERMATITIS IN A CAR FACTORY. Brit. J. Ind. Bed.
(London), Vol. 23:62-66, Jan. 1966.
An outbreak of dermatitis in a car assembly factory is
described; it affected 50 workers who handled rubber
weatherstrips coated with an adhesive. The adhesive was found
to contain para-tertiary butyl phenol (P.T.B.P.) formaldehyde
resin. Of those patch gested 70* gave positive reactions
to the adhesive and 65% to the resin. Improved methods of
handling and personal protection succeeded in arresting the
occurrence of dermatitis. Barrier creams gave no protection in
these circumstances. The episode illustrates the different
preventive control methods which have to be tried when dealing
with a simple skin hazard which cannot be abolished. (Author
abstract)#f
01U11
R. C. Stahman and A. H. Rose, Jr.
EMISSIONS FHOH CARBURETED AND TIMED PORT FUEL INJECTED
ENGINES . J. Air Pollution Control Assoc. 16(1):15-18,Jan. 1966.
E. Control Methods 473
-------
A popular make car was tested. Spark timing and fuel flow
optimization was briefly studied. Performance and economy were
compared between the fuel injected and carbureted versions.
Emission measurements of CO, C02, and hydrocarbon were made
in road tests by proportional sampling and through the California
Cycle by continuous nondispersive infrared instrumentation.
(Author abstract modified)##
01U97
J. L. Blumenthal and K. Nobe
CATALYTIC COMBUSTION AND ADSORPTION KINETICS OF CARBON MONOXIDE
ON CDPEIC OXIDE. Ind. Eng. Chem, Process Design Develop.,
5 (2) :177-183, April 1966.
Studies have shown that cupric oxide-alumina is an effective
catalyst for the complete oxidation of low concentrations of
hydrocarbons and carbon monoxide. The catalytic combustion of
hydrocarbons and CO is of interest in the control of the quality
of automobile exhaust emission. The adsorption and oxidation of
CO on t unsupported cupric oxide catalysts were studied. The
adsorption of C02 was also studied. The objective of the work
was to determine the effect of different catalyst preparation
methods on the adsorption and oxidation kinetics.#f
01550
P. L. Collinson, C. Jones, and D. E. E. Lloyd
VENTILATION PROBLEMS ON RAPIDLY ADVANCING FACES, WITH SPECIAL
REFERENCE TO THIN SEAMS. Mining Engr. (London),
125(71):7«6-762, Aug. 1966.
An assessment of ventilation problems in coal mining is presented.
It is of particular interest today in view of increasing rates of
production and the trend towards thinner seam sections. There is
need to discover the relation between methane emission and coal
output in varying circumstances. The assumption often made that
gas emission is directly proportional to coal output may be a
sufficient approximation for minor increases in output, but may be
wide of the truth where output is doubled or trebled. The reasons
for these variations are not known, but they must be related to the
origin of the gas, particularly to the proportions coming from
strata and from the solid and broken coal. Variations in air
velocity over the cross-sectional area of the face affect the
scouring of gas and the dispersal of dust. This is the type of
information that must be obtained before it is possible to plan
with any degree of accuracy the ventilation requirements of rapidly
advancing faces and the means of providing such ventilation that
the highest levels of output may be attained.##
01623
D.A. Jensen
STATUS REPORT ON COST FACTORS IN EXHAUST CONTROL (INFORMATIVE
REPT. NO. 5). J. Air Pollution Control Control Assoc.
It, (10) 427-9, Oct. 1964.,
474 HYDROCARBONS AND AIR POLLUTION
-------
The costs of devices for automotive exhaust control are
estimated. The total costs paid by the customer are
estimated based on factory installation. These systems include:
(1) exhaust afterburners - flame type; (2) exhaust afterburners -
catalytic type; (3) exhaust afterbutrners - limited mode type; (H)
exhaust afterburners - non-flame type (manifold air); (5)
deceleration devices; (6) engine modification.#f
01645
A. J. Haagen-Smit
THE CONTROL OF AIR POLLUTION. Sci. Am. 210, (1). 25-31, Jan.
196«.
tJsing the development of Los Angeles' control program as an
example, smog, dust, fumes, photochemical reactions, automotive
emissions, control methods, emissions standards, and control
devices are reviewed.f#
01850
J.A. Bolt M. Boerma
THE INFLUENCE OF INLET AIR CONDITIONS ON CARBURETOR HETEPING.
Society of Automotive Engineers, Inc., New York, 1966. 13
pp. (Presented at the Congress of the Society of Automotive
Engineers, Detroit, Mich., Jan. 10-1U, 1966, Paper 660119.)
This paper provides data concerning the enrichment of
automotive carburetors with variation of inlet air pressure
and temperature. These changes occur with weather and the season,
with altitude, and because of underhood heating. The early
opening of the conventional carburetor enrichment value at
altitude can add greatly to the "normal" carburetor enrichaent.
Means for compensating the mixture ratio for these changes in
inlet air conditions are known, but will almost certainly add to
the complexity and cost of the engine induction system. The cost
of improved devices must be compromised with the possible
reduction in exhaust emissions and improvement in fuel economy.
(Author abstract)##
01851
C.R. Begeman
CARCINOGENIC AROMATIC HYDROCARBONS IN AUTOMOBILE EFFLUENTS.
Society of Automotive Engineers, Inc., New York
also published in Vehicle Emissions (Selected SAE
Papers) 6, 163-71, 196«. (Presented at Congress of the Society
of Automotive Engineers, Detroit, Mich., Jan 8-12, 1962,
Paper U«OC.)
This paper is part of the joint effort by the General Hotor
Research Laboratories and the Sloan-Kettering Institute to
evaluate the contribution by automobiles to the trace amounts of
carcinogenic hydrocarbons in the atmosphere. Benzene-soluble
"tar", containing carcinogenic polynuclear aromatic hydrocarbons,
is recovered from the total volune of exhaust and blowby gases
E. Control Methods 475
-------
of an engine operated on "a simulated city driving schedule. Fuel
composition was found to influence both the pyrene, a carcinogen.
Iso-octane and diisobutylene fuels gave only 20% as much "tar" as
did a typical commercial gasoline, and a fuel comprised of equal
volumes of ortho-xylene and benzene gave 70% as much ".tar" as did
gasoline. The emission rate of benzo(a)pyrene with
diisobutylene fuel was only 7X of the rate with gasoline.
Benzo(a)pyrene emission in blowby gas was less than 4% of the
total benzo (a)pyrene emitted from the engine. On the assumption
that benzo(a)pyrene from automobiles settles out of the air
in the same manner as the lead from exhaust gas, automobiles nay
contribute, on the average, about 251 of the total benzo (a)pyrene
in the air over cities. On the other hand, if benzo(a)pyrene is
dispersed with little or no settling, as is the case for carbon
monoxide from exhaust gas, the contribution of benzo(a)pyrene by
automobiles may average about 10%. (Author abstract)ft
0185H
R.S, Reid, J.G. Mingle, W.H. Paul
OXIDES OF NITROGEN FROH AIR ADDED IN EXHAUST POETS. In:
Vehicle Emissions, Part II, SAE Progress in Technology
Series, Vol. 12, Society of Automotive Engineers, Inc.,
New York, 1966, p. 230-2UO. 6 refs. (Presented at the SAE
Automotive Engineering Congress, Detroit, Mich., Jan. 10-14,
1966. Paper 660115)
Tliis paper presents the results of a study made to examine
quantitatively the oxides of nitrogen in the exhaust of an
internal combustion engine installed in a passenger car. The
effects of adding secondary air in exhaust ports, with both a rich
and lean carburetor, and for steady-state conditions, are reported.
Experimental setup and procedures are explained. (Authors'
abstract)f*
01867
K.J. Springer, P. Lepisto, C. Hood
INVESTIGATION OF DIESEL POHERED VEHICLE ODOR AMD SMOKE.
Southwest Research Inst. San Antonio, Tex., Div. of
Engines, Fuels, and Lubricants. (SwRI Proposal 10-U336A)
Nov. 19, 1965. 46 pp.
This is a proposal from the Southwest Institute to assist -the
U.S. Public Health Service in setting reasonable, practical,
and realistic smoke and odor standards for diesel powered vehicles.
This assistance will involve obtaining additional basic data in
the form of dilution ratios and operating conditions most conducive
to the production of odor and smoke. A usable panel technique
for measurement of odor will be developed as will chassis.
dynamometer procedures-for evaluation and test of smoke.and/or
odor control devices. Various control devices will be
evaluated using these chassis dynamometer methods and finally,
fleet evaluation of the most promising control device(s) will be
conducted.t#
475 HYDROCARBONS AND AIR POLLU FION
-------
01873
E. Bartholomew
POTENTIALITIES OF EMISSION REDUCTION BY DESIGN OF INDUCTION
SYSTEMS. In: Vehicle Emissions, Part II, SAE
Progress in Technology Series, Vol. 12, Society of
Automotive Engineers, Inc., New York, 1966, p. 192-211.
(Presented at the SAE Automotive Engineering Congress,
Detroit, Mich., Jan. 10-14, 1966.) Also published as 90th
Congress ("Air Pollution—1967, Part II (Air Quality Act)"
Hearings before the Subcommittee on Air and Water Pollution
of the Comittee on Public Works, U. S. Senate Feb. 8,
Apr. 3-U, 1967, pp. 917-36.
Js an alternative to oxidation of hydrocarbons and carbon
monoxide in the exhaust system, a research program indicates that
the volume of the combustibles discharged from the cylinders can
be minimized by redesign of fuel-induction systems. The
objective is achievable without lowering of the level of
acceleration performance or increase of fuel consumption. A
tw/-stage carburetion system is employed in combination with
a dual or single manifold. The single-barrel primary
stage of the carburetor, which is used alone in cruising up to
about 70 miles per hour, provides good mixture preparation and
close to uniform fuel distribution to the cylinders. The one or
two barrels of the second stage are brought into operation when
maximum performance is desired. Other features of carburetors
and manifolds are described that contribute to emission reduction.
(Author's abstract, modified)f#
02112
0. Westchester.
PREVENTION OF AIB POLLUTION BY FDMES FROM BAKING FINISHES.
Metal Finishing 6U, (10) 702-77, Oct. 1966.
After reviewing regulations, particularly in Los Angeles
County, for regulation of emission of organic solvents into the
ambient air, the author lists critical solvents and their maximum
permissible concentrations as established by the American
Congress of Governmental Industrial Hygienists. He then goes
on to review methods for disposing of waste solvents when finishes
are baked on or cured at higher than room temperature. The most
effective method is catalytic burning of the solvents; this method
is employed in 2500 installations in the US and 1500
installations elsewhere. The disposal of chlorinated hydrocarbons
and sulfur containing compounds is more complex and requires
additional methods and eguipment. Silicone coatings give
Si02 on combustion and coat the catalyst with a fine powder.
The equipment for catalytic burning may be designed in several
arrangements, but aerosol formation and condensation must be
prevented before the vapors reach the exhaust fan, otherwise the
efficiency of the catalyst may be impaired. Some installations
recirculate the hot clean air resulting from solvent conbustion to
help bake the finish.##
E. Control Methods 477
-------
02112
T. Tomioka
(POLICIES ON THE PREVENTION OF AIB POLLUTION DUE TO AUTOMOBILE
EXHAUST GAS.) Kuki Seijo (Clean Air-J. Japan Air
Cleaning Assoc., Tokyo) «, (1) 31-5, 1966.
The toxic effects of exhaust gas components from internal
combustion, engines and possible means of control are reviewed.
Types of engines mentioned are those fueled,w'ith gasoline,
liquid petroleum gas and diesel fuel. Periodic inspection of
vehicles for proper engine performance, improvement of roads and
fuels, and equipping vehicles with supplementary devices for
decreasing exhaust emissions are proposed as control methods.
The filtering system required on 1966 model cars in California is
explained. The principle of the infrared spectrophotometric
analyzer for carbon monoxide and hydrocarbons is discussed, and
the apparatus described.f#
02373
D.E. Rounds
A BIOLOGICAL ASSAY METHOD FOR MIXTURES OF HYDROCARBONS USING'HUMAN
CELLS IN IISSUE CULTURE. Preprint. " (Presented at the Fifth
Conference of Methods in Air Pollution Studies,
California State Dept. of Public Health1, Los Angeles,
Calif., Jan. 31, and Feb. 1, 1963.)
It was observed that serial dilutions of hydrocarbons altered
the growth rate of human fetal lung cells and an established line
conjunctival elements. Growth reached a maximum rate when a
chloroform extract of exhaust from an idling automobile was
diluted to 0.005 of the stock concentration. The exhaust fron
the same automobile, after passing through a catalytic filter,
showed a peak growth effect with a dilution of 0.025. j From
these data it was estimated that the exhaust device removed
approximately 80% of biologically active hydrocarbons.
Applications of, the bioassay method to other problems are
discussed. (Author summary)** *
02U05
AIH-GU&RD SYSTEM FOR CONTROL OF EXHAUST EMISSION. American
Motors Corp., Detroit, Mich. 1965. 13 pp.
American Motors' Air-Guard System for exhaust emission
control was 'designed specifically to meet the State of
California requirements which are based on its
photochemical-type smog. In 1959, the California legislature
enacted an addition,ot the Health and Safety Code called*
"Standards for Ambient Air and 'Motor Vehicle Exhaust."
This legal requirement was adopted*DecemberH, 1959. To meet
the State's standards for exhaust emissions, the Air-Guard
System was developed-and designed to reduce the emission of
hydrocarbons and carbon monoxide from the engine exhaust.
All of American Motors' Six and V-8 engines are equipped
478 HYDROCARBONS AND AIR POLLUTION
-------
with the system. According to California law, 1966 model cars
registered in the State must be equipped with an exhaust
emission control system approved by the California Motor
Vehicle Pollution Board. On July 11, 1965 the Board approved
American Motors' Air-Guard Systen after determining that it
meets all requirements under the California law. The purpose of
this publication is to assist service operators to properly service
and maintain the Air-Guard System in order to assure its optimum
performance for controlling exhaust emission. (Author abstract)#t
02411
EVAPORATIVE LOSS CONTROL DEVICE. Esso Research and
Engineering Co., Linden, N.J. 1966. 31 pp.
The ELCD (an acronym for evaporative loss control device) is a
development of the Esso Research and Engineering Company,
Linden, Sew Jersey. Its function is to prevent the evaporative
emissions of hydrocarbon fuel from automotive vehicles, an air
pollution problem of growing significance. Based on a"
convehicles, an air pollution problem of growing significance.
Based on a controlled adsorption-desorption cycle the ELCD traps
those hydrocarbon vapors which would normally be lost to the
atmosphere and later feeds them into the engine under,controlled
conditions such that they neither alter engine operation nor
increase exhaust emissions of unburned hydrocarbons. A
comprehensive treatment of the ELCD system and its components,
the principles on which it operates, performance data
on equipped cars (including evaporative control and exhaust
emission analysis), the most current available information on
life of this system and a design section which treats the
flexibility inherent ot the controlling parameters of this system,
are described. (Author introduction)#f
0241*2
G. R. Frysinger
A HYDHOCARBON-AIR FUEL CELL 'USING AN ACID ELECTROLYTE. Army
Engineer Research and Development. Labs., Fort1 Belvoir, Va.,
Electrical Power Division. 11 pp., June 1966
CFSTI,DDC AD 634677
The utilization of liquid hydrocarbon fuels in a fuel cell to
produce electrical power is of high practical interest. The
ability to utilize the liquid hydrocarbon fractions available from
conventional petroleum .refineries at energy conversion efficiencies
of 40-60% has the effect of greatly increasing the usable energy
content of our proven petroleum resources. A new fuel cell
concept which utilizes a phosphoric acid' electrolyte offers a
highly compact fuel cell assembly which can be used in a very
highly simplified system for the generation of d. c. electrical
power from hydrocarbon fuels. Either the hydrocarbon can be
reached directly at the electrodes in an anodic oxidation reaction
or the active hydrogen of the hydrocarbon molecules can be
liberated by a hydrocarbon-stem reforming reaction and the
hydrogen subsequently reacted at the fuel eel anode. The
objective of this paper is to describe the electrode processes
involved in each of these alternatives and to discuss the
E. Control Methods 479
-------
hydrocarbon-air fuel cell system which is now possible, based on
the recent achievements from, U.S. Army research investigations.
(Author abstract)ft
02U71)
G. Bergshoeff
IMPROVED ABSORBERS * ^ SAMPLING AIR CONTAMINANTS. Intern. J.
Air Water Pollution 10, (9) 62931, Sept. 1966.
In a discussion on the Technical Note of SKABE (1965a)
and the Letters to the Editor of NASH (1965) and MARTIN
(1965) attention is drawn to a six-fold absorber with special
pump-case, published by the author in the DUTCH CHEMISCH WEEKBLAD
in 1961. The advantages of this absorber over that of SKAKE
(1965a) are discussed, and some suggestions for further
improvement are given. (Author abstract)f#
025D1
(SCIENTIFIC METHODS AND TECHNIQUES TO DECREASE THE POLLUTION OF
THE ENVIRONMENT, THROUGH INHALATION OR INGESTION, AND OF
ACOUSTICAL "NUISANCES.") Moyens scientifiques et
techniques de diminuer la pollution des milieux inhales ou ingeres
et des "nuisances" acoustiques. (Chapter 3: Les pollutions
et "nuisances" d'origine industrielle et urbaine. Tome 1. Leur
prevention et les .problems scientifiques et techniques qu'elle
pose en France.)- Premier Ministre, Delegation generale a la
recherche scientifique et technique. June 1966. pp. 1)7-59.
The functioning of chlorophyll in the course of photosynthesis in
leaves of plants serves as a method of air purification of
sufficient importance to consider its use in control. Vegetation,
like men and animals, can sustain a considerable amount of damage
to the point where the threshold limit of absorption of toxic
substances is exceeded. The three gases causing the most
damage to vegetation are carbon monoxide, the sulfur oxides, and
those containing fluorine. Also to be considered are acid
"smog", toxic "smog", ozone, and nitrogen oxides. Other
industrial pollutants which have a toxic influence, but less
sever and localized, are dusts, hydrogen sulfides, hydrochloric
acid, etc. Ethylene and carbon monoxide cause great damage to the
growth hormones, particularly auxin. The effects of S02,
S03, and H2SOI) are related to the quanity of gas emitted, the
degree of resistance of the species, their state of development,
and the various environmental conditions. The sensitivity of
vegetation to the action of sulfur gases varies essentially as a
function of the speed of absorption of the gas by the leaves.
Through experimentation it has been found that the plant species
which are most sensitive to S02 are chickweed, alfalfa, barley,
oats, wheat, rhubarb, lettuce, endive, spinich, cabbage, and
tobacco. Apples, apricots, peaches, grapes, corn, and beans are
less sensitive, whereas the floral species such as gladiolus, rose,
and lilac offer considerable resistance. Aquatic vegetation is
often used as purifying means for polluted streams. Subsoils
purify themselves of pollutant materials in various ways, including
uptake by vegetation and dispersion in the soil with rain water,
etc. In a section on means of decreasing the inhaled pollutants
480 HYDROCARBONS AND AIR POLLUTION
-------
the following are mentioned: dust collectors, normal methods of
dispersion in the atmosphere, fumes from domestic fires, auto
exhaust fumes, fuel additives, improvement of combustion in
engines, recycling of crankcase gases, post-combustion appliances,
and redesigning of motors. Also given in this section (Chapter
3) is some similar information on ingested pollutants and on
problems of noise ?*
02600
N. Y, Yansheva, I. S. Kireeva, and N. N. Serzhantova
THE PROBLEM OF REMOVING THE CARCINOGENIC PROPERTIES OF, BRICK
COAL. (K voprosu o dekantserogenizatsii ugol'nykh briketov.)
Hyg. Sanit. 29, (10) 13-6, Oct. 196U,
CFSTI: TT65-50023/10
3,<* benzpyrene was found to be present in coal pitch from various
byproduct coke plants of the Ukraine, and in coal briquets in the
production of which pitch was used a binding material. It was
shown that the use of a smaller amount of pitch in briquet pressing
did not markedly reduce the 3,4-benzpyrene content in briquets.
3,4-benzpyrene was likewise detected in the bitumen produced by
Kherson oil refinery, however, its content in briquets Bade with
addition of petroleum bitumen was several-fold lower than in
briquets with pitch. Thermic treatment of briquets proved to be
highly effective for decreasing benzpyrene content in the
product. (Author abstract)##
02637
C. L. Goodacre
BRIEF SURVEY OF THE LITERATURE RELATING TO EXHAUST GAS CONTROL BY
MEANS OF ENGINE MODIFICATION (PART III OF ATMOSPHERIC
POLLUTION: A SURVEY OF SOME ASPECTS OF THE EMISSIONS FROM
PETROL-ENGINED VEHICLES AND THEIR TREATMENT). British
Technical Council of the Motor and Petroleum Industries,
England. Sept. 1965. pp. 65-74.
An appraisal is presented of published work on: air-fuel ratio;
ignition timing; power output and speed; value overlap;
combustion chamber deposits; manifold vacuum; carburetion;
combustion chamber shape; engine cycle variations; spark plugs and
electrical equipment; and pressure fuel systems.##
02638
R. A. C. Fosberry
EXHAUST SYSTEM DEVICES FOR PETROL-ENGINED VEHICLES (PART IV OF
ATMOSPHERIC POLLUTION: A SURVEY OF SOME ASPECTS OF THE
EMISSIONS FROM PETROL-ENGINED VEHICLES AND THEIR TREATMENT).
British Technical Council of the Motor and Petroleum
Industries, England., Sept. 1965. pp. 75-92.
The major work on devices in exhaust systems has been on their
use for the oxidation of hydrocarbons and carbon monoxide. A
common feature of all these devices is that air is added to the
E. Control Methods 481
-------
exhaust stream in order to allow combustion to take place; 3
methods of combustion are used, leading to 3 types of devices:
Catalytic converters, Direct flame afterburners, and Hanifold
air oxidation systems. Devices on which results have been
published have almost exclusively been related to the requirements
of the Californian legislation1for the control of exhaust
emissions; thus it is convenient to discuss performance where
possible in relation to the requirements laid down by California.
These requirements are broadly that in 12,000 miles of normal
driving the average emissions (as measured during a specified
driving cycle carried out at intervals in the 12,POO mile test)-
should not exceed 275 ppm hydrocarbon (measured as hexane on a
nondispersive infra-red gas analyser) and 1.5% carbon monoxide;
certain criteria including ones on reliability, noise, odour and
safety are also stipulated. Five devices (U catalytic and one
direct flame) have been approved by the Californian
M.V.P.C.B. as meeting their requirements; brief details of
these devices and of their performance in the California tests are
given. ft lesser amount of work has been published on the
reduction of oxides of N in exhaust gases. The present relative
status of the different devices is discussed.**
026«8
H. Kuhn and R. Tomingas
ATTEMPTS TO PREVENT THE FORMATION OF POLLUTANTS IN THE EXHAUST
GASES OF TWO-STROKE ENGINES AND DIESEL ENGINES BY ACTIVATING
COBBDSTION WITHIN THE ENGINE. Staub (English Translation)
25 (3) 2-17, MAR. 1965.
CFSTI TT66-510UK/3
Combustion in two-stroke Otto engines and the diesel engine can
be influenced by chemical fuel additives in such a way that
oxidation is catalyzed and the side reactions of dehydrogenation
and cyclization are suppressed. In the two-stroke engine it was
possible largely to reduce the formation of benzpyrene by using
salts and chelates of polyvalent metals, in particular manganese,
and to prevent it completely by means of ether and ether-like
additives. For precipitation of the oil mists and soot particles
the "adhesive oil method" was employed. In the experiments the
two-stroke engine was selected first; checking of the results by
experiments on four-stroke engines is in preparation. In the case
of the diesel engine it has been possible to achieve a reduction
in soot formation with overloading by 10 to 15%. (Author
summary)##
02725
A. P. Banner and E. H. Ilgenfritz
DISPOSAL OF COAL TAR PITCH DISTILLATE OBTAINED FBOH CARBON
BAKING FDBNACE.BY CATALYTIC COHBDSTION. Preprint. J. Air
Pollution Control Assoc. 13, (12)-610-2, Dec. 1963.
(Presented at the 56th Annual Meeting, Air Pollution Control
Association, Detroit, Mich., June 9-13, 1963, Paper No.
63-3l».)
The air pollution problems associated with coal tar pitch fumes
evolved in the manufacture of baked carbon cannot be tolerated due
482 HYDROCARBONS AND AIR POLLUTION
-------
to odor of fumes which contain pyrene, phenanthrene, fluorene,
chtysene and related aromatic compounds. Elimination of coal
tar fumes was obtained by catalytic destruction at a tenperature of
550 C. Complete destruction of aromatic compounds is realized
vith some unburnt free carbon discharged to the atmosphere.
Choice of installation was based upon economics and ability to
eliminate fumes. Preliminary data were obtained from work on a
pilot unit. (Author abstract)##
02737
J. J. Feenan, H. B. Anderson, H. W. Swan, and L. J.
E. Hofer
CHROMIUM CATALYSTS FOR OXIDIZING AUTOMOTIVE EXHAUST. J. Air
Pollution Control Assoc. 14, (4) 113-7, Apr. 196H.
(Presented at the 56th Annual Meeting, Air Pollution Control
Association, Detroit, Mich., June 9-13, 1963.)
The Bureau of Mines, in cooperation with the Public Health
Service, Dept. of Health, Education and Welfare, has
investigated the feasibility of using various metals and metal
oxides as catalysts for the removal of the noxious components of
automotive exhaust gases. The phase of this program reported
here is the study of chromia-on-aluaina catalysts for the oxidation
of Co and hydrocarbons as represented by isopentane in a
continuous flow system. Aqueous solutions of four compounds of
Cr were tried as impregnating media for an alumina support to
study their effect on physical and catalytic properties of the
finished supported catalyst. Catalysts prepared from ammonium
dichromate were considered to be superior to the other preparations
on the basis of uniform dispersion of Cr within the support and
on activity. Preparations containing 0,1,2,4, and 8 percent Cr
were prepared and tested. The activity increased up to 4 percent
with little or no improvement at 8 percent. Three-component
catalysts containing in addition to chromia and alumina, small
amounts of Co, Ag, Mn, Co, and Fe were prepared and tested.
Chronia-aluraina catalysts containing Ag or Cu were more active
than catalysts containing chromia-alumina alone in oxidizing Co
at temperatures from 200 to 500 C; chromia-alumina catalysts
containing Ag were more active in oxidizing isopentane. (Author
abstract) #*
02753
8. Lawrence, III, E. Elsevier, L. A. Ripperton
THE EFFECT OF OPERATING VARIABLES ON AUTOMOTIVE HYDROCARBONS
EMISSIONS. J. Air Pollution Control Assoc. 14, (4) 126-9,
Apr. 1964.
The effect of varying engine load, air-fuel ratio, spark timing,
and compression ratio on a blocked, single cylinder, gasoline
engine was investigated with relationship to the production of
unburned hydrocarbons in the exhaust gas. The study was conducted
on a fully instrumented CFR engine. An increase in engine load
caused no significant change in hydrocarbon emission. At the
theoretical optimum air-fuel ratio the unburned hydrocarbons were
at a minimum. Advancing the spark timing caused a decrease in the
E. Control Methods 483
-------
hydrocarbon content. An increase in the compression ratio caused
an increase in the exhaust gas hydrocarbon content. (Author
abstract)#t
0276U
N.R. Rowe
RECOVERY OF ORGANIC SOLVENT FROM POLLUTED AIB. Preprint.
(Presented at the 56th Annual Meeting, Air Pollution Control
Association, Detroit, Mich., June 9-13, 1963, Paper No. 63-
33.)
Bany volatile organic solvents can be recovered profitably from
the air in and exhausted from industrial plants by activated
charcoal solvent recovery equipment. In some cases, the
recovered solvents are of better quality than the original
purchased material. Proper use of solvent recovery equipment can
prevent air pollution, eliminate fire and health hazards, and
reduce manufacturing costs. (Author abstract) *#'
02973
G. Schienann
REDUCING THE EMISSION OF SMALL OIL-FIRING UNITS WITH SPECIAL
EMPHASIS ON CONTROL METHODS. Staub (English Transl.) 25,
(11) 2-10, NOV. 1965.
CFSTI TT 66-510HO/11
In the case of small oil firing installations the type and
concentration of emissions depend on the combustion process.
Noxious .effects are mainly caused by soot and aromatic
hydrocarbons. Investigations into the possibility of reducing
these emissions show that the most convenient solution of the
problem is as complete a combustion of all combustible emission
components as possible. Practical experience indicates that the
present technical methods permit improvements to be achieved.
Control methods used in heating operations are here of particular
importance because of their effects on combustion. (Author
summary)ft
031U5
W. P. Calvert
AN ABSORBENT FOR PROVIDING CLEAN AIB IN SUBMARINES. Navy
Marine Engineering Lab., Annapolis, Bd. (MEL Rept. No.
3«0/66). ADG. 1966. 18 PP.
CFSTI AD 639 583
The components to be removed from the foul air of a submarine
atmosphere include moisture, C02 and H2, each in a range up to
about 3% by volume, and lesser quantities of contaminations which
are off-gases from men and materials. These latter include the
halogenated hydrocarbons, other hydrocarbons, CO, sulfur gases,
nitrogen compounds, etc, which are in high concentration at their
originating sources but may average to only a fev parts per
484 HYDROCARBONS AND AIR POLLUTION
-------
nillion in the total atmosphere. Occasional situations may occur
Khen much larger quantities of these components enter a submarine's
atmosphere. In addition it is necessary to remove certain
airborne solids and liquids (i.e., dusts, smokes, aerosols, haze,
bacteria, viruses, etc). Since adsorbents separate gases and
vapors and filter airborne solid and liquid particles from a foul
air steam, their capabilities are broadly inclusive. Cocoanut
shell carbon is the adsorbent now widely used by the D. S.
Navy for vents, filters, gas masks, etc. MS 544 is a sodium
aluminosilicate adsorbent which, recently, became a commercial
product. It is able to withstand thermal treatment in air during
repeated activation to desired adsorbency status. It flows easily
An air purification process may need easy flowing adsorbent.
This material is an example of the inorganic adsorbents presently
available. Investigation of adsorbents included comparison of
active carbon with an active inorganic adsorbent (MS 544) for
the removal of Freon-11, Freon-12, C02, H2, moisture, and
background gases and vapors from prepared streams of "foul air,"
Adsorption, various desorptions, and heat activation were
programmed in tests to compare the two adsorbents. Pressure
decrease and clean air purge effects are included. It was
concluded that (1) BS 544 is a safer adsorbent than carbon in a
regenerative process and will remove more unwanted components from
foul air, (2) termination of throughput in an air-purification
adsorbent process is dependent upon the nature of the gaseous
components which are to be removed from foul air; (3) .moisture is a
principal adsorbate in an airpurification adsorption process; (4)
heating is necessary for rapid desorption and for complete
activation prior to subsequent adsorption in a regenerative
air-purification adsorption process.##
03266
G. C. Hass, D. R. Olson, J. N. Pattison, M. P.
Sweeney, and H. Brubacher
THE EFFECT OF COMMERCIAL TUNEUPS ON AUTOMOTIVE EXHAUST EMISSIONS
(PRELIMINARY REPT.). Proc. Tech. Meeting West Coast
Section, Air Pollution Control Assoc., 3rd, Monterey,
Calif., 1963. 63-75 pp.
An exhaust test was conducted oh the car as received. The car
was sent out for tuneup and returned for the "after tuneup"
exhaust test. The cars were then returned to the owners with
specific instructions for them to observe their normal maintenance
habits during the year. The cars are then to be brought back at
intervals of 3, 6 and 12 months for exhaust testing only. The
owners were also asked to keep a record of maintenance costs for a
period of one year. One hundred vehicle owners not involved in
the test program are also keeping a record of maintenance costs for
one year to provide a comparison. Little, if any, improvement in
average exhaust emissions can be accomplished by a conventional
tuneup. Little, if any, improvement in average exhaust emissions
can be accomplished by ordinary dealer tuneups with specific
attention to items affecting emissions. If significant reductions
in exhaust emissions are to be accomplished .by engine maintenance,
techniques and skills must be upgraded over current levels.ft
E. Control Methods 485
-------
03339
S. Calvert.
BASIC STUDY OF AIR POLLUTION CONTROL WET SCRUBBEHS. (INTERIM
PROGRESS REPT.) Pennsylvania State Univ., University Park,
Center for Air Environment Studies. 268 pp. Sept. 1, 1966
The specific aims, method of procedure, and significance of the
research are reviewed. Reprints of work reported since January
1964 are appended; their titles are: "Design of Baffled Conduit
Particle Collectors" "Entrained Particle Collection in Packed
Beds" "Particle Collection in Packed Beds" "A Technique for
Determining Particle Penetration - Diameter Relationships"
"Removal of Small Particles from Air by Foam" "Gas Sorption
by Suspensions of Activated Carbon in Water" "Absorption by
Bubblers in Series" "Sorption by Suspensions in a Sieve Plate
Column" "Deposition of Particles from a Turbulent Stream by
Thermal Force" "Deposition of Particles from a Turbulent
Stream by means of Thermal Force" "Particle Collection in
Secondary Flows" "Aerosol Sampling with a Wide Port Probe"
Reprints of work reported before but published since 1964: "Gas
Absorption in a Ribbon-Grid Column" "Mass Transfer in
Horizontally Moving Stable Aqueous Foams" "Gas Absorption in
a Fin-Wall Conduit" and "Experimental and Analytical Study of
Plate-Type Gas Absorber Dynamics"**
03365
E. Kanz
DUST AS A GERM CARRIER IN WORKING ROOMS. STAUB (English
Transl.) (Duesseldorf) 26, (8) 10-5, Aug. 1966.
CFSTI, TT 66-51159/8
The importance of dust containing germa in working places is
discussed. In addition to sales rooms and other types of public
places, various industrial establishments have dust problems.
In particular, they are found in chemical plants where large-scale
microbiological processing takes place, as in the production of
citric and lactic acids; also this problem occurs in pharmaceutical
plants producing antibiotics, and in packing and food plants.
Hospitals also have to be concerned with controlling dusts. Four
methods of air sterilization are discussed. These include UV
heating ventilation, UV ceiling radiation, triethylene glycol
evaporation and triethylene cold aerosol generation.**
03456
B. W. Jackson W. M. Wiese and J. T. Wentworth
THE INFLUENCE OF AIR-FUEL RATIO, SPARK TIMING AND COMBUSTION
CHAMBER DEPOSITS ON EXHAUST,HYDROCARBON EMISSIONS. General
Motors Corp., Research Labs. 29 pp. (Presented during
National Automobile Week, Detroit, Mich., Mar. 12-16, 1962.)
Investigations of air-fuel ratio and spark tiuing were carried out
using: (1) a laboratory single-cylinder engine, (2) a passenger
car operated at 30 mph road load (cruise) and (3) passenger cars
operated in accordance with the conditions specified in the
486 HYDROCARBONS AND AIR POLLUTION
-------
California Standards for Hotor Vehicle Exhaust Emissions.
The study of combustion chamber deposits was limited to tests in a
single-cylinder engine and in a passenger car operated according
to the California Standards. Air-fuel ratio was found to have a
significant effect on exhaust hydrocarbon euission. However, the
problem of vehicle "surge," associated with leaner air-fuel
ratios, may present a practical limitation to reductions that
otherwise might be obtainable. Retarding the spark timing was
generally found to reduce exhaust hydrocarbon emission in both a
single-cylinder engine and in passenger cars. Seductions
achieved by this method, however, will be accompanied by losses in
fuel economy. The effects of leaning the air-fuel ratio and
retarding the spark timing were additive when used in combination
and consequently produced large reductions in exhaust hydrocarbon
content. The fuel economy effects tend to offset each other when
both methods of hydrocarbon reduction are used. The accunulation
of combustion chamber deposits in both a single-cylinder engine
and in a passenger car caused a significant increase in exhaust
hydrocarbon content. The hydrocarbon emission measured by means
of a nondispersive infrared analyzer sensitized to n-hexane was
always less than the total emission measured with a
flame-ionization analyzer. The ratios of the values obtained with
the flame-ionization analyzer to those obtained with the infrared
analyzer ranged from 1.5 to 5.5. Variations in air-fuel ratio had
little effect on this ratio but retarding the spark timing caused
it to increase markedly. This suggests that spark timing has a
significant influence upon the type of hydrocarbons in exhaust.##
03536
ADTOHOTIVE AIR POLLUTION III. (A REPORT TO THE O.S. CONGRESS IN
COMPLIANCE WITH PUBLIC LAW 88-206, THE CLEAN AIR ACT.)
Preprint. 1965.
Reduced exhaust emissions of hydrocarbons and CO have
become a reality in California with the introduction of the
1966-model passenger cars and light commercial vehicles.
Recognition of the need for still further control measures is
evidenced by the adoption of nitrogen oxide standards by the
California Board of Health. The Department of Health,
Education, and Welfare is implementing the new responsibilities
and authorities conferred by the Motor Vehicle Air
Pollution Control Act. Standards for the control of
enissions from gasoline-fuelled vehicles are being developed
accordingly, to become effective with the 1968 models. Some
additional technical information has become available.
Further studies of the effect of ambient temperature on exhaust
emissions indicate that low temperatures tend to increase
hydrocarbons and CO, particularly following cold-engine starts.
Preliminary results obtained from a study of the effect of leaded
fuels indicate that combustion chamber deposits may not
significantly affect the quantities of hydrocarbons and CO
emitted in exhaust gases. A survey being conducted to measure
CO levels in urban communities suggests that human exposure
to CO may be greater than routine atmospheric monitoring data had
indicated. A number of new projects are being initiated by the
Government to study the performance characteristics of production-
type exhaust emission controls in varied environments, to develop
more definitive data on exhaust emissions from small cars and
diesel-powered vehicles, to learn more about human tolerance of
lead and CO, and to effect control of oxides of nitrogen.
in expansion of industry research in automotive air pollution
E. Control Methods 487
-------
and its control is indicated by the recent activities of
technical associations. (Author summary)t#
03645
S. J. Leach
VENTILATION Of ADVANCE HEADINGS. Colliery Eng. (London)
«3(51
-------
03763
E. F. Spencer, Jr., N. Kayne, M. F. LeDuc, and J. H.
Elliott
EXPERIMENTAL FRCGBAM FOB THE CONTROL OF ORGANIC EHISSIONS FROH
PROTECTIVE COATING OPERATIONS. Los Angeles County Air
Pollution Control District, Calif. July 1959* 37 pp.
This report discusses the progress made in an experimental
program designed to determine the degree to which the emission of
solvent vapors from surface coating spraying operations can be
controlled by adsorption with activated carbon. Twenty-rtwo runs
have been made to date with single solvents and multi-component
solvent.mixtures, representative of industrial formulations. The
experimental work has shown that the control of organic emissions
from surface coating operations by adsorption with activated carbon
is technically feasible. Single solvents or combinations of
solvents in low concentrations are adsorbed.with high overall
efficiency. Solvents immiscible with water.are recovered with
high efficiency. The desorption.of mineral spirits appears to be
the most formidable economic factor as the required desorption
temperature is high and the value of the recovered solvent is low.
A small experimental test oven to investigate surface coating
oven emissions has been installed. Various surface coatings and
resin products will be processed.t#
03796
K. C. Stein, J. J. Feenan, G. P. Thompson, J. F.
Shultz, L. J. E. Hofer, and R. B. Anderson
CATALYTIC OXIDATION OF HYDROCARBONS (AN APPROACH TO AIR
POLLUTION CONTROL). Ind. Chem. Eng. 52, (8) 671-4, Aug.
1960. (Presented at the Division of Petroleum Chemistry, 135th
Meeting Chemical Society, Boston, Bass., Apr. 1959.)
The hydrocarbons in the exhaust gases from automobile engines are
a major source of the eye irritating smog occurring in urban
areas. Catalytic oxidation applied where the pollutants originate
in the individual vehicle is one of the methods of control. In a
search for suitable catalyst components, a large number of .metal
oxides in granular form, unpromoted and unsupported^ have been
investigated by ,a new microcatalytic technique based on gas
chromatography. The most active of the catalysts were, arranged
in order of decreasing effectiveness, the oxides of cobalt, nickel,
manganese, chromium, and iron. It is probable that different
forms or preparations of the same oxide would have .different
activities. In general, the higher molecular weight hydrocarbons
were more easily,oxidized than the lower. Hydrocarbons of a
given carbon number increased in reactivity according to the series
: aromatic, branched paraffin, alicyclic, normal paraffin,
olefinic acetylenic. Fortunately, the olefinic hydrocarbons
generally considered the most undesirable are relatively easy to
remove.##
03797
K. C. Stein, J. J. Feenan, L. J. E. Hofer, and R.
B. Anderson
E, Control Methods 489
-------
CATALYTIC OXIDATION OF HYDBOCABBCNS (TESTS OF SINGLE OXIDES AND
SUPPORTED CATALYSTS IN A MICBOCATALYTIC REACTOR). Bureau of
Bines, Washington, D.C. (Bulletin 608.) 1963. 22 pp.
Pure oxides and catalysts supported on alumina were tested for
activity in the oxidation of hydrocarbons in a microcatalytic
reactor. The active components, oxides or metals, for oxidation
of hydrocarbons were found in the transition series and in the
lanthanide and actinide series. Partly completed d- or f-electron
shells seem to be a criteria for high activity. The 10 most
active elements in the 2 series of catalysts, in decreasing order
of activity, vere: (I) Single Oxides (Co,Hn,Hi,Cr,Fe,Ce,
Ti,Th,Al,Cu); and (II) Supported Catalysts (Cr,Pd,Ru,
Ag,Mn,V,Pt,Fe,D,Cu). The average reactivity of
hydrocarbons in catalytic oxidation was found to decrease in the
following order: 1-pentyne, n-hexane, 2-pentene, cyclohexane,
n-pentane, 2,3-dimethylbutane, benzene, isopentane, and methane.
Some catalysts were unusually effective in oxidizing particular
hydrocarbons. The appendix presents data obtained by the same
method for the catalytic oxidation of methane. The same general
order of activity of catalysts was found in the oxidation of
methane and C(5) and C(6) hydrocarbons. (Author summary
modified)##
03851
L. Baymond
AIB POLLUTION AND THE AUTOMOBILE, L1 Inguinamento
Atmosferico e 1" Automobile. Fumi Polveri (Milan) 6, (9) 235-
«5, Sept. 1966. Text in It.
The differences in air pollution between London (or New York)
and Los Angesles are tabulated. The type of smog in
London is due mainly to particulate matter in the atmosphere
and is usually denser at night, while that of Los Angeles is
due mainly to photosynthesis and photochemical reactions and is
more frequent in the day time. The Department of Public
Health of the state of California decided that a reduction of
80% of hydrocarbons and 60S of carbon oxides is necessary.
The following rules to limit vehicular gas emissions are:
hydrocarbons - 275 parts/million in volume (0.165 moles/100 atoms
of carbon); carbon oxides - 1.5% in volume. The requirements of
gas purification equipment should be the following: The
equipment must be inexpensive and must function properly under
diverse climatic conditions for at least 12,000 miles. It must
be safe and well built and must not cause damage to the people.
Gas must not be allowed to leak to the passengers. The noise
level and the amount of gas consumed should not be higher than
in similar cars that do not use such equipment. Various equipment
of positive ventilation is illustrated, and methods to reduce gas
emissions are described.##
0386U
E. K. Daniels, J. R. Lutz, L. A. Castler
POLLUTION CONTROL AT FERNDALE, WASHINGTON. Proc. Am. Petrol.
Midyear Meeting, American Petrolium Inst. Division of
A90 HYDROCARBONS AND AIR POLLUTION
-------
Midyear Meeting, American Petroleium Inst. Division of
Refining, Los Angeles, Calif., Hay 14, 1958.)
Pollution control at the Ferndale, Wash., refinery of the
General Petroleum Corporation involves the design and operation
of the various processes used to control liquid and air-borne
wastes. Every opportunity is ttaken to regenerate alkaline
solutions used in treating petroleum products, thus enabling reuse
of these solutions and providing a further reduction, in the load
to the biological-oxidation units. When strong spent
caustic and potassium cresylate treating solutions are no longer
effective, they are enriched with the addition of excess
hydrogen sulfide or cresylic, acid, respectively, prior to
sale. The use of stripped hydrogen sulfide gases in the spent
caustic sulfiding tower has helped to reduce the quantity of this
gas that has to be burned and, consequently, has reduced the
emission of sulfur dioxide to the atmosphere. Floating-roof tanks
are used extensively at the refinery to conserve hydrocarbons and
reduce emissions to the atmosphere. The incineration and flare
systems are discussed.##
03872
E. P. Kropp B. N. Simonsen
SCRUBBING DEVICES FOB AIB POLLUTION CONTROL.
Paint Oil Chem.' Bev. 115,, (1«) 11, 14,' 16,.July 3, 1952.
(Presented at the t5th Annual Meeting, Air Pollution and
Smoke Prevention Association of America, Cleveland, Ohio,
June 10, 1952.)
In cooperation with the municipal program, potential sources of
air pollution from refinery operations were investigated.
These investigations showed that, in the Sohio operations, there
were three major sources of possible air pollution, as follows:
1. Acid Treating of Lubricating Oil Stocks; 2. Grease
Manufacture; 3. Asphalt Manufacture. Experimental work with
a pilot-model fog-filter type scrubber has established the
utility of this type unit for absorption of fatty-acid odors, and
sulfur dioxide and hydrogen sulfide from air streams containing
these contaminants. Further work with tunits
these contaminants. Further work with units of.this general type
may reveal other applications. As a result of this program,
commercial units are being installed for the control of sulfur
dioxide, hydrogen sulfide, and fatty-acid odors.
Reducing the steam concentration of asphalt-oxidizer fumes by
means of water sprays can increase the effective capacity of a
fume system to dispose of asphalt fumes by combustion.**
03983
H. F. Hartmann, G. M. Brown, B. B. Kean
DSE OF CHLOBINE DIOXIDE TO BEDUCE VAPOUR PHASE GUM IN TOWN GAS,
J. Inst. Fuel (London) 39, (307) 325-35, Aug. 1966.
Vapour phase gum, caused by the condensation of trace amounts of
nitric oxide, oxygen, and diolefins has;caused troublesome
blockages of pilots and automatic control devices of gas
appliances. This paper deals with the prevention of
E, Control Methods 491
-------
minimizing of gum in the gas by oxidation of the nitric
oxide by chlorine dioxide. It is shovn that
chlorine dioxide will oxidize 9551 or more of the nitric
oxide, in concentrations of up to at least 2<1 p.p.m. in less
thanntwo seconds, and that in favourable circumstances, gum
formation will consequently be reduced to quantities too small
to cause appliance complaints even though the reaction
products are not removed. A considerable amount of control is
necessary to make the process operate efficiently and successful
application in any particular case will depend on the proper
assessment of individual conditions. The protective measures
outlined in the paper were instrumental in eliminating
corrosion from the chlorine dioxide. (Author abstract modified)#t
OU013
K. H. Rhodes
PROJECT STRATOFIRE. S.A.E. (Soc. Automotive Engr.),
Preprint. (Presented at the Automotive Engineering Congress,
Detroit, Bich., Jan. 10-1U, 1966.)
The reduction to practice of a stratified charge combustion system
for automotive engines in the form of a bolt-on competitive product
was attempted in 1960 and 1961, as part of an all-out company
program aimed at smog elimination. The system and devices that
resulted from this Walker Manufacturing Co. project showed
promise as a fuel economy system, but in the end held little
promise for smog reduction. Insights of Projects Stratofire
that led to definition changes, theory modifications, and finally
to the project cancellation are set forth. (Author abstract)It
OH139
J. A. Kenagy
DESIGNING A "CLEAN BOOM" FOR PLASTIC PROCESSING. Bod.
Plastics Utt, (3) 98-9, 171, Nov. 1966.
A solution to the problems of dust and fume control in a facility
handling epoxides, polyesters, and polyurethanes is outlined. A
room complying with Federal Standard 209 for a class 100 clean
room with laminar down-flow was built to contain casting,
encapsulating, and potting operations involving a variety of
plastics, hardeners, and catalysts. Exposure to irritating and
toxic materials, as well as the existence of a fire hazard in the
use of epoxy systems cured with benzyl dimethylamine, polyester
resin systems catalyzed by organic peroxides, and urethane systems
were involved. The hazardous fumes are removed by the,exhaust on
the downdraft benches which discharges to the outside. The
quantity of acetone, amine hardeners, peroxides, and other
flammable or toxic materials is kept to a minimum in the room. A
bank of five blowers recirculates the-air from the space beneath
the floor grating to a plenum chamber in the ceiling where the air
is filtered before being returned through the ceiling. The air
contains zero particles per cubic foot of 0.5 micron and larger.
There is a pop-out escape door in addition to the regular door in
case of fire.*t
492 HYDROCARBONS AND AIR POLLUTION
-------
OH179
Z. Hertvik and 0. Kralik
GAS REMOVAL FROM BITUHINOOS COAL PITS IN THE OSTHAVA-KARVINi
DISTRICT. Czech. Heavy Ind. (Prague) 11, 3<*-6, 1966.
Degassing stations are used to remove gases from bituminous coal
mines, especially in reducing methane exhalation by an average of
30 per cent. The reduced exhalation makes possible an improved
venting of the pits, smaller air shafts, and thus reduced
investment costs. The pits are also prepared for more rapid
accessibility and for seam working. It becomes possible to use
electric -power on a wider scale and thus reduce the use-of
compressed air which is more expensive. The removal of mine gas
is controlled and the possibility of its industrial utilization
investigated. Absolute safety of operation of the degassing
station is ensured by its perfect equipment with safety and control
devices. (Author summary modified)##
OU226
THE DESIGN AND DEVELOPMENT OF THE AIR PUMP FOR THE GENERAL
MOTORS AIR INJECTION HEACTOB SYSTEM. Gen. Motors Eng. J.
1966. pp. 30-5
The development of the General Motors Air Injection Beactor
system for controlling the concentrations of unburned
hydrocarbons and carbon monoxide in vehicle exhaust emissions
required engine modifications and the design of new components.
The most vital component in the system is the air pump, designed
and manufactured by the Saginaw Steering Gear Division. The
pump developed by Saginaw engineers is a semi-articulated vane
type positive displacement pump. The design displacement is 19.3
cu in. per revolution with high volumetric efficiency and low
horsepower consumption. Additional design criteria included
durability consistent with the life of the vehicle and satisfactory
performance without maintenance. (Author abstract)!*
04279
S. T. Gadomski
DRY-PACKED BEDS FOR THE REMOVAL OF STRONG-ACID GASES FROM
BECYCLED ATMOSPHERES. Naval Research Lab., Washington,
D.C., Chemistry Division. (NRL Rept. No. 6399.)- Aug. 30,
1966. 6 pp.
CFSTI, DDC: AD 6H2 27U
Under certain conditions, strong-acid gases can be formed in
recycled atmospheres by-the combustion of halogenated hydrocarbons.
One control measure involves the use of a dry absorbent filter.
Li2C03 has already been used as an absorbent in these filters as
a result of a screening test of a number of scavenger materials.
In this report the absorptive properties of some other potentially
useful materials were examined. Baralyme and soda lime were
superior to L12C03 in air at 76 deg F and over 50% R.H.,
while the silica-alumina catalyst with monoethanolamine (MEA)
impregnant and the silica-magnesia catalyst were almost as
E. Control Methods 493
-------
effective as L12C03. However, Baralyme, soda lime, various
basic materials (MEA, gaseous NH3, Na2C03, and guinoline)
supported on the silica-alumina catalyst, and the silica-magnesia
catalyst were all useless at 1UO deg F. especially under dry
conditions. Li2C03, therefore, still remains as the most
effective absorbent throughout tho range of probable conditions.
(Author abstract)t*
04357
S. Dauer
(COMBUSTION TRAINGLE FOR FLOE GASES FHOH COMPOUND FURNACES.)
Das Verbrennungsdreieck fur Rauchgase aus Mischfeuerungen.
Brennstoff-Kaerme-Kraft (Duesseldorf) 17, (5) 232-7, May
1965. Ger.
In order to utilize high value fuels, residues of production
processes which are not sufficient for the power production
needed, other fuels have to be used in addition and compound
furnaces become necessary. These type furnaces are available for
all sizes of steam generators and varied fuelds can be burned
either individually or combined in one combustion chamber. If
several combustion chambers are used, the flue gases, after the
combustion process, flow combined through the rest of the boiler
surface. However, incomplete combustion may result if flues of
various characteristics are used. The flue gases have to be
controlled and analyzed by chemical or physical methods. For this
analysis, a combustion diagram is of great value. The
construction of such a diagram is discussed in the following
equations: Equation of the enlarged combustion triangle by
occurrence of hydrogen in the flue gas. Equation of the enlarged
combustion triangle by occurrence of hydrogen in the flue gas.
Equation of the enlarged combustion traingle by occurrence of loss
of carbon. Equation of the enlarged combustion triangle by
simultaneous occurrence of hydrogen in the flue gas and loss of
carbon. nfluence of carbon loss on air proportion. Mixed
(compound) fuels. Mathematical formulas are given for the
construction of a combustion traingle.##
0137U
K. Yamazaki and Nenryo Kyokaishi
EXHAUST CONTROLS FOR AIR POLIOTION. (J. Fuel SOC. Japan
Tokyo) UU, (460) 56U-7U, Aug. 1965. Jap.
Principal differences in the burning mechanisms of premixed and
diffusion flames are discussed in relation to carbon or soot
formation in order to elucidate the nature of exhaust from
gasoline,or diesel engine vehicles. The contents of exhaust
pollutants (carbon monoxide, nitrogen oxide, hydrocarbons and
their incomplete combustion products) vary extensively according to
the driving mode of vehicle operation, as in idling, acceleration,
cruising and deceleration. It is important to note that
hydrocarbon emission is extremely remarkable in the deceleration
step. Diesel exhaust is rather clean compared to gasoline
exhaust. Exhaust control devices, catalytic and afterburner,
developed in America are briefly reviewed. Improvement of the
494 HYDROCARBONS AND AIR POLLUTION
-------
engine itself in order to reduce incomplete combustion is
discussed. American estimations of future hydrocarbon emission
under exhaust controls are cited. (Author summary)f*
OU417
ADTO EXHADST STANDARDS WILL TIGHTEN. Chem. Eng. News l»«,
(20) 56-8, Bay 16, 1966.
Stricter standards regarding automobile exhausts are being sought,
necessitating a more sophisticated approach to control systems by
auto manufacturers. It is conjectured that controls based on
reactive hydrocarbons, rather than total hydrocarbons, are likely.
Hany laboratories are presently assembling data on the reactivity
of various hydrocarbons, but much more is needed. The continuing
work on the modification of engines to reduce the emission of
undesirable exhaust products is described. The need for
standards regarding the emission of nitrogen oxides is
controversial. However, research is proceeding on possible ways
to control nitrogen oxides, concentrating primarily on catalytic
systems. A diagram illustrating the formation of photochemical
smog is included.#*
0«H70L
R. H. Johns, R. P. Garwig, and B. Markels, Jr.
CATALYTIC COBBtJSTION OF ATHOSPHERIC CONTAMINANTS IN SPACE VEHICLE
ATBOSPHERES. Atlantic.Research Corp., Alexandria, Va.
May 1965. 70 pp.
DDC,' AD «65 711
The general purpose was to study the kinetics of oxidation of
various atmospheric contaminants by several catalysts. A
differential rate method was utilized to determine a reaction rate
that depended only on catalyst type and was therefore useful for
comparing catalyst performance independent of reactor geometry.
The oxidation of 0.1 per cent of methane and Freon 12 as
contaminants in air was investigated. A reactor and gas
preheater were devised which allowed precise temperature control.
Hopcalite, palladium supported on alumina, vanadium pentoxide,
and silver permanganate were the catalysts considered. Palladium
was found to be more effective catalyst than Hopcalite for
oxidizing methane. Palladium was also effective in oxidizing
Freon 12, but the catalyst was poisoned with respect to further
oxidation of methane. Differential rates at various
temperatures up to 600 F were determined to compare catalyst
performance. Neither vanadium pentoxide nor silver permanganate
significantly oxidized methane at temperatures up to 600 F.#f
OU529
R. J. Everett, L. W. Brewer, G, W. Edwards, A.
Juskiewickz, T. A. Linn, Jr., R. 0. Mills, and A. J.
Jack
E. Control Methods 495
-------
INDUSTBIAL HYGIENE HANDBOOK. Sandia Corp., Albuquerque, N.
Hex., Industrial Hygiene Lab. (Sept. No. SC-RR-64-562.)
Feb. 1965. 152 pp.
This handbook covers procedures, devices, and equipment for
controlling possible occupational hazards at Sandia Corporation.
Occupational hazards are usually divided into two general
classifications: exposure to toxic chemical agents and exposure
to physical agents or environmental factors. Chemical agents can
enter the body by three methods: inhalation, skin contact, or
ingestion. Inhalation and skin contact are the most important
because the majority of occupational diseases result from
inhalation of dusts, fumes, vapors, gases, and mists or from skin
contact with chemical materials. Toxic materials, when inhaled,
are frequently rapidly absorbed into the blood or into the fluids
in the lungs. A classification of the chemical agents is given
which is valuable for control purposes.#t
OU535
K. G. Woodland, B. C. Hall, and'E. E. Russell
PEOCESS FOR DISPOSAL OF CHLOEINATED ORGANIC RESIDUES. J. Air
Pollution Control Assoc. 15, (2) 56-8, Feb. 1965.
A continuous process for the disposal of halogen-containing
organic residues has been developed. This process is based on the
decomposition of wastes into gaseous byproducts by high temperature
reactions with air and steam. The exit gases, which are
essentially carbon dioxide, nitrogen, and hydrogen halides, can be
scrubbed with water, thereby completely eliminating atmospheric
pollution. A unique refractory-lined recuperative heat furnace
has successfully operated in this fashion to dispose of more than
20 million pounds of liquid residues (average decomposition:
60% C12; 35% carbon; and the remainder oxygen, hydrogen, and
others) during the last year. This process is cheaper than most
conventional disposal methods (i.e., ground burial) and offers the
added advantage of complete and permanent disposal. (Author
abstract) ##
OK558
D. P. Thornton, Jr.
PLATINUM OXIDATION CATALYSTS IN THE CONTROL OF AIR POLLUTION.
Platinum Metals Rev. 7, (3) 82-7, July 1963.
A description is given of the control of noxious products in
waste gases by platinum catalysts. Platinum alloys are supported
on specially prepared alloy steel ribbons, formed into mat-like
beds of various sizes and shapes. Temperature required to
initiate catalytic oxidation is discussed. Several typical
applications are cited and schematics are included.ft
496 HYDROCARBONS AND AIR POLLUTION
-------
Oi»581
I. PU Khanin, V. I. Yakovlev, M. B. Kartsynel
A SPHAY-TYPE BENZOIE SCRUBBER WITH BADIALLY-SLOTTED GAS
DISTRIBUTORS, Coke Chem. (USSR) (English Transl.)
(1) 30-5, 1965. Russ. (Tr.)
The aim was to present the results of a study of the
aerodynamics of a new stage-type benzole scrubber with radially-
slotted gas distributors. It has been found that: 1. The .
radially-slotted distributors distribute the stream quite evenly
across the scrubber, irrespective of how the gas is supplied
(radially alpha egulas 0 degrees, along a secant alpha equal 35i
degrees, or tangentially alpha equals 90 degrees); 2.
Increasing the number of plates in the.top and bottom rows of the
distributors from 8 to 16 does not affect the distribution of the
gas; 3. The gas distribution through the scrubber is impaired by
increasing the depth of the slots between the two rows of plates.
Although reducing the depth of the slots improves the
distribution, it also increases the resistance of the scrubber;
1. The distribution of the gas improves noticeably as
it passes through the distributors. There is no doubt that
recovery improves as the number of distributors (and,
consequently, the number of stages as well) increases; 5.
Increasing the flow rate of the gas does not substantially
affect the pattern of its distribution across the scrubber.
However, the'resultant increased turbulence of the gas
jets emerging from the distributor slots improves the
absorption; and 6. The resistance of a commercial stage-type
scrubber with a gas throughput of 8U670 cu m/h would be 53 mm
water gauge. (Author conclusions modified)*#
OU610
B. S. Chittawadgi and A. N. Voinov
MECHANISM OF ACTION OF FERROCENE ON SMOKE REDUCTION IN
DIFFUSION FLAMES. Indian J. Technol. (India) 3, (m) 209-11,
July 1965.
The effect of addition of ferrocene on the smoke point (maximum
height attained by .a flame when a fuel burns in a standard lamp
under standard conditions) of different fuels and on the formation
and growth of carbon particles in a 240 mm diffusion flame was
investigated. A standard smoke point apparatus was used, the
method used being similar to the one recommended in British and
Indian standards. The smoke points of the following fuels were
determined: benzene, isooctane, isooctane-benzene mixture, diesel
fuel (cetane No. 50) and gasoline A-72 (octane No. 68). The
change in smoke point with different concentrations of ferrocene
added to these fuels was determined also. Ferrocene increased the
smoke point of gasolines and diesel oils appreciably. It reduces
the size of carbon particles and increases their specific surface
area. It has been suggested that ferrocene catalytically
accelerates the rate of oxidation of carbon particles and thus
reduces the smoke formation in diffusion flames.ft
E. Control Methods 497
-------
04628
T. V. L. Bao
DIESEL SMOKE. J. Inst. Engrs. (India) (Calcutta) 46, (1)
5-19. Sept. 1965.
This paper studies the feasibility of improving the combustion
characteristics in a Diesel engine with a view to eliminate smoke,
suppress noise and reduce the cost of operation and maintenance.
Based on a study of the reaction kinetics of combustion and the
associated problems, the effects of secondary'fuel injection and
film vapourization on the elimination of smoke are analyzed. The
other features of combustion in a Diesel engine, e.g.,
augmentation of supply of air and its utilization; atomization,
vapour formation, mixture distribution, provision of adeguate
velocity to the air, and construction of the combustion chamber,
are also studied. (Author summary)##
Oi»659
POLLUTION BY EXHAUST: U.S. LAW AND A U.K. SYSTEM. Engineering
(London) 203, (5260) 213-6, Feb. 10, 1967.
A British system for the control of toxic exhaust emissions which
is inexpensive promises excellent results,and minimum power
loss. It is emphasized that California's problem with
photochemical smog and the meteorological conditions which result
in the continual recirculation of the air are extremely rare in
Europe. bScarbon monoxide is considered the more serious
problem. There has been a suggestion that the Los
Angeles atmosphere be analyzed before and after a two-day
ban on motor-cars to determine just how much pollution is caused
by car exhaust. A very important contribution can be made by the
Duplix induction system which employs a hot spot to assist
vaporization in the manifold during part-throttle conditions only.
The Zenith Duplex system vaporizes the fuel in a by-pass or
primary manifold during idling, part-throttle, and over-run
when emissions are at a maximum. At the same time, the primary
manifold is inoperative at full throttle, so maximum
power is virtually unaffected. Charts are given representing
the California regulations based on cold starting, idling,
accelerating, and stopping to resemble normal city driving.
A typical emission trace is given showing hydrocarbon emission
from a standard 1200 cc engine during deceleration, acceleration,
cruising, and idling. The emission with the Duplex induction
'system was 377 ppm of hydrocarbons with only a minor peak at
maximum depression compared to 1638 ppm of hydrocarbons with
severe peaks during deceleration.f#
OU771
L. J. E. Hofer, P. Gussey, and R. B. Anderson
SPECIFICITY OF CATALYSTS FOR THE OXIDATION OF CARBON MONOXIDE
ETHYLENE MIXTURES. J. Catalysis 3, (1-6) 451-60, 1964.
(Presented at the Catalysis Club Spring symposium, Pittsburgh
Pa., flay 10, 1963.)
498 HYDROCARBONS AND AlR POLLUTION
-------
The specificity of 5 different catalysts for the oxidation 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 the 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 <*50
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
temperature was not observed for chromium oxide or copper oxide.
The other 3 catalysts showed significant quantities of
chemisorption for both ethylene and CO. With chromium oxide,
ferric oxide, and cobalt oxide, hydrogen was produced in amounts up
to 2% of the hydrogen in the initial ethylene. (Author abstract)*
04838
R. D. Peed
CONTROLLED ENDO-EXOTHEBHIC OXIDATIOH OF INDUSTRIAL HASTES. Pre-
(Presented at the Oklahoma State Dniv. Conference on
Industrial Wastes, Stillwater, Nov. 16, 1965.)
Time, temperature, and turbulence are factors in disposal by
oxidation. The deciding factor for design temperature is the
proximity of molecules of fuel to molecules of oxygen. Complete
combustion, as defined by the author, does not exist if 500 ppm of
the toxic or noxious material is in the flue gases. Average
target concentration at grade and downwind of the stack is in the
order of 0.10 ppm! or perhaps less. The concentrations of
substances which will cause odor nuisance are restated. The
residence time factor must provide for the time interval required
for conversion of the liquid to the gaseous state. In disposal of
liquid streams and when mineral salts are present, the mineral
exits from the furnace in the form of its oxide in sub-micron size
particles.#t
04856
B. Z. Finfer
FUEL OIL ADDITIVES FOR CONTROLLING AI8 CONTAHINANT EHISSIONS. J
Air Pollution Control Assoc. 17, (1) 43-5, Jan. 1967.
An addition of additives to fuel oils prior to combustion is one
way of reducing combustible contaminant emissions to the outer air.
Reported test results show that some additives improve,
moderately, the combustive properties of fuel oils. Combustion is
also improved but to a lesser degree, in boiler systems that are
deficient in operation and design. Being combustible, polynuclear
hydrocarbons emissions would be reduced by use of additives.
Other types of additives to reduce slagging and inhibit corrosion
from combustion of fuel oils are also available. The cost of
using additives is low. Improved additives are required,
especially ones to better combustion in the deficient boiler
systems. These can be found by research and literature surveys.
Their effectiveness and nontoxicity would be confirmed by
laboratory and field testing. (Author abstract)##
E Control Methods 499
-------
04871
W. M. Jones
THE ADSOEPTION OF BENZENE VAPOUE FROM AN AIR STREAM, BY BEDS OF
CHARCOAL. II. THE RATE-CONTROLLING MECHANISM. J. Appl.
Chem. 16, 349-55, Dec. 1966.
The rate-controlling mechanisms discussed are: (i) mass transport
of vapour in the air; (ii) an irreversible surface reaction,
controlled by a thin, stagnant layer of air around the charcoal
granules; (iii) a reversible surface reaction, also controlled by a
thin layer of air; (iv) diffusion of vapour into the granules.
In each case, a linear equilibrium adsorption isotherm of benzene
vapour by charcoal is assumed. An electrical analogue of the
obtained are discussed. It is concluded that diffusion of vapour
into the granule as the rate-controlling mechanism, gives the best
description of the observed results. (Author abstract**
W. M. Jones
THE ADSORPTION OF BENZENE VAPOUR FROM AN AIR STREAM, BY BEDS OF
CHARCOAL. I. THE MOST EFFICIENT PHYSICAL ARBANGEMENT OF THE
BED. J. Appl. Chem. 16, 345-9, Dec. 1966.
Air is often cleaned by passing contaminated air through a
granular bed of an adsorbent such as charcoal. In such a
situation the rate of flow of air is fixed and there is an upper
limit to the physical size of the bed and an upper limit to the
resistance of the bed to air-flow through it. The problem
considered is the optimum size fo granule to be used in the bed
and the optimum shape of the granule, leading to the longest life-
time of the bed. An empirical answer to the problem is given for
the uptake benzene by d BCNU steam-activated charcoal; apparatus,
experiments and results used are described. The method of working
and the conclusion are applicable to any vapour/solid system.
(Author abstract)##
04888
K. J. Springer
INVESTIGATION OF DIESEL POWERED VEHICLE ODOR AND SMOKE (MONTHLY
PROGRESS REPT. NO. 2, FEB. DK MAR. 15, 1967). Southwest
Research Inst., San Antonio, Tex., Vehicle Emissions
Research Lab. Mar. 26, 1967. 16 pp.
Progress is reported on: catalytic muffler evaluation; engine
derating; exhaust dilution and oxidation; Jacobs engine brake;
fleet test of smoke suppressant; odor correlation chemistry;
statistical analysis; and humidity control.##
500 HYDROCARBONS AND AIR POLLUTION
-------
04892
SBCO Cfeemical Co. Anaheim, Calif. Feb. 1967. 13 pp.
TEE A7LAH7IC RICHFIELD VEHICLE VAPOH BECOVEEY STSTEH.
The nature of the evaporation loss problem is briefly reviewed,
and the control system developed for reducing these losses is
described, ill tank losses daring vehicle operation are prevented
by eliminating" the vent and using a non-venting or one-way fill
cap. The mixtnre of air and hydrocarbon vapor, normally vented
from the tank, is ducted forward through a separate line to a
condenser where any lig_uid condensable at ambient temperature is
separated and returned to the tank. The uncondensed hylrocarbon
plus the air flows from the top of the condenser to the crankcase
ventilation system for induction into the engine where it is burned
as air-fuel mirture. Any vapor which may come from the tank
dnriag the soak period is drawn into the crankcase by the slight
vacuum which accompanies the decline in temperature. Vapor and
excess liquid from the carburetor float bowl, resulting from
boiling of the fuel or from afterfill during a soak, is skimmed
from the bowl and ducted to the condenser for separation. The
liquid flows to the fuel tank and the vapor to the crankcase by way
of the crankcase ventilation system. Only one avenue is open to
the atmosphere - the air cleaner - and the filter element partially
impedes the escape route.#*
04899
I. D. Baigh and U. F. Deeter
COKTEOL OF SITHOGEB OXIDES IH AOTOHOTIVE EXHAUST. API (An.
Petrol. Inst.) Preprint. (Presented at a Session on
Antomobile Exhaust Gas, 27th Hidyear Heeting, American
Petroleum Inst., Division of Hefining, San Francisco, Calif.
Hay 17, 1962.)
Large differences exist in the concentration of nitrogen oxides
in the exhausts from different makes and models of vehicles and
for different modes of vehicle operation. Haximum guantities of
nitrogen oxides are emitted during high-speed cruising with large
incremental increases occurring for each 10-mph increase in speed.
Full-throttle acceleration is another mode of operation which
causes the emission of large quantities of nitrogen oxides.
Hitrogen oxides can be reduced by several methods. Modification
of ignition advance and carburetion and changes in fuel composition
reduced emissions but did not achieve the 80-percent reduction
which was the goal of this investigation. However, the use of
recycled exhaust gas was effective, and reductions of 80 percent or
lore were generally obtained. A modified system for recycling
exhaust gas was developed which offers an operable, inexpensive
method for reducing emissions of nitrogen oxides. Adeguate
vehicle performance was achieved by recycling the exhaust at
elevated temperatures and by designing the system to shut off the
flow at idle and wide-open throttle. Concentrations of carbon
monoxide and hydrocarbons (the latter during deceleration only)
were also reduced. Limited testing with this system did not
reveaX any adverse operating effects or abnormal deposit problems.
The results indicated that moderate changes can be made in the
ignition and carbnretion of those vehicles requiring such changes
E. Control Methods 501
-------
with little sacrifice of nitrogen oxides reduction. Individual
inert gases, such as nitrogen and carbon dioxide, were equally
effective for reducing nitrogen oxides emissions. The
effectiveness appea'rs to be due to a modification of the combustion
process resulting in lower peak temperatures. A thorough study
of combustion should be made to identify those conditions
influencing the combustion phenomenon and to determine the
optimum conditions for reducing the concentrations of nitrogen
oxides. (Author abstract)#t
OU962
R. G. Lunche, E. E. Lerake, R. L. Weimer, and J. A.
Verssen
AIR POLLUTION ENGINEERING IN LOS ANGELES COUNTY. LOS Angeles
County Air Pollution Control District, Calif. July 1, 1966.
51 pp.
Los Angeles County, the largest heavily-industrialized,
semi-tropical area in the world, is afflicted with a serious and
well-publicized air pollution problem. This problem is
accentuated by,average wind speeds of less than 6 miles per hr.,
and temperature inversions on more than 260sdays per year, which
restrict dispersion of the air contaminants generated by the
activities of seven million people. Since 1939 population has
more than doubled, industry has expanded from approximately
6000 establishments to more than 20,000 in 1966, and automobile
registration, gasoline consumption and fuels usage have increased
sharply. In addition to nearly two decades of expenditures by the
District for research engineering and enforcement, industry has
expended during this same period 127 million dollars for the
installation of new control equipment units and 882 million dollars
for basic production equipment. This program is preventing some
5085 tons of various air .contaminants from entering the Los
Angeles atmosphere each day. Cf this total, control measures of
the petroleum industry are responsible for removing some 3425 tons.
The prohibition of burning of high sulfur fuels accounts for
another 535 tons. The ban on single chamber incinerators and open
burning prevents another 605 tons from entering the atmosphere.
The control of air contaminants from mineral and metallurgical
industries accounts for another 420 tons. Of the 5085 tons of
various air contaminants now prevented from entering the Los
Angeles atmosphere from stationary sources'each day, 1195 tons are
hydrocarbons, 1320 tons are S02, 1945 tons are CO, 470 tons
are aerosols, and 155 tons are oxides of nitrogen. The program
will not be complete however, until effective control over the
gasoline-powered vehicle, fuel oil burning and organic solvent
usage is carried out.#f
05147
L. S. Caretto and K. Nobe
CATALYTIC,, COMBUSTION OF HYDROCARBONS HITH COPPER OXIDE. II.
CYCLIC COMPOUNDS. California Univ., Los Angeles, Dept. of
Engineering. (Rept. 63-4.) 1963. 59 pp.
In order to extend the study of the effects of chain length,
saturation, and structure on catalytic combustion of hydrocarbons'
502 HYDROCARBONS AND AIR POLLUTION
-------
applicable to catalytic afterburners for auto exhaust, kinetic
behavior pertaining to copper oxide catalytic.activity with cyclic
compounds was investigated. The experimental apparatus consisted
of a bench scale catalytic reactor and preheater with, controls on
flow and temperature and an electronic analyzer using a flame
ionization detector to measure the hydrocarbon concentrations into
and out of the reactor. Three compounds, benzene, cyclohexene,
and cyclohexane were studied. The flow rates used ranged form 130
liters/hour to 600 liters/hour measured at room temperature.
Initial concentrations used ranged from 190ppm to 2000ppm. The
lowest temperature at which oxidation was measured was 195 C.
The highest temperature used in the experiments was 360 C; at
this temperature all compounds were greater than 90 % oxidized.
The data were found to fit an apparent half order rate equation
with activation energies of 29.9, 26.6, and 14.5 kcal'/mole for
benzene, cyclohexande, and cyclohexene, respectively. The
relative positions of the oxidation rates of benzene and
cyclohexane were approximately the same; the benzene being greater
over the temperature range studied. The cyclohexene rate was
initially greater than the benzene rate but as the temperature
increased, it became less than the benzene oxidation rate. in
error analysis indicated a lower limit was set to the range of
conversion measurements by the increase of experimental errors at
lower conversions. Diffusion calculations indicated that
diffusion played a role at higher conversions. The derived
kinetic equations neglected these points and should not be
rigorously applied to higher conversions. (Author abstract
modified)##
05149
». F. Hamilton, B. Levine, and E. Simon
SMOG ABATEMENT. Lockheed Aircraft Corp., Burbank, Calif.
(Dec. 1, 1959). 48 pp. (Kept. No. 14163.)
Techniques were developed for simulating typical smog polluted
atmospheres. Methods and materials for reducing or preventing
smog formation as measured by ozone level were studied. Several
classes of materials were found effective in various degrees.
Best results were obtained by direct addition of iodine to
polluted atmospheres. Additions were effective both prior to smog
generation by'irradiation or after smog formation occurred.
Attempts to introduce inhibiting materials in gasoline through an
internal combustion engine were unsuccessful. (Author abstract
modified) t#
05155
W. Linville, and H. H. Parmelee
A STUDY OF CHANKCASE VENTILATION SYSTEH CONTROL DEVICE
INSTALLATIONS ON THE LOS ANGELES COUNTY FLEET . Los Angeles
County bSair Pollution Control District, Calif. (June 1961).
83 pp.
Ninety-four vehicles were studied to determine cost, service life,
and effect on the engine. During the nine-month period of the
test, more than 1.5 million miles were run. Two basic types of
crankcase ventilation system control devices were installed: the
E. Control Methods 503
-------
Variable Orifice Metering Valve system, and the Direct Vent
Tube System. Both devices functioned satisfactorily throughout
the test period. The variable orifice metering valve systems
accumulated1957,115 miles on 50 vehicles. No increase in
maintenance or service costs resulted from the use of this system
but the combustion chamber and induction system deposits were
slightly greater than on similar vehicles not fitted with1the
crankcase ventilation system. The cost of the variable orifice
system for new cars will be approximately $6 and for used cars
from $11 to-$35, including labor costs. No service life
complaints were received on the variable orifice system. The
direct tube to the air cleaner type'of ventilating system
accumulated 633,783 miles on"UU different vehicles. The
increased maintenance or service costs resulted from the use of
this system either, but here, too, the combustion chamber and
induction system-deposits were slightly greater than on the
vehicles not fitted with a crankcase ventilation system. The
original material cost for the direct tube system was
approximately $3 per unit with the installation labor costs
approximately $5. The direct vent tube-system required no
servicing throughout the period of the test. Crankcase
ventilation control systems of either of the types tested
effectively reduce the amount of hydrocarbons emitted from the
crankcase; that original cost is moderate, reliability is
excellent, and service expense is negligible; and, although
deposits in the engine are increased slightly, the increase is not
of a magnitude to increase measurably the cost of engine
maintenance.##
05209
F. J. Hoods, and J. E. Johnson
THE IGNITION AND COMBUSTION PHOPEETIES OF ACTIVATED CARBON
CONTAINING ADSORBED'HYDROCARBONS . Naval Research Lab.,
Washington, D.C., Chemistry Div. 'July 28, 1964. 32 pp.
(NRL Rept. No. 6090.)
Activated carbon contained in large filter beds is used in nuclear
submarines for removal of odors and trace contaminants. Because
organic vapors are concentrated in this way in the carbon, a study
was made to get information for assessing.the fire hazards
involved in maintaining the carbon filter in the ventilation
system of the 'submarines. In this study, spontaneous ignition of
submarine-exposed carbons occurred at temperatures as low as 490 F
in air at one atmosphere. 'Exothermic oxidative reactions occurred
in a flow system at temperatures as low as 390 F. Combustion of
carbons containing hydrocarbon produced considerable quantities of
carbon dioxide and carbon monoxide, and significant amounts of
these gases were evolved even under precombustion conditions. Of
a number of carbons which had been used in submarines, the lowest
flash point found was 160 F. (Author abstract)*f
052U
Bureau of Mines, Washington, D. C. (Jan. 1963 i»8 pp.) (Kept.
No. TID-8213.)
DEVELOPMENT OF DEPLETED-URANIUM CATALYSTS FOR DESTRUCTION OF AIH
POLLUTANTS IN AUTOMOBILE EXHAUST (REPORT OF RESEARCH
PROGRESS-FISCAL YEAR 1962).
504 HYDROCARBONS AND AIR POLLUTION
-------
Catalysts were tested for oxidation activity in the continuous
flow system. Four catalysts, all impregnated on alumina spheres,
were active enough to oxidize isopentane from 0.2 percent
concentration to below 0.033 percent at 600 C. in the presence of
2 percent carbon monoxide and U percent oxygen at an.hourly- space
velocity of 10,000", (which corresponds to a reasonably sized
muffler of 1/2 cubic foot volume for an average automobile.) Two
catalysts were also active enough to oxidize the carbon monoxide
content from 2 percent to 1.5 percent at temperatures 'below <)00 C.
A promoted urania catalyst was shown to be effective in oxidizing
automotive exhaust when used in a muffler of a 1/2-ton truck.
With a nonleaded gasoline practically complete conversion of
hydrocarbons and carbon monoxide was obtained during the idle
portion of the cycle and fairly high conversions-of the
hydrocarbons were obtained while cruising at 30 mph. Carbon
monoxide produced by the engine during the 30 mph cruise was less
than 0.3 percent. At this low concentration, carbon monoxide was
not oxidized by the catalyst. However, this quantity emitted to
the atmosphere is not of significant pollutant value. In
operating the engine under idle conditions from a cold start the
temperature of the exhaust is insufficient to start and sustain
catalytic activity. However, during the driving cycle the
temperature of the exhaust leaving the engine is sufficient to
maintain .high catalytic activity. After reaching operating
temperatures (400 C.) the catalytic reactor generates enough heat
to operate effectively even at idle conditions for extended
periods. With a leaded gasoline there was a gradual loss in
catalytic activity. The efficiency of the catalyst in oxidizing
hydrocarbons and carbon monoxide decreased by 23 percent over a
period of 122 hours and 1,366 miles with the leaded gasoline
(2 ml TEL/gallon). This rate of decline is excessive for
commercial application. To retard the decline in activity, a
replaceable zone of unimpregnated alumina spheres, located before
the catalytic reactor, may be sufficient to remove most of the
lead.## .
05250L
K. Nobe, and H. A. Accomazzo
CATALYTIC CCHBDSTION OF HY0HOCAHBONS WITH COPPER OXIDE. I.
Methane, Ethane, and Propane. California Univ.,Los Angeles,
Dept. of Engineering. (Hept. No. 61-83.) Dec. 1961. 39 pp.
The catalytic combustion of hydrocarbons present in low
concentrations is of particular interest in the search for methods
to control air pollution. The results are reported of the
heterogeneous oxidation of methane, ethane and propane with a
CuO-A1203 (1:1) catalyst with a BET surface area of "120 sg
n/ga and a aean pore radius of 65A. The combustion was studied
at initial hydrocarbon concentrations in the range 650 to 5,000
p.p.m., in the temperature range 313 to 591 C and gas space
velocities 6,000/hr. The hydrocarbon concentrations were
measured with a Carad flame ionization analyzer and detector.
The experimental results showed that for gas space velocities up
to 10,000/hr., 90S combustion was attained at temperatures above
580 C, 500 C and U80 C for methane, ethane and propane,
respectively. The results indicated that the degree of
hydrocarbon oxidation increased with increase in chain length.
The experimental kinetic data was found to fit empirical rate
eguations which were one, three-fourths, and three-fifths order
with respect to methane, ethane and propane concentrations
respectively.
E. Control Methods 505
-------
05300
Lodwick, J. R.
CHEMICAL ADDITIVES IN PETROLEUM FUELS: SOME USES AND ACTION
MECHANISMS. J. Inst. Petrol. (London) 50, (t91) 297-308, Nov. 1964.
(Presented at the Northern Branch Symposium, Manchester, England,
Apr. 23, 196U.)
The paper enumerates the types of anti-oxidants, copper
deactivators, corrosion inhibitors, combustion chamber modifiers,
anti-icing compounds, anti-knock agents, and anti-static additives
in current use or proposed for use in the near future. Where
possible the action mechanisms whereby these additives operate have
been given and discussed. (Author summary)
05320
Grant, Eric P.
DO EXHAUST CONTROLS REALLY WORK? In: Vehicle Emissions, Part II,
SAE Progress in Technology Series, Vol. 12, Society of Automotive
Engineers, Inc., N. Y. 1966, p. 291-296. 6 refs. (Presented at the
SAE WEST Coast Meeting, Los Angeles, CALIF., Aug. 8-11, 1966.)
Descriptions of exhaust control systems used on 1966 vehicles are
given. California Motor Vehicle Pollution Control Board (CMVPCB) is
carrying out a surveillance program to gather data relative to the
efficiency of these systems; exhaust emission results obtained on
1966 vehicles in cold- and hot-start tests are presented together
with other data gathered. It was found that, based on emission
tests of tot vehicles in public use, average emissions of 800,000
1966-model cars and light trucks are within California standards of
275 ppm hydrocarbons and 1.5 percent carbon monoxide; emission
levels in public use are higher than in proving ground testing; and
1966-model cars are 70 percent lower in exhaust emissions than
existing cars.
05380
Knopp, H. E. U. Joachim, and G. Baumann
THE INFLUENCE OF GASOLINE INJECTION ON THE EXHAUST GASES OF MOTOH
VEHICLES. (Beeinflussung der Kraftfahrzeugabgase durch
Benzineinspritzung.) Motortech. Z. (Stuttgart) 26, (9) 353-61,
Sept. 1965 and Bosch Tech. Ber, 1 (t) , 206-20, (Sept, 1965). Ger.
(Tr.)
The emission of carbon monoxide, hydrocarbons and oxides of
nitrogen from various engines with intake-manifold fuel-injection
systems, and in some cases from their carburetor equipped
counterparts, was measured. Under steady running conditions, a fuel
injection system offers advantages by making possible to adopt the
characteristics from poin to point to obtain the most favorable
exhaust conditions. This adoption is described for both a
mechanically and an electronically controlled injsection systen.
Fundamental advanatages are obtained with a fuel-injection system
under non-steady running conditions, during acceleration and on the
overrun. A great influence of engine design on hydrocarbon
506 HYDROCARBONS AND AIR POLLUTION
-------
emission is detectable. Gasoline intake manifold injection offers
a sure way of meeting the current requirements of the California
test of a CO content of 1.5 percent by volume. If the limit is
going to be reduced to 1.0 percent as of 1970, as has been
announced then it would seem possible to stay within this value
through additional efforts. As shown in the examples of the snail
and the large engine, it is possible to fulfill the current
hydrocarbon reguirenents of the test, provided the engine design
takes into account the demands made on the exhaust gas. The N02
emission behaves exactly in an opposite fashion to the CO and
hydrocarbon emissions, because it is at a maximum when the other
components reach minimum values. At the present state of our
knowledge it is not possible to influence this through the mixture.
It is fortunate that the percentage of nitrogen oxides at low
partial load values of the California cycle is low. In principle
it makes more sense to provide maximum combustion completion for
the fuel in the combustion chambers, rather than to install
afterburners. Injection offers the additional advantage of smaller
fuel consumption and larger rotational momentum.
05409
B. F. Hrutfiord and J. L. McCarthy
SEKOR I: VOLATILE ORGANIC COMPOUNDS IN KRAFT PULP MILL
EFFLUENT STREAMS. TAPPI 50, (2) 82-58 Feb. 1967.
As part of a program of development of a process for stripping
agueous effluents for kraft pulp mill odor reduction (SEKOR), a
study has been made of the volatile organic compounds that may be
steam-distilled' from kraft pulp mill effluent liguors. Some
compounds have been isolated and characterized by gas
chromatography. The materials studied include an oil isolated
from blow gas condensate, an agueous blow gas condensate, and
several crude sulfate turpentines. Compounds identified include
hydrogen sulfide, methyl mercaptan, dimethyl sulfide,
dimethyldisulfide, methanol, ethanol, acetone, methyl isobutyl
ketone, alpha-pinene, beta-pinene, delta 3- carene, camphene,
limonene, cineole, and alpha-terpiueol. A large number of
additional compounds have been detected. Turpentines from a
number of sources have been analyzed and compared. (Authors'
abstract)##
05415
A. K. Ghosh, D. P. Rajwar, and D. Bhattacharyya
A MICRO-METHOD FOR RAPID TESTING OF CATALYSTS FOR THE OXIDATION OF
COMBUSTIBLE GASES. Chem. Ind. (6), 255- 8 (Feb. 11, 1967).
The micro-method described is of particular use in cases where the
catalyst should be tested guickly, precisely and with minute amount
of the material. The oxidation of combustible gases (hydrogen,
hydrocarbons, etc.) is carried out over catalyst deposited on a
platinum wire-wound mica foil that may be heated electrically.
An embedded thermo-couple measures the temperature at which the
oxidation takes place as well as the extent of conversion.
Provision for sampling of the oxidation products is also made for
periodic analytical checks on the extent of conversion
determined. Both the catalyst and the compensator are placed in
E. Control Methods 507
-------
the flow duct in such a manner that the filaments do not lie
directly in the main stream. Only the convection currents iron
the stream maintain steady supply of gas to the filaments. A set
of aspirators and traps is employed for the supply of the gas
freed from carbon dioxide and moisture. A calibration curve for
methane oxidation is obtained initially by recording the maximum
rise in temperature due to oxidation of methane-air mixtures of
known composition. The curve is used for determining the degree
of conversion of the oxidation reaction. The temperature of the
filament is regulated by adjusting a suitable series resistance and
carefully read by means of the potentiometer bridge. Methane-air
mixture is passed at the rate of 200 ml. per minute. The degree
of conversion is computed from the observed differential
temperature rise and that in the calibration curve. As there is
no need to analyse oxidation products in a separate apparatus, this
method offers an advantage over other methods of rapid assessment.
The observations of the oxidation temperature and of the
corresponding extent of conversion take place almost
simultaneously and the observed repeatability has been found to be
fairly high.**
05471
J. Oliver
THE PAINT FINISHER AND AIE POLLUTION. Prod. Finishing
(Cincinnati) pp. 62-9. Apr. 1967.
Rule 66 adopted by Los Angeles County, July 28, 1966
requiring tighter control of the 550 tons of solvent capor
discharged daily appears to be a precursor of regulatory action
in other areas. The rule was based on smog chamber tests of
the photochemical reactivity of various solvent vapors. Rule
66 prohibits the discharge of more than 15 pounds of organic
material into the atmosphere daily from heat-cured, baked, or
heat-polymerized material unless all organic material has been
reduced 85% or to not more than 15 pounds daily. With air-drying
finishes containing no photochemically reactive solvents
there are no restrictions. Control measures include a greater
use of water - based coatings and the substitution of a mixture
of oxygenated solvents and aliphatic hydrocarbons for aromatic
solvents. Where formulation changes do not control the exhausts
from spray booths or baking ovens, alternative controls include
absorption, liquid scrubbing, incineration, and catalytic
combustion. Substantial tax benefits are under consideration
in some states for companies installing pollution-abatement
equipment.##
05537
Clarke, P. J., Gerrard, J. E., Skarstrom, C. W., Vardi
J., Wade, D. T.
AN ADSORPTION REGENERATION APPROACH TO THE PROBLEM
OF EVAPORATIVE CONTROL. Society of Automotive
Engineers, Inc., New York. Preprint.
(Presented at the Automotive Engineering Congress, Society of
Automotive Engineers, Detroit, Mich., Jan. 9-13, 1967, Paper
670127.)
508 HYDROCARBONS AND AIR POLLUTION ,
-------
An approach to the containment of evaporative emissions of
hydrocarbon fuel from automotive vehicles, using an adsorption
system, is described. The concept of the system is based upon
controlled adsorption-desorption cycling phased to engine operation
modes. Feasibility is shown for both the containment of
hydrocarbon vapors which would normally be lost to t.he atmosphere,
and the feeding of these vapors to the engine under"conditions such
that both exhaust emissions and engine operation are unaltered.
Extensive performance data are furnished on three cars equipped
with exhaust control devices, and system design is treated in a
semiempirical fashion demonstrating the flexibility of the
approach. (Author abstract)
057U2
Middleton, J. T.
CRITERIA FOR CERTIFICATION OF MOTOR VEHICLE POLLUTION CONTROL
DEVICES IN CALIFORNIA. J. Air Pollution Control Assoc. 13 (2), 78-
80 (Feb. 1963). (Presented at the 55th Annual Meeting, Air
Pollution Control Association, Chicago, 111., May 20-24,
1962.)
It is the purpose of this paper to give the criteria for the
acceptance of devices and present some of the data used in
establishing them. It is presently estimated that crankcase
emission control systems are installed on about 10 percent of the
State's eight million motor vehicles and thereby effect a 2 1/2
percent reduction in hydrocarbon emissions. This small but
significant beginning in returning clean air to California will be
greatly increased with the mandatory installation of crankcase
devices on used cars, trucks, and buses.
05822
A, C. Stern
PHOSPECTS FOP EXHAUST COHTBOL BY ENGINE MODIFICATION.
Preprint. (Presented at the Research Conference on Motor
Vehicle Exhaust Emissions and Their Effects, Los Angeles,
Calif., Dec. 7, 1961.)
Automotive research is much needed on internal combustion
engines designed to reduce pollution emissions from their
operation. If progress is to be made toward the smog-free
automobile, a new sense of mission and a lot more fiscal support
has to be given and competent researchers have to be encouraged to
undertake the work. Although we cannot predict the results of
research, the several possible approaches which are available lead
one to be optimistic as to the probability of achieving reduction
in exhaust emissions by engine design modifications,##
05832
F. L. Hartley, C. C. Moore, and J. B. Gregory
THE SMOGLESS AUTOMOBILE. (J. Air Pollution Control
Assoc.) 10 (4) 143-6 (Apr. 1960). (Presented at the 52nd
E, Control Methods 509
-------
Annual Meeting, Air Pollution Control Association, Los
Angeles, Calif., June 22-26, 1959.)
Recent studies show that losses from the carburetor float bowl
and the fuel tank are significant and can amount to 20 to 30% of
the total hydrocarbons emitted from cars in the los Angeles
Basin. The purpose was to show how current fuel systems may be
changed to effectively reduce, if not virtually eliminate, these
losses. Automobiles with intentionally plugged external vents
were operated at altitude and low altitude, employing winter and
summer gasolines, and running under mild, and hot weather
conditions. No complaints were received from any of the
drivers that plugging the external vent has interfered with normal
car operation. A drain-back system was installed which empties
the contents of the carburetor bowl into the fuel tank immediately
when the engine is turned off. This system is fitted with a
vacuum-operated valve which is closed while the engine is running
so that warm gasoline from the carburetor bowl is not continuously
circulated to the tank. The drain time of the carburetor bowl is
approximately one minute. During this drain time some fuel does
evaporate but our experiments show that hot soak losses are
reduced by 95%. The fuel tank was insulated with two sheets of
asbestos paper, a sheet of aluminum foil, and a final layer of
asbestos cloth. On the average, losses from the insulated tank
are reduced by about 70%. A vacuum-actuated valve was installed
which closes the fuel tank vent during engine operation. By
combining both insulation and fuel tank vent closure, fuel tank
losses are reduced by about 90S. A fuel gank cap is provided
which acts both as a pop-off valve in the event pressure exceeds
two pounds within the tank and also as a vacuum breaker which
allows air to go into the tank as it is required. A vacuum
reservoir acts as a delay mechanism in opening the drain-back
valve. A fuel pressure regulator protects the float bowl.##
05859
I. S, Deckert, R. G. Lunche, and E. C. Murray
CONTROL OF VAPORS FROM BULK GASOLINE LOADING. J. Air
Pollution Control Association. 8(3)223-7, 230-3 (Nov.1958).
(Presented at the 50th Annual Meeting, Air Pollution Control
Association, St. Louss, Mo., June 2-6, 1957.)
An intensive development program by the petroleum industry has
succeeded in producing equipment capable of collecting and
dispersing of the hydrocarbon vapors displaced during the bulk
loading of gasoline into tank vehicles. Hefinements to the
various types of loading arm assemblies have overcome the problems
posed by tank settling during loading and liquid drainage from
the loading spout after loading, as well as eliminating "open
topping". Inasmuch as equipment manufacturers have been involved
in the development program, the equipment items comprising a
control system are commercially available. Where the loading into
tank vehicles is performed near existing vapor recovery facilities
(or gathering lines) absorption plants or fuel gas systems, they
can be used to dispose of the vapors. At other locations, such as
bulk terminals or bulk plants, where such facilities do not exist,
a separate package-type disposal system has been devised. This
latter system employs absorption of the displaced vapors in liquid
gasoline at about 200 Ibs. pressure to recover all but a few per
cent of the displaced hydrocarbon vapors. Each of the described
510 HYDROCARBONS AND AIR POLLUTION
-------
types of control equipment has been installed and in operation for
nearly a year and each has proven workable and effective. A
systematic program of maintenance should guarantee continued usage
without excessive costs. Hydrocarbon vapor emissions have been
reduced by about 30 tons daily. These controls represent
investments of approximately three million dollars by the
petroleum industry and payouts are estimated at thirty months to
five years.##
05899
D. S, Hehta S. Calvert
GAS SORPTION BY SUSPENSIONS OF ACTIVATED CARBON IN WATEB.
Environ. Sci. Technol. 1 (4), 325-31 (Apr. 1967).
(Presented at the Symposium on Industrial Air Pollution
Control, 59th Annual Heeting, American Inst. of Chemical
Engineers, Detroit, Mich., Dec. <*-8, 1966).
The objective of this research was to study and analyze the
process of mass transfer as applied to gas sorption by suspension
of absorbent particles in liguid. Hajor factors of interest in
this study are equiplibrium relationships and rates of
transfer. In gas transfer to suspension of absorbent
particles the solute gas first dissolves in the absorbent and from
luguid it is absorbed by the absorbent particles. Thus, there
are transport steps from gas to interface, through liguid, from
liguid to solid, and through solid. It is necessary that there be
a useful adsorption capacity on the wet solid, but high
equilibrium capacity does not necessarily ensure high rates.
The rates and the factors affecting rates must be investigated.
It has been shown that the controlling factor, for the
rates of transfer to suspensions, is the solubility of
the solute gas in water. The results of the study suggest that
the overall efficiency of the system for sorption by
suspensions can not be greater than the intrinsic efficiency of the
system for physical absorption of the compound under the same
hydrodynamic conditions. The solubility of benzene, toluene,
and trichloroethylene in water were determined at 25 C. The
absorption isotherm of C02 on wet Nuchar C-190 was
determined in the range of 0 to 0.003 atm at 25 C. The
absorption capacity of water can be increased to a great extent
by addition of an adsorbent. In the presence of 2% (by wt.)
activated carbon, the capacity of water increases by 0.2 times for
C02, by 21 times for propane, and by 142 times for butane at 1
atm. pressure and 30 C. The overall efficiency for sorption
goes through a maximum with the increase of activated carbon
concentration. The increase is explained by a mathematical
model for the rates of transfer and the decrease is suggested
to be due to hydrodynamic factors. Suspensions would give
a high overall efficiency in a practical contactor for compounds
with high intrinsic efficiency for physical absorption.f#
05929
W. S. Tyler
CATALYTIC OXIDATION OF ODOROUS INK SOLVENT VAPORS. ((Proc.
Tech. Conference, Bid-Atlantic States Sect., Air Pollution
Control Assoc., Newark, N.J.,)) 1-7 (1962).
E. Control Methods 511
-------
This article reports the engineering approach to the development
of controls for fumes emitted during high speed printing opera-
tions. It was found that the kerosene-like solvent used was being
partially oxidized to irritating and obnoxious aldehydes by the
severe drying conditions, i.e., hot circulating air blast of 650 -
700 F. After pilot plant runs to test catalytic oxidation, it
was concluded that 30 to 10% of the recirculated solvent vapors
were oxidized to objectionable materials without a catalyst being
present, and with one present, 90 to 95% of the solvent vapors
being recirculated were converted to unobjectionable C02 and
water. With this encouraging information, the Pt catalyst
installation was made. A second installation provided a six deep
catalyst bed of half the original cross sectional area. This not
only evened out the flow across the bed but appeared to improve
efficiency as evidenced by increased temperature rise across the
catalyst. Location of the catalyst in the circulating systems has
the disadvantage of using about t times as much catalyst as would
be required in the stacks with their much smaller fans. This
disadvantage is more than compensated by the simplicity of
operation and the fuel gas economy. Catalytic oxidation not only
reduces the partly oxidized hydrocarbons discharged but also the
amount of tar formed in process.##
05966
S, T. Yuster, P. Staudhamraer, N. Zuber, and E. K.
Selover
EXHAUST CONTROL DEVICES: AN INVESTIGATION OF NON-CATALYTIC
AFTERBURNING. (In: First report of air pollution studies.)
((California Univ., Los Angeles, Dept. of Engineering.))
(Rept. No. 55-27.) (July 1955).
-------
06032
EFFECTIVENESS OF EXHAUST CONTROLS OF 1966 VEHICLES BY THE STATE
OF CALIFORNIA MOTOR VEHICLE POLLUTION CONTROL BOARD, AUG. 10,
1966- 90th Congress. pp 275-8«. ("Air Pollution-1967, Part
I (Automotive Air Pollution)11 Senate Committee on public
Works, Washington, D.C., Subcommittee on Air and Water
Pollution, Feb. 13-1U, 20-21, 1967.
Based on emission tests of 10U vehicles in public use, the
average emissions of the 800,000 1966-model cars and light trucks
are within the California standards of 275 parts per million
hydrocarbons and 1.5 percent carbon monoxide. Emission levels in
public use are higher than in proving ground testing. This means
that the 1966-model cars are approximately 70S lower in exhaust
emissions than the existing car population. There is a very wide
range of emissions (at least five to one) between individual cars,
even with new exhaust systems. Available data indicate that there
•ay be emission deterioration as mileage accumulates with the
exhaust control systems in public use. 150 private owners of 1966
cars with exhaust control systems and 65 owners of 1965 cars
without exhaust control systems have been interviewed with regard
to the driveability of their cars. Slightly less satisfaction
with driveability was indicated on 1966 models compared to 1965.
However, some makes made substantial improvements in satisfaction
with certain driveability characteristics. Exhaust emission
control is sensitive to proper adjustment and proper servicing of
the engine and control system. Driveability also is affected by
proper engine adjustment. The vehicle manufacturers and car
dealers have done a good job of training mechanics regarding the
exhaust control systems. However, results on the 1966 models
indicate that many engines are maladjusted. Efforts should be
redoubled to develop better approaches to vehicle service.**
06127
Hess, K. and R. Stickel
SOOT-FREE COHBUSTIOS OF PETROCHEHICAL BASTE GASES. Zur
russfreien Verbrennung Petrochemischer Abgase. Chem. Ingr.
Tech. (Beinhein) 39, (5-6) 33<*-00, Bar. 20, 1967. Ger.
It soot formation is to be avoided in the combustion of
petrochemical waste gases, the flame must be supplied with
sufficient oxygen in a mixture of steam and air. The eguations of
reaction (water gas process) and heat content are set up and solved
by an iterative digital computer method. The results were
experimentally checked with a turbulent acetylene flaae.
Concentrations and flow velocity were measured for the onset of
luminosity and generation of soot. Large flow velocities ensure
good mixing with the surrounding air, thereby reducing the required
quantities of steam. For economic reasons it is therefore
desirable to work with high-velocity flames, but the stability of
the flame and the noise generated by it set practical limits. The
numerical results of the theretical and experimental investigations
are represented in 13 diagrams as well as in three schematics for
suggested designs for burners.
E, Control Methods 513
-------
06144
Hirao, 0.
PROBLEMS OF AIR POLLOTION DDE TO VEHICLE EMISSIONS GASES. J.
Japan Soc. Mech. Engrs. (Tokyo) 69,575, 1568-72, Dec. 1966. Jap.
The reduction of air pollution due to automotive exhaust is
estimated to cost the Japanese tax payer $12 million. Likewise, a
great expense will be incurred in correcting pollution from steam
power plants. Automobile exhaust causes pollution in local areas
such as heavy traffic circles. The harmful effects of such
pollutants as CO, S02, NO, hydrocarbonds, formaldehyde, and dusts
are discussed, expecially pollution due to CO. A supplement of
secondary air to convert CO to C02, and the even distribution of
gases to the cylinders would be useful in cutting pollution. The
production of various hydrocarbons by the engine is tabulated.
Another possible method for lessening the concentration of
automotive emissions would be in construction of over- and under-
passes to avoid bottlenecks on the highway. This method would be
cheaper than design and installation of engine modifications for
each car. For example, it is estimated that it would cost $900
million per year for cars in the United States to be properly
equipped to control automotive emissions, which money could more
favorably be used in carefully designed construction of 3000 niles
of highway.
06159
G. C, Patterson
PRESSURE RELIEF AND SLOWDOWN: FUNDAMENTALS OF ENGINEERING
OFFSITES AND UTILITIES FOR THE HPI (PART 6). Petro/Chem
Engr. 39, (6) 53-1, 56, 58, May 1967.
The provisions to dispose of the vapors and liquids discharged by
various pressure-relieving devices such as safety and relief
valves, rupture disks, pressure-control valves, and furnace
emergency blow-down valves are outlined. In the open systems, the
vapors and liquids are permitted to discharge directly to the
atmosphere, primarily within the process unit. In the closed
system, the vapors or liquids are discharged to a flare, burning
pit, or blowdown drum and are used especially with offsite
facilities. Hydrocarbons with a molecular weight greater than 80
are usually discharged to a water-quenched blowdown drum.
Hydrocarbons having a molecular weight of less than 80 which are
discharged on a continuous basis are usually discharge through a
closed system to a flare or burning pit. Hydrocarbons having a
molecular weight of less than 80 which are discharged
intermittently from relief valves or rupture discs are
discharged directly to the atmosphere except where restricted by
local ordinances or where there is a hazard of explosives
concentrations at ground level. Where smokeless flares are
required, one method is to induce greater air flow by a series of
steam jets giving a flame which is invisible in the daytine.
Water-quench blowdown tanks provide a facility in which hot
liquids can be cooled prior to ultimate disposal. A blowdown druffl
and vent can be used for liquid hydrocarbons which are not
expected to vaporize appreciably. The method of disposal varies
with the hazard.##
514 HYDROCARBONS AND AIR POLLUTION
-------
06170
Mencher, S. K.
CHANGE YOUB PROCESS TO ALLEVIATE YOUR POLLUTION PPOBLEH. PettO/
Chem. Engr. 39, (6) 21-«, Hay 1967.
The waste disposal problems involved in the production of olefins
by thermal cracking of hydrocarbons are reviewed as illustrative of
the sophisticated development of by-product usage by the
petrochemical industry and the solution of waste disposal
problems by economically sound methods. Both air and water
pollution are covered because of their close relationship. The
loss of hydrocarbons from a 500 million Ib/yr ethylene plant has
been calculated as 10,430 Ib/day or 0.21 percent loss on the plant
feed. The techniques to maintain a low level of hydrocarbon
emissions include: floating roof tanks to control evaporation loss;
vapor recovery lines to vents of vessels that are continually
filled and emptied; manifolding of purge lines used for startups
and shutdowns to vapor recovery systems7 or to the flare systea;
venting of vacuum jet exhaust lines to recovery systems; shipments
by pipeline rather than by car or truck; covering of waste water
separators; and the use of flare stacks which operate with stean or
air injection to obtain smokeless combustion. The H2S should be
extracted from sour gas streams with a suitable solvent. With
large quantities of H2S it might be advisable to extract the H2S
for eventual sulfur recovery. The mercaptans are converted by
various sweetening processes into odorless disulfides. The
mercaptans can also be stripped from the caustic solutions used for
their absorption by steam, flue gas, or air. Flue gas stripping
converts the mercaptans chemically and the solution can then be
sewered.
06221
THE COLLECTION OF TRICHLOHOETHYLEHE AND PERCHLOEETHYLENE VAPORS,
La Captation des Vapeurs de Tri et de per. ({Galvano
(Paris))) 36, (361) 123, 125-6, 152, Feb. 1967. Fr.
The collection of solvent vapors such as
Trichloroethylene and perchloroethylene from the atmosphere of
work areas is required to prevent the contamination of the air and
to make the operation an economical one by reducing the cost of
degreasing. The classical methods used are based on the
condensation of the vapors on pipes in which cold water is
circulated or by adsorption on activated charcoal. In sone
cases a combination of the two methods is used. The method used
depends on the concentration of the solvent in air, the
temperature and pressure of the solvent, eventual contamination
of the solvent, the degree of recovery desired, and the
limitations imposed by the equipment. Condensation is practical
only in high concentrations of vapor where complete removal of the
solvent from the air is not required. In the use of activated
charcoal it is necessary to reverse the process by vaporizing the
collected vapor with steam for recovery and to permit the reuse of
the charcoal. It is also possible to recover some solvents by
percolation of liquids from decanting operations through
activated charcoal.f#
E. Control Methods 515
-------
06292L
J. Rousseau
ATMOSPHERIC CONTROL SYSTEMS FOR SPACE VEHICLES. (Air
Research Manufacturing Co., Los Angeles, Calif.,) 260p.,
Mar. 1963. (Technical Documentary Hept. No. ASD-TDR-62-527,
Part I.) (Contract No. AF 33(616)-8323.) (Project No.
6146.) (Task No. 614609.)
The studies performed on gas supply subsystems have shown that
supercritical storage of atmospheric constituents is preferable
to other storage methods. Cabin humidity control by the
cooler-condenser process, with subsequent liquid water
separation, seems to be the only suitable method of water
removal at present. The choice of a carbon dioxide management
subsystem is essentially based on the vehicle mission duration.
For short-duration missions, lithium hydroxide appears the
only attractive chemical means of carbon dioxide control.
Depending on the design cabin conditions, carbon dioxide removal
by freeze-out technique is definitely applicable to missions
shorter than two weeks. For moderate to long—duration missions,
carbon dioxide removal by molecular sieve adsorption is
indicated. For long-duration missions, carbon dioxide removal by
the electrodialysis process appears attractive because of the
simplicity resulting from the continuous nature of this process.
The problems associated with oxygen recovery from carbon
dioxide arise from the integration of the carbon dioxide reduction
subsystem with the rest of the atmospheric control system.
Hydrogen required for the process is produced by water
electrolysis. A control problem is associated with desorption of
molecular sieve beds at a rate consistent with stoichiometric
composition of the gases entering the catalyst bed. Heat
recovery from the methanation process also presents a problem.
Trace contaminant removal subsystem design is based on
assumptions relative to the contaminant production rates
within the space vehicle cabin. (Author's abstract, modified) ##
06285
W. R. Calvert
DEVELOPMENT OF AN IMPROVED PROCESS FOR THE CATALYTIC OXIDATION
OF ATMOSPHERIC CONTAMINANTS IN SUBMARINES. (Navy Marine
Engineering Lab., Annapolis, Md.) Jan. 1966. 23 pp.
(MEL R5D Rept. No. 449/65.)
Studies in the development of an improved catalytic oxidation
process reveal that polluted air causes other problems along with
the corrosion which has been experienced in submarines. CO/H2
Burner troubles are explained by data showing inhibition of
Hopcalite due to adsorption of C02 and organic halides and
showing catalyst granules turning to dust because of thermal
fracture. Minimization of air pollutants is necessary, and
preprocessing to remove certain materials before the catalytic
oxidation is a necessary part of air purification. (Author
abstract) f #
516 HYDROCARBONS AND AIR POLLUTION
-------
06305
A. N. Skvortsov, V. V. Kudryashov, V. G. Mukhin
FOAMS FOB DUST CONTROL AT SOB-ZERO TEMPERATURES. (In: Air
pollution in nines - Theory, Hazards, and Control.) Akad.
Nauk SSSR., p. 224-231, 1962. Translated from Russian
CFSTI: TT 66-51043
The possibility was examined of combining compatible
surfactants manufactured by U.S.S.R. industry with
antifreezes for water such as Nad, CaC12 and A12 (304)3,
compatibility being understood as the quality of resulting in a
solution which does not separate into layers and does not produce
precipitates. There were also grounds to assume that in
addition to lowering the freezing temperatures of our foaming
agents these salts would improve the stability of the foams.
A low-cost foam - forming preparation was developed which
consists of an aqueous solution of 1.2* azolyat B (sodium salt
of polyalkyl benzene sulfonic acid) and 6-20% NaCl, the latter
playing the part of stabilizer. The foaming agent makes possible
the preparation of stable foam with a high volume factor at sub-
zero temperatures (down to 16.5C). According to tests made in a
nine at sub-zero temperatures, the foam prepared with the foaming
agent developed by the authors of the present paper can be used for
the fixing of coal dust,##
06179
H. Setzer and A. Kaufman
DESOLFORIZATION OF LIQUID HYDROCARBON FUEL FOB FUEL CELLS.
(Interim technical progress rept. Jan. 10-July 10, 1966).
Pratt and Whitney Aircraft, East Hartford, Conn. (July 30,
1966). 58 pp. (Rept. No. PHA-2885.)
CFSTI, DDC: AD 643183
This report covers the work performed during the period January
10, 1966 to July 10, 1966 on contract DA-44-009-AMC-1446 (T).
Removal of Organic Sulfur Compounds from Liquid Hydrocarbon
Fuels. It was the purpose of this contract to investigate the
feasibility of using, and to select a method for utilizing,
sulfur-learing fuels of the JP-4, CITE or
cell powerplants by desulfurization of the fuel. System studies
were made and catalytic guard chamber materials evaluated
experimentally to select a desulfurization technique and guard
chamber catalyst—absorbent material. These investigations show
that using the optimum desulfurization process with a 100-hour
replaceable cartridge results in approximately a 3% weight
increase in the indirect hydrocarbon-air fuel cell system if
JP-4 with 400 ppm sulfur is used rather than a sulfur-free
hydrocarbon fuel. Two catalysts (both of which are high nickel
content, hydrogenation catalysts) were found to perform very
effectively as catalyst-absorbent materials for desulfurization in
the presence of steam reformer reactants. Finally, a
demonstration test with JP-U containing 470 ppm sulfur was run
using an existing hydrogen generator modified for operation with a
desulfurization cartridge and utilizing recycled dilute hydrogen.
The 200-hour test without loss in performance demonstrates the
potential of this method for utilizing JP-4 or CITE in indirect
hydrocarbon-air fuel cell powerplants. (Author summary)#*
E. Control Methods 517
-------
06512L
D- W. Marshall
CATALYTIC OXIDATION OF METHANE AT LOW SPACE VELOCITIES.
Air Force Flight Dynamics lab., Wright-Patterson AFB,
Ohio, Research and Technology Division. (June 1966). 34 pp.
(Technical Kept. AFFDL-TR-66-56.)
The feasibility of removing methane from an airstream by catalytic
oxidation at low flows was investigated by passing a one percent,
by volume, methane in airstream through an inhouse designed and
fabricated stainless steel reactor. The reactor contained either
Hopcalite, 5% V205, 5% M003 on alumina, or one of the
following materials supported on alumina: 0.5% palladium, 0.5%
platinum, 0.5% rhodium and 0.5% ruthenium. Some discontinuity in
the data reported in the literature on methane oxidation at or
around the transition flow region prompted a closer investigation
in this area. In addition, space velocities around 500 fills per
hour were used to insure chemical eguilibrium and for comparison
with the more common value of approximately 15,000 fills per hour
used in most industrial applications. Experiments performed using
the above catalysts revealed no deleterious effects associated with
operating in the transition flow region, but did point out the
advantage of using high space velocities for maximum catalyst
utilization. The palladium catalyst proved superior to all
others tested and catalyzed the reaction to completion at 560 F,
Conversion versus temperature curves are plotted for each
catalyst flow rate combination and the effect of space velocity on
conversion at constant temperature is shown for the Hopcalite and
palladium catalysts. Variables which affected the accuracy
of experimentation most are discussed and possible improvements
suggested. (Aughor abstract)i#
06534
L. A. Chambers
GASOLINE COMPOSITION AS A FACTOR IN AIE POLLUTION. Preprint.
(Presented at the American Chemical Society Meeting, Atlantic
City, N.J., Sept. 16, 1959.)
The evidence accumulated by the Air Pollution Control District
of Los Angeles for modifying gasoline composition as a means of
reducing the formation of smog was illustrated. Studies were made
with exhaust from engine operations using fuels of high, very low
and intermediate olefin content. The evidence included
correlations between the following: Relationships between fuel
composition and eye irritation; gasoline composition to exhaust
composition; fuel olefins to plant damage; gasoline composition to
aerosol formation; and gasoline compositions to ozone, aldehyde,
and other intermediate formations. No fully adequate conclusion
as to the explicit relationship between gasoline composition and
smog can be formulated at present. It is evident that fuel
constituents influence the smog forming properties of exhausts and
that certain blends of gasoline are superior to others in this
respect.##
518 H/DROCARBONS AND AIR POLLUTION
-------
06611
Bengstorff, G. H.
FORMATION AND SUPPRESSION OF EMISSIONS FROM STEELMAKING PRO-
CESSES. In: (Open Hearth Proc., Philadelphia, Pa.), 1961,
7ol. «<». P- 120-147. 7 refs. (Presented at the «4th Conf., Nat.
Open Hearth Steel Coma, of the Iron 6 Steel Div., Phila. ,
Pa., April 10-12, 1961.)
Bach new information delineating the effect of process variables
on iron-snoke foraation has been developed from experiments on a 2-
lb converter. This information has been combined with detailed
analysis of the reactions between gases and molten iron to provide
valuable clues for understanding the mechanism of smoke formation.
Progress is being made toward achieving this understanding. From
a practical standpoint, it appears that the possibility of adding
tethane to suppress smoke in bessemer converters has merit. The
finding that an increased gas-inlet jet velocity decreases saoke in
top blowing needs verification. If true, it will probably be of
considerable practical importance. (Author's conclusions,
•odified)*t
06633
Constan, G. L.
BASS TRANSFER IN DROPS DNDER CONDITIONS THAT PROMOTE OSCILLATIOH
AHD INTERNAL CIRCULATION (A DOCTOR'S THESIS). (In partial
fulfillment for the degree of Doctor of Philosophy, (Case Inst.
of Tech., Cleveland, Ohio.) 143p, 1961
Single drops supported on hypodermic tubing have been studied in
a wind tunnel to determine the effect of drop oscillation on mass
transfer. The systems studied for the case where internal
resistance controls consisted of absorption of S02 gas by drops
of glycerine, propylene glycol, and ethylene glycol. The results
can be expressed in terns of effective diffusivity. No
significant effect was noted in glycerine, whereas the glycols gave
effective diffusivity values of 2-8. Frequencies, amplitudes,
and internal circulation velocities in the drops were studied by
cinematography, and are compared with predicted magnitudes. The
effect of oscillation on external mass transfer coefficients was
studied by sublimation of napthalene spheres. In the cases where
the vibrational velocity was less than the stream velocity, no
effect vas noted; this is in agreement with heat transfer studies.
A technigue has been developed for studying the effect of internal
circulation on effective diffusivity, using forced circulation
through a drop suspended on hypodermic tubing. A "pseudo-film
thickness" is determined as a function o± circulation velocity,
and presents a means of predicting effective diffusivity. This
technigue has been demonstrated for the system S02 and H20,
giving results in fair agreement with a correlation found in the
literature.t#
E. Control Methods 519
-------
06636
Bureau of Mines, Washington, C.C.
MB POLLUTION RESEARCH PROGRESS REPORT FOR THE QUARTER ENDED
MARCH 31, 1968. In cooperation with the Public Health
Hf.Jlth :°rvi'--.) (f-ir. 11, 19f7) 87 pp.
This report covers progress on research in the folloring areas:
Sulfur dioxide removal from flue gas; Removal of sulfur oxides
from flue gas with manganese oxide and improved regeneration;
Economic evaluation of processes for the removal of sulfur dioxide
from flue gas; Characteristics and removal of pyritic sulfur from
selected American coals; Pollution by chlorine in coal
combustion; Flame characteristics causing air pollution;
Characteristics and photochemical reactivity of vehicular
emissions; Mechanisms of air pollution reactions; Effects of
engine, fuel and combustion system parameters on vehicular
emissions; Composition, smoke and odor of diesel exhausts.ft
06674
M. V. Alekseyeva, and V. A. Khrustaleva
A STUD1 OF AUTOMOTIVE EXHAUST GASES. U.S.S.R. Literature
on Air Pollution and Related Occupational Diseases, Vol. 7,
279-84, 1962- (Gigiena i Sanit.,) 25 (5), 10-4, 1960. Buss.
(Tr.)
CFSTI: 62-11103
Air samples taken in the immediate vicinity of automotive
exhausts during heavy traffic conditions were analyzed for
formaldehyde, acrolein, ketones, unsaturated and aromatic
hydrocarbons, and CO. The data obtained are correlated with the
type of vehicle and type of fuel used. Results showed that
incomplete fuel combustion in motor vehicles was a potent source
of air pollution. The effectiveness of a platinum catalytic
oxidizing device for treatment of exhaust gases was tested and
found to reduce pollution.**
06719
Harkness, A. C. and F. E. Murray
GAS PHASE OXIDATION OF METHYL MERCAPTAN, Intern. J. Air
Water 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 work
the rate of reaction was found to be strongly accelerated by oxygen
and to be inhibited by mercaptan.##
520 HYDROCARBONS AND AIR POLLUTION
-------
06793
S. Nozaki
(SELECTION OF AIR FILTEP.) Kuki Seijo (Clean Air-J. Japan
Air Cleaning Assoc. , Tokyo) 2, (2) 20-9, 1964. Jap.
Various considerations are given to the selection pf air filters
for dusts (not gases): the type of indoor pollution being
controlled, type of filter desired, relation between combination
of filters and efficiency, air resistance, rate of collection,
naintenance, and economics. The kinds of dust collectors
available and the sizes of particles collected are tabulated.
For example, the large cyclone can be used for particles
between 20 microns and 1 mm in size, the small cyclone for
particles between 20 microns and 0.1 mm, the electrical
precipitator for 0.01 to 0.01 mm size particles, and the
supersonic collector for particles 0.05 to 2 microns in size.
Tabulations were made of the collection of dusts and mists of
such substances as cadmium, phosphorus, lead, o-dinitrocresol,
barium, pentachloronaphthalene, sulfuric acid, manganese, etc.
Standard temperatures and humidities were maintained according
to season, the values conforming to U.S. Air Force
Technical Order 00—25—203 for clean rooms. A discussion of the
efficiency and advisiability of using two or three filters is
given. In each case, total air resistance had to be considered.
Calculation for rates of collection are also given.*#
07221
E. Fiala and E. G. Zeschmann
THE EXHADST GAS PBOBLEH OF HOTCB VEHICLES (PART 2). Zum
ibgasproblem der Strassenfahrzeuge (Teil 2). Automobiltech.
Z. (Stuttgart) 67(12), U19-22 (Dec. 1965). Ger.
The CO content of cigarette smoke was determined by means of the
Orsat apparatus and the Draeger probe. The CO concentration
varied between 2 to 5% which is about ten times the concentration
in the engine exhaust gas of an automobile cruising at constant
speed. The origin of unpleasant odors of two-stroke engines was
traced back to strongly heated hydrocarbons forming aldehydes.
The effects of various adjustments of the carburetor on the CO
concentration were determined. Optimal positions of the choke
plate and other adjustable parts of the carburetor were determined
for some compact cars. Photographs illustrate the experimental
set-up, and results are presented in graphs. Ignition limits of
mixtures of air, nitrogen, and n-heptane were determined. The
exhaust gas composition can be improved considerably with little
effort if the loss of some peak power is tolerated.tf
07362
Feist, H. J.
ELIMINATING ODOBS BY CATALYTIC COBBDSTION. ((Die
Geruchsbeseitignng durch katalytische Verbrennung.)) Text in
German. stadtehygiene (Uelzen/Hamburg), 16(3):55-61, Mar.
1965. 11 refs.
E. Control Methods 521
-------
With the rapid growth of the chemical industry, air pollution by
odors has also increased. Catalytic oxidation and reduction offer
possibilities for an economic solution of the problem. The
principles of catalytic reactions are described. In a table the
properties of four catalysts are compared with each other. These
catalysts are: platinum on metal, platinum-palladium on ceramics,
copper-chromium on aluminum oxide, and platinum on ceramics. The
effectiveness of a catalyst depends on the gas mixture, the
temperature, the type of catalyst, and the ratio: volume of
gas/hour/volume of catalyst. The heat generated by the
catalytic process is usually used to preheat the gas before it
enters the catalyst. If the concentration of combustible
substances is sufficient, steam may be produced in addition. An
example is quoted where 47,000 cu. m. gas per hour with a latent
heat of 400 kcal/cu. m. produce 31 tons of steam per hour. The
equipment pays for itself in 2 1/4 years. For gases of low heat
content, catalytic combustion under increased pressure is
advantageous. Host economical is a gas turbine which compresses
the gas and, after it has passed the catalytic chamber, uses the
hot cleaned gas. The use of a gas turbine is recommended for gas
volumes of more than 100,000 cu. m./hr, if -measures for air
pollution control become necessary.##
07560
STAINLESS STEEL ANTI-SMOG MDFFLEBS—CUT AIR POLLUTION. J. Air
Pollution Control Assoc., 9(2):83-84, Aug. 1959.
In August, 1956, installation of anti-smog mufflers was started
on the Log Angeles City Schools' 81 big passenger buses. The
muffler is almost entirely fabricated from chromium-nickle
stainless steel, in order to resist oxidation and corrosion at the
high operationg temperatures. The muffler is designed to dispose
of the unburned fuels presented in the exhaust system of a gasoline
engine. It consists of a primary burning tube (pilot'tube)
through which the bulk of the exhaust gases pass during operations
of low exhaust volume. Air is introduced through an adjustable
opening into this tube and the resulting mixture is ignited by a
long-reach spark plug. The current model was designed for
heavy-duty gasoline-powered trucks and buses with 550 to 750 cu in.
piston displacement. The mufflers have proved to be 97 percent
effective in eliminating smog-producing hydrocarbons from engine
exhausts (one of the principal causes of air pollution) on Los
Angeles City school and Transit System buses. Users report
less back pressure resulting in increased horsepower and gas
mileage and improved engine performance. .Some of the mufflers
have successfully operated more than 100,000 miles without
failure.##
07613
Ridgway; S. L. and J. C. Lair
AUTOMOTIVE AIR POLLUTION: A SYSTEMS APPROACH. J. Air
Pollution Control Assoc., 10(U):336-340, Aug. 1960. 1 ref.
(Presented at the 52nd Annual Meeting, Air Pollution Control
Assoc., Los Angeles, Calif., June 21-26, 1959.)
The application of systems engineering to the control of pollution
from automotive exhaust is illustrated. First, the design and
complex mechanical function of the flame afterburner system are
analyzed. The efficiency of the device is discussed. Secondly,
522 HYDROCARBONS AND AIR POLLUTION
-------
an analysis is made of the natural meteorological modulation of the
concentration of air pollution to form an estimate of the results
that might be brought about by the control of emissions. By
examination of past records, September was found to be the worst
month of the smog season. Concentrations of ozone and carbon
monoxide for the month of September from 1955-1958 were studied.
It vas deduced, on the basis of analysis, that a pollutant which
contributes to smog formation must be reduced in concentration by a
factor of 2 or 3 in order to reduce the worst September
experience .to the level of the best. The efficiency of control
devices required to reduce today's pollution is calculated.##
07620
Suter, H. B.
RANGE OF APPLICABILITY OF CATALYTIC FUHE BURNEBS. J. Air Pollu-
tion Control Assoc., 5 (3):173-175. .184, Nov. 1955. (Presented
at the U8th Annual, Meeting, Air Pollution Control Assoc.,
Detroit, Mich., May 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, or practical and economic. Noncombustible 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
poisons must be absent. Catalytic oxidation units are not bought
"off-the-shelf" but are specially designed for various
applications.
07836
Benforado, David M.
AIR POLLUTION CONTROL BY DIRECT FLAME INCINERATION IN THE PAINT
INDUSTRY.'J. Paint Technol., 39(508):265-266, Hay 1967. 1 ref.
(Presented at the With Annual Meeting, Federation of Societies for
Paint Technology, Washington, D. C., Nov. <*, 1966.)
Direct-flame incineration is discussed and up-to-date information
available is summarized. Direct-flame incineration is an air
pollution control process in which objectionable organic vapors or
organic particulates are converted to harmless carbon dioxide and
water vapor. The organic emissions are destroyed by exposure under
the proper conditions to temperatures of 1000-1400 deg. F in the
presence of a flame. Heat recovery equipment to cut down fuel
costs is usually easily justified. A typical forced draft direc-
flame incineration system with heat recovery showing how solvent
vapors are elminated from a can coating process is presented.
Compared with other control processes for organic emissions, direct-
E. Control Methods 523
-------
flame incineration is capable of achieving a high level of
effectiveness. The basic variables affecting the design of a
direct-flame incinerator are: (1) Incineration temperature; (2) Th(
length of time the contaminated air is held at this temperature;
and (3) The amount of turbulence or mixing designed into the
combustor. Applications in which direct-flame incineration has
been used successfully by paint manufacturers include controlling
the exhaust from: resin and varnish cookers; and phthalic anhydride
plants. Applications in which direct-flame incineration has been
successfully used by industrial finishers include control of
emissions from bake ovens such as automobile can coating, sheet
metal, and wire enameling.
07846
Eobison, J. A. and H. M. Brehob
THE INFLUENCE OF IMPROVED MIXTURE QUALITY ON ENGINE EXHAUST
EBISSIONS AND PEEFOEMANCE. J. Air Pollution Control
Assoc., 17 (7) :1H6-U53, July 1967. 6 refs.
A large, steam-heated, fuel vaporization tank was utilized as a
carburetor in multicylinder engine testing at steady—state
operating conditions. In comparison to normal carburetion, the
tank provided improved air fuel mixture quality, i.e., coapletely
vaporized fuel, thoroughly mixed with air, and at elevated
temperatures. Although not a practical piece of engine hardware,
the tank provided a means of determining the extent of gains to be
made with improved mixture guality. Improved mixture quality
produced slight reductions in rich mixture hydrocarbon and carbon
monoxide concentrations but did not reduce the minimum emissions
of these two exhaust contaminants- Binimum fuel consumption was
similarly unaffected by improved mixture guality. The most
important benefit of improved mixture guality was derived from
improved geometric and cyclic fuel distribution; a substantial
extension of the misfire lean limit. The significance of lean
limit operation and its relationship to reduced exhaust
contaminants is discussed in detail. (Authors' abstract)t#
07881
Grumer, J., H, E. Harris, V. R. Rowe, and E. B. Cook
EFFECT OF RECYCLING COMBUSTION PRODUCTS ON PRODUCTION OF OXIDES OF
NITROGEN, CAEBON MONOXIDE AND HYDROCASBONS BY GAS BURNER
FLAMES. Preprint, Bureau of Mines, Pittsburgh, Pa., «2p. , 1967. 24
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)
Gas appliances designed to lessen the emission of oxides of
nitrogen, carbon monoxide, and hydrocarbons, are desired. The
formation and decay of oxides of nitrogen and carbon monoxide in
the secondary combustion zone of gas-burner flames were
investigated as functions of temperature, cooling rate (temperature
gradient), and degree of recycling of combustion products into the
primary combustion zone of the flame; preliminary measurements wer<
made on hydrocarbons from flames. Recycling, though effective in
reducing nitrogen oxides concentrations in effluent from gas
524 HYDROCARBONS AND AIR POLLUTION ,
-------
appliances, makes the flames longer and less stable. Nitrogen
oxides may be reduced by keeping the primary combustion temperature
as low as possible, preferably no higher than about 3,000 deg. F.,
and by starting to cool the combustion gases as soon as possible to
about 2,300 deg. F at which temperature concentrations,of nitrogen
oxides do not increase within the residence time in most gas
appliances. Concentrations of carbon monoxide are lowered by
recycling of flue gases. The oxidation rate of carbon monoxide is
strongly increased by increasing the oxygen concentration.
Although the point has yet to be proven by future research, it
appears that carbon monoxide concentrations may best be lowered by
appliance designs that allow rapid induction of secondary air into
the secondary combustion zones. Hydrocarbons can escape from gas
burner flames by flowing from the preheat zone of partially lifted
flames through the dead space 'into the surrounding cold atmosphere.
Recycling of combustion gases, very low fuel-air ratio, and very
high flow rates tend to- promote partial lifting of flames from
burner ports. It is possible that the emission of hydrocarbons by
gas appliances may largely be avoided by designing for well-seated
flames on burner ports.
07882
Kaiser, E. R. and S. B. Friedman
THE PYBOLYSIS OF HEFOSE COMPONEHTS. Combustion,,39(11): 31-36, May
1968. 5 refs. Presented at the Symposium on Air Pollution Control
through Applied Combustion Science, 16th Annual Meeting, American
Institute of Chemical Engineers, New York, N.Y., Nov. 26-30, 1967.
Exploratory laboratory tests of destructive distillation of organic
wastes, and the prospects for complete gasification of the organic
matter are reported. The objective is to determine the quantity
and quality of the product gas that might be produced for use as a
hot, raw boiler fuel, and possibly for chemical manufacture.
Results show that by heating to 1500 F out of contact with air, the
organic matter in municipal refuse can be converted to gas, organic
liquids, water and char in roughly equal proportions by weight.
The relative yields will be affected by the rate of heating.
Higher yields of gas result from rapid heating. The fixed gases
have a calorific value of 350-HOO Btu per standard cu ft. The
organic .liquids range from alcohol to pitch. .An extension of the
investigation to include complete gasification and analyses by
chromatography is suggested.
07884L
H. Lew, B. Boodruff, W. Johnson, i. Musa
ION EXCHANGERS IN REMOVAL OF AIR CONTAMINANTS. San
Francisco Bay-Naval Shipyard, Vallejo, Calif., Chemical
Lab.-802«-66, PR-1, ((30))p., March 1967. ((50)) refs.
DDC: AD 808060L
The ability of ion exchangers to be synthesized, modified,
regenerated, or used in customary form to react with gaseous air
contaminants and effect removal of these contaminants from air
was studied. Results show that treated and untreated ion
exchangers will react with a variety of gaseous materials and
thereby cause removal of these materials 'from air. Reactions
E. Control Methods 525
-------
which occur between ion exchange resins and ionized reactants in
aqueous media will likely occur in gaseous systems. The
possibilities of reactions between exchangers and organic
contaminants at nominal temperatures cannot necessarily be
foreseen. Favorable reactions between organic vapors and
exchanged groups on ion exchange resins are being sought.##
07893
Stern, Arthur C.
AIR POLLOTION CONTROL - PROBLEMS FOR THE AUTOMOTIVE
ENGINEER. Preprint, Public Health Service, Washington, D. C.,
National Center for Air Pollution Control, 15p., ((1967)).
(Presented at the National West Coast Meeting, Society of
Automotive Engineers, Portland, Oreg., Aug. 16, 1967.)
The contribution of the automobile and other gasoline power
vehicles to pollution are discussed. The adverse effects and the
contributing pollutants are cited. Control efforts are being
undertaken under the mandate of the Motor Vehicle Air Pollution
Control Act, which authorizes the establishment of standards for
the emission of substances harmful to public health. Compliance
certification of new motor vehicles and engines and the technical
problems involved are discussed. Approaches to vehicular-emission
control are discussed, specially the inter-relationship of engine,
fuel, and refinery design. The corresponding problems of the
automotive engineer are cited.
07971
Kukin, Ira
CHEMICAL SUPPLEMENTS IN AIR POLLOTION CONTROL PROGRAMS. Apollo
Chemical Corp., Clifton, N.J., FL-67-65, ( (32))p., 1967.
12 refs. (Presented at the National Fuels and Lubricants
Meeting, New York, N. Y., Sept. 13-1H, 1967.)
Several classes of chemical additives for petroleum fuels and
coals have been developed that reduce air pollutants from smoke
stacks. These are: (1) combustion catalysts, (2)
smoke-suppressants, (3) oil-ash (slag) modifiers, (4) absorptive
agents, (5) S03 neutralizing agents. The application of these
products to specific air pollution reduction programs is shown by
several case histories involving the following power plants:
(1) i»-cycle diesel trucks, (2) 2-cycle diesel buses, (3) diesel
power generating equipment, (t) gas turbine for peaking operations,
(5) school heating equipment with No. U oil, (6) industrial plant
boiler with Bunker C fuel, (7) refinery boiler burning No. 6 oil
and gas, (8) marine steam plant, (9) utility power plant, (10)
coal-fired utility. These specific examples cover the known types
of polluting materials from fuel and coal burning power plants. A
ready guide for specific utilization of the chemical treatments is
summarized. It has been shown that chemical supplements are 80
to 100% effective for improving the combustion of the fuels
resulting in a decrease of smoke, particulate matter, odors and
aerosols as well as acidic and acrid S03 with a resultant
reduction in stack plume. Chemical supplements appear to be
uneconomical generally to completely eliminate S02 from the
exhaust gases. There are indications, however, that by reducing
526 HYDROCARBONS AND AIR POLLUTION
-------
the aerosols forming soots and particulate matter from the exit
gases, the smog-forming tendencies of S02 are reduced
substantially.#t
08075
Griswold, S. S.
REGULATION OF NEW MOTOR VEHICLES. Preprint, Public Health
Service, Washington, D. C., Division of Air Pollution, 7p.,
1966. (Presented at the National Conference on Air Pollution,
Washington, D. C., Dec. 12-1«, 1966.)
The problem of air pollution from motor vehicles is discussed.
The basis for the discussion is the Motor Vehicle Air
Pollution Control Act. It is an amendment to the Clean Air
Act of 1963 and was signed by President Johnson on October 20,
1965, It is designed to achieve uniform national control by
limiting the emission from all new motor vehicles introduced into
commerce, whether manufactured in the United States or imported
from abroad. It authorizes the Secretary of Health,
Education, and Welfare to establish standards for the emission of
any substance which in his judgment is, or may be, injurious to
public health or welfare and to reguire compliance with these
standards. At the same time the Act specifies that appropriate
consideration be given to technological feasibility and economic
costs in prescribing standards applicable to new motor vehicles or
engines. Federal emission standards were formally promulgated on
flarch 30, 1966. These standards are applicable to the 1968
model year and reflect those currently in effect in the State of
California. To implement these standards, to test for compliance
and, generally, to provide the necessary machinery for insuing that
the public gets the control it needs, the Abatement Branch of the
Division of Air Pollution is establishing a fully equipped
laboratory at the Willow Hun Airport near Detroit. This
laboratory also has the responsibility for evaluating the adequacy
of existing standards and the need for more severe standards and
less complex test procedures. Field surveys of equipped vehicles
In California and elsewhere are also being being conducted.
Initial certification of new systems is approved on the basis of
performance of test vehicles, but the continued approval for
succeeding years will be determined by the systems' effectiveness
when evaluated under realistic driving conditions.##
08080
Kufcin, I.
UTILIZATION OF ADDITIVES IN CONTROLLED COMBUSTION PRODUCTS.
Preprint, Apollo Chemical Corp., Clifton, N. J., 11 p.,
1966. (Presented at the MECAP Technical Symposium on
Combustion and Air Pollution Control, Oct. 25, 1966.)
Practical applications of chemical additives for reducing air
pollution with petroleum fuels are discussed. Successful results
have been achieved in the field by the use of additives for fuel
oils, both distillate and residual fuels. The major pollutants
are: (1) black particulate matter representing primarily unburned
hydrocarbons; (2) sulfur oxides (S02 and S03). With
distillate fuels, where the sulfur content generally is below
0.5*, our primary concern is particulate matter and to a somewhat
E, Control Methods 527
-------
lesser degree, carbon monoxide, aldehydes and nitrogen oxides.
With residual fuels, sulfur, as S02 and S03, is the dominant
consideration, although the ability to reduce black smoke emission
by means of chemical additive is certainly a valuable
contribution to air pollution control. The three effective
classes of chemical additives are: (1) combustion catalysts, (2)
oil-ash slag modifiers, and (3) chemical neutralizing agents.
In some cases, these chemical agents can be combined to give one
or more benefits. In a recent trial at a power plant, one of our
products, SSI-3 (B) , reduced the black smoke at the same time
that it lowered the S03 content of the flue gas from 90 to 5
parts per million. The case histories cited show how chemical
additives are being used to reduce air pollution at the same time
that they make their contribution to better overall fuel
utilization. AAM##
08082
J. Beaney, E. L. Novack
INVESTIGATION OF CATALYTIC COMBUSTION OF IMPURITIES OF AIK.
Bolt, Beranek, and Newman, Inc., Cambridge, Hass.,
Prototech Co., Contract NAS-6085, NASA-111, NASA-CH-66368,
58p. June 30, 1967.
CFSTI: N67-29987
A study was made of the catalyzed combustion of impurities in
air. These studies included laboratory tests of several
configurations of corrugated catalyst support to minimize air flow
resistance and optimize catalyst length- The two catalysts used
were; platinum and palladium, and the three impurities were
hydrogen, carbon monoxide, and methane. A catalytic coil
consisting of parallel corrugated ribbons of chromel
alternated with layers of asbestos coated with precious metal
catalyst, constructed to provide straight-through channels for
air passage, was used to oxidize carbon monoxide, hydrogen and
methane, present as dilute (0.5%) impurities in air. Platinum
when applied to the asbestos was significantly inferior to
palladium for the oxidation of methane. In addition, the catalyst
operating temperature was found to decrease with increasing
surface concentration of palladium, with length of catalyst, and
with decreasing channel size. From this, a plan for an
integrated air purification system including heat exchanger and
insulation was developed, based on a laboratory tested
catalyst. The system should remove virtually all of the carbon
monoxide and hydrogen from the air while leaving a residual of no
more than 250 ppm of methane.t*
0808K
A. Michaels
STATUS BEPOET. (SOLID WASTE DISPOSAL) Preprint,
Philadelphia, Pa., (7) p., (1966). (Presented at the
National Conference on Air Pollution, Washington, D. C.,
Dec. 13, 1966, Paper No. D-1.)
The air pollution contribution made by urban society in disposing
of solid wastes, is discussed. It has been reported that an
average of 4.5 Ibs. of refuse per person each day, is generated.
528 HYDROCARBONS AND AIR POLLUTION
-------
as normally collected for disposal. Although no refuse disposal
method apportionment was available, an attempt was made to
estimate the percentage disposed of by the various methods used
in order to evaluate the relationship of refuse disposal to
air pollution. It is estimated that 10-15% of all refuse is
disposed of by incineration. It is further estimated that ZO to
25* of urban refuse is disposed of by open burning.
Approximately 10% of all refuse is disposed of by landfilling, and
10% by various other methods including hog feeding,' grinding,
salvage and reclamation, etc. The guantity of particulates
emitted by incineration varies from 10-60 Ibs. per ton of
material burned. Open burning accounts for quantities varying
from, 60-100 Ibs. per ton. Particulate emissions are tabulated
for the disposal methods. J In addition to particulate matter,
poor refuse disposal by combustion results in the emission of
gaseous pollutants, particularly carbon monoxide and
hydrocarbons." If all of the refuse currently disposed of by
burning were to"be properly incinerated, the total particulate
emissions would be 800,000 tons per year, harmful gaseous emissions
would be negligible and the total pollution contribution would
be well under 1% of the total annual pollution guantity. Even if
all refuse were to be incinerated properly, the total pollution
emission quantity would be under 1 T/2S. It would appear that the
disposal of refuse by incineration need not cause meaningful air
pollution.t#
08162
Matsak, V. G.
THE PURIFICATION OF AIR POLLUTED BY VAPORS AND GASES. In: Survey Of
0. S. S. R. Literature from Russian by B. S. Levine. National
Bureau of Standards, Washington, D. C., Inst. for Applied Tech.,
Vol. 3, 177-185, May 1960.
CFSTI: TT 60-21175
Methods for the recovery and purification of noxious substances
ejected by gas exhaust and ventilating installations are reviewed.
It was found easier to purify exhaust gases than ventilating air.
The methods include: Chemical purification method. Condensation
method, Liq.uid absorption method, and Absorption by solid
absorbents (adsorption). Present methods for air and gas
purification'can be rendered close to 100 percent free of most acid
and alkali gases, organic solvent vapors and some other gases. But
no effective and cheap method has been found up to the present for
the recovery of carbon monoxide. Purification of air from solvent
vapors, such as gasoline, acetone, acetates, etc. can be used
effectively only in the case of tail gases and not in the •
purification of ventilating air, even though it is effective in
both instances; the. high cost makes its use for purification of
ventilation air economically prohibitive. The possibility of using
solid absorbents, such as activated charcoal and silicagel for the
purification of ventilation air may apply to many cases. The
primary obstacle lies in the high cost of( adsorbent material and in
the consumption of considerable electric energy in overcoming the
pressure drop of recuperating installations.
E. Control Methods 529
-------
08207
Souriraian, S. and Mauro A. Acccmazzo
THE APPLICATION OF THE COPPER OXIDE-ALUMISA CATALYST FOR AIR
POLLUTION CONTROL- Can. 0. Chem. Eng. (Ottawa), 39(2):83-93, April
1961. 8 refs.
The catalytic combustion of 1-hexene present in diluent nitrogen in
the concentrations of 1170 ppm and 3000 ppm by excess oxygen, has
been studied in the presence of CuO-A1203 (1:1) catalyst in the
temperature range 242 deg. to 424 deg. C. and gas space velocity in
the range 4000-16,000 hr.-1. The experimental data on the kinetics
of the reaction were found to fit an empirical half-order law with
respect to the 1-hexene concentration. The presence of water vapor
in the reactants was found to have no effect on the efficiency of
the catalyst at temperatures higher than 400 deg. C. The above
results were similar to those obtained for the catalytic oxidation
of n-hexene studied earlier. The possible use of the above copper
oxide-alumina catalyst for the simultaneous removal of hydrocarbons
and carbon monoxide present in the auto exhaust gases has been
tested, making use of a 1955 six-cylinder automobile engine run on
leaded gasoline fuel. The hydrocarbon and carbon monoxide
concentrations encountered in these studies varied in the range 170-
16,000 ppm and 1-7 percent respectively. It was found that the
minimum initial temperature of the catalyst bed required for the
complete removal of both hydrocarbons and carbon monoxide,
simultaneously, was 226 deg. C. under no load condition, 342 deg.
C. under an engine load of 2.5 hp, 400 deg. C. under an engine load
of 5.1 hp or higher, and 236 deg. C. under deceleration conditions.
The catalyst showed no deterioration in performance even after 100
hours of continuous service in conjunction with the above auto
exhaust gases. Authors abstract
08345
Cooper, Jonathan C. and Frank T. Cunniff
CONTROL OF SOLVENT EMISSIONS. Proc. HECAR Synp., New
Developments in Air Pollution Control, Metropolitan
Engineers Council on Air Resources, New York City, p. 30-41,
Oct. 23, 1967.
Tour different approaches can be taken toward controlling solvent
vapor emissions from industrial and commercial operations. One
way is to avoid air pollution entirely by using water as the
solvent. A second approach is to reduce the severity of the
pollution by changing to organic solvents with low photochemical
reactivity. A third control method is to destroy the escaping
solvent vapors by incineration. When properly designed and
installed this method is very effective and the capital costs
involved are moderate. The fourth type of control method is to
capture the emitted solvent vapors so that the solvent can be
recovered for reuse. Three techniques are available -
adsorption of the vapors in a scrubbing liquid, condensation by
cooling, and adsorption on activated carbon. Of these,
activated carbon adsorption is the most generally applicable and is
capable of achieving the highest degree of solvent recovery, with
resulting attractive payout.**
530 HYDROCARBONS AND AIR POLLUTION
-------
08352
Rowson, H. H.
DESIGN CONSIDERATIONS IN SOLVENT RECOVERY. Proc. HECAR
Symp., New Developments in Air Pollution Control,
Metropolitan Engineers Council on Air Resources, New York
City, p. 11U-128, Oct. 23, 1967.
The growing understanding of the adsorption process has led to the
ability to modify the properties, such as pore size distribution
and overall activity of the adsorbent, to suit the particular
separation that is reguired. This has been accompanied by much
development in the last few years of the fixed bed and fluid bed
mechanical contacting that is available to carry out these
separations, and as a result of these parallel developments, it is
now possible to carry out with very great efficiency a large
number of complicated separations. The fixed bed plant consists
of a number of vessels containing activated carbon into which the
solvent laden gas stream is introduced in turn. The solvent
laden stream is allowed to flow through the carbon bed, the •
solvent is adsorbed onto the activated carbon, and the solvent free
air is discharged into the atmosphere. In the fluidized bed
process, the solvent laden air or gas stream is passed upwards
through the adsorber vessel which contains a number of shallow
fluidized beds of activated carbon. The solvent is progressively
adsorbed onto the carbon, and the solvent free air is discharged
through dust collectors to the atmosphere. This process has a
number of advantages compared with the fixed bed process: 1.
Exceptional contacting between solvent and adsorbent giving very
high efficiencies; 2. Complete continuous automatic operation,
with minimum labor requirements; 3. Competitive in cost for the
medium and larger installation; 4. Low stripping steam usage
(about half that of equivalent fixed bed plants). 5. Low ground
area requirement; 6. High concentration of solvent in recovered
agueous liquor simplifying onward processing; 7. Inherently safe
even with highly inflammable solvents. Factors affecting the
choice of solvent recovery systems include 1. Air flow, 2.
Concentration of solvent, 3. Solvent type and 4. Operating
continuity. For the majority of applications in a well maintained
fixed bed plant, efficiencies of 97% to 9856, defined as the ratio
of solvent outlet to inlet concentration over the adsorber, are
quite easily achieved. In a well run fluid bed plant,
efficiencies of 99% measured over the adsorber are quite readily
attainable. Other new applications for adsorption techniques
include the removal of small quantities of noxious material from
large volumes of air, the separation of hydrocarbon gases, and the
control of S02 emission from power station flue gases.##
08365
Howard G. Haahs, Lennart N. Johanson, Joseph L.
McCarthy
SEKOR III: PRELIMINARY ENGINEERING DESIGN AND COST ESTIMATES
FOR STEAM STRIPPING KRAFT PULP MILL EFFLUENTS. TAPPI,
50(6):270-275, June 1967. 9 refs.
An illustrative, preliminary engineering design and cost
estimate has been carried out relative to the SEKOR-B
E, Control Methods 531
-------
(refluxed column) process. As a basis for such
calculations, experimental determinations have been made of
vapor-liquid equilibrium constants for the sulfur-
containing components. CH3SH, (CH3)2S, and
(CH3J2S2 in dilute concentration in water at 1 atm total
pressure, and, also, for the substances limonene, alphapinene,
and alpha-terpineol, which are major constituents of the
recovered volatile oil. It is shown that all substances are
of higher volatility than water and may be steam-stripped, and that
alpha-terpineol and dimethyl disulfide are the most difficult to
strip from water. The optimum feed/steam ratio, reflux rate,
and number of stages required to strip H2S and the above
components from condensates of a 400 ton/day kraft pulp mill were
calculated. To reduce the concentration of (CH3)2S2 to 1%
of its feed concentration, capital cost was estimated to be
$51,500 to treat 1,000,000 Ib/day of blow and relief gas
condensates. If amortized over a 5-year period, this capital cost
together with operating costs is estimated to result in a total
cost per ton of dry pulp of $0.25/ton for 5 years and of $0.13/ton
thereafter. If the sale of recovered crude SEKOR oils at
$0.04/lb is feasible, and if hot process water is valued
at $0.03/1000 gal, the above costs for treating blow and relief
gas condensates are estimated to approximately $0.07/ton pulp.
The cost and design bases used are described in some detail to
allow potential users to undertake similar calculations compatible
with local conditions, and, thus, to obtain alternate costs per
ton of pulp if so desired. AAM##
08i»76
Sherwood, Peter W.
NEW DEVELOPMENTS IN HYDPOC4RBON GAS TECHNOLOGY. ((Neues aus
der Kohlenwasserstoffgas-Technologie - Folge 13.)) Text in
German. Gas Wasserfach (Munich), 108(15):402-403, April
1967.
Efforts have been made to combat S02 pollution by obtaining
sulfur from stack gases as a by-product. An apparatus from the
Institute of Technology in Tokyo and one developed by
Monsanto work on the same principle. Stack gases containing
0.2% sulfur dioxide are separated from the fly ash and passed
through 7205, thereby converting the sulfur dioxide to sulfite.
Monsanto then condenses the sulfite to 70* sulfuric acid, while
the Japanese add ammonia to the sulfite to form ammonium sulfate,
which can be used as fertilizer. In both methods the purified
waste gas contains only 0.02X sulfur dioxide. Wide use of gas
fuel cells by 1970 is predicted by the Institute of Technology
in Chicago. The cells may be used in mass production items such
as automobiles within 10 years; in some trial cells efficiencies
of 70-80% have been obtained already. The most commonly used
fuel is hydrogen, although the economical production and safe
handling of this fuel still presents problems. Cells using
hydrazine and methanol are under development. For power plants
of 10 to 1,000 kW., paraffin fractions, which are split by a
nickel catalyst at 500-1,000 deg C., seem to be the most
economical fuel for the near future.##
532 HYDROCARBONS AND AIR POLLUTION ,
-------
08488
Lohner, Kurt, Herbert Huller, and Walter Zander
ABOUT THE PROCESS-TECHNIQUE OF THE COMBUSTION OF EXH-AUST GASES IN
GASOLINE ENGINES IN STATIONAHY OPERATIONS. ( (Uber die
Verfahrenstechnik der Nachverbrennung der Abgase von
Ottomotoren bei stationarem Betrieb.)) Text in German.
VDI (Ver, Deut. Ingr.) Z. (Duesseldorf) , 109 (31) : 1488,
Nov. 1967.
To reduce the amount of carbon monoxide and hydrocarbon emission
during the .stationary operation of engines without deleterious
effect on the engine, certain modifications were undertaken. It
was found that complete combustion can be obtained by the
addition of air at a fast or medium engine speed. However at
idling speed enough exhaust gases are formed to make additional
combustion necessary. By adding air directly into the
cylinder during the exhaust cycle, a nearly complete combustion
can be obtained. Since this procedure is expensive, the simpler
procedure of adding the air behind the exhaust valve and providing
combustion by means of catalysts was undertaken. A small
catalyst vessel was constructed for idling speeds with a bypass to
reduce any excessive exhaust gas pressure which might build up at
full speed operation. The catalyst was placed directly behind
the motor to facilitate quick warm-up of the engine. The
catalyst can also be placed near the exhaust vents providing an
afterburner for each cylinder. To obtain a process with few
moving parts, wires with an array of catalyst beads were placed
vertical to the exhaust gas stream. The effectiveness of this
procedure is comparable to the bypass procedure, but the
catalyst must endure temperatues above 1,000 deg C at full speed,
shortening its effective life, since there is no provision by a
bypass.t#
08496
Hoffman, Heinz
EXHAUST GAS PROBLEMS WITH GASOLINE AND DIESEL HOTOBS. I.
GASOLINE ENGINES. : ((Abgasprobleme bei Otto- und
Dieselmotoren. I. Ottomotoren.)) Text in German. Erdoel
Kohle (Hamburg), 20 (8):56«-568, Aug. 1967.
The California Test and the events which produced the
California and U.S. Government laws for the reduction of air
pollution from gasoline engines are described. The differences
between the California and U.S.A. specifications are
outlined. The conditions in regard to air pollution from
gasoline engines in various European cities are discussed and
compared with those found in Los Angeles. The Europa test,'
concerned mainly with CO emission, is described, evaluated, and
compared with the U.S.A. tests which set limits for both CO
and hydrocarbons. The three most important control methods for
exhaust gases are: 1) Catalytic oxidation, which is
unsatisfactory, because the catalyst weakens after 8,000 km.
(it became nearly ineffective at the end of a 23,000 km..test
run). 2) The Chrysler Clean Air Package system, which
depends on a particular combination of gasoline mixture and
ignition time, so that with small alterations in the combustion
E. Control Methods 533
-------
chamber the conditions of the U. S. law are fulfilled. 3) The
exhaust air injection system, which depends on air being blown
into the exhaust system. This system, which is used by Ford and
General Motors, also fulfills the U.S. requirements.##
08536
Miller, B. R. and H. J. Wilhoyte
1 STUDY OF CATALYST SUPPORT SYSTEMS FOR FUME-ABATEMENT OF
HYDHOCARBON SOLVENTS. J. Air Pollution Control Assoc.,17(12):
791-795, Dec. 1967. 8 refs.
In a stainless steel pilot plant system, operating with combined
thermal incineration and catalytic oxidation, studies have been
made of the influence of catalyst-support geometry on abatement
efficiency. Catalyst supports tested were ceramic spherical
pellets, metal foils, and ceramic honeycomb structures, all with
precious metal catalyst. Data obtained cover a range of space
velocities from 30,000 to 175,000 scf/hr-cu ft bed and a range of
catalytic reactor temperatures from 150 to i»50 deg C. " Results
show that optimum fume-abatement performance is ob tained by
combining incineration and catalytic oxidation and that catalyst
support geometry has a significant effect on performance.
(Authors* abstract) '
08567
Derndinger, Hans-Otto
MOTOR VEHICLE ENGINES. {(Kraftfahrzeugmotoren)) Text in German
VDI (Ver. Deut. Ingr.) Z. (Dusseldorf), 108 (19):8«2-8U5, July 1966.
10 refs.
Two new designs in motor vehicle engines are described. In one
engine the compression ratio was raised to 11.2:1 by direct
injection of air into the engine, creating a strong rotation of air
around the cylinder shaft. A savings of 10-20 percent of fuel was
obtained. In the second design the compression ratio was raised to
14:1 to 17:1 by external ignition using a specially developed
spark plug. Greater fuel savings and a low carbon monoxide and
uncombusted hydrocarbon content in the exhaust were obtained. A
detailed description of the California test for automobile exhaust
gas emissions as well as figures for the amount of permissible
carbon monoxide and hydrocarbon emissions in California and in the
United States at large, beginning in 1968, are given. Five methods
to reduce the emission to the California standards are described:
(1) fuel injection; (2) reuse of combustible gases which escape
around the piston into the crankcase; (3) the Chrysler Cleaner Air
Package (CAP); (1) recombustion (a good portion of the combustible
gases can be burned in the exhaust manifold by the addition of air
directly behind the exhaust valve); (5) catalytic recombustion at
low temperatures. At the present time the catalyst is easily
poisoned, particularly by lead deposits. Further technological,
developments along this line are possible.
534 HYDROCARBONS AND AIR POLLUTION
-------
0859U
Gainer, Carl H. and Martinus Hus
ECONOMICS OF HYDKOGEN PRODUCTION AND HYDROTREATING. (Wirtschaf-
liche Herstellung von Wasserstoff und
Hydrotreating.)) Text in German. Erdoel Kohle (Hamburg), 20(7):482-
i|8l», July 1967. 17 refs. (Presented at the Annual Meeting, German
Assoc, for Mineral Oil Science and Coal Chemistry and the
Austrian Society for Petroleum Sciences,Munich,Oct. 138 1966)
The increased upgrading of oil refinery processes—requiring
additional sources of hydrogen—is advocated for Germany. Despite
added costs, such steps should result in financial gains of over 60
percent; moreover, the probable future limitations of sulfur
content in fuels by means of governmental air pollution control
regulation also suggests increased use of such hydrogen refining
processes. Other technical advantages of the use of hydrogen
production facilities are cited. The conditions and costs of
hydrogen production for three different processes (steam methan
pyrolysis, steam naphtha pyrolysis, partial oxidation) are
tabulated. In the future it may be desirable, as an air pollution
abatement measure, to combine thermal power plnats with refineries
so as to convert the heating oil to heating gas through partial
oxidation= should this actually become an accepted practice,
considerable added savings in hydrogen production—hence in
upgraded refinery processes—will be realized.
0860U
Fiala, Ernst, and Zeschnann, Ernst-Georg
IRKSOMENESS OF EXHAUST GAS ODOB. ((Lastigkeit von Abgasgeruch.)
Text in German. VDI (Ver. Deut. Ingr.) Z. (Duesseldorf),
109(2U):1139-1141, Aug. 1967. 5 refs.
The fresh air dilution of automotive exhaust gases at which the
odor was just detected by 10 subjects was used to measure the odor
intensity. The engine was operated at various conditions and with
air added directly toward exhaust valve. The subjects first
breated fresh air, to which untreated exhaust was added until the
odor was detected. The amounts of carbon monoxide and hydrocarbons
were measured at this point, for each of the different operating
conditions. The same procedure was repeated with the addition of
air toward the exhust valve. Graphically presented data show that
while the emission of CO and hydrocarbons considerably diminished
with the addition of air, the odor intensity of the gas increased
significantly.
08831
ZENITH DUPLEX INDUCTION SYSTEM. Automobile Engr., 57(3):96-99,
Harch 1967.
The basic features of the Zenith Duplex Induction System are
presented. The emission of hydrocarbons and carbon monoxide from
the exhaust is effected primarily by increasing efficiency of
combustion in the cylinders. The basic aim is to supply a dry,
but not overheated, mixture to the cylinders. A relatively
small-bore mixture-feed pipe is used in parallel with the main
E. Control Methods 535
-------
manifold, whereby the mixture is taken through an exhaust-heated
chamber and dried. Two throttle valves are employed, one
controlling flow in the main system and the other controlling flow
through the small-bore pipe. An interconnecting linkage is
arranged so that one throttle opens, before picking up and opening
the other. When the main throttle valve is closed the small-bore
system is open. During the initial stages of acceleration from
rest or low speeds, the mixture is diverted through the
exhaust-heated chamber and returned to the main tract down-stream
of the secondary valve. The heat-exchanger box has thin sections
between the exhaust gas and the fuel-air mixture so that the time
lag, between the starting of the engine from'cold and its warming
up sufficiently for control of the mixture, is minimized. With
this system low airifuel ratios can be adopted. Sudden
acceleration does not wet the walls of the manifold as the pressure
within it rises, and therefore a potential source of variation in
mixture strength is eliminated. The mixture does not have to be
enriched for winter conditions. All these features lead to
significant fuel economy as well as reduction of hydro-carbon and
carbon monoxide emissions.##
08837
Kane, J. H.
STATUS FORECAST FOB AIE POLLUTION CONTROL - 1972. Air Eng.,
9(3):33-3«, 37, March 1967.
A forecast of what will happen in the field of air pollution
control in the next five years is presented. The pollutants
covered are smoke, visible dusts, visible plumes, hydrocarbons,
diesel engine fumes and smokes, and oxides of sulfur.t#
09027
California Motor Vehicle Pollution Control Board. Preprint,
( (16) ) p. , May 20, 1967.
EFFECTIVENESS OF EXHAUST CONTROLS IN PUBLIC USE.
Analysis of emissions from automobiles with exhaust control
devices indicates a 70% reduction in hydrocarbons and a 50%
reduction in CO compared to the existing car population in
Califonia. However, the data indicate an emission deterioration
trend with mileage. Some indications of these trends are: (1)
All emission trends go over the hot-start standards of 250 ppm
hydrocarbons and 1.22% carbon monoxide before 12,000 miles is
reached; and (2) All emissions except one manufacturer's carbon
monoxide show significant deterioration beyond the mileage normally
associated with deposit buildup in the combustion chambers.
Spark timing and idle speed inspection data on 50 new cars and 100
privately-owned cars show large percentages of the cars are outside
the tolerances when new and the percentages increase significantly
with time, and mileage indicating that they are being further
maladjusted in the field. It is concluded that car companies must
multiply their efforts in the following areas: (1) Improvement of
basic performance ability of exhaust systems; (2) Adjustment to
factory specifications at the factory; (3) Actual performance of
proper adjustments by dealer service personnel as part of their
training program; and (1) Development of fixed or limited range
adjustments.t#
536 HYDROCARBONS AND AIR POLLUTION
-------
09195
Katherine C. Helltrig
LIQUID FUELS FROM COAL HITH H-COAL. Preprint, Hydrocarbon
Research, Inc., New York, 6p.f 1966. (Presented at
National Coal Association Technical-Sales conference and
Bituminous Coal Research, Inc., Annual Meeting, Sept. 1^-15,
1966, Pittsburgh, Pa.)
The H-Coal process is based upon a new reactor concept known
as the ebullated bed reactor. Dried and pulverized coal
is combined with recycled oil to form a slurry. This slurry
is fed continuously with hydrogen into a reactor
containing a bed of ebullated catalyst. The coal is catalytically
hydrogenated and converted to liquid and gaseous products.
Products are separated and result in fractions of gas, light
distillate, mid-distillate, and vacuum bottoms slurry. In this
reactor system 90* of the coal on the moisture- and ash-free basis
is converted to liquid and gaseous products. Liquid products
from the coal hydrogenation step are hydrocracked, hydrotreated,-
and reformed to produce gasoline. No. 2 furnace oil, and a very
small amount of No. 6 fuel oil. All of the No. 2 furnace oil
can be converted to gasoline if desired. Benzene and liquid
petroleum gas (LPG) may be recovered and sold. An economic
summary for an H-Coal refinery with a nominal capacity of
1000,000 barrels per standard day (BPSD) is presented.
Three cases are presented. The first case produces gasoline
and furnace oil in a ratio of 2 to 1. The second case produces
all gasoline, and the third case is the same as the second
case with the exception that 12,000 PBD of LPG and 3000
BPD of benzene are recovered. Based on the progress made in
development of the H-Coal process it is expected to be ready for
commercialization in the early 1970's and will provide the coal
industry with a means to compete for the gasoline market and to
utilize the large reserves of high-sulfur fuel.##
09325
D. W. Golothan
DIESEL ENGINE EXHAUST SMOKE: THE INFLUENCE OF FUEL PROPERTIES.
AND THE EFFECTS OF USING BARIUM-CONTAINING FUEL ADDITIVE.
Preprint, Society of Automotive Engineers, 23 p., 1967.
11 refs. (Presented at the Automotive Engineering Congress,
Detroit, Mich., Jan. 9-13, 1967. Paper 670092.)
Even though the combustion gases of diesel fuel are much
less toxic than those of gasoline, exhaust smoke has
increased proportionately with the number of diesels in use and
has become a major problem. This paper describes the
influence of base fuel composition on smoke, and the results
of using a barium-containing additive in the fuel. The
toxicological aspects of using the additive are considered,
together with certain other side effects that might arise.
Details are also given of the various means for measuring smoke,
and of existing legislation to control the nuisance. (Author's
abstract)#*
E. Control Methods 537
-------
09329
Sullivan, R. E-, W. Cornelius, and D. L. Stivender
A COMBUSTION SYSTEM FOR A VEHICULAR REGENERATIVE GAS TURBINE
FEATURING LOW AIR POLLUTANT EMISSIONS. Preprint, Society Of
Automotive Engineers, 20p., 1968,. 18 refs. (Presented at the
Combined Fuels and Lubricants, Powerplant and Transportation
Meetings, Pittsburgh, Pa., Oct. 30-Nov. 3, 1968, Paper
680936.)
The combustion system developed for the GT-309 regenerative gas
turbine is used to illustrate pertinent structural, performance,
and exhaust emission considerations when designing for a vehicular
gas turbine application. The development of each major component
and the performance of the combustion system as a whole are re-
viewed. The satisfactory performance and durability potential of
the GT-J09 engine combustion system have been demonstrated by
extensive operation in a component test facility and in several
test cell and vehicle installed engines. Exhaust emissions of
unburned hydrocarbons and carbon monoxide are minimal and are of no
concdrn from an air pollution standpoint. No objectionable
exhaust smoking and odor are produced. As is the case with curr-
ent spark ignited and compression ignition engines, the emissions
of oxides of nitrogen in the present state of development do not
satisfy the proposed 1980 California limit for this air pollutant
on an equivalent weight flow basis. (Authors' Abstract)
09337
Lawrence G., J. Buttivant, and C. G. O'Neill
MIXTURE PRE-TREATMENT FOB CLEAN EXHAUST THE ZENITH
"DUPLEX" CARBURATION SYSTEM. Preprint, Society of
Automotive Engineers, 18p., 1967. 4 refs. (Presented at the
Mid—Year Meeting of the Society of Automotive Engineers,
Chicago, 111., May 15-19, 1967, Paper 67048
-------
The mechanisms of the adsorption process and adsorption equipment
are described with particular emphasis on activated carbon as the
adsorbent, saturation, retentivity, adsorption of mixed vapor, heat
of adsorption and carbon regeneration are included in the
discussions. ' Activated carbon is most suitable for removing
organic vapors. It adsorbs substantially all the organic vapor
from the air at ambient temperature regardless of variations in
concentration and humidity conditions. The limitation for
molecules capable of removal by physical properties is that they
must be higher in molecular weight than the normal constituents in
air. In general, removal is practical for gases with molecular
weight over <*5. Probably the only solvent used with molecular
weight below.t5 is methanol. The design and operation:of the fixed-
bed adsorber, conical fixed-bed adsorber, and continuous adsorber
are described and illustrated. An activated carbon adsorption bed
should be protected from particulate matter that can coat the
surface of the carbon. This can be accomplished by the use of
efficient filters. Corrosion of the bed must also be prevented.
Corrosion can be controlled by the use of stainless steel or by
application of a protective coating of a baked phenolic resin.
Polar and non-polar solvents are equally adsorbed by activated
carbon, but the recovery of polar compounds on stripping with steam
requires an additional step of fractionation to effect a separation
from the aqueous solution. Other solids possessing adsorptive
properties are alumina, bauxite, bone char, decolorizing carbons,
Fuller's earth, magnesia, silica gel, and strontium sulfate.
Their industrial uses are listed.
09795
Chatfield, Harry E. and Ray M. Ingels
GAS ABSORPTION EQUIPMENT. In: Air Pollution Engineering
Manual. (Air Pollution Control District, County of Los
Angeles.) John A. Danielson (comp. and ed.). Public Health
Service, Cincinnati, Ohio, National Center for Air Pollution
Control, PHS-Pub-999-AP-UO, p. 210-232, 1967.
GPO: 806-614-30
Gas absorption equipment is designed to provide thorough contact
between the gas and liquid solvent in order to permit interphase
diffusion of the materials. This contact between gas and liquid
can be accomplished by dispersing gas in liquid or vice versa.
Absorbers that disperse liquid include packed towers, spray towers
and venturi absorbers. Equipment that uses gas dispersion includes
plate or tray towers and vessels with sparging equipment. The
principles of designing plate towers and packed towers are
discussed in detail. The following items are included in the
discussion on packed towers: packing materials, liquid dispersion,
tower capacity, tower diameter,'number of'transfer units, height of
a transfer unit, and pressure drop through packing. An example of
calculations involved in designing a packed tower for the removal
of NH3 is illustrated. Liquid flow, plate design and efficiency,
flooding, liquid gradient on plate, plate spacing, tower diameter,
and the number of theoretical plates are included in the discussion
of plate towers with specific emphasis on bubble cap plates. An
example of the calculations involved in determining the number of
plates required and estimated diameter of a!plate tower is
illustrated. The choice of gas absorption equipment is usually
between a packed tower and a plate tower. Both devices have
advantages and disadvantages. Factors which the final selection
E. Control Methods 539
-------
should be based upon are listed. Spray-type absorbers and venturi
absorbers are also briefly discussed. These towers are primarily
used for removing particulates from gas streams, though they have
some gas absorption applications. The gaseous air contaminants
roost commonly controlled by absorption include S02, NH3,. NOx,
and light hydrocarbons.
100U7
Conn, A. I. and J. B. Corns
EVALtJATION OP 'PBOJECT H-COAL'. American Oil Co., Whiting,
Ind., Research and Development Dept., Contract 14-01-0001-1188
Proj. 612 78p., Dec. 8, 1967.
CFSTI, DDC: PB 1777068
A feasibility study of the 'H-coal1 process is presented which
covers experimental works, conceptual design, and economics. The H
Coal process is the manufacture of hydrocarbon liquids by
hydrogenation of coal. Parts of the process discussed include: Coa
preparation, coal hydrogenation, heavy gas oil hydrogenation, fluid
coking, middle distillate hydrotreating, middle distillate
hydrocracking, naphtha treating and reforming, naphtha recovery,
hydrogen manufacture, hydrogen compression and sulfuric acid and
ammonium sulfate plant. Based upon a thorough study of the process
and the economics involved, the H-coal process is seen to be
competitive with other means of petroleum manufacture.
10U58
Wood, F. C., O.C.Eubank, and J. Sosnowski
HYDRQCRACKING SPREADS INTO NEW AREAS. Oil Gas J.,66(25):83-8U,8
89, June 17, 1968. 11 refs.
Hydrocrackers are built primarily to produce gasoline from heavy
oils, but other product volume and quality demands are influencing
the design of new installations. Equipment modifications, feedstock
properties, yields, and product properties for various hydrocracking
processes are enumerated.
10539
May, Hans and Harry Schulz
A NEW DISTRIBUTING INJECTION SYSTEH AND ITS POTENTIAL FOB
IMPROVING EXHAUST GAS EMISSION. Society of Automotive
Engineers, Preprint, lOp., 1968. 2
-------
Hith the three-dimensional cam, a punctiform scanning of engine
characteristics can be realized. Some results obtained with
this injection system are shown for example, fuel quantity
characteristic, CO and n-hexane characteristic of a i»-cyl
U-stroke engine, injection pressure distribution dependent on
crank angle, and consumption loops for injection and carburetor
operation. {Authors' abstract, modified)##
10568
Schiele, G.
ELECTRIC CLEANING OF WASTE GASES FROM CARBON ELECTRODE BAKING
FURNACES. ((Elektrische Reinigung der Abgase aus
Elektrodenbrennofen.)) Text in German. Aluminium
13(3): 171-17U, March 1967.
Haste gases from carbon electrode baking furnaces contain
extremely fine tar vapors with a range of boiling temperatures.
These vapors can be precipitated most effectively by means of
electrofliters. The gases in many cases must be cooled before tar
vapor removal, due to the differences in boiling temperatures; if
this step were not taken, the amount of tar vapor reaching the
atmosphere would still be too high despite the filter's efficiency.
The industrial application of the electrostatic precipitation gas
cleaning process is described and illustrated.##
10637
Il'nitskii, A. P., A. Ya Khesina, S. N. Cherkinskii,
and L. H. Shabad
EFFECT OF OZONATION UPON ABOBATIC HYDROCARBONS, IHCLUDIHG
CARCINOGENS. ( (Vliyanie ozonirovaniya na aromaticheskie, v
chastnosti ikantserogennye, uglevodorody.)) Hyg. 6 Sanit.
(English translation of: Gigiena i Sanit.), 33 (1-3):323-327,
Jan.-March 1968. ((11))"refs.
CFSTI: TT 68-50UU9/1
The efficiency of ozone in the inactivation of carcinogenic
hydrocarbons was studied. Experiments were performed with
1,2-benzanthracene (BA), 1,2,5,6-dibenzanthracene (DBA),-
9,10-dimethyl-1,2-benzanthracene (DMBA), 3,«-benzpyrene (BP)
and pyrene (P) in various concentrations. Ozone concentration
was O.U g per liter mixture. Ozonation was performed for'periods
1, 2 1/2, 5 and 10 min. Results of experiments demonstrated that:
carcinogenic hydrocarbons are vigorously destroyed by ozone.
Aromatic hydrocarbons vary in their resistance towards ozone,
3,4-benzpyrene appearing to be the most stable. The resistance of
a carcinogenic substance (3,4-benzpyrene) to ozone was found to
vary according to whether it was in solution or adsorbed on
particles of coal, soil, etc., it was found to be less stable in
solution. Ozonation is probably very efficient for the
purification of central water supplies containing dissolved
carcinogens.i#
E. Control Methods 541
-------
10926T
Alekseyeva, B. V., A. S. Ozerskiy, and V. A. Khrustaleva
DECREASING THE CONCENTRATION OF TOXIC EXHAUST FROM AUTOMOBILE
ENGINES. ((0 snizhenii kontsentratsii toksicheskikh
otrabotannykh gazov avtomobil" nykh dvigatelei.)) Translated
from Russian, Gigiena i Sanit. (Moscow), No. 27:3-7, Dec,
1962. 1 ref.
Automobile engines idling during change of gear, braking, or
standing operate in a regime during which the toxicity of exhaust
gases increases substantially. This is due to the fuel rich
mixture yielding a high percentage of incomplete combustion
products. This phenomenon has been studied and an air-fuel ratio
regulator was developed which is mounted in the intake line and
starts operation automatically when the engine idles. Gas
samples with and without the device were analyzed under various
operating conditions. Without the device carbon monoxide
contents ranged from 3.2 to 7.8% while with use of the device it
was only 0.4%. Also the concentration of benzene, acrolein, and
tormaldehyde decreased substantially. The device was tested on
city buses with good results.##
10915
Allt, P. K., P. Datta, W. A. T. Macey, and B.
Semmens
REACTIONS OF SULPHUR-CONTAINING HYDROCARBONS IN AN ELECTRICAL
DISCHARGE. J. Appl. Chen. (London) 18 (7) :213-217, July
1968.
A study has been made into the effects of a low frequency
semi-corona discharge on carbon disulphide, ethyl mercaptan, amyl
mercaptan and thiophene present as 1 2% sulphur/hydrocarbon
mixtures. Semi-corona discharge, which was carried out at
atmospheric pressure, has resulted in the partial desulphurisation
of the sulphur-containing hydrocarbon mixtures. The efficiency of
the desulphurisation was influenced by the techniques employed and
by the nature of the central electrode. In almost all instances
the reactions were accompanied by the formation of solid material.
(Authors' abstract)*#
11033
Gamble, B. L.
CONTROL OF ORGANIC SOLVENT EMISSIONS IN INDUSTBY. Preprint,
Continental Can Co., Inc., Chicago, 111., ((24)) p., 1968.
4 refs. (Presented at the 61st Annual Meeting, Air Pollution
Control Association, St. Paul, Minn., June 23-27, 1968,
Paper 68-48.)
Extensive and careful source testing is required in order to
evaluate a solvent emission pollution problem and to select
suitable emission control equipment. When new equipment is
considered, the system needs which are based upon a study of the
functions to be performed, are determined. Test equipment is
542 HYDROCARBONS AND AIR POLLUTION
-------
important for appraisal of performance of emission control
equipment. For on site,testing, the hydrogen flame ionization
detector offers a reasonable approach for direct reading
instrumentation design. " Control methods for limiting the enission
of solvents can be classified as Process Modification,
Incineration, and Solvent Recovery. Discussion of these
methods are given. Pictures and diagrams of control equipment
and systems,used in the control of organic solvent emissions are
presented.#f
11058
W. Teske
IMPROVEMENTS IN THE PROCESSES AND OPERATION OF PLANTS IN THE
CHEHICAL INDUSTRY LEADING TO REDUCED EHISSION. Staub
(English translation), 28 (3):25-33, Harch 1968.
CFSTI: TT 68-50448/3
The emissions from chemical plants can be reduced, in special
cases, by changing the production process or, .in general, by
using a gas cleaning method. Change in the production process
may be achieved by a basic alteration of the process itself, by
changing the mode of operation, by^modifying the equipment and by
using a different raw material. For this purpose, the
doublecontact method for sulphuric acid production, the pressure
method for nitric acid recovery and the introduction of a covered
carbide furnace are mentioned as examples. The superphosphate
process, viscose process, production of betanaphthol,
production of thermal phosphoric acid and production of
calcium chloride are given as examples for waste gas cleaning.
(Author's summary)##
11234
K. C. Tessier, and H. E. Bachman
FUEL ADDITIVES FOR THE SUPPRESSION OF DIESEL EXHAUST ODOR AND
SMOKE. PART I: PROPOSED MECHANISM FOR SMOKE SUPPRESSION.
Preprint, American Society of Mechanical Engineers, New York
, 8p., 1968. 28 refs. (Presented at the ASME Winter Annual
Meeting and Energy Systems Exposition, New York, N. Y.,
Dec. 1-5, 1968, Paper 68-WA/DGP-4.)
A combination of odor mask and barium containing additive in
diesel fuel is effective in reducing smoke, odor and
irritation from diesel exhaust. It has shown no injurious effects
on fuel systems, exhaust systems or engines. This paper discusses
the engine evaluation of these additives in American diesel
engines. The major implications of using barium additives in
the fuel are discussed as well as possible mechanisms for their
action, of special interest is-a description of the results of
using the Ricardo, high speed cine^technique to visually study.the
combustion of additive treated fuel. 'This technique shows in
a spectacular way that smoke clearing occurs principally in the
combustion chamber. (Authors' abstract; modified)ft
E.' Control Methods 543
-------
11292
EFFECTIVENESS OF EXHAUST CONTROLS ON 1966 VEHICLES. 11p.,
Aug. 10, 1966. 6 refs. California Motor Vehicle Pollution on
Control Board
Emission tests on UQU 1966-model cars with exhaust controls in
public use confirm that the vehicle manufacturers have done a good
job of building cars with low emissions. However, field data on
emissions higher than _»- oving-ground results and some deterioration
of emissions with mileage, indicate that more effort is needed on
emission control in the field. (Author's abstract) ##
Cantwell, E. N., I. T. Rosenlund, W. J. Barth, F. L.
Kinnear and S. W. Ross
A PROGRESS REPORT ON THE DEVELOPMENT OF EXHAUST MANIFOLD
REACTORS. Preprint, Society of Automotive Engineers, Inc.
New York, 56p., 1969. 22 refs. (Presented at the
International Automotive Engineering Congress, Detroit,
Mich., Jan. 13-17, 1969, Paper 690139.)
Exhaust manifold reactor systems using air injection have been
developed to control exhaust emission levels of a variety of
vehicles to less than 50 ppm hydrocarbons and 0.5 per cent
carbon monoxide. These systems have been shown to be compatible
with other control systems used to reduce evaporative emissions and
oxides of nitrogen. Manifold reactors were constructed which
were sufficiently durable to control emissions effectively for
100,000 miles when run in accordance with the mileage accumulation
schedule suggested in the Federal emission control device
certification procedure. Problem areas hampering immediate
application of reactor systems are described. Manifold reactor
units are large and will not fit in the engine compartments of
many vehicles; furthermore, some current engine configurations are
not suited to the installation of reactors. Current reactor
construction techniques are costly and materials of proven
durability are relatively expensive. In addition, at the present
stage of development, some carburetor enrichment is required which
results in lower fuel economy. While preliminary work has
indicated that these problems are probably amenable to solution
much additional development will be required. (Authors'
abstract) #f
11912
S. Puschenburg
EXHAUST GAS MEASUREMENTS DURING A SIMULATED TRAFFIC JAH IN 4
ROAD TUNNEL. ( ( Abgasmessungen bei simuliertem
Verkehrsstau in einem Strassenverkehrstunnel. ) ) Text in German.
Stadtehygiene, 19 (6) : 1 09-1 1 3, June 1968.
Prior to the opening of the Klostervall-Glockengresserwall
Tunnel, the Hamburg Construction Office for Bridge
Construction and Engineering, utilizing 20 diesel trucks and UO
gasoline-powered automobiles (Volkswagens) , tested the
efficiency of the tunnel's built-in mechanical ventilators and
544 HYDROCARBONS AND AIR POLLUTION
-------
studied the problem of diminished visibility from diesel exhausts.
Schematic drawings of the 55m tunnel with locations of measuring,
regulation, and warning instruments are presented. A study
was made of the carbon monoxide (CO), nitrous gases, and benzene
hydrocarbons in the tunnel atmosphere while the vehicles, standing
bumper to bumper, idled for 20 minutes to stimulate the worst-
possible traffic conditions. Following an initial increase during
startup, the CO concentration decreased slightly and thereafter
increased to 20 ppm with the diesel trucks after 50 minutes. CO
increased to 330 ppm after 25 minutes and 380 ppm after 50
minutes with the gasoline-powered automobiles. Neither the lower
explosive limit nor the maximum allowable hygienic concentration
was reached for the benzene hydrocarbons. No evidence of any
danger from visibility impairment was found. Measurements made
at the various measuring stations showed uniform distribution of
CO in the tunnel although none of the air turbulence which
would have been created by moving traffic was present. The
ventilators were able to move the air column towards the tunnel
exit. The study shows that continuous surveillance of tunnel air
for CO is needed and that automatic installations for measuring
and regulating CO and for warning against it are preferred to
manual operations.##
12503
Battelle Bemorial Inst., Richland, Hash.
APPLICABILITY OF ORGANIC LIQUIDS TO THE DEVELOPMENT OF' NEW
PROCESSES FOR REMOVING SULFUR DIOXIDE FROM FLUE GASES. (FINAL PHASE
I.) Contract PH-22-63-19, (11U)p.r March 1969. 32 refs.
CFSTI: PB 183513
A study was undertaken, the purpose being to survey the literature
and, on the basis of the findings, to assess the applicability of
organic liquids to the development of new processes for removing
S02 from fossil fuel fired power plant stack gases. This litera tur
search also extended to the process engineering field to indicate
the preferred methods of contacting the sorbent with the flue
gas and the preferred technique of sorbent regeneration and
recovery of sulfur values. A preliminary assessment of the
applicability of organic liguids for cleaning both smelter effluent
and power plant flue gases were made, and conditions required to
assure adequate effluent gas plume dispersion were reviewed.
Economic factors important to the comparison of organic liguids
as scrubbing agents were reviewed, along with other means of
sulfur dioxide removal.
12998
EXHAUST PURIFIERS CLEAN THE AIR. Mater. Handlin'g Eng. , 2U(8):
108-110, Aug. 1969.
Air inside Armstrong Rubber Company's West Haven, Conn.
warehouse is kept clean by using a combination of exhaust blowers
and LP gas lift trucks fitted with catalytic mufflers. Three
blowers on each of the three storage floors are used to change
interior air in the 600,000 sg ft building. The LP gas-fueled
lift trucks are fitted with PTX purifiers. Platinum on a
special ceramic support catalyzes the oxidation of the CO,
hydrocarbons, and exhaust odors into C02 and H20 vapor. The
catalyst lasts thousands of hours' without requiring replacement.
The purifiers replace the conventional mufflers and work well
E. Control Methods 545
-------
with LP gas, white gasoline, or diesel fuel. They warm up in 30
to 15 sec. Zenith Corp. has equipped its seven tractors and 12
lift trucks with Oxy-Catalyst catalytic mufflers. These vehicles
are fueled with 87 octane naptha gasoline. Exhaust gases are
oxidized into C02 and H20 as they pass through a bed of
catalyst-coated pellets in the purifier. The mufflers require
maintenance after 500 to 600 hrs of use. A 90 psi air stream
is used to blow off carbon deposits and more pellets are added.
After 2000 hrs of operation, the entire catalytic bed is
replaced.
13033
Griffing, Margaret E., Frances W. Lamb, and Ruth E. Stephens
BETHOD OF CONTROLLING EXHAUST EMISSION. (Ethyl Corp., New York,
N.Y.) U.S. Pat. 3,
-------
In purification of exhaust gases from an internal combustion
engine, a catalyst must operate effectively under a range of
temperatures from 400 to 1800 F. A method is presented for
oxidation of the unburned hydrocarbons and the carbon monoxide
components of exhaust gas. The exhaust gas is contacted with
a catalyst consisting of a transitional alumina support containing
from 0.01 to 5 wt % silica, and as a catalytic agent, copper
oxide containing 0.5 to 25 wt % copper and 0.5 to 10 wt % cobalt
or silver and a combination of cobalt and vanadium in oxide form.
The catalyst will operate at the required range of temperatures,
oxidizing the carbon monoxide and unburned hydrocarbons.
13217
Hattia, Manlio M.
PROCESS FOR REMOVING ORGANIC CONTAMINANTS FROM AIR. (Day E
Zimmerraann, Inc., Philadelphia) n. S. Pat. 3,455,089. 4p., July
15, 1969. 3 refs. (Appl. Nov. 27, 1967, 4 claims).
A process is presented for removing organic contaminants from
air by adsorption. This is accomplished in a continuous process
by using several parallel adsorbers, with one or more of the
units being regenerated while one or more remain on stream.
Contaminants driven from the adsorbers during regeneration are
used as fuel for heating the regenerating gases. Adsorbent beds,
such as activated charcoal, that normally are adversely affected
by the very high temperatures associated with direct burning can
be used in the system. Combustion products are preferably
recycled through the adsorber so that only treated exhaust
leaves the system.
13467
Young, Stewart H.
FUME DESTROYING PROCESS. (Thiogen Co., San Francisco, Calif.)
U.S. Pat. 1,094,767. 3p., April 28, 1914. (Appl. August 15,
1911, 5 claims).
Decomposition or reduction of sulfur dioxide and formation of
sulfur occur simultaneously when sulfurous fumes are subjected
to the action of a heated carbonaceous fuel in the presence of
a calcareous substance or solid reagent, or the action of a
highly heated hydrocarbon fuel in the presence of a reagent.
Fumes are then cooled to a temperature at which the sulfur
will not recombine with oxygen. Decomposition is accelerated
by the use of lime, lime rock, or any substance which has the
property of neutralizing the sulfurous acid of the fumes.
13497
Saito, T., E. Shirasaki, and N. Toriyama
STUDIES ON SULFUR IN ACETYLENE GAS GENERATED BY DRY TYPE GENERATORS
AND METHOD OF GAS PURIFICATION. Text in Japanese. J.J. Synthetic
Organic Chem. (Japan), 27 (4):345-351, April 1969. 7 refs.
E. Control Methods 547
-------
This study involved the removal of sulfur components from acetylene
by washing with dilute sodium hypochlorite. Crude acetylene
generated from calcium carbide containing more than 1S calcium
sulfide contained a small amount of hydrogen sulfide. Alpha, beta,
alpha prime, beta prime-tetrachlorodiethyl sulfide was extracted
after purification of the precipitates in the mist separator using
a solution of pH 6.5-7.3. Hydrogen sulfide was effectively
removed by washing crude acetylene with 10S aqueous NaOH before
treatment with sodium hypochlorite.
13551
Faith, w, 1.
AIR POLLUTION ABATEMENT. SURVEY OF CURRENT PRACTICES AND
COSTS. Chem Eng. Progr., 55 (3):38-43, Harch 1959. 8 refs.
Pollutants and control methods of the chemical manufacturing,
pulping, petroleum refining, steel, food, and cement manufacturing
industries are reviewed. Chief pollutants from the chemical
industry are dilute vent gases, acid-mists, waste sulfides,
nitrogen oxides, combustible wastes, and dust. Vent gases
are best controlled by catalytic oxidation, sulfides by
caustic scrubbers, nitrogen oxides by catalytic reduction,
combustible wastes by incineration, and dust by filtration.
No standard procedure has been adopted for abatement of acid
mists. Pulp and paper industry pollutants are fly ash, dust
and odors. Electrostatic precipitators, dust scrubbers, and
spray towers are used to combat these problems. Air pollution
by the petroleum refining industry.is caused by sulfur
compounds and hydrocarbon loss. Sulfur compounds can be
reduced by absorption and hydrocarbons by several control
methods. The main pollutant from the steel industry is
dust, which can be controlled by electrostatic precipitators and
wet scrubbers. The main problem of the food industry is
control of odor, which is combatted by activated carbon
adsorbers. Dust from cement industries is best controlled by
glass fabric bag filters or cyclone collectors. Costs for
1959 are given for the various control methods.
13554
Cohn, Johann G. E.
METHOD OF REMOVING NITROGEN OXIDES FROM GASES. (Engelhard
Industries, Inc., Newark, N. J.) U. S. Pat. 3,118,727. i»p.,
Jan. 21, 196U. 9 refs. (Appl. Oct. 12, 1956, 11 claims).
A process is described for recovering heating values and purifying
waste gases produced by the oxidation of ammonia in the production
of nitric acid. Waste gases are mixed with a hydrocarbon fuel and
the mixture is passed over a 0.1 to 5.0% by weight rhodium and/or
palladium supported catalyst at the reaction temperature of
700-725 F. The heat generated in passing the mixture over the
catalyst may be used to raise the gas temperature or to generate
steam isothermally. Space velocity for the reaction may be in
the range of 60,000-110,000 standard vols of gas/vol of
catalyst/hr. The more hydrocarbon fuel used, the more complete is
the removal of nitrogen oxides.
548 HYDROCARBONS AND AIR POLLUTION
-------
13783
Miller, E. B.
ADSOBPTION BY SILICA GEL. II. Chem. Het. Eng., 23 (25): 1219-
1222, Dec, 22, 1920. (Presented before the Am. Inst. Chem.
Eng., Montreal, June 28, 1920).
The most satisfactory method for recovering solvent vapors after
they have been adsorbed by silica gel, consists of heating the
gel and sending steam directly through it. For volatile solvents
such as ethyl ether, acetone, benzene, and gasoline, 150 C
is considered the optimum temperature to bring about rapid
distillation of the vapors from the gel. It was found- that
using a 1% mixture of ether vapor and air, silica gel adsorbs
an amount of ether corresponding to 14.1% of its own weight;
and, using a 3.08% mixture, it adsorbs 15. 5X of its own weight.
In each case it adsorbed at 8% of its weight at 100% efficiency.
The results of experiments conducted on the adsorption
efficiency for acetone, benzene, and petroleum ether are
presented graphically.
1378«
Messen-Jaschin, Gregori
APPARATUS FOE PURIFYING AIR. (G. A. Messen-Jaschin, Sarnen,
Switzerland) U. S. Pat. 3,434,267. 7p., March 25, 1969.
20 refs. (Appl. Sept. 1, 1965, 9 claims).
An installation for purifying street air from automotive
exhaust gases is described. A number of electrofliters are
located in two rows on opposite sides of the street below
the street level. Venitlators suck in the air to be purified
from the streets and pass it through the electrofilters.
After the air passes through the filter, it is guided through
a combustion chamber where carbon monoxide is converted to
carbonic acid. The apparatus has a separate air-withdrawing
channel connected to each combustion chamber which opens
into the side wall of a discharge gutter.
13865
Schuetze, M.
FINE PURIFICATION OF GASES WITH A HIGHLY ACTIVE COPPER CATALYST.
(Feinreinigung von Gasen mit einem hochaktiven Kupferkatalysator)
Text in German. Angew. Chem., 70 (22-23):697-699, Nov. 26,
1958. 7 refs.
A description is given of a novel, highly active copper catalyst
which is suitable for removal of 02, H2, CO, acetylene, and
sulfur compounds from a large variety of gas mixtures by
catalytic reaction or by absorption. The impurities are
removed at relatively low temperatures, in most cases, down
to the limit of detectability.
E, Control Methods 549
-------
13958
Agnew, W. G.
FUTURE EMISSION-CONTROLLED SPARK-IGNITION ENGINES AND THEIR
FUELS. Proc. Am. Petrol. Inst. Sect. Ill, vol. 49:242-280,
1969. 26 refs.
Future trends in vehicle and gasoline design for the purpose of
meeting increasingly stringent air pollution controls are
discussed. Federal exhaust emission standards for 1970 are more
stringent than those for 1969. Standards now require 10% lower
hydrocarbon and CO emissions and measurement methods have been
changed from a concentration basis to a calculated mass basis.
Emission control systems are improved and are integral with the
power plant and the fuel system. Included in future plans are
evaporative emission restrictions, nitrogen oxides emission
control, and more stringent hydrocarbon and CO emission controls.
New devices available for control include large manifold air
injection reactors, catalytic converters, and alternate
power plants such as gas turbines, external combustion engines,
and electric propulsion. Attention will be given to reducing
the extreme deviations of high volatility gasolines in the
summer and low volatility gasolines in the winter and reducing
eye irritation by reducing the amount of aromatic hydrocarbons
in the engine exhaust gas. Propane may be used since it
permits leaner mixtures. While emission standards are met,
companies will try to maintain or improve present levels of
driveability, reliability, fuel economy, cost, and owner
convenience. At the same time, the oil industry will be making
necessary changes to ensure that the new hardware systems will
operate with the greatest possible satisfaction to the car owner.
14004
Franzky, Dlrich
COUNTERACTING OFFENSIVE ODORS CAUSED BY ORGANIC COMPOUNDS.
(Bekaempfung von Geruchsbelaestigungen, die durch organische
Verbindungen verursacht sind). Text in German. Staub,
Reinhaltung Luft, 28 (3) : 113-119, March 1968. 13 refs.
The importance of removing odorous components from waste air and
exhaust gases is now recognized, but the selection of an
appropriate purification process is complicated by the
proliferation of chemical processes and treatment methods. A
survey of the most popular methods is given and measures that can
be taken to improve conditions in a small plant are pointed out.
(Author summary modified)
14028
FILTRATION OF WASTE AIR FBOH DRY CLEANING MACHINES. (Filterung
der Abluft aus Reinigungsmachinen). Text in German. Wasser
luft Betrieb, 13 (4) : 127-128, April 1969.
The fifth regulation of the Law for the Prevention of iir
Pollution in North Rhine-Westphalia of 1967 is now in effect.
It concerns all machines for cleaning and drying textiles, leather
550 HYDROCARBONS AND AIR POLLUTION
-------
goods, or furs if they operate with chlorinated hydrocarbons
in the form of trichloroethylene or perchloroethylene. The
regulations pertain to all sizes of machines so that tumble driers
and coin-operated cleaners are also affected. In a departure
from other regulations, a specific method for cleaning of the
waste air is required, namely, filtration with activated coal.
The concentration limit cannot exceed 200 mg of solvent per
cu m waste air. Commercially available activated coal is
capable of storing 25 to 35% more solvent than must be regenerated.
For this reason, installation of two filters is recommended.
The efficiency of a charcoal filter is rather high, so lower
concentrations than the prescribed limit concentration are
obtained. since the odor threshold of trichloroethylene
fluctuates between 260 and 520 mg/cu m and that of
perchloroethylene is 360 mg/cu m, the effectiveness of'the
filter can be roughly evaluated by the presence or absence of
odor at the filter outlet. According to the regulations,
official inspections will be made once a year without charge. For
this purpose, the Draeger trace gas-measuring unit will be used.
The solvent retained by the activated coal can be recovered and
returned to the process. Investment costs should be amortized
within two years.
T4036
Taylor, B. E. and E. H. Campau
THE IIEC - A COOPERATIVE RESEARCH PROGRAM FOR AUTOHOTIVE EMISSION
CONTROL. Proc. Am. Petrol. Inst., Sect. Ill, vol. 49:309-327,
1969. 5 refs.
The Inter-Industry Emission Control Program, which now is
comprised of six petroleum companies and five automobile
manufacturers (including four foreign firms), was established in
1967 and expanded in 1968 to pool the research efforts of the t»o
industries in the design and development of a virtually
emission free, gasoline-powered vehicle. Specific targets
call for a 90 to 97* reduction in the hydrocarbon, carbon
monoxide, and nitrogen oxide emissions of a typical vehicle
and are aimed at improving the quality of the Los Angeles Easin,
considered the most critical air shed area in the United States.
Of some 17 research projects begun under the program, those
associated with catalysts, thermal reactors, exhaust gas
recirculation, and modification of fuel properties are receiving
the major current attention, using techniques ranging from
mathematical modeling to component hardware development and
testing, to the building and testing of complete concept cars,
which combine various emission control sub-systems into fully-
functioning automobiles for total emission evaluation,
durability testing, and product acceptability evaluation.
Descriptions of the various research problems and methods are
given. Because of Federal emissions testing requirements,
much of the total effort is directed toward designing exhaust
control systems that can operate at high efficiency almost
from the moment of engine start-up. Summaries are given of
the investigations underway that deal with the fuel and hardware
components of a spark ignition engine; these involve the
development of additives to suppress nitrogen oxide formation,
hydrocarbon combustion-improving additives, hydrocarbon
deposit-modifying additives, surface tension and emulsifying
agents, and the study of the effect of fuel volatility on exhaust
and evaporative emissions.
, Control Methods 551
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14193
Saito, Takeshi
ftUTOMOBILF EMISSION AND MOTOR OILS. (Dorogai HOkO sharyQ ni
saiteki no sekyu tenka ?.ai). Text in Japanese, .lunkatsn (J.
Japan Soc. Lubrication Fngrs.), 1
-------
Engineering Congress, Detroit, Mich., Jan. 13-17, 1969, Paper
690089.)
A calculation technique that accounts for nonlinear relations
between reactivity and mixture concentration was developed and
used to study the hydrocarbon reactivity of evaporation losses
from a variety of original fuels. Results of calculated data
show that diluting the concentration of light olefins in an
original fuel, normally accomplished by additions of butane,
pentane, or saturated base stocks, reduces reactivities of
hydrocarbon evaporation losses. It was concluded that the
effects of fuel composition on evaporation losses is a parallel
study needed for complete assessment of the benefits that
changes in fuel composition may have on photochemical smog
formed from the evaporation losses.
1«297
Hind, C. J.
CLEAN AIB AND THE DIESEL. Indian Eastern Engr. (Bombay),
111 (2) :77-79, Feb. 1969.
A defense of the diesel engine against criticism that it is a
heavy contributor to air pollution is presented. Under ideal
conditions if all gasoline engines were replaced by diesel
engines, the emission of carbon monoxide, aldehydes, and nitrogen
oxides would be reduced, carbon dioxide, hydrocarbons, and soot
would be increased, and sulfur dioxide would be unchanged. Carbon
dioxide is not seen as a health hazard, and hydrocarbons are not
considered dangerous, as they are in parts of the D. S., because
the other conditions necessary for the creation of photochemical
snog, particularly climatic factors, are not present in the 0. K.
Carbon monoxide, possibly the emission most hazardous to health,
would be reduced to almost negligible amounts. Sulfur dioxide
would necessarily be kept to a minimum, since in diesel engines
the sulfur content of the fuel is deliberately kept very low to
reduce internal corrosion of engines. In addition, because the
diesel engine is more efficient than the gasoline engine, the
absolute quantity of fuel oil used would be reduced, thus lowering
the total impurities discharged into the atmosphere. Efforts are
underway to reduce the major pollutants from diesels: smoke
(carbon) and odor (sulfur dioxide). Supercharging by making use
of energy remaining in the exhaust gases to drive a turbine
and compressor, is seen as one way of maintaining a satisfactory
fuel/air ratio for smokeless operation and greater efficiency
as fuel input is increased. Improvements in the combustion
process are being investigated as an engineering goal and to
reduce odorous emissions.
1H326
Hardison, L. C.
A SUHMARY OF THE USE OF CATALYSTS FOR STATIONARY EMISSION SOURCE
CONTROL. Franklin Inst. Research Labs., Philadelphia, Pa.,
Haterials Science1 and Engineering Dept. and Public Health Service,
Durham, N. C.r National Air Pollution Control Administration,
Proc. First Natl. Syrap. on Heterogeneous Catalysis for Control
of Air Pollution, Philadelphia, Pa., Nov. 1968, p. 271-296.
E. Control Methods 553
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Catalysts have been used for about 20 years for oxidizing
hydrocarbons to prevent their emission into the atmosphere.
Initially, all-metal catalysts of the Suter-Ruff type, in which
the active catalytic material is conducted to the surface of a
base metal support by means of an electrochemical process were
used; they were most commonly of the platinum-palladium group.
These continue to be the most widely used catalysts for
stationary source control, but ceramic honeycomb-supported and
particulate-supported catalysts have had significant application.
Particulate catalysts are widely used in petroleum refining and
chemical processes, and to a limited extent in air correction.
Ceramic honeycomb materials have an advantage over particulate
catalysts in that the pressure drop for a given amount of ceramic
surface area is only a very small fraction of that across the
particulates. Hhile the scientific basis of catalysis is not as
clear as that of many of the other industrial arts, the
thermodynamics are sufficiently well known that catalysts can be
characterized with good success. A summary of the thermodynamic
reactions involved in catalysis is given. The use of catalytic
air pollution control equipment in such industries as wire
enameling, kettle cooking (particularly in paint manufacturing),
metal lithographing, the chemical process industries and many
others is described. Additional applications for catalytic air
pollution control continue to appear as regulations and
community standards for air quality become more rigid. An
appendix presents a sample computer analysis of catalytic solvent
burning.
1H333
Dwyer, F. G.
CATALYST SYSTEM HOEPHOLOGI AND DESIGN. Franklin Inst. Research
labs., Philadelphia, Pa., Materials Science and Engineering Dept.
and Public Health Service, Durham, N. C., National Air Pollution
Control Administration, Proc. First Natl. Symp. on Heterogeneous
Catalysis for Control of Air Pollution, Philadelphia., Pa., Nov.
1968, p. 73-86. 13 refs.
Common gaseous pollutants that are amenable to catalytic
transformation are discussed. Sulfur dioxide is eliminated by
catalytic hydrodesulfurization, oxidation with a vanadium
pentoxide catalyst, or reduction with carbon monoxide in flue
gases. Nitrogen oxides are eliminated by reduction with chromite
and copper oxide catalysts, which lose their effectiveness.
Carbon monoxide is removed from atmospheric gases by catalytic
oxidation. More is known about the mechanism of CO oxidation,
which is catalyzed by transition metal oxides and noble
catalysts, than about any other methods. Carbon monoxide also
can be oxidized in the presence of H2 over Mn02, and indium
doped ZnO, based on electronic charge transfer. Mechanisms
for the oxidation of hydrocarbons are similar to those for CO
oxidation but more catalyst efficiency. Interaction of gaseous
pollutants presents a problem in finding the right catalyst.
The complexity of the problem is seen in the exhaust from
internal combustion engines. Here, CO and unbnrned hydrocarbons
are converted by catalytic oxidation and nitrogen oxides are
converted by catalytic reduction. The transition metal oxide
and noble metal catalysts must be supported on a base for ease
of handling, cost, and thermal stability. Problems encountered
in treating industrial gas streams are those of dilution. A
554 HYDROCARBONS AND AIR POLLUTION
-------
further complication arises if the diluent interferes in some
manner with the reaction being catalyzed. Poisoning effects,
which are present in all heterogeneous catalytic reactions, must
also be considered. although none of the catalysts is a panacea,
each brings the solution of air pollution closer.
Lunche, Robert G.
FDME AND ODOP DESTRUCTION BY CATALYTIC AFTERBURNERS. Franklin
Inst. Research Labs., Philadelphia, Pa., Materials Science and
Engineering Dept. and Public Health Service, Durham, N. C. ,
National Air Pollution Control Administration, Proc. First" Natl.
Symp. on Heterogeneous Catalysis for Control of Air Pollution,
Philadelphia, Pa., Nov. 1968, p. 297-320. 6 refs.
The operating and design aspects of the catalytic afterburning
process are reviewed, and its application and effectiveness are
discussed on the basis of the experience of the Los Angeles
County Air Pollution Control District in testing a wide variety
of catalytic afterburners in industrial use. Because of certain
operating characteristics of these afterburners, they represent
a partial oxidation process which produces compounds in the
treated effluents that are often more offensive and odorous
than the original fumes and odors. Investigations by the District
show that partial oxidation produces olefinic and other oxidation
products that often increase the eye-irritating, photochemical
smog-forming potential of treated effluents to levels greater
than those of the original fumes and odors. In general, an
afterburner must oxidize 90% or more of the carbon in the
entering materials to C02 to be judged effective. On the basis
of the District's own experience and reports of others, the
actual performance of catalytic afterburners for reducing
many fumes and odors is considered inadequate. Without an
advance in performance, it does not seem likely that catalytic
afterburners will be able to comply with Los Angeles County's
organic emissions standards unless the operating temperatures
are at a level that renders the catalyst unnecessary,
1«353
Yagi, Shizuo, Kazuo Nakagawa, Akira Ishizuya, and Yasuhito Sato
A STODY IN THE DEVELOPMENT OF EXHAUST EMISSION CONTROLS FOR SMALL
DISPLACEMENT HONDA ENGINES. Preprint, Society of Automotive
Engineers, Inc., New York, 20p. , 1968. 11 refs. (Presented
at the West coast Meeting, Society of Automotive Engineers,
San Francisco, Aug. 12-15, 1968, Paper 680527.)
In the small displacement, high-speed, high-performance spark
ignition engines being developed by Honda, the difficulties
in reducing exhaust emissions without seriously impairing
inherent engine characteristics are different from those
encountered with the large displacement engines generally used
in American cars. The tandem throttle valve system was developed
as a control device to minimize exhausts emissions during the
frequent accelerations and decelerations in normal driving
conditions. The system serves to restrict the flow of fuel
from the low-speed system of the carburetor, to prevent fuel
remaining on the intake manifold wall from flowing into the
E. Control Methods 555
-------
cylinders, and to aid the fuel not restricted from flowing into
cylinders to burn completely by adding secondary air. The
application of an air injection reactor system in small
displacement engines reduced carbon monoxide and hydrocarbon
concentrations. The effect of 'sguish action1 in a hemispherical
combustion chamber on exhaust emissions promotes better mixing
of the gases, thereby increasing the flame speed and resulting
in lore complete combustion in the cylinder. Through research
and development, many of the difficulties were overcome, and
satisfactory results were obtained in exhaust emission control
under certain limited operating conditions.
Massa, Victor F. and George P. Gross
METHOD AND APPARATUS FOB TREATING AUTOMOTIVE EXHAUST GAS.
(Esso Besearch and Engineering Co., Inc., Linden, N. J.) U. S.
Pat. 3,460,901. 3p., Aug. 12, 1969. 6 refs. (Appl. June 11,
1965, 2 claims) .
The invention provides a method for abating air pollution from
automobile exhaust gas. It is concerned primarily with
lowering the emission of unburned hydrocarbons and carbon monoxide
by addition of an oxidation-initiating compound of aqueous
hydrogen peroxide which promotes the conversion of the pollutants
to innocuous CO2 and H20. The liquid oxidant can be aspirated
into exhaust gas for afterburning or injected in other ways
suitable for dispersing it in carrier gas or directly in exhaust
gas ports. An example of a device used for aspirating comprises
a venturi scrubber and jet stream. This device can be adjusted to
vary the amount of the oxidant in response to engine demand. The
carrier gas in which the hydrogen peroxide- water mixture is
dispersed can be air or recycled exhaust gas. By a simple valve
mechanism, flow of the oxidant can be controlled and limited
to .periods of engine operation when unburned hydrocarbon emission
tends to be highest, e.g., acceleration, deceleration, or idling.
The system described can be used with both spark ignition and
compression ignition engines. Further applications of the method
include the treatment of exhaust gases containing lead residues
or halogen compounds present in antiknock additives.
14i»59
Weaver, E. E.
EFFECTS OF TETRAETHTL LEAD ON CATALYST LIFE ABD EFFICIENCY IN
CUSTOMER TYPE VEHICLE OPEBATION. Preprint, Society of Automotive
Engineers, Inc., New York, 8 p. , 1969. 18 refs. (Presented
at the International Automotive Engineering Congress, Detroit,
Mich., Jan. 13-17, 1969, Paper 690180.)
Effects of four levels of tetraethyl lead (TEL) on the efficiency
and life of a commercially available hydrocarbon and carbon
monoxide catalyst were investigated. The four fuels used in
mileage accumulation were the base Indolene with no added
lead and blends containing respectively 0.5, 1.5, and 3.0 ml
TEL per gallon. The vehicles were eight Fords equipped with
289-CID non-emission controlled 2-V engines, unmodified except
for a lean carburetor and the catalytic exhaust system. The
556 HYDROCARBONS AND AIR POLLUTION
-------
eight vehicles were paired off and each pair operated on one
of the four fuel blends. In each pair, a radial flow converter,
which required no supplemental air, was located under the
front seat in one vehicle and near the rear axle in the other
vehicle. Exhaust emissions were monitored at approximately
3000-mile intervals during accumulation of 18,000 miles in
customer-type service. Tetraethyl lead in the fuel adversely
affected the rate of warm up, the ability of the catalyst to
remove hydrocarbons from the exhaust, and accentuated the
differences in performance between front and rear converters
as mileage was accumulated. On non-lead fuel, the catalyst
performed well in preferentially removing olefins and aromatic
hydrocarbons to yeild an exhaust of very low reactivity, until
problems were encountered with losses of catalyst. The
catalyst removed CO, aliphatic aldehydes, and acetylenes equally,
well on leaded or non-leaded fuel. (Author abstract modified)
1UU63
Nelson, Edwin E.
HYDROCARBON CONTROL FOR LOS ANGELES EY REDUCING GASOLINE
VOLATILITY. Preprint, Society of Automotive Engineers, Inc.,
New York, 2Wp., 1969. 20 refs. (Presented at the International
Automotive Engineering Congress, Detroit, Mich., Jan. 13-17,
1969, Paper 690087.)
Evaporative emissions from automobiles can be. reduced by lowering
gasoline volatility. A 3 psi reduction in Reid vapor pressure
will reduce evaporative losses by about 50%. A test program
was conducted to determine if new and used cars presently on the
road in the Los Angeles basin could operate satisfactorily on
lower volatility gasoline. A 12* decrease in total vehicle
hydrocarbon emissions, equivalent to 228 tons of hydrocarbons
per day, could be o.btained by lowering the Reid vapor pressure
by 3 psi. Gasoline with reduced volatility gave acceptable
driveability and could be used to provide a significant reduction
in hydrocarbon emission.
14505
Haritatos, Nicholas J. and Phillip D. Harvey
SULFUR RECOVERY. (Chevron Research Co., San Francisco, Calif.)
0. S. Pat. 3,463,611. 9p., Aug. 26, 1969. 8 refs. (Appl.
May 1, 1967, 11 claims).
The invention presents an economical method of manufacturing
sulfur from hydrogen sulfide and other sulfur compounds present
in the oil fed to a hydroconversion process. It produces a
sufficiently high ratio of hydrogen sulfide to inert gas (usually
carbon dioxide) to recover sulfur by the Claus process. A
purge stream is withdrawn fron a hydroconversion zone recycle
gas stream containing hydrocarbons, hydrogen, hydrogen sulfide,
and other gases. The purge stream is then passed to a partial
oxidation zone where hydrocarbons are partially oxidized to
hydrogen, carbon monoxide, and carbon dioxide. Hydrogen sulfide
and carbon dioxide are removed from the partial oxidation zone
effluent and fed to the Claus process. Hydrogen and carbon
E. Control Methods 557
-------
monoxide present in the oxidation zone effluent are recycled
to the hydroconversion zone. Separation of the hydrogen sulfide
and carbon dioxide in the partial oxidation zone is accomplished
economically by a physical absorption process at 500-2000 psig.
14519
Frysinger, Galen R.
HYDHOGEN SEFOBMING FOE FDEL CELLS. Franklin Inst. Research Labs.,
Philadelphia, Pa., Materials Science and Engineering Dept. and
Public Health Service, Durham, N, C., National Sir Pollution
Control Administration, Proc. First Natl. Symp. on Heterogeneous
Catalysis for Control of Air Pollution, Philadelphia, Pa., Nov.
1968, p. U59-476.
Fuel cells are basically reactors of hydrogen and oxygen. They
are being considered for use in hydrocarbon-air fuel cell engines
which may have better pollution characteristics than conventional
engines. Since oxygen is readily available, the problem is one of
converting liquid hydrocarbons into hydrogen fuel with lightweight
equipment. Direct anodic oxidation is not practical because of
the amount of platinum catalyst required. Another approach to
hydrocarbon reforming is based on the internal reforming cell in
which the catalyst is located next to a silver-palladium anode in
the fuel cell. This anode transmits the hydrogen formed in the
reformer cavity directly to the fuel cell where it is oxidized
electrochemically on an electrolyte. Hydrogen formation depends
on current density of the fuel cell, which is reduced by catalyst
degradation. However, desulfurization cartridges should protect
reformers against excessive catalyst degradation. High
reliability in fuel cell systems is achieved by feeding fuel and
water through digital injection systems rather than through stroke
piston pumps. Fuel cell reactions using hydrogen and oxygen are
clean, since water is the only offgas product. Even using a
hydrocarbon fuel, these cells will enable 1980 emission standards
to be met.
Hamblin, E. J. J. and W. J. Faust
CATALYTIC SYSTEMS FOB LEADED AND ONLEADED GASOLINE EXHAUSTS.
Franklin Inst. Research Labs.r Philadelphia, Pa., Materials
Science and Engineering Dept. and Public Health Service, Durham,
N. C., National Air Pollution Control administration, Proc. First
Natl. Symp. on Heterogeneous Catalysis for Control of Air
Pollution, Philadelphia, Pa., Nov. 1968, p.131-159.
The problems of achieving complete catalytic combustion of
oxidizable components other than unburned hydrocarbons, carbon
monoxide, and nitrogen oxides are discussed. A catalyst
placed in the exhaust system must be capable of dealing with
lead, halogens, sulfur, and phosphorus in all combinations with
oxygen and with each other. The catalyst must have a size and
shape consistent with requirements for good flow distribution
and low pressure drop. The catalyst bed itself and the
individual particles must also not be subject to plugging
by particulate matter. A catalytic converter lowers the
558 HYDROCARBONS AND AIR POLLUTION
-------
concentrations of all pollutants in the exhaust gas stream
and does not manufacture any new ones. The automobile
manufacturers achieved significant reductions in carbon monoxide
and hydrocarbon emission levels by controlling carburetion and
ignition and by adding secondary air to the exhaust system.
However, the still lower levels of emission desired after 1970
will be difficult to attain without further losses in vehicle
performance. They may even be unattainable without catalytic
converters. The use of present-generation catalysts may permit
the recovery of the performance that already is sacrificed
by engine modifications. The development of catalysts which can
operate successfully for extended mileage on leaded fuels was
accomplished. The performance of catalysts on unleaded fuels
is outstanding. With leaded or unleaded fuel, a catalytic
converter coupled closely to the exhaust manifold, under any
engine operating conditions, assures lower emission levels
than any other system.
14608
DePalma, T. V. and B. W. Perga
DIESEL ENGINE POLLUTANTS. PART II. CONTROL. Franklin Inst.
Research Labs., Philadelphia, Pa., Materials Science and
Engineering Dept. and Public Health Service, Durham, N. C.,
National Air Pollution Control Administration, Proc. First Natl.
Symp. on Heterogeneous Catalysis for Control of air Pollution,
Philadelphia, Pa., Nov. 1968, p. 221-234.
A catalytic system to control diesel engine pollutants is
discussed. Catalytic oxidation of pollutants to carbon
dioxide and water is the most desirable method to use.
Several catalysts accomplished the task of odor improvement
and reduction of gaseous combustibles; these are made of
spherical alumina-base materials, one of which contains a
noble metal. The real advantage to the solution of the
environmental pollution problem by catalysis is its operational
persistence. It not only oxidizes odorous oxygenates but
also efficiently consumes other combustibles such as carbon
monoxide and hydrocarbons. converter and catalyst design
criteria are based on maximum throughput from the engine.
Space and mass velocity are selected to give high pollutant
conversion even with maximum exhaust gas output. Gas flow
distribution must be controlled so that catalyst utilization
is complete. This is accomplished by designing low pressure
drop beds, minimizing head losses, and balancing velocity and
static heads within the converter. The design problem becomes
critical when one understands that an exhaust pollution
control system must operate under a very wide range of
conditions. Engine characteristics also affect the performance
of a catalytic system. The two-stroke diesel engine, when
compared to the four-stroke engine, exhausts a greater volume
of gases which are lower in temperature and more dilute. These
conditions diminish the reaction rate for oxidation and make
conversion of pollutants more difficult. System design changes
in the inlet screen have eliminated the sooting of the catalyst
in that area. The need for rapid and accurate evaluation of
exhaust gas odorants is obvious. From the catalyst development
standpoint an accurate appraisal method is necessary in order
to demonstrate subtle differences in performance. A catalytic
system was developed which reduces odor emissions from diesel
E. Control Methods 559
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powered vehicles, which oxidizes hydrocarbons and carbon monoxide
with high efficiency, and which can be fitted into existing
muffler spaces.
1U609
NcLouth, B. F., H. J. Paulus, and A. J. Roberts
INCINERATION OF EPOXY GLASS LAMINATES TO RECOVER PRECIOUS METALS.
American society of Mechanical Engineers New York Incinerator Div.,
Proc. Natl. Incinerator Conf., New York, 1968, p. 171-175. (May
5-8) .
Recovery of precious metals from electrical circuits printed
on epoxy-impregnated fiberglass.laminates was carried out by
incineration of the scrap and rejected printed circuits at
controlled temperatures, which resulted in the liberation of
a considerable amount of unburned hydrocarbons and obnoxious
odors into the atmosphere. The glass laminates consisted of
approximately 65% fiberglass (by weight) and 35% epoxy resins.
The material contained no chlorines and not more than a trace
of sulfur, but 16% petra—bromo had been added to the resins
to permit the use of the final product under various ambient
temperatures. In addition, there was variance in type and
consistency of the epoxy scrap. Based on information obtained
by research on the combustion characteristics of the material,
a prototype unit was constructed and tested. After successful
testing of the prototype unit, a new incinerator was installed
that solved the problem of hydrocarbon and odor emission. A
control system was designed that should assure proper burner
operation and unit temperatures and at the same time be flexible
in case adjustments become necessary in the new unit. The new
incinerator simplifies recovery of the precious metals due
to more consistent ash quality. Polyesters and other plastics,
as well as wool and vinyls have been burned in this incinerator,
all with equal success.
1U723
Derndinger, Hans-Otto
.MOTOR VEHICLE ENGINES. (Kraftfahrzeugmotoren). Text in German.
VDI (Ver. Deut. Ingr.) Z. (Duesseldorf), 110 (21):978-982, July
1968. 8 refs.
Recent developments in the field of exhaust gas cleaning are
- discussed. Since the passage of laws in the 13. S, A. limiting
the concentrations of carbon monoxide and of unburned
hydrocarbons in the engine exhausts, automobile manufacturers
have developed various methods of meeting these legal
requirements. Most of them are based on the principle of
afterburning, e.g., manifold air oxidation and thermal
reactors. The Clean Air Package aims at accurate adjustment
of the carburetor and delays the ignition, guaranteeing a more
complete combustion, although the exit gases have higher
temperatures. Another method is gasoline injection. The
effects of these measures are beginning to be felt. In Los
Angeles, the steep increase in hydrocarbon emissions has been
reversed. Great efforts are being made to reduce the emissions
by 1980 to the 19UO level. To achieve this end, further
560 HYDROCARBONS AND AIR POLLUTION
-------
measures are required. Control measures tend toward a smaller
ratio of combustion chamber surface to combustion chamber volume.
Careful sealing will eliminate the emission of unburned
hydrocarbons from the fuel tank evaporation. The two
toxicants which have received little attention to date by
legislators are lead and nitrogen oxides. In conclusion,
the marketing of two new Wankel engines is mentioned.
14728
Krynitsfcy, John A.
MILITARY PROCUREMENT PROBLEMS RESULTING FROM AIR POLLUTION
CONTROLS. Preprint, National Petroleum Befiners Association,
Washington, D. C., 11p., 1968. (Presented at the National
Fuels and Lubricants Meeting, New York, N. Y., Sept. 11-12, 1968,
F5L-68-61-)
The efforts of the Department of Defense (DoD) to comply with
Federal and local air pollution control regulations are
coordinated by its Environmental Pollution Control Committee,
established in January, 1966. As an example of these efforts,
to comply with Rule 66 of the Los Angeles Air Pollution Control
District which severly restricts the emission of organic materials
to the atmosphere and involves many paints and cleaners used by
DOD installations and contractors, substitute fluids and
solvents are being sought and catalytic incinerators for
destroying the vapors are being employed. A time-phased 5-year
program for compliance is now in effect. The Department, which
may be the biggest buyer of heating oil in the world, is also
greatly affected by standards for Federal facilities limiting
the emission of pollutants from the burning of fossil fuels.
These include limits on particulate emissions, on the visual
density of smoke, on vapor losses from gasoline and other
volatile organic materials, and on sulfur oxide emissions.
Efforts are being concentrated on obtaining adequate supplies
of low sulfur heavier burner fuel oils. DOD has adopted a
policy of converting to fuel of 1% sulfur content as soon as
practical in order to comply with or surpass all local
regulations and provide leadership in pollution control. A
program to monitor the quality of fuels being received from
suppliers is in operation. Five-year plans covering 313
military installations in the three service branches have been
drawn up for the phased and orderly correction of air pollution
deficiencies, and are now under review.
14757
Meites, Leonard
WEB PRINTERS AND AIR POLLUTION CONTROL. Web Printer, 1(6):1-7,
1969.
Air pollution from web printing plants consists mainly of a smoke
problem, which is relatively simple to control with afterburners,
and an odor problem, which presents considerable control
difficulties. The most practical means of counteracting odors
from paper coatings, ink solvents, improperly adjusted gas burners,
and soiled papers is by either catalytic or thermal combustion.
The first works best with a pure gas stream from the press dryer;
in practice, however, the effluent of a press dryer may have
E. Control Methods 561
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impurities which can cause trouble with the catalyst and must
therefore be considered when the system is designed. Direct
flame combustion can handle impurities in the dryer effluent
since its temperature range is from 1000 to 1HOO F. The
initial cost of a catalytic afterburner system is higher than that
of a thermal system, but its operating costs are usually
considered lower, although recently there has been some
controversy on this point. The possibility of controlling
pollution by using mild and low aromatic solvents is briefly
discussed; the inks now used in web presses contain
photochemically-reactant hydrocarbon solvents which violate
regulations such as Hule 66 of the L'os Angeles County Air
Pollution Control District, and therefore require the installation
of highly efficient afterburners. It is noted that the cost of
air pollution control are mitigated somewhat because good
afterburners reduce condensate formation on oven walls and thus
increase production and improve printing quality.
1K830
Beyers, R. A., J. L. Lewis, and J. S. land
PHASE I REPORT. APPLICABILITY OF ORGANIC SOLIDS TO THE
DEVELOPMENT OF NEW TECHNIQUES FOE REMOVING OXIDES OF SULFUH FROM
FLUE GASES. TRW Inc., Redondo Beach, Calif., TRW Systems Group,
Contract PH22-68-H6, Report 10669 6003-RO-OO, 52p., Oct. 31,
1968. 39 refs.
CFSTI: PB 185 887
A literature search was conducted to select promising organic
solids for removing sulfur dioxide from flue gas, and a
preliminary chemical systems analysis for candidate S02
removal materials was performed. Organic materials were selected
on the basis of ability to take up sulfur dioxide, price and
availability, thermal stability, regenerability, and mechanical
properties. Five organic materials were identified which offered
promise for removing sulfur dioxide from flue gas. These were
cellulosics, nigrosin, poly (N-vinylcarbazole), pyrolyzed
poly(vinylchloride), and pyrolized poly (acrylonitrile). The
specific cellulosics were waste newsprint, sawdust and cotton.
The results of the preliminary chemical systems analysis
demonstrate that organic solid sulfur dioxide recovery from flue
gases is economically feasible where certain criteria are met.
The analysis was keyed to thermal regeneration of the organic
solids. However, in the case of cellulosic materials,
chemical reaction and conversion of the products to useful
commodities may also be a feasible process. As so little is
known about the parameters involved in conversion processes
at this time, a consideration of this type of regeneration was
not included. (Author summary modified)
1K850
Trayser, D. A., F. A. Creswick, J. A. Gieseke, H. R. Hazard,
A. E. Weller, and D. W. Locklin
A STODY OF THE INFLUENCE OF FUEL ATOHIZATION, VAPORIZATION,
AND MIXING PROCESSES ON POLLUTANT EMISSIONS FHOH MOTOR-VEHICLE
POWERPLANTS. Battelle Memorial Inst., Columbus, Ohio,
Columbus Labs., Contract CPA 22-69-9, Phase Rept., 1U5p.,
April 30, 1969. 120 refs.
562 HYDROCARBONS AND AIR POLLU FION
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A study of automotive engine induction systems was conducted.
The objective of this non-experimental program was to explore
incentives and approaches for reducing exhaust emissions by
extending the lean-mixture operating limit through improved
induction-system performance. The study was divided into four
major subtasks: development of mathematical descriptions of
induction-system phenomena; evaluation of methods for measuring
mixture characteristics; conception of approaches to the
definition and measurement of mixture quality; and evaluation
of alternative atomization methods. The results of this study
indicated that extension of the present limits, made possible
by improved air-fuel distribution, can lead to modest but
worthwhile reductions in emissions of both unburned hydrocarbons
and carbon monoxide and to substantial reductions in the emission
of nitrogen oxides. Minimizing or eliminating the liquid-fuel
film on the intake manifold walls was concluded to be the most
promising approach to achieving improved distribution. The
liquid film can be reduced by employing atomizing devices that
will produce droplet sizes approaching 10 to 20 microns under
all operating conditions, by designing the induction system
for minimum impaction of fuel droplets, and by heating the
manifold walls to vaporize the fuel that is avoidably impacted.
Recommendations included an experimental program comprising the
design, fabrication, and evaluation of an induction system with
a carburetor employing an alternative, improved atomization
device and a low-impaction intake manifold.
Fukuchi, Tomoyuki and Takeo Yamamoto
A FEW IDEA ON COUNTERMEASURE AS TO BE CONNECTION WITH EXHAUST
GAS FKO« GAS-WORKS AND DAHAGE ON MANDARIN. (Toshigasu
seizokojyo no haigasu to mikan no higai narabini sono taisaku ni
kansnru shokosatsu). Text in Japanese. Kogai to Taisaku
(J. Pollution Control), 5 (9):17-23, Sept. 1969. 22 refs.
Because mandarin oranges fell from trees before the harvest
period, waste gas from a gas works near the orange orchard was
suspected to be the cause. With this idea as a starting point,
the relationship between waste gas and ripening oranges was
examined in a laboratory. The possibility that the ripening
period had been accelerated by other factors, such as hydrocarbon
gases, especially ethylene, was considered. It was reported
by Magill that the tomato is influenced by hydrocarbons such
as ethylene, 0.1 ppm; acetylene, 50 ppm; propylene, 50 ppm; and
butylene, 50,000 ppm. Thus, a very small amount of ethylene
has a great influence on ripening fruit. According to the
result analysis of the waste gas, the assumption that windblown
ethylene influenced the ripening orange is reasonable. The
boiler system for waste gas control is shown. By means of
chemical reactions, ethylene vanished at 260 C. Gas compounds
are first prevented from entering the boiler and are then sent
to a reservoir tank and mixed with catalyst and steam, and
finally discharged in vapor form. By this treatment, the waste
gas compounds are vaporized. Since this boiler system has been
used at the gas works, damage to oranges has decreased.
E. Control Methods 563
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11967
Hein, G. M. and R. B. Engdahl
A STODY OF EFFLUENTS FROM DOMESTIC GAS-FIRED INCINERATORS.
(American Gas Association, Inc., New York, Proj. DGS-3M, 27p.,
June 1959. 24 refs.
Measurements were made of the effluents from nine domestic gas-
fired incinerators, including two new prototype models, five
new commercial units, and two older units. Standard test charges
that typified wet domestic wastes and dry combustible materials,
and two special refuse mixtures were burned. A free-standing
chimney provided natural draft for the units. Sampling and
analytical techniques were based on recognized methods. The
concentrations in ppm in the flue gas and the emission rates in
pounds per ton of refuse burned were determined for aldehydes,
nitrogen oxides, organic acids, ammonia, and hydrocarbons. Grain
loadings and emission rates were determined for particulate
matter which included tarry organic materials. Odor and smoke
density were also determined. Results demonstrated that
significant reduction in emissions has been achieved through
recent improvements in incinerator design. When wet domestic
wastes are incinerated in new units, of up to 6-fold decreases
in the rate of aldehyde emissions are achieved. Decrease in
organic acids is 3-fold; decrease in saturated hydrocarbons is
8-fold. Although nitrogen oxides have increased 3-fold because
of increased gas in the afterburner, their concentration is
still lower compared to other combustion sources. Smoke, odor,
and particulate matter emissions decreased to acceptable levels.
Comparison of these emission rates with those fcom municipal
incinerators shows that the new improved gas-fired domestic
incinerators have lower particulate emissions, and, in general,
egually low emissions of gaseous pollutants. Emissions from
improved gas-fired units were in most cases lower than those fron
other incinerators and large gas- and oil-fired industrial heating
units; they were much lower than those from automobile exhaust.
The results of the study provide a basis for modification of the
present restrictions in certain areas on the use of gas-fired
domestic incinerators and for confirmation of their present
acceptance in other areas.
1H975
Lee, R. C. and D. B. Wimmer
EXHAUST EMISSION ABATEMENT BY FUEL VARIATIONS TO PRODOCE LEAN
COMBOSTION. Preprint, Society of Automotive Engineers, Inc.,
New York, 20p., 1968. 15 refs. (Presented at the National Fuels
and Lubricants Meeting, Tulsa, Okla., Oct. 29-31, 1968,
Paper 680769.)
Differences in the power producing capacities and exhaust
emission characteristics of various spark-ignition-engine fuels
are freguently obscured by interactions involving the particular
engine system used in the comparison. In an attempt to
minimize this problem, gasoline, propane, methane, and a
hydrogen-methane fuel gas were compared in a single cylinder
engine under conditions that were optimum for each fuel. The
resulting data, coupled with an estimated duty cycle
564 HYDROCARBONS AND AIR POLLUTION
-------
representative of traffic service, permitted the development
of internally comparable data on fuel consumption and exhaust
emissions. Smog-inducing hydrocarbon emissions from the exhaust
of a propane-fueled engine can be less than 13% of the minimum
value obtainable with a gasoline fueled engine. Such emissions
would be substantially eliminated with a well designed methane
engine. Engines designed for propane and methane should have
substantially no carbon monoxide in the exhaust, and only
i»0-50% as much nitric oxide as an engine designed for gasoline.
In addition, lower specific fuel consumptions are possible with
propane and methane. These benefits are primarily the result
of better lean combustion performance with the two gaseous
fuels. It is recognized that a fuel gas that might be
steam-reformed from a liquid fuel would have even better lean
mixture combustion behaviour and lower emissions than propane
or methane. (Author abstract modified)
15257
Groezinger, H.
IMPROVEMENTS IN EXHAUST GAS COMPOSITION OF CARBURETOR ENGINES.
(Abgasentgiftung bei Vergasermoteren). Text in German.
Hotortech. Z. (Stuttgart), 29 (9):355-365, 1968. 14 refs. >
Recently developed measures for reducing automotive emissions are
reviewed. The carburetor, the ignition system, the shape of the
combustion chamber, stroke vs bore ratio, design of the intake
pipe, and the cooling system are responsible for the amount of
emissions. The amount of CO and hydrocarbon emissions can be
reduced (1) by oxidizing the CO and the unburnt hydrocarbons
in the exhaust system through air injection (afterburning) and
(2) by limiting the emissions from the cylinders. Optimum
reduction of emissions through afterburning depends on an
adequate air injection, a carefully adjusted fuel-to-air ratio,
and on a proper timing of ignition. Measures involving the
carburetor include a limiting device for maximum and minimum
fuel-to-air ratio at idling engine, a device for thorough fuel
mixing at idling and partially loaded engine, adjustment of
the fuel/air ratio at idling engine to the different frictional
forces of new and used engines, closer tolerance of the bypasses,
exact adjustment of the temperature of the fuel/air mixture to
the temperature of the engine, etc. Transport of the fuel/air
mixture to the cylinders and uniform distribution are of great
importance for emission control. Several illustrations of
the distribution of the fuel/air mixture by various types of
carburetors are given. Improvements through modification of the
carburetor are indicated in graphs. In California, hydrcarbon
emissions by automobiles have been limited to 275 ppm, CO
emission to 1.5%. In 1969, the Federal Republic of Germany
will limit CO concentrations at idling engine to 1.5%.
15271
Andersen, Holger C.
CLEANING OF INDUSTRIAL GASES WITH PRECIOUS HETAL CATALYSTS.
(Industrielle Gasreinigung mit Edelmetallkatalysatoren). Text
in German. Dechema Monograph., 40 (616-6U1):325-33, 1962.
28 refs.
- E. Control Methods • 565
-------
The applications of platinum metals as catalysts for removing
acetylene from olefins, cleaning coke-oven gas, and treating
residual gases from the nitric acid production are reviewed.
Of the family, platinum palladium is particularly suited for the
hydration of acetylene so that only a few ppm remain. Recent
laboratory tests indicate that at gas throughputs of up to
4500 standard cu m/hr/cu m catalyst, .the addition of hydrogen
can be reduced to a mole ratio between hydrogen and acetylene
of 2. In the case of coke-oven gases, acetylene, nitrogen oxides,
carbon oxysulfide, and diolefins are converted into harmless,
easily removable compounds by palladium and ruthenium catalysts.
Catalytic treatment of residual gases from nitric acid
production has three goals: the removal of noxious components,
recovery of the nitrogen in pure form for re-use at the ammonia
synthesis, and production of heat. Recent laboratory tests show
that the process can reduce the nitric oxide content of waste
gases to 9 ppm.
15321
Eberan-Eberhorst, H.
FOBWABD-LOOKING EXHAUST GAS RESEARCH FOR THE AUTOMOTIVE PETROL
ENGINE. (Abgasforschung zukunftsweisend fuer" den Fahrzeug-
Otto-motor). Text in German. Hotortech. Z. (Stuttgart),
30(9):315-323, Sept. 1969. 18 refs.
The influence of engine operation modification on the emission of
such exhaust gas components as CO, hydrocarbons and nitrogen oxides
is discussed. The use of an evaporator helps reduce carbon
monoxide emission to the lowest possible concentration. A spinning
motion in the air intake pipe also reduces the CO content. The
type of carburetion has almost no effect on the CO or hydrocarbon
emission. Study of the influence of temperature cooling agent on
hydrocarbon emission showed that emission could be considerably
reduced by raising the temperature of the agent. When the engine
acts as a brake, hydrocarbon emissions jump to high concentrations
due to misfiring. Spiral-like intake pipes or vortex-imparting
installations in the intake system, tangential inlets or deflector
valves have a considerable influence on hydrocarbon emission, which
is decreased because the wall layer is completely burned due to
the higher turbulence. This however, costs power. Compression
of the intake air and spark timing also reduce these emissions.
With a commonly used idling mixture containing 3% CO, the
hydrocarbon emissions of a 1-liter four cylinder engine were
reduced from 1720 ppm at 30 degree ignition advance to 180 ppm
at 18 degree ignition delay. The emission of nitrogen oxides can
be reduced by exhaust gas return to the fresh air which reduces
the caloric value of the fuel/air mixture and by water injection
into the intake pipe. Tests with the latter method showed that
nitrogen oxide emissions could be reduced from 2000 ppm to 583 ppm.
At lamda equal to one, a 20% addition of exhaust gas has the same
effect as water injection at a water to fuel ratio of 1:2.
15327
Rothe, Wilfried, Karl Achenbach, and Guenther Bretschneider
NEW PROCESS FOR DESULFORIZATION OF HYDROCARBONS AND TECHNICAL
GASES. (Ein neues Verfahren zum Entschwefeln von
566 HYDROCARBONS AND AIR POLLUTION
-------
Kohlenwasserstoffen und technischen Gasen). Text in German.
Erdoel Kohle (Hamburg), 17 (5):352-356, Hay 1964. 37 refs.
J newly developed process for desulfurization of aliphatic,
naphthenic, and aromatic hydrocarbons with sodium oxide or
sodium hydride is described. Gaseous hydrocarbons are passed
over sodiua oxide tablets or granules; the best results were
achieved with a 1:1 mixture of Na20 and NaCl. The reaction of the
sulfur compounds with Na20 follows the equation 2Na20 + BSE
yields Na2S + 2NaOB, where R equals an organic radical or H.
St the prevailing temperature, NaOH dissociates again with
separation of carbon. A theoretical quantity of 124 g Ha20 is
necessary for binding 32 g of sulfur; otherwise 200 kg of the
Sa20-HaCl desulfurizing mixture can bind 25.8 kg sulfur. In
experiments with a scaled-down model, 9 to 10 kg s (more than
70% of the theoretical value) were bound per 100 kg desulfurizing
mass. In the laboratory, gasolines with various boiling points
were evaporated at temperatures from 150 to 200 C and passed over
the Na20-NaCl mass which was heated to 220 C. The results showed
that 95 to 99$ of the total sulfur could be removed. The
successful laboratory results encouraged experiments with a 0.5
ton/day model. Light gasolines with sulfur content of less than
6 ppm and benzenes with sulfur content of less than 5 ppn were
used. The theoretical absorption capacity could not be reached,
owing to traces of moisture and organic nitrogen and oxygen
compounds. The process can also be used for cleaning technical
gases such as nitrogen and hydrogen.
15343
lumiaro, Pentti
THE TECHNICAL PBINCIPLE OF OPERATION OF EXHAUST GAS P0BIFIEBS.
(Pakokaasunpuhdistimien teknillinen toimintatapa). Text in
Finnish. Teknillinen Aikakauslehti, no. 4:71-73, April 1969.
The main principle of exhaust purification for internal
combustion engines is as complete a combustion as possible.
About 20-30% of the hydrocarbons reaching the tailpipe are
derived from crankcase ventilation. The air injection reactor
(AIH) system used by three large 0. S. automobile manufacturers
offers no advantages in terms of fuel consumption and slightly
decreases the net capacity of the motor. The controlled
combustion system (CCS) used by General Motors preheats the
air arriving at the cylinder intake while the motor is warming
up or during idling or low-speed operation. Volvo passenger
cars make use of twin carburetors in conjunction with CCS, which
offers the advantage of a slight fuel economy.. The Chrysler
flotors cleaner air package (CAP) makes use of a special vacuun
valve used in conjunction with new types of carburetor,
distributor, and gear box. This valve interprets motor speed
and load in such a way as to control the timing of ignition in
the distribution. Use of transistorized ignition systems has
been abandoned as impractical, but thyristorized ignition has
been successfully tested on numerous vehicles. Since the
lifetime of motor vehicles in Finland is about 9 years, there
are many American vehicles lacking exhaust purification, whereas
Volvo cars always have had exhaust purifiers as standard
equipment. Exhaust purification laws would thus tend to favor
Scandinavian industry. The argument that domestic manufacturing
E. Control Methods 567
-------
of autos would help combat pollution seems absurd when Finnish
manufacturers are constantly marketing motorized appliances that
foster pollution and have been banned in Sweden for this reason.
151H8
HOT GAS ENGINE REVIVAL. Design Components Eng., no. 2:10-13,
Jan. 15, 1969.
A description of the hot gas engine used to decrease air
pollution by diesel fumes is1 presented as developed by the
Philips Research Laboratories at Eindhoven in Holland. All
hot gas engines depend on compressing a gas at high temperature
and expanding it to a low temperature, allowing the gas to do
work on a piston. Heat is conserved within the engine by
incorporating a heat exchanger between the permanently hot
chamber and the permanently cold chamber. The regenerator
receives heat from the media during expansion and returns it
to the media during recompression, when the gas is again pushed
back into the hot chamber. Host of the multi-cylinder engines
are based on.work carried out on single-cylinder units. The
invention of the rhombic drive enabled the use of the out-of-
phase layout and obviated the need for the pressurized crankcase.
It consists of a geometric shape enclosed by the piston rod yoke
and displacer rod yoke, and their associated connecting rods
at any position during the engine cycle. The working gas is
maintained at high pressure by an ancilliary pump which serves
to vary the mean effective pressure within the cylinder and
the power developed by the engine. A cylinder burner air
preheater shrouds the nest of heater tubes during engine
operation. The "roll-sock1 seal is used to seal the piston rod
and prevent oil frcm entering the cylinder from the crankcase.
Analyses carried out on the burner exhaust gases revealed
the following: 1-2 ppm of unburnt hydrocarbons, 0.007-
0.030% carbon monoxide, and 100-200 ppm nitrogen oxides.
15K53
AUTOMATED LIKE FOR THE PRODUCTION OF EXTRUDED AIR ROTORS. Mach.
Prod. Eng., 113 (2917):7t8-752, Oct. 9, 1968.
The General Motors air injector reactor, used with high-
performance automobile engines and in cars equipped with manual
transmissions, controls the exhaust emission of hydrocarbons and
carbon monoxide. Fresh air is injected into the engine exhaust
ports to produce a higher degree of afterburning and to ensure
that the final exhaust gas composition is acceptable.
Supplementary air is supplied by pumps. Possible methods were
studied for mass production of the air pumps at the rate of
13,000 per day. Raw material and machining requirements were
reduced and stronger parts obtained when the air pump rotors
were cold extruded: the slug is sheared from a bar, coined,
extruded, and restruck. Slug shearing is carried out on a Verson
250-ton press operating at 60 strokes per minute. Sheared slugs
are rolled down a discharge chute to a conveyor which delivers
them to an automatic weighing and segregating unit. Acceptable
slugs drop into one chute; overweight and underweight slugs slide
down separate chutes. Upsetting of the sheared slugs is perforned
on a Bliss 800-ton knuckle-joint press. Upset slugs are washed
568 HYDROCARBONS AND AIR POLLUTION
-------
and receive a normalizing annealing treatment to produce a uniform
structure and a hardness of 45 to 50 Rockwell B. Prior to
extrusion, the slugs are cleaned, phosphate coated, and
lubricated. Extrusion of the rotors is carried out on a Clearing
1500-ton, eccentric, gear-driven mechanical press. Final forming
of the closed bottoms of the rotors is carried out by a testrike
operation performed on a Bliss 1500-ton knuckle joint press.
Piercing of slots in the rotors and formation of notches to
serve as chipbreakers during subseguent machining are performed
on a Danly 100-ton press. External surfaces are finished on
Landis plunge grinding machines; bores are finished on Bryant
Centalign internal grinding machines. Air sealing between the high
and low pressure areas of the pumps is provided by spraying
exterior surfaces of the rotors with an abradable coating.
15513
Jackson, Marvin W.
EXHAUST HYDROCARBON AND NITROGEN OXIDE CONCENTRATIONS WITH AN
ETHYL ALCOHOL-GASOLINE FUEL. Preprint, Society of Automotive
Engineers, Inc., New York, 33p., 1964. 29 refs. (Presented
at Society of Automotive Engineers Summer Meeting, Chicago,
June 8-12, 1964.)
The exhaust hydrocarbon and nitrogen oxide concentrations of a
single-cylinder engine operating on a 25% wt ethyl alcohol-75S
gasoline fuel are compared to those of the same engine operating
on gasoline. Comparisons at an air-fuel ratio below 15.3 indicate
that adding ethyl alcohol to gasoline reduces exhaust
hydrocarbon concentrations but increases nitrogen oxide
concentrations. At an air-fuel ratio higher than 15.3 ethyl
alcohol reduces both hydrocarbon and nitrogen oxide concentrations.
However, tests at the same air-fuel ratio indicate that ethyl
alcohol increases surge and, in some cases, results in a power
loss. To overcome these performance problems, the ethyl
alcohol-gasoline fuel must be operated at about the same percent
theoretical air as gasoline and comparative tests at the same
percent theoretical air show that the additive has little effect
on exhaust hydrocarbon and nitrogen oxide concentrations. The
fuel mixture offers no promise for reducing pollution by
automobiles. (Author abstract modified)
15526
Hitch, B. F., R. G. Ross, and H. F. McDuffie
TESTS OF VARIOUS PARTICLE FILTERS FOR REMOVAL OF OIL HISTS
AND HYDROCARBON VAPOR. Oak Ridge National Lab., Tenn.,
ORNL-TM-1623, 26p., Sept. 7, 1966.
CFSTI: TM 1623
Various filter and adsorbent materials were examined for
possible use in removing oil mists and hydrocarbon vapors. A
controlled flow of oil was injected into a heated nickel
reaction vessel to cause vaporization and some cracking of the
oil. Helium flowing through the reaction vessel carried the
oil mist and hydrocarbon vapor through a filter system. Filter
effectiveness was determined by the use of a hydrocarbon
E. Control Methods 569
-------
detector, gravimetric analysis, and gas chromatographic
analysis. Good removal of mists was achieved by the use of a
combination of felted metal fibers, and ceramic fibers in a
configuration proposed for use in the molten salt reactor
experiment. Granulated charcoal removed hydrocarbon vapors
(C6 and above) in a manner consistent with the established
adsorption isotherms for this material. (Author abstract
modified)
15614
Olesov, N. A.
EFFECT OF NAPHTHENIC SOAP ON THE PROPERTIES OF INDUSTRIAL DUST.
(Deystviye mylonafata na svoystva tekhnologicheskoy pyli). Text
in Russian. Tsement, no. 9:14-15, 1969. 3 refs.
Pilot-plant studies revealed that the introduction of naphthenic
soap into furnace flue gas increases the fluidity of the dust by
approximately 20% and reduces R20 (R is an unspecified radical)
and S03 content of the dust by a factor of about two. The
specific resistivity of a layer of collected dust remained within
the same limits as dust without the additive (1000 to 10,000
megohm—cm) thus maintaining electrostatic precipitator
effectiveness. Addition of naphthenic soap to dry ground raw
material such as cement increased the mobility of the raw
material powder by 6-7% and its volumetric weight by 5-7%. In
addition, the load on the main grinder drive was reduced by 5%,
improving grinder operation and reducing power consumption. The
experiment lasted for 70 hrs, during which time 2.93 tons of dry
naphthenic soap were introduced.
15765
Newman, Daniel J.
ELIMINATION OF NITROGEN OXIDES FROM GAS STREAMS. (Chemical
Construction Corp., New YorX) D. S. Pat. 3,467,492. 6p., Sept.
16, 1969. 2 refs. (Appl. Nov. 6, 1964, 13 claims).
Conventional processes for eliminating nitrogen oxides from waste
gas streams, such as tail gases from nitric oxide production,
involve reacting methane with waste gases in one catalytic step,
after which the waste gas is passed through a waste heat boiler
and/or a gas turbine; or in two catalytic beds with intermediate
cooling. The former method presents difficulties in design and
operation; the second requires an intermediate exchanger or
boiler, as well as ancillary control devices. In the present
invention, nitrogen oxides are eliminated by a seguence involving
two or more catalyst beds. The waste gas stream is divided into
at least two portions; one portion is heated to 900 F and mixed
with a proportion of methane less than the stoichiometric
requirement for complete reaction with the oxygen and nitrogen
oxides contained in the first portion. The gas mixture is then
passed through the first bed where the stream temperature is
raised to 1000-1400 F. Because the reaction with methane is not
complete, the catalyst bed is not subjected to overheating and
deterioration. The reacted gas mixture from the first bed is
then- quench-cooled to 900 F by the addition of a second portion of
570 HYDROCARBONS AND AIR POLLUTION
-------
methane and cold waste gas. If only two teds are used, sufficient
methane is added between beds to react with all the nitrogen
oxides, and a final reacted stream free of nitrogen oxides is
produced from the second bed. Advantages of the process are the
substantial savings resulting from the elimination of the
intermediate exchanger and reduction of the six of the heater
required to preheat gases. In addition, improved operation is
provided because the valves controlling the flow of waste gas and
intermediate mixtures can be operated at low temperature.
15772
Okuno, Tosihide
THE REACTION BAD ODOB SUBSTANCES HITH OZONE. (Akushu seibun to
ozon no hannosei). Text in Japanese. Kogai to Taisaku (J.
Pollution Control), 5 (8):633-639, Aug. 15, 1969. 8 refs.
The removal of industrial odors by the use of ozone oxidation was
studied, and their properties and behavior were described with the
introduction of electron theory. Malodorous components are amine-
ammoniacal compounds, lower aliphatic acidic compounds,
sulfurous compounds, ofefin-paraffin hydrocarbons, and other
organic compounds. Olefinic hydrocarbons have a characteristic
odor and a reaction mechanism for olefinic hydrocarbons and ozone
was described. One of the most general reactions of the carbon-
carbon double bond is an addition of ozone and rearrangement of
the resultant ozonide whereby the ozonide is directly
hydrolyzed by boiling with water. Secondary and tertiary amines
were employed to examine reactivity and reaction products.
Reactivity was determined by measuring residual ozone quantity,
and reaction products were monitored by gas-chromatography.
Tertiary amines reacted extensively with ozone and formed various
compounds. Acrylic ester monomer, used as a raw material of
acrylic acid resin, is very odorous. An oxidation experiment
using acrylic ester and methacrylate was done for the removal of
this odor. Acrylic ester reacted faster than methacrylate; a
reaction of acrylic ester with ozone proceeded relatively fast,
so this odor can most readily be removed by selecting appropriate
reaction conditions. In conclusion, not all odorous components
can be removed by ozone oxidation, due to the difficulty in
reducing 1 ppm of malodorous components to 1 ppb (99.9% removal
rate). Optimum reaction conditions and apparatus must be found
for the use of ozone reaction methods on odorous sources.
15778
PROCESS OF PURIFYING GASES, ESPECIALLY SYNTHESIS - AND FUEL-GASES.
(Gesellschaft fuer Lind's Eismaschinen A. G., Hoellriegelskreuth,
Germany and Lurgi Gesellschaft fuer Haermetechnik m. b. H.)
British Pat. 692,804. 13p., June 17, 1953. (Appl- Sept. 13,
1950, 16 claims) .
A process for purifying gases derived from synthesis, cracking,
hydrogenation, and other chemical processes was invented.
Undesirable components'of the gases, particularly hydrogen sulfide,
organic sulfur compounds, carbon dioxide, resin-forming coapounds,
and low boiling hydrocarbons, are removed simultaneously
in a washing and cooling process. The washing operation' is done
E. Control Methods 571
-------
at 0 C or lower and 2 atra pressure with a polar washing agent.
The washing operation can be carried out in a series of stages with
the same or different washing agent. The freezing point of the
washing liquid must by lower than the washing temperature. The
liquid is usually composed of oxygen-containing compounds such as
low molecular weight alcohols, ethers, esters, ketones, and organic
acids or nitrogen-containing compounds such as ammonia, amines,
and pyridine bases. Complex-forming metal salts may be added
to the washing agent to increase the solubility of all the
components to be washed out. The regeneration of the washing
agent is done in stages to remove the substances separately in a
concentrated form.
15836
Hooker, George W., Lewis R. Drake, and Stephen C. Stowe
SOLPHOB DIOXIDE RECOVERY METHOD. (Dow Chemical Co., Midland,
Hich.) 0. S. Pat. 2,368,545. Up., Jan. 30, 1945. (Appl. Aug. 18,
1939, 11 claims).
A method for recovering substantially pure sulfur dioxide from
mixtures with other gases or low boiling hydrocarbons involves
the absorption of sulfur dioxide in liquified diolefin sulfones,
preferably butadiene sulfone and isoprene sulfone. Equimolar
mixtures of these or other cyclic sulfones, obtained by melting
or by addition of a solvent, have great absorptive capacities
for sulfur dioxide. Gaseous mixtures can be treated in
scrubbing towers or other equipment suitable for extractants.
Sulfur dioxide is evaporated from mixtures by warming the sulfone
solution between 70-100 C, the temperature range below that at
which sulfone decomposes. The vaporized sulfur dioxide is
collected in the usual manner and the extractant is recovered for
further use. Other compounds in the sulfur dioxide mixture are
relatively unaffected by the sulfone treatment. The ratio of the
recovered sulfur dioxide is four times that of sulfur dioxide
recovered by using water as an extractant. In addition, sulfone
treatment, unlike water treatment, does not involve the formation
of a corrosive acid solution. Suggested applications of the
method include the treatment of sulfur dioxide-nitrogen-oxygen
mixtures produced by sulfur oxidation processes and hydrocarbon
mixtures produced by petroleum processes.
15837
Hebbard, George M.
RECOVEHY OF SDIPHOR DIOXIDE AND DIOLEFINS FBOM SOLPHONES.
(Dow Chemical Co., Midland, Mich.) U. S. Pat. 2,384,376. 7p..
Sept. 4, 1945 (ippl. Nov. 3, 1941, 7 claims).
When liquified sulfur dioxide is used to separate diolfins such
as butadiene from cracked-oil gas or mixtures of the gas and
hydrocarbons, a sulfone is formed and then chemically
decomposed to form a gaseous mixture of sulfur dioxide and olefin.
Separation of the sulfur dioxide from the mixture by scrubbing
with water is unsatisfactory because of the heat required for
vaporization and the corrosive nature of the resulting snlfuric
acid. An improved method for recovering sulfur dioxide from a
sulfone thermally decomposes the sulfone, at pressures sufficient
372 HYDROCARBONS AND AIR POLLUTION
-------
to liquefy the mixture, in the presence of a liquid paraffin
hydrocarbon of boiling point higher than the diolefin. The
solvent also effectively separates the reaction products to
inhibit or prevent recombination into the sulfone. Suitable
solvents are hexane, octane, or decane and liquid petroleum
factions such as gasoline,'naptha, or kerosene. The sulfone-
sol vent mixture is passed through the heating zone of a 'sulfone
decomposer* and heated to 120-150 C. Here the sulfone is
partially decomposed into sulfur dioxide and the diolefin. The
resulting liquified mixture is then cooled below 120 C and,
while maintained under pressure, passed to an extraction tower.
Additional quantities of liquified sulfone are passed through the
tower in countercurrent flow. The resulting solution of sulfur
dioxide and sulfone is continuously withdrawn from the bottom
of the tower; the solution of diolefin and 1 quid paraffin
hydrocarbon is continuously withdrawn from the bottom of the
tower. The reaction products of the solution are vaporized
and collected in a form of 95% or higher purity. The solvent
is cooled and returned to the tower for recyling.
15861
Johnson, Ava J.
PKOCESS FOB THE SEPARATION OF ACIDIC GASES FHOH FLUIDS. (Shell
Development Co., San Francisco, Calif.) 0. S. Pat. 2,368,595.
Up., Jan. 30, 19U5. (Appl. Aug. 29, 19U1, 7 claims).
The invention describes process for removing acidic gases, such
as H2S, C02, HCN, S02, found in natural gas, petroleum fractions,
and coke oven gas from a water immiscible fluid. It deals
especially with the purification of normally gaseous hydrocarbons
containing objectionable quantities of H2S. The method consists
of scrubbing the flowing fluid at an elevated pressure of 200-1000
pounds per square in. with a nonalkaline water. A portion of the
acid gas is extracted by the nonalkaline water to form acidulated
water and a first residal fluid. The acidulated water is
separated from the first residual fluid. The residual fluid is
then scrubbed with a lean base solution chosen from organic
hydroxy aoino bases or salts of inorganic strong bases and
relatively weak acids of low volatility. Another portion of the
acid gas is extracted to form a fat solution and a second residual
fluid. The fat solution is separated from the fluid and refluxed
with steam at a lower pressure to produce a vapor composed of acid
gas, steam and a residual lean base solution for use in another
scrubbing cycle. The acidulated water is stripped with steam
vapor to vaporize the acid gas and condense water substantially
free of the acid gas. The invention accomplishes a high degree of
purification of fluid with a sinimum expenditure of heat for
regeneration of the absorption medium.
15862
Rosenstein, ludwig
GAS PURIFICATION AND SEPARATION PROCESS. (Shell Development Co.,
San Francisco, Calif.) 0. S. Pat. 2,368,600. 5p., Jan. 30, 19U5.
(Appl. Jan 2U, 19U2, 5 claims).
The invention increases the efficiency of processes for reaoving
H2S, HCN, C02, etc., from hydrocarbon liquids by reducing the
E. Control Methods 573
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amount of heat required for regeneration or by removing more
inpurity from a spent solution with a given amount of heat. The
fluid is contacted in a scrubber with a heat-regenerable absorbent
solution to form a fat, or spent, solution which contains the
impurities. The absorbent solution i.e., aqueous Na2C03 or
aqueous K3P04, contains a solute which removes the impurities and
a solvent which vaporizes above the boiling point of the
impurities. The fluid is separated from the fat solution which is
regenerated at reduced pressures for further scrubbing. The
improvement in the invention comprises the regeneration of the fat
solution in a primary stripper to produce a lean solution and
vapors. The vapor is composed of gases from the solvent and
impurities. A further portion of the lean solution is regenerated
in a secondary stripper in indirect heat exchange with the vapors
at a greater pressure than in the primary stripper. A secondary
lean solution and secondary vapors are produced which also contain
gases from the solvent and impurities. The vapors from both
strippers are cooled to produce a condensed solvent and vapor
containing the impurities. The solvent is separated from the
vapor and added to the secondary lean solution. The lean
solutions are put into the scrubber in a way that the fluid first
contacts the primary and then the secondary lean solution. Fluids
that can be scrubbed by the process include natural gas, refinery
gas, coke-oven gas, smelter gas, other manufactured gases as well
as liquid hydrocarbons.
15875
Hooker, George B. and Franc A. landee
SEPARATION OF SDLPHOR DIOXIDE AND LOW-BOILING HYDROCARBONS FROM
HIXTURES THEREOF. (Dow Chemical Co., Midland, Hich.) U. S.
Pat. 2,384,378. 5p., Sept. 4, 1945. (Appl. Nov. 3, 1941,
4 claims) .
The invention concerns the separation of mixtures of sulfur
dioxide and aliphatic hydrocarbons, and particulary the separation
of sulfur dioxide and conjugated diolefines to recover each
in an anhydrous and purified form. Separation is acheived
with two extractants: a liquified organic sulfone and a liquid
paraffin hydrocarbon having a boiling point of at least 20 C,
Sulfur dioxide is preferably separated from a conjugated
diolefine having 5 or less carbon atoms by passing it into the
mid—section of an extraction tower. At the same time, a liquid
fraction of petroleum is passed into the bottom of the tower.
A liquified sulfone of the conjugated diolefine is passed into
the tower at the top and dispersed. The flow of liquids is
from the tower is under a superatmospheric pressure so they
remain in liquid form. During the separation process, the
resultant extract of liquid petroleum and conjugated diolefine is
withdrawn from the top of the tower. The extract of liquified
sulfone and sulfur dioxide is withdrawn from the bottom of the
tower, the sulfur dioxide vaporized to leave the sulfone in
condition for recycling.
15895
Saitoh, Takeshi, Kazuhiko Takaichi, Hasakuni Hirata, and Hasaaki
Hattori
574 HYDROCARBONS AND AIR POLLUTION
-------
THE POSSIBILITY OF AUTOMOBILE AIR POLLUTION CONTROL BY LOU
PRESSURE PETROLE INJECTION SYSTEM. (Teiatsu gasorin funsha
hoshilci ni yoru haiki kaizen no kanosei) . Text in Japanese.
Waseda Daigaku Fikogaku Kenkyusho Hokoku (Bull. Sci. Eng. Res,
Lab., Waseda Univ.). no. 45:6267, 1969.
The fact that automobile emissions can be controlled by petrole
injection is well known. The possibility that manifold gasoline
injection at a pressure less than 16 atg can reduce carbon
monoxide and hydrocarbon contents in engine exhausts was
investigated. Injection systems with one, two, three, and four
element pumps and nozzles were used which corresponded to the four
cylinder engine. Carbon monoxide and hydrocarbon concentrations
were measured in various engine loads and speeds and compared
with the carburetor system. The results showed that systems with
only one or two elements could reduce carbon monoxide
concentrations, but not the hydrocarbon content. Three or four
elements in the system were reqired to reduce both carbon
monoxide and hydrocarbon emissions, but this was less than the
expected value. (Author abstract modified)
15911
Tow, Philip S.
CONSIDERATIONS OF THE FEASIBILITY OF CONTROL Of OXIDES OF
NITROGEN. J. Air Pollution Control Assoc., vol. 7:234-240, Nov.
1957. 28 refs.
A review of existing theories of the role of nitrogen oxides and
hydrocarbons in ozone and smog formation is followed by a
consideration of the nature and contribution of various sources
of nitrogen oxides in Los Angeles County and an evaluation of
methods for controlling the oxides. In Los Angeles, nitrogen
oxide emissions are primarily the result of nitrogen fixation in
combustion processes, according to the equilibirum N2 plus 02
equals 2ND. Variables in combustion processes are temperature,
excess air, and in the case of automobiles, engine acceleration
rate. Theoretical and experimental data show that there is no
ready solution for the control of nitrogen oxides as a general
atmospheric contaminant. Much experimental work needs to be done
before satisfactory devices are developed. The importance of
research on the catalytic decomposition of nitric oxide is
stressed. It is also suggested that methods of accelerating vapor
phase reactions of NO may have applications for controlling
nitrogen oxide emissions from stationary sources. Other possible
methods of control discussed are absorption, adsorption, and
changes in the design of combustion equipment or its operation or
changes in fuel.
15966
Jodeck, Paul
METHOD OF SEPARATING SOLPHOR DIOXIDE AND THE LIKE FBOH LIQUID
HYDROCARBONS. (Edeleanu GmbH, Berlin, Germany) U.S. Pat.
1,910,341. 4p., May 23, 1933. (Appl. Jan. 17, 1929, « claims).
A process for evaporating and recovering sulfur dioxide from
mixtures of liquid hydrocarbons and S02 is reported. A mixture
E. Control Methods 575
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is forced under sustained pressure through a series of alternate
heating and separating containers. Sulfur dioxide gas is allowed
to evolve in each heating container and is separated from the
liquid in the following separating container. The remaining
liquid is raised to a higher temperature in the next heating
container. The gas is liquified as it evolves. This is cooled
in another container while still under sustained pressure. The
process has an important application for the refining of mineral
oils, increasing the capacity of the refining plant and
decreasing the cost of treatment.
15995
Herold, Paul and Georg Markus
RECOVERING HYDROGEN CHLORIDE AND SULPHUR DIOXIDE FROM GAS
MIXTURES. (Assignee not given.) U. S. Pat. 2,301,779. 2p.,
Nov. 10, 1942. (Appl. Nov. 19, 19KO, 3 claims).
A method of recovering hydrogen chloride and sulfur dioxide
separately from gas mixtures is described. A gas mixture is Hashed
with a medium liquid which consists of aromatic compounds
containing oxygen in an ethereal linkage and of aromatic compounds
containing oxygen in a phenolic linkage. Suitable compounds
are xylenol and diphenyl ether. The gas mixture may either be
passed through the liquid while it is stationary or led in a
counter-current to the liquid flowing down, preferably in
trickling towers charged with filter bodies. The hydrogen chloride
leaves the washing liquid in a dry state free of sulfur dioxide.
The washing liquid is easily regenerated by expelling the absorbed
sulfur dioxide by heating, applying reduced pressure, or by
subjecting it to both measures simultaneously. The washing
liquid can be reused after cooling.
15999
Bottoms, Robert Roger
PROCESS FOR SEPARATING ACIDIC GASES. (Girdler Corp., Louisville,
Ky.) 0. S. Pat. 1,83«,016. 5p., Dec. 1, 1931. (Appl. Oct. 15,
1930, 7 claims).
A process for the separation of acidic gases from other gases
by the use of an absorbent is described. A gas mixture containing
hydrogen sulfide, carbon dioxide, or sulfur dioxide, is brought
into contact with a liquid or gaseous absorbent. The absorbent
is usually a phenylhydrazine or a hydrazine hydroxide. The
solution is heated to free the absorbed gases and the absorbent
can be recycled.
16020
Clarice, P. J., J. E. Gerrard, C. N. Skarstrom, J. Vardi, and
D. T. Hade
AN ADSORPTION-REGENERATION APPROACH TO THE PROBLEM OF EVAPOHATIVE
CONTROL. Preprint, Society of Automotive Engineers, Inc., New
York, 1»p., 1967. 5 refs. (Presented at the Automotive
576 HYDROCARBONS AND AIR POLLUTION
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Engineering Congress, Detroit, Hich., Jan. 9-13, 1967,
Paper 670128.)
A device for preventing evaporative emissions of hydrocarbon fuel
from automotive vehicles is based on a controlled adsorption-
desorption cycling in a solid adsorbent system using activated
carbon. The system is capable of containing all types of
evaporative emissions: carburetor and tank running losses,
carburetor hot soak losses, and tank diurnal cycle losses.
The three essential components of the system are the canister of
adsorbent, the pressure balance valve, and the purge control
valve. The canister traps the vapors before they can escape
to the atmosphere and holds them until they can be fed back to
the engine. The pressure balance valve maintains metering forces
in the carburetor exactly as originally designed. Hhen the
engine is shut down, the valve closes all external vents and
routes vapors from the carburetor exactly as originally designed.
Hhen the engine is shut down, the valve closes all external vents
and routes vapors from the carburetor bowl to the canister. The
function of the purge control is program stripping of the cannister
and conseguent feeding of the hydrocarbon-laden, purge air stream
to the intake manifold. Evaporative emissions from cars on
which prototype devices were installed were measured according
to proposed California standards for carburetor losses per hot
soak and for fuel tanks. All data fell within a range of 0.3
to 109 grams, well below the proposed gram losses.
16124
Gross, Edward
DRIVING WITH HETHANE. Sci. News, 97(3):73-74, Jan. 17, 1970.
A dual-fuel system was developed which gives cars, trucks, and
buses the option of operating on gasoline or on the compressed
natural gas, methane. Converting the system is a simple matter
and the cost of an entire system is $350 (1970). The few moving
parts in the system and its adaptibility permits its continual
use. There are only three main functional parts to the systea:
the cylinders of compressed methane, the regulator, and the gas-air
mixer. The pressure cylinders, which range from 30-lb units
containing 100 cu ft of gas to 100-lb cylinders containing 300 cu
ft, can be put in or under the flatbed of a pickup truck; in the
trunk of a car; or under, in, or on a bus of truck. The function
of the regulator is to reduce the pressure of the gas coming from
the highly pressurized cylinder so that it can feed into the gas-
air mixer mounted on top of the carburetor. The mixer, the heart
of the system, is the equivalent of a carburetor and air filter
and replaces the ordinary air filter that sits on top of the
engine. Because of the limited mileage (two 300 cu ft cylinders
constitute 120 Biles), the system is not meant to be operated on
natural gas on the open road where auto emissions are not a
problem. It is mainly designed for stop-and-go city traffic.
Advantages include quick starting in cold weather, no vapor lock
in hot weather, and low maintenance costs because of cleaner fuel.
In addition, there is no venting of pollutants froa the fuel and
no safety problem because the natural gas is lighter than air and
rises. Disadvantages include the'amount of space taken up by the
cylinders because the engine is not modified in any way, and also
some power loss at high speeds. The system also accoaplishes a
90% redaction in emission of gaseous contaminants.
E. Control Methods 577
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16156
Bernhart, Alfred
AIR POLLOTION CONTROL EQUIPMENT FOE CABS. Eng. J- (Toronto),
52(12):12-16, Dec. 1969. 15 refs.
In North American cities, cars, trucks, and aircraft contribute
57% of the air pollutants; in los Angeles, the percentage is 68%.
At 50 mph, the average car emits 80 cu m/hr of exhaust gases which
contain 17 Ibs/hr carbon dioxide, 3.5 Ibs/hr carbon monoxide,
0.5 Ibs/hr hydrocarbons, 0.5 Ibs/hr nitrogen oxides, i» gram/hr of
lead particles, and O.t to 0.7 micrograms of benzo (a)pyrene.
Engine exhausts contribute 97% of the total carbon monoxide
emission, plus 65% of the total hydrocarbons, plus 100% of the
nitrogen oxides; crankcase ventilation, 3% of the total carbon
monoxide, plus 25% of hydrocarbons; carburetor, 5 to 10% of
hydrocarbons; and the gasoline tank, 10 to 15% of the
hydrocarbons. Combinations of crankcase emission return systems,
evaporation proof carburetors and gasoline tanks, crankcase
control devices, engine modification systems, or air injection
systems should reduce daily emissions to 2.<* Ibs of carbon
monoxide, 0.05 Ibs of hydrocarbons, and 0.08 Ibs of nitrogen
oxides. The devices will not reduce carbon dioxide emissions,
which are expected to increase from tO to 52 Ibs per day. The
cost of these devices will account for only 1.5% of the purchase
price of a car.
16159
Piatt, V. R.
SUBMARINE ATMOSPHERES AND AIR POLLUTION. Scientiae, 10«(687):358-
374, 1969. 9 refs.
The development of air purification and oxygen replenishment
systems for submarines is reviewed. The absorption of carbon
dioxide, which constitutes about 1% of submarine atmospheres, was
usually accomplished by soda lime in the 1920's and by lithium
hydroxide in the 1930's and 19«0's. Even today these are the
preferred absorbents when logistics permit replacement of used
cannisters or when submergence is less than two weeks.
Regenerative monoethanolamine must be used during the extended
submergence of nuclear submarines. Carbon monoxide
concentrations are kept within threshold limit values by
catalytic hydrogen burners, which also burn most of the
hydrocarbons present. since the major source of hydrocarbons in
submarines are paints, it is advisable to refrain from painting
for a month prior to and during submergence. Of other trace
contaminants, methane is most resistant to catalytic combustion.
Its sources are refrigerator gases and septic systems. Other
sources of gases include solvents, lubricating oils and greases,
medicines, diesel fuel, shaving lotions, and chemical fluids. By
controlling the quantity of these items, the contaminants are kept
to a few ppm at the most. On submarines oxygen is provided by
electrolytic generators that decompose water into oxygen and
hydrogen. Electrostatic precipitators remove most of the aerosols
from smoking and other sources, and filter some of the other
aerosols and adsorbable gases. The equipment is discussed in
terms of its application to open atmospheres.
578 HYDROCARBONS AND AIR POLLUTION
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16184
lang, Ludwig
AN APPARATUS FOE CLEANING THE EXHADST GAS OF AN INTERNAL
COHBDSTION ENGINE. (Nainenkikan no haikigasu o jokasuru sochi),
Text in Japanese. (Paul Heintz Fitteler, Germany.) Japanese Pat.
ShoHU-20525. 8p., Sept. 3, 1969. 1 ref. (Appl. Sept. 7, 1966).
With conventional cleaners for engine exhaust, difficulties arise
in activating the catalyst at low temperatures and keeping the
temperature constant without overheating the catalyst. The
present invention provides a solution to these problems of
catalytic exhaust gas. Exhaust gas is injected with air before
reaching the catalyst chamber which consists of two nozzle units,
one a blender and the other the catalyst housing. The catalyst is
formed into a basket shape. Its upstream side is covered with a
stream-lined thin, solid shell without a hole, its downstream side
with a shell with grooves or holes. one converging passage is
provided around the catalyst along the inner wall of the chamber
and another converging channel provided along the center line of
the catalyst. The end of the channel is partially or totally
closed. The device is a key to the present invention and is a
kind of improved bypass system. The catalyst oxidizes both carbon
monoxide and unburnt hydrocarbons. When the engine speed is low,
e.g., below 60 km/h, the mixture of air and gas is lead through the
catalyst. When the speed is high, the gas mixture is bypassed
around the catalyst, since the catalytic reaction is not required
at high temperatures.
16187
Chikira, Hiroo
EXHADST GAS CLEANER. (Haikigasu seijosochi). Tert in Japanese,
(Assignee not given.) Japanese Pat. ShoH«-22566. 3p., Sept. 26,
1969. 2 refs. (Appl. Hay 13, 1966).
An insulated chamber is located behind an engine manifold. The
interior of the chamber is kept at around 1000 C and provided with
air. Exhaust gas components such as carbon monoxide or
hydrocarbons are instantly burnt away. The device of the present
invention comprises a combustion chamber, a heat insulator, a
preheater, and a stirrer. The cylindrical combustion chamber is
composed of heat-resistant material. The heat insulator, which
consists of layers of reflecting insulators, surrounds the
combustion chamber. The preheater houses the heat insulator. Air
is first heated in the preheater before entering the combustion
chamber. Inside the combustion chamber, a stirrer is provided to
mix the exhaust gas with the air. Since carbon monoxide oxidizes
at 600-660 C, and hydrocarbons at 680-800 C, the chamber
temperature is high enough. The merits of the invention are that
no catalysts are used and that the chamber is compact enough to be
installed in narrow spaces near the engine. There is no loss in
engine power.
E. Control Methods 579
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16427
Downer, Whit
AMMONIA ABSORPTION: REFRIGERATION SELECTED FOR GASOLINE PLAHT.
Refining Eng., vol. 29:C25 to C30, July 1957. 1 ref.
a 200-ton capacity ammonia absorption refrigeration unit at a gas
processing plant chills incoming gas to 0 F for the separation of
gas liquids. The only moving component in the system is an
ammonia liquor pump: widely varying loads are automatically
handled with no mechanical adjustments required. Power
requirements are directly proportional to the refrigeration load.
Liquid recovery, based on the total available in the incoming gas
stream, is propane, 19%; butanes, 47S; and 14 BVP natural gasoline,
95%. This corresponds to a total liquid recovery of 25,800 gal
per day, including 8600 of propane, 7500 of butanes, and 9569 of
natural gasolines. The operation of the ammonia refrigeration
system, low temperature gas separator, and ammonia fractionator
is given in detail. Advantages of the absorption refrigeration
system are its low costs and operating flexibility. Though taking
up more room that a compression plant, the absorption unit is
constructed entirely out-of-doors: no buildings are needed to
protect the equipment. In small size ranges, the initial costs of
absorption systems are relatively high, varying from $700 to $1500
per ton of refrigeration. In contrast, initial costs for units
over 100 tons are less than $400 per ton.
16435
EXHAUST AIH PURIFICATION AND SOLVENT RECOVERY IN GHAVURE
PRINTING. Gravure, 1969:10-12, 6U, March 1969.
The operation and economic aspects of a German solvent recovery
system for gravure printing shops are reviewed. Exhaust air from
rotary presses is first forced through a filter to extract paper
dust and small paper particles and then through one or several
parallel adsorbers filled with activated carbon. Continuous
operation requires at least two adsorbers which can be charged
and regenerated alternately. Regeneration of the activated carbon
is accomplished by steam treatment, followed by drying and cooling
in gravel placed underneath the activated carbon layer. The
economic operation of the recovery system depends on a high
solvent concentration in the exhaust air and on automatic
operation. To eliminate variations in solvent content of the
exhaust gas, each exhaust pipe on the individual printing units
can be equipped with a shutter that closes automatically as soon
as the unit comes to a standstill; air free of solvent cannot be
exhausted. The solvent content of air from the adsorbers is
measured by continuously functioning analyzers. When small
amounts of solvent are detected, the adsorber in question is
automatically shut off from the exhaust air stream. Estimated
operating costs for recovering 98% or more of the toluol used
during printing are between $15-20 per long ton of toluol
recovered.
580 HYDROCARBONS AND AIR POLLUTION,
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16144
Varshavskiy, i. L. and R, V. Gargala
PROTECTION OF CITY MR FROM HOTOR VEHICLE EXHADST GASES.
(Zashchita vozdukha gorodov ot vykhlopnykh gazov avtotransporta).
Text in Russian. In: Sanitation Measures Against Air and Hater
Pollution in the Planning of Cities. (Ozdorovleniye vozdushnogo i
vodnogo basseynov gorodov). Government committee on civil
Building and Architecture (ed.). Lecture series no. 2, Kiev,
Budivel 'nik, 1968, p.56-61.
Carbon monoxide and hydrocarbon levels in areas of heavy traffic
in Moscow exceed permissible levels by as much as tenfold, even
though these conditions are far better than in 0. S. or West
European cities. Studies made in the USSR have shown that the CO
emission per km of travel of a motor vehicle depends on the travel
speed, road quality, and fuel system, but has little connection
with the amount of carbon monoxide given off during idling. Some
50 stations for dynamic testing of individual cars for harmful
emissions have been set up in Moscow. These stations make about
600,000 tests per year. Various means of improving combustion
and eliminating crankcase fumes are reviewed. The use of electric
cars, especially those utilizing direct conversion of chemical
energy of a fuel to electrical energy, is seen as the ultimate
answer to this problem. Research in this area is being carried
out in the USSR.
16184
Salooja, K. C.
CONTROL OF AIR POLLUTION DUE TO PETROL ENGINES. Chartered Hech.
Engr., 15(7):301-305, July 1968. 22 refs.
Four sources of major pollutants from vehicles are discussed.
The exhaust accounts for 6556; the crankcase, 20%; and the
carburetors and fuel tank, the remainder. Among engine design
features, the fuel-air system has the greatest influence on the
emission of pollutants. Fuel injection systems, although nore
expensive, eliminate the drawbacks of carburation. Variations in
fuel composition have little influence on exhaust emission. The
U. S. legal limits for carbon monoxide, hydrocarbons, and
nitrogen oxides in exhaust gasses are given. Methods, such as the
Han-air-ox system, of reducing CO as well as hydrocarbon
pollutants are discussed. The most useful future developments
will be those that improve the performance of the fuel-air
induction system, the exhaust manifold, catalytic converters and
after-burners. In addition, the concentrations of pollutants
in the atmosphere of busy thoroughfares injurious to health must
be determined.
161*86
Carter, J- H-
ADSORPTION PROCESSES, Chem. Process Eng., 47(8):37-44, iug. 1966.
30 refs.
E, Control Methods 581
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The fundamental principles of adsorption by molecular sieves for
the preparation of high-purity materials are discussed. The
concept of 'mass transfer zone' has been utilized in the design of
adrTbers. Both adiabatic and isothermal adsorption are surveyed.
The application of adsorption techniques provides pure hydrocarbon
feedstocks free from sulfur compounds, water, and carbon dioxide.
The physical features of useful adsorbents such as activated
alumina, silica gel and activated charcoal are characterized. The
amount of adsorbate an adsorbant material will take up at
equilibrium is important in determining the maximum capacity of
adsorption equipment. A simple circuit of a fixed adsorber bed,
the most widely-used form of adsorption plant, is shown and
discussed.
SEE PAGE 1041 IN PART II FOR COMPREHENSIVE-INDEX
582 HYDROCARBONS AND AIR POLLUTION
* U. S. GOVERNMENT PRINTING OFFICE ; 1970 O - 408-261
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