Technical Papers From The Leningrad International Symposium On The Meteorological Aspects Of Atmospheric Pollution


AMERICAN INSTITUTE OF CROP ECOLOGY
A RESEARCH ORGANIZATION DEVOTED TO PROBLEMS OF
PLANT ADAPTATION AND INTRODUCTION
WASHINGTON, 0. C.
TECHNICAL PAPERS FROM THE LENINGRAD INTERNATIONAL SYMPOSIUM
ON THE
METEOROLOGICAL ASPECTS OF ATMOSPHERIC POLLUTION
PART III

AICE* SURVEY OF USSR AIR POLLUTION LITERATURE
Volume XIV


Edited By
M. Y. Nuttonson



The material presented here is part of a survey of
USSR literature on air pollution
conducted by the Air Pollution Section
AMERICAN INSTITUTE OF CROP ECOLOGY
This survey is being conducted under GRANT R 800878
(Formerly R01 AP 00786)
OFFICE OF AIR PROGRAMS
of the
U.S. ENVIRONMENTAL PROTECTION AGENCY
~AMERICAN INSTITUTE OF CROP ECOLOGY
809 DALE DRIVE
SILVER SPRING, MARYLAND 20910
1972

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PUBLICATIONS of th« AMERICAN INSTITUTE OF CROP ECOLOGY
Ref.
No.
1	UKRAINE— Ecological Crop Geography of the Ukraine and the
Ukrainian Agro-Climatic Analogues in North America
2	POLAND-Agricultural Climatology of Poland and Its Agro-
Climatic Analogues in North America
3	CZECHOSLOVAKIA-Agricultural Climatology of Czechoslo-
vakia and It* Agro-Climatic Analogues in North America
4	YUGOSLAVIA-Agricultural CI imatologyof Yugoslavia and Its
Agro-Climatic Analogues in North America
5	GREECE-Ecological Crop Geography of Greece and Its Agro-
Climatic Analogues in North America
6	ALBANIA—Ecological Plant Geography of Albania/ Its Agri-
cultural Crops and Some North American Climatic Analogues
7	CHINA—Ecological Crop Geography of China and Its Agro-
Climatic Analogues in North America
8	GERMAN Y-Ecological Crop Geography of Germany and Iti
Agro-Climatic Analogues in North America
JAPAN (I)-Agricultural Climatology of Japan and Its Agro-
Climatic Analogues in North America
10	FINLAND- Ecological Crop Geography of Finland and Its Agro-
Climatic Analogues in North America
11	SWEDEN-Agricultural Climatology of Sweden and Its Agro-
Climatic Analogues In North America
12	NORWAY-Ecological Crop Geography of Norway ond Its Agro-
Climatic Analogues in North America
13	SIBERIA-Agricultural Climatology of Siberia, It* Natural Belts,
and Agro-Climatic Analoguei in North America
14	JAPAN (2)—Ecological Crop Geography and Field Practices of
Japan, Japan's Natural Vegetation, and Agro-Climatic
Analogues In North America
15	RYUKYU ISLANDS-Ecological Crop Geography and Field
Practices of the Ryukyu Islands, Natural Vegetation of the
Ryukyus, and Agro-Climatic Analogues in the Northern
Hemisphere
16	PHENOLOGY AND THERMAL ENVIRONMENT AS A MEANS
OF A PHYSIOLOGICAL CLASSIFICATION OF WHEAT
VARIETIES AND FOR PREDICTING MATURITY DATE5 OF
WHEAT
(Based on Data of Czechoslovakia and of Some Thermally
Analogous Areas of Czechoslovakia in the United States
Pacific Northwest)
17	WHEAT-CLIMATE RELATIONSHIPS AND THE USE OF PHE-
NOLOGY IN ASCERTAINING THE THERMAL AND PHO-
TOTHERMAL REQUIREMENTS OF WHEAT
(Based on Data of North America and Some Thermally Anal-
ogous Areas of North America In the Soviet Union and in
Finland)
18	A COMPARATIVE STUDY OF LOWER AND UPPER LIMITS OF
TEMPERATURE IN MEASURING THE VARIABILITY OF DAY-
DEGREE SUMMATIONS OF WHEAT, BARLEY, AND RYE
19	BARLEY-CLIMATE RELATIONSHIPS AND THE USE OF PHE-
NOLOGY IN ASCERTAINING THE THERMAL^AND PHO-
TOTHERMAL REQUIREMENTS OF BARLEY
.0 RYt CLIMATE fitLATIONSHIPS AND THE USE OF PHENOL-
OGY IN ASCERTAINING THE THERMAL AND PHOTO-
THERMAL REQUIREMENTS OF RYE
21	AGRICULTURAL ECOLOGY IN SUBTROPICAL REGIONS
22	MOROCCO, ALGERIA, TUNISIA-Phyilcal Environment and
Agriculture	
23	LIBYA and EG YPT—Physical Environment ond Agriculture. . .
24	UNION OF SOUTH AFRICA-Physical Environment and Agrl-
cultum, With 5p«!'.iol Reference to Winter-Rainfall Regions
25	AUSTRALIA-Physical Environment and Agriculture, With Spe-
cial Reference feo Winter-Rainfall Regions
26	S. E. CALIFORNIA ond S. W. ARIZONA-Physlcal Environment
ond Aorleulture of the Deiert Regions . , - , .
27	THAI LAND-Physical Environment ond Agriculture
28	BURMA-Phyiical Environment and Agriculture
28A BURMA-Diseases ond Pests of Economic Plants
28B BURMA-Climate, Soils ond Rice Culture (Supplementary In-
formation and o Bibl iography to Report 28)
29A VIETNAM, CAMBODIA, LAOS—Physical Environment and
Agriculture	
29B VIETNAM, CAMBODIA, LAOS-Diseases andPestsofEconomic
Plants	
29C VIETNAM, CAMBODIA, LAOS-Climatological Dota (Supple-
ment to Report 29A)
3QA CENTRAL and SOUTH CHINA, HONG KONG, TAIWAN-
Physical Environment and Agriculture	 $20.00*
SOB CENTRAL and SOUTH CHINA, HONG KONG, TAIWAN-
Major Plant Pests ond Diseases
31	SOUTH CHINA-lts Agro-Climatic Analogues in Southeast Asia
32	SACRAMENTO-SAN JOAQUIN DELTA OF CALIFORNIA-
Physicai Environment and Agriculture .....
33	GLOBAL AGROCLIMATIC ANALOGUES FOR THE RICE RE-
GIONS OF THE CONTINENTAL UNITED STATE
34	AGRO-CLIMATOLOGY AND GLOBAL AGROCLIMATIC
ANALOGUES OF THE CITRUS REGIONS OF THE CON-
TINENTAL UNITED STATES
35	GLOBAL AGROCLIMATIC ANALOGUES FOR THE SOUTH-
EASTERN ATLANTIC REGION OF THE CONTINENTAL
UNITED STATES
36	GLOBAL AGROCLIMATIC ANALOGUES FOR THE INTER
MOUNTAIN REGION OF THE CONTINENTAL UNITED
STATES
37	GLOBAL AGROCLIMATIC ANALOGUES FOR THE NORTHERN
GREAT PLAINS REGION OF THE CONTINENTAL UNITED
STATES
38	GLOBAL AGROCLIMATIC ANALOGUES FOR THE MAYA-
GUEZ DISTRICT OF PUERTO RICO
39	RICE CULTURE and RICE-CLIMATE RELATIONSHIPS With Spe-
cial Reference to the United States Rice Areas and Their
Latitudinal and Thermal Analogues in Other Countries
40	E.WASHINGTON, IDAHO, and UTAH—Physical Environment
and Agriculture
4' WASHINGTON, IDAHO, and UTAH-The Use of Phenology
In Ascertaining the Temperature Requirements of Wheat
Grown in Washington, Idaho, and Utoh ond in Same of
Their Agro-Climatieally Analogou1. Areas In the Eostern
Hemisphere
42	NORTHERN GREAT PLAINS REGION-Prelimlnary Study of
Phenological Temperature Requirement] of a Few Varieties
of Wheqt Grown In the Northern Great Plains Region and in
Some Agro-Cllmatically Analogous Areas in the Eastern
Hemisphere
43	SOUTHEASTERN ATLANTIC REGION-Phenologlcal Temper-
ature Requirements of Some Winter Wheat Varieties Grown
in the Southeastern Atlantic Region of the United States and
in Several of Its Latltudinally Analogous Areas of the Eastern
and Southern Hemispheres of Seasonally Sitrillor Thermal
Condition,
44	ATMOSPHERIC AND METEOROLOGICAL ASPEC TS OF AIR
POLLUTION—A Survey of USSR Air Pollution Literature
45	EFFECTS AND SYMPTOMS OF AIR POLLUTES ON VEGETA-
TION; RESISTANCE AND SUSCEPTIBILITY QF DIFFERENT
PLANT SPECIES IN VARIOUS HABITATS, IN RELATION TO
PLANT UTILIZATION FOR SHELTER BELTS AND AS BIO-
LOGICAL INDICATORS—A Survey of USSR Air Pollution
Literature
(Continued on inside of hack covei i

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AICE-AIR-72-U
AICE* SURVEY OF USSR AIR POLLUTION LITERATURE
Volume XIV
TECHNICAL PAPERS FROM THE LENINGRAD INTERNATIONAL SYMPOSIUM
ON THE
METEOROLOGICAL ASPECTS OF ATMOSPHERIC POLLUTION
PART III
Edited By
M. Y. Nuttonson
The material presented here is part of a survey of
USSR literature on air pollution
conducted by the Air Pollution Section
AMERICAN INSTITUTE OF CROP ECOLOGY
This survey is being conducted under GRANT R 800878
(Formerly R01 AP 00786)
OFFICE OF AIR PROGRAMS
of the
US. ENVIRONMENTAL PROTECTION AGENCY
•AMERICAN INSTITUTE OF CROP ECOLOGY
809 DALE DRIVE
SILVER SPRING, MARYLAND 20910
1972

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TABLE OF CONTENTS
Page
PREFACE 	 viii
ON THE REMOVAL OF IMPURITIES FROM THE ATMOSPHERE
BY CLOUDS AND PRECIPITATION
Ye. S. Selezneva and 0. P. Petrenchuk 	 1
SOME ASPECTS OF THE ADOPTION OF AUTOMATIC METHODS OF
DETERMINING ATMOSPHERIC POLLUTANTS
N. Sh. Vol'berg, G. V. Gal'dinov, and V. Z. Al'perin 	 9
RECORDING OF SULFUR DIOXIDE CONTENT AT THE OUTSKIRTS OF
A CITY. COMPARISON OF MEASUREMENT RESULTS FOR A VALLEY
AND AN ELEVATION
H. Mrose and W. Warrabt 	 18
THEORETICAL AND EXPERIMENTAL STUDY OF THE ASPIRATION
COEFFICIENT OF AEROSOLS
S. P. Belyayev, V. M. Voloshchuk, and L. M. Levin 		 30
MECHANISM OF PHOTOCHEMICAL POLLUTION OF THE URBAN ATMOSPHERE
M. T. Dmitriyev, N. A. Kitrosskiy, and V. A. Popov	 44
PROCEDURE FOR DETERMINING THE CONTENT OF TRACE ELEMENTS IN
PRECIPITATED WATER
T. N. Zhigalovskaya, R. I. Pervunina, V. V. Yegorov,
E. P. Makhon'ko, and A. I. Shilina	 59
CONTENT OF HEAVY METALS IN THE AIR OF CERTAIN REGIONS OF
THE USSR
T. N. Zhigalovskaya, V. V. Yegorov, S. G. Malakhov,
A. I. Shilina, and Yu. P. Krasnopevtsev	 69
ON THE DESIGN OF A MEASURING NETWORK FOR AIR POLLUTION
IN THE GERMAN DEMOCRATIC REPUBLIC
W. Warmbt 	 79
CONTENT OF PHOTOOXIDANTS IN URBAN AIR
Yu. G. Fel'dman			 88
STUDY OF AIR POLLUTION AND ATMOSPHERIC PRECIPITATION
RESULTING FROM ARTIFICIAL MODIFICATION OF CLOUDS
Sh. G. Gavasheli 	 96
iii

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Page
MICROCLIMATIC CHARACTERISTICS AND HYGIENIC EVALUATION
OF THE RELATIVE EMPLACEMENT OF INDUSTRIAL AND
RESIDENTIAL COMPLEXES IN THE REGIONS OF SIBERIA
L. I. Koldomasov and M. T. Zenin 	 100
NUMERICAL CHARACTERISTICS OF METEOROLOGICAL CONDITIONS
ASSOCIATED WITH PERIODS OF HEAVY ATMOSPHERIC
POLLUTION IN WESTERN SIBERIA
I. A. Shevchuk and L. I. Vvedenskaya	 103
EXPERIENCE IN SIMULATING THE PROPAGATION OF NOXIOUS
SUBSTANCES IN THE SURFACE ATMOSPHERIC LAYER OVER
PLANT SITES AND SURROUNDING GROUNDS
V. M. El'terman 	 108
SPECIAL CASES OF VERTICAL CURRENTS
I. G. Diaconescu, M. Frimescu, I. Moroianu, and
A. Moroianu 	 113
SYNOPTIC CONDITIONS OF FORMATION OF A VERY STABLE
ATMOSPHERIC BOUNDARY LAYER
F. Rein 	 118
iv

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CONTENTS OF PARTS I AND II*
of the AICE Translations of the
TECHNICAL PAPERS FROM THE LENINGRAD INTERNATIONAL SYMPOSIUM
ON THE
METEOROLOGICAL ASPECTS OF ATMOSPHERIC POLLUTION
Part I
ABSTRACT
M. Ye. Berlyand
INTRODUCTION
M. Ye. Berlyand
STATUS AND PROSPECTIVE DEVELOPMENT OF METEOROLOGICAL
STUDIES OF ATMOSPHERIC POLLUTION
M. Ye. Berlyand
EFFECT OF THE STABILITY OF THE ATMOSPHERE ON THE
DISSEMINATION OF GASEOUS POLLUTANTS
V. Parchevsky
METHOD OF DETERMINATION OF AVERAGE IMPURITY CONCENTRATION
NEAR AN ELECTRIC POWER PLANT BY MEANS OF AN ELECTRONIC COMPUTER
D. Sepeshi
METHODS OF CALCULATION OF THE SURFACE CONCENTRATION OF A
GASEOUS IMPURITY DISCHARGED FROM AN ELEVATED SOURCE
L. Nemets
RESULTS OF EXPERIMENTAL STUDY OF SMOKE PLUMES FROM THERMAL
POWER PLANTS
B. Bern
ATMOSPHERIC DIFFUSION AND STRUCTURE OF THE AIR FLOW ABOVE A
NONUNIFORM UNDERLYING SURFACE
M. Ye. Berlyand and Ye. L. Genikhovich
PROCEDURE FOR CALCULATING THE POLLUTION OF THE ATMOSPHERE WITH
DISCHARGES OF INDUSTRIAL PLANTS AND THERMAL POWER PLANTS
R. I. Onikul
STATISTICAL FORECASTING AVERAGE ATMOSPHERIC POLLUTION
A. Kaspshitzky
* Part I can be found in Volume XII and Part II in Volume XIII of the AICE Survey of USSR Air Pollution
Literature.
V

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METHOD OF CALCULATING THE DEGREE OF ATMOSPHERIC POLLUTION
K. Budzinsky
ON THE DETERMINATION OF DIFFUSION PARAMETERS FOR
ACTUAL LOCATIONS
A. Lehmann
TURBULENCE IN THE LOWER 500 M LAYER AND DIFFUSION OF
IMPURITIES
I. V. Vasil'chenko and P. A. Vorontsov
ATMOSPHERIC TURBULENCE AT SMALL HEIGHTS
N. Z. Pinus
Part II
AUTOMATION OF INFORMATION PROCESSING INVOLVED IN EXPERIMENTAL
STUDIES OF ATMOSPHERIC DIFFUSION
A. S. Zaytsev
MICROMETEOROLOGICAL CHARACTERISTICS OF ATMOSPHERIC POLLUTION
CONDITIONS
T. A. Ogneva
STUDY OF THE INFLUENCE OF IRREGULARITIES OF THE EARTH'S SURFACE
ON THE AIR FLOW CHARACTERISTICS IN A WIND TUNNEL
S. M. Gorlin, I. M. Zrazhevskiy, and S. P. Ziborova
USE OF PARAMETERS OF EULERIAN TURBULENCE FOR ESTIMATES OF
LAGRANGIAN CHARACTERISTICS
V. I. Ivanov
METHOD OF EVALUATING ATMOSPHERIC DIFFUSION FROM
TURBULENT CHARACTERISTICS
N. L. Byzova
SCATTERING OF SMOKE FROM A HIGH-LEVEL POINT SOURCE
Ye. K. Garger
DIFFUSION FROM A POINT SOURCE OF FINITE TIME OF ACTION
Yu. S. Osipov
USE OF SURFACE OBSERVATIONS FOR CHARACTERIZING THE STATE OF
THE SURFACE ATMOSPHERIC LAYER
G. B. Mashkova
vi

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SULFUR DIOXIDE AND DUST MEASUREMENTS IN MEASURING NETWORKS
OF THE HYDROMETEOROLOGICAL INSTITUTE
0. Muller
EXPERIMENTAL STUDIES OF ATMOSPHERIC POLLUTION IN
INDUSTRIAL AREAS
B. B. Goroshko and E. N. Zasukhin
FIELD STUDIES OF AIR POLLUTION IN THE AREA OF THE
SKAWINA ELECTRIC POWER PLANT
W. Parczewski
EFFECT OF METEOROLOGICAL CONDITIONS ON AIR POLLUTION IN
CITIES OF THE SOVIET UNION
E. Yu. Bezuglaya and L. R. Son'kin
vii

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PREFACE
The present volume constitutes Part III* of translations of papers
presented in Leningrad during July 1968 at the International Symposium on
Meteorological Aspects of Air Pollution. The original papers delivered
at the Symposium were edited by Prof. M. E. Berlyand and published as a
report in 1971 by the Hydrometeorological Publishing House in Leningrad.
The report contains a total of 40 papers, 37 of which are in Russian
and three, in German, together with their accompanying abstracts. In this
volume we present a collection of translations of the remaining papers from
the original report.
A review article by T. A. Ogneva, "International Symposium on Meteoro-
logical Aspects of Atmospheric Pollution" (Izv. VGO**, Vol. 101, No. 4, 1969,
pp. 395-396) provides interesting background material regarding the Symposium.
For this reason we present our translation of Ogneva's paper in the following
paragraphs.
"At the present time, considerable attention is being given to the study
of atmospheric pollution in order to improve the sanitary status of water and
air reservoirs in urban areas and workers' settlements and to intensify
measures aimed at the preservation of nature. In working out the measures
designed to decrease the pollution of air by noxious impurities, a special
role is played by the consideration of meteorological factors, that substan-
tially determine the behavior (dispersal) of impurities in the atmosphere.
This problem was the subject of an International Symposium on Meteorological
Aspects of Atmospheric Pollution, held in Leningrad at the A. I. Voeykov
Main Geophysical Observatory on 22-31 July 1968. The organizers of the Sym-
posium were the State Committee of the USSR Council of Ministers on Science
and Technology (Scientific Council on the Problem 'Protection of the Air
Reservoir from Pollution by Noxious Substances') and the Main Administration
of the Hydrometeorological Service, Council of Ministers of the USSR.
"The Symposium was attended by scientists and specialists (meteorologists,
hygienists, chemists, power engineers, metallurgists, etc.) from Bulgaria,
Hungary, Vietnam, the German Democratic Republic, Poland, Rumania, Czechos-
lovakia, and the Soviet Union. Forty-five reports were delivered, and there
was an animated discussion on the subjects of physical principles and methods
of calculation of dispersal of industrial emissions in the atmosphere; meteoro-
logical parameters determining atmospheric diffusion and intensity of atmos-
pheric pollution; procedures and equipment for observing atmospheric pollution,
* Part I can be found in Volume XII and Part II, in Volume XIII of the AICE Survey of USSR Air Pollution
L X10 1*91 U P6
** Izvestiya Vsesoyuznogo Geograficheskogo Obschestva, Tom 101, vip. h, Iyul' - Avgust 1969.
viii

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and experimental studies of pollution of the atmosphere by noxious impurities.
"On the first day, M. Ye Berlyand (Main Geophysical Observatory) reported
on the status and prospects of development of meteorological studies of atmos-
pheric pollution. He noted the following basic problems in the development of
further research: study of meteorological conditions in the presence of heavy
air pollution, including the mechanisms of turbulent exchange in the presence
of inversions, a complex topography, and urban buildings; development of auto-
matic and recording apparatus; study of the vertical distribution of noxious
impurities; accumulation of observational data and development of methods of
forecasting pollution, etc.
"in the report of I. L. Varshavskiy (State Committee of the USSR Council
of Ministers on Science and Technology), 'Basic Trends of Scientific Research
on Protection of the Mr Reservoir from Pollution' , the problems mentioned as
the major ones involved the study of the biological action and hygienic impor-
tance of atmospheric pollutants, the influence of meteorological conditions on
the distribution of noxious impurities in the atmosphere, the removal of nox-
ious impurities from waste gases of industrial enterprises, and the removal of
toxic components from the exhaust gases of internal combustion engines.
"Considerable interest was elicited by the report of M. S. Gol'dberg
(A. I. Sysin Institute of General and Communal Hygiene) on the 'Hygienic Stan-
dards for the Maximum Permissible Content of Noxious Substances in Atmospheric
Air.' He noted that hygienic standards worked out on the basis of experiments
and actual laboratory and clinical studies constitute the scientific basis of
environmental improvement measures in the struggle with atmospheric pollution,
and make it possible to evaluate the results from the standpoint of providing
the optimum living conditions for the population.
"Papers by a number of members of the Main Geophysical Observatory pre-
sented studies dealing with the physical validation of the procedure for cal-
culating the pollution of the atmosphere with emissions of industrial enter-
prises and steam power plants, an investigation of turbulence in the lower
500-meter layer, an experimental study of pollution in industrial areas on the
territory of the Soviet Union, the establishment of the relationship between
meteorological conditions and air pollution in urban areas, the development of
automatic methods of determination of atmospheric pollutants, etc. There were
also reports on studies conducted in collaboration with Moscow University
(S. M. Gorlin) in which the influence of irregularities of the earth's surface
on the characteristics of the air flow was Investigated in wind tunnels in con-
nection with the problem of impurity diffusion.
"Members of the Institute of Experimental Meteorology (USSR) presented a
series of reports on the study of diffusion of impurities and characteristics
of turbulence from a 300-meter meteorological mast in Obninsk. Individual
reports were also delivered by members of the Institute of Applied Geophysics
ix

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(Ye. N. Teverovskiy), the Central Aerological Observatory (N. Z. Pinus), the
F. F. Erisman Scientific Research Institute of Hygiene (R. S. Gil'denskiol'd
and B. V. Rikhter) , and others.
"Specialists from Czechoslovakia (A. I. Vesecky, head of delegation), the
German Democratic Republic (W. Warmbt, head of delegation), Poland (W. R. Parc-
zewski, head of delegation) introduced the participants of the Symposium to the
broad range of experimental research on the problem of atmospheric pollution.
D. Szepesi (Hungary) reported on studies of meteorological conditions of turbu-
lent diffusion, and G. I. Diaconescu (Rumania), on studies of thermal stratifi-
cation of the atmosphere in connection with the pollution problem.
"All the participants of the Symposium came to the conclusion that at the
present stage of the struggle with atmospheric pollution, the methods of puri-
fication and the construction of high stacks should be combined for the pur-
pose of effectively utilizing the dispersing capacity of the atmosphere.
"The need for an extensive introduction of meteorological investigation
of industrial projects and for the forecasting of air pollution was noted. One
of the primary problems noted was that of validating and standardizing the
methods of calculation of atmospheric pollution, the meteorological and hygienic
procedures in studying the chemical composition of the atmosphere, and the mete-
orological parameters determining this composition."
It is hoped that the papers presented in this volume as well as in the
preceding two volumes will be conducive to a better appreciation of the meteor-
ological-air pollution investigations conducted in the USSR and in a number of
the Soviet-block countries. As the editor of this volume I wish to thank my
co-workers in the Air Pollution Section of the Institute for their valuable
assistance.
M. Y. Nuttonson
May 1972
x

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ON THE REMOVAL OF IMPURITIES FROM THE ATMOSPHERE
BY CLOUDS AND PRECIPITATION
Ye. S. Selezneva and 0. P. Petrenchuk (USSR)
From Glavnoe Upravlenie Gidrometeorologicheskoy Sluzhby Pri Sovete Ministrov SSSR. (Chief Administration of
the Hydrometeorological Service Under the Council of ministers of the USSR.)_ "Meteorologisheskie fispekty
Zagryazneniya Atraosfery". (Meteorological Aspects of Air Pollution.) Sbornik dokladov na mezhdunarodnom
simpoziume v Leningrade - Iyul' 1968 g. (Reports delivered at the International Symposium in Leningrad -
July I960.) Pod redaktsiey d-ra fiz.-mat. nairtt II, E. Berlyanda. (Edited by Prof. H. E. Berlyarid.)
Gidrometeorolgicheskoe izdatel'stvo, Leningrad, p. 255-259, (1971). (Hydrometeorological Publishing House,
Leningrad, (l9?l).)
The last 10-15 years have seen the development of research in the
chemistry of atmospheric precipitation in many countries. Work done along
these lines by the Stockholm Meteorological Institute is widely known [9].
An annual cycle of precipitation composition studies was carried out in the
U.S.A. under the direction of Yunge [8]. During the period of the Inter-
national Geophysical Year, considerable work was done in Czechoslovakia
[10], in the German Democratic Republic [11], and in other European countries.
Since that time, systematic studies of the chemical composition of atmospheric
precipitation have also been conducted by the A. I. Voyeykov Main Geophysical
Observatory with the use of a selective network of hydrometeorological sta-
tions for collecting the precipitation samples [1].
The results of these studies, which thus far have been fairly numerous,
may be treated from different points of view, in particular, from the stand-
point of evaluating the spreading of pollutants from industrial and natural
sources.
The chemical composition and total concentration of dissolved and undis-
solved impurities in precipitation show the degree of pollution of the atmos-
pheric layers through which it falls. An idea of the propagation of atmospheric
pollutants was obtained from the geographical distribution of the total mineral-
ization of precipitation.
Studies made at the Main Geophysical Observatory and the compiled maps
of distribution of the main impurities in the precipitation showed that in
areas distant from industrial plants, under the purest atmospheric conditions,
the precipitation mineralization (i.e., the total ions) amounts to 10-15 mg/1;
in areas of appreciable natural and industrial atmospheric pollution, the
average precipitation mineralization increases to 30-40 mg/1, and sometimes
to higher values. Particularly polluted is the precipitation in industrial
cities and their environs, where the mineralization frequency exceeds 100 mg/1
[6].
- 1 -

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Depending on the mineralization and amount of precipitation, from 5 to
15 tons of substances per 1 km^ fall on the earth's surface with the pre-
cipitation each year over the territory of the USSR, and 20-30 tons or
more fall on cities. The annual amount of dry deposits in cities is much
greater, but it is essential to note that precipitation removes finer aerosols
and gaseous impurities from the atmosphere, in particular, sulfur dioxide,
which readily dissolves in water.
Thus, atmospheric precipitation is a highly important factor in the pro-
cess of self-purification of the atmosphere. An approximate global estimate
of the effectiveness of this process may be given.
On the basis of the above-mentioned studies conducted in different
countries, an average precipitation mineralization of 20-30 mg/1 may be
assumed for the globe (probably, closer to 20 mg/1). Each year, 5 x 10u
tons of water, i.e., about 10^ tons of dissolved salts fall on the earth's
surface. For comparison, let us indicate that the world's industry consumes
2 x lO^ tons of coal per year. As a result of the combustion of this amount
of coal, 4 x 10^ tons of sulfur dioxide or 1.3 x 10^ tons of sulfur is dis-
charged into the atmosphere. Precipitation annually removes 10 8-10 9 tons of
sulfur from the atmosphere (if the average sulfur concentration in the pre-
cipitation is taken to be 2-3 mg/1). Comparison of these data suggests that
on a global scale, the industrial contribution is small and barely amounts
to 5% of the impurities supplied by natural sources, i.e., by the world
ocean, the surface of dry land, and volcanoes.
Mmg/1
Fig. 1. Change of precipitation mineralization
with distance from Leningrad to the east.
When the process is considered on different scales, the relationship
is substantially altered. We will now switch from a global estimate to macro~
and mesoscales.
- 2 -

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As was noted above, in industrialized cities the precipitation mineral-
ization increases markedly in comparison with rural areas. Fig. 1 shows
the change of precipitation mineralization as one moves away from Leningrad.
Within the confines of a large city such as Leningrad, the mean annual miner-
alization amounts to about 45 mg/1, and is smaller in summer and larger in
winter. As one moves away from the city, the mineralization decreases rather
quickly: at a distance of 10-15 km the total concentration of ions in the
precipitation already decreases 2.5-fold, and at a distance of 100-150 km it
changes into the background concentration of 10-11 mg/1, which is character-
istic of this geographical zone. Such a rapid decrease of impurities in
precipitation should be regarded as an indicator of intense scattering of
the impurities in the atmosphere.
The chemical composition of precipitation begins to be formed in the
cloud during the condensation of water vapor on condensation nuclei and
absorption of various impurities by the cloud droplets. In order to evalu-
ate the washing effect of precipitation, it is necessary to study all the
stages of the process. It is necessary to have data on the composition of
the water in the clouds, composition and concentration of atmospheric aerosols,
and finally, composition of the precipitation. To obtain all these data, in
addition to precipitation samples, cloud water and aerosol samples were taken
from an airplane. Flights were carried out for this purpose over the four
major regions of the European Territory of the USSR: north, northwest (mainly
the Arkhangelsk and Leningrad Oblasts) , southwest (the Kiev-Dnepropetrovsk
regions) and southeast (the Trans-Volga). In addition, a number of flights
were made in Western Siberia (Krasnoyarsk Oblast).
M mg/l
Fig. 2. Variation of cloud water mineralization in the
horizontal direction during the flight of 7 December 1963.
- 3 -

-------
From the standpoint of cloud water composition, precipitating clouds
should be treated separately from internal stratified clouds. In all
types of clouds,a large number of samples were collected which were analyzed
in the laboratory under the direction of V. M. Drozdova.
Low stratified clouds, particularly those formed under inversions,
accumulate impurities, which build up under the inversion and fully reflect
the local contaminations of the lower atmospheric layer. Fig. 2 shows the
results of a horizontal flight in such clouds along the Kiev-Dnepropetrovsk-
Odessa route. The flight was conducted in the central portion of an intense
anticyclone occupying the entire European part of the Soviet Union at a
height of 500 m, under an inversion layer. Fig. 2 shows the sharp rise of
the concentration of impurities in cloud water as one approaches the cities.
Near Dnepropetrovsk, the cloud water mineralization reached 300 mg/1. In
the absence of an inversion in this region, the mineralization of water in
stratified clouds is 15 mg/1.
In the northern regions of the European Territory of the Soviet Union
and in Western Siberia, the average mineralization of stratified clouds is
9-12 mg/1. However, under anticyclonic inversion conditions, the mineral-
ization increases here as well, as may be seen in Fig. 3, which gives results
of sounding in the area of Krasnoyarsk. The clouds from which the samples
were collected were located at a comparatively high elevation (above 2000 m)
under an anticyclonic inversion layer. However, the pollutants also reached
up to this height. The total mineralization of cloud water exceeded 30 mg/1,
i.e., reached a very high value for these regions, while the concentration
of sulfur oxides (SO^ ions) was 60-80%.
The chemical composition of the water from frontal precipitation clouds
differs markedly from the stratified and stratocumulus clouds discussed.
On the basis of an analysis of a large number of samples (around 90), the
average mineralization of frontal clouds is 6 mg/1, and it is very stable
in space and time.
Thus, in evaluating the contribution of clouds to the mineralization
of precipitation, the initial value may be taken as 6 mg/1. Higher values
of this quantity in precipitation are obviously caused by washing of the
impurities out of the sub cloud layer.
The process of washing of impurities out of the atmosphere is given
considerable attention in the study of radioactive contaminants [3, 4, 7].
In theoretical discussions it is usually assumed that the rate of washout
of impurities by precipitation is proportional to the concentration of
impurities in the atmosphere dq	Accordingly, the concentration of
dt ~~Qq-
impurities in the atmosphere is expressed by the formula
(1)
where a is the washout coefficient.
- 4 -

-------
2km
(a) 19 December 1965, £ ion = 32 rrg/l;
(b) 16 Kay 1956, ^on = 31 ng/l.
where M ^ is the concentration of
and h is the height of precipitati
The literature contains estimates
of the coefficient a, summarized in a
review article by K. P. Makhon'ko [4].
For radioactive contaminants, O = 10~^
sec"-'- is taken. For nonradioactive im-
purities, the available data on the
determination of O are very scarce.
Here we can also refer to the work of
Makhon'ko [4], who obtained the value
6.7 x 10"5 sec~l for the washout coef-
ficient of atmospheric dust, and the
study of B. G. Andreyev, according to
which a is equal to 1.3 x 10-^ sec~l.
In the calculations below, the washout
coefficient will be assumed equal to
10"4 sec-1.
The amount of substance washed out
of an atmospheric column of height H and
cross sectional area s during time t = T
may be expressed by the formula
1t=T
AQ = //s j dq^_Hsq^ -e-°T). (2)
=o
We then obtain the following fonaula
for the concentration of impurities in
precipitation:
•M==M06n + -j~
-------
of measurements both before and after precipitation. The maximum impurity
contents in regions I, II, III and IV were 20, 60, 145 and 100 yg/m^,
respectively.
The contribution of the 0-250 m layer was estimated on the basis of a
formula characterizing the vertical distribution of aerosol particles N [5]
where NQ is the concentration of aerosol particles near the ground, and C is
some integration constant equal to about 10^ cm, according to experimental
data for average conditions.
It follows from formula (4) that the content of aerosol particles in
the atmospheric column is
and hence, the 0-1000 m layer contains 50% of all aerosols, and the 0-250 m
layer, 20%.
Results of the calculations made with formula (3) are given in Tables
Table 1 shows what fraction of precipitation impurities is determined
by the contribution of cloud water and what fraction is washed out by precip-
itation in the subcloud layer. In the northern regions under pure atmospheric
conditions, the chief contribution (over 50%) is made by clouds, i.e., largely
condensation nuclei of marine origin. In southern regions with heavy atmos-
pheric pollution, the predominant process is washing out, and 70-80% of all
the impurities are acquired in the subcloud layer.
A'W-A'.-jcfjjr.
(4)
(5)
1 and 2.
Table 1
Table 2
Amount of Impurities Acquired by
Precipitation from Clouds and from
the Subcloud Layer
Mineralization of Atmospheric
Precipitation (mg/l)
Region
Method by Which
Obtained
Region
II III IV
II III IV
Calculated from
formula ( 3)
^rom 10,9 16,9 27,0 26,3
Clouds
Subcloud layer
55 35 22 23
45 65 78 77
Actual average 14,1 16,4 30,5 24,8
for several
years
- 6 -
-------
In Table 2, the precipitation mineralization calculated from formula (3)
is compared with the actual mineralization. A satisfactory agreement of the
data confirms that the adopted washout coefficient, 10-^ sec~l, may be con-
sidered characteristic of nonradioactive aerosols.
LITERATURE CITED
]. JIpo3AOBa B. M. h ap. XnMH>iecKiui cocTao aTwoc^cpubix ocaaKOB na EBpo-
neficKofi TCpptiTopiin CCCP. r»iipoiieTeon3jaT, Jl., 1964.
2. Jlede^eB A. H. npomuKifTe.ibtiocTb Ao/Kaeii iia TeppiiTopmi CCCP. riMpo-
MeTcon3,xnT, J!., 1964.
3. M a .1 a x o b C. I\, C o a o a 11 x imi a Jl. R. 0 BMMUBaHiiii aojkacm npojyKTOB
pacnaja paaoira H3 autocijiepbi. C<5. cBonpocw smepHoii MeTeopoJiorHH». roc-
aTOMinflaT., M., 1962.
4. MaxoiibKO K. H. S.ieMCHTapiiue Teopc-nmecKiie npejcTaB^eHHa o BbtMbiBamin
npiiMecu ocajKaMii 113 aTMoc(j>epu. TpyAbi Hnr, Bun. 8, 1967.
5. CeJiesneBa E. C. AtMOC(fiepnue asposo.tii. r«ApoMeTeoH3AaT, Jl., 1966.
6. Cejic3Heaa E. C., Aposnosa B. M. O ecTecTBeKHOM (bone 3arpH3iiennfl
aTMOccfepu h coeTaBe ocaaxoB na TeppHtopiiii CCCP. CO. «CcBpeMeinibie npo-
6jieMbi K.T.iMaTo.ion!i!». THApoMCTeomaat, JI., 1966.
7. CTbipo B. H. CaMCKmimemie aiwoc^epbt or paAiioaKTiiBirux sarpHJHemifi. rua-
poMeTeoii3jaT, Jl., 1968.
8. IOnre X. XnMiiHecKiifi cociaB h paAHoaKTMBiiocTb aT.MOccfiepbi. H3A-BO «Mt[p»,
M„ 1965.
9. Eriksson E. The yearly circulation of chloride and sulphur in nature; meteo-
rological, geochemical and pedological implications. Part I, v. 11, No. 4,
1959; Part- II, v. 12, No. 1, I960.
10. Macku M., Podzimek J., Sramek L. Results of chemical analyses of
precipitation collected on territory of Czechoslovak Pepublic in 1GJ. Prace
Geofysikalnino CJstavu Ceskoslovenske Akademie ved. No 124, 1959.
11. Mrose H. Ergebnisse von Spurenstoffbestimmungen im Niederschlag. Zeitschr.
f. Met., Bd 15, H. 1—6, 1961.
E. S. SELEZNEVA, 0. P. PETRENCHUK
ON THE REMOVAL OF POLLUTANTS FROM THE ATMOSPHERE
BV CLOUDS AND PRECIPITATION *
An important factor of atmosphere selfcleaning is atmospheric
precipitation, the chemical composition of which is determined by
two processes: by water vapour condensation on condensation nu-
clei, and by catching pollutants both in cloud and subcloud layers
with cloud and precipitation elements. — •
The chemical composition and total concentration of soluble and
insoluble pollutants in precipitation is pollution index of those at-
mospheric layers through which they fell out. Precipitation minera-
lization and sulphur oxide content in it increase substantially in in-
dustrial towns and regions.
* Editor's notes The abstract is presented as given in English with the original Russian article.
- 7 -
-------
Clouds contribute, to some extent, to chemical composition of pre-
cipitation. Investigations carried out in the Main Geophysical Obser-
vatory show that the chemical composition of cloud water depends
greatly on meteorological factors. Subinversion clouds formed under
anticyclonic situation are peculiar "accumulators" of pollutions con-
centrated in subinversion layer.
The chemical composition of water from frontal clouds which pro-
duce precipitation is nearly identical for different regions and chan-
ges little with time during precipitation fallout. Mineralization of
cloud water from frontal clouds is equal to 6 mg/litre.
The contribution of cloud and subcloud layers to formation of
chemical precipitation composition is determined on the basis of ex-
perimental data and calculations. The evaluation shows that in the
regions with weak pollution the main amount of pollutants (more
than 50%) comes from clouds, and in the regions with heavy air
pollution washing-out becomes the prevailing process: 70—80% oT
all pollutants are captured in subcloud layer.
- 8 -
-------
SOME ASPECTS OF THE ADOPTION OF AUTOMATIC METHODS OF
DETERMINING ATMOSPHERIC POLLUTANTS
N. Sh. Vol'berg, G. V. Gal'dinov, and V. Z. Al'perin (USSR)
From Glavnoe Upravlenie Gidrometeorologicheskoy Sluzhby Pri Sovete llinistrov SSSR. (Chief Administration of
the Hydrometeorological Service Under the Council of Ministers of the USSR.) "Meteorologisheskie Aspekty
Zagryazneniya Atmosfery". (Meteorological Aspects of Air Pollution.) Sbornik dokladovna mezhdunarodnom
simpoziume v Leningrade - Iyul' 1968 g. (Reports delivered at the International Symposium in Leningrad -
July 1966.) Pod redaktsiey d-ra fiz.-m»t. ntuk M. E. Berlyanda. (Edited by Prof. M.E. Berlyarid.)
Gidrometeorolgicheskoe izdatel'stvo, Leningrad, p. 260-268 (1971). (Hydrometeorologioal Publishing House,
Leningrad, (l97l).)
At the present time, a number of instruments are being designed in the
Soviet Union for the continuous determination of the basic atmospheric pol-
lutants. Their adoption will make it possible to increase substantially the
amount of information obtained, eliminate its delay, and create automatic sy-
stems to warn of the possibility that the maximum air pollution norms may be
exceeded.
The expedience of reducing as much as possible the number of available
gas analyzer models lends great urgency to the problem of selecting the most
rational principles of determination of the substances in question.
Instruments designed for analysis of atmospheric air should be charac-
terized by a high sensitivity. Their transportability is also important. We
shall discuss the most important types of existing gas analyzers from these
points of view.
The highest sensitivity is that of ionization instruments. Thus, flame
ionization gas analyzers used for the determination of total hydrocarbons in
air permit the determination of thousandths of mg/m^, have a short time lag
(of the order of a few seconds), and may be constructed in portable form.
For example, the portable flame-ionization gas analyzer designed by Guerrant
[8] has a sensitivity of the order of 10 Vg/m^ and a time lag of 2 sec. The
instrument is completely self-contained and weighs 12 kg.
For the determination of a large number of inorganic gases, analyzers
have been proposed that are based on the conversion of the component being
determined to the aerosol state by the addition of a suitable gaseous or
vaporous reagent to the air stream. The aerosol formed is determined from
the decrease of the ionization current. The "Billion Air" American gas ana-
lyzer [5] and the domestic "Sigma-l" analyzer,* both operating on this prin-
ciple, insure a high sensitivity of the determinations, but are stationary.
There is reason to believe that portable instruments of this type will ap-
pear in the near future.
* Automatic continuous-action "Sigma-l" gas analyzers. Prospectus of VDN Kh (Exhibition of Achievements
of the National Economy of the USSR), 1967.
- 9 -
-------
Among ionization gas analyzers, those whose specificity stands out are
mass spectrometric instruments, particularly when they are combined with
chromatographs. However, the complexity and high cost of the required equip-
ment and the need of constant and highly qualified operation make their wide
application to the determination of the main atmospheric pollutants imprac-
tical (at least in the next few years). Moreover, these instruments are not
interchangeable in many types of research work.
To determine the qualitative and quantitative composition of atmospheric
pollutants of organic character, unquestionably the most promising instruments
are chromatographic analyzers equipped with various ionization detectors.
Thus, the design of specialized portable or transportable instruments of this
type is highly desirable.
Among instruments based on physical principles we should mention gas
analyzers utilizing the absorption of light in the infrared region of the spec-
trum. These instruments are widely used for the determination of CO, CO2 and
CH4 in various gases. Their advantage is a high specificity, a short time
lag and simplicity of operation. However, the sensitivity of most of them is
insufficient for the determination of CO in atmospheric air. The sensitivity
of these instruments is usually raised by increasing the cell length. Thus,
in the American gas analyzer "Lyra," designed for the determination of CO in
atmospheric air, the cell size is 1 m. Obviously, these instruments can only
be stationary. In the last few years, a certain progress has been made in
regard to the reduction of their weight and size through the use of multipath
cells or an open beam.
Photocolorimetric methods, both manual and automatic, are most widely
used at the present time for the determination of air pollution. Two types
of automatic photocolorimetric gas analyzers are used, liquid and belt types
(Table 1).
In the principle of their operation, photocolorimetric gas analyzers are
versatile instruments permitting the determination of any substance for which
a rapid and sufficiently sensitive color reaction exists. This makes them
convenient for incorporation into sets consisting of several instruments per-
mitting the simultaneous determination of a number of substances [11].
A typical representative of modern liquid photocolorimetric gas analyzers
for determining atmospheric pollutants is the "Imcometer" instrument [7]. It
is designed for determining ozone, sulfur dioxide, nitrogen oxides, hydrogen
sulfide, chlorine, and fluoride ions.
The working cycle of this instrument includes a series of successive
operations: measuring out the reaction liquid, automatic setting of the null
point, passing of the air under analysis, measurement, and emptying of the
cell. The performance of all these switching operations requires suitable
automatic devices, and this accounts for the comparative complexity of this
type of instruments.
- 10 -
-------
Table 1
Photocolorimetric Gas Analyzers
Instrument
Com-
ponent
deter-
mined
Measure-
ment
range,
mg/m3
Basic
error,
%
Refer-
ence
Liquid type

Catalog
Sest
German
firnPFRG'
"Chromoflux"
C12
0-20
10
FK-1501
"Incometer"
no2
°3
0-5
0-0,2
10
5
PI
Belt type
FL-5501
FGTs-ID
H°
-------
Table 2
Conductometric Gas Analyzers
Instrument
Components determined
Measurement
limits for
ng/in3
Reference
"Ul'traEaz-3
"I onoflux*
"Pic of lux"
"KU-?1
so,, h2s, nh3, CO
SCV CS-i. PHa h jin.
so2f hci, nh3
CO, 3asoline vapors
0-5
0-5
0-1
0-50 (CO)
Catalog of
West German
firm "FRG"
Same
[6]
[2]
The need for precise thermostating leads to an Increase in the size and
weight of the instrument. Thus, the "Picoflux" gas analyzer, which is con-
sidered to be transportable, weighs about 35 kg without the recorder.
Among electrochemical gas analyzers, the moat interesting are instruments
based on the coulonometric principle. This principle has been used in elec-
trochemistry for a long time and on a wide scale, hut its special advantages
in gas trace analysis were revealed only in the last few years thanks to the
work of Hersch [9], Novak [10], and several other investigators,
Coulonometric gas analysis is based on the measurement of the current
of the electrode reaction entered into by the substance being analyzed, which
is continually supplied to the coulonometric cell with the stream of the ana-
lyzed gas. In many cases, the reaction proceeds with a 1007o current efficien-
cy based on the substance. This makes it possible to use Farraday1s law to
calculate the concentration being measured without first having to calibrate
the instrument. Participation in the reaction of all the substances supplied
makes for a high sensitivity of the measurements, and this sensitivity can be
achieved without using current amplifiers.
In contrast to other electrochemical methods (for example, conductometric
and polarographic), the magnitude of the current is determined in this case
only by the amount of electrochemically active substance entering the cell,
and is independent of temperature. This makes it unnecessary to thermostat
the instrument accurately and promotes a compact design.
In the USSR, the Experimental Design Office for Automation (OKBA) has
developed and is currently introducing on a large scale a coulonometric gas
analyzer GKP-1 for determining sulfur dioxide in atmospheric air [1]. The
instrument makes use of the principle, proposed by Novak [10], of absorption
of sulfur dioxide by a solution of iodine in sulfuric acid followed by elec-
trooxidation of the iodide ions formed.
- 12 -
-------
In contrast to the instruments proposed earlier, the GKP-1 instrument
uses a nonflow-type arrangement, i. e., the electrolyte in the cell is not
changed. A slight loss of electrolyte, which is due to the bubbling air,
is compensated from a small tank built into the cell by means of an original
arrangement for maintaining a constant level.
Such a design could be realized thanks to the fact that in a coulono-
metric determination, in contrast to other electrometric and photometric
methods, the reagent solution is continually regenerated.
Table 3 summarizes the chief technical characteristics of the most im-
portant gas analyzers, using the determination of sulfur dioxide as an illus-
tration.
Table 3
Characteristics of the Most Important SO2 Gas Analyzers
Principle of

Scale,
Lag»
Basic
Weight,
operation of
Brand
mg/m5
min
error,
kg
gas analyzer

Photocolor-
"Imcometer"
0-0,6
30
5

imetric

Conductometric
"Picoflux"
O
O
1,5
6
35
Coulonometric
GKP-1
0-1,0
0,75
6
7
It is evident from the above data that the coulonometric gas analyzer
has the most desirable set of properties. Having a sensitivity and accuracy
like those of the best photocolorimetric and conductometric instruments, the
coulonometric gas analyzer is distinguished by a short lag and small weight.
The absence of moving parts and a long service life after charging make the
instrument operationally reliable and one that requires a minimum of handling
and of operating time.
The indicated advantages of coulonometric gas analyzers place them in
the rank of the most promising instruments for determining atmopsheric pollut-
ants, and make it expedient to expand as much as possible the number of sub-
stances for the determination of which they can be used. At the present time,
instruments are being developed for the determination of hydrogen sulfide,
chlorine, ozone, hydrogen chloride, etc.
The transportability of the above coulonometric gas analyzer enabled us
to make a study of the atmospheric pollution of Leningrad both at ground lev-
el, with the instrument mounted on a truck, and at a height of 100 m, with
the instrument carried in a helicopter. The results obtained are illustrated
in Figs. 1 and 2.
- 13 -
-------
Fig. 1. Measurement of sulfur dioxide concentrations in
the city by means of the GKF-1 instrument mounted on a
truck.
Measuring time at one point, 3-5 min; number of points of
measurement in the course of a working day, 25-50.
miri
Fig. 2. Measurement of sulfur dioxide concentrations with
GKP-1 instrument mounted on helicopter.
Flight route perpendicular to the wind direction; flight
altitude 100 ir:; speed, 60-70 kra/hr.
-------
Thus, to determine the chief inorganic atmospheric pollutants, the most
promising approach appears to be the development of instruments based on the
coulonometric principle.
Because of the considerable increase in the volume of information that
can be obtained when automatic instruments are used, the problems of process-
ing of this information also assume a major importance. For example, the
digitizing of tape carrying the recording of concentration variations with
time frequently takes more time than the recording itself. Automation of this
process, however, is an independent and fairly difficult problem. Moreover,
without preliminary digitizing, a continuous recording does not provide the
answers to the following questions that are usually of interest to hygienists
and meteorologists: what is the average concentration for the time interval
in question and what is the number of cases in which the maximum permissible
concentration has been exceeded by a certain factor? For this reason, it is
our view that in many cases it is possible and expedient to abandon the tra-
ditional use of recorders as secondary instruments and to replace them with
integrating devices in combination with the simplest amplitude analyzers.
In our view, the development of small and reliable instruments of this type
must not be delayed.
When automatic gas analyzers are used for the determination of air pol-
lutants, the problems of systematic checking of their readings assume a ma-
jor importance. To provide for such control on the spot, it is necessary to
develop simple and reliable measuring devices and also to create a center for
preparing standard gas mixtures.
LITERATURE CITED
1. Ajibnepim B. 3. 11 ,np. ABTOMaTHiecKiift ra3oaHa.ni3aTop a.ih HenpepuBHoro
onpeAe.iemiH cepuHCToro ra3a b aTMOc^epHOM B03Ayxe. Tpyflbi ITO, Bbin. 234,
1968.
2. JlepeBHHKo ,H. T., 3BepeB 10. H. KoiuyKTOMeipimecKaH yCTaHOBxa KV-3
fl.ia onpeae^emiH okhch yr.iepoAa, abyokhcii yr.iepcaa it napoo Cenjima. W3A-
JlMOT, Jl., 1967.
3. H a 3 a p e h k o A. A., K a p a e b a T. M., B o ,i k o b A. C. OTOKo.iopiiMeTpn-
HecKHe ra30aiiaAH3aTopbi n Kompo.-ib mhctotm B03A>xa npoii3BOACTBeiuibix
noMemeiiHM. MXn CCCP, OKBA, CeBepoAoneuK, 1967.
4. IT a B .1 e ti k o B. A. ra3oaiia.iH3aTopbi, .1., 1965.
5. Deisler P. F., McHenry W„ Wilhelm R. Rapid gas analyzer using
ionisation by alpha particles. Anal. Chem., 1955, v. 27, 1366.
6. E n ge 1 h a r d t H. Automatischc Analysengerate zur Immisions und Einmisions-
messung von Luftverunreinigungen. Dechema Monographien, 1965, Bd 54.
219.
7. Fuhrmann H., Winter H. Neue hochempfindliche Gasanalysator zur Int-
missionsmcssung. Wasscr Lult u. Betriub, 1964, Bd 8, 5.
8. Guerrant G. O. Portable instruments based on flame ionisation detectors
for analysis of air trace organic constituents. Analyt. Chem., 1965, v. 37, 4.
516.
- 15 -
-------
9. Hersch P. Galvanic analysis. Advances in Anaiyt. Chemistry and Instrumen-
tation, 1964, v. 3, 183,
10. Novak I. V. A. Polnrogrnphic-coulomctric analyzers. Coll. Czechosl. Cheni.
Commun. 1965, v. 30, 2703.
11, Oil's newest anti-pollution tool. Petrol. Manag., 1966, v. 38, 12, 101.
N. Sh. VOLBERG, G. V. GALD1NOV, V. Z. ALPERlh'
ON THE AUTOMATIC TECHNIQUE FOR PROCESSING OF INFORMATION
ON AIR POLLUTION *
At present, in the Soviet Union a series of instruments for con-
tinuous measurement of air pollution is developed. The necessity of
minimizing the number of types of gas analyzers makes the problem
of introduction of highly sensitive transportable instruments quite
actual.
Ionization methods are especially highly sensitive, in particular,
ionization method of hydrogen flame. A description of a transport-
able gas analyzer of this type destined for hydrocarbon determina-
tion in the air is given.
Among other ionization gas analyzers, mass-spectrometers are of
special interest. But the complexity of these instruments makes it
expedient to use them only for investigation purposes.
The most perspective instruments for quantitative and qualita-
tive analysis of air pollution are chromatographic analyzers supplied
by different ionization detectors. Therefore, the development of spe-
cial transportable instruments of this kind is very desirable.
For carbon oxide determination, the optic-acoustic principle is
rather perspective. The instruments of this kind are developed which
possess high sensitivity. For instance, gas analyzer GMK-3 has a
scale of 0—40 mg/m3 and is transportable.
Widely used at present are liquid photocolorimetric gas analyzers,
but they have rather complicated mechanism and large sizes. Neces-
sary sensitivity is usually reached by concentration of determined
substance from large air volume; this stipulates substantial inertia
of these gas analyzers.
Instruments based on electrochemical principles are more sensi-
tive. Among them, coulonometric analyzers possess especially favou-
rable features and high sensitivity along with small weight and si-
zes. So, developed in the USSR, transportable coulonopolarographic
analyzer on sulphur dioxide GKP-1 has sensitivity and precision of
the best photocolorimetric and conductometric instruments. High
metrological qualities of coulonometric gas analyzers place them
among the most perspective instruments for air pollution determina-
tion and make it expedient to enlarge the number of substances de-
termined by them.
~Editor's note: The abstract is presented as given in English with the original Russian article.
- 16 -
-------
To simplify the treatment of large information volume received
from automatic instruments, it is expedient to refuse, in some cases,
the utilization of recorders at the exit, employing integrating mecha-
nisms instead of them coupled with the simplest amplitude analy-
zers.
Systematic control of automatic instruments is one of the most
important conditions for receiving reliable measurement results. De-
velopment of precise dosimeters is necessary for supplying the pos-
sibility of conducting in situ control.
- 17 -
-------
RECORDING OF SULFUR DIOXIDE CONTENT AT THE OUTSKIRTS OF A CITY.
COMPARISON OF MEASUREMENT RESULTS FOR A VALLEY AND AN ELEVATION
H. Mrose and W. Warmbt GDR (German Democratic Republic)
From Glavnoe Upravlenie Gidroraeteorologicheskoy Sluzhby Pri Sovete Ministrov SSSR. (Chief Administration q
the Hydrometeorological Service Under the Council of Ministers of the USSR.) "Meteorologisheskie Aspekty
Zagryazneniya Atmosfery". (Meteorological Aspects of Air Pollution.) Sbornik dokladov na mezhdunarodnom
simpoziume v Leningrade - Iyul* 1968 g. (Reports delivered at the International Symposium in Leningrad -
July 196a.) Pod redaktsiey d-ra fiz.-mat. naiflc M. E. Berlyanda. (Edited by Prof. It. E. Berlyand.)
Gidrometeorolgicheskoe izdatel'stvo, Leningrad, p. 269-280, (1971). (Hydrometeorological Publishing House
Leningrad, (1971).) *
1. Formulation of the Problem
In characterizing the air pollution in a city, much attention is given
to the distribution of sulfur dioxide over the city and its environs. At
the same time, it is assumed that the sulfur dioxide concentration in densely
populated areas is markedly different because of the presence of a large
number of different emission sources. In order to find out how representa-
tive the results of a single point of measurement are for a large area, we
recorded the sulfur dioxide concentration at two points on the outskirts of
Dresden from 12 January to 14 April 1968. The measurements involved the
use of two sulfur dioxide recorders of Novak's design, kindly supplied to us
for testing by the Hydrometeorological Service of CSSR.
2. Location of the Points of Measurement
The point of measurement at Wahnsdorf was located near the Wahnsdorf
Meteorological Observatory at an elevation of 246 m above sea level and
about 100 m above the valley.
The point of measurement at Radebeul was located in the Meteorological
Service building at an elevation of 122 m above sea level. The Radebeul
region consists of a residential area surrounded by gardens and green planti^
The distance between the points was 1.4 km. There were no major industrial
plants around these points within a distance of approximately 3 km.
3. Method of Measurement of Sulfur Dioxide
Concentration after Novak
The method of measurement of sulfur dioxide concentration after Novak
[5, 6] is based on the following principle. Air is drawn through sulfuric
acid containing iodine. In this process, sulfur dioxide reduces an equivaler»
amount of iodine to iodide ions according to the reaction
S02 +12 + 2H20 = sor - + 4H+ -1- 21-
- 18 -
-------
The iodide ions formed are reoxidized Co iodine on a platinum anode.
The electric current required by this process is a measure of the iodide
ions and thus of the sulfur dioxide concentration. Use of Faraday's law
permits the calculation of the amount of iodine ions and hence, of the
amount of sulfur dioxide from the measured current intensity. Knowing the
equivalent weight of sulfur dioxide, Faraday's constant, and the suction
rate of air, one can determine the sulfur dioxide concentration from the
formula
where i is the measured current (yA) and v is the flow rate of air (ml/min).
A diaphragm pump was used to introduce a 3% sulfuric acid solution into
the anode compartment through a glass vessel filled with iodine crystals
(Fig. 1). The air studied was also passed through this vessel. This air
together with the sulfuric acid solution then entered the cathode compartment,
from which it was drawn together with the spent sulfuric acid by a teflon
pump. A voltage of about 0.3V was applied to the electrodes. This voltage
was less than required for decomposition of sulfuric acid, so that the cur-
rent was maintained only by the oxidation of iodine ions. The measured cur-
rent was recorded with a recorder having a scale from 0 to 50 mA and a clutch
mechanism. The chart speed was 2 cm/hr.
4. Testing of Novak's Method and of the Measuring Instrument
The readings of Novak's analyzer were checked by comparing them with
sulfur dioxide concentration measurements obtained by the specific method of
West and Gaeke [8], which involves the use of para-rosaniline and sodium
tetrachloromercurate (TCM). We obtained the following equation for regression
curve, relating the data of Novak's method (y) to those of the TCM method (x):
S02 ==• i (mg/m3)
E - electrolysis vessel, A - leveling
vessel, - pump; T - attachment for
drop formation, J - vessel for iodine,
F^ - acid, ?2 - acid used, P2 - suction
pump, S - recorder, V - voltmeter.
Fig. 1. Novak's gas analysis apparatus
for determining sulfur dioxide.
y — 1.050* -j- 0,002 (mg/m3)
- 19 -
-------
with a confidence interval (P = 95%) for the constants
Afc — 0,182, Aa — 0,035.
Comparative measurements made by Herrmann [3] in the industrial dis-
trict of northern Bohemia led to nearly identical results (Table 1). It
follows from the table that both methods yield practically the same results.
Table 1
Comparative Measurements of Sulfur
Dioxide Concentration Made by Using
Novak's Method and the TCM Method
For Wahnsdorf
After Herrmann
0,97
0,96
0.002
-0,001
1,05
0,99
Note, r is the correlation
coefficient.
In order to check the reproducibility of
the data obtained by Novak's method, we con-
ducted parallel measurements at Wahnsdorf by
using two of Novak's instruments. We thus
obtained the following regression equation
for the readings of the first instrument (x)
and second instrument (y)
y — 0,961a: — 0,003 (mg/m3)
with confidence intervals (P = 95%) for the
constants
bb = 0,033, Aa = 0,005.
The confidence interval for the standard deviation of the individual
quantities from the regression curves for P = 95% is
AS - - 0,03 (mg/m3).
The inaccuracy of the readings is thus equal to approximately one part
per million (10-^).
5. Evaluation of Measurement Results
The half-hourly averages for the first 30 minutes were determined by
graphical interpolation of the data of readings given by Novak's instrument.
Table 2 lists the arithmetic averages D for all the measurement results,
and also for 0, 6, 12 and 18 hours. It is characteristic that only slight
differences in concentration exist between Wahnsdorf and Radebeul. An exam-
ination of the average values shows that the sulfur dioxide content in the
valley (Radebeul) is approximately 20% higher than on the elevation (Wahnsdor
This difference is explained, on the one hand, by the fact that industrial
plants and residential areas are concentrated in the valley, and on the other
hand, by the fact that the conditions produced in the valley are not as con-
ducive to the dispersal of emissions as the conditions associated with the
elevation, particularly in stagnant situations.
- 20 -
-------
Table 2
Average Values of Sulfur Dioxide Measured by Novak's Method in Wahnsdorf from
12 January to 14 April 1968
Point
General
Average
0 Hours
6 Hours
12 Hours
18 Hours
n
D
rt
D
n
D
n
D
n
D
Radebeul
Wahnsdorf
Difference
2172
2085
0,117
0,099
0,018
270
264
0,085
0,084
0,001
272
260
0,136
0,121
0,015
271
263
0.143
0,121
0,022
271
265
0,103
0,084
0,019
Note, n - number of measurement; calculation of average values for fixed
hours also included data of observations made one hour before and one hoifp
after the observations.
The average daily variation of sulfur dioxide concentration in Radebeul
and Wahnsdorf shows a difference in amplitude but not in phase (Fig. 2).
The experimental values at both points were observed at the same time; the
maximum concentration appeared around 9 A.M., and the minimum concentration,
around 2 P.M. The average value of the daily fluctuation was 0.09 rag/m3 in
Radebeul and 0.07 mg/m^ in Wahnsdorf. The maximum in the early morning
hours is explained by the start of operation of industrial plants and a
negligible turbulent exchange of the air masses in the presence of a stable
atmospheric stratification. Heating in the evening hours causes only a
slight increase in concentration, which is weakly manifested at the points
of measurement around 6 and 7 P.M. The concentration minimum around 2 A.M.
is explained by a slight emission during the nighttime hours. It is inter-
esting to note that because of a better exchange, the sulfur dioxide con-
centration at the elevation changes little during the period from 4 P.M. to
2 A.M.
mg/ra5
Pig. 2. Average daily variation of sulfur
dioxide con cent ration in Radebeul (l) and
Wahnsdorf (2).
+ 8 12 fG 20 24 hours
To get an idea of the recurrence of any given sulfur dioxide concentra-
tions, Figs. 3 and 4 show the distribution of total frequencies for the
periods of 0, 6, 12, and 18 hours. Since the sulfur dioxide concentration
values are distributed in accordance with the lognormal law, not the normal
- 21 -
-------
%
99
95
SO
N>
tsj
5
1

1
|

MPC
/
<
Sty
/
//
s /
~ /
~ /
/ /
//
' 1
1
1
1

1^'
2/
1

1 .1 11.
1
1

0,02 0,1 0£ 0/t mg/m^
Fig. 3. Distribution of
total frequency of average
daily S02 values in Radebetil
(l) and Wahnsdorf (2).
Fig. 4. Distribution of total frequency of average con-
centration values for different observation periods in
Radebeul (a) and Wahnsdorf (b).
-------
law, they are arranged along a straight line on a logarithmic probability
plot. No large differences are observed between Radebeul and Wahnsdorf.
It also follows from Table 3 that the total concentration values with 95%
frequency, which were used in the literature in different ways to determine
pollution, differ insignificantly for the two points. It should be noted
that concentration values with 95% frequency in Wahnsdorf substantially
surpass the corresponding values in Radebeul at 12 M. and less substantially
at 6 A.M. and 6 P.M. It follows that the sulfur dioxide concentrations at
the elevation are sometimes higher than in the valley. We are referring
to cases in which emissions from industrial plants and residential sections
in Dresden-Radebeul are carried by southeastern winds in the direction of
the elevation.
Table 3
Total Sulfur Dioxide Concentration (ng/m^)
with 95# Frequency
Point
Average
Value
For
Period
lime, Hours
0
6
12
18
Radebeul
Wahnsdorf
0,25
0,24
0,25
0,25
0,35
0.37
0,39
0,49
0,27
0,29
In order to establish the relationship between the average daily values
of the two series of measurements, correlation coefficients were determined
and the regression curve was plotted. The calculations were not made by
using all the average daily values, but only values for the 1st, 4th, 7th
days, etc., since consecutive mean daily values are not independent from one
another. The correlation coefficient between the measured values in
Wahnsdorf (x) and Radebeul (y) is
r = 0.918
The regression curve is expressed by the equation
y^-= 1,154* 4-0,005 (mg/m^).
For P-95%, the constants have confidence intervals
Afr =--= 0,192, Aa = 0,0l8,
The results confirm the already-stated slight differences in sulfur
dioxide concentrations between the valley and the elevation.
Let us consider in more detail some individual examples of recording
of like and unlike daily variation of sulfur dioxide concentrations at the
two points.
- 23 -
-------
The variation of half-hourly average concentration values for the
period of 4-10 February 1968 shows a close relationship between these
values at Radebeul and Wahnsdorf (Fig. 5).
As an example of like variations of sulfur dioxide concentrations,
let us consider the tracing of the recording of 27 January (Fig. 6). In
the valley and at the elevation, an increase of the sulfur dioxide concen-
tration was observed at about 12 M. , and a decrease was noted past 2 P.M.
From the wind velocity and direction tracings in Wahnsdorf one cannot infer
the possible causes of these fluctuations. It is possible that the gaseous
emissions were spreading through the valley in a broad front. Such changes
are by no means explained, as is frequently done, by local influences such
as emissions from neighboring houses.
mg/m5
a)
b)
0,8
0,6
0,4
02
0
0£
0,6
0,4
Of
0
.0.21

0.19

0.13

0.14

0.311

0.12

J
Ik
1
A
w
1

A,
¦
L /
kA*
i
4

5
6
7
8
3
10lt19S8e
.0.19

0.12

0.09

0.11

0.12

0.30
0.09

!/
K.
A
i
1

1 ,

i.-

Fig. 5. Variation of sulfur dioxide concentration (average values
obtained) in Radebeul (a) and Wahnsdorf (b) from It to 10 February 1968.
An unlike variation of sulfur dioxide concentration is illustrated by
observations of 14 April 1968 (Fig. 7). On that day, appreciable concen-
tration fluctuations were observed in Wahnsdorf, whereas they were absent
in Radebeul. An explanation of this may be found by examining the recording
of wind gustiness in Wahnsdorf. In the southeastern flow, short-term fluctu-
ations in wind direction and velocity were observed since midnight, during
which the sulfur dioxide concentration decreased as a result of turbulent
mixing. One is struck by the brief increase in sulfur dioxide concentration
at about 8 A.M. in Wahnsdorf. Concentration peaks of this kind are observed
when the earth's surface is heated and the night surface inversion breaks
down as a result of thermal convection. At the same time, the sulfur dioxide
accumulated under the inversion spread toward the ground as a result of
suddenly produced turbulent motions. In Radebeul, the inversion broke up
later than at the elevation, i.e., at about 9 A.M.
- 24 -
-------
rag/m5
0,2

- a)

- b)

-h

_L
Wind direction

¥t

#ntTTr*T1*nr*1

•

10 12
14
16
18
20 hours
Fig._6. Like variation of sulfur
dioxide concentration in Radebeul (a)
and Wahnsdorf (b), 27 January 1968.
ng/m5
0,4
Of
o
o,s
-a)

JV-

—f
s~

OS
0,2
o
rE
)

™A

A
\

180° direction
SO
360
360
270
180
m/sec wind Velocity
lO
10
%

1 I—I
PF.J*
10 hours
Fig._7. Unlike variation of sulfur
dioxide concentration in Radebeul (a)
and Wahnsdorf (b), 14 April 1968.
-------
K>
en
5
£
N
N
W
m/s^c_
15
10 \

n-——

...
L_L | .J

i
.

* I

1 1
SOi Mg/rc5
QJ

¦ •¦v

... 1

— i

20 2f 22 23 24
2\M.
Fig. 8. Variation of sulfur dioxide concen-
tration with changing wind direction in
riaie'Deui ll) and Sataisiorx crt, -\1 arii
-15", 15-14 January 1968.
'Vka'
jje/e"
13 14
P.M.
Fig. 9, Variation of sulfur dioxide
concentration during passage of warm
"iTurjV.
1 - Radebeul, 2 - Wahnsdorf.
-------
After the breakup of the inversion, fluctuations of wind direction
caused by convection were observed at the elevation. The sulfur dioxide
concentration decreased rapidly, since the wind changed direction from
south-south-east to east, and no more air polluted with smoke emissions
reached the point of measurement. An intensification of the wind after
10 A.M. led to a further mixing and thus to a decrease in sulfur dioxide
concentration. It is evident from this example that a difference in sulfur
dioxide concentration in the valley and on the elevation appears when local
circulation systems arise under conditions of attenuated exchange.
rag/m5
1,0
OJB
o,s
0,0
OA
¦a)
i5

:3b*
I

fa ^
1
4 6 8 10 12 M 16 18 20 hours
3 3 \ ] J S \ 1 2
Fig. 10. Variation of sulfur dioxide concentra-
tion, 9 February 1968.
In addition, differences in sulfur dioxide concentration were observed
in the presence of unlike wind direction and velocity and unlike turbulent
state in the valley and on the elevation, as for example on 14 January 1968
during a clearly manifested passage of a warm front. On 13 January, Central
Europe was under the influence of a cyclone located over Iceland. At about
10:30 P.M., the wind direction in Wahnsdorf changed to south-south-east
(Fig. 8), and air with a high sulfur dioxide content began spreading from
Dresden to both points. Warm air coming from the west reached Wahnsdorf in
the afternoon hours on 14 January (Fig. 9). The passage of the warm front
was confirmed by temperature and wind recordings (15^®). As the wind inten-
sified and turned in a west-south-west direction, the mixing increased, and
the concentration decreased. At that time, Radebeul was still surrounded
by cold air. While the sulfur dioxide concentration on the elevation had
already decreased, it was still increasing in the valley under a quasi-hori-
zontal interface acting as barrier layer. Around 5 P.M., the warm air
reached the valley, and sulfur dioxide concentration decreased rapidly.
In conclusion, we should also consider the sulfur dioxide variation of
9 February 1968. On that day, the highest concentrations of the 1967-68
winter season were measured (Fig. 10) , and the valley of the Elbe was shrouded
in mist and fog with weak southern winds.
- 27 -
-------
As a result of small-scale circulation processes, large fluctuations
of sulfur dioxide concentration were observed in the morning hours at both
points. Later, because of an absence of exchange, the concentration in the
valley and on the elevation increased. In Wahnsdorf, the maximum concen-
tration was 0.75 mgym3 (10 A.M.), and in Radebeul it reached 1.04 mg/m^
(11:45 A.M.). At midday, the cloudiness decreased, the wind changed direc-
tion from south-south-east to south-south-west, and by 12 M., as a result
of the development of mixing, the concentration decreased to 0.40-0.30 mg/m^
at both points. At about 8 P.M., a further decrease of the sulfur dioxide
concentration took place when rain fell and the wind turned in a west-south-
west direction.
Conclusions
Measurements of sulfur dioxide concentration on the outskirts of Dresden
showed that insignificant differences in this concentration exist between a
valley and an elevation. The daily variation of sulfur dioxide concentration
and daily variation of the frequency distribution in the valley and on the
elevation were similar. Differences exist only when the exchange conditions
in the valley and on the elevation are different, for example, in stagnant
situations and during the passage of fronts. The area of a large city consti-
tutes a voluminous source in the boundary zone of which the sulfur dioxide
concentrations show insignificant differences in the horizontal and vertical
directions. This was confirmed by measurements at two points separated by a
distance of 1.4 km, with a height difference of 120 m.
LITERATURE CITED
!. Braun R. G. und Wilson M. J. G. The variation of atmospheric sulphur
dioxide concentration with altitude. J. Air Wat. Poll., v. 5. 19S|.
2. Doerffel K. Statislik in der analytischen Chcmie. VEB Deutscher Verlag fur
Grundstoflindustrie. Leipzig, 1966.
3. Herrmann G. Ergebnissc von Paraitelmessungen dcs SOi—Gehaltes der At-
mosphare nach der Pararosanilin-Methode {S02 MesskoffcT) und einem cou-
fomefn'scfien Verfafiren (SG^Analysafor frfij fn ater CSSR. Bench! 1'echn.
Univ. Dresden Inst. f. Pflanzenchemie Abt. Rauchschadenforschung Tharandt.
4. HoscheleK- Ergebnissc von Messungen des Schwefeldioxidgehaltes dcr Luft
in Karlsruhe und ihre statistische Bearbeitung. Staub, 25 (1965) 102—112.
5. N o v a k J. V. A. Polarograph.-coulometrische Analysatoren fur Spurunstolfkon-
zcntrationen von S02 — Int. Symposium fiber Luftreinhaltung und Verwer-
tung von S02 und Flugasche aus Dampkraftwerken I, Liblice Okt. 1965.
6. Novak J. V. A. Polagraphic-coulometric analyzers measurement of low con-
centrations of sulphur dioxide. Collect. Cechoslov. Chem. Commun,, 30 (1965)
7. Stratmann H. und Buck M, Vergleichsmcssungen mil dem Silikagelver-
fahren und dem TCM-Verfahrcn zur Bestimmung von Schwefeldioxid in der
Atmosphare. Int. J. Air Wat. Poll., 9 (1965) 199—218.
8. West P. W. und Gaeke G. C. Fixation of sulphur dioxide as ciisulfitomercu-
rate (II) and subsequent colorimetric estimation. Analvt. Chem., 28 (1956),
1816—1819.
- 28 -
-------
H. MROSE, W. WARMBT
REGISTRATION OF SULPHUR DIOXIDE CONTENT IN THE VICINITY
OF A CITY — COMPARISON OF MEASUREMENT RESULTS IN A VALLEY
AND ON AN ELEVATED PLAIN*
The results of sulphur dioxide concentration measurements in
the suburbs of Dresden are stated which were carried out in two
points situated in the valley of the Elbe in Radebeul (I20m over the
sea level) and on an elevated plain near Meteorological Observatory
in Wahnsdorf (246m over the sea level) from January to April 1968.
The distance between the points amounts to 1.4 km. Continuous re-
gistration of sulphur dioxide concentration was done with the help
of Novak gas analyzers mounted in these points on the height of 2m.
The control of reproducibility of measurement results after the No-
vak method which was carried out in Wahnsdorf with simultaneous
utilization of two analyzers showed a good agreement of data. Di-
vergence of measurement results amounts to 7% on the average,
which is probably due to different velocities of solution flow in the
instruments.
The results of sulphur dioxide concentration measurement with
the help of analyzers were compared with concentrations received by
standard method of West-Gaeke. It was found that both methods
gave practically similar results. Correlation coefficient between con-
centrations received by parallel measurements using different meth-
ods amounts to about 0.96.
The results of continuous measurements of sulphur dioxide con-
centration are analyzed in detail at two points. Similar diurnal con-
centration course was observed, mainly, with maximum about
9 o'clock and minimum about 2 o'clock at both points. The average
daily amplitude of sulphur dioxide content amounts to 0.09 mg/m3
in Radebeul and to 0.07 mg/m3 in Wahnsdorf. A slight difference in
concentrations which amounts, on the average, to about 20% may
be explained by possible dilution of sulphur dioxide at a station
situated higher up.
Synchronism in the course of concentrations measured at both
points is disturbed during the passage of the fronts and wind direc-
tion change and also in the presence of stagnant situations in the
region of high pressure and formation of local circulation systems.
Typical examples of sulphur dioxide concentration registration are
cited for various meteorological conditions.
Editor's note: The abstract is presented as given in English with the original Russian article.
-------
THEORETICAL AND EXPERIMENTAL STUDY OF THE
ASPIRATION COEFFICIENT OF AEROSOLS
S. P. Belyayev, V. M. Voloshchuk, and L. M. Levin (USSR)
From Glavnoe Upravlenie Gidrometeorologicheskoy Sluzhby Pri Sovete Ministrov SSSR. (Chief Administration of
the Hydrometeorological Service Under the Council of Ministers of the USSR.) "Meteorologisheskie Aspekty
Zagryazneniya Atmosfery". (Meteorological Aspects of Air Pollution.) Sbornik dokladov na mezhdunarodnom
simpoziume v Leningrade - Iyul' 1968 g. (Reports delivered at the international Symposium in Leningrad -
July I960.) Pod redaktsiey d-ra fiz.-mat. naulc II. E. Berlyanda. (Edited by Prof. M. E. Berlyarid.)
Gidrometeorolgicheskoe izdatel'stvo, Leningrad, p. 281-294 (1971). (Hydrometeorological Publishing House.
Leningrad, (l97l).) 1
In studying aerodisperse systems, particularly aerosol pollutants of the
atmosphere, it is very important to understand the physical processes involved
in the aspiration of an aerosol into a given collecting device used for sam-
pling. If the collection is improperly organized, substantial distortions of
the concentration and size distribution function of the aerosol particles (par-
ticle spectrum) may arise, making the collected sample unrepresentative. The
present paper is devoted to the study of these distortions and to the deter-
mination of the feasibility of introducing appropriate corrections.
The distortions of aerosol characteristics introduced by the aspiration
process may be characterized by the aspiration coefficient £. For an iso-
disperse aerosol fraction, it is defined as the ratio of the particle concen-
tration in the collector G to the particle concentration in undisturbed space
(flow) G co far from the aspirator.* The difference of £ from unity will de-
termine the degree of destortions caused by the aspiration. In our view, these
distortions are chiefly determined by 1) the inertia of the aerosol particles,
which causes a difference between the trajectories of aerosol particles and
those of particles of the gas medium (e^); 2) the deposition of aerosol parti-
cles in the connecting lines of the collector (Ej); 3) the rebound of aerosol
particles from parts of the aspirator located close to the intake hole, follow-
ed by penetration of these particles into the collector (Er). For liquid-
particle aerosols, this phenomenon may be substantially complicated by atom-
ization of the droplets. On the whole, the coefficient £ may obviously be
represented in the form of the product.
The present paper is devoted to the study of the value of E^.
A more or less systematic experimental study of the distortion of an aer-
osol sample during aspiration was made long ago (Fahrenbach [7]; Zimmerman [8].)
~For a polydisperse aerosol, one can determine the corresponding mean integral value of the aspiration
coefficient.
- 30 -
-------
This question has been treated in many papers, Including those of May and
Druett [9]; Watson [10]; Walter [11]; Badzioch [12], Theoretical studies of
aspiration were made by Davies [13]; Levin [5], Voloshchuk and Levin [3, 4],
and Yur'yev [6],
It should be noted that experimental studies of aspiration are very con-
tradictory, and frequently cannot be compared since the work was carried out
on a polydisperse aerosol, and only the weight concentrations of dust were
determined in the sample and in the flow. However, even the results of
- 31 -
-------
experiments in which isodisperse aerosols were used are in poor agreement
with one another and with theory. As an illustration, Fig. 1 shows values
of e for aspiration into a tube, taken from the papers of Fahrenbach 1),
Zimmerman 2), Badzioch 3), and Walter A). Given here are the dependences
of £ on the ratio u/«OT (u being the average velocity in the intake tube
and the velocity of the incoming flow). Results of experiments with
isodisperse aerosols are illustrated with values of the Stokes number k
representing the ratio of the inertial forces acting on the aerosol par-
ticle to the viscous forces ( k= , where us is the particle settling
rate, 1 is the characteristic dimension, for which the tube radius is taken
in Fig. 1, and g is the acceleration due to gravity).
As is evident from Fig. 1, when «/«<* = 1 (the so-called isokinetic sam-
pling), for a number of experiments e^ | , but Walter gives e_= 0.5. In
Walter's experiments, even the tendency of £ to change with uju« differs
from the results of other authors (e = 1 when «/«« = 5,5) »
All this makes the study of aerosol aspiration a timely pursuit aimed
at determining £ values, which, by introducing suitable corrections into
the characteristics of a collected sample, will make it possible to obtain
a correct representation of the characteristics of the aerosol studied.
Theoretical papers on aspiration deal with the determination of the
aspiration coefficient , which may also be defined as the ratio j of a
flow of particles, through any surface ^ imagined in the region of the
stream, to the flow through this surface of inertialess particles moving
far from the aspirator in the same manner as inertial particles:
In the general case, the magnitude of e± depends on the Stokes number and
other parameters
where Li are some geometric flow parameters (for example, when the aerosol is
sucked into a tube, the ratio of its inner diameter d to the outer diameter
D, etc.), and Re and Re* are the Reynolds numbers of the particle and flow
respectively.
1. Theoretical Studies of Aspiration
(2)
(3)
- 32 -
-------
To find e±, it is necessary to solve two difficult problems involving
the determination of the field of velocities of inertialess particles u(r)
and field of velocities and concentrations of aerosol particles moving in the
field u(r). Since a detailed discussion of the procedures involved is beyond
the scope of this paper, we refer the reader to [5, 3, 4, 6], We will here
confine ourselves only to a description of the results obtained.
Aspiration of aerosol particles into a tube (axisymmetric problem) or
slit (two-dimensional problem) from a flow parallel to the walls of the tube
or slit was studied in [3, 4]. This involved a discussion of two extreme
types of streams of the gaseous phase in the tube (slit), unseparated and sep-
arated (Kirchhoff type), characterized by inertial separation of flow from
the edges of the tube (slit). Figure 2a shows diagrams of stream lines for
unseparated flows, and Fig. 2b, for separated ones (the shaded area represents
the so-called dead zone, i. e., rest zone separated from the flow by a free
boundary). Obviously, both diagrams constitute mathematical models of flows,
and the actual flow must differ from them. However, it is our impression
that the actual flow will constitute something intermediate between the above
models, since in the first case the influence of the wake is completely ne-
glected, and in the second case, the strongest wake apparently develops as
compared with the real wake.
uo>0; a.0 *0
u0<0; uo*0
b)

uo>0;
-f0
Fig. 2. Stream patterns.
- 33 -
-------
As the dimensionless velocity field for the two-dimensional case (slit)
we took the velocities in two-dimensional Bord mouthpieces which on the com-
plex plane z = x + iy are described by the formulas
U = 1 -f K0;; U2 = ^ In
u = 1 -f T,z = la — Y:
(4)
ln(-j--l); (5)
where the complex velocity ux = ux-—iuyt and 5 is a complex parameter. Equa-
tion (4) describes the unseparated flow in a Bord mouthpiece (Fig. 2a) on
which impinges from infinity a flow parallel to the abscissa axis at veloc-
ity u x> I when x = —00 and velocity u = 1 + uQ inside the Bord mouthpiece
when A'->+oo# Similarly, Eq. (5) describes the corresponding separated flow.
In describing the velocity field in an axisymmetric tube (Bord mouthpiece),
use was made of the numerical solution to the problem, obtained by Vandrey
[14] and describing separated flow.
The ratio u/ux is commonly considered for characterizing the aniso-
kineticity of a flow in a tube (slit). For theoretical formulas, it is more
convenient to use the anisokineticity coefficient
Which depends uniquely on this ratio. Here Q is the discharge of the gase-
ous medium through the aspirator. To unify the formulas, the quantities re-
ferring to unseparated potential flow past a slit are denoted by subscript
0; to separated flow past a slit, by subscript 1, and to separated flow past
a tube, by subscript 2.
If «o<0( the flow within a tube (slit) is decelerated, and the wake
forms outside the aspirator. Then, in all three cases,
*=l+«0 » * = +
(7a)
When «o>0 (the flow within the aspirator is accelerated)
tt(0) = l+M0, a — 1 + 1 Uq ;
u(' = 1 -f- 0,5k0 , = — 1 H 1 o,5w0 ' s — ^« 2.
(7b)
(7c)
- 34 -
-------
The presence of the multiplier 0.5 before uQ in (7c) is due to the fact that
in separated flow of the type under consideration, the region of motion of
the carrying medium in the aspirator occupies only a certain middle portion,
so that when

The following asymptotic formulas* were used to determine the aspiration
coefficient for the entire slit or tube in [3] and [4]:
•.(«=•?'(*)+
s-ai
i°{(^n - <8a>
where the asymptotic value (for k-+oo) of e»(&) is
s — 2
•?,(ft) = H« = 0,1,2.3...
E0(k) =
2e
\-i
Et(k)-
k = (2«)"
4 (3e 2 - e~x), ^ = (2«)_1
2 V^{-l + Msln-l-r(l--J-)x
x[,T'V"> 4"*.£.)]}, t>±
£,<*)=- 2.825 - -ff!L + - (1.936 - +
+T^)^ + (o.n.+^ + -1^r)«^-
(8b)
(8c)
(8d)
(8e)
Table 1 gives values of E»{k) f and the corresponding values of Es for
different u/u<*> (or a ), and k are given in Table 2.* The asymptotic values
of local aspiration coefficients near the axis of symmetry of the slit or
tube were found in the same manner. Analysis of the results obtained shows
that: a) the aspiration coefficient for the tube (slit) is by-and-large
linearly related to the anisokineticity coefficient Cl (therein lies the ad-
vantage of introducing ot); b) the effect of the wake on the aspiration
*By kcr is meant a value of the Stokes number for which, near the edges of the tube or slit there
takes place a total "quenching" of the uniform linear motion that the particles execute in an undisturbed
flow (for more detail, see [5, 2]).
- 35 -
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Table 1
Values of the Functions Eg(k)
*k
£o(*>
£,(*)
£2(*)
r.k
£o(*)
£, (*)
E2(k)
0,5
1,0
2,0
0,270
0,370
0,484
0,153
0,258
0,395
0,19
0,32
0,51
5,0
10,0
0,646
0,755
1,000
0,590
0,720
1,000
0,79
0,91
1,00
Table P
Values of £s(k) for Different s, a and k
(for a given 01, the first rows correspond to s = Q, the second rows to s = 1,
and the third rows, to s = 2)

Ilk

X
0,5
1.0
2,0
5,0
10,0
ov
"0
'-^Kp
-0,80

0,704
0,793
0,744
0,613
0,684
0,592
0,483
0,528
0,368
0,396
0,424
0,272
0,2
0,2
0,2
4,0
8,0
8,0
0,800
0,778
-0,60
0,838
0,908
0,886
0,778
0,845
0,808
0,710
0,763
0,694
0,612
0,646
0,526
0,457
0,568
0,454
0,4
0,4
0,4
1,5
3,0
3,0
0,225
0,187
-0,40
0,892
0,939
0,924
0,852
0,897
0,872
0,806
0,842
0,796
0,741
0,764
0,684
0,698
0,712
0,636
0,6
0,6
0,6
0,667
1,333
1,333
0,067
0,024
-0,20
0,946
0,969
0,962
0,926
0,948
0,936
0,903
0,921
0,898
0,871
0,882
0,842
0,949
0,856
0,818
0,8
0,8
0,8
0,250
0,500
0,500
0,012
+0.25
1,068
1,038
1,048
1,093
1,064
1,080
1,121
1,099
1,128
1,162
1,148
1,198
1,189
1,180
1,228
1,25
1,25
1,25
-0,200
-0,200
-0,200
0,012
+0,50
1,135
1,076
1,095
1,185
1,129
1,160
1,242
1,198
1,255
1,323
1,295
1,395
1,378
1,360
1,455
1,50
1,50
1,50
-0,333
-0,333
-0,333
0,042
+ 1,0
1,270
1,153
1,190
1,370
1,258
1,320
1,484
1,395
1,510
1,646
1,590
1,790
1,755
1,720
1,910
2,0
2,0
2,0
-0,500
-0,500
-0,500

+2,0
1,540
1,306
1,380
1,740
1,516
1,640
1,968
1,790
2,020
2,292
2,180
2,580
2,510
2,440
2,820
3,0
3,0
3,0
-0,667
-0,667
-0,667
0,332
+ 4,0

2,480
2,032
2,280
2,936
2,580
3,040
3,584
3,360
4,160
4,020
3,860
4,640
5,0
5,0
5,0
-0,800
-0,800
-0,800
0,800
- 36 -
-------
coefficient decreases with increasing Stokes number k and increases in direct
proportion to the absolute value of the anisokineticity coefficient ctj c) for
k^"(10-100)kcr, the aspiration coefficient differs markedly from both
e(£ = oo)=l-fa and e (£ = 0) = 1. For example, when a 0,5 with k»10kcr,
—- -f e<®>)~0,84, and when k~100kcr, -4-[e(0> + e<0)]~0,63, whereas in this case
*> 2 oi .
e(oo) = 0,5 ; d) in many cases, the influence of the wake on £ may be neglected.
For example, when |a|^0,5, and k> 0.3, the difference —e<°> , referred to
— [e<°' + E(0j]i amounts to less than 47>; e) other things being equal, when 0t<0 ,
2 0 1
e(k) for a tube is less than for a slit, and when ot>0, vice versa, i. e.,
for the axisymmetric case, £ is closer to unity than to the corresponding
planar case; f) the aspiration coefficient for the central portion of aspi-
rators may differ substantially from the total coefficient. For s = 0, this
difference is much greater than for s equal to 1 and 2. The formation of a
wake with decreasing inhomogeneity of the velocity field in the entrance por-
tion of the aspirator decreases the inhomogeneity of the local aspiration co-
efficient.
For large values of uo, formulas (8) do not solve the problem. For this
case, the small parameter method was used to find values of the aspiration
i/ nk
coefficient for a slit in the form or a power series in k=——
u
6,(ft')=l -n/ -foOfe'2), 5 = 0,1, — 0,- (9a)
sin2 n
H = 4" f av
Slftfa 1 — (!+»)-
[1— (I+a)Jll2L+(l + a)2i^f '
i1. = 4-a2Tr^jdv{-rf^+6~Tf^v) 2sIn20-*T' (9b)
0
where 0 (v) satisfies the transcendental equation
0(v) = TC^rotanf _ ctn^i- Oc)
For s = 0, formulas (9) hold for the entire interval of variation of
i. e., for—l^a<<» , and when s = lt only for—^—— • The values
3
of Mo a°d JJJ for some values of a are given in Table 3. For a-* J+0f the
- 37 -
-------
following asymptotic relation holds:
p, = a' | 0,451 0,664 (1 - j - a) -| ¦ 0 [ (1 -{- a? j }. (1 Q }
Comparison of (9) and (10) with the formula
e(ft')=- 1 -0,451ft' - 0,148ft'2-}- 0 (ft'3), (11)
obtained in [8] shows that when a-*-—1+0, they coincide asymptotically. If
l^a^ 0,7 » i» e-> k/«oo>3,3j formulas (9) and (11) coincide to within
157o. For the axisymmetric
Table J
Values of tue Functions )J_ ) (a)
and
Px(a)
1
"0
Ho
a
"0
Ho
-1,00
cc
0,454
+0,05
-0,048
-0,242
-0,95
19
0,440
+ 0,10
-0,091
-0,233
-0,90
9
0,428
+0,20
-0,167
-0,221
-0,80
4
0,405
+0,40
-0,286
-0,199
-0,70
2,333
0,383
+0,60
-0,375
-0.182
-0,60
1,5
0,362
+0,80
-0,444
-0,168
-0,50
1,0
0,342
+ 1,00
-0,500
-0,156
-0,40
0,667
0,322
+ 1,50
-0,600
-0,133
-0,30
0,429
0,303
+2,00
-0,667
-0,117
—0,20
0,250
0,285
+2,50
-0,714
-0,104
-0,10
0,111
0,267
+3,00
-0.750
-0,945
-0,05
0,053
0,258
+3,50
-0.778
-0,0865
0
0
0
+ 4.00
-0.800
-0.0800
a
-0,85
-0,80
-0,75
-0,70
-0,65
-0,60
-0,55
-0,50
—0,45
"0
Hi
11,333
0,413
8,000
0,402
6,000
0,389
4,667
0,374
3,714
0,359
3,000
0,344
2,444
0,325
2,000
0,306
1,636
0,284
case, the following value was obtained in [5] :
e(ft") = 1 -0,80ft",
(:U)
where
k"-
2k
Vu
- 38 -
-------
2. Experimental Studies of Aspiration
The experimental study of the aspiration process was carried out on a
special stand that made it possible to photograph the tracks of aerosol par-
ticles aspirated into a cylindrical tube from a flow. The stand consisted of
a closed-type wind tunnel in which the intake tube studied was mounted. By
blowing in isodisperse particles (spores of various plants were chiefly used)
at a certain distance from the tube (ahead of the flow), one can obtain an
aerosol flow that is partially sucked into the tube. Two flash lamps located
in a vertical plane illuminated in the flow a parallelepiped measuring
53 x 80 x 1.5 mm. The flow was photographed in the direction of the 1.5 mm
side. Patterns of flow of aerosol particles past the vertical meridional
plane of the intake tube were thus obtained. The photographs were taken
under two sets of illumination conditions: 1) when the pulses were rela-
tively long (of the order of 10 msec), and 2) when the illumination consist-
ed of three short consecutive pulses (of the order of 25-200 ysec).
In the first case, it was convenient to determine the particle trajec-
tories from a photograph, and in the second, from the distance between the
particle track lines one could determine the velocity field of the particles.
A detailed description of this stand is given in [1]. This stand can be
used to study both aspiration and deposition of aerosol particles from a flow.
The study was made on tubes up to 2.5 cm in dismeter at flow velocities from
2 to 20 m/sec with particles from 10 Pm in diameter.
By determining on the photographs the limiting paths of aerosol parti-
cles, which are defined by the particles entering the tube and flowing past
it, one can measure the tube diameter of these limiting trajectories $ in
the unperturbed region of the flow (at a distance of 5-6 tube diameters),
and use it to determine the aspiration coefficient
G
Su.
(13)
The value of u was determined from measurements of the flow rate of air
through the aspiration tube. The errors thus determined by the aspiration
coefficient did not exceed 10%.
In order to be able to compare the experimental and theoretical data, we
first conducted experiments with a very thin-walled tube (the wall thickness
was 1% of the inner tube diameter a ).
Results obtained from the study of the dependence of e on «/"<» for Stokes
numbers of 0.8, 1.2 and 5.2 and for the thin-walled tube are shown in the graph
of Fig. 3. For comparison, the same graph gives the theoretical curves for the
- 39 -
-------
si
v
Fig. 3. Theoretical (l) and experimental (2) curves of aspiration
coefficient £•,' for thin-walled tubes, end Badzioch's data for
x = 5.1 (3).
£
Qr
0/5 °.6 0,7 o,8
1,1
1,3
.4—
WO/a.
1,7
. 0 f>1
* 1,3
o
1.7
IS
FiS. 4.
MeaS,Jred values of ±!
oM
.. ^ fo:r thick-walled tubes
(Stokes number k = 1.24),
- 40 -
-------
corresponding Stokes numbers. It should be noted that the agreement of the
theoretical and experimental data is fully satisfactory, and as the Stokes
number increases, the difference between these two kinds of data decreases.
In order to determine the influence of the wall thickness on the aspi-
ration, a special series of experiments were carried out with tubes having a
relative wall thickness h/d equal to 0.02, 0.3, 0.7, and 1.5 (here h is the
absolute tube-wall thickness). The results obtained are illustrated in Fig. 4,
with data of one of the series of experiments. As shown in Fig. 4, for a
given number k, the graphs of the functions ®2/d2 versus w/u„ in log-log co-
ordinates are straight lines whose slope is independent of the tube wall
thickness (to a first approximation). In addition, even for an isokinetic
collection of the sample, ^ 1. Thus, if the wall thickness is substan-
tially different from 0, the sample collected tinder isokinetic conditions
will not be representative. Strictly speaking, for a tube with thick walls
and for a polydisperse system, the sample will not be representative at any
intake velocity, since for the given values of u(u<*\ one can have e = I for
only one value of k.
Thus, in the range 0,2 < k <20 when the sample is collected from the aer-
osol flow, to minimize the difference between the characteristics of the sam-
ple and the aspirated aerosol, two conditions are required: it is necessary
to provide for isokinetic conditions of collection and to construct a tube
with the thinnest possible wall thickness. Otherwise, suitable corrections
must be introduced.
It may be postulated that the disagreement of the experimental results
(see Fig. 1) is due to the fact that in different experiments, the wall thick-
ness of the actual tubes was different and determined different values.
However, a study of the photographs of the process of aspiration into thick-
walled tubes showed that substantial rebounding of the particles off the
end plane of the tube walls is possible, and that most of the particles are
sucked into the tube after rebounding. Obviously, in a gravimetric deter-
mination of the concentration (used by all the authors of the papers cited),
all the particles that have entered the tube as a result of rebounding off
its end plane become suspended in the total sample with the remaining parti-
cles.
In our experiments, however, we studied the "purely inertial" aspiration
(determined by the interaction of inertial and hydrodynamic forces), and parti-
cles that rebounded off the end plane of the tube were not considered. Appar-
ently, this as well as the fact that the other authors consider the influence
of certain other secondary effects (for example, the deposition of particles
inside the tube) explains the discrepancy in the experimental results. As
proof of this statement, we will.cite the results obtained in one of the most
comprehensive studies of Badzloch [12] (see Fig. 1). However, in contrast to
the work of Badzioch, we give a different notation to the points obtained for
- 41 -
-------
the same Stokes number but differing only in the mechanical properties of the
particles. It is obvious that for the same values of u/ua0 and k, the aspira-
tion coefficient should assume a completely defined value regardless of the
particle material. As is evident from Fig. 1, in Badzioch's experiments, the
results obtained for silicate catalyst particles differ markedly from those
obtained for zinc particles. Apparently, this unambiguously confirms the pre~
sence of a substantial rebounding of the particles off the leading edge of the
tube. It may be postulated that particles that have rebounded off the sili-
cate catalyst are sucked in to a greater extent than zinc particles. Moreover
using data obtained by photographing the aspiration process, one can state *
that the so-called dead zones obtained by Walter [11] by photographing aspira-
tion with a long exposure are but the image of particles of incoming aerosol
that rebounded off the tube during the exposure. For this reason, the conclu-
sions reached by Walter should not be applied to pure inertial aspiration,
but to aspiration complicated by other secondary effects. These conclusions
are valid only for a given tube (of a given shape), given particles (of given
material) and given aspiration conditions.
LITERATURE CITED
1. B e .1 a e b C. n. .rI;i6opaTopnaa ycTanoBKa a.ih ii3yit3. aT.\ioc({>. ii
OKeana, 4, 1968.
4. B o o m y k B. M., JleBiiii Jl. M. Hccjie^oBamie no acniipaium aspoao.iefi.
TpyAw H3M, Bun. I, 1969.
5. JleBHji Jl. M. Hcc.iejoBnmifi no ({iii3hkc rpy<5o;uicnepcHbix a3po3o;ieii. H3a.
AH CCCP, (W., 1961.
6. IO p b c b H. M. AcniipamiH aaposojia iepe3 mejib KoneMHoft uiiipmibi. MexamiKi
)kiukocth ii ra3a, A"» 4, 1937.
7. Fahrenbach. Die Dynamik ties Staubes und ihr Einfluss auf die Staub-
gehaltmessungcn. Forschung Ing. Wes., v. 2, No. 11, S. 395, 1931.
8. Zimmerman E. Z. Messung von Flugstaub in Rauchgasen. Verein. Dtsch.
Ingen., v. 75, 1931, S. 481.
9. May K-, Druett H. The pre-impinger of selective aerosol sampler. Brit. J.
Ind. Medicine, v. 10, p. 142, 1953.
10. Watson H. H. Errors due to anisokinetic sampling of aerosols. Amer. Hy-
giene Assoc. Quart., 15, No. 1, p. 21, 1954.
11. Walter E. Zur Problematik der Entnahmesonden und der Teilstromentnahnie
fur die Staubgehaltsbestimmung in Stromcnden Gasen. Staub. H. 53, S. 880,
1957:
12. Badzioch S. Collection of gas-borne dust particles by means of an aspirat-
ed sampling nozzle. Brit. J. Appl. Phys., v. 10, p. 26—32, 1959.
13. D a V i e s C. N. The sedimentation of small suspended particles. Symposium oil
Particle Size Analysis. Suppl. Trans. Inst. Chem. Eng., v. 25, p. 25, 1947.
14. Van drey F. Die Einstromung eines idealen Flussigkeit in eine kreisformige
Bordasche Miinduny. fngenieur Archive, Bd. XI, 1940.
- 42 -
-------
S P BELYAEV, V. M. VOLOSHTCHUK, L. M. LEVIN
THEORETICAL AND EXPERIMENTAL INVESTIGATIONS
OF ASPIRATION COEFFICIENT*
The methods of evaluation and experimental measurement of as-
piration coefficients are worked out for slots and tubes which deter-
mine the relation of aeroso! particle concentration in inflowing cur-
rent and in aspiration mechanism.
Aspiration coefficients for large and small numbers k are
calculated under potential flow patterns with and without breakaway
for a case of Bord flat nozzle. Interpolation for mean Stocks num-
bers is carried out and applicability boundaries of obtained results
are shown. The influence of wake and anisokinetic motion of aerosol
particles on aspiration coefficient is analysed. Analogous results are
received for Bord axis-symmetric nozzle (a model of axis^symmetric
thin-walled tube) under potential flow pattern with breakaway. Aero-
sol aspiration into a slot situated inside a flat canal is investigated.
Aspiration coefficients for tubes with different relative thickness
of the walls h(D are received with the help of track photographing
method of isodispersed aerosol particles, It was found that aspiration
coefficient E and ratio ufu„ are connected mutually by inverse po-
wer law
E = A(h]D, k)(uluj~ew.
where u is mean velocity in the tube, ua is velocity of inflowing
current, while A(u/D, k) -*¦ 1 at /t/D-+-Oand is decreased with in-
crease of h/D. The comparison of experimental and theoretical data
carried out for little h/D (thin-walled tubes) showed good conver-
gence. The obtained results, both theoretical and experimental differ
substantially from experiment data of Badzioch and Walter and are
in bad agreement with Watson data. This can be explained by the
fact that we investigate aspiration determined only by interaction of
inertial and hydrodynamic forces which is not complicated by the oc-
currence of particle break off from the edges and their sedimenta-
tion on tube walls.
~Editor's notes The abstract is presented as given in English with the original Russian article,
has been slightly edited.
- 43 -
-------
MECHANISM OF PHOTOCHEMICAL POLLUTION OF THE URBAN ATMOSPHERE
M. T. Dmitriyev, N. A. Kitrosskiy, arid V. A. Popov (USSR)
••'-.-c:.: Clavnoe lipravlenie Gidroir.cteorologicheskoy Sluzhby Pri Sovete Ministrov SSSR. (Chief Administration ot«
iiycrometcoroloGical Service Under the Council of Ministers of the USSR.) "Meteorologisheskie Aspekty
li:. ~.-ya:;ner,iya Atmosfery". (Meteorological Aspects of Air Pollution.) Sbornik dokladov na mezhdur.arodnom
v Lcningrade - Iyul' 1968 g. (Reports delivered at the International Symposium in Leningrad -
July 1565.) Pod rcdaktsiey d-ra fiz.-mat. nauk M. E. Berlyanda. (Edited by Prof. M. E. Berlyarid.)
Cidro«tccrol:',icheskoo izdatel'stvo, Leningrad, p. 295-309, (1971). (Hydrometeorological Publishing Housn
lo.-.in^-ad, (1971).) ¦ »
Photochemical reactions in atmospheric air are of interest from the
-eophysical as well as the sanitary-hygienic point of view. Of the 26 gases
occurring in pure air, in addition to oxygen, photochemical reactions may
involve the participation of nitrogen oxides, ozone, sulfur dioxide, formal-
dehyde, ammonia, and halogens. However, these substances are present in
very slight amounts whose sum total does not exceed 0.3 mg/m^, so that the
photochemical reactions involving them are not in any way significant.
Of practical importance may be only the photochemical formation of
ozone in the surface layer. Nevertheless, analysis of the daily variation
of ozone concentrations associated with meteorological conditions shows that
of the four main sources of ozone formation, the most effective process is
the photochemical oxidation of oxygen on clear days in autumn or spring, due
to the penetration of short-wavelength radiation into the troposphere (with
the ozone concentrations reaching 50-80 yg/m^ in some cases). The most fre-
quent increases in ozone concentrations (to 100-150 yg/m^) are due to penetra-~
tion of air masses from the lower stratosphere. Among other sources of ozone
may be mentioned its formation preceding storms, 2 to 4 hours before precipi-
tation [3], during which the concentrations reach 200-250 yg/m^, and the
formation of ozone during lightning flashes, snowfalls, and snowstorms.
Under natural conditions, the photochemical formation of ozone takes
place most frequently during oxidation of tree resins in coniferous forests,
or during oxidation of seaweed thrown up onto the shore, this being associates
with an increase in ozone concentrations to 50-60 yg/m^. However, it is
obvious that all natural processes of ozone formation in the surface layer,
which undoubtedly are of practical hygienic importance, may be completely
neglected in comparison with the photochemical formation of ozone in the pol-
luted atmosphere of cities in which the ozone concentrations reach 2 mg/m^ q^.
more [6].
Industrial emissions and motor transport considerably increase the numbe
of secondary components of atmospheric air, and this in turn increases the ^
quantity of photochemical reactions taking place in air and sharply increases
their effectiveness. Studies of the composition of atmospheric pollutants
show that as a rule, air contains many more chemical substances than are nre<5
- 44 -
-------
in the emissions of chemical plants or motor transport. This is due to
numerous chemical reactions occurring in atmospheric air. Under the influ-
ence of physicochemical factors, chiefly short-wavelength radiation, atmos-
pheric pollutants undergo various transformations through photolysis (upon
irradiation with sunlight), ozonolysis (in reactions with ozone), hydrolysis
(in reactions with water vapor), pyrolysis (decomposition on heating), oxida-
tion (reaction with oxygen), etc. Moreover, atmospheric pollutants and the
new chemical substances formed enter into reactions between themselves, so
that the quantity of products of these reactions is greatly increased.
In a sanitary-hygienic sense, the reactions of greatest interest are
physicochemical ones, which form new atmospheric pollutants whose toxicity
substantially exceeds that of the initial compounds. Thus, exhaust gases
form acrolein, aldehydes, ketones, organic peroxides. As the molecular
weight of the compound formed increases, its concentration decreases, but the
toxicity rises sharply. A particularly toxic compound formed in the atmos-
phere and first observed in urban air is peroxyacetyl nitrate (molecular
weight, 121.05) and other compounds of its homologous series [6]. This type
of processes also includes the formation of the so-called photochemical smog
in the air of large cities and industrial centers. In this case, in addition
to a strong biological effect (acute irritation of the upper respiratory
tract and eyes, aggravation of asthmatic diseases, etc.), there is a sharp
decrease in visibility. For this reason, in the presence of a high pollution
level and a sufficiently intense solar radiation (above 0.5 cal/cm^ min), large
American cities appear to be engulfed in a yellowish blue fog [6].
However, both laboratory and full-scale studies show that the formation of
photochemical smog takes place gradually, in the absence of obvious indications
(mist, acute irritation of the eyes) , with urban air always containing the
same compounds as are present in smog. The main components of photochemical
smog are photooxidants (ozone, organic peroxides, nitrate and nitrite, com-
pounds of the peroxyacetyl nitrate series), nitrogen oxides, carbon monoxide
and dioxide, hydrocarbons (alkanes, alkenes, aromatics), aldehydes, ketones,
phenols, methanol, ketene, epoxides, various radicals, etc. In an intense
photochemical smog, in the air of American cities, the concentrations of ozone
reach 2 mg/m3 (20 times the MPC of work areas), those of nitrogen oxides,
6 mg/m3 (60 times the mean daily MPC for atmospheric air) , while the hydrocarbon
concentrations reach 1.5-2 g/m^ [6].
The influence of meteorological conditions on chemical reactions in atmos-
pheric air substantially complicates their investigation. In this connection,
simulation methods assume a major importance in the study of this problem under
laboratory conditions. The purpose of simulation is to study the chemical
mechanism of the processes and to create concentrations of oxidants and other
newly formed pollutants that correspond to photochemical smog. In particular,
we used the photochemical, electronic-chemical, electric-discharge and thermo-
chemical methods. For example, ozone and nitrogen oxide concentrations charac-
teristic of photochemical smog are formed by passing pure air across an electric
- 45 -
-------
field. The simulation method was also used to study the formation of heavy
ions during the combustion of various substances, the action of electrons
on air containing nitrogen oxides, ozone, olefins, vapors of ethanol, acetone
acetaldehyde, tetrahydrofuran, hexane, dioxane, heptane, nitrobenzene, etc.
mole/cm^ sec x 10"
Fig. X. Dependence of overall reaction rate
of formation of ozone and nitrogen oxides in
pure air (mol/cm3 sec x 1CT ) on (as a function
of) electron energy.
Photochemical reactions in air were studied, particularly in the presence
of substances that are the most frequent atmospheric pollutants. Because of
the experimental difficulties involved in the determination of the threshold,
energies of photochemical processes, the irradiation of air in the various
experiments was conducted at a pressure of the order of 0.1 Torr with slow
electrons whose energy was varied by an electric field (method of critical
potentials).
Fig. 1 shows the overall reaction rate as a function of the electron
energy, obtained for pure air. The curve was obtained by differentiating th^
experimental dependence of pressure in a closed vessel on the electron energy
the reaction products being diverted onto a cooled surface, and for this *
reason each consecutive rise of the curve corresponds to the critical potent^
of a new reaction.
From the data obtained one can draw a conclusion concerning the course
of the following photochemical reactions (the numbers of which correspond to
- 46 -
-------
the numbers given in Fig. 1) in pure air and with the corresponding thres-
hold energies and wavelengths of light:
Process
Electron
Energy,
eV
Wave-
.length,
nm
(1) 0~ + 02 + Af-Of + M
3,0
407
(2) °2(32«~) + 02 — 03 + O
6,1
200
(3) + N2 —NO+ +NO
12,2
100.
(4) 0+ + N2 — NO+ + N
13,5
90
(5) + 02 —NO+ + NO
15,6
78
(6) N^ + Oj-NO^ + O
24,0
51
Below 3 eV (407 nm) no reaction takes place in pure air, and as the
energy increases, the formation of ionized ozone is observed, caused by
the appearance of negative ions of 0-atomic oxygen (reaction 1). However,
this process takes place only in the presence of an excess of free electrons,
and therefore it is practically undetectable in the presence of ultraviolet
radiation. An intense formation of ozone takes place at an electron energy
of 6.1 eV (200 nm), which corresponds to the appearance of excited oxygen
molecules that are not yet able to dissociate (reaction 2). When positive
oxygen ions appear at 12.3 eV (100 nm), a slight formation of nitric oxide
begins that is then somewhat intensified during ionization of atomic oxygen
at 13.5 eV or 90 nm (reaction 4). An intense formation of nitric oxide
takes place during ionization of molecular nitrogen at 15.7 eV or 78 nm
(reaction 5). The formation of nitric oxide is substantially accelerated
during the dissociative ionization of nitrogen at 24 eV or 51 nm (reaction 6).
The method of critical potentials was also used to study the mechanism of
chemical reactions in air in the presence of nitrogen oxides and ozone.
Fig. 2 shows the rate of formation of ozone and nitrogen oxides as a
function of the electron energy in air in the presence of nitrogen oxides
and ozone. Whereas ozone is formed in air in accordance with reaction (2) at
an electron energy of 6.1 eV (curve 2), the formation of ozone in a mixture
of air and nitric oxide begins only at an electron energy of 2.1 eV or 580 nm
(curve 3). A much more intense formation of ozone takes place in the reaction
of nitrogen dioxide with oxygen at an electron energy of 3.1 eV (curve 1),
which corresponds to a wavelength of light of 395 nm. At an electron energy
of 7 eV, the reaction rate of ozone formation in the presence of nitrogen
dioxide is 5-6 times as high as in pure air. The formation of nitric oxide,
which begins in accordance with reaction (5) at 15.6 eV (curve 4), takes place
to the same extent in pure air and in the presence of ozone (black points).
The formation of ozone in the presence of nitric oxide and nitrogen dioxide
may be explained by the excitation, dissociation or reaction of nitrogen
- 47 -
-------
oxide molecules and the secondary reaction of atomic oxygen:
NO*-fOa — N0, + 0, (7)
NOj-AA—NOa—NO + O. (8)
NO^ + 0,—NO + O3. <9>
0 + 0,-f Af—03 + jW. (10)
It is interesting to note that the formation of ozone from nitric oxide
begins at a lower electron energy than from nitrogen dioxide. However, in
the latter case the reaction rate is higher. This fact may be accounted for
to some extent by the influence of pressure on reaction (2). Whereas the
formation of ozone from the dioxide is a molecular reaction (reaction 9),
the rate of ozone formation from nitric oxide is almost completely determined
by a slower termolecular reaction (reaction 10). Thus it may be expected
that at atmospheric pressure, at which the termolecular process is more prob-
able, the rate of photochemical reactions of ozone formation from nitric
oxide is not very different from the reaction in the presence of nitrogen
dioxide. Under the influence of radiation of ultraviolet lamps, the forma-
tion of ozone takes place at wavelengths up to 253 nm (1), but the main
reaction with a quantum yield of about 2, corresponding to reactions (2 and
10), takes place at 180-220 nm, which is in accord with reaction (2), re-
corded during the action of electrons. At wavelengths above 200 nm, the
quantum yield quickly decreases to 0.1 molecule per absorbed quantum. For
the 180-253 nm wavelength range of the spectrum of PRK (straight mercury-
quartz) gas-discharge lamps, the energy yield of ozone in air amounts to an
average of 22 molecules per 100 eV, or 395 g/kW-hr (for a quantum yield of
1.2).
¦1 -1?
mole; itrf- see x 1C
Fig. 2. Reaction rate in the presence
of nitrogen oxides and ozone versus
electron energy.
1 - formation of ozone in a mixture of
air and nitrogen dioxide, 2 - in pure_
air, 3 - in a mixture of air and nitric
oxide,_b - formation of nitric oxide in
pure air and in the presence of ozone
(black points).
- 48 -
-------
Fig. 3 gives values of the energy yield of ozone formation during the
action of the PRK lamp, mounted at the center of the chamber, as a function
of its volume. Inasmuch as the degree of absorption is small (less than 15?)
when the dimensions of the chamber are of the order of a few meters, and
the yield of ultraviolet radiation does not exceed 15%, the ozone yields
obtained, amounting to 2-4 g/kW-hr of the lamp's energy, are considerably
below the photochemical energy yield.
Additional studies have established that the formation of nitric oxide
and nitrogen dioxide under the influence of radiation in the 180-253 nm wave-
length range initially occurs via ozone, and later, mainly via nitrous oxide,
which is a product of a termolecular reaction that is not detected because of
its low rate at low pressures.
The following reactions take place in this case:
0,-A/W02-fO, (11)
Ni + 0 + M — N20 -f M, <12)
N20 + 0-> 2NO, (13)
NO -f- 03—~ N02 -j- 02, (14)
NO + O-t-M — N024-Af. (15)
The quantum yield of photochemical
oxidation of nitrogen does not exceed 0.03
molecule, and the energy yield is no greater
than 0.4 molecule of nitrogen dioxide per
100 eV (7 g/kW-hr). Thus, when PBK type
lamps act on pure air, 50-60 times less
nitrogen oxides are formed than ozone. The
formation of ozone in air containing nitric
oxide under the influence of ultraviolet
radiation takes place with an energy yield
of 460 g/kW-hr, and in pure air containing
nitrogen dioxide, 680 g/kW-hr. Thus, nitrogen
oxides accelerate the formation of ozone only
slightly in the presence of light with wave-
length up to 25 3 nm. When nitrogen dioxide
is decomposed at wavelengths up to 395 nm,
the process of ozone formation is not limited
to the depletion of nitric oxide (process 7),
since its concentrations are restored in
reaction (8). The formation in (8) of atomic oxygen and also nitric oxide, and
the subsequent formation of ozone (reactions 7 and 10) are key factors in
Fig. 3. Yield of ozone in chamber
with PRK lamp as a function of
chamber volume.
1 - PRK-7 lamp, 2 - PRK-4 lamp
- 49 -
-------
bringing about the photochemical reaction in atmospheric air. Since, however
the formation of ozone according to reaction (10) is a much faster process
than the oxidation of nitric oxide, the rate-determining step in the photo-
chemical reaction in atmospheric air is the oxidation of nitric oxide. More-
over, in a slow process of nitrogen oxidation, the ozone formed interacts
with nitric oxide, so that its steady-state concentration remains insignificant:
In the photochemical formation of ozone in the presence of nitrogen oxides
nitrogen atoms are also formed to a slight degree, particularly in the follow^
ing reactions:
NO*-f O —02+N. (16)
NO* + NO — N02 -f N. (17)
NjO + O—N02 + N. (18)
The chief process of formation of nitrogen atoms is reaction (16), in
which the excitation energy of initial atoms does not exceed 1.5 eV, which
corresponds to a wavelength of 800 nm. The energy yield of formation of
nitrogen atoms does not exceed 0.1 atom per 100 eV, but the reactions between
them, organic compounds, and ozone may lead to the formation of highly toxic
nitrogen containing oxidants (5). The presence of hydrocarbons leads to the
photochemical formation of peroxides and other oxygen-containing compounds
that readily give up an oxygen atom, and are thus able to oxidize nitric
oxide and form ozone. As a result of the accumulation of perioxides and
acceleration of the oxidation of nitric oxide, the energy yield and concentra~
tions of the ozone formed in the presence of hydrocarbons increase by a factoj-
of 3-5, as in the case of the influence of nitrogen oxides. A substantial
influence of hydrocarbons on the rate of the photochemical reaction is observ©^
only when the concentration of hydrocarbons exceeds that of nitric oxide by a
factor of not less than 2-3.
In a static system, when ultraviolet radiation with a wavelength above
260 nm is used, which cannot induce photochemical reactions in pure air, the
kinetic equation for the formation of ozone in air has the form
/ ~
*(03)^A/1-'1N0T ]/ jno] +2 , (19>
j = i
where v(0^) is the rate of ozone formation, I is the intensity of ultraviolet
radiation, [NO] is the nitric oxide concentration, C-^ is the hydrocarbon con-
centration, a, is the ozone-forming efficiency of the hydrocarbon relative to
nitric oxide, dependent on the chemical properties of the hydrocarbon, and k
is a proportionality coefficient.
- 50 -
-------
To confirm the results obtained, of major interest are measurements
made with a DRVE-200 type lamp. A study of the spectral emission character-
istic of this lamp showed that the lower boundary of its spectrum begins at
280 nm, and the main fraction of ultraviolet radiation is located in the
295-320 nm range, which is close to the spectrum of natural radiation. It
was found that when pure air is irradiated, no ozone and no nitrogen oxides
are formed. When air is irradiated in the presence of nitric oxide and
hydrocarbons, the concentration of oxidants after 1 hour reaches 3 mg/m^
for 1-hexene, 1 mg/m^ for tetrahydrofuran, and 0.7 mg/m3 for cyclohexane
(Fig. 4). The highest ozone-forming efficiency is displayed by unsaturated
hydrocarbons.
ng/m5 Photochemical reactions may take
place with practically any organic pol-
lutants. For this reason, their
hygienic importance is particularly
great in emissions of low-toxicity com-
pounds in large concentrations. In
atmospheric air, the photochemical oxi-
dation of these compounds may lead to
the formation of toxic products harmful
to public health. As an example, let
us cite an experiment with air contain-
ing ethyl alcohol (i.e., a weakly toxic
compound present in the emissions of
the hydrolysis industry). The experiment
consisted in studying air on a mass
spectrometer before and after a physico-
chemical action (by using the simulation
method under laboratory conditions).
The data obtained are shown in Fig. 5 in
the form of a dependence of the ioniza-
tion current (proportional to the con-
centration) on the time of recording on
an automatic potentiometer. As is evi-
dent from the figure, before the irradia-
tion, only the ethanol peak was recorded. After the irradiation, the ethanol
peak decreased slightly, but peaks of new compounds appeared. The identifica-
tion of the compound was made by using a magnetic field whose strength was
monitored during the recording. The mass spectrograms obtained made it possi-
ble to determine the concentrations, which are listed in Table 1.
Fig„ 4, Concentration of oxidants as a
function of irradiation tine for DRVE-200
lamp with a chamber volume of 100 1, con-
centration of nitric oxide of 10 mg/m?. _
and hydrocarbon concentration of 35 mg/nr.
1 - 1-hexene, 2 - tetrahydrofuran,
5 - cyclohexane.
As is evident from the table, the physicochendcal action caused ethyl
alcohol to form at least seven new compounds. Of these, three (methanol,
acetaldehyde, and formaldehyde) are much more toxic than the initial pollutant,
ethanol. As a result, the concentrations of acetaldehyde and formaldehyde
formed after the physicochemical action exceeded the MPC approximately 900-fold.
- 51 -
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mg/1
70
15

a)
to
1
20
IS
10
b)
TJ
x:
u x:
O
>a
W
Af\ A, /v £Ll
10 15 min.
Fig. 5. Mass spectrogram of the products of photo-
chemical reactions of ethyl alcohol in air before (a)
and after irradiation (b).
Table 1
Products of Photochemical Reactions of Ethyl Alcohol in Air and Toxicity
Factor Before and After Irradiation
Compound
Chemical
Formula
Initial
Mixture,
mg/l
Mixture
Obtained,
mg/1
MPC For
Work Areas
Ratio of
Concentra-
tions to
MPC
Ethanol
G;H-,OH
24 (2
15,1
1
15,1
Methanol
CtfjOH
—
0,11
0,05
2,2
Acetaldehyde
CH3CHO
—
4,45
0,005
890
Formaldehyde
ch2o
—
0,93
0,001
930
Methane
ch4
—
0,85
—
—
Ethane
c2h6
—
0.73
—
—
Acetylene
c2h2
—
0,31
—
—
Ethylene
c2m4
—
1,65
—
—
Toxicity Factor (relative
24,2
1837
—
—
to MPC)

52 -
-------
Whereas in the initial mixture the ethanol concentration exceeded the MPC
24-fold, in the mixture obtained after the physicochemical action, the con-
centrations of the four main toxic substances (formaldehyde, acetaldehyde,
ethanol and methanol) exceeded the MPC 1840-fold. Thus, after the action
was applied, the toxicity of the mixture formed increased 76-fold.
Since ethyl alcohol is a fairly stable chemical compound with saturated
bonds, it may be expected that similar results can be obtained with any
other compounds of lew toxicity. For compounds with unsaturated bonds, the
role of physicochemical factors is obviously much greater.
If one proceeds from the fact that radiation with wavelength of less
than 290 nm completely fails to penetrate down to ground level, the following
conclusions may be drawn from the above photochemical study. The formation
of nitrogen oxides and ozone in pure air is almost completely excluded. The
largest amount of ozone is formed by the action of light with wavelength of
less than 580 nm in air polluted with nitric oxide (this process is also
observed in the wintertime). The chief formation of ozone, resembling atmos-
pheric pollution in character, may take place under the influence of light
with a wavelength, of less than 395 nm in air polluted with nitrogen oxides.
The rate-determining step in the overall process is the oxidation of nitric
oxide. The presence of hydrocarbons, mainly unsaturated ones, intensifies
the processes of oxidation of nitric oxide and accumulation of ozone, and
promotes the formation of nitrogen-containing organic compounds. The reactions
between ozone, atomic oxygen and nitrogen, nitrogen oxides, and organic com-
pounds lead to the formation of a group of oxidants that are the components of
photochemical smog.
Full-scale observations were made in different cities under different
meteorological conditions. The principal results on the concentrations of
ozone (or oxidants) are shown in Table 2. It is evident from the table that
under the conditions associated with the polluted atmosphere of cities, sub-
stantial ozone and oxidant concentrations are observed which considerably
surpass the ozone concentrations in pure air. Thus, in the summertime in the
center of Moscow, concentrations up to 400 yg/m^ were observed, with the ozone
concentration proportional to the concentration of nitrogen oxides and to the
square root of the concentration of hydrocarbons. The ozone concentration in
the wintertime reached 10-200 yg/m^. In Baku, the total amount of oxidants
at the intersection of Samed Vurgun and Bakikhanov Streets was 70-80 yg/tn^,
and in the area of the Karayev Petroleum Refinery, up to 150 yg/m^. In sunny
weather, the averaged concentrations were 2.5 times, minimum ones 2.3, and
maximum ones 1.9 times as high as in cloudy weather. In southern cities, the
average concentrations in cloudy weather were 2 times as high as in Moscow,
and in sunny weather, 1.5 times, which is due to more solar radiation. On the
basis of individual observations, the maximum concentrations in Moscow are
higher than in southern cities, which may be due to a higjher content of
exhaust gases.
- 53 -
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Table 2
Ratio of Average, Maximum and Minimum Values of Ozone Concentra-
tion in Sunny and Cloudy Weather for Different Points
Point
Number of
Concentration
Obsei*-
vations
Av.
Min.
Max,
Moscow:

Pogodinskaya St,
Samotechnaya PI,
Krasnaya Presnya St,
75
75
112
2,3
4,5
2,2
3,0
4,0
1,9
2,0
1,5
2,4
Kotel'nicheskaya Quay
44
1,5
2,1
2,0
Baku:
Vurgun St.
Im. 22 Parts'yezda
55
17
2,3
3,0
3,0
2,5
2,0
1,2
Karayev Petroleum
Refinery
Yerevan, Markaryan St,
30
32
2,2
1,8
2,0
2,0
1,9
1,3
Batumi, Petroleum
Refinery
Average
45
2,0
2,5
2,0
2,3
2,3
1,9
Since one of the most sensitive indices of the occurrence of photo-
chemical reactions is the oxidation of nitric oxide, the dynamics of the
ratio of nitric oxide to nitrogen dioxide concentrations under different
conditions was investigated. All the emission sources of nitrogen oxides
contained over 95% nitric oxide in the total oxides. It is generally assume^
that nitric oxide rapidly oxidizes in air as a result of the reaction
2NO -f 02 —2N02 (20).
Moreover, the kinetic equation of the oxidation of nitric oxide by
oxygen corresponds to a third-order reaction, and the rate of the oxidation
reaction is proportional to the square of the nitric oxide concentration.
For this reason, reaction (20) has real significance only at concentrations
of the order of 1 g/m^, which are practically never found in atmospheric ait
At a concentration of 50 mg/m^, the oxidation of 50% of nitric oxide takes
place in 10 hours. Hence, at a concentration of 5 mg/m^, such a degree of
oxidation will be reached only after 40 days. Thus, reaction (20) practical!
does not occur under the conditions prevailing in atmospheric air. However
in atmospheric air, the ratio of NO to NO2 changes continuously as a result*
of reaction (7).
As an example, Fig. 6 shows typical variations of the ratio of nitric
oxide to nitrogen dioxide concentrations with the time of day. For a total
content of nitrogen oxides from 20 yg/n»3 to 2.5 mg/in^, the minimum value of
this ratio is 1.8-2.6 in summer and 4.8-8.5 in autumn and winter. On the
- 54 -
-------
average, in summer, of the total oxides, N0~ accounts for 18% in autumn
and 9% in winter.* As is evident from the figure, soon after midday, the
ratio of nitric oxide to nitrogen dioxide concentrations is rapidly restored,
and the concentration of nitric oxide again becomes much larger than that of
the dioxide. This is undoubtedly due to the subsequent interaction of nitro-
gen dioxide with atmospheric moisture, whereby the bulk of the NC^ deposits
with the aerosol, and the remainder is discharged into the air in the form
of nitric oxide. Nitric oxide does not react chemically with moisture and
Fig. 7 shows the variations of oxi-
dant concentrations with the time of day,
which reveal a distinct relationship to
the action of solar radiation. Whereas
at 8-9 A.M. the oxidant concentration
was 30-60 yg/m^, around 12-2 P.M. it rose
to 80-170 yg/m^. Starting at 3 P.M., the
oxidant concentration decreased, and by
7 P.M. amounted to only 10-20 yg/m^.
The character of this dependence remains
unchanged for different geographic zones.
Comparison of the data of Fig. 6
and 7 shows that the decrease in nitric
oxide concentration corresponds to an in-
crease in oxidant concentration and vice
versa, indicating a close relationship
the time of day in autumn (l) and summer (2). between these two processes.
The unquestionable relationship
between the formation of oxidants and the discharge of hydrocarbons is
evidenced by the data shown in Fig. 8. As the distance from the local emis-
sion source increases, the concentrations of oxidants rapidly decrease. At
a distance of over 1 km, the concentrations of oxidants correspond to the
background values. In a study of air under conditions of pollution with
exhaust gases of motor transport, no relationship was established between the
concentration of oxidants and the height of sampling. Thus, at the level of
the 12th floor of a highrise building on Kotel'nicheskaya Quay in Moscow,
the concentration of oxidants was an average of 20% higher than at ground
level, whereas the concentration of oxides was slightly reduced [4].
The concentration of oxidants is affected by other meteorological elements
in addition to the solar radiation intensity. The concentrations of ozone and
other oxidants decrease with increasing wind velocity, absolute air humidity,
* [sic.-transl.].
is practically insoluble in water.
- 55 -
-------
Fig. 7. Concentration of oxidants as a function
of the time of day.
1 - Baku, Karayev petroleum refinery, 2 - Moscow,
Samotechnaya Plaza, 3 - Baku, street intersection.
ng/m
Fi§. 8. Average concentrations of
oxidants versus distance fron local
emission source in Baku at the Karayev
petroleum refinery.
-------
and rising air temperature. Ozone and other oxidants disappear from air
almost completely in summer during precipitation [3]. As the atmospheric
pressure rises, the oxidant concentrations increase slightly, but the
strongest effect on the increase of oxidant concentrations is caused by
temperature inversions associated with the formation of stagnation zones.
It follows from the data obtained that the concentrations of oxidants change
under the influence of meteorological elements as do ordinary atmospheric
pollutants, with the exception of solar radiation and air humidity. As the
radiation intensity increases, the concentrations of oxidants rise, and as
the humidity increases, they decrease, whereas for ordinary pollutants (for
example, sulfur dioxide) the opposite relationships are observed.
Thus, the full-scale studies performed confirm the basic relationships
leading to photochemical reactions in atmospheric air. In addition to physi-
cochemical studies, an experimental approach to the study of the biological
effect of photochemical reactions is being developed at the present time.
Chambers with quartz lamps in which different substances are irradiated have
been constructed for this purpose. A study of the biological effect of oxi-
dants established that the odor threshold for ozone (in comparison with pure
air) is 18-22 pg/ni^. The adapted threshold of continually perceived odor
(when the subjects are placed in rooms with changing ozone concentration) is
200-250 yg/m3. An acute irritation of the mucosa of the eyes is observed
at concentrations of 500-700 yg/m^. The laboratory and full-scale studies
conducted indicate the urgency of the problem of studying photochemical
reactions in a polluted atmosphere for cities and industrial centers under
the conditions prevailing in the USSR, so that research on this problem will
be continued and expanded.
LITERATURE CITED
1. H m h t p ti c b M. T. HeKOTopbie (J>miiKO-xnMii>iecKne nponeccbi b B03iiyxe. H3B.
AH CCCP, cep. (j)ii3. aTMocc{>. » oKeaiia, t. I, Ks 3, 1965.
2. ,A m it t p h c b M. T. miiKO-xiiMU'iecKne npoucccw, npiiaojauiiie k o6pa30Baimio
h pa3^oi«CHiiio okiic/iob a30Ta b B03Ayxc. Tpyflbi HUHTMn, Ns 13, 1965.
3. ilMHTpHCB M. T. nponios rpo30Bbtx Aowacii. Ilpiipoaa, Ms 7, 1965.
4. Amhtphcb M. T. ZI,03hi iioiiii3>ipyiouicro imyicmm, B.iiiniouuic na cocraB aT-
MOC(t>epu. ATOMHaa sncpniH, t. 16, JSTs 3, 1964.
5. JlMiiTpneB M. T., KiiTpoccKiifi H. A. H3yMe»ne MexaHii3Ma 4>h3iiko-xiimii-
MecKHx pcaKuiift b aTMoc(|)epiiOM B03ayxe. Maiepiia.iu Koii(j)epeiim!» Heicth-
tyTa oCmefi ii KOMMyiia.ibHOfi riiniciibi hm. A. H. Cwcmia AMH CCCP no mo-
ral* Haymiux ucc.ie.iOBa tin A 3a 19GG roa, M., 1967, CTp. 14.
fi. Motor Vehicles, Air Pollution and Health. US Government Printing Office,
Washington, 1962.
- 57 -
-------
M. T. DMITRIEV, A'. A. KlTROSSKfY, V. A. POPOV
MECHANISM OF PHOTOCHEMICAL POLLUTION OP TOWN ATMOSPHERE *
Intensive photochemical reaction in atmospheric layer can go on
in the presence of substantial concentrations of nitrogen oxides and
2—3 times as large concentrations of hydrocarbons. In this case, pho-
tochemical ozone formation begins under the influence of radiation
with the wave length less than 580nm, while in clean air the wave
length necessary for this process amounts to 253nm. Ozone forma-
tion goes on at oxidation of nitrogen oxide under the influence of
light with wave length up to 580nm and at excitation of nitrogen
dioxide by radiation with the wave length up to 395nm. Hydrocar-
bons speed up oxidation of nitrogen oxide which is rate-deter-
mining step.
Natural investigations of photochemical reactions in polluted air
showed that in sunny weather concentrations of ozone and oxidants
are 2—2.5 times as high as in foggy weather. The ratio of nitrogen
oxide concentration to that of nitrogen dioxide which amounts to
20—40 at night decreases in the daytime up to 2—5, and then returns
again to initial values. For all this, concentrations of ozone and oxi-
dants minimal at night increase sharply in the daytime, especially
in sunny weather. Oxidant concentrations decrease significantly with
the increase of distance from a local source of hydrocarbon emission.
Under the influence of meteorological factors (wind velocity, tempe-
rature, atmospheric pressure, lapse rate, precipitation) oxidant con-
centrations change like common atmospheric pollution.
With the increase of radiation intensity and decrease of air hu-
midity, oxidant concentrations of photochemical origin are growing,
while concentrations of common pollution are diminishing.
While studying biological effect of oxidants, it is established that
the threshold of comparative smell amounts to 18—22 mcg/m3, the
threshold of continuouslfereiVsmcll is 200—250 mcg/m3, and strong
irritation of mucous eyes membrane is observed at 500—700 mcg/m3.
* Editor's note: The abstract is presented as given in English with the original Russian article
out. lisis been slightly edited.
- 58 -
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PROCEDURE FOR DETERMINING THE CONTENT OF TRACE ELEMENTS IN
PRECIPITATED WATER
T. N. Zhigalovskaya, R. I. Pervunina, V. V. Yegorov,
E. P. Makhon'ko, and A. I. Shillna (USSR)
From Glavnoe Upravlenie Gidrometeorologicheskoy Sluzhby Pri Sovete Ministrov SSSR. (Chief Administration of
the Hydrometeorological Service Under the Council of Ministers of the USSR.) "Meteorologisheskie Aspekty
Zagryazneniya Atmosfery". (Meteorological Aspects afAir Pollution.) Sbornik dokladov na mezhdunarodnom
simpoziume v Leningrade - lyul' 1966 g. (Reports delivered at the International Symposium in Leningrad -
July 1968.) Pod redaktsiey d-ra fiz.-wt. natfk H. E. Berlyanda. (Edited by Prof. M. E. Berlyarid.)
Gidrometeorolgicheskoe iidatel'stvo, Leningrad, p. 310-519 (1971). (Hydroneteorological Publishing House.
Leningrad, (1971).)
The determination of the content of trace elements in precipitated water
and cloud water is of interest in connection with the study of the washing out
of atmospheric pollutants by precipitation and the study of transport of cloud
masses. Such determinations can give results that are of interest in the geo-
physical and hygienic sense only when sufficient data are available, and it is
therefore necessary to have a method of determination that is as little time-
consuming as possible. In addition, because of the low concentration of ele-
ments in rain and cloud water, the analytical procedure should be highly sen-
sitive, and the preliminary preparation of samples should be as simple as pos-
sible in order to minimize the probability of introducing contaminants.
The object of the present work was to develop a sensitive spectral pro-
cedure for the simultaneous determination of the following trace elements in
samples of precipitated water: lead, chromium, vanadium, manganese, cadmium,
nickel, cobalt, molybdenum, copper, zinc, bismuth, aluminum, and titanium.
These components were selected as the most important ones for air hygiene.
In most cases, the content of trace elements in atmospheric precipita-
tion is below the sensitivity of a direct determination. To raise the con-
centration of the elements studied, preliminary concentration is employed.
1. Selection of the Method of Concentrating Trace Elements
in the Analysis of Rain and Cloud Water
At the present time, the following concentration methods are used in ana-
lyzing liquid samples for the content of trace elements:
(1) extraction [3, 2];
(2) cation exchange [1, 9];
(3) evaporation [2].
In selecting the concentration method, analysis of samples of rain and
- 59 -
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cloud water for the content of trace elements should consider the following:
(a) degree of concentration;
(b) probability of introduction of contaminants;
(c) time and labor required when the method is used for mass analyses.
Comparative values of the degree of concentration by means of the above-
indicated methods are cited by V. Ya. Yeremenko [3], Concentration by ex-
traction makes it possible to obtain the highest degree of concentration.
However, along with the high degree of concentration, the extraction method
also has its drawbacks. One of them is the use of a large number of reagents
which must be thoroughly purified.
Higher grade reagents, i. ., chemically pure ones (c. p.), contain a
comparatively large number of impurities amounting to hundredths of a percent
and only in acids (hydrochloric, nitric, sulfuric) not more than 2 x 10-3°/, Qf
impurities are allowed [6, 8], Such amounts of impurities do not affect the
results in the analysis of samples with high concentrations of elements.
In the analysis of samples containing trace quantities of elements of
the order of 10-^ mole/1 or less, these reactants must be additionally puri-
fied. When a large number of trace elements are determined in the same sample
the extraction method requires a separate isolation of the group of elements
by various extracting agents, and this presents a certain difficulty in the
application of this method to mass analyses of samples.
Concentration by cation exchange involves a lesser degree of concentra-
tion as compared with extraction. However, this method makes it possible to
use a smaller number of reactants, mainly, hydrochloric acid of v. p. grade
and a cation exchanger. Hence, fewer contaminants are introduced in the
course of cation exchange. Nevertheless, when concentrating trace elements
by cation exchange, one must consider the results of blank tests. Following
the concentration, the background levels of the trace elements may be higher
than the ones being determined, since according to our calculations, acid of
v. p. grade contains 1-5 x 10-5 mg/ml of impurities. Thus, when 50 ml of 4
N hydrochloric acid is used for elution and an overall 100-fold concentration
as in our case, the method is applicable to trace element concentrations of
the order of 1 x 10"*3 mg/1 in the sample. In this case, the background con-
centrations of the elements entering the sample with the acid amount to approxj
mately 2 x 10-5 mg/ml. We used this method to determine the trace elements in
rain water in cases where the sample volume was 1-2 Jt. The use of the method
loses meaning when it is mecessary to analyze samples less than 1 H in volume.
The difficulty of using the method in mass analyses for the content of trace
elements lies in the preparation of the cation exchanger.
Evaporation yields the same degree of concentration as cation exchange,
but in contrast to the latter, the evaporation method uses only one reagent,
hydrochloric acid. In evaporation (especially in glass vessels), the con-
centrate obtained may be contaminated with additional impurities due to a
- 60 -
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certain solubility of the glass [7], For this reason, it is recommended that
the evaporation be done in platinum or quartz crucibles. Other preventive
measures aimed at achieving an adequate purity should also be employed, name-
ly: the sample shoud be evaporated in portions over a water bath, the cru-
cible containing the sample being covered with an inverted funnel. To de-
crease the adsorption of the elements on the walls of the vessel used for evap-
oration, hydrochloric acid of c. p. grade should be used in the amount of 1 ml
per 100 ml of sample.
If a sample with a volume of 100 ml is brought down to 1 ml, the amount
of acid in the sample following the concentration remains equal to 1 ml. One
ml of hydrochloric acid of v. p. grade, which we used, contains about 1 x 10" 5
mg/ml of each of the elements. Let us postulate that the trace element being
determined is present in water in a concentration of about 1 x 10~3 mg/1 or
1 x 10"^ mg/ml, this being one order of magnitude larger than the concentration
of the element in 1 ml of acid, and hence, fully admissible. We used the meth-
od to analyze samples less than 500 ml in volume. In this case, the errors
introduced by the reagents were slight.
In the determination of trace elements in cloud water collected during
the study of the washing out of atmospheric aerosols, or in the determination
of trace elements in rain collected in fractions, the sample volume may be
less than 100 ml. For the latter case, we developed a method of concentra-
tion by electrolytic deposition on a carbon electrode. The method consisted
in isolating from the sample the elements being determined by depositing
them on a carbon electrode 3 mm in diameter serving as the cathode. The pre-
treated electrode was placed in a beaker containing the sample and connected
to the anode compartment by an electric bridge. A platinum wire placed in a
beaker containing 0.1 N nitric acid of v. p. grade served as the anode.
The intensity of the spectral lines, proportional to the amount of sub-
stance deposited on the electrode, depends on the method of treatment of the
electrode, current intensity, acidity of the solution and electrolysis time,
as shown in Tables 1, 2, and 3.
Table 1
Deposition Coefficient as a Function of the Normality of Solxrtion (I =» 20 mA»
electrolysis time t = 2 hours, C = 0.005 og/l)
Normality
of solu-
tion, N
Ni
Bi
AI
Pb
Mn
Cr
Fe
Mo
V
Sn
Cd
Ti
Cu
Zn
Co
0,5
0,1
0,01
0,61
0,5
0,46
0,75
0,88
1,04
1,25
1.04
0,22
0,30
0,22
0,9
0,82
0,36
0,24
0,92
1,81
1,84
0,15
0,36
0,38
0,42
0,3
0,21
0,08
0,35
0,55
0,78
0,87
2,15
2,2
0,80
1,35
1,85
0,3
0,45
- 61 -
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Table 2
Deposition Coefficient as a Function of Current I/itensity
(C.01 N, electrolysis time t = 2 hours, C = 0.005 mg/l)
Current
intensity,
mA
Zn
Fe
Bi
A!
Ti
Sn
V
Mo
Pb
Cm
40
20
10
1,15
0,39
1,28
0.63
0,51
0,57
0,32
0,28
1,17
0,77
0,64
0,41
0,3)
0,21
0,2)
0,08
0,18
0,42
0,20
1,30
0,42
0,12
2,5
2,20
1,68
Table 3
Optical Densities of Spectral Lines ir, the tlectrodeposition
of Metals From 10 ml of Solution with 0.0025 mg/1
Concentration of Each Metal
Electrolysis
time, hr
Fe
Nl
Co
V
Cr
Mn
Sn
1
0,6
0,16
0,22
0,20
0,23
0,35
0,13
2
1,65
0,25
0,40
0,22
0,22
1,74
0,23
3
1,48
0,22
0,25
0,20
0,20
0,78
0,26
Electrolysis of
1,01
—
—
—
—
—
—
distilled water,

2 hours

Relative sensi-
3-10-8
2-10-a
2 ¦ 10"?
2-10-x
2-10-8
2-10-a
2-10-8
tivity, i>

Electrolysis
time, hr
Pb
Zn
BI
Al
Cd
Cu
1
0,34
0,35

0,98
0,28
1,97
2
0,58
1,50
0,15
1,40
0,25
2,80
3
0,88
1,57
0,42
1,32
0,29
2,14
Electrolysis of
—
0,49
—
0,57
—
1,28
distilled water,

2 hours

Relative sensi-
5-10-8
3-10-s
1 • 10-8
3-10-8
2-10-7
l-10-io
tivity, %

The electrolysis conditions were selected on the basis of these experi-
ments. The concentration method described combines the enrichment and dep-
osition of the sample on the electrode. This raises the degree of concentra-
tion and shortens the time of analysis by a factor of 3-4. The method was
checked on solutions of salts of trace elements in doubly distilled water and
on samples of the deposits, and was compared with the evaporation method.
During the combustion of a sample deposited on the electrode by electrodep-
osition, the intensity of the lines of the elements increases as a result of
a more uniform coating of the electrode and a stronger bond between the ele-
ments and the electrode material. As a result, the sensitivity of the deter-
mination of the trace elements increases by one order of magnitude.
- 62 -
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On the basis of a check of the applicability of the above-indicated con-
centration methods to the analysis of rain and cloud water samples for the
content of trace elements, it was concluded that the concentration method
should be selected to conform to the initial volume of the sample.
The actual volume of a single sample of rain or cloud water, collected
at temperate latitudes, may be no larger than 500 ml. For this reason, we
carried out the concentration by using an evaporation method that we devel-
oped for analyzing rain water for the content of trace elements. In the case
of analysis of samples less than 100 ml in volume, the electrolytic concen-
tration method was used, followed by spectral determination.
2. Development of the Method of Spectral Analysis
The method of emission spectral analysis permits the simultaneous deter-
mination of a large number of elements in a single sample with a sufficiently
high sensitivity of the analysis.
The sensitivity of the spectral analysis depends chiefly on the mode of
introduction of the sample into the discharge and on the characteristics of
the discharge plasma. For this reason, we conducted preliminary experiments
to study the sensitivity of the spectral method as a function of the mode of
introduction of the sample into the discharge and of the discharge conditions.
In so doing we attempted to make the analysis as little time-consuming as
possible, since this is an indispensable requirement in the mass analysis of
samples.
Following the preliminary concentration, the samples of rain and cloud
water were analyzed spectrally by using the method of three standards. Ac-
cording to the procedure we developed, the samples of rain and cloud water
are analyzed without being converted to a dry residue. This facilitates the
standardization, makes it possible to increase the accuracy and sensitivity
of the method, and eliminates the necessity of grinding and mixing the sam-
ples during their preliminary treatment. Thus the probability of introduc-
ing contaminants is decreased, and the analysis becomes less time-consuming.
The standard solutions are prepared separately for each of the elements
being determined: Pa, Cr, V, Mn, Cd, Ni, Co, Sn, Mo, Cu, Zn, and Ti. The
substances we used to prepare standards of c. p. grade are shown in Table 4.
The latter also lists weighed samples based on 250 ml of solution with a con-
centration of 1000 mg/1 of the element being determined.
The material from which the laboratory ware and the containers for stor-
ing the standard solutions were prepared may also be a source of contaminants
and cause a decrease in the concentration of the solutions they contain. In
[4], it is shown that much smaller amounts of contaminants enter the liquids
from the polyethylene containers in which they are stored than from glass
containers. Moreover, after prolonged storage of standard solutions in poly-
ethylene ware, the composition of the solution remains practically unchanged.
- 63 -
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In the above-described method of preparation and storage of standards, the
concentration of the elements subsequently changes at a slow rate, so that
it may be considered constant over a period of six months. In the analyses,
mixtures of standard solutions of different concentrations were employed.
These mixtures were prepared by the method of successive dilution. Thus,
mixtures containing all the elements being determined in concentrations of
25, 10, 5, 2.5, and 1.25 mg/1 were prepared from standard mixtures with a
concentration of 1000 mg/1. Before the analysis, the standard solutions are
poured into clean weighing bottles and diluted four times with doubly dis-
tilled water. In diluting the standards, it is necessary to use laboratory
ware made of stable "pyrex" grades of glass or quartz.
Table b
Substances Used for Preparing Standards
Standard,
1000 mg/l
Recommended
compound
Amount,
mg
Solvent
Remarks
Aluminum
A1 metal
250
HCI
Dissolve with
Nickel

heating
Nl(OH)2
394
HCI
Iron
FeCl3 • 6H20
1211
HCI

Cobalt
Co(OH)3
466
HCI

Zinc
Zn metal
250
HCI

Tin
Sn metal
250
HCI

Vanadium
nh4vo3
574
HCI

Cadmium
Cd(OH)2
325
HCI

Bismuth
Bi metal
250
HN03+HCI
Dissolve with
Chromium

heating
K2Cr04
933
HCI
Manganese
MnCI2 • 4H20
901
HCI

Copper
Cu metal
250
HNO3 + HCI
Dissolve with
Molybdenum

heating
Mo metal
250
HCI
Lead
Pb(N03)2
400
HCI

To excite the spectra, the samples and standards are introduced into a
discharge obtained with a standard arc generator. The electrodes used were
of spectroscopically pure carbon, and this made it possible to achieve a
sufficiently high excitation temperature and purity of the discharge plasma
[5, 10].
In order to study the intensity of the spectral lines as a function of
the current intensity, electrode shape, and depth of penetration of the sam-
ple into the electrode, special experiments were set up. It was assumed that
the location of the sample on the electrode surface makes it possible to in-
crease the accuracy of the analysis, since the vaporization of the sample wil^
be independent of the differences in electrode porosity. We showed that the
sensitivity of the analysis could be increased by decreasing the convection
currents. To this end, one should select the current intensity and discharge
frequency so that the electrodes heat up only on the surface where the sample
- 64 -
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has deposited. The use of plane electrodes arranged vertically could also
result In a decrease of the convection currents.
Experiments on the intensity of spectral lines of the elements as a
function of the method of electrode surface treatment and discharge condi-
tions were used to select the conditions of excitation of the spectra. Re-
producibility of the analysis is achieved by the absence of mutual influence
of the elements. To this end, after the electrodes have dried, a drop of a
sodium solution with a sodium ion concentration of 1000 mg/1 is deposited
on each electrode.
A DG-2 generator is used as the excitation source. The spectra are
photographed at a current intensity of 3.5 A and an exposure of 10 sec.
Above this intensity, as shown by high-speed motion-picture data, explo-
sive phenomena are observed near the electrode surface. This causes a de-
crease of sensitivity and increase of random errors.
The evaporation of the samples from the end surfaces of the electrodes
and the excitation of the spectra are carried out with vertical electrodes,
the distance between the electrodes being 2.5 mm. The spectra of the ele-
ments being determined, excited in an alternating-current arc, are obtained
by means of a type ISP-28 quartz spectrograph and recorded on aerial photo-
graphic film with a sensitivity of 1300 u. GOST-0.85 and a contrast of 2u •
The analytical lines of the elements being determined are photometered on an
MF-2 microphotometer. The film background near the photometer lines is used
as the internal standard. The concentrations of the elements are determined
from the photometric data for the standards and samples.
We found that when this procedure is used and the concentration of one
element exceeds the others by a factor of 10^, the line intensities of the
other elements remain constant within the measurement errors. Thus, there
is virtually no mutual influence between the elements.
Table 5
Intervals of Concentrations of the Elements Being
Determined in fiain Water
iSlejnent Concurtratioris,
Gen aentrtii oris
ys/i
lie/*
Sn
V
Fe
Ni
Mn
Cr
Bi
1,0-60
1,0-60
0.05-60
2,0-60
1,0-60
3,0-60
0,3-60
Al
Co
Pb
Zn
Cu
Cd
Mo
0.3-30
0,4-60
2,0-60
0,2-60
0,12-6
2,0-60
0,5-30
- 65 -
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Under the conditions of the experiments described, the mutual influence
is mainly due to the plasma temperature, concentration of thermal electrons,
and distribution of matter over the discharge radius.
Because of the high sodium content (20 yg) relative to the amount of
sample (0.1 Ug), the sample composition has no influence on the above-enu-
merated factors, since the discharge temperature is determined in this case
chiefly by the ionization potential of the sodium atoms, and this accounts
for the good reproducibility of the spectral line intensity for different
contents of the element present in the sample in higher concentration.
The limits of applicability of the simultaneous spectral determination
of the trace elements present in the sample in different proportions are
shown in Table 5.
The relative mean square error amounts to not more than 207=, for a sen-
sitivity of the method of 10~9-10~10 g of the substance on the electrode
(Table 6).
Table 6
Sensitivity of Spectral Analysis in the
Determination of Trace Elements

Fe
Nl
Co
V
Cr
Mn
Sn
Pb
Authors' data
5-10-9
MO-a
M0-8
9-10-9
2-10-8
4-10-9
7-10-9
2-10-9
Literature
data
5-10-b
3.10-8
5-10-9
4-10-9
4-10-9
1.10-9
2-10-8
~

Zn
Bl
Al
Cd
Cu
Mo
Ag
Authors' data
1-10-8
5-10-9
3-10-9
2-10-8
5-10-n
3-10-9
2-IO-n
Literature
data
4 10-8
2-10-8
1-10-8
1 -10-7
—
—
—
Table 7 gives an example of the use of the spectral procedure described
in the analysis of rain water for the content of trace elements. Similar data
on the lead content of rain water samples are given in [11],
Table 7
Content of Certain Trace Elements in
Rain Water (mg/l), 1967.
Date
Cr
Mn
Kl
Al
Sn
Pb
24 IX
26/IX
28'[X
30/IX
2/X
0,02
0,01
0,02
0,02
0,01
0,03
0,03
0,01
0,01
0,01
0,02
0,02
0,02
0,06
0,01
0,03
0,08
0,05
0,01
0,03
0,01
0.01
Hone
0,01
0,01
0,01
0,04
0,03
0.1
0,01
- 66 -
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Conclusions
1. To determine the content of trace elements in rain water, the concen-
tration method must be selected in accordance with the volume of the sample.
2. Concentration by cation exchange should be used when the sample volume
is over 1 1.
3. For a sample volume of less than 500 ml but more than 100 ml, the con-
centration should be carried out by evaporation.
4. For a sample volume of less than 100 ml, we worked out a method of
concentration by electrodeposition, which shortens the analysis time by a
factor of 3-4.
5. The extraction method is not convenient for analyses of rain and
cloud water.
6. The proposed method of spectrochemical determination of the concen-
tration of trace elements makes it possible to perform the analysis in the
concentration range from 1 to 100 yg/1 with an average relative error of not
more than 20%. There is virtually no mutual influence of the elements in the
proposed procedure.
LITERATURE CITED
1. A/iec kobckhh B. B. h flp. KouuetrrpHpoBaHHe h onpeaeneHne MHKpos.ieMen-
tob npn riiapoxHMimecKHx noncKax pyAHbix MecTopoKASHHii. H3A. J1TH. JI.,
1957.
2. ApoaAOBa B. M. ii Ap. Xmiimecioift cocTaB aTMOc^epubix ocajKOB Ma EBpo-
neficKoii TeppmopiiH CCCP. rHApoMeteoimaT, JI., 1964.
3. E p e m e ii k o B. 3. CneK-rporpacfumecKoe onpeAe.ieHHe MHKposjieMeHTOB b npn-
poflHux Boaax. H3fl. AH CCCP, 1960.
4. 3HJib6epuiTeftH X. M. 3aBOA. Jia6.. 28, 680 (1962).
5. 3njibGepiiJTefiH X. H. O HeKOTopux Meioflax cneKTpa/ibHoro aiiajiHsa pac-
tbopob. ^KT0K, XXV, Bbtri. 8, 1955.
6. KapnxHH JO. B., Aare^og H. H. Mhcthc xiiMHiiecKHe peaKTHBbi. Tocxhm-
H3flaT, Jl., 1955.
7. KopeHuan H. M. Aiia.niTimecKaa xhmhh Majibix KOHueHTpaiwft. Hsa. «Xh-
mhh», 1967.
8. XHMHiecKHe peaKTHBbi h npenapaTbi. IIoa peA. B. H. Kysxeuoaa. Tocxhm-
H3AaT, JI., 1953.
9. Ill b a ft k o d a M. fl. CyjieSHan xhmhh. MeArna, M., 1959.
10. J a nc h H., M a y e r F. Mikrochem., 35, 310, 1950.
11. Terr Haar G. L., Holtzman R. L., Lucas H. F. Nature, vol. 216,
October 28, 1967.
- 67 -
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T. N. GIGALOVSKAYA, R. I. PERVUNINA, V. V. EGOROV,
E. P. MAHONKO, A. I. SHI UN A
THE ESTIMATION OF MICROELEMENT CONTENT IN THE WATER
OF PRECIPITATION*
Sensitive spectral method of simultaneous content determination
of some important, in hygienic respect, microelements, such as lead,
chromium, vanadium, manganese, cadmium, nickel, cobalt, molybde-
num, copper, zinc,bismuth, aluminium, titanium, in the samples of
precipitation and cloud water is described.
As the content of microelements in atmospheric water is usually
too low to be evaluated in a direct way, the possible means of sam-
ple enrichment are discussed in detail and the area of their employ-
ment is evaluated. While analyzing liquid samples for concentrating
microelements determined in them, methods of extraction, evapora-
tion, and method employing an ion-exchange resin are mainly used.
The examination and analysis of different means of microelement
concentrating in the samples of rain and cloud water showed that
the concentrating method must be chosen in accordance with initial
sample volume. The value being more than one litre, it is necessary
to use ion-exchange resin method; evaporation method, worked out
for atmospheric waters, is recommended when the sample volume is
less than 500ml, but more than 100ml. For sample volume less than
100ml, a specially elaborate method of concentrating by electrolytic
precipitation is proposed which consists of isolation of investigated
microelements from samples on carbon electrode serving as a cat-
hode. The extraction method is inconvenient for atmospheric water
analysis.
According to the method developed by the authors atmospheric
water samples are analyzed spectrally without their conversion into
dry residue on three standard methods. As an excitation source the
alternating-current generator is used. The spectra of determined ele-
ments excited in alternating-current arc are received with the help
of quartz spectrograph and are registered on high-sensitive aerofilm.
Analytical curves of determined element content are evaluated on
microphotometer.
In this paper the means of putting sample on electrode and intro-
ducing it into the charge are described and applicability of simul-
taneous definition of spectral microelements contained in the sample
are evaluated:
It is shown that the proposed method of chemico-spectral deter-
mination of microelement concentration allows to carry out the ana-
lysis in concentration range from 1 to lOOmcg/1 with the mean rela-
tive error not more than 20%. The mutual effect of the elements is
practically absent.
* Editor's note: The abstract is presented as given in English with the original Russian article
but has been slightly edited. '
- 68 -
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CONTENT OF HEAVY METALS IN THE AIR
OF CERTAIN REGIONS OF THE USSR
T. N. Zhigalovskaya, V. V. Yegorov, S. G. Malakhov,
A. I. Shilina, and Yu. P. Krasnopevtsev (USSR)
From Glavnoe Upravlenie Gidrometeorologicheskoy Sluzhby Pri Sovete Ministrov SSSR. (Chief Administration of
the Kydrometeorological Service Under the Council of Ministers of the USSR.) "Meteorologisheskie Aspekty
Zagryazneniya Atraosfery". (Meteorological Aspects of Air Pollution.) Sbornik dokladov na roezhdunarodnom
simpoziume v Lenin grade - Iyul' 1966 g. (Reports delivered at the International Symposium in Leningrad -
July 1966.) Pod redaktsiey d-ra fiz.-m»t. nautc H. E. Berlyanda. (Edited by Prof. M. E. Berlyarid.)
Gidrometeorolgicheskoe izdatel'stvo, Leningrad, p. 320-329, (1971)* (Hydroneteorological Publishing House,
Leningrad, (l97l)>)
Heavy metals entering into the composition of the earth's atmosphere,
in particular, Pb, Cr, V, Mn, Cd, Ni, Co, Sn, Mo, Cu, Zn, A1 and Ti, are
classified as trace elements, since they are present in air samples in
amounts of 10~2-10-12% [2].
Despite the negligibly small content of trace elemtns in living and
nonliving nature, they play an extremely important part in biological pro-
cesses. The atoms of trace elements enter into the composition of organic
molecules, and also into the composition of the internal medium of the
organism, ensuring the regulation of its most important processes [6]. A dis-
turbance of the equilibrium of trace elements in the organism leads to patho-
logical deviations from its normal activity. Such disturbances may take
place in the case of excess (or deficiency) of individual elements in the
environment, despite the ability of higher organisms to extract the needed
elements from the environment in the necessary amounts. When they enter
the organisms in excess, some of the trace elements (mainly lead) may have a
toxic effect. In this respect, it is important to have accurate data on
the content of trace elements entering the atmosphere as a result of the
activity of industrial enterprises.
The study of the behavior of trace elements in the atmosphere also has
important meteorological aspects. They include primarily the study of the
laws of propagation of trace elements in the atmosphere from pollution,
sources, and attempts to develop methods of forecasting the levels of their
concentrations in atmospheric air. The reverse problem is also possible,
i.e., the use of trace elements as tracers in the study of certain meteorologi-
cal phenomena. Information on the content of trace elements in the atmosphere
may aid in the explanation of the chemical nature of condensation nuclei and
their behavior in the atmosphere. Some trace elements may also be useful in
many geophysical studies. Thus, their presence in the high layers of the
atmosphere and also in the surface layer of air in areas distant from indus-
trial plants (for example, above the ocean, at the poles) permits an evaluation
of the chemical composition of aerosols of cosmic origin [7].
- 69 -
-------
All of the above indicates the importance of studying the distribution
of trace elements in the environment and provides the basis for its treat-
ment as a medical-biological, hygienic, and geophysical problem.
However, in determining trace elements it is necessary to deal with
some major difficulties involved in the measurements of trace amounts of
the elements being analyzed. Such measurements are possible only when very
delicate methods of analysis are used. This is probably why only a few works
are known thus far that are devoted to the study of the content of trace
elements, particularly heavy metals, in atmospheric air [9, 10].
Heavy metals in the atmosphere enter into the composition of solid
aerosol particles. In accordance with literature data, above industrial areas
[8, 9, 10] the variation range of the concentration of solid aerosol particle
in atmospheric air extends from 100 Ug/m^ in areas of light pollution to
4000 ]Jg/m^ in London during a heavy smog. The average values at the center 0£
vast industrial areas and cities such as Los Angeles and Cincinnati vary from
200 to 800 yg/m^, and in small towns the average concentrations range from
100 to 200 yg/m^.
The object of the present study was to obtain preliminary data on the
content of certain trace elements entering the atmosphere as a result of human
activity in various regions of the Soviet Union. To this end, the contents 0£
lead, chromium, vanadium, manganese, cadmium, nickel, tin, molybdenum, copper
and zinc were determined in samples of atmospheric dust collected in 1965-^7
The data given below constitute the first correlation of the material
obtained.
The samples were collected by means of filtering-ventilation equipment
consisting of a medium-pressure centrifugal fan at the inlet connection of
which was mounted a filter holder with filtering material of brand FPP 0.5 ^2
in area. From the known velocity of the drawn air, time of operation of the
device, and area of the filter, the volume of air which passed through the
device was calculated. The devices operated around the clock for one month.
The filters were replaced once a day. After separating the gauze layer, the
filters collected during a month at each point were ashed at 500°C. Mean
monthly samples were thus obtained. The weight of the ash of clean filters
amounted to an average of 250 mg per month. The weight of the dust collected
during a month frequently amounted to several tens of grams. For this reason
our calculations neglected the weight of the ash of clean filters as compared*
with the weight of the sample. The content of trace elements in the clean
filters varies over a wide range, but is always two orders of magnitude less
than their content in the ash of filters containing a dust sample. This made
it possible to neglect the content of trace elements in the clean filters.
Analysis of atmospheric dust samples for the content of the above-indic
trace elements was carried out by using the method of emission spectroscopy i-
- 70 -
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The ashed filters containing the sample are burned in an alternating-current
arc. The radiation of excited atoms of the sample is decomposed into a
spectrum by means of an ISP-28 spectrograph. The spectrograph is recorded
on aerial photographic film with a sensitivity of 1200 u. GOST 0.85. After
photometering the obtained spectra on an MF-4 microphotometer, the content
of each of the elements is determined. The method we used is characterized
by a sensitivity of 1 x 10~^®-1 x 10~® g on the electrode depending on the
element being determined. The relative mean square error of the method is
jj20% of the content being determined.

1,4

1,0
Oft
0,6
0,4
Of
1
2
3
«
5
/
/
The concentration of trace elements
in air depends on a set of complex
meteorological factors, intensity and
periodicity of action of pollution
sources, and nature of the terrain. The
content of trace elements in the atmos-
pheric surface layer of a specific
region may have a seasonal variation
depending on the state of atmospheric
stability, wind direction and velocity,
and degree of washing out by precipita-
tion.
\
i T —i '***•' — f ' ' '*"*'
Fig. 1 shows the variation of the
total concentration of trace elements
which we determined over the course of
a year in different regions of the
Soviet Union. As follows from the graph,
in the air of the maritime regions of
the south (curve 1) and north (curve 2)
of the country, the content of trace
elements increases slightly during the
summer months, and remains practically
constant the rest of the year. In the
maritime region in the east of the
country (curve 3), the concentration of
trace elements in atmospheric air is much
greater than over the northern and southern coasts of the country. The content
of trace elements decreases sharply only during the summer months. This is
probably due to the direction of the prevailing winds, which in the summer months
have a preferred direction from the sea to dry land in these regions [5]. The
high-mountain region of Pamir (curve 4) is characterized by an increase in the
concentration of trace elements during the summer months, which may be explained
by the absence of precipitation and gentle winds during that period, with a
consequent weak vertical exchange in the atmosphere [5]. A marked decrease in
the concentration of trace elements in these regions was observed in May for
both the total concentration and the content of individual trace elements. This
is due to the washing out of aerosols from the atmosphere by spring rains [5].
/ // /// IV v VI VII VIII IX x XI XII
Fig. 1. Total concentrations of trace ele-
ments in the air of certain regions of the
Soviet Union.
1_- maritime regions of the south, 2 - mari-
time regions of the north, 3 - maritime
regions of the east, 4 - high-mountain regions
of Pamir, 5 - regions of industrial cities
- 71 -
-------
A correlation of the content of trace elements with the annual variation of
the amount of precipitation for the high-mountain region of Pamir is shown
in Fig. 2b. In the atmospheric air near industrial cities (curve 5, Fig. 1)
an approximately 5-fold reduction of the concentration of all the elements
took place during the summer months. This correlates satisfactorily with
the annual variation of monthly precipitation for the given region, attesting
to the washing out of trace elements by atmospheric precipitation (Fig. 2a) .
A characteristic element that is continually present in the atmosphere
of industrial cities is lead, which enters the atmosphere primarily during
the combustion of fuel (for example, gasoline, coal, kerosene, etc.). At
the same time, the lead content of atmospheric air is strictly standardized
because of the high toxicity of its compounds. It is of interest, therefore
to examine data on seasonal changes of lead in the atmosphere in the vicinity
of industrial cities of the country during the period from 1965 to 1967, pre-
sented in Fig. 3 (curves 4, 5). For comparison, the same figure shows curves
of seasonal variations of the lead content in the atmosphere of maritime and
high-mountain regions of the country (curves 1, 2 and 3 respectively). The
lowest lead concentrations in atmospheric air were observed in the maritime
cities of the south and north of the country. However, in the maritime
region of the east of the country, the lead concentration is slightly higher
and varies little during the first half of the year, but grows considerably
in September-November. It should be noted that in the vicinity of industrial
cities (Fig. 3, curves 4 and 5), the total lead content in 1967 was lower
than in 1965, i.e., by a factor of 1.5-2. However, in both 1965 and 1966-67
winter concentration maxima were observed. Similar seasonal variations are
observed in the surface air in the case of natural radioactive isotopes, for
example, radon [4]. A constant source of radon is the earth's surface. The
cause of the observed winter maximum in both cases is a weak vertical mixing
of air in the lower atmospheric layer in winter, when frequent surface temper^-
ature inversions are typical.
For the purpose of sanitary control, it is necessary to have information
on the magnitude of the absolute concentration of individual trace elements
(for example, lead, chromium, vanadium, etc.) and the total content of dust
in atmospheric air. The mean annual values of the concentration of individual
trace elements which we obtained for the continental and maritime regions of
the Soviet Union are shown in Table 1. For comparison, the table also gives
reported data on the content of certain trace elements in the air of industri
cities and suburban areas of the U.S.A. [8, 9, 10], Bulgaria [1], and also
data that we obtained from an analysis of aerosol samples above the ocean at
0° latitude and 180° longitude.
Data on the content of chromium, cadmium, nickel, molybdenum, and cobalt
are lacking in the literature and are given here for the first time.
We should note the very high level of lead concentration in the air of
industrial cities of the U.S.A., more than 40 times as high as the lead
- 72 -
-------
rng/m
Fig. 3. Annual variation of Pb
concentration in the surface air
layer for different regions of
the USSR.
-------
Table 1
Mean Values of Dust Concentration and Certain Trace Elements in the Surface Atmospheric Layer (

Elements
+>
O
W
-P -P
e c
Cm
O
c
-P-H
a
a> w
+> -p
c: c
Regions
Year
Pb
Cr
V
Mn-
Cd
Nl
Sn
Mo
Cu
Zn
Dust conten
© Q)
-P E
£ CD
O i—1
O 0>
r—1 CD
<3 O
O tn
EH -P
Relative co
traoe eleme
dust
Industrial cities
of the USSR
1967
0,0301
0,0144
0,0166
0,031
0,0195
0,0211
0,0083
0,0184
0,096
0,040
40
0,2954
0,0074
Maritime cities
of the USSR
1967
0,0023
0,008
0,0085
0,015
0,0045
0,017
0,0045
0,0044
0,014
0,047
46
0,1252
0,0027
Industrial cities
of the U.S.A.
[5. 6]
1956
1,34
—
0,019
0,154
—
—
0,025
—
0,19
—
145
1,728
0,0119
Industrial cities
of Bulgaria
[9]
1960
1,0-0,5
—
—
0,45-0,20
—
—
—
—
—
—
—
—
—
Suburban areas of
the U.S.A .[5, 6]
1956
0,30
—
0,002
0,04
—
—
0,01
—
0,01
—
86
0,362
0,0042
Ocean (180° 1,
0°iaD
1966
0,004
0,0008
0,0005
0,0009
—
0,0015
0,002
0,0004
0,016
—
8.7
0,0109
0,0012
-------
concentration in the industrial regions of the USSR. The content of the
remaining elements in the industrial regions of the Soviet Union is 2-3 times
less than in the industrial cities of the U.S.A. In the maritime regions of
this country, the content of most elements is one order of magnitude less
than in industrial cities inside the continent. In samples taken above the
ocean, the concentrations of all the elements with the exception of lead,
tin, and copper are approximately one order of magnitude less than the concen-
tration of these elements in the atmosphere of maritime cities. The higher
content of lead, tin, and copper in samples taken over the ocean is probably
due to contamination of the samples during their collection on the ship.
This applies particularly to the lead content. The lead content was determined
in about 40 samples taken on a ship during a cruise in the winter of 1966. In
other samples, the lead concentration ranges from 5 x 10"^ to 3 x 10"^ yg/m^,
this being due to pollutants discharged by the stack of the ship and falling
on the filter.
In addition, Table 1 lists data on the content of dust, total content of
trace elements and ratio of the sum of the trace elements to the total con-
tent of dust, i.e., the concentration of the indicated trace elements in dust.
The dust concentration in the atmosphere of maritime cities of the USSR is
higher than that in the air of industrial cities in the center of the country.
The difference in concentrations is close to the dust concentration above the
ocean. Thus, the increase in dust concentration above the maritime cities as
compared with cities of the continental regions of the country should probably
be attributed to marine salts.
The dust concentration above industrial cities of the U.S.A. is approxi-
mately 3.5 times the corresponding values for this country and close to the
maximum permissible dust norms in the USSR. However, the concentrations of
trace elements in dust in 1 m^ of air were found to be similar in both cases.
The concentrations of trace elements in dust in 1 m^ of surface air of mari-
time regions of the USSR and suburban areas of the U.S.A. were also similar.
For atmospheric dust above the ocean, the ratio of total concentrations of
trace elements to the concentration of dust is approximately one order of
magnitude less than the corresponding ratio for the air of industrial cities
of the continent. Hence, the concentration of trace elements in the dust of
the surface atmospheric layer is a measure of the degree of pollution of air
with aerosols of industrial origin.
As a result of the above study it may be stated that at the present time,
no excess over the established sanitary norms was observed in the average
content of trace elements and in their maximum content in the air of the
regions of the USSR that we studied. The variation of the concentration of
trace elements for continental regions correlates with the amount of precipi-
tation, attesting to the presence of processes of self-cleaning of the atmos-
phere as a result of washing out. However, because of the growth of industrial
cities, the concentration of dust and other polluting ingredients including
trace elements may increase in the atmosphere of the globe. From this stand-
- 75 -
-------
point, there is need for organizing a regular checking of the content of
these impurities in the air of industrial regions, and also regions distant
from the pollution sources, in order to determine the variations of the
background on a global scale. In this connection, it is of interest to
collect air samples over the ocean and at high altitudes.
The preliminary data on the content of trace elements in the surface
atmospheric layer, which are presented here, are also of interest in connec-
tion with the study of the chemical composition of the atmosphere and pro-
cesses of atmospheric self-cleaning, which remove dangerous impurities. fhe
table and graphs were compiled on the basis of an analysis of 180 mean monthl
samples collected at different points of the Soviet Union in 1965-67, with
simultaneous determination of 11 elements in each sample. This volume of
work was carried out during a comparatively short period of time, thanks to
the use of a semi-rapid spectral method of analysis of adequate sensitivity
that we developed. In the future, it is intended to carry out the sampling
and analysis of the samples systematically at a large number of points to
determine their content of lead, chromium, vanadium, manganese, cadmium,
nickel, cobalt, tin, aluminum, titanium, molybdenum, copper, zinc, and iron
which hygienically and geophysically are the most important elements. For
comparison, it is intended to conduct analysis of samples taken above the
ocean and in the polar regions.
On the basis of the results obtained and of the experimental measurement
particular attention should be directed to the necessity of observing certai^8
operational requirements in collecting and analyzing samples of atmospheric
aerosols for the content of trace elements.
In collecting aerosol samples on ships and in polar regions, it is neces
sary to select the sampling site so as to exclude the possibility of contamir^
ation of the sample during the operation of internal combustion engines and
by other sources. In analyzing samples for the content of aluminum and iron
contact between the filters and the metal parts of the filter holder is inad~
missible.
Clean conditions must be provided during ashing of the filters, and to
this end the ashing should be carried out in closed platinum or quartz
crucibles.
To exclude a background contaminated with trace elements present in the
ash of clean filters, it is necessary to ash and analyze the clean filters
of each batch.
When the sampling is conducted in slightly polluted regions, an impinge
can be used, and its working surfaces should be coated with polyethylene
When the samples are collected on filters in slightly polluted regions
for example, above the ocean or at high altitudes, the content of trace *
- 76 -
-------
elements in the sample is comparable to their content in a clean filter.
In order that the content of trace elements in the sample be above the
background produced by the filter, it is necessary to draw a large volume
of air through the filter and to know the exact ash content of the clean
filter and the content of trace elements in this ash. The weight of the
ash must be measured to within 0.1 mg. Data thus obtained may be useful in
evaluating the pollution of the lower layers of the earth's atmosphere.
LITERATURE CITED
1. B .1 w c k o b a fl., KypnaxoBa T. 3arpsi3HeHHe aTMocdjeptioro B03Ayxa b Co-
$hh. Xhapojiophh h Meieopo.ionm, rofl. XVII, kh. 2. CocJihji, 1968.
2. G p e m e h k o B. H. CneiaporpaifwHecKoe onpeae.neHHe MHKpcw/ieMeHTOB b npn-
poAHux Boaax. M3A. AH CCCP, M„ 1960.
3. h r a ^ o b c k a a T. H. h ap. MetoflHKa onpeaeJieHHH coaepwaHMH MHKposjie-
MGHTOB B Boae aTMOC(})epHb[X OCaflKOB. Cm. HaCTOfllUHii c6opHHK.
4. Ma Ji ax ob C. T, WepHwmeBa IT r. O ce3omiwx HSMeHeHHHX KOHtteHTpa-
UHii paAOHa H TopoHa b npn3e.MHOM c.ioe aTMOctfepbi. B c6. «PaAHoaKTHBHbie
H30Tonbi b aiMoci))epe h hx Hcno^b30BaHiie b MeTeopojiorHH*. AT0MH3AaT,
1965.
5. CnpaBOHniiK no K.ntMaTy CCCP. Beiep, ocajiKii, Bbiri. 8, 21, 31, 10, Bbin. I, 12,
20, 30, 27.
6. Tomcoh H. M. MiiKpco-ieMeiiTb! kbk MeAtrnHHCKan, CHOJionwecKan h rHnienH-
tecKast npoC^e.MW. BecrmiK AMH CCCP, Ns 5, 1950.
7. eTT B. ATMOC({)epHaa nu.ib. HJ1, M., 1961.
8. lOiire X. XiiMtmecKHft cocTaB h paAHoaKXHBKocTb aiMoccJjepu. H3a. «Mhp», M.,
1965.
9. Chambers L. A., Milton I. F., Cholak C. E. A comparison of parti-
culate loadings in the atmospheres of certain American cities. Presented af
Third National Air Pollution Symposium. Pasadena, California, 1955.
10. Ma gill P. L„ Hoi den F. B., Ac k ley C. Air Pollution Handbook. Mac-
Graw-Hill, New York, 1956.
T. AT. G1GALOVSKAYA, V. V. EGOROV. S. G. MALAKHOV,
A. J. SHI UNA, Yu. V. KRASNOPEVZEV
THE CONTENT OF HEAVY METALS IN THE AIR OF SOME REGIONS
OF THE USSR*
Data on content of lead, chromium, vanadium, manganese, cad-
mium, nickel, tin, molybdenum, copper, and zinc which get into the
atmosphere as a result of human activity are given. These microele-
ments were determined in samples of atmospheric dust collected in
different regions of the Soviet Union in 1965—67. The sampling was
* Editor's notes The abstract is presented as given in English with the original Russian article but
has been slightly edited.
- 77 -
-------
carried out with the help of filter-ventilation installation on Pctrya-
nov filter with area of 0.5m2 which was changed once a day. The
filters employed during each month were burned down and ash resi-
due received in such a way was analyzed with the help of emission
spectroscopy method developed by the authors. This method is cha-
racterized by sensitivity of 1.10~10—1.10-8 g on electrode in depen-
dence on determined element. Relative mean-square error of the met-
hod amounts to 20% of evaluated content.
The values of total microelement content in the air are given for
some regions of the USSR during the whole year. Marked influence
of meteorological factors (in particular, wind direction and precipi-
tation) on concentration value is noted. Microelement content in the
air closely correlates with annual course of monthly precipitation
amount which indicates on significant washing-out action of precipi-
tation. Lead content in the atmosphere is separately considered the
presence of lead is due mainly to burning down the fuel. The high-
est lead concentrations of order of 0.16 mcg/m3 are discovered near
industrial towns such as Kuibyshev, Semipalatinsk, Novosibirsk in
spring and in the neighbourhood of Magadan in autumn. Lead con-
tent amounts to Jess than 0.05 mcg/m3 in the atmosphere of seaside
regions of the country and to 0.05—0.08 mcg/m3 in highland regions.
The values of dust content and absolute microelement concentra-
tions in the air for continental and seaside regions of the Soviet
Union and also the data of aerosol content over the ocean at the la-
titude of 0° and longitude of 180° in 1966 are compared with litera-
ture data on microelement content in the air of industrial cities and
country regions of the U. S. A. and Bulgaria.
Fulfilled investigations show that at present mean and maximum
concentrations of determined microelements in the air do not exceed
stated sanitary norms in the examined regions of the USSR. How-
ever, in connection with growth of industrial towns it is necessary to
carry out regular control of microelement content for evaluation of
background variation in global scale near industrial areas and also
in the regions removed from pollution sources.
- 78 -
-------
ON THE DESIGN OF A MEASURING NETWORK FOR AIR
POLLUTION IN THE GERMAN DEMOCRATIC REPUBLIC*
W. Warmbt GDR (German Democratic Republic)
From Glavnoe Upravlenie Gidrometeorologicheskoy Sluzhby Pri Sovete Ministrov SSSR. (Chief Administration of
the Hydrometeorological Service Under the Council of Ministers of the USSR.) "Heteorologisheskie Aspekty
Zagryazneniya Atraosfery". (Meteorological Aspects of Air Pollution.) Sbornik dokladov na mezhdunarodnom
simpoziume v Leningrade - Iyul' 1968 g. (Reports delivered at the International Symposium in Leningrad -
July 1968.) Pod redtktsiey d-ra fii.-mt. niuk M. E. Berlyanda. (Edited by Prof. M. E. Berlyarid.)
Gidroneteorolgicheskoe izdatel'stvo, Leningrad, p. 330-336 (1971). (Hydroaeteorologioal Publishing House,
Leningrad, (l97l).) '
1. INTRODUCTION
With the increase in industrialization and of transportation,
and with the density of population, pollution of the air with
gaseous and solid trace materials has become a real problem of
our technological age. The need for solution is pressing.
In view of this situation, all the questions and measures to
be applied to the problem of air pollution in the German Democratic
Republic [GDR] have been coordinated centrally in the Commission
for Maintenance of Air Purity. The work of the commission was
expressed in the Order for Maintenance of Air Parity published
by the Council of Ministers of the GDR in 1966. In this order,
the Meteorological Service is assigned the mission of measuring
the basic load of air pollutants, particularly the dust and
SO2 concentrations, in the various climatic regions of the GDR.
On the other hand, the air pollutants in the major industrial
and population points, as well as in working places, are
measured by the Hygiene Institutions. Some large factories have
begun further to set up their own measuring networks for dust and
SO2. In the design of a measuring network for air pollution,
the Meteorological Service is also observing the recommendations
of the Aerology Commission of the WMO (CAe - IV/Doc. 11, p. 7),
according to which the purpose of the National Meteorological Service is
to establish air pollution measuring networks in non-metropolitan
areas in order to measure the so-called background concentration.
* Editor's note: This report was originally presented in German. Its English translation has been supplied
by APTIC.
- 79 -
-------
2. ORGANIZATION
The measuring network of the Meteorological Service,
German Democratic Republic, will encompass 13 synoptic stations
set up in different climatic regions (central mountains, flat
land, Baltic Sea Coast). For comparative reasons, stations
will also be placed in regions of differing population density
in the network.
So as to obtain the most complete survey possible of
the trace material content of the atmosphere, the measuring
network also includes stations at which atmospheric trace materials
and even the ozone near the ground and the radioactivity of the
air and precipitation are already being measured. Simultaneous
measurements of various trace materials are important not only for
Q>
meteorological evaluation of the experimental results, but also
for determining the complex biological action of air pollutants.
The Meteorological
Service has been per-
since 1952, and radio
activity measurements
in a 9-station network
since 1956. Figure 1
shows the distribution
of the stations in the
air pollution measure-
ment network.
ozone measurements in
a 6-station network
forming ground-level
xi *2
Figure 1. Distribution of
stations in the air pollution
measuring network.
1. Ozone. 2. Radioactivity.
3. Dust, SO2.
- 80 -
-------
The Wahnsdorf Meteorological Observatory is the administrative
institute for scientific processing of the measurements, as
well as for the construction and maintenance of the measuring
network. It is also concerned with testing measuring methods
and measuring equipment for air pollution research and with
problems of measuring network planning. Problems of trace
material diffusion are worked on by the Technical Meteorology
Group of the Meteorological Service in Potsdam.
3. MEASURING METHODS AND EQUIPMENT
Since 1965, the dust content of the air has been determined
in connection with measurements of the radioactivity of the air.
The air is drawn through a membrane filter which is as hydrophobic
as possible. Czechoslovakian-made filters are used in the net
(Type RUFS Synpor 2, Diameter 35 mm, mean pore diameter 2.5 nm).
The filter is protected against precipitation and sedimentation
of large dust by a small roof. The intake height is 2 m. About
60 m^ air is drawn through the filter in 24 hours. The filter
traps only the fine or suspended dust with particle radii less
than 20 (jm. The filters are weighed with a sensitive spiral
spring balance before and after air sampling. The weight dif-
q
ference and the air volume give the dust content in mg/m .
The SO2 content is measured by the pararosaniline method
of West and Gaeke. Measurements are made at the hours of 0, 6,
12, and 18 Central European Time. Samples are taken for a period
of 1 hour, or for 30 minutes in more strongly polluted areas.
The air flow drawn in is 50 liters per hour. Each station has
a spectrophotometer (Spekol) made by the Carl Zeiss Peoples
Factory at Jena for colorimetric measurements. The West and
Gaeke measuring method has been made obligatory in the RGM
area for SO2 measurements because it is specific for SO2.
The toxicity of the 0.1 M solution is a disadvantage of this
method, as it contains 27.2 g mercuric chloride (HgCl2) per
liter. We were able to reduce the amount of poison and perform
measurements with a 0.01 M solution without injuring the
*
Translator's Note: Unknown geographical area.
- 81 -
-------
sensitivity and reproducibility of the measurements. Because of
the GDR Poison Law, however, the observer responsible for
making the SC^ measurements at the station must pass a poison
examination in order to get a partial poison license.
k. PLANNING OF THE MEASURING NETWORK
In the performance of network SO2 measurements, it is
important to make the choice of measuring sites so that the
measurements are representative for the area in question. We
have studied this question in the framework of parallel measure-
ments of SO2 concentration in the regions of Dresden and
Radebeul. We recorded the SO2 concentration with two Novak
analyzers (CSSR). One of these devices was at the Wahnsdorf
Meteorological Observatory and the second was in Radebeul,
1.4 km away from the observatory. Similar measurements have
recently been made between Wahnsdorf and a measuring site in
the city region of Dresden 10 km from the Observatory. There
is also an altitude difference of 120 m between Wahnsdorf and
the measuring sites in Radebeul and Dresden. We found that, on
the average, there were neither large differences in the averages
nor in the daily course between these measuring sites. From this,
it follows that local differences in the SO2 content are slight
for measuring sites which, as in our example, are within the
range of influence of large area sources, as the lower layers
of the atmosphere are well mixed horizontally and vertically
with SO2•
Sampling problems appeared only at the measuring site
at the Grosser Inselsberg mountain station at 910 m altitude
in the Thuringer Forest. The station is in a two-story building
complex which also contains the central heating system. With
low background concentrations, differences of 10 to 20 times
the unperturbed measurement appear on the windward and lee
sides of the building, depending on the wind direction. As
high wind speeds occur more frequently at this altitude than
on flat land, turbulence in the lee of the building is
- 82 -
-------
at times particularly pronounced, so that exhaust gas fumes can
arrive at the intake opening, depending on the position of
the intake and the wind direction. In order to eliminate this
effect, the intake position was placed at the tenth level of
the television tower.
Another important question of measuring network planning
concerns the establishment of the measuring times. Although
use of recording equipment for SO2 measurement is planned, it
was studied whether differences appear if averages, frequency
distributions, and immission characteristics are calculated
from a selection of measuring times or from 24 half-hour
measurements. We established that measurements of SC>2 content
at the times of 0, 6, 12, and 18 hours Central European Time
are sufficient for comprehensive characterization of the
air pollution situation, because there were no differences
from the statistical measurement coefficients calculated from
24 half-hour measurements.
5. EVALUATION OF THE MEASUREMENTS
It is planned that after 1 January 1969, all the measurements
of trace materials will be converted to punched cards and eval-
uated centrally at a computer institute. In the future, measure-
ments from the hygiene and industrial measuring networks are also
to be processed in the same form. Finally, the results of
simultaneous SO2 and dust content measurements will be reported.
6. RELATIONS BETWEEN THE DUST AND S02 CONTENT
The daily average of dust and SO2 content during the heating
period in Wahnsdorf show very close relations. As can be seen
from Figure 2, there was a quasi-parallel course of the dust
and SO2 content in the months of October to February 1965/6 and
1966/7.
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SO^ ig$5
0,00
C.iO
0,20
0

.....

J
s

k_
L/>
A
\T
k

/v
/

/'
V
0,2>t
0.16
O.OS
0
S02
0,60
0,40
0.20
0
dust
1366
dust
Q,2U
0,16
0,08
0

f
K

\ r

/
\

1
L

/ 1

r y

10 20
Oct.
10 20
Nov.
10 20
Dec.
10 20 10 20
Jan. Feb,
Figure 2. Dust and SO2 concentration in Wahnsdorf, October -
February, 1965/6, 1966/7 ( smoothed values).
In order to compensate for accidental fluctuations in
the graphic presentation, the measurements were smoothed
by a 5-day running average. For the period from October to
February, the correlation coefficients of the unsmoothed
values are 0.85 for 1965/6 and 0.80 for 1966/7. In order to
Figure 3. Dependence of the dust and SO2 content on wind direction
a. October 1965 - February 1966.
b. October 1966 - February 1967.
- 84 -
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eliminate the conservation tendency of the meteorological
diffusion processes, only the values of the first, third,
fifth, etc. measuring days were considered for the correlation
calculation. Also, as Figures 3 and 4 show, both trace
materials show a dependence on wind direction
Figure 4. Dependence of the dust and SC^ content on wind speed.
a. October 1965 - February 1966
b. October 1966 - February 1967
and wind speed. But it is worth noting that there are distinct
differences between the two years in the concentration curve
for the trace materials. These can be ascribed to differences
in the diffusion processes. In the summer months there is
no relation between the dust and SO2 content. For the period of
March to September, 1966, the correlation factor was 0.29.
In the summer, the suspended dust consists not only of emissions
from industry and house fires, but also in part of mineral
dust which has been blown up. By convection, the dust enters
into the higher layers of the air, from which it is only
slowly removed by sedimentation. Sulfur dioxide is likewise
transported by convection into higher air layers, but it
is gradually converted to a sulfate aerosol, so that the
SO2 concentration is lower in the summer than in the winter.
0,30 —V-
: \
85 -
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7. CONCLUSIONS
Air pollution problems will increase in importance in
all countries in the coming years as a result of the construction
of new industrial centers and cities. Thus it should be the
primary goal of all institutions interested in maintenance of
air purity to aim at close technical-scientific and
organizational cooperation in the planning and construction
of air-chemical measuring networks, so as to guarantee
that the measurements will be comparable.
ON THE CREATION OF A NETWORK OF POINTS FOR OBSERVATIONS
OF ATMOSPHERIC POLLUTION IN THE GERMAN DEMOCRATIC REPUBLIC*
(ABSTRACT)
W. Warmbt (German Democratic Republic)
By decision of the Council of Ministers of the German Democratic Republic
the Hydrometeorological Service of the country has begun organizing studies of*
atmospheric pollution. This involves the participation of 13 meteorological
stations located in different climatic zones outside the industrial and densely
populated points at which measurements of ozone concentration and radioactivity
had been made earlier.
The dust content is determined by filtering a known volume of air (approxi-
mately 60 m^ per day) through membrane filters of Czechoslovak manufacture and
weighing them before and after the filtering. The sulfur dioxide concentration
of air was determined by the West-Gaeke method. The samples were collected
3 times a day for 1 hour, and in heavily polluted regions, for 30 minutes at an
air suction rate of 50 l/hr.
The paper presents results of measurements of dust and sulfur dioxide con-
centrations carried out in Wahnsdorf in the winter periods (from October throuoK
February) of 1965-67. An almost parallel course in the variations of sulfur
dioxide and dust concentrations with time was observed, with correlation factors
of 0.80 and 0.85 between the quantities measured.
To study the air pollution in cities and industrial centers and in order to
substantiate the maximum permissible norms for concentrations of noxious pollu_
tants, specialized vans have begun to be used. Such mobile laboratories are
provided with equipment for determining the concentration of sulfur dioxide,
* This is a translation of the original Russian abstract accompanying this German paper.
- 86 -
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carbon monoxide, carbon dioxide, hydrocarbons, nitrogen oxides, acrolein,
and lead dust. The content of carbon monoxide, carbon dioxide, and hydro-
carbons is recorded automatically. At the same time, the air temperature
and humidity, visibility, and wind direction and velocity are measured.
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CONTENT OF PHOTOOXIDANTS IN URBAN AIR
Yu. G. Fel'dman (USSR)
From Clavnoe Upravlenie Gidrometeorologicheskoy Sluzhby Pri Sovete Ministrov SSSR. (Chief Administration of
the Hydrometeorological Service Under the Council of Ministers of the USSR.) "Meteorologisheskie Aspekty
Zagryazneniya Atmosfery". (Meteorological Aspects of Air Pollution.) Sbornik dokladov na mezhdunarodnom
simpoziume v Leningrade - Iyul' 1966 g. (Reports delivered at the International Symposium in Leningrad -
July 1966.) Pod redaktsiey d-ra fiz.-mat. nairtc II. E. Berlyanda. (Edited by Prof. II. £. Berlyarid.)
Gidrometeorolgicheskoe izdatel'stvo, Leningrad, p. 537-3H, (l9?l). (Hydrometeorological Publishing House
Leningrad, (197l).) *
Photooxidants are toxic products formed in atmospheric air from auto-
motive and industrial emissions as a result of complex photochemical reac-
tions stimulated by ultraviolet radiation of the sun. Products that, in
addition to their biological activity, have a harmful effect on vegetation
and reduce the visibility include ozone, peroxyacetyl nitrate (PAN), nitrogen
oxides, formaldehyde, acrolein, free radicals, organic peroxides, finely
divided aerosols, etc.
The pollution of air with oxidants, first noted at the end of the 1940's
in Los Angeles (U.S.A.), has now become a serious problem for many American
cities — New York, Washington, San Francisco, etc.
In the U.S.A., scientific research institutions are looking intensively
for the various chemical and physical agents responsible for the formation
of photochemical smog. An extensive network of observation stations record-
ing the level of urban air pollution has been created. In particular, in the
state of California, there are 16 such stations, according to the data of
which the maximum hourly concentrations of oxidants during the summer period
of 1954 in Los Angeles were 0.63 tng/m^, and the maximum 5-minute con cent rat ions
0.71 mg/m^ (based on hydrogen peroxide). In 1965, the indices of air polluti0 '
by oxidants were approximately at the same level in that area.
The conditions favoring the formation of photochemical smog by reactive
organic compounds and nitrogen oxides in the presence of a high air pollution
level are an abundance of solar radiation, temperature inversions, and low
wind speeds.
The oxidant concentrations are subject to great variations, but they
follow certain patterns: as a rule, low nighttime concentrations are followed
by a substantial increase in the early morning, then a peak takes place that
remains over the entire course of solar radiance and disappears with the sun-
set. The highest concentrations are usually observed at noon.
Reports have been published on the oxidant pollution of the air reservoi
of Italian cities. Kanitz [28] observed typical products of Los Angeles smog
- 88 -
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— PAN and other homologs of this series, peroxypropionyl nitrate (PPN) and
peroxybutyry 1 nitrate (PBN) in the air of Genoa.
Observations made by V. A. Popov [8] in Moscow, Baku, and Batumi demon-
strate the presence of oxidants in the air of these industrial centers of the
country. Thus, in Moscow, the maximum total concentration of oxidants based
on Popov [8] in Moscow, Baku, and Batumi demonstrate the presence of oxidants
in the air of these industrial centers of the country. Thus, in Moscow, the
maximum total concentration of oxidants based on Popov's data was 0.1 mg/m^,
in Baku, 0.15 mg/m^, and in Batumi, 0.04 mg/m^.
The problem of the biological effect of oxidants as a new environmental
factor has attracted the attention of researchers ever since the population
of Los Angeles first reported mass complaints of eye irritation.
The irritant effect of oxidants is attributed by researchers primarily
to the action of formaldehyde, acrolein and PAN.
According to the data of 135] , in which the irritant effect of individual
oxidants was studied experimentally, among the most sensitive persons, eye
irritation is observed from exposure to formaldehyde in a concentration of
0.12 mg/m^.
Studies by American authors prove that the inhalation of air containing
even moderate concentrations of oxidants, determined in the atmosphere during
periods of photochemical smog, are dangerous to persons with disturbances of
the respiratory system.
Motley et al. [33] report the results of a study of the influence of
photochemical smog on the respiratory function of 66 volunteer subjects, 46 of
whom suffered from pulmonary emphysema. The authors came to the conclusion
that the inhalation in the course of 2-3 days of air containing a large amount
of oxidants, 0.4-1.47 mg/m^, causes a decrease in the volume of maximum pul-
monary ventilation and a decrease of the vital capacity of the lungs, the
changes being more pronounced in persons suffering from pulmonary emphysema.
In a study of the possible relationship between asthma attacks and air
pollution, a correlation was established in [34] between the number of
attacks of this illness and the content of oxidizing substances in air.
A survey of the population of Los Angeles revealed that 40% of the per-
sons questioned were worried by air pollution. Three-fourths of this number
complained of eye irritation. One hundred thousand inhabitants of the state
of California stated that air pollution affects their breathing. Some per-
sons changed their residence because of air pollution [21].
The toxic effect caused by photochemical smog is thought to be substan-
tially related to the action of ozone, which makes up an appreciable part
- 89 -
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of the total amount of oxidants.
It is well known that in low concentrations, ozone is observed almost
everywhere in the surface layer of air as a natural factor. According to
observations of ozone [41, 4, 5, 11 etc.], its concentrations in the layer
up to 2 km from the earth's surface are highly variable and depend on the
time of year, latitude, time of day, and local conditions. These concentra-
tions range from thousandths of a milligram to 0.15 mg/m^ and amount to an
average of 0.01-0.04 mg/m^.
The irritant effect of ozone in concentrations of 0.2-1.0 mg/m^ on the
mucosa of the eyes is noted in [3, 7, 29, 34].
According to the data of [22, 13, 38], the ozone concentration in the
air of Los Angeles climbed to 0.6-1.0 rng/m^ during a photochemical smog.
According to many researchers, the inhalation of air containing increased
ozone concentrations causes a decrease in the resistance of the organism.
Thus, after a 3 hour exposure of white mice to ozone in concentrations of
0.1-0.98 mg/m^, followed by infection with streptococcus aerosol, a 25% in-
crease in death rate among the animals was observed as compared with the
control [19].
A similar effect of increased death rate of animals is noted in [38],
based on data of exposure of newborn mice to ozone in concentrations of
0.19-0.38 mg/m^ in 7-hour periods in the course of three weeks.
The action of PAN and its homologs on man was studied only in brief
exposures. These compounds affect the respiratory function in the manner of
other oxidants. In essentially healthy students who inhaled PAN in a concen~
tration of 1.5 mg/m^ for 5 min, a statistically significant increase in oxygen
consumption was observed. In a concentration of 2.5 mg/m^, this substance
has a more irritant effect on eyes in a 12-min exposure. However, the role of
PAN among other lacrimators is not completely clear, since it is less toxic
in pure form than in the composition of photochemical smog [36],
The object of the present study was a further accumulation of data on
the total content of oxidants and individual oxidizers (ozone and nitrogen
dioxide) in the air of a large city. Another objective was to study the ver-
tical scattering of oxidants in order to obtain a comparative picture of the
pollution of atmospheric air at the level of the lower and upper floors of
high-rise apartment buildings, which are being widely incorporated into typic
residential construction.
Literature data on the content of atmospheric pollutants at different
levels from the ground are scarce. Attention is drawn to the studies made bv
M. K. Kharakhinov [10], which showed that the carbon monoxide concentrations
at the height of the 22nd floor of a high-rise building in Moscow are almost
- 90 -
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the same as the concentrations at a level of 1 m from the ground.
Analogous data of vertical distribution of dust were obtained on the
same site by G. I. Sidorenko [9]. He also found that at the height of
the 22nd floor, the number of microorganisms is 63.6% of the number at a
height of 1.5 m above ground.
According to [2], in a study of the content of noxious pollutants in
the air above a motor roadway and in residential apartments on the first
three floors, the highest level of carbon monoxide concentrations was associ-
ated with the upper floors. The concentrations of nitrogen oxides in the
street and in third-floor apartments were the same.
To determine the total amount of oxidants, we used a method based on
the reaction of oxidation of phenolphthalin to phenolphthalein [31]. The
reddish-violet color formed was compared on the spot with an artificial
scale. The sensitivity of the method is 0.1 yg per 5 ml of the solution
studied.
The ozone content was determined spectrophotometrically with the reagent
dihydroacridine [6]. The method is based on measurement of the optical den-
sity of an ethanol solution of acridine, formed by reacting ozone with
dihydroacridine.
To determine the nitrogen dioxide, the air was passed through a solution
of potassium iodide, then a standard analysis using Griess reagent was carried
out on a photoelectrocolorimeter [1]. In addition to the determination of
the indicated substances, the air was analyzed for the content of one of the
most toxic components of automotive exhaust, carbon monoxide, by means of a
TG-5 gas analyzer [1],
The subject of this study were two 12-story apartment buildings located
next to roadways with no gap between the road and the safety* line. One of
the buildings (object a) was situated next to a highway with a traffic flow
of 2000-2400 cars per hour, and the other (object b) , with 1500-1800 cars per
hour. The number of cars was counted visually.
The air samples were collected during the summer-autumn period of 1967
directly on the highway and on balconies on the 8th and 12th floors.
The collection of air samples was associated with the recording of
meteorological conditions, intensity of solar radiation, and rate of traffic
flow. The period of the studies was associated with sunny weather and occasional
variable cloudiness without precipitation; the air temperature was 12.8-26°,
the relative humidity 27-73%, the wind velocity 0.2-2.1 m/sec, and the pressure
738-765 mm. The intensity of total solar radiation ranged from 0.02 to 1.08
cal/cm^ min. On the objects studied, 245 determinations of the total amount of
* Translator's notes Literally the red line.
- 91 -
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of oxidants, 66 of ozone, 135 of nitrogen dioxide and 2 87 of carbon monoxide
were carried out (total of 733) tests).
Fig. 1 gives average and maximum values of the concentrations of these
ingredients, determined in the street and on balconies of the 8th and 12th
floors. As is evident from the figure, the highest oxidant concentrations
were observed on object a. Although these concentrations decrease somewhat
with height, the indices obtained on all the levels have similar values
(0.166, 0.134, and 0.125 mg/m^ respectively).
The maximum oxidant concentrations were found during the period of
11 A.M.-l P.M., when the highest intensity of solar radiation was observed
(1.08 cal/cm^ min). As the intensity of solar radiation diminishes, the
oxidant concentrations decrease, indicating the photochemical nature of their
origin.
In cloudy weather and particularly during rains, the oxidant content of
air decreased to 0.01-0.02 mg/m^.
The nitrogen dioxide concentrations on object a remained unchanged up
to the level of the 12th floor, exceeding the MPC for this residential area.
As far as the indices of ozone content are concerned, their hygienic signif-
icance is difficult to evaluate because of a lack of a maximum permissible
concentration for atmospheric ozone. However, we note that the ozone concen-
trations in the street as well as at the height of the 12th floor (0.03-0.035
mg/m3) are twice as large as its odor threshold, 0.015 mg/m^j according to
M. E. Eglite [11],
Fig. 1. Concentration (mg/m^) of photooxidants and
carbon monoxide in the air of motor roadways for
objects a and b.
1 - average concentrations, 2 - maximum concentrations,
5 - MPC (maximum one-time value for atmospheric air).
- 92 -
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Thus on the major motor roadways surveyed in this cycle of observations,
the pollution of air with oxidants and nitrogen dioxide extends to the
higher floors of high-rise residential buildings.
Familiarization with the literature on this problem shows that the
limited number of substances forming a photochemical smog were identified with
a sufficient degree of accuracy.
Experimental studies should be made on the threshold and inactive concen-
trations of oxidants by using the sensitive tests employed for standardizing
atmospheric pollutants in the USSR. It is also very important to determine
whether oxidants in the concentrations recorded in the air of industrial
centers of the country are biologically active.
In this connection, future development of research should be conducted
in the following principal directions:
(a) study of the photochemical pollution of urban air in different
climatic zones, taking the local meteorological conditions into account;
(b) simulation of the concentrations of the main ingredients of photo-
chemical smog observed in nature, for the purpose of studying the effect on
the organism of animals and man;
(c) development of ameliorative hygienic, sanitary-planning, sanitary-
technical and other measures aimed at protecting the air of cities.
A particularly timely step toward a successful solution of the formu-
lated problem is the participation of agencies of the Meteorological Service
in full-scale observations in different cities.
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Ju. G. FELDMAN
ON PHOTOOXIDANT CONTENT IN THE TOWN AIR*
Photooxidants are toxic products which are formed in atmo-
spheric air from motor transport and industry emissions as a result
of complex chemical reactions stimulated by ultraviolet solar radia-
tion. To these products possessing the ability to harm vegetation and
to decrease visibility along with biological activities refer: ozone,
nitrogen oxides, peroxyacetylnitrate (PAN), organic peroxides, for-
maldehyde, acrolein, fine-dispersed aerosols, free radicals, etc.
The object of this work was the accumulation of data on sum-
mary content of oxidants, and of ozone and nitrogen dioxide separa-
tely, in the air of the city. Besides, the determination of concentra-
tions of one of the most toxic components of automobile exhaust,
i. e. carbon oxide, was carried out. The sum of oxidants was deter-
mined on reaction with phenolphthalin, ozone with dihydroacridine,
nitrogen dioxide with Griess reagent, and carbon oxide on gas analy-
zers TG-5, respectively.
The content of these substances in the air was studied both di-
rectly on roads with motion intensity of 1500—2400 cars an hour,
and on balconies of the 8th and 12th storeys of the houses situated
on these roads.
The obtained results show that oxidant concentrations on all the
levels are close quantities (0.166, 0.134, and 0.125 mg/m3, respecti-
vely), though they decrease with height to some extent.
Maximum oxidant concentrations were found in the period of the
most intensive solar radiation, that is from 11 a. m. till 1 p. m. Oxi-
dant content in the air was decreased to 0.01—0.02 mg/m3 at dull
weather and during the rain, especially. Nitrogen dioxide concentra-
tions remained unchangeable up to the level of the 12th storey sur-
passing maximum permissible concentration for residential area.
Ozone concentrations amounted to 0.03—0.035 mg/m3 both at the
bottom and at the height of the 12th storey which exceeds its smell
threshold of 0.015 mg/m3 by factor of two. In this connection, limited
and non-acting photooxidant concentrations have to be determined
experimentally on tests usually used for pollution normalization.
* Editor's notes The abstract is presented as given in English with the original Russian article but
has been slightly edited.
- 95 -
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STUDY OF AIR POLLUTION AND ATMOSPHERIC PRECIPITATION
RESULTING FROM ARTIFICIAL MODIFICATION OF CLOUDS
Sh. G. Gavasheli (USSR)
Pre;.-. Glavr.oe Upravlonie Gidrometeorologicheskoy Sluzhby Pri Sovete Ministrov SSSR. (Chief Administration
the ilydror.oteorolocical Service Under the Council of Ministers of the USSR.) "Keteorologisheskie Aspektv
Z;jcry,-j;',ncriiya Atmosfery". (Meteorological Aspects of_Air Pollution.) Sbomik dokladov na rr.ezhdunarodnom
sir.'.po^iurr^; v leningrade - Iyul' 196Q g. (Reports delivered at the International Symposium in Leningrad _
ut:ly lvo5.) Pod rcdoktsioy d-ro fiz.-iwt. naulc M. E. Barlyanda. , (Edited by Prof. M. E. Berly&rid.)
Cidroneteorol^ieheskoe izdatel'stvo, Leningrad, p. 345-3^8, (l97l). (Hydrometeorological Publishing House
(1971).) •
At the present time, extensive work is being done on the prevention
of damage done by hail, and on the development of precipitation and the
scattering of fogs by means of various chemical agents. The development
of methods of modification of meteorological phenomena and the improvement
of existing ones constitute one of the major problems of modern science.
In recent years, extensive work on protection of vineyards from hail
damage has been conducted in Georgia and other republics. The chief reagent
used for hail prevention at the present time is lead iodide. Lead is widely
distributed in nature: in air, soil, water, plants, and the human and animal
organisms.
The lead content of the atmosphere and atmospheric precipitation has
been studied by V. I. Baranov, I. I- Vilenskiy, M. N. Bykov, A. S. Zykova,
V. A. Ryazanov, 0. P. Shalamberidze, and others. The effect of lead on
public health and its action on the organism have been studied by 0. S. Yesy^
tina, A. A. Letavet, Ya. Z. Matusevich, N. I. Tarasenko, M. K. Khachatryan
and L. N, Khvil'ni tskaya.
It is well known that the chief sources of air pollution with lead are
ferrous metallurgical plants, lead-ore dressing, printing type, and storage
battery plants, etc.
Our aim was to study the degree of pollution of the atmosphere resultin
from cloud modification. To this end, sampling of atmospheric precipitation^
and air and their subsequent analysis were organized.
The chief requirement for a sampling instrument is that the latter
itself must not introduce any additional contaminants into the samples beine
collected. We therefore constructed a special "precipitation collector"
instrument made of 8-10 ram plexiglas.
The precipitation collector consists of two main parts, a receiving
vessel and a lid. The receiving vessel is in the shape of a quadrangle with
a receiving surface of 58 x 60 cm. The lid of the precipitation collector
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is a rectangle whose lower side has a half—thickness groove for tightly
covering the receiving vessel.
Before the precipitation, the lid is removed by means of a special
handle, and placed at an angle in the rear portion of the receiving vessel
so that the atmospheric precipitation falling on the inner side of the lid
flows directly into it. Thus, the lid perforins a dual function: first, it
protects the receiving part of the vessel from dust in rainless weather,
and secondly, during precipitation, it almost doubles the receiving surface
of the instrument, permitting the collection of a large number of samples
of atmospheric precipitation.
The collected samples are poured from the receiving vessel through a
drainage hole into a special polyethylene vessel, which is sent to a
chemical laboratory for analysis.
During the expeditions, samples of air were taken for chemical analysis
and determination of their lead content. The method consisted in the
following: air was pumped through a Kipp instrument, containing doubly dis-
tilled water, with the aid of the so-called dust accumulator of type UA-T-80,
which directly measured the total amount of drawn air. The lead particles
present in the air remained in the doubly distilled water on passing through
it.
There are a good number of methods of determination of lead in different
samples. A given method is used as a function of the problem at hand. For
our purposes, i.e., in determining lead in atmospheric precipitation and in
air, the sulfide method was employed.
The protection of vineyards from hail damage on the territory of Georgia
is carried out mainly in Kakhetya in the valley of Alazini River, this being
the region with the most advanced viticulture in the Republic.
The installations for introducing the reagents into the clouds were
mainly located on the mountain tops and slopes of the Caucasian and Gomborskiy
ridges. The bulk of the reagents introduced into the clouds precipitate out
in the central part of the Alazini valley. For this reason, most of the pre-
cipitation collectors were placed in this region.
In 1964-67, 210 samples of atmospheric precipitation were collected in
which the lead content was determined. From the data obtained it follows that
the highest average lead concentration in atmospheric precipitation was ob-
served in Chotori in 1966 and amounted to 0.0054 mg/1, whereas in Telavi it
was 0.0014 mg/1, and in Leliane, 0.0023 mg/1.
The maximum amount of lead in single samples of atmospheric precipitation
was also obtained in Chotori on 12 June 1968 and amounted to 0.0200 mg/1. In
97 -
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Telavi, the maximum amount was observed in 1967 and amounted to 0.0035 mg/1
(in Chotori, no atmospheric precipitation was collected in 1967).
On 12 June 1966 in Kakhetya there was a total cloud cover, a thunder
storm began at approximately 11:30 A.M. and continued until 3-4 P.M. There
was a pouring rain, and the wind was gentle in the northern and northwestern
directions. On that day, cloud modification work was being carried out by
expeditions of the Geophysical Institute of the Academy of Sciences of the
Georgian SSR and the Trans Caucasian Scientific Research Hydrometeorological
Institute.
Similar cases of increase of lead content in precipitation as a result
of cloud modification were obtained on other days, for example, 25 May and
24 June 1966.
This direct relationship between cloud modification and increase of
lead concentration in precipitation was not always observed. It is probable
that various factors are involved here: the amount of lead introduced into
the clouds, meteorological conditions, number of precipitation collectors
located on the territory studied (for observation of the region of maximum
pollution), etc.
It is of interest to note that an increased lead concentration (0.0214
mg/m3) was also obtained on 13 and 14 June 1966 in atmospheric air. Cloud
modification was carried out on 12 and 13 June.
It is necessary to compare the data obtained with the maximum permissible
concentration adopted in the USSR.
The maximum permissible concentrations (MPC) of lead in atmospheric pre-
cipitation have not yet been established. It should also be noted that not
enough studies have been made thus far on the determination of lead in atmos-
pheric precipitation. However, one has to assume that the MPC of lead in
atmospheric precipitation should be higher than in drinking water (0.1 mg/1).
On the basis of the above, it may be concluded that despite the fact that in
some samples the lead content of atmospheric precipitation is fairly high,
it still remains below the maximum permissible concentrations.
The situation is different in the case of the amount of lead in atmos-
pheric air. In most of the collected samples, the amount of lead in the
atmospheric air of Kakhetiya was found to be greater than the MPC, and on
some days, much greater. For example, on 13 June 1968 in Chotori, the value
of 0.0214 mg/m^ was obtained, whereas the MPC in the USSR for populated areas
is 0.007 mg/m3.
Thus, as a result of artificial modification of clouds, the amount of
lead in atmospheric precipitation increases, but it still remains below the
- 98 -
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maximum permissible concentration. As far as the air is concerned, the
amount of lead increases considerably, and at some individual points
exceeds the PMC by a factor of 30-35.
Sh. G. GAVASHEU
INVESTIGATION OF AIR POLLUTION AND ATMOSPHERIC PRECIPITATION
AS A RESULT OF ARTIFICIAL MODIFICATION OF CLOUDS*
In the last few years work on modification of meteorological phe-
nomena is performed on a large scale. On considerable areas of
Georgia protection of agricultural crops from hail is fulfilled. Lead
iodide is used as a main crystallizing reagent employed in artificial
modification of clouds. It is interesting to evaluate to what extent air
and precipitation are polluted after introduction of this reagent into
clouds.
From 1964 Scientific-research Hydrometeorological Institute of
the Caucasus carries special investigations with purpose of determi-
nation of air pollution level at modification of clouds. Air and preci-
pitation sampling and their analysis on lead content is done. For
precipitation sampling a special sampler was constructed
which consists of collector with a lid. The latter protects the colle-
ctor from the dust and during the precipitation increases the samp-
ling area nearly twice. This allows to collect large amounts of preci-
pitation for the analysis on lead content. For air sampling Kipp's
instrument is used through which investigated air is passed.
Air and precipitation samples were taken during expeditions in
Georgia while conducting artificial modification of clouds. On the
whole, 210 samples of precipitation and 20 air samples were analy-
zed for 1964—67. Obtained data analysis shows that lead amount in
precipitation increases at modification, but still remains less than
maximum permissible concentration. The largest mean lead concen-
tration in precipitation was observed in Chotory on the 12th of June,
1966. It amounts to 0.02 mg/1. As to the air, the lead amount in it
considerably increases at modifications, sometimes surpassing maxi-
mum permissible concentration in 30—35 times. On June 13, 1966 in
Chotory the measured lead concentration in the air was equal to
0.024 mg/ms and exceeded maximum permissible concentration in
about 34 times.
* Editor's notes The abstract is presented as given in English with the original Russian article.
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MICROCLIMATIC CHARACTERISTICS AND HYGIENIC EVALUATION OF
THE RELATIVE EMPLACEMENT OF INDUSTRIAL AND RESIDENTIAL COMPLEXES
IN THE REGIONS OF SIBERIA
L. I. Koldomasov and M. T. Zenin (USSR)
From Glavnoe Upravlenie Gidrometeorologicheskoy Sluzhby Pri Sovete Ministrov SSSR. (Chief Administration of
the Hydrometeorological Service Under the Council of Ministers of the USSR.)^ "Meteorologisheskie Aspekty
Zagryazneniya Atmosfery". (Meteorological Aspects of Air Pollution.) Sbomik dokladov na mezhdunarodnom
simpoziune v Leningrade - Iyul' 1966 g. (Reports delivered at the International Symposium in Leningrad -
July 1966.) Pod redaktsiey d-ra fiz.-mat. nauk M. E. Berlyanda. (Edited by Prof. M. E. Berlyaiid.)
GidrometeorolgichesRoe izdatel'stvo, Leningrad, p. 349-351, (1971). (Hydrometeorological Publishing House,
Leningrad, U971J.)
A very important factor in the modernization, design, and construction
of cities and in the planning of new industrial centers is a scientifically
valid consideration of microclimatic characteristics of the region. Most
important is the influence of the topography, which is usually responsible
for the generation of local air circulation, and largely determines the
conditions of transport of noxious emissions of industrial plants toward
residential areas and hence the degree of atmospheric pollution. Under
dissected relief conditions, the wind roses differ markedly from one another
even at closely situated meteorological stations. For this reason, in solv-
ing urban construction problems, particularly in determining the relative
location of industrial and residential complexes, it is important to study
the local microclimatic characteristics. Their underestimation in many
cities of the country has led to a considerable increase in air pollution.
The Applied Climatology Section of the Novosibirsk Branch of the Hydro-
meteorological Center (formerly, a branch of the Scientific Research Institute
of Aeroclimatology) since 1958 has been conducting (in collaboration with the
Novosibirsk Scientific Research Sanitation Institute) extensive microclimatic
and sanitary-hygienic surveys of certain cities in which meteorological obser-
vations and the collection of air samples are combined at 12 to 15 stationary
points. At these points, the concentrations of dust, soot, and a number of
gaseous ingredients are regularly determined.
As we know, data given in climatological handbooks do not include a
whole complex of meteorological data that are required for characterizing
the conditions of propagation of noxious emissions. In particular, the hand-
books do not contain information on the frequency of dangerous velocities
and directions of the wind (average and for the observations periods), or on
the continuous duration of periods with calms and with gentle winds.
The propagation and concentration of impurities are strongly affected by
temperature inversions, which limit the ascent and dispersal of noxious
- 100 -
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emissions from plant stacks. In winter, inversions in Siberia are observed
almost daily, their frequency in the cold half of the year amounts to 90%
or more, and their thickness frequently exceeds 500-600 m. The distance
between the points of radial sounding in Siberia is very large. In this
connection, studies were made for the purpose of working out methods of
calculation of the frequency of inversions that are dangerous from the
standpoint of atmospheric pollution, using surface and pilot balloon obser-
vations. In particular, satisfactory relationships were observed between
the average and maximum frequency of winter morning inversions and the
frequency of days with a weak mean daily wind velocity.
The problems of relating such observations (1-2 years) on the wind
velocity to long-term data of a local meteorological base station were
studied.
In work over rugged terrain, a study was made of the distortion of air
currents flowing from the plants to sites intended for residential construc-
tion, primarily in the presence of weak and moderate wind velocities. In
addition, the effect of different types of industrial sites and of residential
buildings on the air pollution was investigated.
To determine the influence of noxious emissions on the sanitary living
conditions, a questionnaire was submitted to the population, and the state of
health of the children living in various parts of the city was surveyed.
In one city with a developed metallurgy, a metallometric survey was
made within a 30 km radius in collaboration with geologists, which showed
that as a rule, increased metal concentrations in the soil are observed in
zones where high average concentrations of the metal are present in the dust
collected from the air.
Correlation and analysis of the data of the studies made it possible to
supply a comprehensive microclimatic and hygienic evaluation of the territory
of certain cities to the planning and design agencies. Variants of the rela-
tive emplacement of industrial facilities and populated areas were evaluated,
boundaries of sanitary protective zones were refined, and recommendations
were given on the selection of sites for public rest and recreation areas and
for planting greenery.
- 101 -
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L. 1. KOLDOMASOV, M. T. 7.ENIN
MICROCLIMATIC PECULIARITIES AND HYGIENIC ESTIMATION
OF MUTUAL LOCATION OF INDUSTRIAL AND RESIDENTIAL COMPLEXES
IN THE REGIONS OF SIBERIA*
Scientifically valid calculation of local conditions and microclima-
tic features has a great significance for reconstruction, planning and
building of existing towns, and projection of new industrial centres.
It is very important to take into account the influence of terrain
relief, especially in complex conditions of mountain and foot-hill re-
gions where local winds usually occur which determine transfer con-
ditions and the level of air pollution by industrial plants.
As the result of integrated microclimatic and sanitary-hygienic in-
spection o? some Siberian towns it has been found that underestimation
of local features often leads to substantial pollution of residential
regions by noxious industrial emissions which affects human health.
As investigations show the highest air pollution by nitrogen oxi-
des, phenol, dust, sulphur oxide, and other ingredients is usually
marked at calm or light (up to 2 m/sec) wind and in the presence
of ground and elevated inversions with thickness not less than 300 m.
If such weather continues more than two days the concentrations of
noxious emissions above maximum permissible values are observed,
as a rule, on the whole territory of the town.
For the estimation of air pollution level and discharge distribu-
tions on town territory and for the definition of boundaries of sani-
tary-protecting zones for main enterprises, it is necessary to carry out
integrated microclimatic and sanitary-hygienic inspection during at
least two cycles.
In towns with developed metallurgical industry, copper, nickel,
iron, manganese, zinc, etc., are accumulated in the soil during many
years. The distribution of separate ingredients content in the soil on
the territory of the town and its suburbs can be revealed with the
help of metallornetric survey and in such a way it is possible to re-
ceive indirect characteristics of air pollution.
Microclimatic investigations are carried out in new industrial
regions on the basis of which recommendations are given on the
choice of the best variants of mutual location of industrial and re-
sidential complexes.
* Editor's note: The abstract is presented as given in English with the original Russian article,
but has been slightly edited.
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NUMERICAL CHARACTERISTICS OF METEOROLOGICAL CONDITIONS
ASSOCIATED WITH PERIODS OF HEAVY ATMOSPHERIC POLLUTION
IN WESTERN SIBERIA
I. A. Shevchuk and L. I. Vvedenskaya (USSR)
From Glavnoe Upravlenie Gidrometeorologicheskoy Sluzhby Pri Sovete Ministrov SSSR. (Chief Administration of
the Hydrometeorological Service Under the Council of Ministers of the USSR.) "Meteorologisheskie Aspekty
iagryazneniya Atmosfery". (Meteorological Aspects of_Air Pollution.) Sbornik dokladov na mezhdunarodnom
simpoziume v Lenin grade - Iyul1 I960 g, (Reports delivered at the International Symposium in Leningrad -
July 1966.) Pod redaktsiiy d-r* fiz.-m»t. nitric U. C. Berlyanda. (Edited by Prof. M. E. Berlytrid.)
Gldroneteorolgicheskoe lzdatel'stvo, Leningrad, p. 552-356, (1971). (Hydroaeteorologioal Publishing House,
Leningrad, (1971J-)
Studies of the meteorological conditions associated with periods of
heavy atmospheric pollution in industrial cities of Siberia are being con-
ducted at the Novosibirsk Regional Hydrometeorological Center for the pur-
pose of working out recommendations of methods to be used for warning
interested agencies of impending periods of possible heavy pollution.
The material used in this study consisted of regular daily observations
of the propagation of emissions from industrial plants and from transport
in several cities of Siberia. Data for 1962-64 and 1966-67 were used.
The observations were made at stationary points of the cities and along
special routes on trucks. Samples of air for analysis of dust, soot,
nitrogen oxides, carbon monoxide, and sulfur dioxide were taken at the
earth's surface and high in the air by using a helicopter. The data obtained
were used to determine the average and maximum concentrations of the ingred-
ients at various points of the cities for every 24-hour period.
The period of heavy atmospheric pollution was considered to include cases
in which in a specific city, the highest average concentrations of two or
more ingredients were simultaneously retained for over two consecutive days.
Thirty-three such periods were isolated during the periods considered, 15 dur-
ing the warm time of the year and 18 during the cold. Overall, periods of
heavy pollution amounted to 208 days.
Based on data of meteorological and aerological observations, the average
and maximum wind velocities, vertical thermal gradient of the layer and aver-
age horizontal pressure gradient on the ground and at a level of 850 nib, cal-
culated as a Laplacian, were considered in the lower 2-kilometer layer for
each day of the isolated period (the average wind velocity taken in the layer
was the arithmetic average of velocities at 6 levels — ground, 100, 200, 500,
900 m above the earth's surface and 1500, 2000 above sea level).
- 103 -
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Analysis of the material showed that in the regions of Siberia, a pro-
longed and appreciable increase of the ingredient concentrations near the
earth's surface is most likely to occur under conditions of a low-gradient
baric field in the presence of a stably stratified air mass; this generally
confirms the results of studies on other territories.
The baric field in the region of Siberian cities for cases involving
an increase in atmospheric pollution was diverse in character (anticyclonic,
cyclonic and hyperbolic points). However, it almost always caused an atten-
uated air transport to a height of 1.5-3.0 km.
In the plains of Western Siberia, for cities with plant stack heights
from 20 to 100 m, the specific characteristics of the state of the lower
atmospheric layer during periods of heavy air pollution had the following
values.
(a) concentrations: I - nitrqgen oxides, 2 - sulfur dioxide, 3 - soot,
4 - dust;
(b) baric gradients! 1 - or the earth's surface, 2 - on 850 nib. surface
1. The average horizontal baric gradient at sea level was 0.75-2.5 mb/
500 km, and on the 850 mb surface, 0.75-3.0 mb/500 km. Simultaneous analysis
of average concentrations and average horizontal baric gradients in February
and July (Fig. 1, 2) clearly shows a relationship between high concentrations
and minimum gradients.
2. The average wind velocity in the layer up to 2 km is preserved in
the range from 2 to 6 tn/sec. The maximum velocity at one of the levels in
- 104 -
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the layer is not more than 7 m/sec in summer and not more than 10 m/sec in
winter.
3. A stable stratification in the 2-kilometer layer is preserved
during an entire 24-hour period. At night, a surface inversion is bound
to be observed. In winter, the thickness of the inversion layer is not
less than 800 m, and the maximum temperature gradient in it is not less than
2°C./100 m. In summer, the thickness of the inversion layer is not less than
100 m, and the maximum temperature gradient in it is not less than 1°C-/100 m.
Differences in the meteorological characteristics of the 2-kilometer
layer of the atmosphere during periods of heavy pollution in winter and
summer are due to the temperature difference between the emissions and the
ambient air in different seasons of the year.
When the above conditions are preserved, high concentrations of gaseous
ingredients are observed during the entire period. The maximum dust concen-
tration at the earth's surface is observed when, after a period of stagna-
tion, the wind begins to intensify at the earth's surface, and the inversion,
breaking up at the bottom, changes into an elevated inversion. When a frontal
weatherparting passes through a city, even under conditions of a diffuse
baric field, a decrease in the concentrations is observed both on the ground
and high in the air, independently of whether there is or is not any precipi-
tation as the front passes.
1
NO,
Soot StiZ
Fig, 2. Variation of average concentrations of ingredients (a) and
average baric gradients (fc) for July 19&?.
Notation same as in Tig. 1.
- 105 -
-------
To determine the probability of appearance of conditions promoting
an increase in atmospheric pollution, results of daily radiosonde observa-
tions for 5 years (1962 through 1966) for Novosibirsk were processed.
Graphs of the probability of appearance of unfavorable stratification under
atmospheric stagnation conditions were plotted for different seasons of
the year (Fig. 3).
\
i i I I 1 1 ui-
0 200 400 600 800 1000 0 200 400 SOO&HM
i i i i i 1 1 1—
0123 4501 aeg/MO«
Fig. J. Probability of appearance of unfavorable
stratification under atmospheric stagnation con-
ditions in winter (a) and suirner
1 - thickness of inversion layers, 2 - temperature
lapse rate in inversion layers.
The numerical characteris tics of horizontal baric gradients, wind
velocity and intensity of inversion layers during periods of heavy atmos-
pheric pollution, shown in Table 1, may be used for forecasting conditions
causing a dangerous increase of the concentrations. The basis of such fore-
casting is the calculation of a future baric field on the ground and at the
850 nib level, and also the analysis of the variation in the stratification
of the air mass.
Table 1
Meteorological Characteristics of the State of the Atmosphere Pro-
mot ing a Considerable Increase in the Concentration of Industrial
Emissions near the Earth's Surface.
Season
Laplaoian
Wind Velocity ii
in 2 km layer,
ir./ sec
Maximum Temper^
ature Lapse Rate
in Layer, deg/lOOa
[Thickness of
[Stable Layer, m
i
Ground
850
Average
Maximum
In Summer
In Winter
0,75-2,5
0,75-3,0
2-6
<10
>-1
>-2
>100
>800
- 106 -
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LITERATURE CITED
1. EejrfluiOBii M. A. H Ap. MerojiiKa aspojiorimecKiix Ha6;noflennii a.™ H3y>ienna
pacnpocTpaKeHHfl npiiMeceft ot flbiHOBbix Tpy6. Tpyau TrO, Bbin. 158, 1964.
2. B b e a e h c k a r /I. H. h Ap. HeKOTopwe xapaKTepHCTHKif MeTeopo.iornKecKHx h
aspocHHonTKMecKHx yc.ioBnft saAbiM/ieHim b r. HobochShpckc. TpyAhi HHHAK,
Bhin. 48, 1967.
3. BopoHKOB n. A. HeKOTopwe 3aAami aspo.iorimecKHx Ha6.nioiiennA npn Hcc.ie-
AOBaHHH pacnpocTpaneHHH awmobwx CTpyft, Tpyflfai TID, Bbin. 158, 1964.
4. CoiibKHH JI. P. Toaoboh xoa ii cHHonntiecKasi oCywoB^eHHocTb TeMnepaiyp-
hwx npo<}>H.neft b hh)khcm 500-MeTpOBOM c.noe. TpyAH rro, Bbin. 185, 1966.
5. COHbKHH /I. P. CHMOtlTHHeCKHe yCJIOBHH (fopMHpOBaHHH HHBepCHft B HHJKHeM
500-MeTpoBOM moc. TpyAW rrO, Bbin. 172, 1965.
6. Ill e b h y k H. A. AspocHHonTHiecKHe yc.ioBHH ycTaHOB.ieHna AJiHTejibHbix nepno-
Aob MaKCHMaflbHoro 3arpn3Hennn B03Ayxa b r. KeMepoBo. Tpyau HHHAK,
Bbin. 42 (2), 1966.
7. Elmer R. The relative importance of some meteorological factors in urban air
pollution. Sec. Techn. Rept., 1962, No. 5.
/. A. SHEVCHUK, L. I. VVEDENSKAYA
NUMERICAL CHARACTERISTICS OF METEOROLOGICAL CONDITIONS
WHICH ACCOMPANY THE PERIODS OF STRONG AIR POLLUTION
IN WESTERN SIBERIA*
On the basis of regular observations of pollutant distribution on
the territories of Siberian towns in 1962—64 and 1966—67, the pe-
riods are marked out when the sharp increase of background concen-
trations of pollutants was observed. The analysis of meteorological
and aerological observations during these periods showed that the
background concentration increase is connected with stagnant atmo-
spheric state. In the article there are stated particular numerical
characteristics of meteorological elements near the ground surface,
baric gradients, mean and maximum wind velocities, and stratifica-
tion of the lower layer in the periods of strong air pollution.
~Editor's note: The abstract is presented as given in English with the original Russian article.
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EXPERIENCE IN SIMULATING THE PROPAGATION OF NOXIOUS SUBSTANCES IN THE
SURFACE ATMOSPHERIC LAYER OVER PLANT SITES AND SURROUNDING GROUNDS
V. M. El'terman (USSR)
From Glavnoe Ifpravlenie Gidrometeorologicheskoy Sluzhby Pri Sovete Miniatrov SSSR. (Chief Administration of
the Hydrometeorological Service Under the Council of Ministers of the USSR.) "Meteorologisheskie Aspekty
Zagryazneniya Atmosfery", (Meteorological Aspects of Air Pollution.) Sbornik dokladov na raezhdunarodnom
siraposiuiK v Leningrade - lyul' I960 g. (Reports delivered at the Irtternational Symposium in Leningrad
July
Gidfo
Leningrad,
iiaiposiuiK v Leningraae - lyui' lyoo g. ^«eports aenverea at trie irreernationao. symposium in Leningrad _
luly 196S.) Pod redaktsiay d-ra fii.-wt. nauk H. E. Barlyanda. (Edited by Prof. M. E. Berlyarid.)
iidrometeorolgichesttoe izdatel'stvo, Leningrad, p. 357-361 C 197*1 J• (Hydrometeorological Publishing House*
Leningrad, (1971).)
Interesting results on the simulation of air currents in the atmosphere
have been obtained at the A. I. Voyeykov Main Geophysical Observatory and
Moscow University [2],
Work on simulation of the processes occurring in the surface atmospheric
layer is also being conducted at the All-Union Central Scientific Research Insti-
tute of Labor Protection, All-Unlon Central Trade Union Council [7]. Since 1963
the concentrations of noxious substances in the atmosphere have been determined
bere in a wind tunnel on models of newly designed industrial plants and of those
undergoing modernization. Studies have been made on two major chemical works,
plastics factories and aluminum plants, two synthetic rubber plants being modern-
ized, a blocked building of large width, and other plants.
The studies performed made it possible to find better solutions to the
design of plants, and to determine the sites, heights and maximum amount of
emissions of polluted air for which the purity of the surface atmospheric
layer required by sanitary norms is maintained#
A simulation procedure based on the following assumptions was used in
this study. From the equation of turbulent diffusion describing the process
of impurity transport in atmospheric air, the following similarity criterion
may be proposed:*
•^ = idem, (1)
where v is the flow velocity, L is the characteristic dimension, and K is the
coefficient of turbulent exchange.
According to [6], the following relation applies to the coefficient of
turbulent exchange K.
'/, t'h
* — (2)
where e is the dissipation energy.
* As was shown by the experiments, relative to the Reynolds criterion, the process studied is Belt-
s' milar for Re > 2000.
- 108 -
-------
From (2) and (1), assuming that ^ = constant, we find
= —Idem. (3)
Hence, the scales of velocities, lengths and dissipated energy may be mutually
related by the expression
cv = (ctct),,\ <
-------
difference, then the Archimedes criterion is*
(5')
From the Archimedes criterion, the following equation relating the scales of
the quantities is obtained:
Six scales enter into Eqs. (4) and (6). If one takes c = 1 (since all
the experiments are carried out under earth gravity conditions), and Cf = 1,
which makes it possible, in simulation with air, to have a model with physi-
cal constants of the medium closer to nature, only four scales remain. Hence,
if one specifies two scales, the other two are determined by jointly solving
Eqs. (4) and (6).
Thus, if the velocity scale is excluded from Eqs. (4) and (6), we obtain
Considering that admixtures of noxious sulstances have no substantial
influence on the flow (the change of the specific weight of the mixture is
considered by the Archimedes criterion), from the formula determining the
discharge of the substance, we find
where cq is the concentration scale and c^ is the scale of discharge of the
noxious substances.
Thus, having created a model that is geometrically similar to nature, and
maintained the similarity of the fields of physical constants at the boundaries
by means of Eqs. (4), (7) and (8), one can carry out the calculation for the
model, and after conducting the experiments on it, convert the results to full
scale.
*In meteorology, the parameter B = ^ * similar to the Archimedes criterion (where H is the height,
assumed equal to 2m,AT is the temperature difference at heights of k and 1 m, and v is the wind velocity at
the height of 2 m), is used for the characteristic, determined by the temperature distribution, of the stabil-
ity of the surface atmospheric layer.
(6)
(7)
(8)
- 110 -
-------
However, the fulfillment of conditions (4) and (7) causes a complication,
since it leads to a model with small scales for the speeds and large ones for
the temperature difference. To simplify the simulation, regions were studied
in which "partial" (limited) self-similarity of the process is observed in re-
lation to the characteristic criteria.
The experiments showed that in the surface atmospheric layer, where the
impurities are propagated, within the confines of a plant site, the turbu-
lence is substantially determined by the conditions of flow around the build-
ings (flow disruption at sharp edges and formation of vortex zones at the
buildings). The initial flow turbulence has little effect on the concentra-
tion distribution. Thus, self-similarity takes place relative to the Karman
criterion.
In a model study of the propagation of impurities over the grounds sur-
rounding a plant, the process is investigated in a substantially larger space
(in both area and height). Perturbations caused by flow around the buildings
have no substantial effect on the flow in this volume. The turbulence in the
volume studied will depend considerably on the initial turbulence of the in-
coming flow. In this case, the process will not be self-similar with respect
to the Karman criterion. Even if a situation (topography, structure, etc.)
similar to nature is created on the windward side of the model at a substan-
tial distance (of the order of 4-6 heights of the space studied), similarity
conditions cannot always be produced in this case either. In such cases, in
the air flow incident on the model, it is necessary to create artificially
a turbulence corresponding to the natural turbulence, and to maintain it at
the necessary level over the entire length of the test section of the wind
tunnel.
It has been established experimentally [5] that for low values of the
Archimedes criterion, the flow may be considered isothermal with a suffi-
cient degree of accuracy. The literature [1, 5] indicates that in the prop-
agation of nonisothermal plumes in a stationary medium, the distortion of the
plume path caused by gravitational forces may be neglected if the criterion*
Ar < 0.005.
For nonisothermal flow of a plume in a stream, Yu. V. Ivanov 13] pro-
poses, as the parameter characterizing the similarity, the ratio of the
velocity heads in the flow and in the plume . v P. , where v and p are the
ogp0
velocity and density of the flow and vQ and pQ are the velocity and density
of the plume leaving the stack. This parameter may be used to find the
boundary of the zone of "partial" self-similarity.
~In this case, the criterion is determined by assuming the characteristic dimension (stack diameter),
average exit speed of air from the stack Vq, and the temperature difference Al between the air leaving the
stack and the air in the surrounding medium.
- Ill -
-------
As was shown by experiments with two models of different scales, when
¦) / v2p
the magnitude of the product is Ar y— <0,05 , the presence of noniso-
1 v20po
thermality may be neglected with an error of not more than 127= (and mainly
in the direction of higher concentrations in a model of smaller scale).
vl
In the presence of self-similarity with respect to the criteria ^— and
Ar, only the fulfillment of geometric similarity is required.
LITERATURE CITED
1. B a t y p ii ii B. B. Ochobu npoMbiui-iemioft BeHTinsimiH. ripon3,aaT, M., 1965.
2. Top^HH C. M., 3 p a >k e b c k ii ft H. M. Hcc.ieAOBaime b.hihiihh nepoBiiocTcu
aeMiiou noBepxiiocTii na xapaKTepitCTiiKii B03aymnoro noTOKa b aspofliuiaMH-
lecKoA Tpy6e. Cm. nacTonmiiH cdopiiHK.
3. H B a h o b IO. B. SKcnepHMeiiTa.ibiioe Hcc.ieacmaiiiie CTpyii, pa3BHBaiomnxcH b no-
TOKe. C6. TpyaoB «Teopi(n it pacicr BeiiTH.-iiiuiioinibix CTpyfl», JL, 1965.
4. J1 o A UK ii c k h A Jl. T. MexamiKa wiuiKocTefi ii ra30B. rociexinjaT, M., 1957.
5. JIsixobckiiA JX. H., C bi p k h ii C. H. AspoaiiiiaMiiKa (jjaneiia, BbiTeKaramer.)
b cpeay apyroft n^omocTH. >KypHa;i TexinmeeKOii h3iikh, Bbin. 9, t. IX, 1939.
6. O6yxoa A. M. Pacnpenejieiuie aiieprnii b cneKTpe Typ6yjienT!ioro noTOKa. ZlAH
CCCP XXXII, 1941 ii H3B. AH CCCP, cep. reorpai}). h reoi})ii3., A1? 4 ii 5, 1941.
7. 3 ji b t e p m a ii B. M. Beimi.Tamisi xh.miimcckiix npoii3BojcTB. Grpoi'iii.'uai, M,
1967.
V. M. ELTERMAN
ON EXPERIMENT OF MODELLING OF NOXIOUS SUBSTANCE
DISPERSION IN THE SURFACE AIR LAYER OVER PLANT TERRITORIES*
In the USSR Central Institute of Labour Protection scientific
work is conducted tin diffusion process modelling in the surface air
layer. Investigations for some large industrial plants were carried
out which allowed to find the best decision of enterprise planning
and to determine necessary stack heights.
For evaluation of data received by modelling, similarity criteria
are suggested both for the case of isothermal and non-isothermal
currents in which characteristic length scale, mean velocity, and ve-
locity of turbulent energy dissipation are taken into account. Flow
regions are pointed in which automodelling exists in accordance with
these criteria. In such regions observance of only geometric simila-
rity is recommended.
~Editor's note: The abstract is presented as given in the English with the original Russian article.
- 112 -
-------
SPECIAL CASES OF VERTICAL CURRENTS
I. G. Diaconescu, M. Frimescu, I. Moroianu, and A. Moroianu
RSR (Romanian Socialist Republic)
From Glavnoe Upravlenie Gidrometeorologicheskoy Sluzhby Pri Sovete Ministrov SSSR. (Chief Administration of
the Hydrometeorological Service Und«r the Council of Ministers of the USSR.)_ "Meteorologisheskie Aspekty
Zagryazneniya Atmosfery". (Meteorological Aspects of Air Pollution.) Sbornik dokladov na nezhdunarodnom
simpoziume v Leningrade - Iyul' 1968 g. (Reports delivered at the Iirternational Symposium in Leningrad -
July 1966.) Pod redaktsiey d-ra fiz.-m»t. nauk li. E. Berlyanda. (Edited by Prof. M. E. Berlyarid.)
Gidroneteorolgichesltoe izdatel'atvo, Leningrad, p. 362-366, (1971). (Kydroneteorologioal Publishing House.
Leningrtd, (1971).)
The investigation of air pollution with emissions of industrial plants
consists primarily in the study of the patterns of distribution of pollutants
with time and in the space around the sources. A number of computational
formulas have been derived for this purpose [1, 8, 11].
It is well known that the propagation in the atmosphere of pollutants
discharged by industrial plants depends on different, simultaneously opera-
ting factors: characteristics of the emission (amount of pollutants discharged,
their nature and physicochemical properties, and stack height of parameters
that can be determined in advance), orography and roughness of the terrain
(parameters determined experimentally), wind and atmospheric turbulence
(parameters determined experimentally and theoretically).
Consideration of all these factors operating simultaneously introduces
certain difficulties into the theoretical treatment of turbulent diffusion of
noxious substances, and for this reason some of the solutions obtained are
based on simplified hypotheses. Primarily, they exclude the distorting effects
caused by irregularities of the relief and study simplified models of air
motion [5, 3].
In conformity with the above, various authors, including 0. Sutton [9-11],
F. Pasquill [8], M. Ye. Berlyand [1, 2] and others obtained some definite
results.
In the general case, turbulent diffusion is described by the equation
where q is the impurity concentration, u is the wind velocity, w is the
vertical rate of deposition of the impurity, k2 and ky are the corresponding
coefficients of turbulence, the x axis is parallel to the mean wind, the y axis
is perpendicular to the x axis in the horizontal plane, and the z axis is
directed along the vertical.
(1)
- 113 -
-------
Thus, in addition to the wind velocity (u) , frequently assumed to
be constant, atmospheric diffusion is acted upon by the vertical rate of
deposition of the impurity and also by the coefficients of turbulence kz
and k , i.e., parameters whose values and variations are usually the subject
of hypotheses.
For a dissected relief of the terrain, the vertical motions change
substantially and play a significant role in turbulent diffusion.
The determination of the vertical motions of air is usually carried
out by means of classical methods (pilot-balloon sounding by means of two
theodolites). We processed the data obtained by using methods that per-
mitted us to carry out the processing in a comparatively short time.
The first method consists in processing the sounding data by means of
a specially constructed slide rule. The values indicated on the slide rule
are logarithms of trigonometric functions and of the numbers 1 to 10. By
using this slide rule, one can obtain the distance from the point of takeoff
of the balloon to its projection on the horizontal plane and the coordinates
of the projection point and of the balloon heights. The time variation of
these elements is determined graphically.
The second graphical method, although less accurate, was used to obtain
the data rapidly, this being convenient under expeditionary conditions. This
method consists in repeating, on a horizontal plane, the motions of two
theodolites tracking the balloon by using two angle gauges located in the
desired scale at a distance equal to the length of the base of the theodolites.
The angle gauges have a slit along the length of the ray, the slit passing
through the division of 0°. The position of the balloon, projected on the
horizontal plane, is noted at the intersection of two slits. The projection
is made on tracing paper attached to graph paper, on which one reads off the
distance from the launching site to the balloon projection point, the balloon
height at different times, and then the wind direction and velocity.
The air current in valleys or across ridges is caused by horizontal
gradients of pressure and temperature in the atmosphere and also by the con-
figuration of the relief, which includes additional components [4].
A special role in the propagation of impurities is played by mountain-
and-valley wind. Changes in the direction of a mountain-and-valley wind
which take place in the morning and evening exert an influence on the mixing
of impurities and their motion which is not considered in Eq. (1). Observa-
tions made in a valley make it possible to distinguish the direction of the
air currents and also the fluctuations in the wind rotation level.
The characteristics of mountain-and-valley wind are substantially deter-
mined by the degree of dynamic turbulence caused by the relief and dependent
on the wind velocity and wind direction relative to the ridge and valley.
- 114 -
-------
Thus, vertical motions assume a complex character (Fig. 1). By making obser-
vations in the same valley with the aid of two theodolites in order to deter-
mine the vertical motions, we detected eddy currents with a horizontal axis.
Thus, on 12 October 1966 at 8 A.M. in fair weather, the balloon was lifted
by ascending current to a height of 1900 m, and then sharply dropped to a
height of 900 m in 1 min. The eddy lasted until noon, slowly diminishing
and gradually descending toward the ground, so that in 4 hours it reached
the zone between 200 and 100 m. In their stability and intensity in the
mountain zone, such eddies are of special interest to aviation. Let us note,
however, that such turbulent motions play a decisive role in the propagation
of impurities.
The indicated facts complicate a theoretical solution of the problem
of atmospheric diffusion in valleys, where the wind intensity is attenuated,
and the recurrence frequency of calms exceeds 50%. For this reason, the
problem should be solved experimentally for each specific case.
On flat terrain, the effect of dyftamic turbulence virtually disappears.
For this reason, here one can successfully use equations of type (1). How-
ever, in these zones it is important to consider processes of thermal origin
caused by the influence of differences in the underlying surface (vegetative
cover and particularly, surface of the water).
In order to study the vertical currents near the Danube, observations
were made simultaneously near the river and at a distance of about 10 km
(with a level difference of approximately 90 m). It was thus found that
descending currents exist above the Danube. At the same time, above dry
/pIB
1 2 3* 5 6 7 8 9 10 11 12 13 f5interval
Fig. 1. Vertical notions of air in the mountain zone
(8 A.M., 11 October 1966).
1 - experimental curve, 2 - theoretical curve,
3 - air currents.
- 115 -
-------
land, ascending currents arise which together with the descending ones
produce a barrier zone that may strongly affect the turbulent diffusion
of noxious substances. On the basis of observations carried out in the
course of 20 days during the period from April to October 1967, it was
found that such a barrier zone near the water extends over 300-400 m.
Because of the daily heating of dry land in the morning during the warm
period of the year, ascending currents are formed that encompass the surface
air layer and extend to a height of 300 m, where they encounter the descend-
ing currents of convective origin, usually observed above a water surface
(Fig. 2). The position of the barrier zone in these places is responsible for
a special type of propagation of impurities. The latter rise from the surface
and collect around the barrier, then are transported at this level along the
direction of the wind.
The ascending and descending currents
corresponding to morning convection differ
around the Danube from the motions at a
distance of 10 km from this river. Occa-
sionally, descending currents in the layer
from 6 to 700 m thick with speeds of over
7 m/sec were observed near the water.
Thus, by using operative methods of
determination of vertical currents, we dis-
tinguished characteristics typical of
mountain zones and zones near a water surface.
Intense eddy currents dangerous for aerial
navigation and playing an important part in
the propagation of impurities around sources
are observed in the mountain zone. Near the
river, descending currents were observed,
and also horizontal barrier zones at a height of 300-400 m, which should have
a substantial influence on the propagation of noxious substances.
The study of vertical currents together with the determination of impurity
concentrations should be an essential component of experimental studies of the
determination of noxious substances in the vicinity of sources and particularly
in zones of nonuniform relief. The nature of the underlying surface and the
ruggedness of the relief act on the dynamic and thermal turbulence, and hence,
on the distribution of impurities around the source, complicating the use of
classical formulas of turbulent diffusion. In zones of dissected relief, it
is necessary to determine the directions experimentally or to solve the problem
by methods applicable to each individual case.
Fig, 2. Average velocity of verti-
cal currents near the water.
- 116 -
-------
LITERATURE CITED
1. B e p a h h a M. E. MeTeopoflorHMecKne npo6.ieMbi oCecneMeiiHa microTbi aTMO-
c«|)epbi. MeTeopo^orHH h rHApojionm, Ni 11, 1967.
2. B e p ji a h a M. E., T e h h x o b h h E. XL fl e m b si n o b ii m B. K. HeKoTopue
aKTyaJibHue Bonpocu ncc.ieflOBaHim aTMoc^epnofi TpyAM ITO,
Bhin. 172, 1965.
3. Bopohuob n. A. AspOjiorHMecKiie ltcc.ieaoBaHHH norpainiMHoro c.ion atMO-
cepbi. rMflpoMeTeoH3flaT, JI., I960.
4. flbdKOHccKy T. h up. PacnpocTpanemie aspojojiefi b io.iiiHe BOKpyr jicto>i-
HHKa. Pa6oTU MH, ByxapecT, t966.
5. fltSKOHecKV T. h ap. BapnauHa cienemi ycTofiiHBocTii Boaayxa npn3eM-
Horo aoa. nayMHan ceccHH MeTeopo.iorimecKoro HHCTHTyTa, ByxapecT, 1966.
6. JI aft x t m a h A- JI. H3iiKa norpammHoro c.ioh aTMOccfepw. rHApoMeTeoH3aaT,
7. Mohhh A. C.( Ht^om A. M. CTaTHCTimecKaji nupoMexaHiina. Tom 1, 1965
8. F. Pas qui 11. The estimation of the dispersion of windborne material. Met.
Mag., 90, 1961, 33.
9. O. G. Sutton. The problem of diffusion in the lower atmosphere. Quart.
Journ. Roy, Meteor. Soc., 73, 1947. 257.
10. O. G. S u 11 o n. A theory of eddy diffusion in the atmosphere. Proc. Roy. Soc.,
135, A, 1932, 143.
11. O. G. Sut ton. Micrometeorology. London, 1953.
/. 0. DIACONESCU, M. FRIMESCU,
I. MOROIANU, A. MOROIANU
PARTICULAR CASES OF VERTICAL CURRENTS *
Observation results of vertical air motion peculiarities in moun-
tainous region and over some parts of underlying surface with
sharply different characteristics (land-water) are stated which are
interesting from the point of view of their influence on pollutant
distribution. Basic method of pilot-balloon observations was used for
vertical motion measurement. Observations of mountainous valley
found the presence of stable eddy current with horizontal axis mar-
ked between levels of 200 and 1900— 1000m during four hours. Si-
multaneous observations near the Danube and at the distance of
10km showed that downcurrents exist over it. Up-currents covering
surface air layer and distributing up to the height of 300—400m ap-
pear over the land in the morning and at noon in the warm season.
At this height they meet downcurrents near water surface forming
a peculiar obstruction zone preventing pollutant distribution above
this level. Downcurrents in trie layer with thickness of 6—700m and
velocities more than 7 m/sec were sometimes observed near the water
surface.
* Editor's note: The abstract is presented as given in English with the original Russian article.
- 117 -
-------
SYNOPTIC CONDITIONS OF FORMATION OF A VERY STABLE
ATMOSPHERIC BOUNDARY LAYER
F. Rein CSSR (Czechoslovak Socialist Republic)
From Glavnoe Upravlenie Gidrometeorologicheskoy Sluzhby Pri Sovete Ministrov SSSR. (Chief Administration of
the Hydrometeorological Service Under the Council of Ministers of the USSR.) "Meteorologisheskie Aspekty
Zagryazneniya Atmosfery". (Meteorological Aspects of Air Pollution.) Sbornik dokladov na mezhdunarodnom
simpoziume v Leningrade - Iyul' 1968 g. (Reports delivered at the International Symposium in Leningrad -
July 1966.) Pod redaktsiey d-r« fiz.-mst, nsuk M. E. Berlyandn. (Edited by Prof. M. E. Berlyarid.)
Gidrometeorolgicheskoe izdatel'stvo, Leningrad, p. 567-571, (l97l). (Hydrotasteorological Publishing House,
Leningrad, (1971J.)
As we know, air pollution in industrial regions depends considerably
on the thermal stability of the atmospheric boundary layer. In this connec-
tion, it is of interest to consider cases of development of a very stable
atmospheric boundary layer of large vertical thickness.
The present study deals with the synoptic conditions of emergence of
such cases in the nonuniform landscape of the northwestern part of Czechos-
lovakia.
A very stable boundary layer may be characterized with the aid of the
mean temperature lapse rate, whose magnitude does not exceed +0.4°C./100 m,
i.e., all the inversions and isothermies together with small positive values
of the temperature lapse rate are included. As far as the characteristics of
the structure in height are concerned, two variants have been proposed on the
basis of empirical treatments: (a) the lower boundary of a very stable layer
coincides with the earth's surface, and (b) the lower boundary of such a layer
is at a certain height (of the order of 10-100 m) above the earth's surface,
above a layer with a high positive lapse rate.
The wind velocity at the upper boundary of a stable boundary layer is
characterized by frequent and abrupt increases.
The above results in an empirical model of the possible structure of a
very stable boundary layer, shown in Fig. 1. One can distinguish two types
of vertical temperature distribution under the upper boundary of the boundary
layer (a very stable stratification from the earth's surface or only from a
certain height above the surface) together with two independent velocity pro-
files (a slight or sharp increase in velocity near the upper boundary of the
b ound ary 1aye r).
Empirically established types of a stable boundary layer were studied on
climatological data for the northwestern region of Czechoslovakia. This region
is located in an area with a nonuniform hilly relief and contains a concentra-
tion of many industrial plants as a result of which the air pollution reaches
high proportions.
- 118 -
-------
-------
To determine the frequency of cases of a very stable boundary layer
with a thickness of the order of several hundred meters above the surface,
we used data from aerological observations in this region, supplementing
them with temperature measurements from meteorological stations in the moun-
tains and valleys.
Based on data of climatological treatment of a five-year series of
measurements (1956-60), the following results were obtained: a group of cases
with a very stable boundary layer was observed for an average of 29% of the
days per year, and the frequency is marked by a sharply defined annual varia-
tion (Fig. 2). Of this number, a 75% frequency is reached by cases denoted
by a^ in Fig. 1, i.e., those involving a very stable stratification directly
from the earth's surface. In the distribution of cases from the standpoint of
the wind profile (based on measurements of stations in the valleys and mountains) '
the frequency is 53% for group b-^ and 47% for group b£ (groups a^ and &2 being
independent of groups b^ and b£)•
% —¦
30 -
20 -
10 -
i i r
H SWa Wa Sm,SWc2 Sa £a wc SEaNWa Bc Ec NWC Cc
Fig. 3
Thus, from climatic data one can determine that the empirical groups a^,
, bj, and b£ of a very stable boundary layer are characteristic of this
region. We will later try to find their relationships to synoptic situations.
First of all, the question arises, in what synoptic situations can one
expect the formation and development of a vertically thick, very stable boundary
layer in the landscape studied. The general answer is supplied by Fig. 3, which
shows the relative frequencies of days with stable boundary layers of the total
number of days with individual synoptic situations according to the classifica-
tion of Koncek and the author.
- 120 -
-------
It is evident from Fig. 3 that a very stable boundary layer arises
relatively often in the presence of the Middle European anticyclone (H),
i.e., in 34% of the days when an anticyclone is observed.
The second frequency group is formed by synoptic types with a southern
component of advection, i.e. , the southwestern anticyclonic (SWa) and cyclonic
(SWC^ SW^) types, together with the southern and southeastern anticyclonic
types (Sa - SEa). The remaining cases are of no particular interest from the
standpoint of their frequency.
If this result is compared with the frequency of appearance of dense
fogs in the lowland of the region studied, a good agreement of the advection
values will be noted. Most fogs are observed in calms and in advection with
a southern component, practically no fogs being observed in synoptic situations
with a northern component. This phenomenon is apparently due to the fact that
northern winds descending from the mountain ridge with a considerable turbu-
lence do not promote the development of a thick, very stable boundary layer.
The next objective was to study the dependence of individual types of
a very stable boundary layer (a-^, a2, b^, b£) on the synoptic situations.
The frequency distribution of groups a and a2 is as follows: the first
constitutes 75% of all cases of a very stable boundary layer and appears
primarily in anticyclonic situations. Group a2 is observed in 25% of the
cases and mostly in cyclonic situations.
Groups b^ and b2 are distributed in the manner of groups a^ and a2*
Group b^ is observed in 73% of the cases, appearing primarily in the central
anticyclone and in the remaining synoptic situations with a slight tropospher-
ic advection. Cases b2, which account for 23%, arise when advection predomin-
ates, i.e., on the outskirts of baric formations.
Thus, this paper has attempted to establish a relationship between the
very stable boundary layer in the northwestern part of Czechoslovakia and
synoptic situations.
The boundary layer, which reaches an altitude of several hundred meters
above the surface and is practically uniform over a distance of tens of kilo-
meters, is a mesometeorological object related to the action of local radia-
tion factors and to the influence of macrocirculation fields.
From this point of view it is clear that a stable boundary layer depends
on anticyclonic situations. However, in about one-quarter of the cases, a
very stable boundary layer is observed in this area in cyclonic situations.
Such a situation arises mainly when anticyclones alternate with cyclones with
such a direction of advection that this area is not situated on the lee side
of Krusne Mountains.
- 121 -
-------
Work on details of the structure of the boundary layer in the investi-
gated region is continuing.
F. REIN
SYNOPTIC CONDITIONS OF APPEARANCE OF VERY STABLE
BOUNDARY AIR LAYEk*
The investigation results of occurrence frequency of powerful and
very stable boundary layer (mean lapse rate < 0.47100m) are sta-
ted in dependence on synoptic conditions for nothern-western part of
Czechoslovakia, distinguished by hilly relief and high level of air
pollution by industrial plant emissions. With the help of climatolo-
gical treatment of aerological observation series for 5-years it has
been found that such a layer can be met in 29% of days a year, its
frequency having distinctly expressed annua! course with minimum
in summer and maximum in winter. Very stable boundary layer
arises most often in the presence of Middle-European anticyclone
(34% of days in which anticyclone is observed). Synoptic situations
with southern advection component form the second of frequency
group, out of which 25% of cases refer to cyclonic situation. It is
marked that in 75% of cases observed chiefly in antjcyclonic condi-
tions the lower boundary of a layer with small lapse rate coincides
with underlying surface, and sharp increase of wind velocity occurs
at the upper boundary.
* Editor's note: The abstract is presented as given in English with the original Russian article.
- 122 -
-------
46 THE SUSCEPTIBILITY OR RESISTANCE TO GAS
AND SMOKE OF VARIOUS ARBOREAL SPECIES
GROWN UNDER DIVERSE ENVIRONMENTAL
CONDITIONS IN A NUMBER OF INDUSTRIAL RE-
GIONS OF THE SOVIET UNION-A Survey of USSR
Air Pollution Literature
47 METEOROLOGICAL AND CHEMICAL ASPECTS
OF AIR POLLUTION; PROPAGATION AND DIS
PERSAL OF AIR POLLUTANTS IN A NUMBER OF
AREAS IN THE SOVIET UNION-A Survey of USSR
Air Pollution Literature
48 THE AGRICULTURAL REGIONS OF CHINA
49 EFFECTS OF METEOROLOGICAL CONDITIONS
AND RELIEF ON AIR POLLUTION, AIR CON-
TAMINANTS - THEIR CONCENTRATION,
TRANSPORT. AND DISPERSAL-A Survey of USSR
Air Pollution Literature
50. AIR POLLUTION IN RELATION TO CERTAIN
ATMOSPHERIC AND ME TO R O LOG I C A L
CONDITIONS AND SOME OF THE METHODS
EMPLOYED IN THE SURVEY AND ANALYSIS
OF AIR POLLUTANTS-A Survey of USSR Air
Pollution Literature
51. MEASUREMENTS OF DISPERSAL AND
CONCENTRATION. IDENTIFICATION, AND
SANITARY EVALUATION OF VARIOUS AIR
POLLUTANTS, WITH SPECIAL REFERENCE TO
THE ENVIRONS OF ELECTRIC POWER PLANTS
AND FERROUS METALLURGICAL PLANTS
—A Survey of USSR Air Pollut on Literature
52 A COMPILATION OF TECHNICAL REPORTS ON
THE BIOLOGICAL EFFECTS AND THE PUBLIC
HEALTH ASPECTS OF ATMOSPHERIC
POLLUTANTS - A Survey of USSR Air Pollution
Literature
53 GAS RESISTANCE OF PLANTS WITH SPECIAL
REFERENCE TO PLANT BIOCHEMISTRY AND TO
THE EFFECTS OF MINERAL NUTRITION - A
Survey of USSR Air Polution Literature
54 THE TOXIC COMPONENTS OF AUTOMOBILE
EXHAUST GASES: THEIR COMPOSITION UNDER
DIFFERENT OPERATING CONDITIONS, AND
METHODS OF REDUCING THEIR EMISSION - A
Survey of USSR Air Pollution Literature
55 A SECOND COMPILATION OF TECHNICAL
REPORTS ON THE BIOLOGICAL EFFECTS AND
THE PUBLIC HEALTH ASPECTS OF
ATMOSPHERIC POLLUTANTS — A Survey of USSR
Air Pollution Literature
56 TECHNICAL PAPERS FROM THE LENINGRAD
INTERNATIONAL SYMPOSIUM ON THE
METEOROLOGICAL ASPECTS OF ATMOSPHERIC
POLLUTION (PART I) - A Survey of USSR Air
Pollution Literature
57 TECHNICAL PAPERS FROM THE LENINGRAD
INTERNATIONAL SYMPOSIUM ON THE
METEOROLOGICAL ASPECTS OF ATMOSPHERIC
POLLUTION (PART II) - A Survey Of USSR Air
Pollution Literature
Riprinti From various periodical*.
A INTERNATIONAL COOPERATION IN CROP IMPROVEMENT
THROUGH THE UTILIZATION OF THE CONCEPT Of
AGROCLIMATIC ANALOGUES
(The Uie of Phenology Meteorology and Geographical
Latitude for the ftjrposes of Plant Introduction and the Ex-
change of Improved Plant Varieties Between Variout
Countries.)
B SOME PRELIMINARY OBSERVATIONS OF PHENOLOGICAL
DATA AS A TOOL IN THE STUDY OF PHOTOPERIODIC
AND THERMAL REQUIREMENTS OF VARIOUS PLANT
MATERIAL
*C AGRO-CLIMATOLOGY AND CROP ECOLOGY Of THE
UKRAINE AND CLIMATIC ANALOGUES IN NORTH
AMERICA
D AGRO-CLIMATOLOGY AND CROP ECOLOGY OF PALIS-
TINE AND TRANSJORDAN AND CLIMATIC ANA-
LOGUES IN THE UNITED STATES
E USSR-Some Physical and Agricultural Characteristics ol the
DroughtAreo and Iti CI Imatlc Analogues In the United States
F THE ROLE OF BIOCLIMATOLOGY IN AGRICULTURE WITH
SPECIAL REFERENCE TO THE USE Of THERMAL AND
PHOTO-THERMAL REQUIREMENTS OF PURE-LINE VARI-
ETIES Of PLANTS AS A BIOLOGICAL INDICATOR IN
ASCERTAINING CLIMATIC ANALOGUES (HOMO-
CLIMES)
•Out of Print
Requests for studies thould be addressed to the
Amei ran Institute of Crop Ecology, 809 Dale
Drlv-.- Silver Spring, Maryland 20910.
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