62-11103 Price $5.00
U.S.S.R. LITERATURE ON AIR POLLUTION
AND RELATED OCCUPATIONAL
DISEASES
Volume 7
A SURVEY
by
B. S. Levine, Ph. D.
INTRODUCTION BY VERNON G. MacKENZIE, CHIEF
DIVISION OF AIR POLLUTION, PUBLIC HEALTH SERVICE
DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE
Distributed by
U.S. DEPARTMENT OF COMMERCE
OFFICE OF TECHNICAL SERVICES
WASHINGTON 25, D. C.
-------
U.S.S.R. LITERATURE ON AIR POLLUTION
AND RELATED OCCUPATIONAL
DISEASES
Volume 7
A SURVEY
by
B. S. Levine, Ph. D.
u.s. Public Health Service
(Health, Education, and Welfare)
Research Grantee
Washington, D.C., U.S.A.
-------
Other translations, books and surveys by Dr. B. S. Levine dealing with
U.S.S.R. air pollution control and related occupational diseases available from
U.S. Department of Commerce, Office of Technical Services, Washington 25, D.C.
Sanitary Protection of Atmospheric Air,
Purification of Industrial Discharge
Gases from Suspended Substances.
Limits of Allowable Concentrations of
Atmospheric Pollutants. Book 1.
Limits of Allowable Concentrations of
Atmospheric Pollutants. Book 2.
Limits of Allowable Concentrations of
Atmospheric Pollutants. Book 3.
Limits of Allowable Concentrations of
Atmospheric Pollutants. Book 4.
U.S.S.R. Literature on Air Pollution
and Related Occupational Diseases.
A Survey. Volume 10
U.S.S.R. Literature on Air Pollution
and Related Occupational Diseases.
A Survey. Volume 2.
U.S.S.R. Literature on Air Pollution
and Related Occupational Diseases.
A Survey. Volume 3.
U.S.S.R. Literature on Air Pollution
and Related Occupational Diseases.
A Survey. Volume 4.
U.S.S.R. Literature on Air Pollution
and Related Occupational Diseases.
A Survey. Volume 5.
U.S.S.R. Literature on Air Pollution
and Related Occupational Diseases.
A Survey. Volume 6.
U.S.S.R. Literature on Water Supply
and Pollution Controlo
A Survey. Volume 10
59-21092 3.00
59-21113 2.15
59-21114 3.00
59-21115 3.00
61-11148 2.75
60-21049
3.50
60-21188
4.00
60-21415
4.00
60-21913
4.00
61-11149
3.50
61-21982
4.00
61-31601
3.50
The following is available from Academic Press, Inc., 111 Fifth Avenue, New
York 3, N.Y.
Russian-English Medical Dictionary,
By Stanley Jablonsky.
Edited by B. S. Levine.
11.00
. -ii-
-------
For comparison of metric and customary units from 1 to 10 see Handbook of Chem-
istry and Physics published by the Chemical Rubber Publishing Co., 2310 Superior
Avenue, N.E., Cleveland, Ohio.
Inches and millimeters, inches and centimeters, feet and meters,
U.S. yards and meters, U.S. miles and kilometers -
Square inches and square millimeters, square inches and square
centimeters, square feet and square meters, square yards and
square meters, square miles and square kilometers -
Cubic inches and cubic millimeters, cubic inches and cubic
centimeters, cubic feet and cubic meters, cubic yards and cubic
meters, acres and hectares -
Milliliters and U.S. ounces, milliliters and U.S. apothecaries'
drams, milliliters and U.S. apothecaries' scruples, liters and
U.S. liquid quarts, liters and U.S. liquid gallons. (Computed
on the basis 1 liter - 1.000021 cubic decimeters).
Liters and U.S. dry quarts, liters and U.S. pecks, decaliters
and U.S. pecks, hectoliters and U.S. bushels, hectoliters per
hectare and U.S. bushels per acre. (Computed on above basis).
Other pertinent conversion tables are presented on succeeding pages.
RUSSIAN ALPHABEr WITH TRANSLITERATION
A a A a P p R r
E c5 B b C c S s
B B Vv T T T t
r r G g Yy U u
.II:.n D d q, F f
E e E e X X Kh kh
)KJK Zh zh ~ ~ Ts ts
3 3 Z z q 'q Ch ch
:vI ~ I i ill m Sh sh
11 11 I i II{~ Shch shch
K It Kk b1 hI Yy
JI JI L 1 1, L Mute soft sound
MM Mm :3 3 E e
H H N n 1010 Iu iu or Yu yu
o 0 0 0 R Si Ia ia or Ya ya
11 IT P p
-iii-
Page 2941
Page 2948
Page 2949
I
Page 2950
Page 2951
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U..S.S..R. LITERATURE ON AIR POLLUTION
AND RELATED OCCUPATIONAL
DISEASES
INTRODUCTION
This is the seventh in a series of English translations
of the Russian literature on air pollution by Dr. Benjamin S..
Levine..
Through the medium of these publications and four
special reports to date on "Limits of Allowable Concentrations
of Atmospheric Pollutants", Dr.. Levine has undertaken to make
available to all who are interested in air pollution problems
in this country a large resource of technical information on
the subject which otherwise would not be readily available..
In this edition sixty papers deal with the medical,
chemical, physical, engineering, instrumentation, and other
aspects of the problem..
A paper on "Carboxyhemoglobin in the
Blood of Persons Directing City Traffic" reports the highest
levels of blood COHb which have come to our attention.
"City
Street Air Pollution by Autotransport Using Ethylated Gasoline"
concludes with the drastic recommendation that "the use of
ethyl lead gasoline be discontinued.."
Volume 7 also covers
a wide range of other subjects; it includes:
"Effect of
-iv-
-------
Superphosphate Production Discharges on Children's Health'A;
"Electroencephalographic Determination of Threshold Reflex
Effects of Atmospheric Pollutants", and several papers dealing
with the control of pollutants from coke ovens and with
techniques and instrumentation for the analysis of air pollutants.
The Public Health Service is appreciative of Dr. Levine's
important contributions to the current literature on the subject
of air pollution.
I would recommend consideration and evalua-
tion of this information by all concerned for possible application
to their respective fields of interest.
y.~~~~
Chief, Division of Air Pollution
Public Health Service
Department of Health, Education,
and We lfare
-v-
-------
A C K NOW LED G E J4 E N T.
By way of grateful acknowledgement each item in this collection is headed
by the original title (in translation), name of the author or authors, institu-
tional affiliation, and periodical or book from which the item was selected.
The volume, issue number, year of publication, and inclusive pages are indicated
for the convenience of those who may wish to consult the Russian original, or
may wish to make reference to same.
I wish to express my grateful appreciation to Mr. Vernon G. MacKenzie,
Chief of the Public Health Service Division of Air Pollution for the introduc-
tion he has written to this volume.
FOR E W 0 R D.
This volume has been organized on the same basis as were Volume 5 and
Volume 6 in that representation was given to a variety of phases of air pollu-
tion with emphasis on what might be designated as theoretical work of an en-
gineering character. In his introduction Mr. MacKenzie briefly evaluated the
material collected in this volume. He called attention to a few selected papers
which typify the scientific awareness and directness with which U.S.S.R. sci-
entists engaged in the field of environmental health approach the solution of
some urgent and perplexing problems in air pollution. A translation of Book 5
of Professor V. A. Ryazanov's Committee is about to go to press. The material
contained in that book illustrates the path-finding spirit of Professor Ryaza-
novls colleagues and coworkers, a tendency to self-criticism, and to a reevalu-
ation of old values. Mr. MacKenzie quite appropriately concludes his introduc-
tion by saying: "I would recommend consideration and evaluation of this in-
formation by all concerned for possible application to their respective fields
of interest." In addition to Mr. MacKenzie's recommendation the undersigned
can only say that it expresses the purpose and intent of the translations past
and future. In this connection it is the plan of the undersigned to conclude
the series with an appropriate index volume for purposes of quick and conven-
ient reference.
B. S. Levine, Ph. D.
3312 Northampton Street, N.W.
Washington 15, D.C.
-vi-
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Contents
Introduction
Section A.
Vapor Tension and Vaporization of Substances in Moving Air.
V. G. Matsak. Gigiena i Sanitariya.
Deposition of Particles from a Gas Stream on an Isolated Cylinder.
(Theoretical). L. V. Radushkevich. Zhurnal Fizicheskoi Khimii.
Aerodynamic Investigation of Electrostatic Precipitator C-180 Model.
P. J. Kuleshov. Koks i Khimiya.
Raising the Efficiency of Electrostatic Precipitators, Type C-140.
P. J. Kuleshov. Koks i Khimiya.
Construction Defects in Tubular Electrostatic Precipitators
(Electrofilters). P. J. Kuleshov. Koks i Khimiya.
Mechanization of the Gas Analyzer ORSAT. A. P. Razbegaeva.
Koles i Khimiya.
A Venturi Apparatus for Ammonia Absorption from Coke Gas Without an
Atomizer. P. A. Semenov, Yu. V. Tuman~v and O. S. Chekhov.
Koks i Khimiya.
Homogram for the Reduction of Actual Coke Gas Volume to Normal at
Zero Degrees Centigrade, 760 mm of Mercury and of 4,000 Cal/nm3 of
Heat Capacity. L. S. Blokh. Koks i Khimiya.
Section B.
Reducing Gas Emission During Coke Oven Cha~ging. T. P. Varshavsky,
R. G. Agapov, F. A. Mustafin and V. A. Permyakov. Koks i Khimiya.
Smokeless Coke Oven Charging. I. Ya. Mezentsev. Koks i Khimiya.
Hew Method for Ammonia Absorption from Coke Gas. G. D. Kharlampovich,
M. V. Goftman and N. D. Rus'yanova. Koks i Khimiya.
Differential Absorption of Ammonia and Pyridine Bases from Coke Gas.
V. M. Iagasov, V. P. Kholoptsev, N. Kh. Nemirovskii, V. G. Loparev
and G. D. Kharlampovich. Koks i Khimiya.
Catalytic Removal of Nitric Oxide and Acetylene from Coke Oven Gas.
M. P. Korsh and F. P. I vanovskii. Zhurn. Priklad. Khimii.
Section C.
Colorimetric Determination of Lead in Atmospheric Air.
Gigiena i Sanitariya.
Determination of Manganese in Urine. S. I. Yakushina.
Farmakologiya i Toksi.kologiya.
Rapid Method for the Determination of Carbon Monoxide in
Working Premises. D.B. Vaskevich, A. I. Bulycheva and
P. A. Jlel'nikova. Vodosnozhenie i Sanitarnaya Tekhnika.
V. A. Morosov.
the Air of
-vii-
iv
1
10
21
30
38
44
47
54
56
64
69
77
85
93
94
97
-------
Seotion C - Continued
Comparative Evaluation of Some Methods for the Determination of
Beryllium and Its Compounds Applioable to Air Analysis.
K. S. Bykhovskaya. Gigiena Truda i Professional'nye Zabolevaniya.
Phenol Determination in the Presence of Polyatomio Phenols in the Air
During Foundry Casing Pouring. S. S. Gurvits and T. I. Sergeva.
Gigiena Truda i Professional'nye Zabolevaniya.
Perfecting Direot Gas Sample Taking for the Determination of
Benzene Hydrooarbons. S. G. Faingol'd. Koks i Khimiya.
An Automatio Gas Analyzer for the Determination of Benzene Hydro-
oarbons in Coke Gas. A. T. Bendik and A. E. Eidelman.
Koks i Khimiya.
Determination of Simultaneously Present Cyolohexanon and of
Cyolohexanonoxime. A. S. Maslenikov. Gigiena i Sanitariya.
Colorimetrio Method for the Determination of Ammonia in the Air
Using Phenol and Sodium Hypochlorite. K. I. Poletayev and
N. A. Andreyeva. Gigiena i Sanitariya.
Low Temperature Baoteriological Air Investigation. E. Yu. Zuikova.
Gigiena i Sanitariya.
Determination of Nitrogen Oxide in Coke Gas. N. A. Gruzdeva and
L. A. Khokhlova with the aid of V. G. Shevchenko. Koks i Khimiya.
Electroencephalographic Determination of Threshold Reflex Effect
of Atmospherio Pollutants. K. A. Bushtueva, E. F. Polezhaev and
A. D. Semenenko. Gigiena i Sanitariya.
Determination of Benzene, Toluene and Xtlene Simultaneously
Present in the Air. E. G. Kachmar. Gigiena i Sanitariyao
Gas-Liquid Radioohromatograph. M. I. Yanovskii and G. A. Gaznev.
Vestnik Akademii Nauk S.S.S.R.
Quantitative Determination of Low 3,4-Benzpyrene Concentrations with
Fine Structure Fluorescent Spectrum. P. P. Dikun.
Voprosy Onkologii.
Collecting Air Samples for the Determination of Nitrogen Dioxide.
E. V. Alekseeva. Gigiena i Sanitariya.
Seotion D.
Hydrogen Sulfide Oxidation in the Organism. A. I. Gunina. Trudy
Vsesoyuznoi Konferentsii po Keditsinskoi Radiologii, Eksperimental'-
naya Jleditsinskaya Radiologiya.
Benzene and Its Homologues as Poisons in Eleotrical Winding and
Insulation Plants. A. P. Rusinova. Gigiena Truda i Professional'nye
Zabolevaniya.
Hygienio Evaluation of Hydrogenated Coal Gasoline. Z. E. Grigor'yev.
Gigiena Truda i Professional'nye Zabolevaniya.
-viii-
102
108
114
116
121
125
127
130
137
143
148
153
169
172
176
181
-------
Section D - Continued
Olfactor,y and Taste Analyzer Changes in Chronic Carbon Disulfide
Intoxication. V. G. Osipova. Gigiena Truda i Professional'nye
Zabolevaniyao
Effect of Benzanthrone Poisoning on Liver Function. L. I. Slutskii.
Gigiena Truda i Professional'nye Zabolevaniya.
Hygienic Characteristics of Tantalum and Niobium (Rare Metals)
Dusts. Yu. L. Yegorov. Gigiena Truda i Professional'nye Zabolevaniya.
Pathogenic Properties of Some Dusts Occurring in Ferrous
Metallurgy Production Plants. B. A. Katsnel'son. Gigiena Truda i
Professional'nye Zabolevaniya.
The Blastomagenic Effect of Polyvinyl Chloride. A. Kh. Kogan
and V. N. Tugarinova. Voprosy Onkologii.
Effect of Metallurgical Plants Emissions on Children's Health.
D. N. Kalyuzhnyi. Gigiena i Sanitariya.
Effect of City Air Pollution on the Population's Health.
R. A. Babayants. Vestnik Akademii Meditsinskikh Nauk S.S.S.R.
Hygienic Properties of Murmansk Ultraviolet Radiation.
N. M. Kaikov. Gigiena i Sanitariya.
Vitamin C in the Organism in Connection with Atmospheric Pollution
by Discharges from Synthetic Chloroprene Rubner Manufacture.
M. K. Khachatryan. Gigiena i Sanitariya.
Effect of Non-Occupational Factors on the Course of Carbon
Bisulfide Poisoning. B. E. Saf'yan. Gigiena i Sanitariya.
Ionic State of Air in Living Quarters and Its Hygienic
Significance. A. A. Minkh. Gigiena i Sanitariya.
Sanitization of Gumbrin Clay Processing. E. O. Kossovskii.
Gigiena i Sanitariya.
Hand Lead Contamination of Workers in Contact with Ethyl Lead
Gasoline. I. I. Brekhman, V. A. Matyukhin and N. K. Fruentov.
Gigiena i Sanitariya.
Section E.
Duration of Carbon Monoxide Excretion from the Body. L. A. Tiunov,
T. I. Sokolova and V. P. Paribok. Farmakol. i Toksikol.
Experimental Study of Working Conditions and Atmospheric Air
Pollution with Ethylmercuric Chloride During Treatment of Cereal
Grains in the Omsk Oblast. Z. Z. Bruskin. Gigiena Truda i
Professional'nye Zabolevaniya.
Carbon Monoxide in Typical Auto-Tractor Machine Shops.
N. K. Val'chuk. Gigiena i Sanitariya.
City Street Air Pollution by Autotransport Using Ethylated
Gasoline. F. I. Dubrovskaya. Gigiena i Sanitariya.
-ix-
186
191
198
206
213
220
224
237
240
244
249
256
260
262
264
271
275
-------
Section E - Continued
A Study of Automotive Exhaust Gases. M. V. Alekseyeva and
V. A. Khrustaleva. Gigiena i Sanitariya.
Effect of Superphospate Production Discharges on Children's
Health. Z. Ya. Lindberg. Gigiena i Sanitariya.
Two Cases of Acute Carbon Monoxide Poisoning. N. V. Grin and
Zh. I. Pokrovenko. Gigiena i Sanitariya.
Carboxyhemoglobin in the Blood of Persons Directing City Traffic.
A. A. Vasil'eva and M. D. Manita. Gigiena i Sanitariya.
Effect of Poisoning with Some Phospho-Organic Insecticides.
Yu. S. Kagan and Ye. I. Makovskaya. Arkhiv. Patologii.
Section F.
Modern Approach to Air Dustiness in Workshops. E. V. Khukhrin.
Gigiena i Sanitariya.
Present-Day Status and Future Problems in Sanitary Protection of
Community Atmospheric Air in the U.S.S.R. Yu. D. Lebedev.
Gigiena i Sanitariya.
Sanitary Protection of Atmospheric Air in Poland. Ya. Yuste
Gigiena i Sanitariya.
Third All-Union Conference on Methods for Air Dust Pollution Studies.
P. N. Torskii. Gigiena i Sanitariya.
Third All-Union Conference on Sanitary Protection of Atmospheric
Air. L. F. Glebova and S. I. Murovannaya. Gigiena i Sanitariya.
Some Problems Connected with Sanitary Conditions in Cement Producing
Plants. A. K. Belevitskii. Gigiena i Sanitariya.
-x-
279
284
289
290
294
301
309
318
321
325
330
-------
Vapor Tension and Vaporization of Substances in fuoving Air.
V. G. Matsak.
Gigiena i Sanitariya, No.8, 35-41, 1957.
The purpose of this report is to place at the disposal of engineers and
hygienists working in the field of sanitary technology concrete and basic data
regarding vapor tension and rate of vaporization of different inorganic and
organic substances in moving air. Particular emphasis is placed in this paper
on substances, and especially toxic substances, most cOIT~only used in indus-
trial technology.
Such information should allow hygienists to evaluate the
potential danger associated with vaporization of toxic substances in relation
to their physico-chemical and toxicological properties, and sanitary engineers
to apply it in their computation of air ventilation in general and of quanti-
tative determination of the degree of air charged with vapor of high-molecular
substances, and in correctly distributing incoming and exhaust air, and in
computing other means required for the sanitary improvement of labor conditions.
Vapor tension of any substance within certain temperature limits can be ex-
pressed by the following logarithmic generaliz~tion:
A
log Pn = T + B
(1)
In which P represents the tension of saturated vapor of a given substance in
n
mID of mercury at absolute temperature T; A and B are constants characteristic
of any substance.
Handbooks dealing with such and similar phases of sanita-
tion present tables of such constants. Determination of vapor tension by gen-
eralization (1) usually is accompanied by a tedious search for data in differ-
ent handbooks and frequently leads to errors. Therefore, it is suggested that
sanitary engineers use the nomograms presented in this paper, especially where
a 5% error is permissible. One of the nomograms shown in Fig. 1 was proposed
by Professor V. A. Kireev. In this nomogram hexane and water play the part of
basic substances. The present author modified this nomogram by adding to it
16 new substances.
For nitro- and amino-compounds this author constructed a
special nomogram; included in the latter are also substances which follow a
similar law of change in saturated vapor tension at different temperatures;
this nomogram is shown in Fig. 2.
A third nomogram, shown in Fig. 3, was con-
structed by this author for vapor tension of some melted metals and salts.
Nitrobenzene and lead vapors were taken as standards in this nomogram.
-1-
-------
Fig. 1. Nomogram for saturated vapor
tension of chemically pure substances,
according to V. A. Kireev and the
pre sent author.
1 - methylsilicane; 2 - propadiene;
3 - methyl chloride; 4 - chlorovinyl;
5 - butadiene; 6 - ethyl chloride;
7 - isoprene; 8 - methyl formate; 9--
pentane; 9a - diethyl ether; 10 - ethyl bromide; 11 -
methylene chloride; lla - carbon bisulfide; 12 - ethyl
for~mate; 13 - chloroform; 14 - n-hexane; 14a - carbon
tetracbloride; 15 - benzene; 15a - trichlorethylene;
16 - ethyl acetate; 16a - dichlorethane; 17 - fluoro-
benzene; 18 - n-heptane; 18a - ethyl propionate; 18b -
propyl acetate; 19 - toluol; 19a - tetrachloroethyl-
ene; 20 - n-octane (w); 21 - n-octane (1); 22 - chlo-
robenzene; 23 - bromobenzene; 24 - n-decane; 25 -
iodobenzene; 26 - naphthalene; 26a - camphor; 26b -
diphenyl; 26c - anthracene; 27 - ammonia; 28 - meth-
ylamine; 29 - acetone; 30 - methylol; 31 - ethylol;
31a - formic acid; 32 - water; 32a - propyl alcohol; 33
butanol; 34 - propyonic acid; 35 - isobutyric acid; 35a
n-butylene glycol; 37 - ethylene glycol; 38 - glycerol;
mercuric chloride.
Example for nomogram use:
as-
sume that it is necessary to deter-
mine saturated vapor tension of car-
bon tetrachloride at 200. In the
legend appended to Fig. 1 carbon
tetrachloride is listed as No. 14a.
Place ruler so that its edge passes
through point 14a and the point
corresponding to 200. The point at
which the ruler edge intersects the
vertical line of vapor tension rep-
resents the vapor tension of carbon
tetrachloride at 200, it is eQual
very closely to 90 rom of mercury.
Assume again that it is nec-
essary to determine the boiling
temperature of methylamine; this
substance is listed among the legend
-2-
S tJ s'
, '. _"",dig'
For , JOI}f.i' I F
I I or
hexane: 3000 \ water
I ,
: 2000 .27
,l \
I fOOD '
,
28
#
68 200
I
Q8J~0 100
12~/
1J-fiajf4 50
1St] 15 //0
'(;tr- 1 16 30
I/O 18
186 19
!go 20
21 22
I
24 , 23
,
I
r25
260,# 26
I
266+
I
,
,
,
,
,
,264
,
,
I
tv
-fJO
-50
- 40
-JO
.500
- 20
- 10
o
10
20
30
40
50
60
70
80
90
100
ffO
120
130
140
160
180
0,5
R
0,2
0,05
U. U2
/J,Of
20
28
,
I
,
I
I
,
I
~29
,30
~ 3'
3![;.~1
32
J2Q
'133
330.
~34
35 ~
I
,
. \ 3.5 0
368\
3?~
I
\
I
I
I
I
39. t ~~Q
I
I
I
I
I
\
R,
,;;
-10
o
(0
2(1
JO
/.;0
50
60
'10
80
IJO
fOO
ffO
120
13[)
140
IjO
I?O
f90
200
220
24(1
270
300
330
360
{I, 005
- acetic acid; 33a -
- valeric acid; 36 -
39 - mercury; 39a -
/0
5
2
I
0.1
-------
data as No. 28; place the ruler so that its edge passes through points 760 rom
o
and point 28. It will be found that the boiling point of methylamine is -4 .
. 0
The saturated vapor tens~on of lead at 500 ,
~
o
,
I()
f.
I
#0
J
.JfJ
4
40
511
60
IJ(J
(J(J
100
"0
120
IJII
140
150
/6()
'10
'III
190
200
2'0
220
2tIO
260
210
IOO
J20
.140
!IN "9.
500
«10
300
'00
150
f{J(J
so
40
JO
10
10
j
4
3
\
a
,
a~ tp
0.;
0.'
0.1
0,05
0,04
0. OJ
0,03
0. 0'
0,00J
0,004
o,OOJ
0. 002
0,001
1000
according to nomogram 3 amounts approximately to
0.00001 mID of mercury. This corresponds to a lead
concentration of 0.0043 mg/m3. However, premises
in which melted lead is processed fre~uently contain
higher lead concentrations in the air. This may be
due to the fact that lead vapor condenses in the
form of minute particles which gradually fallout
of the air. The lead aerosol concentration depends
upon the rate of such particles sedimentation and
fre~uently exceeds the lead vapor concentration at
the time of vaporization.
It should be noted that
some lead compounds, such as lead sulfide and lead
chloride vaporize illore easily than met~llic lead;
this can be seen in nomogram No.3.
In the air of
industrial premises, where scrap lead is being melted,
as in some chemical plants, the above condition may
considerably enhance the concentration of lead or
of lead compounds in the air.
Methods presently
used for the collection of air samples containing
Fig. 2. Nomogram for saturated vapor tension of
chemically pure substances according to the present
~t~r. I
1 - nitrogen tetroxide; 2 - isopentane; 3 - phos-
phorus trichloride; 4 - nitromethane; 5 - chlo-
ropicrin; 6 - sulfur chloride; 7 - tetranitro-
methane; 8 - arsenic trichloride; 9 - acetic an-
hydride; 10 - dimethylaniline; 11 - aniline; 12 -
phenol; 13 - benzoyl chloride; 14 - o-toluidine;
15 - methylaniline; 16 - p-toluidine; 17 - ethyl-
aniline; 18 - nitrobenzene; 19 - o-nitrobenzene;
20 - diethylaniline; 21 - antimony trichloride;
22 - m-nitrotoluol; 23 - p-nitrotoluol; 23a - di-
methylparatoluidine; 23b - ~uinoline; 24 - phthalic
anhydride; 25 - o-nitrotoluol; 25a - diphenyl; 26 -
nitroglycerine; 27 - arsenic trioxide; 28 - di-
benzylketone; 29 - n-nitroaniline; 30 - trinitro-
toluol; 31 - mercuric chloride; 32 - anthra~uinone.
-3-
-------
0,3
O,~
0,3
0,:1
0.0'
0,04
0,03
0.02
o,(J(
O,OOj
0,0114
0,003
o. OO:J
0.001
0, {)(J(Jj
0. fXJ04
o,fJ(}()j
0. 0002
o,OOIJf
~0tXJf1:1
aablf
o,(XJ()O 3
fJ,JJIJOO2
U,OOaJ'
IWH9
'0 A8.
j
.0
J
2
1,3
CIf
Zn
1,0
.~:l
0,1
_ON
PU
Sn.
Fig 0 3.
iD
- 44(J
"jlJ
.4fJt)
470
4BQ
4~l
5«J
S10
5ZIJ
SJI
Sf{)
~
SM
$'7fI
no
StItJ
IJOO
/IN)
II:1II
bO
M1
t1!/II
IJM}
67fJ
UII
...
,..
no
7:lO
?N
iINJ
7tlO
?aJ
100
120
uo
..
RO
90fJ
I1IIIJ
~
P/li1
980
1000
lead are limited to the use of nitric acid as
the absorber; this procedure may be satisfac-
tory for purposes of total lead determination
in the air regardless of its state - metallic
or chemical compound. Knowledge of maximal
vapor tension of a substance under usual mete-
orological conditions enables the hygienist to
determine its concentration in the air. For
this purpose use should be made of the gener-
alization proposed by this author in coopera-
tion with Professor A. K. Khotsyanov in 1944:
PM
n
C = 18.3
(2)
In this generalization C represents concentra-
tion in mg/li; M represents the molecular weight
of the substance; P represents saturated vapor
n
density of the substance at 10 - 200 and stand-
ard atmospheric pressure.
Example: assume that vapor tension of
acetic anhydride saturated at 200 = 2.7 rom of
mercury, as shown in nomogram 2.
It is neces-
sary to determine its maximum possible concen-
tration in the air. Use generalization 2, sub-
stitute 2.7 for P and 92 for M; calculation will
show that maximal possible concentration of
acetic anhydride at 20° amounts to 15.5 mg/li.
Where it is desired to know what concentra-
tion may form in a benzene tank after it has been
drained at 100, generalization 2 should be used
as shown above.
As a rule the benzene tank is never drained
completely.
Some of the benzene remains in the
tank, especially in the presence of rust, dust,
Nomogram for saturated vapor tension of chemically pure
substances according to the present author.
-4-
-------
or other similar substanceso
For this reason "empty" tanks may contain satu-
rated vapor of the original volatile substances.
As the benzene vaporizes,
the air temperature in the benzene tank at first drops; however, due to heat
transmission by the tank walls the temperature rises and becomes e~ual to that
of the outside air.
According to nomogram 1 saturated benzene vapor tension at 100 e~uals 40
mm of mercury. Molecular weight of benzene is 780 To obtain corresponding
concentration use generalization 2, as shown below:
c =
P . M
n
18.3
40 . 78 = 170 mg/li
18.3
This benzene concentration is 3,400 times in excess of the limit of allowable
benzene concentration specified in N 101-54.
plosive concentration.
It is also in excess of its ex-
It is known that vaporization rate of water and other substances is pro-
portional to the differences in the saturated vapor tension of the substances
at the surface of the vaporized substance and its vapor tension in the sur-
rounding area.
In most instances under practical industrial conditions va-
porization of non-a~ueous substances in mobile air differs from water vapori-
zation by the fact that the vaporization extends into air containing none, or
only a slight amount, of the substance vapor. For instance, where benzene
vaporized into air containing 1 mg of benzene per li;
in the air will be 20 times as great as the allowable
such a benzene concentration will represent only 003%
its vapor conce~ltration
concentration; at 200
of complete saturation.
The temperature of a substance vaporizing in moving air drops depending
upon its volatility. In the case of easily volatilized substances, such as
ether or carbon bisulfide, the temperature may drop by tenths of degrees.
This phase of physical chemistry has been studied inade~uately.
The tempera=
ture drop of evaporating water has been well studied within the range of
energetically moving air which approximates the temperature drop in a sling
thermometer. In 1938 this author derived a generalization for the determina-
tion of temperature of evaporating water, and in 1951 he derived another gen-
eralization for the determination of temperature of surfaces of any vaporizing
substance into mobile air.
In instances where moving air into which a sub-
stance vaporized contained none or only negligible amounts of this substance
vapor, the generalization becomes as follows:
-5-
-------
34.5 Pn . M
0.24 tc = 0.24 tlim + (L + Cp . tlit) (B - Pn) 1000
(3)
In which t represents the temperature of the moving air at a given distance
c
above the surface of the vaporized substance; tlim represents the limiting
temperature toward which the surface of the vaporized substance tends; L
represents the latent temperature of vaporization of the substance at 0 tem-
perature in cal/kg; C represents the specific heat under constant vapor pres-
p
sure of a substance in cal/kg; Pn represents tension of saturated vapor of the
substance in mm mercury at tlim; B represents atmospheric pressure in mm of
mercury 0
With the aid of this generalization determinations were made of tempera-
tures toward which surfaces of different substances were tending during their
vaporization into moving air.
Determinations were then made as follows:
the
thermometer bulbs of the sling psychrometer were moistened with different sub-
stances, such as alcohol, chlorobenzene, aniline, etc., which have different
boiling points. Results of the experiments are presented in Table 10
TABLE
1.
Temperature of substances during evaporation into mobile air.
Substance
Mercury
Diphenyl
Naphthalene
Nitrobenzene
Aniline
Chlorobenzene
Amyl alcohol
Benzene
Ethyl alcohol
Dichlorethane
Acetone
Ethyl ether
: Boiling
: point at
~ 760 mm
~ pressure
. .
: : Temperature of
: :
E Air E evaporating substance
: temperature: :
~ ~Calculated; Experi-
: : . mental
. . .
3600
2550
218°
210.8°
184°
1320
137. 7°
80°
78.70
83.7°
56.10
34.6°
20°
20°
200
20°
200
20°
200
20°
20°
20°
20°
20°
19.997°
19.950
19.6°
19.1°
1808°
12°
14°
-50
20
-20
-170
-28°
19.6°
19.10
18.9°
130
15°
00
50
1°
Analysis of the data in Table 1 shows the following:
-6-
: Vapor tension
~ in mm
~ mercury at
~vaporization
~ temperature
:of substance
0.0012
0.03
0.05
0.22
0.3
6
2
17
1l.6
16
28
43
-------
a) The temperature drop during vaporization of substances having a b.p.
above 250° in moving air and at standard atmospberic pressure is negligible;
b) For substances having a b.p. ranging between 184° (aniline) and 218°
(naphthalene) the vaporization temperature drop ranged between 0.4 and 1.20;
c) For substances having a b.p. ranging between 132 - 137.70, the vapori-
zation temperature ranged between 6 - 8°;
d) For substances having a b.p. of approximately 800 the vaporization
temperature drop in dry air can be as high as 20 - 25°.
In case of low boiling substances the drop in vaporization temperature
may approach computed values, if the air is dry.
In the case of air contain-
ing moisture, the temperature cannot drop below the dew point.
Rate of water vaporization has been well studied. Of the many generaliza-
tions proposed for the calculation of rate of water vaporization in moving air,
the one proposed by the All-Union Therwotechnical Institutes gives results
most nearly approaching experimental values.
S = (2209 + 17.4 V) (Pn - Pl) (4)
In which S represents vaporization rate in g/m3/hr; V represents air movement
in m/sec.; (Pn - Pl) represents the difference in vapor tensions of the va-
porizing water and of the water vapor in the air immediately over the water
surface.
The vaporization process of other substances differs from that of water
vaporization in the following:
a) Vapor density of a substance differs froffi vapor density of water in
proportion to its molecular weight.
Thus, the density of benzene vapor at same
atmospheric pressure is greater than that of water in the proportion of 78:18 =
4.3 in which 78 is the molecular weight of benzene and 18 is the molecular
weight of water.
b) A substance normally vaporizes into air containing none or only neg-
ligible amounts of its vapor, i.e., considerably below saturation. Thus, in
1 mg/li concentr~tion of benzene at 200 it will be only at the point of 0.3%
saturation. Under such conditions the absolute value of Pn - Pl approaches
P , the tension of saturated vapor of the substance at its vaporization tem-
n
perature 0
This author hypothesized that vaporization rate of water and of other
substances '"as sir.lilar to steam passing through openings at slight pressure
-7-
-------
differences.
Linear rate of steam passing as above described can be expressed
by generalization 5.
Q=Y
2g . "p
y
(5)
In which Q represents steam passage rate in m/sec.; g represents force of gravi-
ty acceleration which is equal to 9.8 m/sec.2; ~p represents pressure differ-
ences in kg/m3; y represents weight of 1 m3 of steam in kg.
From generalizations 4 and 5, generalization 6 was derived for the calcu-
lation of vaporization rates of substances in moving air.
s = (5.38 + 4.1 V) P 1M
n
In which M represents the molecular weight of the substance; other symbols have
same designations as in equation (4). The correctness of this generalization
was checked by tests made for the cletermination of vaporization rate of toluol
with a b.p. 1040, chlorobenzene with a b.p. of 1320, aniline with a b.p. 1840,
naphthalene with a b.p. 2180 and water in air moving over the surfaces of such
(6)
substances at the rate of 0.25 - 5 ill/sec.
Results of the tests are shown in
Table 20 Analysis of data in Table 2 show that values computed by generaliza-
tion 6 closely approximated experimental values. Therefore, it is suggested
that gravimetric vaporization rates of substances in the air be determined using
equation 6.
Temperature of vaporizing substances can be computed according to equation
3, or it can be determined approximately using Table 2 by analogy with some
other substance.
Determination of saturated vapor tension at the substance's vaporization
temperature can be determined with the aid of the proposed nomograms.
Thus,
if it is desired to determine vaporization rate of nitrobenzene spilled over
an area of 2 m2 at 200 air temperature with the air moving at the r",te of 3
m/sec. in the absence of radiation heat, then it will be found in Table 1 that
the surface vaporization temperature is 19.10. The vapor tension of nitro-
o
benzene .at 19.1 , as indicated in nomogram No.2, is equal to 0.22 mID of mer-
cury.
The molecular weight of nitrobenzene is 123.
Substituting numerical
values in equation 2 as shown below:
S = (5.38 + 4.1 V) P 1M = (5.38 + 4.1 . 3) 0.22 1123 = 43 g/m2/hr
n
-8-
-------
TABLE
20
Computed and experimental evaporation rate into mobile air.
Dates
.
~ Sub-
~stance
.
.
.
.
. . .
: : Q :
: I : 0 :
: rl : °H Q) :
:.rI 8 .:.p ON :
:.0 O:rn'IJS:
:OQQ):HCt-iO:
: 8 .01 U) : 0 H :
: :Po;:jQ:
: H ~ H : rn U1 °H :
: ..-4 -P Q) : :> :
: ~ °H Po: r:LI :
: : Evaporated
OJ 80) .
H : H : substance in
;:j :;:j Q):
-P : -P -P 0 : g per hour
Hrn :rnQ)rn:
.01 H : H ~ '+-t:, :
~ Q) : Q) H: Ex- : Cal-
po:poct-i;:j: .:
6 : S 0 U1 :per~- : cu-
Q):O) : :
-P:8 :mental:lated
: Dif- :
~ference ~
~between ~
:experi- :
~ mental;
; and ;
: t d:
Notes
: : : : : : : :compu e :
5 12 22° 7° 3.01 2.98 +1 Air was
22 June Toluol 3 12 22° 7° 1.94 2.03 -4.5 dri ed in
1954 1 12 22° 7.1° 1.16 1.09 +6.4 this
0.5 12 22° 7.3° 0.78 0.86 -10 experiment
5 12 17.2° 13° 1.92 1.95 -1.5
18 - 20 Chloro- 3 12 17.2° 13° 1.4 1.34 +4.5
May benzene 1 12 17.2° 13 . 2° 0.775 0.725 +6.9
0.5 12 17.20 13.4° 0.6 0.56 +7.1
5 8 17.20 160 0.06 0.061 -1.6 Data of the
second
27 May- 3 8 17.2° 16° 0.041 0.038 +8 series of
Aniline 1 8 17.2° 16.2° 0.018 0.02 -10
8 June 0.5 8 17.20 16.20 0.014 0.015 -6.7 experiments
0.25 8 17.2° 16.2° 0 . 014 0.013 +6.7 are
presented
5 24.6 17 .3° 17° 0.03 0.03 0 By loss in
weight
5 24.6 17.3° 17° 0.031 0.03 +3 By analysis
3 24.6 17.3° 17° 0.021 0.022 -5 By loss in
weight
1 - 17 Naph- 3 24.6 17.3° 17° 0.023 0.022 +5 By analysis
June thalene
1 24.9 17.30 170 o. on o.on 0 By loss in
weight
1 24.6 17.3° 17° 0.01 O.Oll -10 By analysis
0.5 24.6 17.3° 17° 0.01 0.009 +10 By loss in
wei,ght
25 June 'ilater 5 12 22° nO 0.75 0.76 -1.30
2
It will be found that the rate of nitrobenzene evaporation from an area of 2 m
amounted to 86 g/hr. Such an amount of vaporized nitrobenzene can pollute a
considerable volume of air. According to N 101-54 the limit of allowable ni-
trobenzene concentration is 0.005 mg/li, or 1 g/m3. At nitrobenzene evapora-
tion 86 g/hr, the concentration created in the ventilated air volume will equal
17,200 m3/hr.
-9-
-------
Deposition of Particles from a Gas. Stream on an Isolated Cylinder.
(Theoretical).
L. V. Radushkevich.
Zhurnal Fizicheskoi Khimii, Vol. .32, No.2, 282-290, 1958.
The process of flowing aerosol onto a fixed obstruction is related to
deposition of smoke, vapor and dust on filters made of fine-fibered materials,
such as cotton, wool, uiixtures of cellulose and asbestos, etc. (lJ. There-
fore, in theoretical deposition investiGations, one usually studies the prob-
lem of aerosol particles deposition on a thin cylinder, localized in the stream
and acting as fibrous lilaterial element.
In spite of the numerous investiga-
tions, the process of aerosol filtration by means of fibrous materials can not
be regarded as well understood from the empirical or theoretical standpointso
Experimental data in the field of filtration indicated that the process can
not be explained on the basis of a single causative factor of deposition.
Therefore, theoretical considerations are usually based on the effects of
several causative factors, among which are: a) inertia deposition; b) depo-
sition as a result of direct interception; c) diffusion deposition; d) gravi-
tational or sedimentation deposition; and sometimes e) electrical deposition.
The role of anyone factor changes with the size of particles in any isolated
section, with the flow velocity, the diameter of the filter fibers, and with
other causes.
The present theoretical analysis deals with the effect of two factors:
diffusion and direct interception; this is in accord with the simplest process
of filtration of highly dispersed aerosols where the inertia and sedimentation
deposition factors can be disregarded. The primary purpose of the present in-
vestigation is the determination of the relation between filtrational effective-
ness and the size of aerosol particles.
Knowledge of this is of importance
since such dependence is especially characteristic of fiber filters, used in
all filtration experiments. Notwithstanding certain disagreements among dif-
ferent authors, specific filter selectivity can be regarded as an established
facto Filters will retain (prevent the passage of) the finest and coarsest
particles; on the other hand, the effectiveness of sedimentation is minimal
even in the case of medium dispersal. A theory of particles deposition from
an aerosol flow upon an isolated cylinder lilay be formed by regarding the phe-
-10-
-------
nomenon as a special class of the orthokinetic coagulation of polydispersed
sols in a state of flow. A similar theory of spherical particles coagulation
was developed by MUller [3J, who studied the motions of coarse aerosol parti-
cles suspended among fine particles.
An analogous mechanism was in operation
in the case of aerosol particle deposition on a stationary obstruction, such
as a cylinder, which acts as an adsorption body.
Let us now investigate the viscous flow of gas around a cylinder of in-
finite leng~h in the range of extremely small magnitudes of Reynolds numbers
(Re ~ 0.1).
This corresponds closely to practical conditions under which
fibrous materials are used in most technical installations [4J.
For simplicity
the study will be limited to a case in which the cylinder is stationary and
the linear velocity Vo of the unbroken flow is constant. Assume that spherical
particles of radius r of a monodispersed aerosol were carried by an air flow
while they were simultaneously undergoing Brownian movement, tpe intensity of
which was determined by diffusion coefficient D.
Considering that the velocity
vector v was of constant magnitude and direction, place a cylinder of radius
o
R perpendicular to the flow. Some particles, being carried in t~ direction
of the flow while undergoing Brownian movement, approach the cylinder and
In accordance with experimental
,
data related to minute particles (~ 1 - 5 ~) assume that any impact between the
cylinder surface and the particles results in the adsorption of the latter [5J.
eventually come in contact with its surface.
The problem narrows down to the determination of the number of particles which
settle in this manner per unit time and per unit length of the cylinder, given
the particle and cylinder radii, the veloci~y of the constant flow, the con-
centration of aeFosol particles N at a distance from the cylinder, and the
o
parameters of the dispersed medium characteristics.
The differential eQuation of forced diffusion in flow (in motion) is:
D div grad N + (v grad N) = ~~
Under stationary conditions becomes:
D div G + (vG) = 0
(1)
in which N is the particle concentration in the proximity of the cylinder and
G = grad N.
It is known that in cylindrical coordinates:
" 1 0 G O~ 1 o2N o2N
dl v G = dl v grad N = - - p - + - - + -
P C\p oP. p2 o
-------
whereupon:
oN I aN oN
G = grad N = e - + e - - + e -
p op ~ p o~ Z oZ
In this case o2N/oz2 = 0 and v = O. Therefore, eQuation
z
(1) takes the form
of:
D [1 Q.... (pG ) + 1 0
p op p p o~
G~J " -
(Gp vp + G~v~)
(2)
To solve the posed problem it is enough to establish the gradient in the
immediate proximity of the cylinder. It is clear that a particle can approach
the cylinder surface at a distance eQual to its radius r; hence, interception
takes place on a projected cylinder coaxial with the original radius a = R + r.
The present computation is limited to instances in which r < R, therefore,
th f 1 f 1 1, htl t th R Under such condi-
e range 0 va ues 0 p are on y s 19 y grea er an .
tions one may assUQe that G = 0, in which case eQuation (2) assumes the form
~
of:
D 1 Q.... (pG ) = - (G v )
o ap p p p
or:
Vo
~ In (oG ) = - D
up p
Upon integration this eQuation becomes:
(3)
In (pG )
p
p
- - 1 f
- D.
R
vd,o+C
p
(4)
Here, a lower limit is assigned to p = R, since there is no flow on the cyl-
inder surface and v = O. Integration constant of C can be determined by ex-
p
amining the process of aerosol diffusion toward the cylinder in the absence
of flow, N = 0 always on the surface of the cylinder and N = N at an infinite
o
distance from the cylinder surface. An analogous problem related to the theory
of heat conductivity was solved by Carslaw and Jaeger [6J for an infinitely
long cylindrical recess (void or hollow) in unlimited space. The solution is
presented in the form of an integral with a Bessel function.
However, its
computation is cumbersome, therefore, a table of values was eventually prepared
by Jaeger and Clarke L7J and by Perry and Berggren [8J.
When applying the
solution of the above mentioned authors to the solution of the problem of dif-
fusion in the Qirection of a cylinder the following formula may prove of value:
-12-
-------
dn
dt = DNoLF(x)
in which dn/dt is the number of particles deposited per unit time and per sec-
tion length L on the cylinder; F(x) is a dimensionless function of argument
x = Dt/R2, the values of which can be found in the publications of the above
mentioned authors. At x >- 3.0 the ~rocess becomes static and F(x) = const. m
k.
Numerical values of constant k can be seen in a nomographic curve of the
function F(x).
This value proved to be k ~ 4.38.
The concentration gradient
at the surface of a cylinder under static conditions can be determined easily
by comparing the above solution with the usual expression for diffusion flow:
N b
o
Gp = R = R
in which b
k/2w.
Accordingly the integration constant:
C = In (N b)
o
By substituting this expression in formula (4) the following expression is
derived:
In (oG )
p
p
= - i S vp dp
R
+ In (N b)
o
or:
oG
p
N b-
o
p
exp (- i S v p dP)
R
Accordingly:
p
exp (- i J
R
Thus, the number of particles dn/dt settled per unit time from the flow
b
G = N -
pop
vp dP)
(5)
onto the cylinder section of length L is equal to the number of particles
diffused over the surface of the coagulation range. It is evident that with
p = a we have:
211
DL S G
o p
Substituting G at p = a by its value as shown in formula (5):
P
dn
dt -
adcp
= a
-13-
-------
2rr
~~ = DNoLb J
a
exp C - i J v 0 dP) dcp
R
(6 )
o
The deposition effectiveness D represents the ratio between the number
of particles desposited dn/dt and the number of particles carried by the flow
per unit time in the direction of the projected cylinder surface perpendicular
dn/dt
D = N v eL
o 0-
for 0 = 2R, we have:
2rr
= ~\ J
o 0
a
exp (- i S v p d;O) dcp
R
(7)
to vector v .
o
I. e. ,
Formula (7) gives the general solution to the problem of particles deposition
from a flow to a cylinder; however, it can be applied only if the species of
the radial component velocity function Vo is known. As a rule this function
cannot be found around the cylinder, although it is possible to find an appro-
priate expression for it in a particular case. In instances of small Reynolds
numbers, Vo may be represented by Lamb's forulula [9J, which holds true for
Re ~ 0.1 at p < 2R. Recently, Davies [lOJ used Reynolds values of 0.2, 20
and 2000, at great distances and derived a more precise expression. In the
present study we are not investigating the deposition of large particles, for
which r >- R, and are limiting ourselves to the range of small Reynolds numbers
and we need only avail ourselves of Lamb's formula for radial component of
velocity, and formulate:
[1 R2 PJ
v = A cos cP - (1 - - "'\ - In -
o 2, 1'2 j R
(8)
where:
A = Vo [0.5 + In ~J -1 and y = 1. 781072
Here, the Reynolds number has the value of Re = vo0/~, where 0 = 2R or the
diameter of the cylinder, and ~ is the kinematic medium viscosity. Substituting
expression (8) into fOrulula (7) and integrating, we find:
2rr
T) = ~ J'
v ~
o 0
where Pe is Pekle's diffusion number; Pe = vo~/D and Io(B) is a Bessel function
of the zero order of the first kind of imaginary argument. For the sake of
brevity B in formula (9) is expressed as follows:
e-B cos cP dcp = 2rrDb I (B) = 2rrb I (B)
v ~ 0 "[P'eJ 0
o
(9)
-14-
-------
B = 4.0044 ~In LRe] [~ ~ - ~ 1 ~ P - (1 + ~) In (1 + ~)J (10)
~ = r/R. By this procedure, the final expression characterizing deposi-
'ilhere
tion effectiveness is presented as an explicit function of non-dimensional
criteria, Pe, Re and ~.
D = f (Pe, Re, ~)
Formula (9) can be simply expressed as:
D = kY
where k = 4.38 and:
Y = I (B) [Pe]-l
o
A knowledge of this function helps to determine relation between the deposi-
tion effectiveness and the radius of the aerosol partir-les on the one hand and
the flow velocity on the other.
Discussion of results. First, let us examine the variation range of in-
dividual components entering into formula (11) as applied to the actual con-
ditions of filtrational action. Let us direct our attention to the fact that
variable B, as shown in expression (10), can be represented as the product of
two factors:
B = UV
In which:
v = ~ ~ - ~ 1 ~ ~ - (1 + ~) In (1 + p)
is a function of ~ only, whereas:
(12)
U = lPe] (4.0044 - 2 In [Re])-l
(13)
involves two characteristics Pe and Re.
Let us examine the variation ranges of V and U resulting from the prac-
tical conditions of aerosol deposition and let us note the characteristics of
variations in argument B.
Some calculated values which can be regarded as
typical are listed in the following table to which reference will be made
later.
1.
Function V = vCa). Materials used in filtering aerosols are made of
generally of extremely small diameter (1 to 10 ~ occasionally up to
Layers of such material assure good filtration of particles within
fibers
20 ~).
diameter range of 0.04 - 0.08 ~ and occasionally 1 - 3 ~.
More coarsely dis-
persed aerosols are separated by other methods.
The indicated intervals fo~
-15-
-------
4! = 20f!; v = 5 cm/sec; Re = 0.07145
0
d=2ri D'107 i i [V]'105 . . . ~ yo 105
ipe'10-3i U.IO-3 . [B] I (B)
f! : 2 : ~ . 0
:cm /sec: .
0.04 380.0 0.002 0.000262 0.263 0.02835 7.43 10-8 1.0000 380
0.10 71.5 0.005 0.00414 1.399 0.15068 6.238 10-6 1.0000 71.5
0.40 8.47 0.020 0.260 11. 806 102720 3.307 10-3 1.0000 8.47
1.00 2.75 0.050 3.914 36.36 3.9177 0.1533 1.0057 2.77
1.40 1.92 0.070 11. 22 52.15 5.620 0.630 1.1017 2.12
2.00 1.28 o. 100 29.55 78.28 8.4336 2.492 3.270 4.18
2.40 1.05 0.120 49.95 95.20 10.250 5.120 30.327 31. 84
2.80 0.89 0.140 77.10 112.10 12.080 9.300 1451. 40 1291. 70
3.00 0.83 0.150 94.56 120.60 12.993 12.286 31620.0 26216.0
d and ~ determine the range of parameter~. Obviously, change in this magnitude
generally lies within the range of 0.02 and approximately 10 and at times 20.
In the present calculation we limited ourselves to the range of small ~ values,
since for large ~ values Lamb's formula becomes inaccurate.
Therefore, later
on we will deal with cases in which particle diameters are less than the cylin-
der diameter,
i.e.,
in the interval between 0.002 and 0.2.
However, even values
of this order cover a sufficiently wide field of filtration and formula (12)
indicates that at ~ > 0, the value of V is negative. The absolute value of V
increases with an increase in p, varying greatly in the interval of our present
interest as can be judged by the above table. Here V increases by 6 orders of
magnitude with an increase in ~ by 2 orders of mab~itude.
2. Function U. The present problem is characterized by extremely large
Pekle values which is a condition of the small diffusion coefficients which is
an intrinsic property of aerosols.
determined by the generalization:
It is known thi:it the magnitude of D can be
D = ldP
where P is the mobility for spherical particles:
P-~
- 61Trf!
in which ~(r) is a function of the particle radius, tending to approach unity
in the Cdse of large particles, vhen r is sisnificantly greater than A, the
-16-
-------
length of the free path of an air molecule; ~ is the air viscosity.
in a general case:
Therefore,
At a ter:lj)erature T
D=kT .PiEl=K~
611'11 r r
2930 C, when ~ 1.81 x 10-4
poise, 'I'le hCive:
K = 1.176 . 10-11 cm3/sec
This function may be expressed by the well-checked formula of Millikan [llJ:
~(r) = 1 + ~ (0.864 + 0.29 . e-l.25 riA)
r
Using these formulas and taking A = 1 x 10-5 em, D was computed for parti-
cles of different sizeso Some typical data are listed in the table. Attention
must be given to the fact that the value of D varied within a wide range (three
orders of magnitudes) from the finest particles under present consideration
(r = 0.02 ~) to the coarsest (r = 1.5 ~). It should be noted that we have to
limit ourselves to low flow velocities, since we are dealing with a laminar
current in the proximity of the cylinder. This requirement is met by extremely
small Re numbers and with correspondingly low velocities not exceeding 10 em/sec.
It should be noted that the velocities used in Langmuir's theory do not exceed
3.5 em/sec. This range of velocities corresponds closely to actual conditions
of filtration through fibrous materials.
for a thin cylinder the product of ~v is of small value and does not exceed
2 0
-0.02 cm /sec., when values of Re attain the maximal limit, in this case 0.1.
More accurate results are obtained at Re < 0.1. In spite of the small values
Therefore, it follows generally that
of ~v , the Pekle numbers lie between the
o
and several hundred thousand (see table);
values, the value of Pe increases. Under
limits of the order of several hundred
moreover, as d = 2r assumes brreater
conditions of the present problem
changes in the Pekle numbers are of greater significance since Pe is not only
a component of the expression of function U, but also of the basic formula ex-
pressing the relative deposition effectiveness [llJ.
The Reynolds number is
of relatively less significance in relation to the magnitude of U in the inter-
val of r values here dealt ilith: this is indicated by formula (13). The size
of U increases slightly as Re diminishes.
Generally, as particle sizes increase,
the U function increases rapidly, covering a range of magnitudes of three orders
in passing from the smallest particle to the largest.
Values of U are small at
lower velocities; however, increase in r still has the same effect.
-17-
-------
The present analysis of chan6es in U and V leads to the conclusion that
the magnitude of B, the product of two increasing functions of particle radii,
ought to increase rapidly in passing from small to large particles. Data in
the table show that in the interval of present interest, i.e., of particle
diameters ranging from 0.04 to 3.00 ~ the value of B increases by more than
eight orders of magnitude. This is reflected in considerably greater changes
in the Bessel function I (B). In view of the minuteness of B for the smaller
o
particles under consideration I (B) remains equal to unity for a time; it then
o
increases, slowly at first, then sharply, until it reaches values in the order
of several thousands; at this point the following asymptotic formula can be
applied:
I (B) ~ eB (2nB)-1/2
o
Results of calculations are shown in the table.
The noted changes in I (B)
o
are valid for other velocities and particle diameters. In practically all
cases of particles with diameter d ~ 0.4 ~ it can be assumed that Io(B) = 1,
,~hereas for d > 2 ~ increase in the values of I (B) will increase rapidly.
o
The characteristic variable, Y, here introduced which represents the
relative deposition effectiveness, is expressed as the product of two functions
[PeJ-l and I (B); the first function decreases with the increase in d = 2r
o
and the second function increases. For small sized particles when CPeJ-l is
of high value and I (B) is at its minimal value [I (B) = IJ, their product
o 0
is comparatively large. As d increases the reciprocal Pekle number diminishes;
at the same time I (B) increases, though slightly, so that the product (value
o
of) Y is small. With the increase of d, the function I (B) eventually increases
o
sharply, and the product increases significantlyo It can be concluded, there-
fore, that function Y has a minimum in the region of medium sized particles.
Data in the table illustrate this fluctuation in deposition effectiveness.
Thus, the present calculation confirms the existence of particle deposition
selectivity on the surface of a cylindrical obstruction, and in a simpler basic
form reflects the experimentally established selective aerosol filtration by
fibrous materials.
Supplemental studies showed that the position of Y(r) minimum was a func-
tion of vo and of the particle diameter; however, we are not concerned here with
an analytical expression of a functional extreme, but limit ourselves to a par-
-18-
-------
1.9 Y,
I;
')
v
2
I
u
I;
d=2r,p
= 1 cm/sec; 2 - Vo =
cm/sec; ~ = 20 ~;
Yl = Y . 105.
,
2
J
1 - Vo
5
ticular example.
Curves in the illustra-
tion are plots of calculations for v = 1
o
cm/sec. and for v = 5 cm/sec. at ~ = 20 ~.
o
Calculations were made for r > 0.2 ~ at
points 0.2 ~ apart.
A comparison of the
two shows that increase in velocity shifts
the minimum into the region of smaller size
particles and to a dr~wing together of the
arms of the curve, while the minimal ef-
fectiveness Y. decreases. Calculations
mln
based on other values for cylinder diameter,
point to the conclusion that depositional
effectiveness was higher for small diameter
cylinders than for large ones, and that in-
crease in cylinder diameter shifted the minimum into the region of coarser
particles.
The deposition of particles from a gas flow onto a cylinder has been
analyzed from the viewpoint of a single process and in the present calcula-
tions there was no need to analyze it from the viewpoint of an artificially
broken up combination of mechanisms, as is generally done in other similar
studies. Ultimately it was found that a functional relationship existed be-
tween the deposition effectiveness and the minimum size of particles, which
is in agreement with the results of Qualitative tests. This functional aspect
can be interpreted to a degree in the usual manner, i.e., it can be reasonably
assumed that the course of the left arm of the curve was a pure function of the
diffusion deposition, whereas the course of the steeply ascending right arm
of the curve represented the process of direct interception. The above analysis
of the behavior of the defined functions offers the possibility of determining
the extent to which the above explanation held true. It appears obvious that
as long as the function I (B) remained eQual to 1, Y(r) was determined solely
o
by the magnitude of Peklets number, i.e., it was a function of the diffusion
coefficient, whereas (variable) criterion ~ may be considered eQual zero, i.e.,
in this range the ultimate particle size did not affect the depositional prod-
ess (V ~ 0). On the other hand, rapid increase in Y beyond the minimum was con-
nected with the predominating role of direct interception when, with the in-
-19-
-------
crease in B the beometric dimensions of the particles bebin to manifest their
effect even though the value of the diffusion coefficient remained finite.
Thus, unlike the Langmuir theor,y, our calculations showed that both
mechanisms affected the course of the process inseparably; however, pure
diffusion deposition can be separated in studies within the range of small
particles. Langmuir's calculation method is of more universal application,
Slnce it includes the tangential component of velocity v~ with the aid of
which the number of deposited particles can be determined at all times and
in the presence of any mechanism when the total volume of particles is known.
Under such circumstances it becomes necessary to separate and analyze each of
the elementar,y mechanisms theoretically introduced for the purpose of simplifi-
cation and supplemental assumptions. In this connection it must be admitted
that factors which ~ere taken into account, such as diffusion and the geometric
particle dimensions were the factors which deteruined the lower possibility
limit of particles deposition onto the cylinder throughout the entire range
of practically significant dispersion.
Thus, the present method of calcula-
tion, based on a minimum number of asswoptions appears to have led to a ration-
al explanation of the deposition mechanism, although, admittedly it did not
solve completely the entire complex problem of aerosol filtration.
Conclusions.
1.
The present analysis of the static process of aerosol particles de-
position onto a cylinder from a flow was made with the aid of convection dif-
fusion differential equation; such analysis indicated that deposition effec-
tiveness was a function of size of particles, cylinder radius (or diameter)
and of the linear flow velocity. In instances of particles of finite geometric
dimensions the total process can be described as a simultaneous effect of dif-
fusion and of direct interception.
2.
Deposition effectiveness as a function of particle radii has its mini-
mum in the instance of any flow in the presence of a small Reynolds number and
a Lloderate r/R ratio; this is in agreewent \Jith most experimental data obtained
in the study of aerosol filtration.
-20-
-------
Bibliography.
1. E. 8 t a f for d a. W. 1. 8 m i t h, Ind. a. Eng. Chern., 43, 1346, 1951.
2. W. 8 ell, VDI, Forsch. H. 347, I3erlin, 1931.
F. Albrecht, Phys. Zs., 32,48,1931: I. Langmuir, Office Sci. Re-
search a. Development, Report .J\~ 865, 1942; Journ. Meteor., 5, oN!: 5,175, 1948;
H. A. Y h c, AAl'I, 81,1013,1951; C. N. D a v i as, Proc. Phys. 80c. (Lon-
don), 63, 288, 1950; Proc. Inst. Mech. Eng. (London), 1, 185, 1952; C. Y. C hen,
Chern. Reviews, 55, 594, 1955; H. F. Johnstone a. !vl. H. Roberts,
Ind. Eng. Chern., 41, 2417,19'19; .C. J. 8 t air m 0 n d, Trans. Inst. Chern. Eng.
(London), 28, 130, 1950; JI. ,I. "I e B II H, AAH, 91, 1324, 1953; H. En g e 1-
h a r d, Zs. Elektrf>chem. 31, 590, 1925; CM. TaKme H. F r e un d Ii c h, Ka-
pillarchemie, 1926, CTp. 785: A. K a II f man n, Zs. VDI, 8, 593, 1936; H. L. G r e-
e n, «Smoke.) (B KHure J. 1. Her man s: «Flow properties of disperse systems».
rn. IX, CTp. 344-381, Amsterdam, 1953); E. A. Ram ski II a. W. L.
And e r son, 10urn. Colloid 8d., I), 416, 1951. .
3. H. 1\1 ii II e r, Kolloid-Beihefte, 2-7, 223, 1928; eM. TaKme B c6opH. «RoarymllJ;HfI
KOJIJIOll,[{OBI>, OHTH, 1936. eTp. 14.
4. H. A. II> Y K e. MexaHIIKa aapaoJIeii:, Ma,[{-Bo AH CCCP, 1955, CTp. 189.
5. H. A. II> Y K e. iK3TII> , 6, 139, 1936.
6. H. 8. Car s I a w a. 1. :. 1 a a gar, Proe. London Math. Soc. (2), 46, 361, 1940.
7.1. C. laeger a. ~Iarthn Clarka, Proe. Roy. 80c. Edinburgh, (1\),61,
223, 1 !J12.
8. H. L. Per r y a. W. P. 11 e r ~ g ran, University of California P"blicnliolls
in Engineering, 5, 59,1944; eM. TaI,me B Kllure M. 1 a k 0 h, .Heat lransfcn. New
York, 1949, CTp. 265.
9. r. JI a M 6, fJl,[{po;(IIIIaMHHa, fTII, M.- ll., 1947.
to.C. N. Davies, [2J.
11. R. A. ~I i II i k a n, Phys. Rev. (II), 21, 217, 1923.
Aerodynamic Investigation of Electrostatic Precipitator C-180 Model.
P. J. Kuleshov.
(Zaporozhie Coke-Chemical Plant).
Koks i Khimiya, 1958, No. 12, 30-35.
Electrostatic tubular precipitators types C-140 and C-180 are widely used
by U.S.S.R. coke-chemical plants for purifying coke gases of tar and oil. Of
68 electrostatic precipitators used by the coke-chemical industry at the begin-
ning of 1958, 46 were type C-140 and 22 type C-180. The sulfur department of
the Zaporozhie Coke-Chemical Plant has three electrostatic precipitators type
C-180 which are installed in front of scrubbers. The purpose of such installa-
tion is to purify the gas from oil drops and from sublimated naphthalene carried
-21-
-------
over by the gas as it passed through the benzene scrubbers, to prevent 10s8 in
the absorber solution effectiveness, and, consequently, in the sulfur removing
operation efficiency. Basically the construction of electrostatic precipitators
types 0-180 and C-140 is identical. Electrostatic precipitator type c-180 is
trade named because it has 180 precipitating electrodes; it is 4600 mm in di-
ameter. Therefore, it is logical to aSSUille that basic defects in construction
and bas distribution over the precipitator cross section found in type C-180
will be essentially the same as in precipitator type C-140. With this assump-
tion in wind, studies were rDade in the plant I s laboratory of the aerodynamics
of electrostatic precipitator type C-180 in model form. The model was made
of plastic material on 1:10 scale. Air flow through the model precipitator
was created by a fan which forced through the model over 1000 m3 of air per
hour. A full view of the model installation is presented in Fig. 1.
---- - In investigating the aerody-
namics of the electrostatic pre-
Fig. 1. Model of electrostatic
precipitator 0-180.
cipitator model a study was made
first of the effect of "live" area
of the lower perforated distribution
screen of the inflow conduit inside
the electric precipitator and of the
location of the double T-shaped
supports on gas flow distribution
and on pressure drop reduction.
Comparison of results of individual
experiments was made by constructing
graphs of gas flow velocities over the filter cross section and of the computed
coefficients of irregular or unequal distribution [lJ, which was done as fol-
lows: all gas flow velocities determined in the precipitating electrodes
were plotted on the ordinate in the order of increasing values; the number of
electrodes of corresponding gas flow velocities were plotted along the abscissa.
The resulting curve assumed the form of a broken line which depicted the gas
flow distribution over the precipitating electrodes. Accordingly, as the dis-
tribution tended towards greater regularity the broken line curve tended to
become a straight line, and ~ versa. This method of plotting produced a
true picture of bas flow distribution over the precipitating electrodes and
-22-
-------
constituted a convenient comparison of different ex~erimental r8sults. In
this way, it was established that the lower Qi~tribution screen constituted
the basic element the correct design of ;;hich wie;ht assure even gas flow dis-
tribution over tne precipitutin6 electrodes; it was also shown that the per-
forated lower distribution screen originally desib~ed for electrostatic pre-
cipitator C-180 had a resistance coefficient of C = 142 and a "live" perfora-
tion area of 12.8%.
Perforated distribution screen No.1 was made on the principle of geometric
similitude and was tested in the model precipitator in ten experiments. Depend-
ing upon the position of the supporting beams the coefficient of uneQual dis-
tribution ranged between 0.35 and 0.511, indicating th~t gas flow distribution
over the model precipitator cross section was irregular. With prevailing high
resistance coefficients the re-distribution of gas flow velocities beyond the
perforated distrioution screen can be considerable, thereby creating a new d~s-
tribution irre5~larity in complete reverse order to the original irregularity
of gas velocities distribution effected by the perforated screen. It was con-
cluded, therefore, that perforated distribution screen No.1 had a resistance
coefficient of 142, and could not effect eQual distribution of gas flow ve-
locities 0
Experiments were then made with distribution screen No.2 with a "live"
or perforated area of 28.0% and a corresponding resistance coefficient of C =
21.5. This was the 82nd experiment; it yielded a coefficient of uneQual dis-
tribution of 0.288 as compared with 0.509 and 0.511 in experiments 70 and 71,
correspondingly, in which the previously described perforated distribution
screen No.1 was used.
In addition to manifesting a superior distribution
of gas flow, perforated distribution screen No.2 effected a considerable re-
duction in the pressure drop.
Distribution screen No.3 had a "live", or perforated area of 35% and a
resistance coefficient of C = 11.8. This slightly raised the coefficient of
uneQual distribution, clearly indicating that an increase in the "live" area
of the perforated gas distribution screen above 28% lowered the gas flow dis-
tribution regularity over the electric precipitator cross section.
It was
shown in previous studies [2J that an inside angular shaped gas intake conduit
distorted the gas distribution with the precipitator and in addition increased
its resistance.
Leaving the conduit at a high velocity the gas created vor-
-23-
-------
texes which enhanced the degree of uneven gas flow distribution already exist-
ing in front of the perforated diLtribution screen.
Determination of gas flow velocities over the precipitating electrodes
of the model had shown that due to the prevailing uneven flow distribution no
gas flow passed over 13 of the precipitating electrodes, and consequently
these electrodes did not participate in the gas purification. Added to this
should be another 6 precipitating electrodes through which passed the supports
of the broaching frame of the coronary electrodes and gas purifying function
of which was nil. This made a total of 19, or 10%, of the precipitating
electrodes which were dead in so far as the function of gas purification was
concernedo Fig. 2 is a diagramatic presentation of gas flow velocities at
all 180 precipitating electrodes based on the results obtained with the ex-
perimental precipitator model.
Based on an analytical study of the velocity
distribution, all gas flow velocities were classed into 5 groups, each desig-
nated by a distinguishing mark, as shown in Fig. 2. The marks in the diagram
indicate that gas flow velocity dis-
u
L
Designations
.over 10 m/"eeGjt"--- 4.0-5.9
~ 8.0-9.91?J. m/see
... - "./see '(Q -- 1.0-3.9
o - 6.0-7.':1 Om/see
m/"ee ~ 0.0 m/sec
Fig. 2. Diagram of velocities
distribution over the electrostatic
precipitator cross section.
tribution over the precipitating
electrodes was extremely uneven.
I
~ost of the precipitating electrodes
over which the gas flow passed at a
rate of 10 m/sec. were grouped in the
central portion of the precipitating
electrodes, the distribution of which
followed a more or less vertical
diametrical pattern; at the extreme
right, also running in vertical di-
rection, were electrodes over which
no gas flow was passing and, con-
sequently, did not contribute to the
gas purifying efficiency of the elec-
trostatic precipitator. An attempt
was then wade to determine the cause
of the uneven gas flow velocity dis-
tribution over the cross section of
the electrostatic precipitator model.
-24-
-------
To accomplish this uleasurements were made of the
section line I-I passing through the axis of tt9
section line II-II perpendicular to the direction
dynamic pressures along the
intake conduit, and along
of I-I, at points marked
and at points 3 and 4 above
1 and 2 below the perforated distribution screen,
depicted in Fig. 3.
the perforated distribution screen, using a core-type pneumometric tube, as
Gas flow velocity distribution curves along section II-II,
where most of the inactive electrodes were located, are presented in Fig. 3.
The graphs show that due to the high resistance and distortion introduced
into the gas flow distribution over the precipitator cross section, and also
due to the asymmetrical gas delivery by the gas conduit inside the electro-
static precipitator, areas were created at points 3 and 4 above the distribu-
tion screen where the gas flow distribution was of negative direction; these
are indicated by dash-shaded areas in
5
4
3
2
f
Fig. 3. Dynamic pressure distribu-
tion over cross section along II-II
above and below the perforated
screen.
Fig. 3; gas flow of the opposite direc-
tion may also be seen at such points.
Inactive precipitating electrodes were
also found in these sections. Thus,
data related to the gas flow distribu-
tion in spaces above and below the per-
forated distribution screen inside the
electrostatic precipitator model corre-
sponded to gas flow velocity measure-
ments obtained at points of outflow
from the precipitating electrodes, as
shown at point 5 of Fig. 3, and are,
therefore, in complete agreement with
the theory of equalizing effect of the
perforated distribution screen.
In experiments Nos. 85 and 86 the
inside downward directed section of the
gas inflow conduit was removed, using
the same perforated distribution tubeo
Measurements were made of the dynamic
pressure at each precipitating elec-
trode and the coefficient of total un-
-25-
-------
equal distribution calculated for each experiment. On the basis of the results
it was concluded that the removal of the inside downward directed angular part
of the gas inflow conduit improved the gas flow distribution along the pre-
cipitator cross section consider~bly, lowered the apparatus resistance and
obviated the conditions which were responsible for the formation of vortexes
in the space below the distribution screen.
Thus, in experiment No. 66, per-
formed with the angular downward directed part of the gas inflow conduit in
operation, the coefficient of unequal distribution amounted to 0.350; in ex-
periment No. 85 (the original text has it as No. 35 B.S.L.) to 0.142, and in
experiment No. 86 to 0.135. The broken line curves in Fig. 4 depict gas flow
~ distribution in experiment No. 66 with
\Yep
~6
/
.;' .r
"p.
I 66
~ ~
,. -1" ~
/ ~ Exp.
,. 86
r- r
L J
~ W
;
,.J~ I
r t!
..
t
f
r
U
20 41} 6,(J B.
~5
1,4
1,3
12
tf
to
0,9
0.8
0.7
11,6
,,~
11,4
1/3
0.2
'0 ItXJ 170 140 1611 180
Number of electrodes
Fig. 4. Curves of velocities
distribution over cross section of
model electrofilter; experiment
No. 66 with inside downward
directed gas inflow part, and
experiment No. 86 v~i th inside
inflow part removed.
the inside angular portion of the gas
inflow conduit intact and gas flow dis-
tribution in experiment No. 86 with the
inside part of the inflow conduit re-
moved.
The perforated 6as flow distributing
screens are fastened inside industrial
electrostatic precipitators by means of
3 double T-shaped supports placed across
the apparatus with the screens super-
imposed upon them.
The supports under
the screens form grooves or troughs along
which the incoming gas flows. It is
natural that such an arrangement should
affect the manner of incoming gas spread-
ing underneath tfie perforated screen, and
as a consequence, the course of the gas
distribution.
The character of such ef-
fect was 8tudied experimentally with dif-
ferent arrangements of the double T-shaped
supports and with the inside angular down-
ward directed part of the gas inflow con-
duit removed. The following 3 arrange-
ments of the screen supports were inves-
-26-
-------
tigated: 1) the double T-shaped supports were fastened above the perforated
screen, which obviated their affecting the wanner of bas distribution; 2) the
double T-shaped supports were fastened below the distributing screens perpen-
dicular to the axis of the inflovving bas; and 3) the supports vvere fastened
below the gas distributing screens parallel to the axis of the inflowing ~as.
Measurements were then made of the dynamic pressure at each of the precipitating
electrodes using screens types No.1, No.2 and No.3 (previously described).
Coefficients of unequal distribution obtained in each of the tests are listed
in the table below.
Data in the table show that with the use of perforated
screens Nos. 2 and 3 best gas flow distribution was obtained when the double
T-shaped supports were fastened below the screen in a position perpendicular
to the axis of the inflow bas conduit.
.
Number~
of ~
.
screeni
.
.
.
Location of double
T-shaped supports
: Below the screen
: Parallel: p
E to the E ~rpen-
: . l' : dlcular
screen ~ axl~ 0 ~to inflow
:gas lnflow: d "t
: d "t : can Ul
: con Ul :
Above
the
1
2
3
0.296
0.132
o. 118
0.258
0.0625
0.0636
The primary purpose of this
study was to increase the productive
capacity of the electrostatic pre-
cipitator without sacrificing its gas
purifying efficiency. To that end
experimental data obtained ';vi th the
electrostatic model type C-180 pre-
cipitator were used in computing the
highest possible productivity rate
with the inside part of the gas in-
flow conduit removed and replacing original screen No.1 having a perforation
0.142
0.0817
0.102
area of 12.8% with perforated screen No.2, tested in experiment No. 91, having
a perforation area of 28% of the total screen area.
Curves in Fig. 5 depict
the distribution of gas flow velocities over the cross section of the model
precipitator in experillient No. 67 with the electrostatic filter lilodel type C-180
as originally desi5~ed, and in experiment No. 91 with the inside angled section
of the inflow conduit removed and perforated screen No.2 replacinb' original
screen No.1.
Curves were constructed on the assumption that average flow
velocity Wi through the precipitating electrode could be brought up to 2
av
m/sec. without adversely affecting the gas purifying efficiency of the appa-
ratus. This was previously demonstrated by this writer's studies of the aero-
dynamics of electrostatic precipitator type C-140. In fact, production capacity
of the precipitator was enhanced by 48.3%.
-27-
-------
w
Wq
(
EXfJ. 67
t~
w'cp
Exp.
91
Mtp
0.6
4.
42
20
180
1,0 6IJ BQ 100 110 140
Number of electrodes
Fig. 5. Curves of velocities distribution
over the model cross section. Experiment
61 with original screen (No.1) and inside
dmmward angled inflow part, and experi-
ment 91 with original screen (No.1) and
inside gas inflow part removed.
150
The capacity of installed
electrostatic precipitators fully
accorded with the volume of puri-
fied gas under operating condi-
tions in most production plantsp
and there appeared no need to
raise the production capacity of
the installations. Under suoh
conditions the opportunity pre-
sents itself to reduce the ve-
looity of the gas flow for the
purpose of enhancing the degree
of gas purifioation.
In planning
new installations and expanding
activities of existing production
departments full use can be made
of the experienoe and data ob-
tained from the study on the in-
crease of eleotrostatic preoipi-
tator production oapacity. As was previously mentioned, increase in produo-
tivity capacity was attained in experiment No. 91 in which the inside angular
downward directed part of the gas inflowins oonduit was abolished and perforated
distribution screen No.1 was replaced by screen No.2 whioh had a greater per-
centage of "live" or perforation area; in addition, these changes had also
reduced the pressure drop of the entire electrofilter. Thus, as was shown in
experiment No. 61 with model electrostatic filter, the resistance, or pressure
drop of the entire apparatus, which originally amounted to 125 mm of water
column, was reduced to 43 mID after the introduction of the above mentioned
changes 0
Reduction in the dynamic resistance, or pressure drop, thus amounts
to 82 mm of water column in the model, which is equivalent to 4 mm of the water
column in the actual commercial electrostatio preoipitator, on the basis of
total dynamic pressure in the industrial electrostatio filter of 16 mm of
water column. Two diagrams are presented in Fig. 6 of bas flow velocity dis-
tribution over the electric filter oross section with the use of original
perforated distribution screen No.1 as obtained in experiment No. 61, and of
-28-
-------
Experiment 67
~.~
..~ .~~.
t2)~~
~mH .~ ~
~~
~
ExperirlJent 91
~
1-
~ e~e!~
. over 10 m/sec.
~ 8.0-9.9 m/sec.
Ct 6.0-7.9 m/sec.
e 4.0-5.9 m/sec.
~ 1.0-3.9 m/sec.
00.0 m/sec.
Figo 60 Diagram of velocity distri-
bution over the electrostatic pre-
cipitator model with original screen
(experiment 67), and with new screen
and inside projecting inflow part
removed (experiment 91).
sallie velocity obtained in experiment
No. 91 after the previously described
changes have been introduced.
The
Zaporozhie Coke-Chemical Plant has
three type C-180 electrostatic pre-
cipitators in~talled in front of the
sulfur-removing scrubber.
The pre-
viously described changes have been
introduced into one of these filters,
as a result of which its pressure
drop Was reduced and its gas purify-
ing efficiency was increased.
Un-
fortunately, it is not possible to
present actual data regarding the
reduction in pressure drop and im-
provement in gas purification ef-
ficiency for technical reasons.
It
is hoped that introduction of the
same type of changes in the other 2
electrostatic filters will present
the possibility of determining the
slliillllary facts in all 3 electric
filters 0
Conclusions.
An aerodynamic study was made
of the operation of electrostatic
precipitator type C-180 on a 1:10
model basis. The purpose of the in-
vestigation was to arrive at prac-
tical chan6es which IrJight effect
better gas flow distribution over
the electrofilter cross section and thereby reduce its pressure drop and en-
hance its gas purifying efficiency. As a result of such investigation the
following 2 changes have been introduced: a) the inside ~rotruding angular
-29-
-------
downward uirected part of the gas inflow conduit has been abolished; b) the
original perfor~ted g3S distributing screen No.1 which had an open area amount-
ing to 18% of the total screen area was replaced by screen No.2, the open area
of which amounted to 28% and in some cases by screen No.3. Characteristics
of screens Nos. 2 and 3 are described below:
Screen No.2
Screen No.3
Number of perforations
Diameter of perforations in mm
Distance between center to
center of perforations in ulID
Total live or open area in ~ercent
in relation to total screen area
Coefficient of resistance
595
100
160
680
110
160
28.0
2105
35.0
11.8
Bibliography.
1. Cnoco~ BMQHCneHHH K. H. p. onHcaH B C~opHHKe 15, Coo~~eHHH
rHHpOKoKca, MeTannyprH3~aT, 1955.
2. ROKC H XHMHH, 1956, m 4, CTp. 45-49.
Raising the Efficiency of Electrostatic Precipitators, Type C-140.
P. J. Kuleshov.
(Zaporozhie Coke-Chemical Plant).
Koks i ~limiya, 1956, No.4, 45-49.
Electrostatic precipitator type C-140 designed by Giprogazoochistka
(Government Institute for Designing Uas Purifying Installations) is widely
used for purifying coke gas of tars. The designed capacity of the precipitator
is 28,000 nm3/hr, whereas the capacity of a single coke oven battery for gas
is 22 - 23,000 nm3/hr. 1/ Thus, one electrostatic precipitator is required
for cleaning gas produced by one coke oven battery.
A typical coke-chemical
1/ nm3 - adjusted to norm~l temperature and pressure.
-30-
-------
plant consists of 4 coke oven batteries of 65 coke ovens each; it is usually
equipped with 5 electrostatic precipit~tors:
4 in oper2tion ~D~ 1 in rS5srve.
Electrostatic precipitators type 0-140 gener~lly oper~te dt Li6h ef~iciency
and attain a 98% coke gas purification if properly utilized. Ho-"ever, if
type 0-140 electrostatic precipitator is selected v,ithout regard to its de-
si6ned capacity, or if one precipitator is used in serving 2 oven batteries,
the efficiency of the installation l.lay 1'5.11 to 82%.
This situation led to
the present study of :::srodynaraic factors controlling the efficient olJerc:ction
of 0-140 electrostatic precipit~tors.
Tests L'1ade at the Zaporozhie Ooke-Ohen.ic:.:.l
Plant in 1952 - 1954 using an experimental n~odel as \:ell as an oper&ting elec-
trostatic precipitator, type 0-140, have shown [lJ that the fl&t bas distrib-
uting perfor",ted metal screens \Vi th 12 perforations plowed across the Ylorkin€;
chamber of the precipitator in front and behind the precipitating electrodes
did not assure an equalized distribution of the gas flow across the precipitators:
the gas passed in greater volumes through the central tubular electrodes than
throu6h those at the periphery.
A char6e increase in the peripheral tU0ular
electrodes presented the possibility of raisinb the generQl productivity of
the electrostatic precipitators by approxi~&t61y 100%.
For the study of the gas flow distribution across the electrostatic pre-
cipitators, a Qodel electrostatic precipitator ty~e 0-140 ~as u~cie 1/20 of the
original size, in accordance \-li th all usual principles of model .;-,aking.
-aith
this model a study was wade of v2rious constl'uctional eler,:ents dlich normally
affected the 5E1S distribution over the cross section of electrostatic precipi-
tators, and ways were found for increasing their efficiency. Results of that
study were described [2J and incorporuted into practice. New distribution
screens have been installed in the Zaporozhie Ooke-OheLlical Plant electro-
static precipitators Nos. 1 and 3, as recol~ended by the author, Dilich brought
about an increase in the precipitators productivity up to 4.3 - 44 nm.3 lilr, '.vith
a 97% purifying coefficiento
Basic deduca ti ons drri ved d ciurint; thi s study
of Gas flow distribution ivere confirmed inde~endently by I. E. Idel'chik [3J.
Numerous experiwents were performed with individual precipit~tor sections and
correspondin6' gas flow velocity chi:i.rts 118re plott ed.
This ~r&phic ~ethod of
presentin6' gas flow distribution dici not inciic:::.te the t::;i:i.S voluuie ;e.ssed, ,-;hich
should constitute a basic chi:i.re.cteristic of i:i.n appropri~te precipit_tor con-
struction.
It was considered necess2.r;y to develop a criterion ='or the cleter-
-.31-
-------
mination of bas flow distribution over the cross section of a precipitator by
a single value. The comparison of individual tests and the complete evalua-
tion of their characteristics were of importance to this study; for this pur-
pose a convenient determinator was developed, nlliDely, the coefficient of uneven
gas flow distribution - C.D.D., which characterized the deviation in rate
of gas flow from the median.
>.
-P
.r-!
o
o .
rl 0
(j) (j)
:> rn
............
~ s
o
rl Q
<;; .r-!
f-i
.r-!
<~
In Fig. 1 the horizontal line
represents the median gas flow rate
(v ) and the stepped-up curve
av
represents actual gas flow rates.
The median line and the stepped-up
n,
n6
(,~7
n
curve form 2 e~ual areas, the sum
of which characterizes the degree
of uneven bas rate distribution over
Number of precipitating electrodes
Fig. 1. Curve of air distribution
over the precipitating electrodes. the precipitating electrodes in any
electrostatic ~recipitator. This relation, designated here as C.D.D., will
tend towards zero with improvement in gas flow distribution.
Mathematically its value can be expressed as:
Fl + F2
C.D.D. =
v
av
o n
By mathematical transformation it can8e changed to:
va v (Nl - N2) + ~v2 - ~vl
C.D.D. =
vav . n
where v is median velocity of gas flow in m/sec.; Nl is the number of pre-
av
cipitating electrodes where gas flow velocity is below the median; N2 is the
number of precipitating electrodes where gas flow velocity exceeded the median;
r.v2 is the sum of gas flow velocities above the median; ~vl is the sum of gas
flow velocities below the median; n is the number of precipitating electrodes.
Values of C.D.D. derived from this formula present a complete picture
of gas flow velocities distribution across the electrostatic precipitator.
This coefficient was used in the st~dy of the effect of screen design and of
other construction elements in electrostatic precipitators on the distribution
of gas flow, etc. Of all construction details greatly affecting the gas dis-
tribution across electrostatic precipitators, the way of gas delivery is the
most essential. The pxesent way of gas delivery to electrostatic precipitators
-32-
-------
type C-140 create whirling and turbulence in front of the perforated dis-
tributing screen and greatly affect gas velocity distribution. These flows
and turbulences were recorded visually by a special silk thread screen and by
a horizontal pneumametrical manometer tube.
Several ways of gas delivery were studied in an attempt to lessen the ef-
fect of gas delivery on gas flow velocity distribution.
o
rl
~ 40
~
Q)
-P
rn
E:
lIT!
I I I I
LJJ
,
~ !
~ 30
>::
.r!
Q)
~
;:j
i1J
~ 20
~
~
C)
.r!
~
>::
~fO
}EXP.
I / I 42
\.}/ I
'+-1 !
I ' I
II I '
I I
I I I
- -r-- --,-
, I
i~
"-
"
"
5J /if 57 59 10
of electrodes
Fig. 2. Curves of dynamic air
pressure distribution along I-I
section; solid curve with inside
6as inflow extension; dash curve
with inside inflow extension
removedo
~
~
electrodes
fig. 3. Curves of velocity changes
in the precipitatin€ electrodes
along II-II section; solid curves
lith upper perforated screen; dash
curves with upper screen removed.
A lateral gas inflow
was tried in connection with a distributing
screen which was made previously in con-
nection with central gas inflow resulting
in poor gas flow distribution.
are plotted in Fig. 2.
Results
Curves in Fig. 2 show that distribu-
tion of .gas flow velocities resulting from
lateral gas inflow (Test No. 42) improved
as compared with the central gas delivery
(Test No. 26).
This accorded with the
C.D.D. values which were for Test No. 42 -
0.187 and for Test No. 26 - 0.427.
Thus,
installing a lateral gas delivery and
eliminating the inside part of the bas
inflow conduit considerc..bly improved the
gas distribution across the electrostatic
precipitator without additional construc-
tional changes; it also lessened the pres-
sure drop of the electrostatic ~recipitator.
The perforated screen constituted
a basic factor in gas flow distribution
across the electrostatic ~recipitator.
Therefore, most of the research was
given to the study of an appropriate
screen construction.
Air flow velocity
determinations were made at several
electrost&tic precipitator cross sections
during its work with and without the up-
per section.
Results of these tests,
-33-
-------
at cross section II-II, are plotted in Fig. 3. It can be seen that both curves
ran a near parallel course, indicatiQg that the upper distributing screen had
no effect on gas flow velocities. Therefore, in the Zaporozhie Coke-Chemical
Plant all ~op distributing screens in all electrostatic precipitators have
been removed, which reduced the precipitator pressure drop.
A study was made also of several types of distributing screens; with a
"live" (perforation) area of geometric similitude and with "live" areas of
geometric dissimilitude.
Results have shown that distributing screens of the
geometric similitude type did not bring about even distribution of gas flow.
It has been known that in the presence of turbulence gas flow velocities at
the walls of an electrostatic precipitator were considerably lower than in the
center. Therefore, distributing screens of geometric similitude "live" design
did not assure a uniform distribution of gas flow across the entire cross sec-
tion of an electrostatic precipitator.
More effective distribution of the gas
centrically towards its periphery.
flow can be achieved by the use of a screen with a resistance decreasing con-
The latter condition can be achieved either
by increasing the number of perforations or their diameters concentrically in
direction of the
i><
H
Q)
+"
co
i!;
~ 30.
s::::
0'-;
20
o
0'-;
~
s::::
~
Fig. 4. Curves of dynamic
pressure distribution in the
precipitating electrodes.
Thus far no one has offered a method
for the calculation of such a screen.
In an attempt to equalize gas flow ve-
locities, a screen was made in which the
"live" or open area was in a reverse ratio
to the corresponding gas flow velocities
in front of the screen.
Screens, made on
this principle, were tested under regular
working conditions and yielded good re-
sults. Other attempts were made to in-
crease the gas velocities at the screen
periphery by using a screen with a larger
"live" or open section and with a ring-
shaped slit around its periphery. The
"live" section or area of openings of this
screen amounted to 32%. Results of such
experiments have shown that a screen of this
type improved considerably the gas dis-
-34-
-------
tribution across the electrostatic preci~it~tor.
Fig. 4 c0ntains dynawic
pressure distribution curves of the model electrostutic preci~it&tor, which
~as tested with the usual screens of even, and exp8ri~ental screens with
varL.ible perforation distributions und "'lith a screen having a ring-shaped
slit around its ~eriphery.
in the following table.
C.D.D. vulues of corresponding tests are listed
Effect of "live" screen area (total perforated area) on coefficient
of uneven velocity distribution.
Experi-
ment No.
: , : "Live" : Screen:
:Screen: :.:
: :screen area:reslstance :
: No.4: . t: ff . . t :
: :In percen :coe lClen:
C.D.D.
26
44
50
49
46
52
54
56
58-62
(averages)
10
1
8
3
9
5
11
12
13
1106
15.2
8.2
30.0
27.8
2203
26.8
37.9
32.0
177 .0
96.5
379.0
18.5
22.5
39.6
24.3
9.6
15.4
0.427
0.365
0.284
o . 235
0.227
0.146
0.180
0.237
0.066
bcreen type
Screen perforations of
geometric similitude
Ditto
Di tto
Ditto
Ditto
Screen perforations of
geometric dissimilitude
Ditto
Ditto
Peripherul ring-shaped
slit
A screen with a ring-shaped peripheral slit brou~ht about best gas dis-
tribution; it was easily machined, it lowered the pressure drop of the electro-
static precipi to. tors , it did not require preliminary calculations ; it can be
recommended for all electrostatic precipit~tors built with a centrally located
inside gas delivery.
On the basis of test results obtained with a model, a
screen as described just above with a riQb'-shaped slit at its periphery, was
made and tested under actual plant conditions in one of the operating electro-
stLttic precipitators.
Duta on giiS velocities ,vitL this screen cOLJpared with
those obtained I'li th the old type screen VJ8re plotted in curve form in Fig. 50
Course of the curves in Fig. 5 shm'l that .vi th the new t;ype of screen gas
distribution velocities across the electrostatic precipitator considerably
improved, which permitted to increase its productivity by nearly 100% without
lowering its gas purifying efficiency.
A supplemental study was made of the effect of fastening the lo~er ends
of the precipit~ting electrodes on the productivity of the electrostatic pre-
-35-
-------
o
0)
ill 49
'S-
s::: 117
.r!
~I
5'1
Fig. 5. Curves of air
velocity distribution in the
precipitating electrodes; solid
curve with original (old)
screen; dash line with new
design distribution screen.
cipitators.
It has been known that the
manner in which the tubes were fixed at
the bottom partition in the precipitators
and the thickness of the tube walls de-
termined the uJOde of the gas entry into
the tubes, which had a considerable effect
on the resistance coefficient of the tubes
[4J. The nearer the gas entrance was to
the partition wall, the smoother was the
turning action of the gas flow at its en-
trance into the precipitating tubes and the
lesser was the resistance. In the electro-
static precipitator model used in this study
the lower ends of the tubular precipitating
electrodes were fixed flush with the partition wall.
A study was made of the
Fig. 6 shows the effect of the
gas flow distribution over its cross section.
manner in which the tubular electrodes were fastened to the partition wall
on the air or gas flow distribution over the cross section of the model electro-
static precipitator.
s:::
.r!
0)0
Hrl
~ i>4 IHJ
ill
0) H
H 0)
PI+>
(1j
o ~
.r!
~ ~ 1.
s:::
A>
The C.U.D. values also support the significance of the
manner in which the tubular electrodes are
57
"9
6"
53
67
69 70
65
Number of electrodes
Fig. 6. Curves of air pressure
distribution along section I-I;
solid curve with electrodes not
fixed to end wall; dash line
curve with electrodes fixed to
end wall.
fastened or suspended in the electrostatic
precipitators. For example, in test No.
26, where the tubular electrodes were not
fixed to the partition wall, the C.U.D.
was eQual to 0.427; in test No. 41, where
the tubular electrodes were fixed to the
partiti9n wall, the C.U.D. was 0.149. The
above facts show that fixing of the tubular
electrodes to the partition wall signifi-
cantly affected the gas distribution inside
the electrostatic precipitators. This fact
should be taken into consideration in the
newer designs of the electrostatic precipi-
tators.
-36-
-------
Conclusions.
1.
The described method of evaluating uneven distribution of bas flow
velocities (C.D.D. - coefficient of uneven distribution) permitted to evaluate
objectively and with precision the effect of the precipitator design on the
gas flow velocities distribution.
2.
The upper distributing screen had no effect on the distribution of
the gas flow across the electrostatic precipitator, and should be removed.
30 Removal of the gas delivery extension from inside the electrostatic
precipitator reduced the pressure drop and improved the gas flow distribution
across the electrostatic precipitator.
4.
A distribution screen with a variable "live" area (geometric dis-
similitude type) and with larger openings at its periphery considerably im-
proved the gas flow distribution.
5. The best gas flow distribution over the electrostatic precipitator
cross section was attained with a screen having a large (32%) and even "live"
(opening) section over its entire area and a ring-shaped slit at its periphery.
The resistance of this screen was low, it was easily machined and its installa-
tion is recommended in all industrial electrostatic precipitators C5J.
60 The installation of this new type of screen in an industrial electro-
static precipitator resulted in a 100% increase in its productivity without
noticeable lowering in its gas purifying efficiency.
Such increases in the
productivity of the electrostatic precipitators makes possible a 40% saving
in equipment investment.
7. Fastening of the precipitating electrodes onto the partition walls
considerably improved the gas distribution across the electrostatic precipi-
tator and lowered its hydraulic resistance (pressure drop).
Bibliography.
1. fl. H. KYMUlOS. I1CCJle.aOBaHHe a3po.aHHaMHKH 3JleK-
TPocllBJlbTpa C-140. cCoo6IUeHHe fHnpOKoKcu, Bbln. XII,
MeUJlJlyprH3.aaT, 1954.
2. fl. H. KYMUlOB. 113yqeHHe Ha IoIO.aeJlH .aBH>KeHH!I H
pacnpe.aeneHB" nOTOKOB ra3a no CeQeHHIO 9J1eicrpoctiHJlb-
Tpa. cCoo6lUeHHe fHnpoKOKcu, Bb/n. XV, MeTlJIJlyprH3-
.aaT, 1955.
3. H. E. HiJellb'lulC. Pacnpe.aeJlelfHe nOTOKOB KaK cpe.a-
CTBO nOBb/lUeHH!I 9(jJ(jJeKTHBHocTH 9J1eKTp04lBJIbTpOB.
cl(OKC II XHYH":' N2 I. 1956.
4. H. E. HiJeJlb'lUIC. fH.D.paBJIHQecKoe c:onpoTHBJleHHe,
r0C9HeprOH3.aaT, 1954.
5. fl. H. KYIieUlOB. 113MeHeHHe KOHCTPYKI{HH pacnpe.ae-
JlHTeJlbHOA pelUeTKH B 3JleKTP<>4tHJlbTpaX C-140. C60pHHK
pal{HOllaJlH3aTOpcKHX npe.aJloJKeHHIi, BHe.apeHHb/X B npo-
H3BO.aCTIlO. Bb/n. 56, MeTaJlJlyprH3)laT. 1955.
-37-
-------
Construction Defects in Tubular Electrostatic Precipitators (Electrofilters).
P. J. Kuleshov.
(Zaporozhie Coke-Chemical Plant).
Koks i Khimiya, 1958, No.1, 43-46.
Electric precipitators types C-140 and 0-180, used in coke-chemical plants,
have many construction defects which lo~er their efficiency and complicate their
use.
The following is an analysis of their fundamental defects followed by
sug66stions for their elimination.
Defects in insulating boxes and insulators.
Many plants recently experi-
enced breakdowns of base insulators PO-l while the electrostatic precipitators
were operating.
This was accompanied by gas ignition and conse~uent stoppage
of the precipitators! work for long periods of time. A study of the cause of
the insulators! breakdown showed that the construction of the corona-electric
holders was faulty and could not ITlaintain uninterrupted operation of the elec-
tric precipitators.
The base insulators broke down due to the fact that their
inner surface was in the gas atmoslhere of the electric precipitator where the
temperature was nearly constant.
The outer surface of the insulators ~as heated
by the steam jackets of the insulator boxes.
The steam pressure was subject
to con@on fluctuations within the conduits, and there were sporadic steam shut-
downs for heating purposes.
Under such fluctuations in the surrounding tempera-
ture the insulators developed cracks, filled with air and soon broke down. The
air inside the insulator boxes gradually formed an explosive mixture resulting
in danger of explosion by a short circuit spark at times when current tension
overlapped on the surface of the base insulator.
~uperficial instead of care-
ful investigation of the conditions existing inside the insulator boxes also
contributed to this situation.
Gas penetration into the inside of the insulator box also occurred through
leaks in its protective lining. The protective lining must be made of a high
quality lnaterial, such as technical grade glycerin and litharge, which has a
sufficient density and good mechanical qualities. It is clear that maintenance
of strictly constant temperature is of primary importance in preventing the
destruction of the base insulators. Accordingly, it is necessary to place a
reducer on the heating system pipeline, so that the steam for heating the in-
sulator box will never be cut off. This will consider~bly improve the working
-38-
-------
conditions of the base insulators. Newly constructed tubular electric precipi-
tators should be provided with an electrical heating system for the insulator
boxes and should be equipped with means for rebulating their temperature by
remote control. At the Zaporozhie, Voroshilov and other coke-chemical plants
insulators PO-l had been replaced by a chain of 4 suspension-type insulators
PTs-4.5. This change removed the cause of insulator cracking and the precipi-
tators breakdown. The Government Institute for Desigining Gas Cleaning In-
stallations (Giprogazo-ochistka) recently designed new electrically charged
insulator boxes for electric precipitators C-7,2 with a passing through in-
sulator PNV-35 and a chain of insulators P-4.5 or PTs-4.5. To assure a depend-
able operation of this particular assembly in electric precipitators types C-140
and C-180, it is recommended that the insulator boxes and the supports for the
corona-electrodes be chdIlged according to the design worked out by the "Gipro-
gazo-ochistka" as shown in Fig. 1.
Blow-off
candle
Insulator P-4.5
Protection box
for PNB-35
Insulation
boxes
.'-'i
PNB-35 \'
Electricity ,9s
supply t:]; I
-------
degree of electric tension delivered to the electrodes. Regardless of the fact
that electric precipitators types C-140 and C-180 were desi~TIed for 70 ~v, most
plants operated them at below 50 ~V, because of previous experience YJith de-
fective precipitator construction and installation, when tension exceeding 50
KVv, caused spark-overs between electrodes and short circuiting. Feeding low-
ered electric tension to such electric precipitQtors served also as a reserve
for efficiency improvement. According to the theory of electrostatic pre-
cipitation of suspended particles an increased tension enhanced the gas puri-
fication efficiency of the precipitator. Therefore, in installing electro-
static precipitators serious attention must be paid to the Quality of the
precipitating electrodes and to the proper adjustment of the corona-electrodes
in order that the potential they have been designed for may be attained.
This
can be accomplished by using a steel wire of not less than 3.5 - 4 mlm in di-
ameter as the corona-electrodes. Under such conditions corona ignition will
occur at a potential higher than in regularly used corona-electrodes of 2 mlm
in diameter.
Such increase in the diameter of the corona-electrodes will also
increase their mechanical stability.
This is of importance to precipitator
operators, since most breakdowns were due to short circuits caused by torn or
burned-out corona-electrodes.
The wire used for the corona-electrodes must be
of highest Quality, without dents or nicks, well annealed and thoroughly
straightened out. Extreme electrode strain by weights or by the corona-frame
should not be permitted. The weights which keep the electrodes straight shall
pull freely over their guides (bearings) in the lower corona-frame and shall
have carefully machined long necks for attachment to the corona-electrodes.
As a rule, corona-electrodes are made of steel wire; however, in one of the
precipitators of the Zaporozhie Plant the corona-electrodes were made of 2 mlm
high chrome content nickel-chrome wire. They have been in operation for one
year, and are still in good working condition. Corona-electrodes should not
be made of low chrome cuntent chrome-aluminum wires because of their rapid
deterioration.
Inoperative precipitating electrodes. The most important construction
defect in electric precipitators now in use and in those now being designed,
is that not all precipitating electrodes are active gas purifiers. For example,
4 precipitating electrodes in electric precipitator type C-140, and 6 elec-
trodes in precipitator type C-180, through which pass the weights supporting
-40-
-------
Ghe lower frame of the corona-electrodes, did not function as gas purifiers.
i}iprogazo-ochistka must take this into considerution and must make chan68s which
Mould enable all precipitating electrodes of the electric precipitators to
operate at full efficiency. Converting the tubes, through which pass the weight
supporting the lower frame of the corona-electrodes, into precipitating elec-
trodes would improve consider;J.bly the gas purifying operation.
Improved gas distribution in-the electric precipitators. Studies made by
the Zaporozhie Coke-Chemical Plant, as vlell as by the Girpogazo-ochistka, brought
out construction faults in electric precipitators types C-140 and C-180, which
caused uneven distribution of gas flow over the working cross-section of the
precipitators and which lowered their efficiency.
One of the construction
elements that affected the distribution of the gas flow over the entire cross-
section of the precipitators was the way gas entered the precipitator.
The
gas conduit extension inside the precipitator obstructed part of the distributi~g
screen. A conical device installed at the entrance was suppos8d to equalize
the gas flow over the cross-section of the precipitator; instead, it created
turbulences and vortexes which aggravated the existing gas distribution uneveness.
In studying the aerodynamics of the precipitator, it was found that a lateral
delivery of the gas and removal of the gas delivery protruding inside of the
precipitator improved the cross flow distribution of the gas.
This improvement
also lowered the pressure drop of the precipitators.
The basic effect on gas
distribution throughout the entire cross-section of the precipiti..ttor was ac-
complished by the distributing screen.
Precipitators ty~es C-140 and C-180
have 2 identical gas distributing screens - one in front, and another in back
of the precipitating electrodes.
Elsewhere (see Koks i Khi!1liya, No.4, 1956) it was shown that the upper
distributing screen played no part in the gas distribution. On the contrary,
by creating an additional point of resistance, this screen wade servicing and
access to the corona- and precipitating electrodes difficult.
is recommended that the upper distributing screen be removed.
Therefore, it
Existing lower
distributing evenly perforated screens in the precipitators did not assure
proper and equal gas flow distribution across the precipitator.
To rewove this
deficiency in the Zaporozhie Coke-CheDlical Plant different screens were used
with wore free openings and with an additional circular slit around its edge
(see Fig. 2).
-41-
-------
~f26'~m ~ 3
----- ----~ ~_2~0 - _t - -~
C:>
<::>
'>
,.---.,
..--r ,- '--
---: . -~ \)
../
112' ~ ~ Ie ~
I /. .~..
~$- $~$-o $
675 ( ~ 1$0 ~ IH-
~ ~ ~~ ~4I.
~
800 0-& ,1' t\~~
~ 1~oO $ ..
. I
,,,, $ t
,r--.
.... ,,,,,
';',
8fO ~ ~~ to
700 v
1175 .0 'i
! $-.
"~ 7'
t--
;.:
'<>
<>-
Figo 2. New type distribution
screen for electrostatic
precipitator C-140.
The open gas passing area in this
type of screen was 32.0% instead of
11.6% as in the old type of screen.
The new screen assured an adequately
equalized gas stream distribution over
the entire transverse section of the
precipitator
the capacity
and practically doubled
of the precipitator without
gas purifying efficiency.
lowering its
Moreover, this type of screen aided in
the run-off of the tar and reduced the
pressure drop of the precipitator.
An
improvement in the gas flow distribution
over the cross-section of the precipi-
tators was achieved also by installing
2 screens instead of one, as in the new
C-7,2 precipitator designed by Gipro-
gazo-ochistka. Another serious fault
in the construction of the electric }Jrecipitators was the single terminal
fixation of the precipitating electrodes. The upper ends of the tubular pre-
cipitating electrodes were attached to a special screen by means of seams flush
with the screen body. The lower ends of these precipitating electrodes were
left hanging freeD The gas entering the intertubular spaces created a turbulence
Tests showed that by
directly at the entrance to the precipitating electrodes.
the gas flow distribution over the
fastening the lower ends of the electrodes
lowering in the pressure drop.
enitre cross-section of the electric precipitators improved, accompanied by a
It must be stated here that Giprogazo-ochistka,
in its latest designs of electric precipitators, removed many constructional
defects in types C-140 and C-180 electric precipitators. For example, the 1'01-
lowing improvements have already been incorporated:
the upper distributing
screen was removed, flow distribution through the entire cross-section of the
electric precipitators was improved by removing the projecting inflow conduit
from inside the precipitators and installing 2 distributing screens in its
place; the construction and operation of the suspended insulators were markedly
improved; provision was wade for a blow-off valve; the precipitator housing
-42-
-------
was heCit insulated; many additional chanb"es ';;ere incorporated 'lihich improved
considercibly the efficlency of the electric precipitators.
Cut-off slide 6ates or valves in the
off the electric precipitators in case of
electric precipitators. For shutting
accident, or for regularly planned
6ates (valves) in the front and in
repairs, the closing 0: the cut-off slide
the back of the precipitators has De en done usually by hand, '.,hich consumed
much time and the services of several men working simultaneously.
Ignition
of gas in the precipitators occurred lately in several plants necessitating
their rapid shutting 01'1'0 None of the plants made extra provision for such
an eillergency and the shutting-off of the slide gates (valves) was usually
uelayed. This brought to the forefront the necessity for fast servicing of
the shut-off slide gates (valves) at both ends of the electric precipitators
by means of an electrically operated remote control.
This should expedite
the shutting-off and the starting of the electric precipitators.
Furthermore,
this arrangement should facilitate the control of electric precipitators'
operation.
Determination of O~Yhen content in the gas.
The major drawback in bX-
ploitation of electric precipitators, which are usually placed in front of
gas blowers, is the need for constant control of the 6as oxygen content.
A
considerable vacuum, existing in this part of the gas conduit, is the cause
of air sucking into the bas conduit \Ii th a formation of an explosive mixture
and a consequent danger of ignition of this air and Gas mixture inside the
electric precipitator.
For the detection of such danber the gas in the elec-
tric precipitators must be tested reb~larly every half-hour for oxygen content,
using a hand gas analyzer type GKhP-3.
Hence, a competent analyst ItlUst be
always on duty in the section of the electric precipitators.
Such arrangement
for gas-oxygen control cannot be regarded as satisfactory because:
1) the de-
termination of oXYLen concentration in the gelS test tube is usually delayed,
since it takes 10 - 15 fllinutes to make just the analysis; 2) it requires full
time duty of a special wan at the electric yrecipitD.tor.
Instead, the ex-
plosive focus should be detected by an automatic gas analY:0er at the point of
air sucking in; it should be equipped \'Ii th an automatic signal system adjusted
for a maximwn permissible oxygen content in the b'as.
Gas load of the electric precipitators and their designed production ca-
paci ty .
The efficiency of electric precipitators is closely rel~ted to their
-43-
-------
output capacity. The latter must be coordinated on a parallel basis 0ith the
gas output capacity of the coke ovens. Lacking this, the electric precipitators
cannot be used efficiently. For example, the production capacity of electric
precipit~tor type C-140 is 28,000 m3 of normal bas. According to Giprokoks
(the Goverrunent Institute for Designing Coke Plants), purification of gas re-
ceived from each coke oven b2ttery of 22,000 - 23,000 m3 of normal gas required
the installation of one type C-140 electric precipitator. A aiscrepancy will also
be found upon comparing the gas producing capacity of 4 or 6 coke oven battery
plants with the gas cleaning capacity of 2 or 3 electric precipitators of type
C-180 used for cleaning coke gas of tar and oil.
It must be mentioned that the throttle valve at gas exits in electric pre-
cipitators designed for rebvl~tin6 the voluwe of 6~S passing through them were
not usable, due to lack in the original design of devices or instructions for
maintaining any desired volume of gas flow.
at the earliest possible opportunity.
This deficiency should be corrected
Mechanization of the Gas Analyzer ORSAT.
A. P. Razbegaeva.
(Zaporozhie Coke-Chemical Plant).
Koks i Khimiya, 1958, No.4, 53-54.
Control of coke oven heating is based on the analysis of its combustion
products (6'ases) and concentrd.tions of C02' 02 and CO. The simplest and lJ.jost
frequently used apparatus in such control work is gas analyzer O~SAT. Trans-
fer of the combustion b~ses from the burette into the absorption tube of b~S
analY:6er OB.SAT VJas usually done b;y laboratory technicians by Iilanually lowering
and raising the water pressure flask. Generally a laboratory technician work-
ing \Ii th one gas analyzer;Jas able to make up to a maximum of 25 analyses in an
8-hour working day, thus requiring the services of at least 3 or 4 laboratory
technicians to check the oper~tion of 6 coke oven batteries. To facilitate the
-44-
-------
work for the laboratory technicians and to increase their productivity the
Zaporozhie Coke-Chemical Plant developed a method for mechanical transfer of
the resulting gases from the burettes into the absorption tubes.
This appa-
form an assembly unit.
ratus consists of a water pressure flask and a rubber bulb or balloon which
Each gas analyzer must be equipped with such an as-
sembly. As shown in the schematic drawing each rubber bulb is operated by a
spring type pusher activated by one of several eccentric cams on a common
shaft. The cams are set so that at a given time interval only one pusher is
brought into action.
The device operates as follows: as shown in the schematic drawing each
section of the mechanism consists of a rubber bulb (balloon) connected by a
2 3
«
o
10 II 9
'" ~-~"5;e:-,t'll [QZj::-1
'\'. ! 0;' -'?t-.{ ~) ,
\ ':""1''';'' ~~ _../ ... .,--'
.~ . ~ . "
~~H~~IJ'~~~'~l f,F1TJ1~~ I
/ ~~1L .~ ~~ ,,~
I /',1 /
I
/
/
2
7
3
6
5
12
II
GI
.D
"
-+'
...
II>
.D
.D
"
a:
4
Plan of mechanized gas analyzer work.
1 - Electric motor; 2 - coupling; 3 - reducer; 4 - water pressure flask; 5 -
cam; 6 - shaft bearing; 7 - shaft; 8 - panel; 9 - pusher; 10 - pusher rod
director; 11 - vertical stay; 12 - rubber ball.
-45-
-------
rubber tube and rubber stopper to a ~ater-filled pressure flask .Ihich in turn
is connected to the burette of the ORSAT gas analyzer. As the eccentric earn
advances the pusher, the latter compresses the rubber bulb forcing its air
into the wLter pressure flask, then forcing the water into the burette, forcing
the combustion gases collected in it to pass into the absorbing tubes of the
gas analyzer. As the pushers gr2dually return to their neutr~l positions the
rubber bulbs expand and suck in the ::tir, thereby releasing the pressure within
t~a ~l~sk; the replaced water returns from the burette into the pressure flask
.Ihich in turn creates a partial vacuum in the burette and tie g~ses return from
the absorber ~~)aratus into the burette.
1'he mechanism is built to operate 4
rubber bulbs each connected to a separate ~ressure flask, thus servicing 4
O.dd~cI.'r ana1.yzer,:; ':5L,ul t.::..neously j e~B,bling one laboratory technician to attend
to 4 bas analyzers and to perform about 90 analyses in an 8-hour shift.
Since
each bas an~lyzer has its own b~lloon, pressure flask and burette, the analyst
n!ay, if he wishes, incorporate more apparatuses into operation or he may dis-
connect some from the chain.
Moreover, the independent operation of each unit
enables tDe use of the setup whether all or only part of the units are in
operation.
The analysis is performed as follows:
the gas sample to be tested is
collected manually into a calibrated burette.
From the burette 30 01 of the
gas is transferred, again manually, into the absorber apparatus after y,hich
the apparatus is connected with tte rubber balloon.
Such a procedure will
prevent the sucking in of the absorbing fluid from the absorber apparatus into
the burette caused by 6as volume decrease as the result of partial gas absorp-
tion.
The apparatus is attached to the rubber balloon when the latter is at
the start of the compression stage.
The remaining units are then attached
consecutively as described above.
After all units have been attached, the
first unit is disconnected,
the 6dS is transferred into the calibrated burette
c.nd the residual o'QS volume detenl,ined.
The volume difference is a ilieasure of
the C02 content. Thi]~y ml of the bas are then transferred from the measuring
burette into the second absorber apparatus for 02 absorption, and the apparatus
abain placed into operation. An identical procedure is used in determining the
CO contento
Results of the tests mCide \'Ii th gas analyzer ORSAT manually and by the
automatic procedure are listed in the following table.
-46-
-------
Results of compur~tive analyses.
Percent of
absorbed C02
Mechanized: Manual
apparatus ~apparatus
: Percent of
~ absorbed O?
:Mechanizedz Manual
~apparatus ~apparatus
24.2 24.0 0.6 0.8
22.6 22.4 2.2 2.4
8.6 806 4.6 4.4
23.8 2306 1.4 106
6.8 7.0 5.2 5.4
23.2 23.4 1.4 1.4
6.4 6.4 4.2 4.4
19.4 19.2 4.8 5.0
24.0 24.2 1.0 1.2
23.8 23.6 1.4 1.6
Data in the table show that
differences between the testing
procedures were within error
limits normal for an apparatus
of this type.
Adoption of the mechanical
procedure of combustion gas
analysis facilitated the work
of the laboratory technicians,
increased their productivity,
and freed one technician for
other lacoratory work.
The ap-
paratus is now in continuous
smooth operation.
A Venturi Appar2.tus for Ammonia Absorption from Coke Gas
vii thout an Atomizer.
P. A. Semenov, Yu. V. Tumanov and O. S. Chekhov.
(From the Moscow Institute of Chemical Machine Building).
Koks i Khi~iya, 1960, No.8, 34-37.
Present day apparatus used in the chemical industry in connection with
mass exchange processes are the lliost metal consuming and the le2st efficient.
Attempts made by many investigators to enhance the process of mass transmission
resulted in the construction of different types of apparatus operated on the
direct current principle which sharply enhanced the comparative rate of phase
movement and as a consequence, the apparatus efficiency.
The Venturi appa-
ratus equipped with an atomizer is a bood example of same.
~ll Venturi appa-
the throat.
ratuses can be divided into 2 groups on the basis of water introduction into
To the first gTOUp belong Venturi apparatuses in which the water
-47-
-------
is brought to the throat by pressure; to the second group belong apparatuses
in which the water is injected into the throat by the gas flow itself (see
Fig. 1). A Venturi apparatus without the atomizer feature has many advantages
over absorbers in which the liquid is supplied by pressure. Among such ad-
vantages the following are the most important: 1) the simplicity and compact-
ness of the construction due to the fact that the absorber and separator are
combined into one feature; 2) absence of the sprayer and of the supplemental
parts such as delivery pumps, intermediate containers, communications, etc.;
3) the ease with which circulation of the liquid can be attained by the over-
flow attachment (see Fig. 1); 4) the ease with which a many-stage apparatus
can be assembled from the construction parts shown in Fig. 1 without resort-
ing to additional equipment when it is necessary to separate the spray from
the water delivery at different stages.
On the basis of these advantages it can
be recommended that an atomizer-free Venturi
be constructed for wide acceptance by many
industrial production plants and particularly
by those which deal with suspended dust-con-
taining gases or with gas-liquid systems which
Gas
inflow
form sediments in the course of processing
Ll]. Among mass exchange processes accom-
panied by sediment formation the most widely
used is absorption of ammonia from coke gas
by a weak solution of sulfuric acid, which
forms crystalline ammonium sulfate separated
Fig. 10 Basic plan of spray-
free Venturi absorbero
in the absorption process.
Bubblers in use
at present in connection with this process
are bulky, cumbersome and are characterized by a pressure drop of 500 - 600 rnm
of water.
It had been suggested that the Venturi absorber equipped with the pressure
method of liquid supply into its throat be employed for the intensification of
the rate of ammonia absorption from coke gas. Results of experiments performed
by these authors along the above-suggested lines indicated that the Venturi
absorber possessed a number of advantages over the bubbler. However, the use
of the Venturi in its present construction can not be applied to the gas puri-
-48-
-------
fication process under consideration because the ammonium sulfate crystals
separated from the solution invariably clogged the atomizer and all connec-
tions leading from ito
On the other hand, methods could be found to eliminate
the separation of the aUllilonium sulfate crystals as suggested by M. D. Kuznetsov
and others, by preventing the solution from reaching the point of saturation.
The attainment of this necessitated complication of the system because supple-
mentary parts must be added to the installation for the solution evaporation
and crystallization.
This invariably leads to an increase in the size of the
installation which is the complete opposite of the principles of simplicity
and compactness characteristic of the Venturi absorber. The same authors
suggested that the process of absorption be accomplished in two steps or stages.
If this principle is to be followed the installation would be even wore complex
than the bubbler installation and its dimensions would be still bulkier.
In
addition, there is no g~arantee that danger of the atomizer clogging by foreign
and adventitious solid particles would be eliminated.
Above considerations led
the present authors to conclude tLat the process of ammonia absorption from
coke bas by sulfuric acid could be best accomplished by means of Venturi ab-
sorbers minus the atomizers in which the injection liquid was carried by the
gas flow itselfo
Therefore, a study was made of the Venturi apparatus built
on such principles.
As a first step a study was made of mass transmission in
the gaseous phase by the method of water absorption of ammonia from the air-
ammonia mixture. Simultaneously with the mass transmission a study was made
of the apparatus hydraulic pressure (pressure drop) in relation to the flow
rate of the gas through the Venturi throat (w) and rate of spray (L/G). Am-
monia concentration changed upon entering the apparatus within the limits of
0.5 - 2.0% by volumeo
Studies were conducted within velocity limits of air-
ammonia mixture in the Venturi tube throat ranging from 30.0 to 72.5 m/sec.
and spray chan6es ranging between 0.3 and 10.0 li/nm3 of the gas. Air con-
sumption was deterriJined by pressure transmission to a normal diaphragm set at
a sharp angle.
Fluid consumption was recorded by a flowmeter.
Ammonia was
delivered from a gas pressure tank controlled by a needle valve and a flow-
meter.
Every experiment was evaluated on the basis of ~aterials used and
produced.
Three types of Venturi apparutus were investigated in which the
conic diffusor angles differed. The throat diameter in each of the Venturi
apparatuses measured 20 mm, length of throat 3 Ulill, and the conic diffusor
-49-
-------
o
angles were correspondingly 8, 11 and 30. Results of experiments with masS
transmission indicated that with value of L/G equal in all ca~es and rate of
gas w the productivity coefficient of the apparatus in all three instances
r
was the same, indicating that the conical diffusor angle had no effect on the
degree of ammonia absorption as shown by curves in Fig. 2. The dash curve
in this fig~re is a plot of the functional relationship between productivity
coefficient and gas flow rate in
tests with rate of ammonia absorp-
y~
'00
90
60
70
M1.,.
"
50
.
.50 51
J6 44
6D
71J Wr m/ see
Figo 2. Functional relation between
coefficient of productivity efficiency
and gas flow rate inside the apparatus.
Solid curves - ammonia absorption by
water; dash curve - ammonia absorption
b3 acid.
Spray L/G = li/nm: 1 - 10; 2 - 9; 3 -
8; 4 - 1; 5 - 6; 6 - 5; 7 - 4; 8 - 3;
9 - 2; 10 and 11 - 0065.
tion by a solution of sulfuric
acid. Concentration of sulfuric
acid was 6.8%, rate of spray 0.65
li/nm3. A comparison of this curve
with a similar curve produced when
water instead of sulfuric acid was
used under identical conditions of
spray rate indicated that in both
cases the productivity coefficient
had nearly identical values, or to
be exact, in case of sulfuric acid
it rose by
M. D.
rators (2J
5% only.
Kuznetsov and collabo-
studied ammonia absorp-
tion from coke gas by an ammonium
sulfate solution acidified w~th
6.0 - 6.5% H2S04 and attained a 91 - 99.8% absorption accompanied by low rate
of water consumption ranging between 0.35 - 1.1 li/nm3. The solution acidity
gradually fell to 4.0 - 4.5%. The original ammonia concentration in the gas
was ~ 10 g/nm3. These authors noted a contradiction in the correspondence
between the data and the rate of absorption as recorded by those authors in
the report citedo
Thus, a simple check calculation indicated that with a rate of liquid
consumption amounting to 0.35 li/nm3 the reported rate of gas absorption
ranging between 91 - 92% would be unobtainable even in instances in which the
entire acid would enter into the reaction, and that under such conditions
maximum degree of gas absorption would range between 19 - 80% and never above.
-50-
-------
On the other hand, if the acid concentration were 4.0 - 4.5%, as shown by those
authors, then with a rate of liquid consumption equal to 0.35 li/nm3, the rate
of absorption should not exceed 34%, at rate of liquid consumption of 0.65
li/nm3 the rate of gas absorption should not exceed 56%, and at the rate of
liquid consumption amounting to 1.1 li/nm3 the gas absorption should not ex-
ceed 95%. Accordingly, the data on mass transmission obtained with experiments
in water absorption of alMlonia can be applied with a reasonable degree of ac-
curacy to ammonia absorption with weak solutions of sulfuric acid.
f(J{J(J
" mm water C18
8fJO
6fJO
"10
100
,.
JO
'"
70 wr m/ see
(0
Fig. 3. Functional relation between
pressure drop loss and gas flow rate.
Solid curves - pressure drop of spray-
free absorber; dash curve - absorber
pressure drop according to
M. D. Kuznetsovo
Spray L/G = li/nm3: 1 - 10;
8; 4 - 7; 5 - 6;.6 - 5; 7 -
9 and 12 - 0.65; 10 - 2;
2 - 9; 3 -
4; 8 - 3;
11-1.
Fig. 3 contains curves repre-
senting functional relationships
between the apparatus pressure drop
and the rate of gas passing through
a Venturi apparatus having a conic
diffusor angle of 80. Each curve
in this graph represents a constant
value of L/G. The dash curve rep-
resents the functional relationship
between the apparatus pressure drop
and the rate of gas flow at a con-
stant water spray consumption amount-
ing to 0.65 li/nm3 as shown by the
data of M. D. Kuznetsov and others.
Curves in the figure indicate that
at constant rate of water spray
consumption the pressure drop rec-
ommended by Kuznetsov and his col-
laborators is 2 to 3 times as high depending on the particular rate of water
spray consumption. It should be noted here that in the experiments here re-
ported determinations were made of the resistance of the Venturi tube and of
the separate construction of the apparatus, whereas in the experiments of
Kuznetsov and his collaborators the cyclone resistance was not taken into con-
sideration when determining total loss of pressure.
Accordingly, the true
difference in the results should be even greater.
The effect of increase in
the conus diffusor angle on the resistance (pressure drop) of the apparatus
at gas flow rate of 40..0 m/sec. is shown in Fig. 4. The course of curves in
-51-
-------
Fig. 4. Effect of diffusor conus
angle on the pressure drop of ab-
sorber with a Venturi spray tube.
Spray L/G = li/DID3: 1 - 10; 2 - 9;
3 - 8; 4 - 7; 5 - 6; 6 - 5; 7 - 4;
8 - 3; 9 - 2; 10 - 1; 11 - 0.5.
400
J.p,mm
300
1(/0
100
70
"
o
fO
10
Gas outflow
Liquid
inflow
Gas
inflow
- ------,
I
,
I
----~
that figure shows that with the in-
crease of ad within the range of low
spray resistance slightly increased
and dropped slightly within the range
of high spray values. Similar results
were obtained in studies with differ-
ent rates of water spray consumption.
It should also be noted that with an
]0
increase in the volume and velocity of
the spray loss of pressure increased
0.1. .C
considerably with the increase in the
in the conus diffusor angle.
The fact that resistance in the
atomizer tube falls with the increase
in the conus diffusor angle suggests
that an angle of ad = 300 should be used in
all types of Venturi absorbers operating at
spray density exceeding 3 - 4 li/nm3, since
this resulted in a reduced loss in pressure
and smaller apparatus dimensions.
A comparison
of the data obtained on mass exchange and
pressure fall in the apparatus leads to the
conclusion that ammonia absorption from coke
gases should not be conducted at high gas flow
rates from the viewpoint of energy consumption
since the productivity coefficient of the ap-
paratus increased to an insignificant degree
whereas the pressure drop sharply rose. For
example, at L/G = 10 li/nm3 and w = 40 m/sec.,
r
~ = 88% and 6p = 350 mm of water, with simi-
lar L/G and wr 60 m/sec., ~ = 94% and 6P =
860 mm of water.
Fig. 5. Construction plan
of a two-stage Venturi ab-
sorber for sulfuric acid
absorption of ammonia from
coke gas.
-52-
-------
iuaillonia absorption from coke gas by sulfuric &cid is Ii.O~t 2.dv2.DtOJ.e,'8ous
when performed in two stages; at rate of gas flow through the Venturi thro2.t
amounting to 40.0 m/sec. and rate of water spray amounting to 6 - 7 li/nw3
of acid per each stage, the productivity coefficient of the entire 2.;p~ratus
would range between 99.0 - 99.5% ~t total resistance (pressure drop) of 350 -
400 mm of 'ivater.
A plan of the apparatus construction is presented in Fig. 5.
The volume of li~uid running over from the upper stage to tbe
lo,;sr sl:ould
e~ual the volume of fresh mother li~uid supplied to the up~er staGe. The
re~uired moistening degree (spray) is att~ined by repe~ted circulation of the
solution in each stage of the apparatus.
Reserve fluid which assures the
re~uired degree of spray or moisture is deteTI,lined experimentally or by pre-
liminary trials. At gas flow rate 40,000 - 45,000 ill3/hour an a~par~tus of
the proposed construction should measure as follows: height - 6.0 to 6.5 m;
conus diameter - 2.0 to 2.2 ill; throat diameter - 0.45 m; ana conus diffusor
angle - 300.
Bibliography.
1. B. M. MaTpo30B, B. M. PaMM M r. M. IDcOBa. Cooo~eHMe 0
HaY~HO-TexHM~eCKMx paooTax HMYM~, 1958, Bbill. 6-7, 168.
2. M.~. KY3He~OB, ill. M. Cara~oBCKM~ H E. B. ITOITOBa. KOKC M
XMMI1JI, 1959, N2 2, 32.
-53-
-------
NomograQ for
at Zero
the Reduction of Actual
Degrees Centigrade, 760
4,000 Cal/nm3 of Heat
L. S. Blokh.
Coke Gas Volume to Nonnal
IT~ of Mercury and of
Capacity.
Koks i Khimiya, 1956, No.1, 45-46.
Under practical plant conditions it fre~uently becomes necessary to reduce
to actual gas volume as recorded by various types of i:;as weters to normal vol-
ume.
In calculating saturated gases at temperatures below the dew point it is
also necessary to take humidity into account.
In the case of coke gas reduc-
tion to normal volume is accomplished according to formula (1):
0.663
(1 - V ) (10330 + p) Q
wv
105 (273 + t)
(1)
V
np
3
in which V is the volume of water vapor in 1 m of saturated gas at given
wv 3
temperature in m ; p is the gas pressure in mID of water column;
temperature in Co; Q is the heat capacity of the factual 6as in
gas. The value of V is usually found in an appropriate table.
wv
has been found it in still necessary to go throu6h 8 different steps
t is the gas
3
Cal/nm of dry
After V
wv
to obtain
final result s, which is a tiL;e-consuming procedure.
Hence, the need for a
nomogram with the aid of which V could be determined vii th practical precision
np
with t, p and Q known without searching for
the value of V from the table.
wv
The nomogram herein presented was checked and found to satisfy all practical
re~uirements. It is made up of e~ual distribution points and of vertical
parallel scales based on formulas having 4 variables. In constructing the
nomogram calculation formula (1) was reduced to the following:
V = TPQ . 10-7 m3
np
(2)
in which
T =
66.3 (1 - V )
wv
(273 + t)
(3)
and
P = 10330 + p
(4)
Moduli of logarithmic scales of initial variables are taken at identical values
in which case the scale modulus of the unknown variable will be reduced to 1/3.
Moduli of logarithmic scales of initial variables have been taken as e~ual 1 m.
Scale 1 was based on formula (3) and graduated for variable t in the range of
-54-
-------
"'f. 1(1"
. t
.fl'
"/WI
35°
...
.s
..
'8
n')
e
c
CO°
I.
p
o
<..>
II>
3 0 ~
(; 490 (00 c
>
02flJ
.xJO ..
~ ;
'0 ~
..
...
a.
'"
'"
'"
25° .::
II>
...
::J
10° ~
...
(50 1l
e
II>
fir ....
'"
'"
CD
II>
-"
o
<>
of'
O.
3
t,JIJ
of 2
-5'
-'11"
Key
o
JMJ
'"
.
...
"to
-
..,
4
o 0
- 10 and + 50 ; scale 2 was based
on formula (4) with variable p in
the range of 0 to 800 mID of water
columno Logaritllinic scale 4 with
modulus AQ = 1 m is constructed for
values of Q in the range of 3,800
and 4,500 Cal/nm3. Logarithmic
scale 5 with modules
1
'3 m = 333.3
mm
Ay
np
Scale 3 is a blank vertical straight
line located halfway between scales
1 and 2. Scale 5 coincides with
scale 2 and is located halfway be-
tween scales 1 and 4. The key in
the upper right hand corner demon-
strates the method in which the nomo-
gram is used. For example: assume
Nomogram for reduction of actual coke
gas volume to normal. that a volume of coke gas has to be
reduced to normal under the following practical conditions: t = 300 C., p =
700 mm of water column; Q = 4,300 Cal/nm3 of dry gas. Using the nomogram join
the point which corresponds to 30 on scale 1 with the point indicated as 700
on scale 2 and note where the line intersects blank line 3.
This point is then
con~ected with the point corresponding to 4,300 on scale 4; the point of inter-
section with scale 5 represents the Y value which is equal to 0.997. Symbols
np
in formula (1) are then substituted as indicated below:
y = 0.663 (1 - 0.0419) (10330 + 700) . 4300 = 0.994
np 105 . (273 + 30)
The relative determination error is established as follows:
(0.997 - 0.994)/
0.997 - 0.003 or 0.3%, which is permissible for practical purposes.
-55-
-------
Reducing Gas Emission During Coke Oven Charging.
T. P. Varshavsky, R. G. Agapov, F. A. fuustafin and V. A. Permyakov.
(Nizhne-Tagil'sk Coke-Chemical Plant).
Koks i Khimiya, 1956, No.2, 23-30.
Improper coke oven charging is the chief cause of air pollution with coke
gas and coal dusto
In the Eastern U.S.S.R. coke plants, coal for coke oven
use is crushed and screened, so that 92 - 95% of the particles are not over
3 ~Wl in diametero Some plants add coal kerosene or coal oil to increase the
weight of the coke oven charge. Such a procedure of wetting powdered coal
with hydrocarbons in the presence of an original 6% moisture enhances the in-
tensity of air pollution with dust and coal gases and violates working con-
ditions in the vicinity of and over the coke ovens. The All-Union Scientific
Chemical Institute (VUKhIN) and the N.-Tagil Coke-Chemical Plant have been
conducting an investigation with a view to developing a method for loading
coke ovens by steam injectors, which might cut down air pollution to a minimum
by reducing coal gas and dust escspe from the hatches and risers.
1.
Charging crew working conditions above coke ovens.
Observation showed
that average time of gas and dust escape through hatches amounted to 4 minutes
30 seconds and from stand-pipes to 5 minutes 29 seconds to 6 minutes and 33
seconds.
A special diaphragm [1, 2J was used for the determination of the
amount of gas escaping frollJ coke ovens.
the portable diaphragm were as follows:
Coke oven charging and operation of
the coal delivery car carried 14.5
tons of powdered coal; as the loaded car was posed over the open hatch, all
3 cunker lids were opened sirDultaneously and the coal ch~rge run into the oven
chamber. Immediately after the coal unloading the delivery car was Dloved away
and the first and second hatches and rising pipe vlere closed. The risers
remained disconnected from the gas collecting main, and the coal charge inside
the oven was not levelled. The third hatch remained open, and the portable
diaphragm was placed over it and carefully tightened to prevent any bas from
escaping, thus forcing all gas coming from the oven to pass into the atmosphere
through this diaphragm. This procedure enabled to determine changes in gas
pressure created by the portable diaphragm in a group of coke ovens. Amount
of gas escaping into the atmosphere during coke oven charging was determined
from data obtained on the gas temperature, chemical analysis and moisture.
-56-
-------
Experimental data showed that the Quantity of 6as escaping into the atmosphere
from one oven was 66.04 m3. For a coke installation of 4 batteries the llJonthly
loss of gas amounted to 842,000 m3.
In March of 1954 a work time study was made of a single delivery and load-
ing car operation. Moisture content in the coal charge at the time of this
study was 5.5%, and the screened coal contained 93.2% of particles up to 3.0
mm in diametero The coal delivery car remained over the hatch 3 minutes 15
seconds. The reserve, or idling time per delivery car per oven averaged 3
minutes 9 seconds. During October of the same year the work time study was
repeated. It was found that the coal delivery car was delayed for 34 seconds.
At this time the coal moisture was 6.3% and particles up to 3.0 mID in diameter
constituted 91.2%.
This indicated that an increase in powdered coal moisture
Concentration of coal dust in the air in
content increased the charging time.
the delivery car operator's cabin was checked next.
This lnvestiGation was made according
at 1.1 - 1.8 m from the cabin floor.
Air samples were taken
to regulations for determining dust concentration in the air of industrial
establishments [3J. Results showed that coal dust concentration in the de-
livery car operator's cabin at the time of coke oven charging ranged between
218.8 - 383.1 mg/m3, as compared with the maximum allowable limit of 10 mg/m3.
2. Coal loading into coke ovens with one gas collector by steam injec-
tion. The existing method of coke oven charging allows insufficient free
passage for the gas collected beneath the arched oven ceiling, and there is
no provision for its removal from the oven through the stand-pipe. D~ring a
new charge the powdered coal is heaped up to the arched oven ceiling (Fig. 1),
which causes the gas to escape through the hatches.
r--- --
I .
1117
U sefu I length
-- - -- .
-- ..
Fig. 1.
----- at start of charging
---- during level I ing
Old system of charging
coke ovens.
The coal accumulation heaping
up to the coke oven ceiling acts as
an obstructing partition which in-
creases the gas pressure in sepa-
rated sections inside the coke
ovens.
Determinations of static
air pressure developed during coal
charging into the coke oven were
made with a U-shaped manometer.
Results showed that gas pressure
-57-
-------
at the first hatch, before the oven was connected with the gas collecting
main, fluctuated from 5 mm to 45 mm, and at the third hatch from 5 rom to 270
mm of ~ater. Maximum pressure at this third hatch was noted during levelling
of the coal charge in the oven. The latter measurements were checked with
the lids of the first and second hatches down.
pressure did not exceed 1 mm of water.
With the hatches open, gas
The static gas pressure under the
arched ceiling of the oven, between the first and second hatches reached 200
mm during the levelling operation, alternately dropping to about 4 - 5 rom,
except during the first minute, when it was 20 - 45 mm of water. The static
pressure in the riser pipe during coal charging varied from 1.5 to 5.5 mm of
water.
water; however, at the start of the charging operation it rose to 18 mm of
1.
On the basis of the above the following conclusions can be drawn.
The main obstruction to gas passage under the arched oven ceiling
was caused by the formation of a partition during the coal unloading from the
second bunker of the delivery car.
20 The levelling bar acted as an additional obstruction to the gas Clr-
culation under the arched oven ceiling.
Static air pressure measurements in the coke oven chambers suggested
several ways of coal charging ;Jhich wight reduce the resistance to the gas
developed:
The following method for oven charging was
passage into the riser pipe.
the coal charge was started with unloading the first bunker of the
delivery car, with the second and third bunkers tightly closed. The coal de-
livery car was then moved 2 m aside. The attendants covered the first hatch
tightly and proceeded to the second bunker in an identical manner.
After the
and discharged the coal from the third bunker.
second bunker was emptied the attendants removed the lid from the third hatch
After all bunkers were emptied
Figo 20
First step of new coke oven
charging system.
-58-
the levelling bar was brought into
play for a time, the duration of
which varied with the moisture
content in the coal charge.
The
manner in which the oven charging
was done is shown in Figs. 2, 3
and 4.
Data on charging coke ovens
by recommended procedure with coal
-------
401
---
.'
'. .. .
'. " ~ . ",,!.' -,,' ..':': . .. .
Figo 3. Second step of new coke
oven charging system.
~, , '" "..
,',', .
Fig. 4. Third step and levelling
stage of new coke oven charging
system.
of different woisture content are shown in the following table.
Important factors in charging coke ovens by the new method.
: : :S' It :Simulta-:Charging:Leveling:Simulta-:
: : : lIDU a- : : . : . : :
: : : i neous :tlme of :tlme af-: neous :
: :p : neous .(. ): 0: :(. ):
:p t: ercent :(. 1 ): slngle :experl- :ter re- : slngle :
: ercen : f 3 0: slng e : .: 1 : : :
D t: f :0 -: h . :charglng: menta :moval of:starter :
a es: 0: :c arglng: . : .:. : .:
: . t :mm par- : °th d :wlth wet:ovens In:dellvery:charglng:
: ltiOl sure: ° 1 non ry: ( 0 ): ° : 0: :
: : tlC es: 1. : olled :mlnutes: car, ln : of dry:
: : :coa In: 1 0: d :. : 1. :
: : : ° t :coa In: an :mlnutes :coa In:
: : :mlnu es : ° : d: d :. :
: : : :mlnutes :secon s :an sec.:mlnutes:
Notes
20/11:1
22/X r
26/X"\
29/X r
29/X,
31/X r
22/~
26/~r
31/X
18/XIL
23jXIJ
6.2
92.0
14.45
15.41
Dry
charge
6.8
90.7
14.2
5-21
1-00
15.1
8.22
90.1
14.08
15.24
6-42
15.12
Ditto
6.04
91.58
14.79
1-06
15034
15.3
12-00
1-00
Ditto
5.86
91.0
14.9
15.77
1-13
15.28
Wet
(oiled)
charge
5-52
16.27
5-56
15.28
1-03
Ditto
In the case of dry coal charge where W = 8.2% a non-smoking oven charge
p
can be assured by reducing the coal charge by 1.3 tons. A one coke oven charge
generally averaged 12 minutes and occasionally 14 minutes. Accordingly, the
new producedure cannot be recommended for coke oven charging with coal con-
taining 8% or more of moisture.
Slight gas leakage on top of the coke oven was
noted when the ovens were charged by the new procedure with coal containing
-59-
-------
6.8% of [.lOisture; the charge had to be reduced by 0.9 tons. Loading time for
one oven rose to 6 - 7 minutes, as compared to 4 minutes by the old procedure.
Gas and dust escape into the air from coke ovens charged with dry coal con-
taining 6.2% moisture was noticeably lower in comparison with old procedures.
It was also noticed that gas formation occurred at the very start of the coal
charging operation (from the bunk8rs into the oven). Durins the levelling
operation occasion21 gas and dust eruptions were noticed coming from the third
hatch and sometimes from the first and second hatches. Charging time of one
coke oven took 5 to 6 minuteso Charging coke ovens with wet (oiled) coal of
W = 6.0% by the new procedure reduced the escape of gas and dust considerably.
p
During coal unloading from the delivery car bunkers and during the coal charge
levelling inside the oven, gas escaped through the gap between the telescopic
bunker chute and its seat in the hatch, if they had not been properly connected.
After the coal delivery car was removed from the top of the oven the third,
i.e., last, hatch continued to emit gas until it was closed, but less intensely
than usual. Time reQuired for charging one oven chamber was 6 minutes ex-
elusive of the time consumed by the charge levelling operation.
November 23 of the same year a second battery of 23 coke ovens were
charged with coal by the new procedure in the course of a second shift. In
that time 35 ovens were unloaded and 34 ovens were charged as against the usual
output of 56 ovens.
The production volume was not fulfilled due to the longer
time reQuired for their preparation. However, intensity of air pollution was
markedly reduced as compared with results of preceding tests. According to
preliminary calculations the gas escaped into the surrounding atmosphere was
reduced by about 79%. The average dry coal charge for the plant amounted to
14.9 tons as against 15.28 tons and the average for that shift at the second
battery of coke ovens, amounted to 15.45 tons. Time consumed for loading one
oven was 6 minutes. The steam injector pressure varied, as in the previous
experiments, between 10 and 8 atmospheres. On the basis of results obtained
in this study it can be stated that:
10 A new procedure has been developed for charging coke ovens by steam
injection \Ihich lowered considerably the pollution of air with coke gases and
dust. The procedure lias tested under actual industrial operating conditions.
20 The drawbacks of this procedure are: a) need to lower the size of
the coal charge by 500 kg for coal with 6% moisture, and b) a 2 minute increase
in the oven charging time.
-60-
-------
3.
The following changes are recommended for the improvel11ent in the
efficiency in charging coke ovens:
a.
Coal 10~QS in the first and second bunkers of the coal delivery
car should be increased, and in the third bunker decreased; hence, the bunker
capacities should be chanbed accordingly.
b.
The coke oven charging time should be shortened by Glechc:nizing
the opening and closing of the hatch lids and of the levellin~ beam operation.
c.
To make more precise fittinbs between the bunker telescopic
chutes and their seats in the hatches.
The new procedure offers the above advantages only when the coal charge
moisture is not in excess of 6%.
3.
Development of steillJ injection procedure for ch~rbinb coke oven e~uip-
ped with two ~as collectors.
In 1953 the Nizhne-Tagil Coke-Chemical Plant in-
iti&ted experiLlents in the use of steam injection smokeless charbing of coke
ovens.
During the first period of the tests, charging of coke ovens was done
according to prevailing ways of operating coke ovens.
Coal varying in llioisture
between 5.5 and 7.5% was tested.
Gas and Qust concentrations on top of coke
ovens decreased only slightly when stearn injection was applied to ordinary
procedures of coke oven charging.
Therefore, a new ~rocedure for coke oven
charging was tried e~uipped with two uprisers.
Special features of the new
procedure were as follows:
stearn injection ~as started as soon as coke ovens
'Iiere ready for the charge and.7i th both risers closed.
Then the oven was
charged with coal from the first and third delivery car bunkers with the lid
of the second hatch closed.
After uischarging the coal from the first and
third bunkers the coal deliveI"'J car was [llOved aside 3 f:leters Villi le the attend-
ants locked the lids over the empty buru~ers.
The coal delivery car was then
brought back and the coal from the second bunker discharged into the opened
control oven hatch.
The levelling bar window was opened as soon as the first
and third bunker hatches vlere locked, and the levelling of the cOed charge
was started simultaneously with coal charging through the control (second)
hatch from the sl:ocond bunker of the coal delivery car.
Co(;,l chaTee levelling
facilitated and speeded up the coal disch~rge from the second bunker and the
coal ch~rge levelling insiue the oven.
This procedure of coke oven charging
'"Jas tried G.uring May 1955 with the following types of c00.1:
8.3% moisture
content; screened coal of 93.2% size 3 mrn; and sinGle 15.8 ton chiLrse of
dry coal.
-61-
-------
The proposed procedure yielded a smokeless coke oven charging with steam
injection of 8 to 10 atm. pressure.
Gas escaping into the air was reduced by
90 - 95%.
IIi th an incre:o..se in the coal !Jloisture up to 7.5% the efficiency of
coal charging by this procedure increased. No gas escaped through the open
hatches during coke oven charging except at the end of coal charge levelling
inside the oven, when some bas escaped for 5 to 10 seconds from the first
hatch. .~fter the levelling bar was withdrawn from the oven the gas escape
stopped. Vith this procedure of coke oven charging battery oven coking time
was reduced to 14 hours 50 Llinutes. Time for loading one oven with coal did
not exceed 3 and occasionally, 4 minutes.
This new coke oven charging procedure necessitated the rebuilding of
battery ovei1S Nos. 5 and 7. The two end delivery car bunkers were enlarged
to handle the coal charges of not less than 6.5 tons and the capacity of the
n:iddle bunker vias reduced to not more than 4.5 tons.
This reduced considerably
the coal loading time as well as the levelling operation.
The ulain charact er-
istics of the new procedure ~or ch~rbing coke ovens can be described briefly
as follows:
1.
Free passage was created for the gas to enter the riser pipes under
the arched coke oven ceiling during the entire coal charging operation.
2.
Absolute elimination of outside air sucking into the oven, which made
stec.m injection more effective than -vvith the old coal charging procedure.
The
I,Ioscow Coke-Chemical Plant adopted the new coal charging procedure developed by
the Nizhne-Tagil Coke-Chemical Plant.
It was noted that charging coal into coke ovens by steam injection was ac-
companied by a tendency on the part of the coal to enter through the risers into
the Gas collectors. This increased tlle ash content in the tars up to 40% and
cloc;'[;ed tLe e;,:!.s mains c.nd valves vl'i th heavy coal tar wastes.
In addition, the
quanti ty of heavy coal tar \Iastes increased; these heavy coal tar products can
not be removed by clal'ifyine uethods, nor do they completely settle out of
suspension by gravity. Steam was then forced through the risers for 3 to 5
minutes ir;mledLLtely after 8:1ch fresh coke oven chiJ.rge, cutting off the steam
injectors at the same tir1le. This completely freed the risers of the heavy
coal tar ~uste clogging.
Cleaning g'as collectinu' luains of heavy coal ti:U wastes
cdn be achieved by running in stei:I11 through valves placed equidi::;tantly at the
bottom of the ~as mains. This wetLod is being tried now at the N. Tagil Coke-
Cher.1ical PLmt 0
-62-
-------
The following experiments are nmv being conducted for the recluction of
the ash content in heavy coal tar products:
a.
tIeans are investigated for the removal of forlIled heavy coal tar wastes
by existing facilities, i.e., by iruproving the oper:J.tion of existing r;rechanical
separators.
b.
A high velocity air current or cyclone is being adopted during the oven
charging for the removal of coal dust from the gas before it reached the gas
mains.
Results indicated that the above described studies ~ere promising.
This
will reCluire extensive new experiu;ental studies and specially designed new
eCluipment and apparatus.
Conclusions.
1.
A procedure was developed for charging coke ovens eCluipped with a
single ~as collecting main which improved consider~bly working conditions on
top of coke ovens.
The procedure is applicable only to coke oven charging with
coal of not r.1ore than 6% moistl,ITe.
The Institute must conduct additional tests with the procedure of coke oven
charging where only a single g&S collecting outlet was available.
also be conducted for coal delivery car redesib~ingo
Studies must
2.
A new procedure for charging coke ovens with 2 gas collecting outlets
has been recommended and is now in use industrially-
3.
Coke oven charging by steam injection caused coal dust to be carried
away into the gas collecting mains; therefore, the Dethod of steam injection
is not now used in the Eastern U. S. S.R. coke-cher,lical pl&nts.
40
Results thus far obtained with experiments coniucted on cleaninb coke
bas before it reached the 6GS collecting mains and the lilechanical seyarators
cip:t-'edred pror,li sing.
Bibliography.
1. A. H. MaRapOB, M. H. illepMaH.
MeTa~~yprM3~aT, 1953.
20 B. M. KyCTOB, C. E. Bece~OBCRM~.
ROHTpO~R, MeTa~~yprM3~aT, 1946.
3. r. M. rOp~OH, M. ~. ITeMcaxOB. KOHTpO~~
YCTaHOBOR, MeTa~~yprM3~aT, M., 1951.
PaC'leT ~pocce~bHDIX YCTPOtiCTB,
ITpM60pbr TerUOBoro
nbIJI e y~ aB~ M B aJO~ MX
-63-
-------
Smokeless Coke Oven Charging.
I. Ya. Uezentsev.
(Zaporozhie Coke-Chemical Plant).
Koks i Khimiya, 1958, No.4, 28-30.
The problem of iill~roving sanitary workinb conditions atop coke ovens
during charging and of reducing atmospheric air pollution with coke gas and
coal dust has received considerable attention in the U.S.S.R.
In July 1956
a conference was called for the discussion of methods used by coke plants to
attain smokeless charging of coke ovens.
By conference resolution the in-
dustry was recommended to adopt the method used by the l:oscow Coke-Chemical
Plant. The Zaporozhie Coke-Chemical Pladt used the ste~Jj injection method
from the start of its operation in charging coke ovens to sanitize working
conditions atop the coke ovens and to lower air pollution with coke sases and
coal dust.
Adoption of this method created some difficulties.
'.fuen thi s
method was applied to charging coke ovens with crushed coal containing 91 -
925~ of particles up to 3 mm in diameter the amount of ash in the coal tar in-
cre&sed up to 0.22% as against 0.1% ~ith crushed coal of larger size particles,
,;,'hich in turn proiuced a defective e;rade of pitch coke.
To avoid this, coke
oven ch<.rg'ing in that plant has been done by the following procedure since
1954:
before filling the oven chanber with the coal and before stopping the
coal feeding from the delivery car bunkers, all hatches on top of the oven
rer.lained o~)en.
The oven '"as connected \,i th the e-;as collectinEo' lLiain before
starting the coal levelling oper~tion, and the ste~n injection was commenced.
By this procedure of coke oven charging the steam injection time was reduced
to 70 seconds and the c.r;lOunt of ash in the heavy coal tar Vlaste was reduced.
The e;~s passinG throue;h the riser pipes at the start of the charging operation
is of lo~ value. It consists of (in percent): C02 - 2.5; CO - 1.3; C H
m n
9.1; H2 - 9.9; CH4 - 11.3; N2 - 65.0 and 02 - 0.9. The 65% nitrogen in the
gas iniicates that at the beginning of the oven charging air passed through
the risers from the oven interior whicb contained some CO and C02 formed by
the burning coal.
This author I'Jas assigned the jJroblem of determining the advantae;es and
dis:::.dvantages 0:: steu.m injection used at the 1J:oscow Coke-Cher;jical and the
Zaporozhie Coke-Chemical Plants to attain sEiokeless coke oven charging.
Uncler
-64-
-------
investigation were coke oven butt8ries with 2 gas col18ctLn~ wains.
The co;.).l
clelivery c~r \Vas equipjJed 'iJi th i:J. sjJ8cial wechcmL.iIn ",111ich enubled louuing its
bunkers \,i th exact volumes of coal.
Hatch lids of tlle coal delivery cur bunkers
opened ~ncl closed automatically in a set order.
Each uunker vms equipped Iii th
an automatic type H7 vibrutor.
Removing and replacing the hatch lids was done
automatically at the exact stops of the cOOLl delivery car.
The levelling bar
al::oo operatedJ.utOlnaticully und its stroke awounted to 5.5 meters.
Loading
openinc;'s in the bunkers j,leasured 420 mm in dia!lleter and the hatch openings
measured 432 mm in dim,leter.
Coal delivery cars were equipped with telescopic
automatically ti6htening chutes.
Tar and heavy tar waste collection was done
in mechanical separators which were cleaned before and after each run.
Gas
pressure and temperature during coke oven charging were checked through open-
ings in the risers at 300 ll@ above the oven top.
(oiled) coal weighed 17 tons.
~ single oven charge of wet
During this oven charge study 976 coke ovens were tested in the Zaporozhie
plant while in full operation.
Each oven ~as char~ed with 17 tons of coal.
The
first and second bunkers of the coal delivery cur held 5.5 tons of coal each,
the third bunker 6 tons. The coal flloisture -..Jas 8.43% and the C>.sh 7 .4/~. The
coal .Jeighed 0.729 t/m3. Screenc;d sizes of the coal i"lere as follows (in per-
cent): class,> 6 mm - 1.6; 6 to 3 mm - 7.3; < 3 !illll - 91.1, 44;'; of tile latter
llieasured 0.5 mm and less in dic.S e",ci:J.j,-ine;' into the c:.tLios1,here.
-15.4
-26.0
G~s escaped lnto the atwos~here
for cibout 4 - 5 secon~s thr~u~h
+11.0
the control hatch, only be10re coal
loadinb an~ before iD~ertinb the
-65-
-------
levellin~ b~r into the oven ch~mber Lifter emptying tbe third bunker.
tons of t~r proJuced ~uriD~ the investigation contuined 0.115% of ash.
The 480
Total
ash in the tur amounted to 480 x 0.115/100 = 0.552 tons.
The ash entered the
tar during the cOCil char6'e with the lJowd.ered coal; accordingly, coal carried
off \,Jith the ';dS durine;' oven charging amounted to 0.552 x 100/7.4 = 7.46 tons.
Heavy tars collected l~uring' the investib'ation amounted to 1.8 tons, making the
total coal loss equal to 7.46 + 1.8 = 9.26 tons, or 9.26 x 1000/976 = 9.49 kg
per single oven, or 9.49/17 = 5.45 kg per single oven ch~rge. During the
charging olJer~tion the oven vias under steam injection for about 170 seconds
',.Ihile the co:d IJas being levelled.
to 0.49 x 60/170 = 3.3 kg per load.
Losses from one oven per r,linute aUlounted
As soon as
coal levelling ~as completed
and steam injection was discontinued the top layer of small coal particles
fused and the discharge of bas and coal dust into the atmosphere stopped.
During the investigation of coke oven loading by the vrocedure used in
the Moscow Coke-Chemical Plant tests ~ere mude of the operation of 923 coke
ovens. The ovens Ivere ch~rged as follows: first, two end bunkers of the de-
livery car were emptied and the hatches covered; the r.liddle bunker was then
emptied 01 its coal load.
The total coal load auounted to 17 tons.
The first
and third bunkers in tIle co,d delivery c",r contained 6.25 tons each, the second
(middle) 4.4 tons.
Hhen the extreme bunkers Viere loaded with l,;ore coal than
sjJ8cified, trouule was exp8rienced in charging the coal into the oven chambers
;Jithout the use of the levelling bar. The coal contained 8.55% of moisture
and 7 ~5% of 3sh. 'rhe coal weighed 0.717 t/m3, and ivas of the followin5' frac-
tional corjlpositio~: > 6 mm - 1.8~~; 6 to 3 mrn - 6.8%; < 3 rmn - 91.4%, 447; of
the latter consisted 0: particles of 0.5 DIm or less in diameter.
Injection
stearn pressure ~as 6 atnl. with a partial vacuum at the bottom of the riser pipe
during the levellinb oper~tion of 19 n~, and with a closed levelling bar port-
hole of 26 mm.
:ii th the cniJ.rge completed, the coke oven was connected to the
bcis collecting [.Jain \d th the riser reb'istering a j,Jre",sure of 11 Dilll.
Results of investibdtions showed th&t time consumed from the start of coal
feedinG into the oven to the end 01 the levelling 0iJeration, in accordance with
the procedure used in the 1:oscow Coke-Chemical Plant, equalled 330 seconds; by
the procedure of the Zaporozhie Coke-Chemical Plant the time con",umed was only
240 G8conds. Correspondingly, the time consumed in levelling the coal inside
the oven was 320 minutes Bbainst 170 cinutes.
During testing the ~oscow Coke-
-66-
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Chemical Plant procedure 455 tons of tar was produced \lith 2 0.153% ash c0ntent.
Total ash in the tar weibhed 455 x 0.153/100 = 0.696 ton.
In utter ''IV ords,
\;ith
a coal ash content of 7~5% the loss, including bcis loss, WaS equivalent to
0.696 x 100/7.5 = 9.28 tons of coal. Ei~ht tons of hsc:.vy t:J.r \Iaste proclucts
,;ere produced during the investigation Qaking a total dctuu.l charge loss equiva-
lent to 9.28 + 8.0 = 17.28 tons of coal, o~ a loss of 17.28 x 1000/923 = 18.73
kg of coal per charge, or a loss of 18.73/17 = 1.1 kg of coal per ton. Losses
during 320 seconds of steam injection were 18.73 x 60/320 = 3.5 kg/min.
The loss of coal from the coke oven per minute, including loss of ~as,
was practically identical in both tested procedures, or in actual fib~res 3.3
kg/min. in the Zaporozhie Coke-Chemical Plant and 3.5 kg/min. in the 1~oscow
Coke-CheBical Plant. It follows t~at the aD.ount of ash in the tars and in
heavy tar wastes extracted by the se}arators lias in direct proportion to the
time the ovens '.vere under steam injection during the coal chargin[ operation.
There Vias also a direct proportional relation bet'iJeen the stem;] injection
pressure and the loss in coal dust with the gas. It ~as noted that at ~arti21
vacuum of 8 u@ at the bottom of the risers, a complete gas collection was not
assured, but the size of the coal particles decreased oelow 105 IT@.
.n. drop
in partial vacuum at the bottom 01' the riser to 19 Il1Ll assured cowplete collec-
tion of the gas during the coal charging operation with coal particles size
increase to 2 mID.
With increase in time of oven chargin5 by the 1ioscow Coke-
Chemical Plant procedure there was 21so a ti~e lag in tlle work cycle of the
coke pusher from the mOQent of coke unloading to the end of coal loading,
amounting to 761 seconds as against 681 seconds, required by the Zaporozhie
Coke-Chemical Plant procedure. Additional increase in work intensity of the
coke pusher under work conditions existing at the Zaporozhie Coke-Checical
Plant presented the danger of a possible breakdown in the coke delivery.
Tests were also ::1:c,de "ith the following procedures for chare;in5 coke
ovens.
The total load of coal delivery car ','Ias [;;ade up as follows:
in the
first bunker - 6.3 tons, in the second - 4.5 tons, and in the third - 602
tons. Charging the oven char.aber was done by sir.lul taneously unloading the
end bunkers of the deli very car and 22 seconds later er.lptying the central
bunker.
\lith this procedure of coke oven charging all three bunkers contained
about 200 kg of residual coal before the levelling b~r was set into o~er~tion;
coal levellin6 was accomplished by two strokes.
uas was escaping throubh the
-67-
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hatches for about 5 - 6 seconds until the levelling bar began to operate.
Total time consumed from starting the coal feed from the bunkers to the end
of coal levelling ~mounted to 190 seconds.
This third method of oven charging
was the most rational of the three methods teste& from the point of view of
smoke elimination and prevention of coal dust being carried into the gas col-
lecting mains.
After the working crew mastered tbe unloading of the bunkers
and levelling of the coal charge inside the oven, the complete loading tUle
was reduced to 170 seconds, and the gas loss in coal equivalent was reduced
to a minimum.
Conclusions.
10
Coal dust carried off by gases during coke oven charging was directly
proportional to time of steam injection.
Coal dust and ash were carried off
by the gas under the following working conditions: if the coal contained 8.5%
of moisture; if 91% of the coal particles measured 3 mm or less in diameter
and the partial vacuum at the bottom of the riser was 19 ll~. Under such con-
ditions 3.5 kg/min. of coal dust were being carried away by the gas.
2.
The injection steam pressure IllUSt produce a partial vacuum at the
bottom of the riser of not less than 19 mm if the coke oven charging is to be
attained without any gas escape.
3.
The procedure adopted by the Moscow Coke-Chemical Plant for smokeless
coke oven charging can be used with coal containing 7% moisture.
4.
Coke oven charging in accordance with the procedure of the Moscow
Coke-Chemical Plant at the Zaporozhie Coke-Chemical Plant, where the coal
moisture content ranged between 8 and 10% had shown that it lengthened the
oven loading time, increased the work intensity of the levelling bar, greatly
increased the rate of coal dust pick-up by the gases, and increased the ash
concentration in the separated tar to 0.153% as against 0.115% by the usual
procedure of the coal loading. On the other hand, the efficiency of smoke
abatement was considerably higher with the procedure used at the fuoscow Coke-
Chemical Plant than by the procedure of the Zaporozhie Coke-Chemical Plant.
5.
The most promising procedure of coke oven charging was the third which
consumed considerably less time than either of the other two methods.
-68-
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New Method for Ammonia Absorption from Coke Gas.
G. D. Kharlampovich, 11. V. Goftman and N. D. Rus'yanova.
(From the Ural Polytechnic Institute).
Koks i Kbimiya, 1960, No.4, 34-41.
The ammonium sulfate method presently used for ammonia absorption from
coke gas has some basic shortcomings:
a) The resulting ammonium sulfate is of low quality as a fertilizer;
b) It requires the use of large quantities of sulfuric acid;
c) The technology of the process lacks adaptability for the production
of new substances from the ammonia contained in the coke gas.
In view of the above, it would seem more appropriate to concentrate on
obtaining more valuable products than ammonium sulfate.
Such products or sub-
stances should contain a higher percentage of bound ammonia and should con-
stitute less bulky types of fertilizer manufactured only from coke-chemical
raw product s.
Such substances could be urea, saltpeter, different types of
liquid ammonia fertilizers, including liquid ammonia. Of these urea is the
most valuable product. It has 46% bound nitrogen and in addition its prop-
erties make it one of the most widely used ar~lonia compounds in the production
of plastics, lacquers, plywood glue, foam plastics, etc. (1, 2, 3J. Urea is
also used in lar5e quantities in animal husbandry as a cattle protein rein-
forcer (1, 4J. Net cost of ammonia produced on a large scale with modern
equipment is about the same as the net cost of saltpeter which is one of the
cheapest produced fertilizers E4J. Coke gas of an 8-battery coke-chemical
plant contains ammonia sufficient for the production of 25 - 30 thousand tons
of urea annually; this amount compares favorably with the amount of urea syn-
thesized by one of the largest present day urea producing plants CIJ. The
products enumerated are produced from pure armnonia; therefore, it is essential
that the ammonia recovered from coke-chemical gas be obtained in a highly
pure state, at the Sffiue time keeping the cost of its recovery at a low level.
The present authors studied cycle methods for the recovery of amnlonia
from coke gases by weak solutions of acid and polybasic acid salts.
It was
hoped that the use of cycle absorbers might enhance the capacity of the solu-
tions to absorb aroolonia, and, what is more, would insure selective ammonia
-69-
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absorption from coke sas.
The chemistry upon ~hich such a process is based
can be represented by the following formula:
tl
NH3 + HAn ~ NH4An
t2
in ~hich RAn represents the acidity and t2 > tl.
Ammonia separation at higher temperatures is accomplished by increased
ammonia salt hydrolysis and by an increased rate of ammonium hydroxide de-
composition as per equations below:
NH4An + H20 ~ Iffi40H + RAn
NH40H ~ NH3 + H20
An analysis of the equation for the purpose of obtaining constants of
weak acid salts and weak bases hydrolysis showed that high rate of ammonia
catchin5 at 30 - 600 and a favorable recovery rate at 100 - 1200 were attain-
able with an acid having a dissociation constant ranging between 3 x 10-7 and
-8
6 x 10 , or with an acid salt at equivalent dissociation constant at any stage
of the process. Use of weak acids for ammonia catching by suitable processes
has been described previously in the patent literature [5 - llJ. However, in
most instances ammonia recovery from coke gas has not been studied.
On the
other hand, report~ of studies on the subject of ammonia recovery from coke
gas [5, 6J failed to present adequate information regarding conditions under
which recovery has been attained and of the advantages of any of the absorbers
used. Results of absorber studies lead to the following conclusions:
1.
Borates, phthalates and oxalates could not be used because of their
low solubility in water, and, consequently, the degree of ammonia absorption
by such solutions did not exceed the degree of ammonia absorption by plain
water.
2. Ammonia absorption by double substituted ammonium citrate is revers-
ible. The high solubility of citric acid is conducive to a high degree ammonia
absorption (up to 95 g/li). However, this is counterbalanced by the high cost
of citric acid.
3.
Amnlonium acetate in aqueous solution at 500 liberates 50% of its am-
monia and becomes converted to the acid salt according to the following formu~a:
CH3COOH . CH3COONH4
-70-
-------
It appeared at first that the high ammonium acetate solubility in water
fllight offer a rational means for o:mrnonia absorption according to the follow-
ing equation:
CH3COOH . CH3COONH4 + NH3 ~ 2CH3COONH4
However, a thorough and detailed study of the process showed that by concen-
trated all@onium acetate solutions it was possible to separate only a small
part of the absorbed ammonia at 100 - 1200; in addition, along with the am-
monia there were carried over large quantities of acetic acid; and further-
more,
solutions of ammonium acetate corroded the equipment, in particular the
acidic acetates.
4.
Phenol solutions or liquid phenol fractions absorbed ammonia revers-
ibly in quantities of 1 mol. for each 2 oxygroups.
Reaction rate between phenol
and au@onia was considerably below that of organic acids.
Bubbling coke gas
through phenol solutions rapidly oxidized the latter.
Phenol sulfonic acids
could not be used as absorbers of a!mnonia from coke gas due to the fact that
arrmlOnia became permanently bound to the sulfo group and, therefore, could not
be recovered; accordingly, the capacity of sulfonic acid solutions to absorb
ammonia depended entirely on the number of phenolic hydroxyls in its molecule.
5.
Most promising in this respect appeared to be monobasic phosphates;
their oolutions easily absorbed au@onia and even ~ore easily liberated it in
the process of recovery.
However, the use of ~otassium phosphate is not prac-
tical due to its low solubility in water. Monosodium phosphate has a higher
solubility than any other phosphate; however, its fllixed salt NaNH4HP04 is also
sparingly soluble in water, which renders the use of sodium acid phosphate un-
fit for the purpose. Best results were obtained with a solution of au@onium
acid phosphate, the solubility of which is graphically presented in Fig. 1.
A study ~as then made of factors controlling rates of absorption and
recovery.
For this purpose deterl11inations were made of dnllIlOnia vapor tension
over mono- and dibasic phosphate solutions and their Dlixtures at different
temperaturEs.
Results are listed in T~ble 1.
Data in the table show that monobasic phosphate solutions could be uoed
o
under practical conditions for the ubsorption of C\fllfnonia from coke gas at 60 .
Recovery of dibasic phosphates of awmonia should be llJJ.de at 100 - 1200. Com-
plete1:1111mOnia recovery from dibasic phosphate solutions was not uttainable.
Under practical conditions the processed solution will contain 75 - 80% of
-71-
-------
the monobasic and 20 - 25% of the dibasic phosphates after recovery. ~ata on
re~uired solution concentrations, spray density and au@onia absorption capacity
attainable at different temperatures are presented in Table 2.
Ammonia absorption can also be attained by combining a part of it as tri-
basic phosphate. However, saturation of the solution to the point of formation
of tribasic phosphate raises ammonia absorption
only by 7 g/li corresponding to 10.% of the tri-
basic phosphate concentration (solution 7). Fur-
50
10
20
30 IdJ 50 60
Temperature in CO
Figo 1. Solubility of
ammonium phosphate.
1 - monobasic; 2 - dibasic;
3 - dibasic solution con-
centration attainable ~ith
ammonia absorption by sat-
urated monobasic solution;
4 - tribasic.
ther increase in ammonia concentration in the
tribasic phosphate solution lowered the absorption
coefficient due to the high ammonia vapor tension
over the tribasic phosphate solution.
In addition,
as the tribasic phosphate concentration continued
to increase it began to fallout from the solution
in crystalline form. Generally, an ammonia ab-
sorption rate amounting to 50 - 60 g/li by solu-
tions of monobasic phosphate was attainable at
40 - 500.
A study was made of pyridine vapor tension
over the Blillilonium phosphate solutions in connec-
tion with an investigation of a method described
TABLE
1.
Ammonia vapor tension over surface of NH4H2P04 and (lnI4)2HP04 solutions.
S" IU-1
t i on I
Concentr~tlon :G/II of I I
/ I . . So I u -
9 I I ammon I a : t . I
:(~H4)2.:absorbedl Ion I
pH at
No. INHliH2POlii HPO I by I 900 I
4 :NH4H2POIi:
30 1 40 I
NH3 vapor tension in mm mercury
Temperature in CO
50 I 60 I 70: dO. 90. 100:
:Ammonla
:produc-
: tion
: .capac i ty
110 120.. .
: I n 9/11
I 430 3.8
2 376 62 7.9 4.4 0.00 0.00 0.00 0.00 0.00 0.00 O. 10 0.37 0.66 1.21
3 322 123 15.7 3.0 0.00 0.00 0.00 0.04 0.11i 0.56 0.68 1.62 3.90 7.70 3.1
4 215 245 31.5 5.7 0.17 0.18 0.51 1.86 2.11 2.39 8.46 20.00 18.~
5 108 367 47.0 6.6 0.33 0.49 0.77 2.36 Ii .41 11.60 57.00 69.30 33.4
6 490 63.0 7.6 3.35 6.68 12.40 23.40 52.50 81.40 158.00 327.00 50.4
7 490 70.0 9.1 4.12 7.60 15.50 57.4
Notes: I) Monobasic ammonium phosphate saturated at 400 (430 g/Ii) was taken as the basis of the in-
vestigation. 2) Ammonia productivity capacity was determined on the basis of possible 80;& (NH4)2HP04
recovery (ammonia residual - 12.6 g/Ii).
-72-
-------
TABLE
2.
Concentration of monobasic phosphate and degree of aD~onia absorption
at different temperatures.
Index
40
Tewperature in Co
50
55
NH4H2P04 solution concentration in g/li.....
Limit of ammonia absorption degree..........
G/li of ammonia absorption under
working conditions........................
430
63 (70)
51 (58)
530
75 (80)
60 (65)
490
72 (79)
57 (64)
Note: Data in parenthesis represent degree of ammonia absorption by tribasic
phosphate solution.
fU5,
QD
::r::
~ 420
s:::
.rl
ill
~ 0.(5
ctl
,0
Ct-!
o 410
s:::
o
.rl
ill
~ 405
.p
H
o
~ Q,Uf
>-
40 50
Temperature in CO
Fig. 2. Vapor tension of pyridine
bases over aD~onium phosphate
solutions.
1 - NH4H2P04 - 430 g/li, pyridine
bases 2 g/li; 2 - NH4H2P04 - 430
g/li~ pyridine bases 5 g/li; 3 -
(NH4)2HP04 - 490 g/li, p~ridine
bases 0.5 g/li; 4 - (NH4)2HP04 -
490 g/li, pyridine bases - 1.0 g/li.
6(J
previously by the present authors [13J.
Results are shown in Fig. 2. Results
indicate that even un~er equilibrium
conditions pyridine bases were poorly
absorbed by ammonium phosphate.
There-
fore, it is recommended that they be
absorbed differentially [12J. A study
was then made of the conditions con-
trolling illillnonia absorption from coke
gases using an installation of 6 - 8
m3/hr capacity in the coke-chemical
department of NTMK. Ammonia was ab-
sorbed by a disk-type column made of
plexiglass. Plates of different type
and shapes were used in the test; they
were set 150 mm apart. Plan of the
apparatus is presented in Fig. 3.
.Am-
monia catching was conducted at 36 -
400; the solution contained 390 g/li
absorption capacity was 57 g/li. Results
llli4H2P04' and the limit of affiQonia
are shown in Table 3.
Data in the table show that ammonia absorption by a solution of monobasic
phosphate can be as high as 50 - 60 g/li; this was accompanied by a high degree
of absorption selectivity- This was shown by the fact that the absorption of
-73-
-------
.,
a
e
5
Fig. 3. Plan of experimental setup.
1 - Heat exchanger; 2 - small pressure
tank; 3 - waterbath (water jacket); 4 -
absorber; 5 - drying column; 6 - flow-
meter; 7 - inflow slide valve; 8 -
outflow valve; a - direct (inflowing)
gas; b - monobasic solution; c - dibasic
solution; d - return (outflowing) gas;
e - hot watero
TABLE
d
pyridine bases ranged between 2 -
5% and volume of acid gases cir-
culating in the solution was neg-
ligible. The installation effi-
ciency was high, as shown by the
fact that a 5-disk setup brought
about practically complete remov-
al of ammonia from the coke gas;
this was in good agreement with
results of graphic calculation of
number of disks required theo-
retically. No noteworthy changes
were observed in the solution ab--
sorption capacity.
Recovery con-
ditions were investigated using
an experimental laboratory in-
stallation. Results of experiments
conducted at atmospheric pressure
3.
Ammonia absorption by monobasic phosphate.
: Content in : Content in : Percent of G/ Ii of :
: :G as con- : ra w gas :purified gas a.. on i a a.l1onia :G/ I i of
Exp.: Ty pe of No. Spray in g/n.3 in g/nl13 absorbed absorbed :pyridine
: : .: :
No.: disks of SUlllptlon density : :Pyri- : :Pyri- : :Pyri- : : :bases in
Idiakslin ~/hrlin li/.3 A..o- dine A_- dine A..o- : dine eo.- Prac- :solution
I I : I I I : : :plete :tical
nia Ibases: nia Ibases nia abases
I I : : I
6ell-
shaped 3 6 0.11 6.2 0.16 0.32 0.45 91+.2 2.1 53.0 42.0
2 Ditto 3 6 0.09 6.5 0.46 0.38 0.4At 93.8 4.4 67.0 56.0 D.40
3 Ditto 4 6 0.10 6.5 0.16 97.4 63.0 52.0
4 Di tto 4 6 0.09 6.4 0.20 97.2 68.0 57.0 0.45
5 Di tto 4 6 0.12 6.7 0.46 0.18 0.45 97.3 2.1 56.0 45.0 0.32
6 Ditto 5 6 0.08 4.7 0.00 100.0 61.5 51.5
7 Di t to 5 6 0.11 6.4 0.00 100.0 58.0 47.0
8 Trough- 4 9.5 0.10 6.5 0.75 88.5 37.5 46.5
shaped 4/9
9 Ditto 2/5 4 6 0.11 6.5 0.09 98.9 58.0 47.0
10 Di tto 5 6 0.11 6.5 0.00 100.0 59.0 48.0
Notes: I) In establ ishing co.plete or theoretical allmonia absorption by a solution, ammonia in the mono-
basic forlll .as subtracted frOil total a..onia. 2) In deter.ining a..onia absorbed under working condi-
t i 0'6 i nco.p I ete alllllon i a recovery .as taken into consl derat ion. 3) Lowered am lion i a content in the gas
.as caused by the fact that a part of it beca.e dissolved in the condensate and was deposited in the
gas conduit.
-74-
-------
or above showed thdt 75 - 80% of the ammonia bound during monobasic alillllonia con-
version to dibasic could thus be liberated. Using a desorber having an efficiency
equivalent to theoretically computed 8 - 10 disks and changing the reflux number
from 0.9 to 3.0 it was possible to liberate ammonia either in the form of 15 -
20% aqueous solution or as 97 - 98% ammonia gas. Plan of the technological model
for the absorption of ammonia from coke gas with the aid of monobasic phosphate
solution is shown in Fig. 4.
During the investigation viscosity determinations were made of mono- and
Results are presented
dibasic phosphate solutions at different temperatures.
in Fig. 5.
An investigation was made of the corrosion-resistance properties of dif-
Results
are shown graphically in Fig. 6.
ferent materials to mono- and dibasic ammonium phosphate solutions.
Results showed that alloyed steel and non-
ferrous metals were completely corro-
6
,
s
z
I
I
I
,
Fig. 40 Technological plan of
ammonia catching.
1 - Absorber; 2 - regenerator; 3 -
heat exchanger; 4 - cooler; 5 -
fractionator; 6 - heater; 1 - mono-
basic solution collector; 8 - dibasic
solution collector; 9 - pumps; 10 -
gas blower (exhaust fan); 11 - ab-
sorber for ammonia removal from flue
gases; 12 - apparatus for ammonia
blowing off from tar water; a - coke
gas; ~ - tar water; B - flue gases;
I" - monobasic solution;.n - dibasic
solution; e - ammonia or ammonia
water; ~ - coke gas in catching
pyridine bases.
sion resistant against the effect of
r""\ .
~ 11
~ f7
~ t'
U)
oM t5
o
PI t"
o~ 13
s:: '2
o
:;:; ,t
~ '0
o
U) 9
~ ,
:>. 7
.p
o~ I
g S
U)
~ (,
III
SD
iii
!II
7/J
8D
Temperature in CO
Fig. 5. Viscosity of phosphate
solutions.
1 - NH4H2P04 solution, 400 gjli;
2 - NH4H2P04 solution, 490 i/li;
3 - tNH4)~HP04 solution, 490
g/li; 4 - tNH4J4HPO solution,
550 g/li.
-15-
-------
f..i
cd
(])
~
~
~
.r-!
(])
~
~ 0
~
o
.r-!
en
o
f..i
f..i
o
o
~ -1
rl
2
I
4
-2
80
90 tOO
5"
60
70
Temperature in CO
Fig. 6. Corrosion resistance
of different materials to
NH4H2PO 4'
1 - Steel St-3; 2 - copper;
3 - steel X-17;
4 - steel X-.25.
f..i
;::$
o
,.q
~............
ON 0
.r-! S
en-.......:...
o ~
f..i
f..i (])
o 0
o ~ -I
cd
~~
rl en
.r-!
en
~ -2
2J
50
fflJ
Time in hours
Figo 7. Effect of inhibitors on
corrosion rate at 300.
1 - Control (no inhibitor); 2 -
0.2% quinoline bases plus 0.2%
KSCN .
monobasic ammonium phosphate solutions.
Steel St-3 was corrosion susceptible to
solutions of monobasic ammonium phosphate,
but was completely corrosion resistant to
dibasic ammonium phosphate solutions.
The
corrosion resistant property of steel St-3
to monobasic ammonium phosphate solution
was considerably enhanced by the addition
to the solution of small quantities of
quinoline bases L13], as can be seen from
the curves shown in Fig. 7. Hence, absorbers
and heat exchangers used in this work can
be made of steel St-3.
Ammonia absorption from coke gas can
also be accomplished using technical ammo-
phos, which is a mixture of mono- and di-
ammonium phosphates.
After a single cir-
culation this mixture will invariably con-
sist of mono-ammonium phosphateo
Conclusions.
The method herein described possesses
the following advantages over other methods:
10 It assures a high degree of ammo-
nia absorption and selectivity for the re-
moval of ammonia from coke gases.
2.
Ammonia absorption should be done
at ordinary gas temperature (40 - 500),
since this is the temperature range of coke
2flJ
gas delivered by gas blowers; it requires
no cooling and no purification from naph-
thalene.
3.
Ammonia absorption .can be accom-
plished by small dimension absorbers of
low pressure drop (100 - 120 mm of water).
-76-
-------
4.
At any given salt concentration in the solution the ammonia absorbing
capacity of a solution is independent of ammonia concentration in the gas and
of its temperature.
5.
The new method increases the choice of derived commercial products to
fit the range and nature of different industrial interests, permanent or sea-
sonal.
Economic outl~s and expected returns should be given serious considera-
tion before the recommended procedure of ammonia catching is installed.
Bibliography.
1. H. A. r 0 .II b JI 6 e p r, M. A. n 10 JI x 0" C It a H,
C. Ll. cJ> P II JI M a H, B H. 3 a r p a H " " II bI A. Xl6l'H'le-
CKaA HaYKa H npOMblWJleHHOCTb, 1956, ,. 6, CTp. 669.
2. 3. H. 5 a p r. TUHonorHA CMHTey...eatn.x nnacn-
'leCKHX Mace, 1954, rOCXHMH311aT.
3. A. cJ>. He a HOB. XH\lH'IecX" .8)'1U H npoMblw,
.IIeHHOCTb, 1956, Nt 2, CTp 213.
4. B. A. K JI e B K e. >KnX, 1959, 30. M 22,. CTp. 1725.
5. L. Be r g lei d. repM. naTeHT 27U 209 OT 19/Xll
1911 r., UHT. no C, 1914. I. 831. .
6. W. Bon e, G. Fin C h. A HrJl. 1I8TeHT 222 587 OT
3D/X 1924 r.,UHT. no C. 1925, I. 880.
7. E. M una k ala. S. 1 m 8 mot 0, K. M i h a r 8.
AM. nneHT 2707670, 1955; UHT. no C 19.'\5. 49, 12789.
8. E. M u n 8 kat a, S. 1m. mot 0, K. M i h a r a.
AM. naTeHT 2 707671. 1955. UHT. .no C. 1955, 49, 12789.
9. Sin nSTeHT, 1953.5177.
10. Sin. nSTeHT, 1950. 1793.
11. J. B I hr. Brennstoll-Chemie, 1955, 35, 9/10, 129.
12. r. Ll. X 8 P ,1 a iii no 8 H 'I, B. M. K a r a COB.
KOKC H XHMHA, 1959, Nt 5. CTJ} 30.
13. H 11. P Y C b RHO 8 a. M. B. r 0 ell T. a H, n. ~,-
By p M H CT P eH KO. JKnx. 1958, 31. 5, cyp. 748.
Differential Absorption of Ammonia and Pyridine Bases from Coke Gas.
v. M. Kagasov, V. P. Kholoptsev, N. Kh. Nemirovskii, V. G. Loparev
and G. D. Kharlampovich.
Koks i Khimiya, 1960, No.6, 32-350
Light pyridine bases constitute highly valuable basic raw material for
the production of many chemical substances.
Practical experience in the
U.S.S.R. and reports found in foreign literature indicate that coke gas, as
a source of naturally occurring pyridine bases, has not been adequately uti~
lized, especially by the method of ammonia saturation. The greater part of
-77-
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the pyridine bases was allowed to escape with the gas in the process of ammonia
saturation. The extent of pyridine bases lost was determined by physico-chemical
conditions prevailing in the saturator CIJ. With the introduction of new meth-
ods of ammonia utilization in the production of phosphates, etc., the simulta-
neous absorption of ammonia and pyridine bases became non-feasible.
The purpose of this study was to develop a differential method for the ab-
sorption of ammonia and pyridine bases from coke gas (lJ, thereby sharply in-
creasing the recovery of pyridine bases and obviating the shortcomings prevail-
ing in the process of simultaneous absorption of ammonia and pyridine bases.
The study was conducted on an industrial scale at the appropriate department
of the Chelyabinsk Metallurgical Plant in cooperation with the Department of
Fuel and Chemical Technology at the Ural Polytechnic Institute during April -
June of 1959 (2J.
Plan and method of study. The plant where the study was conducted had an
acid scrubber installed in the upper section for the absorption of ammonia from
the coke gas at times when the saturator was not in operation. The procedure
of the experiments was as follows: coke gas was run into saturator (1) where
the ammonia was removed by absorption. From saturator (1) the gas was passed
through an acid tank (2) and from there through an acid scrubber (3) for the
removal of pyridine bases. While passing through the scrubber the gas was
washed by an acidifying solution of pyridine sulfate circulated through the
systemo Excess of the latter solution was caught in scrubber pan (4) and from
coke
gas
9
~
to
centrifuge
gas to
benzene
scrubbers
to pyridine
installation
Technological plan of differential ammonia and pyridine
base absorption from coke gas.
6 - circulating saturator pan; 7 - common pit; 8 - pumps; 9 - gas preheater.
-78-
-------
there ran into collector (5), from which the solution was returned to the cir-
culating system. During the experiments, the number of which was limited, the
volume of circulating pyridine sulfate was within the range of 3.5 - 5.0 m3,
which obviated any solution excess. The acid scrubber was of the packing
filler type and had the following characteristics: diameter 4.5 m, total
height 14.49 m, packing ceramic (Raschig) rings measuring 80 x 80 x 8 mm,
height of operating packing 4.96 m, and of drying section 0.98 m. Experi-
ments were performed in two steps:
in the first step the study was limited
to the removal of pyridine bases from the gas after passing the saturator
under normal operating conditions.
In this case the gTeater part of pyridine
was caught in the saturator and the remaining portion of pyridine bases was
removed by absorption in this scrubber.
From the saturator this solution was
run into the pyridine installation.
In the second stage of the experiment the study covered the course of
differential absorption of awmonia and of pyridine bases. In this case the
pyridine bases were accumulated to the point of dynamic eQuilibrium between
the bases and the gas in the mother solution.
To accomplish this the movement
of the mother solution from saturator No.1 into the pyridine installation was
discontinued; this stopped the solution in the circulating saturator from over-
flowing into the common trough, thereby stopping the interchange or intermixing
between the mother solution in saturator No.1 and the solutions in other satu-
rators.
However, due to daily solution deoxidation in saturator No.1 and a
conseQuent drop in acidity caused by the addition of water, the solution was
entirely renewed; simultaneously the concentration of pyridine bases uropped
from 21 - 22 g/li to 4 - 5 g/li.
It was necessary to check the maximal satu-
ration of the vat of saturator No.1 with pyridine bases under operating con-
ditions prevailing in the solutions of two other saturators of the pyridine
installation; for this reason the saturator was not deoxidized over a period
of 5 - 6 working shifts.
Table 1 presents data on the operation of saturator No.1, and of the
oxidizing scrubber and data on the saturation of solutions with pyridine bases
and on the concentration of pyridine bases in the gas.
Absorption of pyridine
bases and their accumulation in the solution occurred at scrubber solution
tem~eratures ranging between 48 - 530.
Results of laboratory studies showed
th~t solution oxidation must be of a concentration which would allow the pres-
-79-
-------
TABLE
1.
. : Tecnnolo:)ical :Pyridine bases:
..Tecnnolo~ical scrubber Pyridine bases in "as
I scruboer per-: in solution I in 9/1 i :
. performance system :forrr,ance System: in Qj Ii
Exp.1 501u- : 801u- : Pres- I Hater: 801u- :
No.: tion : tion I sure Ijacket: tion: b
. . . t .d.t 8cru-
:temper-:acldlty:drop In: emper-:aci I Y:
ature: in : mm : ature: in I ber
: in CO :percent: water: in CO :percent:
z :Before I After ;Reov-
. Satu- :scrub- :scrub- :ery in :
. rator
ber ber Ipercent:
Notes
1st stage:
Absori-tion of pyridine bases with installation in operation.
50
12.5
20
53
60.3
8-10
0.050
0.003
91j .0
2nd stage:
Absorption of pyridine bases with installation not in operation.
2 48 8.6 15 50 1j.5 1j9.0 22.7 0.115 0.003 97.5
3 50 6.5 15 50 6.0 76.0 18.0 0.110 0.005 'j5.5
1j 48 6.9 10 50 3.8 111.1 22.0 O.~O 0.009 97.5
5 53 7.7 10 59 5.1j 95.0 38.2 O.lb1j 0.008 ~5.3
6 52 8.5 10 59 2.4 100.0 32.7 0.735 0.060 ~2., Scrubber solution
7 52 8.4 10 59 4.5 131j.6 33.7 O.1j30 0.030 ~3.0 In Heak
8 50 12.0 20 55 4.1j 1j7.6 11j.9 0.105 0.007 93. circul..tion
9 51 12.7 20 58 2.6 52.3 32.2 0.1j20 0.030 92'j Scrubber solution
10 50 6.6 10 52 7.2 119.9 25.7 0.105 0.\>10 90.5 in very weak
II 1j8 7.0 20 52 6.2 59.0 16.0 0.180 0.020 89.0 circulation
ence of acid pyridine sulfate in the solution. Further work showed that an
average 30% pyridine sulfate in the presence of a slight amount of aIilllloniurn
sulfate at 0 effect on the rate of absorption of pyridine bases.
50 had no
Maximal satur8.tion of the scrubber solution with pyridine bases amounting to
134.6 g/li was not necessarily the limiting concentration. The maximal con-
centration of 134.6 g/li was the result of the particular experimental con-
ditions.
Degree of pyridine bases absorption was determined primarily by the mode
of operation of the circulating scrubber pump. Comparison of analytical data
showed that under conditions of comparable pyridine base saturated solutions
and under practically the same pyridine base concentrations in the gas prior
to its entrance into the scrubber, loss of pyridine bases \lith the gas, upon
emerging from the scrubber, depended only upon volume of circulating fluid.
~lliere circulation was inade~uate scrubber packing became incompletely mois-
tened, allowing the gas to pass through without pyridine base desorption.
It should be noted thdt when solution
circulation was near normal, the pump
operated below its capacity; this was indicated by the fact that under the
conditions of operation it supplied 40 - 45 m3/hr, and in some instances 25 -
30 m3/hr, despite the fact that it was designed to supply 60 m3/hr. However,
-80-
-------
even at full capacity operation the pump could not supply the actually required
minimal 90 m3/hr. Despite the aoove discussed impediments, the degree of pyri-
dine oases aDsorption from the colee gas amounted to 95.5 - 97.7%, and even with
a circulation of 30 m3/hr the degree of pyridine oases aDsorption amounted to
93%.
It was necessary to determine conditions which Drought aoout dynamic
equiliorium between the content of pyridine oases in the gas and the mother
solution in the saturatoro
The concentration of pyridine bases in the gas
before entering the saturator, where the actual study was performed, ranged
3
between 0.39 - 0.46 g/nm. Temperature of the saturated vat under normal
o
operatin6 conditions ranged between 50 - 53. The pyridine installation with
regard to the illother solution operated only in connection with the saturator
under study, and the concentration of pyridine oases was as low as 8 - 10 g/li.
A comoined study was made of the following three factors: temperature, oxygen
content of the saturator mother solution, and concentration of pyridine bases
in the latter. Results showed that equiliorium oetween concentration of pyri-
dine bases in the saturator mother solution and the gas appeared under the fol-
lowing conditions:
o
Temperature of the saturator vat in C..................... 55 -
Percent of oxygen in the saturator vat..................... 3
Content of pyridine oases in the saturator vat in g/li..... 35
Under practical operating conditions and vat saturation at 30 -
60
- 4
- 40
40 g/li
of pyridine oases the degree of saturator vat acidity is of greatest signifi-
cance for equiliorium attainment due to the fact that it is difficult to create
wide range temperature changes. A drop in acidity under such conditions to
2.4%, for example, caused some pyridine bases bound with the mother solution
to pass into the gas; this was accompanied oy an increase in the content of
pyridine oases, in the gas leaving the separator, to 0.735 g/nm3; and vice
versa with rise in acidity to 5 - 7% and pyridine bases content in the mother
solution to 30 - 40 g/li pyridine oase aDsorption from the gas by the solution
in the saturator vat continued. Increasing the saturator mother solution
acidity during its deoxidation disturoed the equiliorium, and the pyridine
oase concentration in the gas, as it emerged from the saturator, oecame reduced
to approximately 0.1 g/nm3. However, in the process of differential aDsorp-
tion of ammonia and pyridine oases oeyond all saturators, the deoxidation
-81-
-------
process had no effect on the rate of pyri~ine base absorption; this is due to
the fact that with ~ drop in a9idity of the mother solution after its deoxida-
tion to normal value of 3 - 4%, pyridine bases previously absorbed from the gas
at a higher acidity again pass into the gaseous form.
Part of the pyridine sulfate solution obtained during the operation of
the acid scrubber became neutralized, as it passed through the pyridine in-
stallation, by mixing with the saturator mother solution, after a slight amount
of it was added to the scrubber solution. Reprocessing solutions saturated
with pyridine bases up to 150 - 200 g/li can be obtained in a continuous manner
by mixing it with a small amount of saturator mother solution; this can also
be done intermittently.
In the latter case, as a result of reduced ~uantity
of reprocessed solution and greater saturation with pyridine bases, a solution
volume collected over a month can be reprocessed in 3 - 5 days. Reprocessing
solutions of pyridine sulfate containing 150 - 200 g/li of bases has many ad-
vantages over the present technological procedure; the volume of the neutral-
izer can be reduced and the ammonia balance can be considerably increased.
Thus, in separating of 1 ton of pyridine bases from a solution containing 150
g/li at 7% free acidity, eleven times as much of ammonia is re~uired for the
neutralization of the free acid as for the neutralization of the saturator
mother solution which contains 10 g/li of bases and 5% free acidity. The
remaining free ammonia can be utilized in neutralizing sulfates of heavy pyri-
dine bases in the tar distilling department.
Dissociation constants of low b.p. compounds, such as pyridine and its
closest homologues, are of considerably lower magnitude than of high boiling
point compounds, and the steam tension is considerably lower; this set of con-
ditions creates a state of selective pyridine base sorption, which constitutes
one of the shortcomings of simultaneous ammonia and pyridine trapping. Con-
nected with this is the loss with the gas of most valuable low boiling point
pyridine bases. The use of differential absorption should improve the ~uality
of the pyridine bases. The validity of the above considerations was verified
by laboratory tests as follows: pyridine bases found in different concentra-
tions in gases emerging from the saturator, from the saturator solutions
(derivative bases) and from the acid scrubber, were fractionated. Loss in
pyridine bases with ammonium sulfate were slight, amounting to 0.04 - 0.06%
in the following instances:
in obtaining ammonium sulfate with low content
-82-
-------
TABLE
20
.
.
.
.
.
.
.
f-t :
OJ :
,0:
8 :
;j :
~ !
-P :
s:: :
OJ :
8 :
0'-; :
f-t :
OJ :
Pi :
~~
Fractional composition in percent
in 100% water-free bases
. . . s::
:>-- >::: ~ : 0
. 0 . :J . .rt
: rod .rI : s:: :-f-:J
:S::'0-P:0f-t : 0
: cO ... C) :.rI Q) : cd
: C\J ed : -P >0: f-t
:a1.. f-t:OOrl: '+-i
: ...Cf-f: cO 1£\:
:00 :f-t'LJrl: 0
: r-I °rt C): Cr-t Q) : 0
: I.f', s:: 0'-;: rl 0: 0
:rl »>:::rlrl-P: C\J
: rl ~: ctl .rI :
: I O'LJ:-p-p :
: 0 .rI : 0 U) :
: L.1'\.rI +=' : 8.rI : rl
:1""'") Pied: 'LJ : I.f',
:rl rl: : rl
.
.
: 0
: 0
: 0
I i
. ,0
. ~
.
.
.
.
.
.
Pyridine bases absorbed in the
saturator bath at average
loss of bases with the gas 2808 15.8 9.4 54.0 26.6 19.4
after the saturator 0.15
g/nm3
Pyridine bases absorbed in the
saturator bath at loss of 23.5 14.9 8.3 46.1 23.2 30.1
bases with the gas beyond ~he
saturator 0.20 - 0.25 g/nm
Pyridine bases absorbed in the
acid scrubber from the gas
beyond the saturator at aver- 49.4 14.4 8.1 12.9 18.6 9.5
age bases co~tent in the gas
of 0.10 g/nm
.
.
.
. .
. .
. .
: I :
. on .
: H s:: :
: »0:
. ~'r!.
: +=>:
: 0 0 :
: 0 cO :
: N ~ :
: rl~ :
: I Q) :
: Q:
: 0 0'-; :
: Ord :
: rl :
. .
. .
I
o
o s::
0'-; 0
Pi 0'-;
I-P
d 0
ed
o H
I.f','+-i
I""'")
rl 0
0'-;
I s::
»
C\Jrl
C\J
rl
Nature of experiment
1
2
3
of free sulfuric acid, especially after centrifuging; in reducing the amount
of tarry substances and during a thorough removal of the tarry substanceso
The above described acid scrubber used in checking the differential method
of catching ammonia and pyridine bases did not prove the most efficient for
the purpose. Preliminary computation showed that pyridine bases absorption
from 2 coke batteries could be accomplished by 1 small packed scrubber or by
a special type of column - 2.5 m in diameter and 2.5 - 3.0 m high. Results
also showed that a 100 g/li concentration of pyridine bases in the circulation
fluid affected only a slight corrosive effect, not exceeding the one produced
by the saturator mother fluid.
The method of differential ammonia and pyridine bases absorption can be
employed expediently with the processes currently used in the production of
ammonium sulfate in spray-type saturators, especially of the improved type.
The use of this differential method in connection with any other procedure of
-83-
-------
ammonia absorption is not recoL~ended.
In connection with the production of
ammonium sulfate the method of differential ammonia and pyridine bases ab-
sorption can be used in a modified way by combining the differential and
simultaneous trapping of the two substances.
In this modified process the
scrubber .solution and a small amount of the saturator mother solution become
neutralized, as a result of which some pyridine bases are trapped in the satu-
rator vato
Conclusions.
1.
Experiments conducted on an industrial scale showed that differential
ammonia and pyridine bases absorption was feasible practically, and that nearly
98% of the substances contained in coke gas could be recovered.
20 A 135 g/li concentration of pyridine bases solution was obtained by
this process reducing to 10 - 6% the solution volume carried over into the
neutralizer.
30
This process also reduced the volume of ammonia required for the de-
composition of the pyridine sulfate bases.
40 The quality of the pyridine bases was also improved due to the ab-
sorption of more valuable components, such as pyridines and picolynes.
50 The method of differential separation of aWtionia and pyridine bases
from coke gas can also be applied to the separation of awmonia with the aid
of sulfuric acid, using for the purpose spray-type saturators or in connection
with other methods of coke gas component trapping.
Bibliography.
1. r.~. Xap~aMllOBM~ M B. M. KaraCoB.
m 5, CTp 30-32.
2. B 3KcnepMMeHT~LHO~ ~aCTR pa60TM npRHRMa~R
HHJKeHepbI qM3 B. B. CDrpe~RKoB, A. M. JR'aPHOX,
A. M. KY~LKoBa H R. M. llaTpMKeeBa.
KOKC H llMMJI,
1959,
y~acTHe
R. E.. IIJyMaKoBa,
-84-
-------
Catalytic Removal of Nitric Oxide and Acetylene from Coke Oven Gaso
M. P. Korsh and F. P. Ivanovskii.
Zhurno Priklad. Khimii, Vol. 29, No. 10, 1561-1568, 1956.
Coke oven gas contains small amounts of nitric oxide and acetylene, both
are dangerous adIilixtures.
Through the interaction between nitric oxide, oxygen
and diolefin hydrocarbons, tarry substances are formed which settle in different
parts of the fractiondting eQuipment and may cause explosions.
The fact that
coke oven gas contains nitric oxide and its ability to form nitrogen-containing
tars, capable of disintegrating explosively, was established in 1926 - 1928 [lJ.
The sources of nitric oxide formation in coke oven gas were studied by Shpolyan-
skii and Filippov C2J and others [3, 4J.
Measures have been proposed to prevent
or to lessen the formation of nitric oxide and of tarry substances, such as
changes in the hydraulic cycle of coking ovens, use of denitrified sulfuric
acid for washing coke oven gas, etc. The proposed measures lowered nitric
oxide content in coke oven gas. However, the complete removal of nitric oxides
appears as the only effective way of combatting the accumulation of potentially
explosive tars. Several methods have been proposed for the removal of nitric
oxide:
by dry absorbents, by liQuid absorbents, and by catalytic hydrogena-
tion C5, 9J.
The present paper is devoted to a study of the catalytic conversion of
nitric oxide at atmospheric pressure with the aid of metallic sulfide catalyzers.
Reduction of nitric oxide with simultaneous fixation of the oxygen was studied
by these authors C9J at 400 - 5000 using a copper-nickel catalyst. Later, the
use of an iron catalyst was mentioned in a Russian patent CIO]. The metallic
catalysts in Question were used for the reduction of nitric oxide only in the
case of purified gases which contained no sulfur compounds and reQuire high
temperatures.
Catalytic removal of nitric oxide from coke oven gas, which always con-
tained sulfur compounds, reQuires the use of a sulfur resistant catalyst.
Tropsch and Kassler CIIJ studied catalysts resistant to sulfur compounds con-
sisting of molybdenum and tungsten sulfides impregnated into a porous carrier.
The investigators in Question tested a series of catalysts containing from 1
to 23% of ammonium sulfomolybdate.
The results obtained by them could not be
utilized, since complete decomposition of nitric oxide reQuired a temperature
-85-
-------
of 2300. In tests made by the present authors complete removal of nitric oxide
was achieved at 1500 with molybdenum sulfide appropriately activated. Catalysts
proposed in 1935 [12J consisting of sulfides of iron, nickel, cobalt and copper
on a porous carrier proved the most active.
~ith these catalysts it was pos-
sible to completely remove the nitric oxides, and simultaneously convert the
acetylene at a relatively low temperature (130 - 1500). Best results were
obtained with iron and nickel sulfides.
The use of cobalt and nickel compounds
for the catalytic removal of nitric oxide ~as later described by Tupholm [13J.
According to Shneider (14J iron sulfide, especially in the presence of hydroben
sulfide, proved to be a good catalyst for the removal of traces of hydrocyanic
acido The purpose of the present investigation was to find catalysts suitable
for the conversion of nitrogen and acetylene contained in coke oven gas into
substances which presented no danger at any stage of coke-chemical processes.
Experimental part. Catalysts and gas mixtures were prepared for study in
concentrations corresponding to amounts usually contained in coke oven gas.
Special attention was given to freeing the initial gases of oxygen. All tests
were made by simultaneously analyzing the initial and final gases for the con-
tent of corresponding components in the gas mixture.
This method obviated many
errors resulting from changes in the gas composition in the course of time,
especially since the work was done with such highly unstable and reactive gases
as nitric oxide and hydrogen sulfide.
For the same reason gaseous mixtures
containing nitric oxide and mixtures containing hydrogen sulfide were prepared
and stored in separate vessels and mixed only as they entered the contact
oven.
A nitrogen-hydrogen mixture was used in the experiments as the carri~r
gas, to which known amounts of nitric oxide and of hydrogen sulfide were added
(Fig. 1). The nitric oxide, measured with capillary (1), was introduced into
burette (2), where it was mixed with the nitrogen-hydrogen mixture. Final dilu-
tion to the desired concentration was achieved in mixer (3), into which the
nitric oxide was forced by mercury. The calculated amounts of nitric oxide
in the mixture were verified by check analyses. The hydrogen sulfide mixture
was diluted with the nitrogen-hydrogen mixture in large bottle (4) and stored
over a layer of vaseline oil. The hydrogen sulfide content of the mixture was
checked analytically. The gaseous mixtures thus prepared were directed into
contact oven (5). The nitric oxide, passing through mixer (3) passed via flow-
-86-
-------
~
I t
I
H
Q)
.p
('(j
~
~
111111'1111'1.
~ ~ / ,
--
"." I
::..
c:::.
~
'"
~
Figo 1. Plan of installation for
catalytic removal of nitrogen oxide
and acetylene from coke gas. See
text for details.
~
...,
meter (6), and the mixture containing
the hydrogen sulfide ~ flowmeter (7).
After the gas was removed from the
contact oven through stopcock (8), it
was directed for analysis of the hy-
drogen sulfide or nitric oxide by
closing correspondingly stopcocks
(8) and (9). For the determination
of nitric oxide the gas, having passed
through the alkali scrubber (10),
drier (11), and flowmeter (12), entered
the analytical apparatus. The latter
consisted of a vessel containing
potassium permanganate solution (13)
(to remove the nitrogen dioxide from
the nitric oxide), and an absorption
vessel (14), containing Ilosvai rea-
gent to absorb the formed nitrogen
dioxide, which was then determined
colorimetrically.
In many cases,
after leaving the contact oven, the
gas was diluted with pure nitrogen
or nitrogen-hydrogen mixture from
flask (15), as an auxiliary step.
Sulfides of molybdenum, copper, cobalt,
nickel and iron were tested as cata-
lysts in the conversion of nitric
oxide and acetylene.
Catalysts were prepared as fol-
lows:
a) Sulfomolybdenum catalysts
were prepared by mixing a weighed
portion of ammonium molybdate dis-
solved in a small volume of water,
with 4 ml of 20% ammonia and heating
-87-
-------
the mixture on a waterbath.
The solution was then saturated with hydrogen sul-
fide to obtain ammonium sulfomolybd~te.
The hydrogen sulfide used for the sat-
uration was first freed of impurities, especially of arsenic compounds, to
avoid poisoning the catalyst. The sulfomolybdate thus obtained was applied
to porous carriers (pumice, silicagel, aluminum oxide, etc.), which had been
thoroughly washed and calcined. The size of the grains was 2 - 2.5 mm. The
catalyst was calcined in open air at 2500 to decompose the aIT@onium salts; it
was then reduced with hydrogen containing about 30% hydrogen sulfide. Simi-
larly, catalysts were prepared which contained 5, 15.5 and 30% molybdenum
disulfide.
b) Catalysts of sulfides of iron, ni~kel, cobalt and copper were prepared
by impregnating porous carriers with solutions of nitrates of corresponding
metals.
Amounts of nitrates were selected in such a way that after reduction
with hydrogen sulfide catalysts contained up to 30% of metal sulfide.
The dry catalyst was calcined in open air at 2500 until the nitrate was
completely decomposed.
The catalyst was then loaded into a reaction tube and
with gradual temperature elevation reduced using a Ditrogen-hydrogen uixture
containing 30% hydrogen sulfide. It was found that the activity of the catalysts
depended on the reduction temperature, each having its optimum, which ranged
o
between 200 to 400. Sulfide catalysts could also be prepared by different
methods. Kirkpatrick [15J described a number of reactions by which nickel sul-
fide catalysts could be prepared.
Tests of sulfide catalysts for conversion of nitric oxide. The catalysts
prepared by the above-described method were tested in the apparatus (Fig. 1)
in two series: in the first series, the sulfides of copper, cobalt, iron and
nickel were investigated for the conversion of nitric oxide. Results of these
investigations are listed in the table in which mean values are presented for
a number of experiments; they are also presented graphically in Figs. 2 and 3.
It can be seen from the table and Fig. 2 that best results were obtained with
nickel and iron sulfides. A high degree of conversion was obtained with iron
sulfides, with a volume rate of 3000. In Fig. 2 the catalysts are presented
conventionally in the form of si~ple sulfides. Data presented for molybdenum
in the table were obtained with a sulfomolybdenum catalyst containing 30%
molybdenum disulfide. The effect of molybdenum disulfide concentration on the
degree of nitric oxide conversion is shown in Fig. 3.
-88-
-------
Nitrogen oxide reduction by metallic sulfides.
Temperature
in CO
: Content in original gas
ENitrogen oxide i Hydrogen
. 3/ 3 . sulfide
E. in cm m E.
in percent
: Content of :N" "d
: "t "d : 1trogen OX1 e
:n1 rogen OX1 e : d t"
:" Of" d : re uc 10n
:1n pur1 1e gas:" t
: ° 3/1 3 : 1n percen
: 1n cm m :
Copper sulfide, volume rate = 1200.
130
150
200
4.53
2.75
2.93
0.25
0.25
0.25
1.37
0.39
0.00
69.2
86.5
100
130
150
Cobalt sulfide, volume rate = 1200.
3.19 0.25 0.88
2.78 0.25 0.12
71.2
95.74
80
120
150
200
Nickel sulfide, volume rate = 1200.
3.44 0.25 0.53
3.14 0.25 0.20
2.80 0.25 0.04
3.10 0.25 0.00
Iron sulfide, volume rate = 3000.
3.34 0.25 0.09
3.69 0.25 0.06
3.32 0.25 0.00
84.8
94.7
97.1
100
100
130
150
96.94
98.4
100
Molybdenum sulfide, volume rate = 1200.
100
120
150
4.41
3.91
4.54
0.65
0.28
0.76
1.60
0.48
0.12
64.2
88.5
97.5
80
A
fOO
J
A
tOO
'0'0
100
120
fIfO
160
6
200
60
80
Z
t
40
10
180
10 15 20 25 30 5
Fig. 3. Effect of molybdenum sul-
fide content in carrier on degree
of nitrogen oxide reduction.
A - nitrogen oxide decomposition
in percent; B - percent of
molybdenum sulfide.
Temperature in Co: 1 - 100;
2 - 130; 3 - 150.
Fig. 2. Effect of different
catalyzers on degree of nitrogen
oxide reduction.
A - percent of nitrogen oxide reduc-
tion; B - temperature in Co.
Catalyzers: 1 - CoS; 2 - GuS;
3 - NiS; 4 - FeS.
-89-
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Tests of sulfide catalysts for conversion of acetylene. In the second
series of experiments, the sulfide catalysts were used to convert acetylene.
For this purpose the gas ~as passed over the catalyst as a mixture containing
0.055 to 0.18% acetylene. As the mixture left the catalyst tube, the gas was
analyzed for its acetylene content by a colorimetric method, comparing the
formed copper-acetylide color with a standard scale of known concentrations.
Acetylene was removed from sulfur-containing gases by sulfides of iron, copper,
cobalt, molybdenum and nickel. The first three catalysts manifested insuffi-
cient activity at 150 - 3000 temperature interval. In tests made with sulfides
of molybdenum and nickel, total conversion of acetylene at volume rate of 2000
was obtained at 3000 for the former and 2800 for the latter catalyst. It must
be pointed out that in these experiments the acetylene content of the mixture
was considerably higher (0.05 - 0.18%) than in the coke oven gas. Therefore,
these sulfides can also be used for removing acetylene from coke oven gas.
Discussion of results.
The study of catalytic removal of nitric oxide
and of acetylene using sulfide catalysts has direct bearing on gas purifica-
tion in the presence of sulfur compounds.
The above tests demonstrated that
nitric oxide and acetylene disappeared from the gases as they passed over the
catalysts in question. The direction of ~te general courses of the reaction
was studied next.
In the presence of hydrogen in the system under considera-
tion, the following reactions must take place:
NO + 2.5H2 = NH3 + H20
NO + H2 = 0.5N2 + H20
NO + H2S = 0.5N2 + H20 + S
(1)
(2)
(3)
The probability of any of the reactions taking place is determined by
specific free energy changes. Changes in free energy in the above reactions
were obtained using thermodynamic data.
Without going into details of the
calculation method used, negative free energy values were obtained which are
shown in Fig. 4; the values indicate that all three reactions are thermo-
dynaruically possible. The direction and speed of the reaction are determined
by the use of a suitable catalyst. Tropsch and Kassler (llJ showed that the
basic principle of the method used by them for freeing coke oven gas of nitric
oxide with molybdenum svlfide is the catalytic hydrogenation of nitric oxide
to ah@onia at 2300. No ~llinonia was produced in ex~eriments performed at 130 -
1500 in the presence of iron and nickel sulfide. It was noted that the cold
-90-
-------
A
8300J - ..l.--
l------~
IDW[ ~--
4JOOO~' I '5
o 200 !f00 600
parts of the reaction and gas outflow pipes
became gradually coated with a thin layer of
sulfur. A reaction between nitric oxide and
hydrogen sulfide apparently had taken place
with the deposition of free sulfur.
The removal of acetylene from coke oven
gas, together with the catalytic conversion
of nitric oxide are of considerable importance.
Figo 4. Effect of tempera-
ture on free energy changes.
A - Free energy changes 6F;
B - temperature in Co.
Reaction 7: NO + H2S =
0.5N2 + H20 + 1/6 S6;
Reaction 2: NO + H2 =
0.5N2 + H20. Reaction
3: NO + 5/2H2 = NH3 + action directions of catalytic conversion of
H20. acetylene in gas mixtures: a) decomposition
to carbon and hydrogen; b) conversion by water vapor; c) hydrogenation of
acetylene to saturated hydrocarbons; and d) polymerization. In the present
case, the first two reactions appear less probable, in view of the small water
vapor content of the gas, the low temperature and the absence of soot in the
products of the reaction and on the catalyst. The probability of the thermo-
Upon entering a deep cooling apparatus together
with coke oven gas acetylene corrodes the
copper portions of the apparatus forming ex-
plosive copper acetylide. Data found in the
literature point to the following possible re-
dynamic process of acetylene hydrogenation into ethylene according to equation:
C2H2 + H2 .... C2H4
(4)
is determined by the free reaction energy changes according to the following
equation:
o 0
6F ~ 6FC H - 6F C H
2 4 2 2
or, in final form:
6Fo = -36720 + 8.35T In T - 0.0022T2 - 38.6T
Below are presented values for free energy of acetylene hydrogenation re-
actions as derived by the last equation:
°C 25 100 150 200 300 500
-6Fo 34136 32985 32050 31184 28170 24939
The values indicate possibilities according to which the reaction of
hydrogenation of acetylene can proceed. The last one can proceed even at
ordinary temperatures. Thus, in the presence of a large excess of hydrogen
-91-
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in the coke gas and with the use of a suitable catalyst, the reaction of hy-
drogenation of acetylene appears highly probable. Many reports appeared in
the early literature on the hydrogenation of acetylene into ethylene and ethane
with the aid of platinum and iron groups as catalysts.
Conclusions.
1.
Active catalysts were found for the complete conversion of nitric
oxide and acetylene in gases containing sulfur compounds. Such catalyzers
were sulfides of iron, nickel and molybdenum impregnated into a porous carrier.
20 Experiments were conducted with a.nitrogen-hydrogen mixture contain-
ing nitric oxide and hydrogen sulfide in concentrations close to those found
in coke oven gas; complete conversion of nitric oxide was obtained with nickel
and iron sulfides at 130 - 1500 at a volume rate of 1200 - 3000.
3. Complete removal of acetylene from sulfur-containing gases at an
acetylene concentration of 0.05 to 0.18% was achieved at 200 - 2800 in the
presence of molybdenum and nickel sulfide catalysts at volume rate of 2000.
Bibliography.
[1] P. SChuftan,. Von den Kolden u. den MiIlt.ralUlen, 1,205 (1928); 11,31
(19?9); Brennstoff-chemle, 13, 104 (1932).-[21 M. A. illnOJIRHCKUH 'H
B. C. «DUJIHlInOD. HOKC U XFI'MMII, 10 (19:17).-[3] B. 11. HYCTOB H
JI. H. HOJIIIHAp. HOKCOBhlll ra3. MeTan"ypl'1I3~aT (1947).-[4] B. «D. rorlIH H
JI. 11. 3 JI 0 T II H. r J1y60!
-------
Colorimetric Determination of Lead in Atmospheric Air.
V. A. Morosov.
(From F. F. Erisman Sanitary Research Institute, Moscow).
This paper was published in Gigiena i Sanitariya. It is regretted that
reference to year, volume, issue number and pages have been lost.
In the presence of lead quinalizarin yields a characteristic color which
is easily recognized in the presence of 0.005 y of Pb in 2 mI. In making
quantitative lead determinations this author used the following standard com-
parison scale: test tubes containing 0.05, 0.1, 0.25, 0.5, 1.0, 2.0 and 4.0 y
in 2.0 mI. The developed color ranged from yellow to bluish-rose, with the
control tube having a slightly yellowish color. The water used in the prepara-
tion of the standard scale must have a pH 6.2 - 6.4. Such water was obtained
by double distillation followed by 20 minutes boiling.
Quinalizarin also produced a color in the presence of copper, zinc and iron.
Hence, for the determination of lead these interfering metals must be removed.
This was accomplished by the method of Golubeva: test solution was treated
with 25% ammonia and ammonium chloride, 1 H solution of Ha2C03 and KCl. The
method for removal of interfering metals was checked and found satisfactory.
Samples of air dust were collected by the ash-free filter paper method,
aspirating the air at the rate of 2 li/min. After the sample has been col-
lected the filter paper was boiled for 5 minutes in 3% nitric acid; the nitric
acid solution was then placed over a boiling waterbath and gradually evaporated
to dryness. The dr,y residue was dissolved in water, placed into a centrifuge
tube. Two ml of 25% ammonia solution, 0.2 ml 25% ammonium chloride solution,
0.1 ml 1 H Na2C03 solution and 0.1 ml 1 N KCl solution were added. The mix-
ture was brought to a boil and centrifuged; precipitate was washed with ammo-
nia and distilled water, again centrifuged, treated with 10% solution NaOH,
again brought to a boil and again centrifuged.
The plumbite solution was neutralized with 3% solution HN03 to weak acid
reaction, placed into a porcelain evaporating dish and evaporated to dryness
over a waterbath; the dry residue of lead nitrate was dissolved in 2 ml of
water. At this point the eight tube series (including the control) of stand-
ard solution was prepared as described above. To all tubes of the standard
scale and to the tube containing the test sample add 5 drops of 0.002% of
-93-
-------
quinalizerin solution in acetone, allow to rest 2 - 3 minutes and compare
colorimetrically.
The method was used in determining lead concentrations in atmospheric air
in the proximity of a metallurgical plant, in industrial emissions containing
lead, aspirating 50 - 200 ml of the polluted air, depending upon the Pb con-
centration anticipated. Analytical results showed that the air samples con-
tained lead in the range of 0.05 to 2.75 y/m3.
Determination of Manganese in Urine.
S. I. Yakushina.
(Institute of Labor Hygiene and Occupational Diseases of the Academy of
Medical Sciences, U.S.S.R., Moscow).
Farmakologiya i Toksikologiya, Vol. 18, No.1, 54-56, 1955.
I. D. Gadaskin showed in 1939 that manganese entered into the composition
of normal human and animal tissues and organs in small amounts. Most methods
for the determination of manganese in tissues are based on the principle of
its oxidation to manganic acid. Lead dioxide, ammonium persulfate, potassium
persulfate and potassium periodate are usually used as manganese oxidizers.
The polarographic method of manganese determination has also been used to
some extent. The most widely employed method for manganese determination is
the one in which manganese is oxidized to its semivalent form and determined
colorimetrically. This method has been used by Nifontova in 1936 for the
determination of manganese in the air. In that method manganese is oxidized
by ammonium persulfate in the presence of silver nitrate as a catalyzer. In
1948 Michlin used this method for the determination of manganese in biological
substrates. The problem of the present author was to establish the presence
of inorganic and organic manganese compounds in rabbit urine.
Check tests of
the Kichlin method made with standard solutions of manganese have always
yielded satisfactory results. It was noticed, however, that irregular color
-94-
-------
densities were obtained in the preparation of the manganese scale. Experi-
ments indicated that the cause of this was in the improper concentration of
different acids. Final results indicated that most satisfactory standard
scale was obtained with 15 - 11% sulfuric acid. The use of 20% sulfuric acid
was discontinued.
In the experimental tests urine was used to which a solution of manganese
salt was added at the rate of 0.04 mg per unit volume; analytical results
yielded 0.032 - 0.04 mg, which is equivalent to 10 - 100%.
Treatment of the precipitate with sulfuric acid in a funnel and evapora-
tion of the solution as proposed by Michlin usually consumed much time. To
obviate this the following simplification was introduced: the washed precipi-
tate and the filter were placed into a beaker, covered with 15% hot sulfuric
acid and left stand for 20 minutes, at the end of which the solution was fil-
tered through an ordinary filter and the manganese determined in the filtrate.
The simplified method yielded satisfactory results as indicated in Table 1.
In determining combined manga-
nese 500 ml of the urine were evapo-
rated to dryness over a boiling
waterbath. The dry residue was then
treated with a combined solution of
TABLE
1.
Determination of inorganic manganese
compounds in human urine without
digestion (mineralization).
. : Kg of)(n : Percent
Test i Kg of )(n i by . sulfuric and nitric acids. After
No. ! of )In by
i added i analysis : l' the material had become completely
: ana YSl.S
1 0.04 0.038 95 digested it was transferred to a
2 0.04 0.038 95 porcelain dish and evaporated to
3 0.04 0.038 95 dryness. The dry residue was treated
4 0.04 0.038 95
5 0.04 0.038 95 with 15% sulfuric acid and filtered;
manganese was then determined in the filtrate
as described above.
Check tests have indicated that the use of 15% sulfuric acid as a modifica-
tion to the method yielded satisfactory results. It was noted, however, that
in the 'process of evaporation the solution occasionally developed a yellow
color; it was also considered that much time was consumed by the process of
sulfuric acid solution evaporation to dryness. Therefore, the sulfuric acid
was diluted with water to a 15% concentration and the manganese determined
directly.
-95-
-------
TABLE
..1..
It was further demonstrated
that the acid conoentration affected
the determination; it was necessar,y
Determination of manganese
with digestion.
1
2
3
4
0.04
0.04
0.04
0.04
0.036
0.036
0.04
0.04
90
90
100
100
to dilute the acid to a concentra-
tion not exceeding 5 - 6 N. Results
obtained by this modification are
listed in Table 2. The procedure
Test i Mg of Mn : Mg of Mn : Percent
: :. by ! of MIl by
No. : added
: : analysis: analysis
of the modified method is as fol-
lows: add to the urine 500 ml of
strong ammonia; 6 - 8 hours later
filter the specimen through a Buchner filter; wash 2 or 3 times with hot water.
Transfer the filter with the precipitate to a beaker and cover with 15% solu-
tion of sulfuric acid. Leave stand for 20 minutes and filter again through
filter paper. The filtrate is used for the determination of Kn ions. The
standard scale is prepared from a solution of manganese sulfate.
In making quantitative manganese determinations take 500 ml of the urine
and evaporate to dryness over a boiling waterbath, first adding 2 - 3 ml of
concentrated H2S04. Digest the dry residue with a mixture of sulfuric and
nitric acids, after digestion has been completed and nitric acid fumes have
been eliminated with perhydrol, add water to the flask so calculated that
the final acid concentration will amount to 15%. This can be done titramet-
rically; after this proceed with the manganese determination as described
above. The method was tested with urine specimens of rabbits poisoned with
manganese chloride over a period of 10 months. Results indicated that manga-
nese was eliminated with the rabbit urine in the form of inorganic and organic
compounds. The 24-hour urine specimen was then divided into 2 equal parts,
one for the determination of inorganic manganese compounds and the other for
the determination of total manganese. Results are shown in Table 3. Tests
were also made which indicated that the modified method can be used for the
qualitative and quantitative determination of manganese in human and animal
tissues and organs.
Conclusions.
1. Inorganic manganese compounds in biological media are determined
directly in the filtrate, thereby eliminating unnecessary steps, such as a
-96-
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TABLE
3.
Determination of manganese in urine of
rabbits administered manganese chloride.
T t: :1 . : :Percent of
:s iTotal )In£ n0»nrgan1cl Organic linorganic
.1.1 o. : : :)In .z. u-
: : : an
1
2
3
4
5
6
7
8
9
10
0.08
0.2
0.2
0.3
0.4
0.15
0.08
0.04
0.096
0.12
0.048
0.048
0.04
0.032
0.12
0.036
0.012
0.016
0.032
0.02
0.032
0.152
0.16
0.268
0.28
o. 114
0.068
0.024
0.064
0.1
60
24
20
10.6
30
24
15
40
34
16
second processing of the speci-
men with sulfuric acid followed
by its evaporation.
2. In determining total
organic and inorganic compounds
the urine is wet digested with
a mixture of sulfuric and nitric
acids and the nitric acid com-
pletely driven off, following
which the residual sulfuric
acid is diluted to 15%, as
shown by ti t rame try , and the
manganese ions determined di-
rectly in the solution.
Bibliography.
r a Jl. a C K H H a 11. .Lt. OnpeJl.e.neHlle npOMhIlIIJIeHHhIX Heopral/Jll'lecKHx JlJl.OB 9 opra-
HH3Me, JI., 1939. - H II cjJ 0 H TO B a M. B., JI36. npaKTHKa, 1936, N!! 5, CTp. 26. - M H x-
JI H H C. 51., apMaKOJI. H TOKCHKOJI., 1948, T. XI, M I, CTp. 39-42.
Rapid Method for the Determination of Carbon Monoxide
in the Air of Working Premises.
D. If. Vaskevich, A. I. Bulycheva and P. A. Mel'nikova.
Vodosnozhenie i Sanitarnaya Tekhnika, 1956, No.1, 12-13.
Improvement in the quality of planned and installed ventilation apparatus
in industrial premises requires that they be checked for their efficiency.
At present the determination of sanitary-hygienic efficiency of ventilation
is considerably impeded by the laborious procedures of chemical air analysis
for the content of deleterious vapors and gases. Shortening the time for the
determination of deleterious substances may aid considerably in finding the
cause of ventilation installation defectiveness and in the early removal of
-91-
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such causes and, consequently, in raising ventilation efficiency in industrial
and working premises.
Carbon monoxide is a most widely occurring industrial POiSOD; it is present
in garage exhausts, in foundries, thermic generator, and many other produotion
departments. The importance of timely determination of oarbon monoxide concen-
trations in the air of working premises need not be emphasized. The present
method for carbon monoxide determination, as described in GO~ 5612-50, is
based on the oxidation of carbon monoxide to carbon dioxide by iodine pentox-
ide. This method is time-consuming, cumbersome, and not alw~s practical.
In the course of a working ~ the laboratorian can perform, at the most, 5
or 6 analyses; the procedure requires a special comparatively complioated set-
up and the services of qualified analysts. The offioial method can not be used
for the determination of carbon monoxide concentrations directly at the work-
er's position. The procedure carried out with the usual type of apparatus
requires several days. The method presents considerable difficulties when it
becomes necessary to colleot and analyze many air samples in a short time.
For instance, in making a general inspection of ventilation efficiency in a
molding and oasting room of a foundry of medium size, it becomes necessar,y to
collect and analyze 30 - 50 air samples in a brief period of time.
The VTsSPS Koscow Institute of Labor Protection developed an indicator
method for the determination of low carbon monoxide concentrations in the air
of production premises. The method is based on passing the tested air for 3 -
5 minutes through an indioator tube filled with a special white powder (Fig.
1). As the carbo. monoxide passes through the tube, the powder aoquires a
greenish-violet color, the intensity of whioh is proportional to the oarbon
monoxide concentration in the air. The intensity of the developed color i.
then compared with the color of a specially prepared standard series of tubes
representing CO concentrations in the range of 0.01 - 0.4 mg/li. The proce-
dure requires 10 minutes and the determination oan be made directly on the
spot.
~~:'=='~~6":~~~=~:~~'~
Sanitary regulation I 101-54 prescribed that where work was performed
continuously 8 hours per ~, the carbon monoxide concentration in the air
should not exceed 0.03 mg/li; in
rooms in whioh work was performed
during 2Q-minute intervals the
Fig. 1.
Indioator tube.
-98-
-------
carbon monoxide concentration in the air may be as high as 0.2 mg/li. Tested
air in working premises frequently contains pollutants which might interfere
with carbon monoxide determinations; in such instances the interfering admix-
tures may be caught by a special cylinder filter connected to the indicator
tube in such a way that the air passes through this filter before entering
the indicator tube. The cylinder contains two layers of calcium chloride and
activated charcoal. In the process of air passing through the indicator tube
acid vapors are given off which corrode the walls of the metallic aspirator.
To eliminate this the air is passed through a tube filled with alkali saturated
cotton. The indicator tube and the connected filter cylinder are placed into
a special housing. This assures the straight line flow of the air through the
filters and the tube and simplifies the air sample collection and facilitates
the transportation of the setup. The final setup in its casing is shown in
-- - ---- - -
\~:=~'~~~J~~~:;;;;r;;;'
-'~,.J""
..
o
c -
~ .~ ~
\Ii +oJ ~ -e
I ~.;;
l-
.- ....
C> 0
I 2 4 3
Fig. 2. Indicator assembly.
1 - filter with activated charcoal; 2 -
indicator tube; 3 - filter with
a~lized cotton; 4 - case.
----
~
..
~
'",,-
.-...
Fig. 2. Depending upon the
concentration of CO in the
air, the latter should be
aspirated through the tube
in volumes of 1 Ii or 150 ml.
The air is passed through the
setup with the aid of a me-
tallic water level aspirator, one
tank of which was above a water col-
lecting tank at a definite height.
A pet cock is arranged between the tanks
by means of which it is possible to
regulate the outflow of water so that
in a period of 3 - 4 minutes either
1 Ii or 150 ml of air could be aspi-
rated. The general view of the setup
If}
6
is shown in Fig. 3.
Here the indicator
tube (1) is connected with 2 filters
(2 and 3) and through them is connected
by means of a rubber tube (4) to aspi-
rator tanks (5) which are attached to
a special stand (6). The aspirator
-99-
-------
can be carried around by a rubber attachment (7). Aspirator tanks are inter-
connected by a rubber tube (8) in the middle of which there is inserted a four
way stopcock (9). Before sample collecting a Moore pinchcock (10) is placed
over rubber tube (8). The apparatus is equipped with a standard set of colors
(comparator) (11). There is also a case (12) which contains reserve indicator
tubes and ampules (13) with the drying agent and activated charcoal. For
storage or transportation purposes the setup is placed into a special box (14).
The sample taking and color comparison are accomplished as follows: the
indicator tube is first cut open at both ends by a small file and the end
marked by rings is connected to the filter containing the activated charcoal;
the other end of the indicator is connected to the second filter containing
alkalized cotton.
This is then connected to the water aspirator by means of
a rubber tube. The setup is then brought to the point of sample collection,
and the Moore pinchcock over rubber tube (8) is released. As the water runs
out of the upper tank the air is sucked in through the indicator tube, and if
carbon monoxide is present in the air the indicator l~er will become colored.
At the end of the air sample collection, that is, at the end of the water out-
flow, the indicator tube is disconnected from the filter and the color com-
pared with the standard set, each tube of which is marked by its equivalent
carbon monoxide concentration in mg/li. If the color developed in the in-
dicator after aspirating 1 Ii of air is of greater intensity than 0.09 mg/li,
which is the highest equivalent of the standard series, a new sample of 150 m1
of air is then aspirated as previously described through a new indicator tube,
compared with the standard and the result multiplied by a corresponding fac-
tor. Some results obtained by the authors with this procedure are shown in
the following table. For control purposes results obtained with the same
samples of air by the standard regulation method are presented for comparative
purposes. It should be noted that collection and analysis of air samples
were not performed by members of the laboratory with which the authors are
associated, but by laboratory personnel of corresponding industrial enter-
prises or of local sanitary-epidemiological stations. Thus, it is seen that
the proposed rapid indicator method for the determination of carbon monoxide
in the air yielded reliable results under different industrial production
conditions.
-100-
-------
Plant and department
(practical) conditions.
: Kg/Ii of CO found
~ . New
i Standard i indicator
method I method
.
0.028 0.02
0.012 0.01
0.033 0.03
0.039 0.03
0.022 0.02
0.04 0.045
0.045 0.045
0.034 0.045
0.011 0.01
0.02 0.02
0.02 0.01
0.11 0.12
0.02 0.02
0.01 0.01
0.04 0.045
0.006 0.01
0.056 0.06
0.015 0.015
0.055 0.06
0.059 0.06
0.02 0.02
0.02 0.02
0.014 0.015
0.01 0.01
!Jone Wone
Bone Wone
0.028 0.015
0.018 0.015
Comparative data of CO determinations and industrial
Vaitovich foundr,y, casting department
Plant "J3oretz", casting department
)(oscow coke gas plant, generator department
Garage of KChM U.S.S.R. laboratory
Minsk-Xlrov Kachine Plant, welding department
Grodno building materials combine, kiln department
-101-
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Comparative Evaluation of Some Methods for the Determination of
:Beryllium and Its Compounds Applicable to Air Analysis.
M. S. :Bykhovskaya.
(Institute of Labor Hygiene and Occupational Diseases, A.M.S., U.S.S.R.).
Gigiena Truda i Professional'nye Zabolevaniya, Vol. 1, .0. 6, 49-53, 1957.
Many methods have been recommended for the determination of small amounts
of beryllium in different substances. The methods can be grouped as follows.
10 Colorimetric methods using quinalizarin, naphthazarin, p-nitrobenzene-
azoorcin, 1,4-d1oxyanthraquinone-2-sulfonic acid, aluminone, alizarin blue :Bi,
thoron, arsenazo, B-resorcino1, beril10n II, and other substances. At a given
pH each of these reagents changes the color and intensity of its solution in
the presence of the beryllium ion; final determination is made by comparison
with a standard solution. Minimum determinable amounts of beryllium vary froll
0.2 to 2 y in the volume of solution under study.
2. Fluorescence methods based on the reactions of beryllium ion with
morine, l-amino-4-oxyanthraquinone, 1,4-dioxyanthraquinone, and other sub-
stances. MiniDIUID amounts of beryllium that can be determined by these methods
range from 0.05 to 1 y.
3. Spectrographic methods based on measurement of the difference in
darkening of the beryllium line and of the element used for comparison: alu-
minum, thallium, cadmium. The beryllium excitation spectrum is obtained with
a carbon arc fed by direct or alternating current of 10 - 16 A, as well as
with a condensed spark. The minimum determinable amounts of beryllium, ac-
cording to literature, range from 0.005 to 1.0 y. Most of the reagents recom-
mended for colorimetric and fluorescence determination of beryllium are not
specific. Such ions as Kg, Ca, Cu, Zn, AI, Fe, Kn, P04' and others interfere
with the determination.
In this connection, it becomes necessary to remove or mask the interfering
ingredients. It is suggested, for example, that beryllium be precipitated with
phosphates of calcium, iron, aluminum and manganese, with subsequent removal of
several cations by electrolysis on a mercury cathode [lJ, or extraction of
the acetylacetonate of beryllium with benzene C2J, with subsequent decomposi-
tion of the acetylacetonate and re-extraction of the beryllium with 5 B HCl.
Trylon :B [3, 4J, the disodium salt of ethylenediaminotetra-acetic acid, which
-102-
-------
fo~s very stable complexes in alkaline solution with many elements of groups
II and III, has found wide use in analytical chemistry of beryllium for the
removal of the interfering elements. The beryllium complex is unstable at
this pH and is readily decomposed; therefore, it can be determined directly
without removal of the admixtures. I. P. Alimarin, I. K. Gibalo, and others
made use of the difference in stability of the acetylacetonates and of beryl-
lium complexes and of other metals. Different forms of chromatographic analysis
have also been described for the separation of beryllium from mixtures.
The purpose of the present study was to compare several methods for the
determination of beryllium in the airo The work was conducted with standard
beryllium solutions and also with artificial mixtures containing fixed amounts
of calcium, magnesium, iron, aluminum, zinc and manganese.
A comparative
evaluation was made of the methods for the determination of beryllium with
morine, l-amino-4-oxyanthraquinone, 1,4-dioxyanthraquinone, quinalizerin,
thoron, I-resorcinol, arsenazo, and beryllon II. Simultaneously, the tests
were made with trylon B in an attempt to counteract cationic interference and
to separate the constituents by paper chromatographic partitioning. Results
showed that the fluorescence method with morine [1, 5J was the most suited for
the purpose. Korine (pentahydroxyflavone) formed with beryllium an intra-
formational complex having a characteristic yellow-green fluorescence in solu-
tions exposed to ultraviolet radiation. With a beryllium content of 0.02 to
0.8 y in 5 - 10 ml, the intensity of the beryllium solution glow is propor-
tional to the concentration; with larger amounts of beryllium it is difficult
to distinguish any difference in the intensity of the glow.
Optimal pH for this reaction was about 13. Sulfates, chlorides, and
nitrates reduced the intensity of the fluorescence. The fluorescence of
beryllium solutions was more intense in alkalized distilled water than in
solutions of neutralized acids. Minimum determinable amount of beryllium in
aqueous solutions was 0.01 V; in neutralized acid solutions it was 0.05 y.
Depending upon their quantitative levels in the solution under study, a number
of elements extinguished the fluorescenoe of beryllium solutions to a greater
or lesser extent. A particularly high degree of extinction was manifested by
iron and manganese. It has been established that oaloium, magnesium, zino,
manganese, iron and other elements did not interfere with the beryllium deter-
mination if trylon B was added to the solution before the addition of alkali."
-103-
-------
Trylon B had no marked effect on the intensity of the fluorescence of beryl-
lium solutions.
The fluorescence method for the determination of beryllium with l-amino-4-
oxyanthraquinone and 1,4-dioxyanthraquinone possessed the same sensitivity.
Minimum determinable amount of beryllium in alkalinized distilled water was
0.05 y, in neutralized acid solution, I y. The presence of Ca, Kg, Cu, Zn,
AI, Fe, Mn, Si, P04' and other.ions had a greater effect upon the intensity
of the solution fluorescence than in the reaction with morine. It was estab-
lished that the extinguishing action of metal ions was eliminated by adding
trylon B to the solution.
In a comparative evaluation of the colorimetric methods based on the re-
action of beryllium ion with quinalizerin [6J, thoron [7J, arsenazo, N-resor-
cinol [8J, and beryl Ion II L9J, best results were obtained with the latter.
The reagent was more stable than quinalizerin and gave better contrast trans-
itions of color with changes in the amount of beryllium. The advantage of
beryllon II over arsenazo and N-resorcinol rested in the fact that when the
reaction occurred under optimal conditions at pH 11 - 13, the effect of m&D1
accompanying cations could be eliminated by adding trylon B. When the reac-
tion took place with arsenazo and B-resorcinol, try10n B also formed a complex
with beryllium. Upon addition of beryl10n II at pH 11 - 13, solutions con-
taining the beryllium ion took on a color ranging from dark blue-violet to
light blue. Under such conditions, a control sample free from beryllium as-
sumed a reddish-violet color. Minimum determinable amount of beryllium tested
in neutralized acid solution was 0.5 y.
A standard scale should be prepared ranging from 0.5 to 4 y at 0.5 y in-
tervals. Amounts of beryllium greater than 4 y yielded no distinguishable
differences in the intensity of the light blue coloration. It was shown that
the simultaneous presence in the solution up to 500 y of magnesium or calcium,
up to 10 Y of iron, or up to 100 Y of aluminum did not interfere with the
beryllium determination, provided that trylon B was added to the solution.
Supplemental studies were made by the method of ascending partitioning paper
chromatograp~ using rapidly and slowly filtering chromatographic paper issued
by the Leningrad Paper Factory. The paper was washed with a mixture of acetone
and hydrochloric acid. For the development of the chromatogram, a universal
indioator was tested, which consisted of an alcoholic solution of 8-oxyquinoline
-104-
-------
and an 0.02% morine solution.
After it had dried, the chromatogram was kept
in ammonia vapor. Under ultraviolet irradiation beryllium spots acquired a
greenish-yellow color. The glow intensity and the size of the spots increased
with the beryllium concentration. Most complete separation of beryllium fram
iron, aluminum, calcium, magnesium and manganese was obtained with butyl or
isobutyl alcohol saturated with concentrated hydrochloric acid. Fluorescence
intensity of spots obtained with 0.01 ml solutions containing 5, 10, 25 or
15 y of beryllium was readily distinguishable, but the spots were of irregular
shapes and tended to diffuse. Results indicated that the method of partition-
ing paper chromatography, with the above-indicated varieties of paper, and
subsequent determination of fluorescence intensity of the spots by comparison
with standard spots may be used as a semi-quantitative orientation method.
Subsequent investigations pointed to the promising character of the
spectrographic method for the determination of small amounts of beryllium.
The work was performed with ISP-22 quartz spectrograph. Spectral excitation
was obtained with an alternating current carbon arc (16 A). The 0.015 mm
spectrograph slit was illuminated with a three-lens condenser system. The
analytical interval between electrodes was 2.5 mm and was kept at this value
through the entire period of spectral excitation. Kost reproducible results
were obtained when beryllium was evaporated from an electrode with an aperture
depth of 8 mm and an inside diameter of 1.5 mm; under such circumstances,
complete evaporation of the beryllium t~ok place in 2 - 2.5 minutes. A mix-
ture of one part by weight of aluminum sulfate and three parts by weight of
spectrally pure powdered carbon was used as the electrode filter. The sensi-
tivity of the method was 0.3 y of beryllium per test sample.
The following procedure for performing the analysis is recommended:
Collection of air samples and preparation for analysis. If beryllium
and its compounds are present in air in the form of an aerosol, the sample is
collected at the rate of 8 - 10 Ii/min. on "blue ribbon" filter paper, fastened
in the shape of a cone with a special clamp. The vapor is aspirated at the
rate of 2 - 3 Ii/min. in 2 consecutively joined glass absorbers equipped with
a No.2 porous plate. Distilled water was used for water-soluble compounds
and 10% hydrochloric acid for metallic beryllium and for other substances in-
soluble in water as the absorption solutions for the vapor and as a solvent
for beryllium extraction from the filter. The filter paper was transferred to
-105-
-------
a glass beaker and treated two or three times with 5 - 10 ml of the solvent.
The solution was drawn off by suction after each washing. The wash solutions
,
were combined, and their total volume measured. In calcining beryllium oxide
the filter paper was transferred to a crucible, moistened with several drops
of concentrated nitric acid, placed in a muffle furnace, and ashed at about
5000. After cooling, 2 mI. of concentrated sulfuric acid was added and heated
on a sand bath until the precipitate dissolved. The sulfuric acid was driven
off and the residue dissolved in 20 ml of 10% hydrochloric acid.
Analysis using morine. Place 1 ml of the test sample in one colorimetric
test tube and 5 ml in another. At the same time prepare a standard scale with
a beryllium content of 0, 0.05, 0.1, 0.2, 0.3, 0.4 and 0.5 y. Solution volumes
in the standard scale and test sample are then brought to 5 ml with 10% hydro-
chloric acid. Add to each tube 0.5 ml of a 10% solution of trylon B, and
neutralize with 10% sodium hydroxide to a weak basic reaction using litmus
paper as indicator. Now, add to each tube 0.1 ml of 0.02% alcoholic solution
of morine and mix thoroughly. Leave stand for 10 minutes and compare intensity
of the yellow-green fluorescence of the sample with that of the standard scale
under filtered ultraviolet illumination.
If the test sample does not contain impurities that extinguish the lumi-
nescence, trylon B need not be added. If distilled water is used as a solvent,
the standard scale is prepared with a beryllium content of 0, 0.01, 0.02, 0.03,
0.04 and 0.05 y of beryllium. The volume of the solution in the test sample
and in the standard scale is brought to 5 ml with distilled water.
Analytical procedure using "beryllon II !REA". Place 1 .1 of the sample
into one colorimetric tube and 5 ml into another. Simultaneously prepare the
standard scale with ber,yllium content of 0, 0.2, 0.4, 0.8, 1, 2, 3 and 4 y of
beryllium. Raise volume of solutions in the test sample and in the standard
scale to 5 ml with 10% hydrochloric acid and add 0.5 ml of a 10% trylon B solu-
tion to each tube; neutralize the acid with 20% HaOK solution to the point at
which congo (red) paper assumes a violet color, then add an excess of 0.05 mI.
Now add 0.5 ml of an 0.02% beryllon II solution to each test sample and stand-
ard scale solution, carefully mix; leave rest for 5 minutes and compare with
the standard scale, remembering that if the analyzed volume of the test sample
contained more than 4 y beryllium, the differences in the intensity of the
light blue coloration would not be discernible.
-106-
-------
Chemically pure beryllium sulfate or some other soluble salt can be used
in the preparation of the standard solution.
Preparation of the test sample and analysis
Place the filter paper into a platinum wire loop
by the spectrographic method.
and ignite over an agate
of three parts spectrally
Add a small amount of alcohol
mortar containing 100 mg of a mixture consisting
pure carbon dust and one part aluminum sulfate.
present in the air together with
beryllium, only spectrally pure car-
bon dust should be used as the charge.
Intensity of the beryllium line darken-
ening is measured with respect to the background.
and homogenize thoroughly and evaporate the alcohol with warm air. Prepare
standard scales similarly to contain 0, 0.3, 1.0, 3.0 and 10.0 y of beryllium
in 100 mg of charging mixture. Test samples and standard scales thus prepared
are loaded into the aperture of the electrode to the tip and photographed on
a single photoplate, beginning with the control standard containing no beryl-
lium and through those of higher concentrations, ending with the test samples
to be analyzed, by such procedure each standard and test sample are photographed
3 times at slit width of 0.015 mm. The carbon arc is fed by an alternating
current of 220W and current intensity of 14 - 16 A. Exposure is 2.5 minutes.
The photoplate is developed, fixed, washed, and air dried. The spectrograms
are photometered with the YF-2 microphotometer, and determinations made of
o 0
mean darkening difference (AS) of 2348.6 A beryllium and of 2367.1 A standard
aluminum comparison line. Construct a graph as shown in the figure below
plotting 10gC along the abscissa and AS along the ordinate. The amount of
43 beryllium in the test sample can be
.0.6
elJ.5 determined with this nomogram. The
.o,~ functional relationships between 10gC
+~1
+0./
+0.1
D
~ b.l
-1.1
-c
" ....4i-frNJ-IU-U,' 0 -u,/ ~o.N.~+0..N6+o. 7+0.6+0.1+1.011
. .' t
4J{ 'I J{ 101
Calibrated graph.
and AS within the 0.3 - 10.0 Y range
follow the course of a straight line.
In instances when aluminum is
Conclusions.
1.
The most sensitive and promising methods for the determination of
beryllium in the air of industrial premises are: the fluorescence method with
morine and the colorimetric determination with beryllon II.
-107-
-------
2. Use of trylon B as a complex-former eliminated the effect of many
interfering elements and made possible the determination of beryllium in the
presence of calcium, magnesium, iron, zinc, aluminum, and manganese, without
their preliminary separation.
3. The spectrographic method of beryllium determination yielded promis-
ing results.
4. The method of paper partitioning chromatography appeared promising
as a semi-quantitative method for the determination of beryllium in the presence
of caloium, magnesium, iron, manganese and aluminum.
Bibliography.
A..u.oun n. n., IOII,HC B. B.'t}'J[p. XliII. MyPIl., 1956, T. 22. e. 4,
e:I'p. 622--526.....If.r 0 p 10 m. B8 B. r. 388. "'8"1.. 1!l55, T. 21, M 2, c:Tp:tJ.18-14'J.-
1< Y! H e u ~ B B. H. JKYPH. aHaRHT. XHM., 1955e}6 10, CTJ. 276-285,8'11\. a p 8.. 0-
811" r. r. Tall .e, 1956. M II, np. 4JO-4,)4.~ ell !I'U E. B. KOIKIpllllf'TpH1tCXoe
onpeAMetl8e CReAOB Mt'T8J1J1OB. M.- n., I 94::J, CTp. 154:m. lIJ.e p e m e 8 C It 8. . H C.
n~ROHam.v...e IIHTOXC1IUUHH cjJTopOepHRJlReM. M., 1936 ~K 1 e m p e.r e r P. W..
Martin A. P. Anal. chern., 1960. v. 22. p. 82"-831.--KToribara T. Y.. Shu.
man R. E. Anal. chem., 1953, v. 25, p. 1594-1697.
Phenol Determination in the Presenoe of Polyatomic Phenols in the Air
During Foundry Casing Pouring.
S. S. Gurvits and T. I. Sergeva.
(From the Physioo-Chemioal Laboratory of the All-Union Soientifio-Research
Institute of Labor Proteotion VTsSPS).
Gigiena Truda i Professional'nye Zabolevaniya, Vol. 2, No.4, 50-53, 1958.
Short pouring has become an important attainment of the foundry industry
within the last 10 years. Casings used in this prooess are made of a speoial
mixture consisting of finely ground quartz and heat reactive rosin, mostly
phenol-formaldehyde rosin, made with phenol [C6H50H], tricresol rC6H4CH30H]
and xylenol [C6H3(CH3)20H]; of late pitoh tar has been used as binding mate-
rial. As a rule, any of these binding materials contained not more than 6%
~f free phenol, exoept for oresol rosin whioh contained 11 - 12% of free
-108-
-------
phenol. From the viewpoint of industrial hygiene this is a factor of con-
siderable importance, since in the process of outer casing and core prepara-
tion the sand-rosin mixture has to withstand a heat ranging between 240 -
4500 and during metal pouring it has to be able to withstand a temperature
ranging between 1300 - 14000.
It has been known that determination of phenol in the air of production
premises presented no difficulties, especial~ when the Kilon color reaction
or the paranitroaniline diazotizing or sulfanilic acid diazotizing reactions
were used. However, the utilization of the above reactions for the determina-
tion of phenol in the air as a rule, presents some difficulties under foundr,y
conditions during the process of pouring; this is due to the fact that ex-
traneous color shades came into pl~ which masked the basic character of the
color reaction.
The cause of such interference is found in the complex com-
position of heat wood destruction rosin and of other rosins; according to
data found in the literature wood rosin contained not only monoatomic but also
polyatomic phenols, such as [C6H4(OH)2'C6H3(OH)3J. The problem under study
concerned the development of conditions which would permit the separation of
monoatomic phenol from the above mentioned mixture, so that it could be reli-
ably determined by the colorimetric method. The authors aimed at developing
a procedure which would permit the microgram determination of phenol, hydro-
quinone, pyrocatecin, resorcin and pyrogallol simultaneously present in aqueous
solution.
Data found in the literature indicated that action of peroxide on benzene,
o
and in particular of hydrogen peroxide, in the presence of a catalyzer at 45 ,
resulted in the formation of mono-, di- and triatomic phenols. I. I. Ioff.
and E. V. Sokolova showed that the application of concentrated solution of
hydrogen peroxide can break down monoatomic phenol without the presence of
a catalyzer and without the application of heat, while at the same time having
no practical effect on carbolic acid (phenol). The present authors used this
as the principle in their studies for the development of conditions required
for phenol determination in the air of premises where metal casing pouring
was practiced.
Preliminar,y laborator,y studies were conducted as follows: known quantities
of phenol, hydroquinone, pyrocatecin, resorcin, and pyrogollol solutions were
placed into conical flasks of 50 - 60 ml capacity, the total volume was then
-109-
-------
made up to 10 ml; this was followed by the introduction of 2 ml 1 N NB40H,
0.5 ml of perhydrol (hydrogen peroxide) mixed and left stand tor 2 hours
at room temperature. Excess of hydrogen peroxide was decomposed by the addi-
tion of 0.05 g Mn02.4 (1). The solution was then filtered through cotton.
Quantitative determination of phenol was then made according to the diazo-
tization reaction with sulfanilic acid. This reaction possesses a high degree
of sensitivity. Molar extinction coefficient determined by these authors with
a photocolorimeter FEK-K for the color reaction under consideration was equal
to 14,085, whereas for the Milon reaction the extinction coefficient was only
1305. Standard color scale most convenient for use in comparing colors was
prepared as follows: final volume was made up to 10 ml with water, and after
mixing was left standing for 10 - 15 minutes. See Fig. 1.
Standard color scale for the determination of phenol by the method of
combined azo- and diazotizing with sulfanilic acid.
Oolorimetric test tube: 0 2 3 4 5 6 7 8 9
.
number i
)(1 of 0.01 mg/li phenol 0 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
solution
Corresponding to ~g 0 2 3 4 5 6 7 8 9
of phenol
Ml of 1 N NH40H 1 1 1 1 1 1 1 1 1
)(1 of 10% Na2C03 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
solution
)(1 diazotized 1 1 1 1 1 1 1
sulfanilic acid 1 1
f)
~ 0..70
~ 0,.12
II} 0.28
~ 0.21
'tj 0.20
r-f 0.10
~ 0.12
..-1 0.08
~ o./N
o
-- ~-
.J
"7
.."..
f--- -- .....
......
, .J """
I Y
.JV ,
"'"
V I I
I""" I ~
1
J
g
"
.)
6
8
2
,7
10
The following reagents are re-
quired for the preparation of the
diazo solution: a) solution of
0.0836 g of sulfanilic acid (H2NC6
H4S03H.2H20) in 200 ml of water; b)
0.0345 g of sodium nitrite (NaN02)
C.P. in 100 ml of water; c) 0.1 N
HCl solution.
Phenol concentration in mg/IO ml
Fig. 1. Photocolorimetric determi-
nation of phenol with
diazosulfanilic acid. by placing 10 ml of solution (a), 2.5
ml of solution (b) and 87.5 ml of solution (c) into a 100 ml volumetric flask.
The diazo solution will keep for 2 - 3 days at 0 - 50. Results of quanti-
The sulfanilic acid is diazotized
-110-
-------
tative determinations listed in Table 1 illustrate the utility of the stand-
ard color scale and the high sensitivity of the determination method.
TABLE
1.
Results of quantitative evaluation of phenol standard oolor scale
by the sulfanilic diazotizing reaction.
. : Difference between actual and
~g of i ..,.g of phenol determined : determined in percent
: :
phenol I .
: By.direct Photocolori- i By direct : Photocolori-
used I visual method metrically i visual method i metrically
:
2.0 2.0 2.0 0 0
2.4 2.25 2.4 -6.3 0
2.5 2.15 2.5 +9.1 0
3.0 2.15 2.8 -8.3 -6.6
3.5 3.5 3.6 0 +2.8
4.5 4.5 4.55 0 +1.0
5.5 5.5 5.5 0 0
6.5 6.5 6.5 0 0
1.5 1.0 1.45 -6.3 -0.6
8.0 8.25 1.1 +3.1 -3.1
8.5 9.0 8.5 -5.9 0
9.0 9.0 8.9 0 -1.1
Note: Photocolorimetric determinations were made in colorimetric cups
of 20 mm inside diameter using a green light filter.
Tests were made with aqueous solutions of mixtures of phenol, hydro-
quinone, pyrocatechin, resorcin and pyrogallol. Results showed that in oxi-
dizing microgram quantities of the above mixture of phenols by the method
previously outlined, phenol remained practically unchanged, while hydroquinone,
pyrocatechin, resorcin and pyrogallol were completely destr9yed by the oxi-
dation. Results of experimental tests are listed in Table 2.
TABLE
2.
Phenol
Mg of substance in 10 ml of analyzed fluid : Determined
!Hydroquinone:P.Yrocatechin: Resorcine I Pyrogallol: "D" values
1.52
1.52
1.52
2.2
2.2
2.2
2.2
2.6
2.2
2.2
0.330
0.310
0.316
Higher phenol values than actual began to appear only with a triple ex-
cess of polyatomic phenols. Praotical determinations were made in the foundry
departments of "Stankolit" and in the Moscow brake producing plant in the
-111-
-------
TABLE
3.
Time and place
: Phenol found in
! mgfli of air
:"Stankolit": Brake
i plant i plant
Immediately
after pouring
3 minutes later
6 minutes later
9 minutes later
12 minutes later
15 minutes later
18 minutes later
21 minutes later
24 minutes later
30 minutes later
0.019
0.035
0.027
0.057
N one found
None found
None found
0.012
0.012
0.012
0.037
0.097
0.025
0.003
None found
None found
None found
None found
None found
None found
section which employed the method
of casting into quartz sand forms
held together by PS-l (peskovaya
smola - pitch tar), or shale rosin,
or tar binders. Air samples were
collected by aspiration at the rate
of 0.5 Ii/min. through two Zaitsev
absorbers, each containing 5 ml of
water. At the end of sample col-
lection the content of the two ab-
sorbers was poured into a ground-to-
fit glass stoppered bottle of 50 -
60 ml capacity and oxidized as pre-
viously described. After the catalytic decomposition of the excess of ~drogen
peroxides with chemically pure pyrolucite (Mn02) the solution was filtered
through a compact cotton filter into a 50 ml volumetric flask. The precipitates
collected on the filter were washed 3 times with 5 ml of water. The sample was
neutralized with 2.2 ml of 1 N solution of HCl, followed by the addition of 5
ml of the diazotizing sulfanilic acid solution, 0.5 ml of 10% solution of Na2CO)
and 5 ml of 1 N solution of NH40H; the volumetric flask was then left standing
for 15 minutes at 0 - 50, the volume was made up to the 50 ml mark with water,
well mixed and the quantitative phenol determination made as above described,
using the previously pre-
pared standard color scale,
and the colorimetric com-
0.35
po. o,Jfl
.p
";;1 IJ,U
~
~ 0.11
r-f
cd o.lJ
o
......
~ o.u.
o
"
/' v
...
..,,/ /'
/' /"
V I--""
.....
", V
2 ~ 5 6 m n U M q ~ n u u
~g of phenol in 10 ml
0.01 0.02 O,OJ o,fl40.0.5 0.05 0.07 0.06 0.09 0.'0 0.11 fl.!}
Kg of phenol in 50 ml of solution
Fig. 2. Photocolorimetric phenol determination
by diazosulfanilic acid after separate oxidation.
-112-
parison made by the visual
method. Simultaneously,
the standard scale range
of 0.02 - 0.12 mg of phenol
was processed the same as
the sample.
See Fig. 2.
Following are shown
results of phenol determi-
nations in the section of
gas emission in the depa~-
-------
ment of form casting into the casing prepared from quartz sand and held together
by the previously described rosin and pitch binders. Totally different results
were obtained by analyzing air samples by the old method, i.e., without the
preliminary peroxide decomposition of the polyphenols and the intermediates
resulting from heat decomposition of the binders.
For comparative purposes results of same air sample analyses are presented
made by the old and new procedures, i.e., with and without preliminary peroxide
treatment.
TABLE
4.
Type of analysis
. .
:Exp.:
. .
i No.:
: :
During
pouring
Phenol found in mg/li of air
13 minutes i6 minutes i9 minutes i12 minutes
: later: later 1 later i later
Samples not
oxidized
Ditto
Samples oxidized
Ditto
I
II
I
II
1.6
1.0
0.08
0.019
1.0
0.017
0.035
1.0 0.175 0.25
1.0 0.35 0.15
None found None found None found
0.027 0.057 None found
As was to have been expected, values obtained by the old method were 20 -
60 times as high as they should have been taking into consideration actual
concentration of phenol contained in the binders.
Conclusions.
A procedure was established for the determination of phenol in the air of
foundry department for casting metallic forms using casings prepared from quartz
sand held together by binders of different types of rosins and pitch tar, which
emitted phenol into the surrounding air simultaneously with polyatamic phenols
and other intermediate products of binder materials decomposition by the high
heat used in casting. The basic principle of the new procedure is the decom-
position of intermediates secondary to phenol by hydrogen peroxide, according
to the method of Ioffe and Sokolov. Phenol values in excess of actual began
to appear with a triple excess of polyphenols over phenol.
Bibliography.
An e K C e e B a M. B. Onpe.ll.enellHe Bpe.ll.llbiX Bew.eCTB B B03.11.yxe npOH3BO.ll.CTBeHII..X
nOMew.eHHA. M., 1954. - JI. a B bI.II. 0 B B., ]I e 6 e.ll. e B A., nOli 0 Map ell K 0 6. MeTo.ll.bI
KOHTpOJlR B03.11.yxa B npOH3BO.ll.CTBeHII..x nOMew.eIlHRX xJlon'laTo6YMaJKH"x 4Ia6pHK. M.,
1953.- C r 0 S s C. F., Be van E. J. Heiberg Th. Ber. 1900, Bd. 33, S. 2015-2018.-
MarH.IJ,coH 0 10., npe06paJKeHCKHA H. A. B KII.: TpY.ll.bI lIayqlloro XHNHKO-
cIIapManeBTII'IecKoro HH-T8, M., 1926, B. 16, CTP. 65-67. - 11 0 4141 e 11. 11., Co K 0 JI 0-
88 E. B. )l(ypu. npHKJI. XUMHH, 1945, T. 18, N~ 4-5, CTp. 273-278.
-113-
-------
Perfecting Direct Gas Sample Taking for the Determination
of Benzene Hydrocarbons.
s. G. Faingol'd.
(From the Yasinovsk Coke-Chemical Plant).
Koks i Khimiya, 1958, No.1, 52-53.
It frequently becomes necessar,y to determine the concentration of benzene
hydrocarbons in the gas of individual batteries and also in individual coke
ovens under practical working conditions.
Such determinations have been made
by the method of activated charcoal absorption. The system of drawing off
and of absorbing the gas for purposes of analysis by the activated charcoal
method frequently necessitates interruption of operation due to the faot that
the gas diverting pipe and the gas absorption system become clogged with tar
and form condensates during sample collection. Therefore, the Yasinovsk Coke-
Chemioal Plant had introduced some changes into the operation of the gas
diverting system and into the absorption apparatus, to eliminate the pre-
viously existing difficulties in collecting gas samples. The changes made
possible uninterrupted gas sample collecting. The modified apparatus required
no constant watching; only once every 3 or 4 hours was the setting of the meter
corrected to insure the required rate of gas flow. The plan of the setup is
illustrated in Fig. 1.
. 1
L-J
Fig. 1. Plan of the drawing off
(suction) installation.
The gas was drawn off fro. the
direct (raw) gas conduit (1) behind
the throttle valve, i.e., at the
section which maintains an even gas
composition of minimal dilution. A
vertical pipe (2) 30 mm in diameter
and 1200 mm high extended from the
gas conduit; a metal (iron) water
cooled condenser (3) 1000 mm long
and 30 mm inside diameter was at-
tached to the vertioal pipe at a
descending angle. The tar and condensate ran into the small condenser tank
which was equipped with a spigot for the removal of the tar condensate. The
consecutive gas cooling in the vertical air cooler (5) and in the water cooler
-114-
-------
reduced the concentrations of tar and water vapor in the gas entering the
preparation apparatus. The plan of the absorber setup is illustrated in Fig.
2. Gas purification was accomplished in a consecutive order by passing through
two glass absorbers (1) containing
30% sulfuric acid solution, an empty
safety glass container (2), two glass
absorbers (3) filled with cotton,
small tanks (4) filled with bog ore,
and a control flask (5) filled with
copper sulfate to take care of the
presence of sulfuric acid before the
gas entered the two adapters (6)
filled with activated charcoal.
8
Figo 2. Plan of the absorber
installation.
1 - manometer; 8 - vacuum pump;
9 - gas meter.
The empty safety flask (2) serves
as a receiver of any acid which, in
its absence, might have been carried over into the cotton on one side and of
the copper sulfate into the bog ore on the other side in the event of reverse
suction. Insignificant as the described changes may appear, i.e., passing
the gas through 30% sulfuric acid solution and then through the absorbent
cotton, they nevertheless made possible uninterrupted operation of the setup.
This was due to the fact that upon passing through the sulfuric acid solution
the gas was deprived of its moisture and of the tar it may have contained,
leaving only traces of tar upon the absorbent cotton; and since the gas was
deprived of its moisture the possibility of water vapor condensation was
eliminated. Equally effective was the purification of the gas from hydrogen
sulfide by the bog iron ore.
By the new method gas samples were collected from two batteries over an
extended time. The rate of gas flow during gas sample collection varied be-
tween 600 - 100 Ii/hr. The gas drawing off system needed no cleaning through-
out the entire period of gas collection and ana~sis, despite the fact that
such an emergency had been anticipated. On the basis of successful operation
experienced by the Yasinovsk Coke-Chemical Plant with the new setup, it is
recommended that the new method of collecting direct (raw) gas samples for the
determination of benzene hydrocarbons be adopted widely by coke-chemical plants.
-115-
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An Automatic Gas Analyzer for the Determination of
Benzene Hydrocarbons in Coke Gas.
A. T. Bendik and A. E. Eidelman.
(Zaporozhie Coke-Chemical Plant).
With the assistance of M. E. Ni, emark K. M. Bragilet skaya,
A. S. Kusnenko and L. I. Orendarenko.
Koks i Khimiya, 1958, No.2, 38-40.
The efficiency of benzene scrubbers is judged by the loss of benzene
hydrocarbons in the return (purified) gas. Existing chemical tests for the
determination of such losses are imperfect because they are time-consuming
and lack precision; most important is the fact that the analysis is delayed
so that the results refer to a completed shift and, thus, prevent timely in-
formation of a current shift in the normal operation of the scrubber. The
Zaporozhie Coke-Chemical Plant has been conducting operational check tests
of the automatic analyzer type OP-3301 developed by the Leningrad Station,
Soviet Union Bureau Designing Apparatuses for Gas Analysis ("G5IG3-AGA"). The
operational principle of this gas analyzer is based on the utilization of the
property of benzene hYdrocarbons to absorb wave lengths of 230 to 270 ~ in
proportion to their concentration. In the construction of this gas analyzer
use was made of the latest photo-electrical and electronic devices.
The basic plan of this gas analyzer, Type OP-3301, is shown in Fig. 1.
Coke gas entering this analyzer passes first through an electrostatic pre-
cipitator (1) in which the gas is
cleared of all dust and vapor im-
purities; it then passes through
chamber (2) where the gas is puri-
fied of all components interfering
with the analysis, then passes
through chamber (3) which regulates
the uniformity (in time) of gas
deliver.y into work chamber (4).
Next to the latter is the control
chamber (5) which is filled with
air. Part of the bactericidal
,~----' "
r,
~~. 9 [ W
'lJ ,L!, - 7
I' 1~:.a -.' - !!!!5
, ,- /2 c:::::> c::::> ---u
~" ~I05 ~-
,
6"
Figo 1. General plan of the
gas analyzer 0
-116-
-------
ultraviolet lamp (6) light emission is directed into two optical chambers (4)
and (5), both equipped with flat quartz windows at their ends, a shutter mecha-
nism of two diaphragms (7) and (8) and two photoelements (9) and (10).
In the absence of benzene hydrocarbons in the tested gas the electrical
voltage of 50 cycles frequency at the resistance loads of the photoelements is
of equal magnitude but of opposite phases and, therefore, the electrical volt-
age (tensions) at the entr,y into electronic system (11) is nil. With the ap-
pearance of or increase in the benzene concentration in work chamber (4) the
current of the photoelement (10) decreases and as a consequence, tension
develops at the entry of the electronic system (11). The electronic system
enhances this tension and directs it into a reversible motor (12). The latter
begins to rotate, closes the shutter diaphragm (7) and thereby reduces the
rate of UV transmission flow and of the current of the photoelement of com-
parator chamber (5). Rotation of the reversible motor (12) continues until
the flo" of UV radiation through the work chamber (4) and the comparison
chamber (5) become equalized. With the decrease in the concentration of
benzene in work chamber (4) the reversible motor (12) starts to rotate in
an opposite direction thereby restoring the balanced condition of the optical
system. The shaft of the reversible motor carries a graduated diso (13) which
indicates the benzene concentration in g/m3 of gasJ the shaft also carries a
remote slide transmission (14) connected by wires with a secondary automatically
reoording apparatus (15). There are other auxiliar,y devices whioh are parts
of the apparatus, the details of which are not here described but "hich regu-
late the current supply and work chamber (4) tamperatures.
Tests of gas analyzer "GP-3301" under working plant conditions with the
oooperation of "UKhII" and "GSKB-PGA" (110W OlEA of analytioal apparatus)
brought out the need for making many ohanges and additions in the construo-
tion of the apparatus. The most essential factor whioh insured preoision in
the work of the gas analyzer was the requisite of a higher chemical gas puri-
fication than was originally provided for. It was also necessary to incorpo-
rate into the apparatus a supplementar,y tension stabilizer of the current fed
into the booster of the photoelaments. The original load resistance of the
photoelements of 0.25 vt were replaced by load resistance of 2 vt. The system
of distance transmission with the auto-recording millivoltmeter "SG" was re-
placed b.1 a system having an automatically recording electronic potentiometer
-117-
-------
"EPD". These changes and additions insured a dependable 24-hour automatic
operation and recording of the analyzer. Check tests showed that determina-
tion errors did not exceed 0.5 g/m3.
The apparatus was then tested in analyzing gases purified according to
provisions by washing with a 5% potassium permanganate solution mixed in 1:1
with a 15% orthophosphoric acid solution, followed by absorption of the naph-
thalene by picric aoid; it was found that in 2 - 3 hours all gas passage in
the oleaning ohambers were completely choked by precipitated impurities. Ad-
ditional absorbers were installed containing 83% sulfuric aoid and 80% of
alkali. After that the gas purification proceeded satisfactorily; precipita-
tion of solids stopped and the apparatus worked satisfactorily. Results of
comparative analyses for the content of benzene hydrocarbons in the gas by the
TAB L E 10 method of absorption by activated
oharooa1 and by the automatic
gas analyzer are shown in Table
g/~ of benzene hydrocarbons:
in the gas !
Aid' t d b :Acoording to the:Difference
tSh n ~cta et' Y!results of acti-! in g/m3
e au oma ~c: t d ba 1:
: va e c rcoa :
gas analyzer: b t. :
: a eorp ~on :
Note:
1.43
1.25
1.67
1.48
1.48
1.14
1.67
1.12
-0.05
+0.11
o
-0.24
Apparatus zero adjusted hourly.
TABLE
2.
gjm3 of benzene hydrocarbons:
in the gas !
As indicated byiAcoording to the:Difference
the automatic iresu1ts of acti-i in g/.3
gas analyzer i vated charooal :
: absorption i
Note:
4.09
4.00
2.05
1.59
2.56
2.38
3.48
3.64
2.03
1.49
2.51
2.53
+0.61
+0. 36
+0.02
+0.10
+0.05
-0.15
Apparatus zero adjusted hourly.
-118-
1.
Cleaning of the gases
prior to analyzing for benzene
by the method of activated char-
coal and by the automatic gas
analyzer method was done iden-
tically. Data in the table show
that with careful supervision of
the analyzer operation and by a
periodic correction of its zero
position, the apparatus assured
results coinciding with those
yielded by the usual test method.
Tests were then made with gases
purified only by 83% sulfuric
acid and 30% NaOH. Results are
listed in Table 2.
The listed results show
the high sensitivity of the ap-
paratus, its ability to dupli-
-------
cate results; results also show importance of proper gas purification before
running it into the apparatus and that gas impurities markedly shifted the ap-
paratus zero position. Deviation from the zero point on the apparatus during
its continuous work was established by special observations and notes made ever,y
2 hours. It was found that zero mark always shifted in the direction of in-
crease, serving as additional proof of the insufficient gas purification of
unsaturated compounds which easily polymerize under the effect of ultraviolet
radiation. Further increase in the gas purification by using a greater number
of absorbents failed to obviate the necessity of adjusting the apparatus zero
point. The fact that shifts in the zero point position basically depended
upon the tested gas purity was verified by checking the apparatus on three
successive days without gas passage through it. The apparatus performance
was normal producing a circle-shaped curve free of any shifts.
There remained the problem of absolute removal from the gas of all com-
pounds which deposited a thin film on the work chawber windows. Formation of
the film increased the shift in the analysis results by as much as +0.7 g/m3
per 24 hours. Therefore, it is necessary to be watchful of the condition of
the windows in the work chamber and to wash them daily. Incorporation of new
physical methods of analysis and of controls, as a rule, calls for a revision
of maqy concepts and definitions. In this instance it concerns benzene losses
in the return gases. "Benzene losses" is the term which denotes quantity of
hydrocarbons absorbed by activated charcoal from a measured volume of gas
after it had been freed of hydrogen sulfide, carbon dioxide, hydrogen cyanide
and naphthalene. The talk is generally about "benzene losses", even though
it is well known that the hydrocarbons absorbed from the gas by activated
charcoal represent a complicated mixture in which benzene proper and its
homologues constitute a minor portion.
Concentration of aromatic hydrocarbons in raw benzene of return gas is
approximately 50% and varies directly with the extent of the losses. In evalu-
ating the results yielded by the automatic gas analyzer on the concentration of
benzene hydrooarbons the fact must be borne in mind that the analyzer records
only the content of aromatic hydrocarbons and that "other losses" were held
back by the process of chemical purification. Therefore, the amount of beB-
zene losses indicated by the apparatus are considerably lower than the losses
arrived at by analysis with activated charcoal. Comparative tests were con-
-119-
-------
to 3,6
CIS
~ :j4
Q) oJ?
..c:I
+> 'If
ducted to determine extent of loss
variations yielded by both methods
of analysis. Results are listed in
Fig. 2.
..c:I
+>,...... Z4
-ri EI
II~ ~o
~ ~ 1,6
O.ri
rl
(2
I
Prior to making analysis by the
accepted method of absorption by
activated charcoal, the gas was
freed only of hydrogen sulfide,
hydrogen cyanide, carbon dioxide and
naphthalene. Results of such analyses
are listed in Fig. 2 in the order of
~8
0,4 I
0,0 f 2 j- .. S 6 7 8 9 10 11 12
Analysis number
Fig. 20 Results of comparative
analyses made by different methods. increasing benzene content in the gas.
The lower section of each column presents data of the automatic gas analyzer,
while the total column heights represent losses as determined by the activated
charcoal method. The black plots in Fig. 2 show that the activated charcoal
Q)
s;:
Q)
N
s;:
Q)
IX!
absorbed an additional amount of hydrocarbons accounted for as benzene loss.
With the introduction of the automatic gas analyzers for plant production con-
trol it becomes necessary to revise present W$YS of evaluating benzene losses
in the return ooke gases beoause the automatio analyzer indicated the real
content of benzene hydrooarbons.
Results thus far obtained with the automatic gas analyzer in determining
the content of benzene hydrocarbons indicated that with further improvements
in its oonstruction the apparatus oan be made to serve as a finer and more
accurate instrument for control of raw benzene absorption from coke gaso
-120-
-------
Determination of Simultaneously Present Cyclohexanon and of Cyclohexanonoxime.
A. S. Kaslenikov.
(Department of Preventive Disinfection of Gor'kii Regional
Sanitary-Epidemiological Station).
Gigiena i Sanit ariya , Vol. 24, No. 12, 71-73, 1959.
This author previously described a method for the determination of cyclo-
hexanon based on its discovered property to form an azo dye with the salt of
H-acid diazonium. (See B. S. Levine, Survey of U.S.S.R. Literature on Air
Pollution and Related Occupational Diseases, Vol. 1, Department of Commerce,
O.T.S. No. 60-21049, pp. 196-201). The salt forming reaction can be presented
as folloWSI
coo c=o
110-[ [' ( 0 HC-[ 0 C-OH
[' HzC ,CHz COC-NON-HC CHN=N-mc
l.. 11-[ \~H H[ CH HC CH
+ rllC CHZ = HzC CHZ +2HX
~ ,.~ ~ ~ ~ ~
..~ e') So CHz.S C Sa '"' 0 S C Sa
'I; [H LH J'/J ~ ",) CH CH J'/J ~ "> CH CH ':J'-¥
In the cou~se of reaction between the cyclohexanon and the H-aoid diazonium
salt the cyclohexanonoxime becomes deoximized to a great extent. In the
presence of nitrous acid the deoximizatiom of cyclohexanonoxime proceeds at
a rapid rate im s quantitative manner.
It was found that the addition to
the solution containing cyclohexanonoxime of substances which, accordi~g to
G. Keyer, form double salts in the presence of ketoximes prevented the de-
oximation of cyclohexanonoxime. Results of the present author's studies
showed that rhodenide, tartaric acid and tartrates, sodium sulfite and methanol
were also capable of preventing the process of cyclohexanonoxime daoximation.
This property of cyclohexanonoxime to become deoximized quantitatively under
one set of conditions and to remain completely unaffected under other condi-
tions offers the possibility of utilizing the reaction of the azo dye forma-
tion in the determination of cyclohexanon and of cyclohexanonoxime when
simultaneously present in the studied medium.
The present author tested this possibility with positive results. Analysis
ot a mixture of cyclohexanon and cyclohexanonoxime can be made by usual colori-
metric methods as wall as by the method of colorimetric titration with stand-
-121-
-------
ard aqueous solutions of the azo dye. The azo dye needed for the preparation
of the standard solution to be used in the analytical colorimetric titration
procedure and the technique of the procedure were described by this author
previously.
Determination of cyclohexanon in the presence of cyclohexanonoxime.
Reagents required: 1) Diazo solution of H-acid, 0.25% of the monosodium
salt of H-acid and 0.1 N solution of sulfuric or hydrochloric acid are mixed
just before use in a 1:1 ratio with 1.0% solution of sodium nitrite;
2) 20.0% solution of sodium hydroxide;
3) Standard solution of c,yclohexanon containing 50 v/ml for use in the
colorimetric analysis with the aid of a set or by a millimolar solution of the
aao ~e (0.758 mg/ml) for use in the colorimetric titration method. One.l of
the millimolar solution of the azo ~e is equivalent to 98 y of cyclohexanon
or 113 y of cyclohexanonoxime.
The analytical procedure. Place 1 ml of the sample solution into a test
tube and add 1 ml of methanol, 0.5 ml of sodium hydroxide solution and 0.5 ml
of the H-acid diazo solution and mix well. Leave rest for 2 minutes and dilute
to volume of 10 ml with distilled water and make the colorimetric determination.
In determining cyclohexanon by the method of colorimetric titration plaoe 1 .1
of water into the control tube, add equal amounts of the reagents and dilute
with water to the volume of 10 mI. Now add, a drop at a time, the standard
solution of the diazo dye to match the color intensity in the tube containing
the tested sample. Calculate final cyclohexanon concentration on the basis
of the amount of standard dye used in the titration. Results of cyolohexanon
determinations by the method described are listed in Table 1.
Determination of cyclohexanonoxime in the presence of oyclohexanon.
Rea~ents required: 1) 1.0% solution of sodiua nitrite;
2) 5.0% b.1 volume of hydrochloric acid;
3) Alkaline mixture prepared by mixing 50% of BaOH and 5.0% solution of
sodium sulfate in 1:1 ratio;
4) Solution of diazotized H-acid, prepared a8 above described;
5) Standard solutions of cyclohexanon or of the aso ~e prepared as
described above.
-122-
-------
TABLE
1.
Results of cyclohexanon determination in the presence of cyclohexanonoxime
using the diazonium H-acid colorimetric titration method.
T ak:en i
Cyclohexanon . : Cyclohexanonoxime :
~n Y i in mg i
y
Qyclohexanon found
:
~
%
1
3
5
10
20
22
28
35
0.02
0.05
0.10
0.5
2.0
2.5
2.5
3.7
1.1
2.8
4.9
10.4
19.6
23
23.6
36
110
93.3
98
104
98
104.5
102.1
102.8
Analytical procedure. Place 1 .1 of the cyclohexanonoxime containing
solution into a test tube and add 0.2 ml of the sodium nitrite solution and
0.2 ml of the hydrochloric acid solution and mix well. Leave rest for 1 minute
and add 0.5 ml of the alkaline mixture and 1 ml of diazotized H-acid. Leave
rest for 5 minutes, dilute to 10 m1 with water and make the colorimetric deter-
mination.
In making colorimetric cyclohexanonoxime determination by the method of
colorimetric titration place 1 ml of water into a control test tube and add
reagents in same quantities as they were added to the sample-containing tube,
dilute to 10 ml with water, and add the standard azo dye dilution drop at a
time until color intensity in the control tube matches that in the sample con-
taining tube. Calculate final cyclohexanon concentration on the basis of the
standard azo dye used, bearing in mind that 7.85 Y of the diazo dye .a8 equiva-
lent to 1.13 Y of cyclohexanonoxille. Results of cyclohexanonoxime determina-
tions in the presence of cyolohexanon by the method of colorimetric titration
as above described are listed in Table 2.
In determining cyclohexanonoxime and cyclohexanon in the air use water
as the absorber. Aspirate the air through three successive absorber flasks
each containing 5 ml of water at the rate of 15 - 20 Ii/hour to a total volume
of 15 - 20 Ii. Remove 1 ml from each absorber tube for the determination of
cyclohexanon and 1 ml from each for the determination of oyclohexanonoxime
by the above outlined procedures.
-123-
-------
TABLE
2.
Results of cyclohexanonoxime determination in the presence of cyclohexanon
using the colorimetric titration method.
Taken : C,yclohexanonoxime found
:
Cyolohexanonoxime : . : %
: Cyolohexanon in Y i y :
in Y I :
2 10 1.74 87
3 20 3.2 106.6
8 50 7.6 94
10 50 10 100
15 50 16 106.6
20 100 19.6 98
25 200 26 104
33 200 34 103
38 300 37 97.4
40 300 41 102.5
Conclusions.
10
A method is described for the determination of cyclohexanon and cyolo-
hexanonoxime simultaneously present in the medium.
by the usual method of colorimetry or by the method
with a standard solution of the azo dye.
2. Determination of cyclohexanon or of cyclohexanonoxime by the H-acid
diazo salt can be made with aqueous solution samples as well as with air sam-
Determinations can be made
of colorimetric titration
pIes.
3. Determination error in small amounts of cyclohexanon did not exceed
10% and of small quantities of cyclohexanonoxime did not exceed 13%.
Editor's remark: Published for purposes of discussion and expression of
opinion.
Bibliography 0
Mac~eMHMKOB, A. c. rMr. M caH., 1958, m 3, CTp. 80. -
AHa~M3 OHpe~e~eHMR CTpoeHMR opraHM~eCKMX coe~MHeHMH.
KMeB, 1935, CTp. 417.
MeHep, r.
XapbKOB-
-124-
-------
Colorimetric Method for the Determination of Ammonia in the Air Using
Phenol and Sodium Hypochlorite.
K. I. Poletayev and N. A. Andreyeva.
Gigiena i Sanitariya, Vol. 24, No.6, 73-74, 1959.
Determination of ammonia in the air of industrial and residential premises
has been made largely by the colorimetric method using Nessler's reagent. The
sensitivity of this method fully met the needs of sanitary control of the at-
mosphere. For this reason it has been used wide~ in sanitary-chemical in-
vestigations. However, the chemical reaction on which this method is based is
not speoific. This method can not be used when the air contains aldehydes
suoh as formaldehyde or acrolein, and hydrogen sulfide. In sanitary-chemical
studies situations are frequently encountered in which the air contains alde-
hydes and hydrogen sulfide simultaneously with ammonia. Therefore, an attempt
was made to develop a specific method for the determination of small amounts
of ammonia in the air in the presence of aldehydes and/or hydrogen sulfide.
The fact has been known that phenol and sodium hypochlorite yielded a
dark blue color in the presence of ammonia salts. The intensity of the de-
veloped color depended on the concentration of the ammonium salts in solution.
Several variants have been used in the preparation of sodium hypochlorite;
likewise, different sorbents were used to absorb ammonia
from the air.
A
combination was finally arrived at for the detection of 0.0003 mg of ammonia
in 5 ml of the sample, which is entirely satisfaotory for the sanitary evalua-
tion of the atmospheric environment of industrial and residential quarters.
The method. Ammonia is absorbed from the air by passing it through 2
successive Petri absorbers, each oontaining 10 ml of 0.02 N H2S04. Rate of
air aspiration should equal 60 Ii/hour. After aspiration has been completed
5 ml of the absorber solution is taken from each of the absorber tubes and
plaoed into 2 respeotive oolorimetrio oups. A set of oolorimetric standards
is prepared as follows: set up a series of 12 test tubes; prepare a standard
solution of (NH4)2S04 oontaining 0.01 mg of ammonia per ml; plaoe none in the
first tube; beginning with the seoond tube and up, plaoe sucoessively 0.05,
0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0 ml of the standard am-
monium sulfate solution. The amount of ammonia in the seoond tube is equiva-
lent to 0.0002 and in the last tube 0.01 mg. Next, the volume in all tubes,
-125-
-------
tests and standards, is brought up to 5 ml with 0.02 N sulfurio aoid solu-
tion. This is followed by the addition of the following: 1.0 ml of 4.0%
aqueous phenol solution and 0.5 ml Xa-hypoohlorite solution prepared as fol-
lows: first determine the amount of aotive ohlorine in the hypoohloride of
lime, whioh should range between 30 - 35%. To do this dissolve 3.5 g of the
lime in a 1000 ml volumetrio flask; take 50 m1 and p1aoe into an Erlenmeyer
flask with a ground-to-fi~ stopper; add 10 - 15 m1 of 1Q% of XI solution and
10 ml of 30% aoetio aoid; titrate 5 minutes later against the liberated I2
with an 0.1 N solution of sodium thiosulfate (Na25203) to the appearanoe of
a faintly yellow oolor; add a few drops of staroh and titrate oautiously drop
by drop until the faint yellow oolor just disappears.
One ml of the 0.1 N thiosulfate solution is equivalent to 0.003546 g of
ohlorine. Having established the oontent of active ohlorine, take 100 g of
the chloride of lime and thoroughly mix for 15 minutes with 170 ml of water;
keep on stirring and add 70 g of Na2C03 dissolved in 170 ml of water. The
mixture will thicken at first and will then liquefy. The supernatant liquid
is then separated from the sedimented solid by a suitable method. The clear
fluid is diluted with an equal amount of ammonia-free distilled water. Ten
minutes after the Ha25203 solution has been added to the tubes containing the
tests and the standard solutions, the blue color intensity in the tubes oon-
Ammonia concentration obtained
with parallel analyses of wa-
ter solutions using Nessler's
reagent and with phenol and
Na-hypochlorite method.
Nessler
method
results
in mg
0.241
0.146
0.12
0.113
0.042
0.022
0.018
0.016
0.009
0.006
: Phenol-
s
: hypo-
i chlorite
:
! results
: in mp:
0.238
0.15
0.118
0.112
0.045
0.023
0.023
0.012
0.007
0.008
.
.
.
i Dif-
i ferenoe
in mg
0.003
0.004
0.002
0.001
0.003
0.001
0.005
0.004
0.002
0.002
taining the test solution is oompared with
the color of the standard tubes. Color in
the standard tubes can be relied upon for
24 hours, and the hypochlorite solution will
keep for 15 days. The sensitivity of the
method should be 0.005 mg in the colorimetrio
volume used; however, the sensitivity must
be oheoked by control tests and improved if
so needed. Aldehydes, suoh as formaldehyde
and aoro1ein, as well as H25, in ooncentra-
tions up to 1 mg per test did not interfere
with the ammonia determination.
In the
presenoe of amines, such as methylamine, di-
methylamine, eto., the method lost its
specificj.t;r.
Results of o9mparativ8 OOD-
-126-
-------
trol tests are presented in the table. Differences between the results of 2
tests did not exceed 0.001 - 0.003 mg. Results of tests made under practical
industrial conditions proved the suitability and applicability of the pro-
posed method.
:Bibliography.
:>K II TKO BaA. C. 3KcnpeccHblP MeTO~bJ onpe:leJIt'HflH np('J1HbIX ra30B fI napoB
n n03.1\':\e ..'lPOMbI!lJ.~eEHLlx npellnpll5lTlliL M.-JI., 1946. - vi 0 v fl. r oTo~leTpHYeCKHj;j
\11\11I'Il'CKIlIl aHamn (KO.10pIIMeTpll51 H HcljJe.10\ICT!,1I5I). M., 19:15, T. 1. - K 0 r a H 1-1. 6.
I' KH.: MeToJ1bl IICCJieJ10B3Hlli'( 110 rllrHeHC Tl'y.~a Ha npoIl3uo.~cTBe. M., 1953, CTp. 115.-238.
Low Temperature Bacteriological Air Investigation.
E. YU. Zuikova.
CA. N. Sysin Institute of General and Community Hygiene).
Gigiena i Sanitariya, Vol. 24, No.4, 77-79, 1959.
Winter studies of atmospherio air microflora in Arctic central zones and
in the troposphere frequently have to be conducted at low temperatures. Studies
of bacterial atmospheric air population at low temperatures are difficult and
have been inadequately investigated. Most recent methods of bacteriological
air investigation have been based on catching the microorganisms in a fluid
medium, such as water, physiologioal saline, broth, etc., or on meat-peptone
agar. Fluid and solid nutrient media freeze rapidly at minus 3 - 5°. In ad-
dition the bacterial content of the atmospherio air is usually 10. in winter,
and the process of sample collecting takes a considerably longer time during
which the media freezes even at -5°. Canadian investigators S. K. Pady and
C. D. Kelly suggested ooating the collecting Petri dish bottoms with silico-
organic gels of consistency not affected by low temperatures; the air organisms
caught by the silico-organic gel are then covered with the agar medium. In
1954 R. :B. Kitchell and his co-workers suggested the use of soluble gelatin
foam filters.
-127-
-------
In investigating atmospheric air microflora at low temperature this author
used polysiloxane solutions, the viscose consistency of which did not change
within the range of +20 and -600. Met~let~lpolysiloxane solution has a vis-
cosity of 52 centistokes and ethylpolysiloxane solution No.4 has a viscosity
of 45 centistokes. These and polysiloxane, a high-vacuum lubricant trade-
marked D.S., were used in this study.
Samples were collected by the Pady and Kelly method in Petri dishes coated
with the above polysiloxane solutions and lubricant. The Petri dishes with the
polysiloxane were sterilized for 2 hours at 1800 dry heat. Samples were col-
lected using the Krotov apparatus, and the inoculation was done by pouring
nutrient agar into the dishes. At the same time control samples were collected
similarly into Petri dishes containing meat-peptone agar. This pouring method
was suited to quantitative determinations of microorganisms in certain air
volumes, but it had the following shortcomings: a) the under surfaoe of deep
bacterial growth excluded the possibility of making differential species studies;
b) when inoculation was done by the pouring method, spreaders developed in 40%
of the samples, which interefered with accurate quantitative determinations.
Best results by the agar pouring method were obtained in Petri dishes coated
with the polysiloxane lubricant, which reduced the number of developed spread-
ers. By the method of polysiloxane lubricant, 73% of air bacteria were oaught
using the Krotov apparatus as compared with the number of air bacteria developed
on beef-peptone agaro Samples of air bacteria collected with liquid polysiloxane
could not be counted due to spreader development.
In view of the shortcomings of the pouring method the meat-peptone agar
imprint method was tried next, using glass tablets coated with liquid poly-
siloxane, and later discs made of special glass-lacquer fibers trade-marked
LSK-1 coated with liquid polysiloxane; this film lost none of its elasticity
within the +200 to -600 temperature range. Glass lacquer LSK-1 films were
placed in Petri dishes, the bottoms of which were coated with li~uid poly-
siloxane and sterilized at dry heat. Air samples were collected after which
LSI-1 discs were used in making imprints on meat-peptone agar (two imprints
from each diso). Usually 1.5 - 2 times as many colonies developed in the first
dish as in the seoond. Counts were made of the total of both imprints. A
parallel control determination was made by the Krotov apparatus. Eight series
of tests were made at -4.4 to -10°, and 12 at -10 to -21.60. Eaoh test series
-128-
-------
consisted of 12 samples by the imprint method and two control samples by the
meat-peptone agar method. The bacterial air content in the control samples
ranged between 120 and 1090 bacteria per 1 m3. The bacterial air content ob-
tained by the liquid methylethylpolysiloxane disc imprint method ranged between
118 and 550 bacteria per 1 m3; by the liquid ethylpolysiloxane coating method
between 126 and 538 per 1 m3; and by the polysiloxane lubricant coating method
between 88 and 405 per 1 .3. Compared with the control bacterial counts on
meat-peptone agar, the liquid methylethylpolysiloxane imprint method yielded
a count amounting to 61%, the liquid ethylpolysiloxane coating method yielded
a 63% count, and the polysiloxane lubricant coating method yielded a 38% count.
Prolonged low temperature storage of dishes containing discs coated with liquid
polysiloxane had no effect on the physical properties of the LSK-1 material or
of the fluid polysiloxane, which proved of value when the preparations had to
be stored or transported over long distances without the use of special warming
measures.
On the basis of the presented results the following can be recommended:
in low temperature quantitative bacteriological studies preference should be
given the method of pouring into dishes coate~ with polysiloxane lubricant.
Where quantitative and qualitative determinations of air microflora are to be
made at low temperatures, the imprint method should be employed using discs
made of LSK-1 material coated with liquid methylethylpolysiloxane or ethyl-
polysiloxane. The imprint method requires double the nutrient media and dishes
due to the double imprint procedure. Final results should represent the sum
of both imprint counts.
The above described imprint and pouring methods can be used in studies of
air microflora at cold regions or during cold months of the year, depending
on the purpose of the investigation, i.e., whether only quantitative or quan-
titative and qualitative results are sought. It is recommended that the poly-
ailoxane lubricant be used in connection with the pouring method, and fluid
methylethylpolysiloxane or ethylpolysiloxane be used in connection with the
imprint method.
Bibliography.
Pa~, S. M., Kelly, C. D., Science, 1949, v. 110, p. 181. - Mitchell, R. B.,
Fulton, J. D., Ellington, H. V., Amer. J. Publ. Health, 1954, v. 44,
p. 1334-1339.
-129-
-------
Determination of Nitrogen Oxide in Coke Gas.
N. A. Gruzdeva and L. A. Khokhlova with the aid of V. G. Shevchenko.
Koks i Khimiya, 1960, No.4, 41-48.
Exact determinations of small quantities of oxides of nitrogen [lJ is an
important part in the control of hydrogen production from coke gas by the proc-
ess of deep cooling. Microanalytical methods for the determination of oxides
of nitrogen in coke gas are based on oxidation of nitrogen oxide in the coke
gas by means of appropriate liquid oxidizers. The nitrogen dioxide thus pro-
duced is absorbed by water accompanied by formation in equal quantities of
nitric and nitrous acids according to the following equations:
(1)
2N02 + ~O - IIN03 + Hll02 (2)
According to OST 10233-40 and GOST 8330-51 the method of Shuftan has been
used in the U.S.S.R. since 1940 as the standard method for the determination of
oxides of nitrogen. The final concentration of nitrogen oxide is determined
using the Shuftan correction curve, or Stepanovts nomogram. According to ref-
erences (2, 3 and 8J the Shuftan method and its correction curve have not be-
come popular in Germany, Czechoslovakia, and France. Instead, the control
method for the determination of small-quantities of nitrogen oxide based on
the principle of peDnanganate oxidation has found wide application. The basis
of the method can be illustrated by the following equation:
2NO + 02 - 2102
910 + 3H2SO 4 + 2D1n04 ... 5N02 + ~SO 4 + 2KnS04 + 3H20
(3)
The present authors studied the precision of the standard method using
an analytical setup as shown in Fig. 1. A series of mixtures of nitrogen,
nitrogen-hydrogen and coke gas were prepared. Doses were delivered from a
1 ml microburette divided into 0.01 ml and equipped with a three-way stopoock
(1), a glass bottle with sealing fluid (13) and a mixer (6). Before an ex-
periment was begun the entire setup was flushed for 1 hour by passing through
it pure moisture-free nitrogen or coke gas mixed with oxygen. By raising
bottle (13) any desired amount of nitrogen oxide can be forced out of the
microburette. Before dose delivery the oxygen supply was cut off, stopcooks
P, Rand» were closed foroing the nitrogen out through stopcock L. After the
oxide of nitrogen was forced into the mixer stopoook L was closed and stopcocks
-130-
-------
Oxygen
...
Nitrogen
-
t2
Fig. 1. Setup for the determination of NO in coke gas.
1 - Buffer tube; 2 - flowmeter; 3 - CaC12 drier; 4 - 10.4 Ii flask; 5 - ab-
sorbers containing metaphenylenediamine solution; 8 - cylindrical water
jacket for heat control of burette 1; 9 - four-way outlet tube; 10 - Gries
solution glass container for gas purification; 11 - 15% H2S04 solution con-
tainer; 12 - 20% NaOH solution container.
P and R were opened and the gas was directed by opening stopoock K from the
capillar,y opening of the three-way stopcock of the microburette.
Nitrogen oxide was obtained by a reaction of 50% sulfuric acid solution
and a mixture of sodium nitrate and potassium iodide in III proportion [6J.
Nitrogen oxide purity was determined by the volume titrametric method improved
by the present authors. The principle of the method is as followsl nitrogen
oxide is converted to nitrogen dioxide with a 3% hydrogen peroxide solution;
the reaction mixture containing nitric and nitrous acids was then titrated
with a solution of sodium hydroxide. The concentration of nitrogen oxide was
then determined using the Shuftan logarithmic curve (as per GOST) and the
result computed by formula (4) was compared wi th the amount of nitrogen oxide
forced into the gas flow. The concentration of nitrogen oxide in the gas was
computed using formula (4).
(a + al) . 0.01 . 2 . 1000 3
NO - V . f ml/m (4)
in which NO represents ml of nitrogen oxide per m3 of the gas, a represents
the amount of standard solution in ml the color of which was of the same in-
tensity as the color in the first absorber, al represents the amount of stand-
ard solution in ml the color intensity of which was the same as in the solu-
tion in the seoond absorber, 0.01 is the quantity of nitrogen oxide in ml equiv-
alent to 1 ml of the standard solution, 2 is the multiplication factor which
accounts for the fact that only half of the nitrogen oxide in the gas partici-
-131-
-------
pated in the reaction; V represents li of the gas under analysis, f represents
the standard temperature and pressure correction coefficient. The method was
checked for precision; results are shown in Table 1.
TABLE
1.
Results of checking the Shuftan method accuracy.
: 3 ! ml/1I3 of NO :Degree of trapping I
T t iml/m of: by analysis: in percent ;
es .vO.: A rd' : A rdi .
N :~ 1ntro-: : ceo 1ng: : cco ng:
O. . . . . :
. i duced iComput8d i to GOST iComputed ! to GOST !Computed
: : : corrected: :corrected:
Relative error
in percent
:According
i to GOSl'
:
: corrected
1
2
3
4
5
6
1
2
3
4
5
Artificial mixture of nitrogen and nitrogen oxide
1054 1.86 13.2 120.75 857 +20.75 +757
1.73 1.35 11.5 77.61 662 -22.39 +562
1028 1.33 1105 103.55 898 +3.55 +798
1.27 1.22 11.0 96.19 866 -3.81 +766
1.16 1.30 11.4 112.00 982 +12.00 +882
5.71 5.10 22.5 89.26 394 -10.74 +294
Artificial mixture of coke gas with nitrogen oxide
2.77 3.24 19.2 117.08 696 +17.08 +596
2.07 1.48 15.6 71.76 755 -28.24 +655
2.12 2.00 18.0 93.84 845 -6.16 +745
0.93 0.87 12.8 93.25 1370 -6.75 +1270
0.79 0.82 8.6 103.66 1470 +3.66 +137L
Data in the table shows that results obtained by the standard method ex-
ceeded the actual values by 6 times, whereas the computed results were close
to actual concentrations before making the recommended corrections. It is
interesting to note that values obtained after adjusting the experimental re-
sults with the aid of Stepanov's nomogram [7J, as recommended by GOST, deviated
fram actual values to a still greater degree. Results of the present investi-
gation showed that the precision of the discussed analytical procedure depended
upon the complete removal of moisture from the gas. This was verified by the
fact that after passing the gas through dried CaC12 and through a layer of
alkaline lumps analytical experimental results were in complete agreement with
actual values.
The reliability and preoision degree of the permanganate method were
checked next using the setup as recommended in GIAF (4 and 5J. The relative
error of the permanganate method amounted to an average of ::I: 17%.
As a result
-132-
-------
of the investigation the following
determination of nitrogen oxide by
ratus was chosen for the oxidation
changes were made in the method for the
the permanganate method: a simpler appa-
of the gas; its construction is illustrated
in Fig. 2.
The apparatus cylinder is filled with glass beads moistened by a continuous
flow of fresh potassium permanganate solution. Colorimetrio comparison is made
using a photoco1orimeter. Determination of sodium nitrate solution concentra-
tion was made with a specially constructed graduated curve of changes in color
intensity. The curve is shown in Fig. 3. Concentrations of chemically pure
sodium nitrate in Griss solution are plotted along the abscissa and color
density (intensity) along the ordinateo
Test solutions obtained after XO absorption from the coke gas are poured
into photooolorimetrio oups of 20 mm and the oolor intensity determined photo-
co1orimetrioa11y, using a green light filter. The photo colorimetric reading
is then interpreted with the aid of the graduated
curve. Data presented in Tables 2 and 3 show
that the permanganate method yielded results
of the same degree of precision with the VUKhii
-
(Ml
0.-
P-a fl.7fJfJ
~
.ri
::. In 0,6110
. s::
CD
~ 't:I
... rl 0,510
cd
(,) 0.400
-ri
+"
Pt
0 O/XIO
0, 2ft)
~ ~ 0/00
o
Fig. 2. Xitrogen
oxidation apparatus.
~ Ld'
P'1 f1"
,II
P
V
V
/
,/
,I
tt)
l)
V
~
[j
0.'
49
(I
~2 q3 4. 4$ ql 41 41
m1 of nitrate solution
Figo 3. Graduated curve for the determina-
tion o~ sodium nitrate ooncentration in
working solutions.
-133-
-------
TABLE
2.
Results of checking the accuracy of the
permanganate method for the determination
of n~trogen in the gas with a recovering
oxidiser and nitrogan as the carrier.
P t:m1/mj of:m1/m3 oflp t:Re1ative
eroen I NO" : NO : ercen I "
f 0: ~n- I re- :t d:error ~n
o 2: I I rappe :
Itroduoed:covered I : percent
0.48 5.41 4.60 85.00 -15
0.18 5.74 5.92 103.28 +3.28
0.89 9.35 7.26 77 . 63 -22.4
0.48 5.41 5.04 93.00 -7
0.89 4.93 5.85 118. 77 +18.77
TABLE
oxidiser as with the GIAP oxidizer.
Results also indicated that the
presence of oxygen and freedom
from ammonia and hydrogen sul-
fide were factors of importance
in obtaining reliable results.
Parallel tests were made for the
comparative evaluation of the
Shuftan and permanganate methods.
The tests were made at the Kemerov
Coke-Chemical Plant using the
3.
Results of checking the accuracy of the permanganate method for the
determination of NO in the coke gas with a recovering oxidizer.
Peroent of
02 in
coke gas
I
I ml/m3 of
i NO in-
:
: troduced
.
:
: Color of :Color with:
I original ladded NO, I
:gas, ml of: ml of i
I "t t I "t t :
: n~ ra e : n~ ra e :
i solution i solution i
ml/m3 of
NO found
i i
:Percent of:
INO derived I
. .
. .
. .
. .
: I
Relative
error in
percent
0.5 2.80 002 1.95
0.5 2.22 0.2 2.40
0.5 2.74 0.3 2.20
0.4 5.58 0.3 4.05
TABLE 4.
Results of comparative ana~ses of NO deter-
minations in coke gas at the Kemerov Plant
as yielded by the permanganate method and
by GOST.
ml/mj of NO found by GOST :ml/mj of NO by
According to : According to i permanganate
Shuftan curve: formula (6)*: method
5.0
8.6
5.9
5.2
5.8
6.8
0.360
0.883
0.445
0.334
0.540
0.510
0.324
1.126
0.567
0.405
0.573
0.557
B.S.L.
* Probably meant formula (4).
-134-
2.45
2.77
2.38
4.74
80.27
124.78
87.15
85.03
-19.73
+24.78
-12.85
-14.97
GIAP absorber. Results of par-
allel tests made under identioal
conditions are presented in
Table 4. Data in Table 4 show
that the 2 methods yielded dif-
ferent results. The NO concen-
tration determined by the stand-
ard method yielded an average of
6.23 ml/m3 and the permanganate
gave an average of 0.58 ml/.3.
It sh ould be added that uncor-
rected results yielded by the
-------
standard method computed with the aid of formula (4) were of the same order
of magnitude as the resulte obtained with the permanganate method.
The procedure for the determination of nitrogen oxide in coke gas by the
permanganate method is as follows: the coke gas is passed through a hygro-
scopic cotton filter (Fig. 4), freed from tar, ammonia, rosin-forming sub-
stances, hydrogen sulfide, CO2 and higher oxides of nitrogen. The purified
gas is passed into a packed oxidizer (6) at the rate of 24 li/hr where the NO
is oxidized into N02 by an acidified solution of potassium permanganate. The
apparatus cylinder is continuously flushed through the experiment with a fresh
solution of potassium permanganate coming under pressure from bottle (8). The
entire setup must be leak-proof, as shown by an appropriate check. Any well
qualified analyst should be intimately familiar with any apparatus testing
procedure. The gas to be analyzed is then forced through the apparatus for 15
minutes and the apparatus is connected with oxidizing chamber (1) which is
filled with 14 ml Griss reagent. The gas is run in until the solution in the
first absorber acquires a color of sufficiently high intensity, which usually
takes 15 - 20 minutes. The solutions to be tested are poured into 20 mm color-
imetric cups and are evaluated colorimetrically in an appropriate photocolor-
imeter equipped with a green light filter after which the amount of sodium ni-
trate is established using a graduated curve shown in Fig. 3. If necessary the
examined solution can be diluted to 50% with Griss reagent and the colorimetric
results multiplied by 2.
Figo 4. Plan of NO determination
in return coke gas.
1 - 15% H2S04 solution; 2 - 15%
H~S04 solution; 3 - 20% NaOH solu-
tlon; 4 - Griss solution; 5 - Flow-
meter; 8 - 2% KMn04 solution; 9 -
safety catch bottles.
Gas
inflow
----
-135-
8
-------
The potassium permanganate solution is prepared by adding 35 ml of 50%
H2S04 solution to 965 ml of 2% potassium permanganate solution.
The results herein reported show that the permanganate method is simpler
and easier to manipulate; however, the standard method has been widely used
and is now known to many analysts; therefore, its application in control work
in coke-chemical plants may be continued with the following mandatory changes
and supplements to GOST 8330-57:
1) The Shuftan curve and Stepanov nomogram corrections should not be used;
content of nitrogen oxide in the gas should be computed according to formula
(4);
2) Use the more sensitive and more stable Griss reagent for the absorption
of nitrogen dioxide;
3) Use 75% H2SO4 solution for the removal of tar-forming (rosin-forming)
substances from the gas.
Technical specifications of GOST 8330-57 in relation to the content of
nitrogen oxide in coke gas should be re-evaluated and, if necessary, revised.
Coke-chemical plants and manufaoturers of nitrogenous fertilizers should ac-
cumulate comparative factual information regarding nitrogen oxide content in
coke gas prior to and after its purification by the permanganate method and by
the method of oxidation with 02' accompanied by changes suggested by VUKhIN.
Conclusions.
10 Results proved the nonsuitability of the existing standard method of
nitrogen oxide determination in coke gas as specified in GOST 8330-57. The
method yielded results 6 - 8 times higher than actual NO concentrations in the
coke gas. The use of Shuftan curve or Stepanov nomogram corrections only
distorted the results and should be deleted from GOST.
2. The use of the permanganate or oxygen gas method for the control de-
terminations of NO concentrations in coke gas, which do not require the use
of correction factors, yielded more reliable and more accurate results.
I. B. <1>. 3J10T'\I\I \I n. 11. rOfilfH. r;ry60!r0e ()..
JlaJKlleH~e KOKCOIBoro rala. rOCX~M~311aT, 1947.
2. Secbaum et Hartman Brennstoff-Chem., 1935, 16,4;
3. Spanily, Paliva, 1955, vol. 35, Ni 6, p. 163-167.
4. H. H. n 011 R K 0 B II n. A. X 0 l1 a K. 3a,BO;J.cxaJl
JlaOOparoJ}IIR, 1951, Ni II, CTp. 1300.
Bibliography.
5. n. M. K 0 H TOp 0 B ,\I q. 3aB~CK8R Jla60paT04l"'"
1951, N2 II, CTp. 1295.
6. r. Y. Be 6 6. OKIICJlbI a3OTa, nor JlOIlJ.eRlle H HX n.
pepaOOTKa, TeXII3JIaT, XapbKoB, 1931, CTp. 15.
7. B: A. .1. Ten a .R 0 B. X KMCTpO II, 1935, M 2, CTp. lul
8. Plerram Chemle et Industrie, 1953, VIlI, vol. 70,
N2 2, p. 189-96.
-136-
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Electroencephalographic Determination of Threshold Reflex Effect of
Atmospherio Pollutants.
K. A. Bushtueva, E. F. Polezhaev and A. D. Semenenko.
(From the Department of Community Hygiene and Clinical and Experimental
Physiology, Central Institute of Post-Graduate Medicine).
Gigiena i Sanitariya, Vol. 25, No.1, 57-61, 1960.
Recent scientific studies indicated that determination of allowable limit
concentrations of atmospheric air pollutants can be made by the methods of eye
adaptation to darkness, optical chronaxy, pneumography and plethysmography.
Such studies have been conducted usually by way of establishing minimal con-
centrations of a pollutant substance in the air which induced a shift in some
functional activity of the organism reoordable by any of the above-mentioned
methods. The meohanism of such determinations is based on the ability of the
external factor (air pollutant) to stimulate the central nervous system, which
in turn, affected the reaction of one or another functions of the organism,
functional changes thus elicited were then recorded objectively and automati-
cally. It must be borne in mind, however, that such mechanism of functional
response to external stimulation was the result of a highly complex central
activity reacting at different intensities to different chemical stimuli. As
a consequence, the sensitivity of the above-described physiological methods
differed greatly.
This paper is a report of attempts on the part of the present authors to
test the suitability of the eleotroencephalographic method for the determina-
tion of maximal single allowable concentration limits of air pollutants. As
the first step tests were made of the effect of odor-emanating substances and
other stimulating or irritating substances on reflex responses. Automatic
recording of electrical brain activity represents a direot means for the
detection of states of stimulation generated in cortical cells by external
chemical stimulators. Electric brain activity was recorded by means of a
4-lead amplifying device, 4UN4, and by an ink-recording apparatus ChR-I in
connection with an encephalograph trade named "AI'var". Test persons were
selected after medical examination indicated that their olfactory analyzer
functioned normally, as shown by the a-rhythm. Test persons were placed into
an isolated screen-protected room. A small glass cylinder was firmly fixed
-137-
-------
in front of the test person, through which a continuous stream of air was passed
at the rate of 30 Ii/min. At any desired moment the pure air was mixed with a
given amount of the tested gas and passed through the cylinder. Desynchroniza-
tion of central electrical activity or depression in the a-rhythm were used as
indexes of the effect induced by the odor-emanating substance under investiga-
tion.
Tests were made with S02 which possessed a clearcut olfactory effect, with
H2S04 aerosol which usually affected the trigeminal nerve apparatus. Tests
were performed by 2 types of modified procedures. The first procedure was based
on the effect produced by individual substances under study on the electro-
encephalogram (EEG). The series of experiments was conducted with S02 con-
centrations ranging between 5 - 0.6 mg/m3. Sulfur dioxide gas in 5.0 - 0.9
mg/m3 ooncentrations elicited a clearcut desynchronization. At concentrations
ranging between 5.0 - 3.0 mg/m3 desynchronization usually appeared over the
entire period of S02 administration; at lower S02 concentrations desynchroniza-
tion usually lasted between 2 - 6 seconds of a 2o-second gas effect test. In
some cases desynchronization appeared in the course of 302 administration and
in others immediately upon the introduction of the S02' as shown in Fig. 1.
~,
Z/I
a
b
c
d
--.~
v-
Time in seconds
Fig. 10 Electroencephalogram of des~chronization produced by inhalation of
. 0.9 mg/m3 of S02.
Upper l~ne: I - moment of gas inflow; 2 - gas flow discontinued.
a - right hemisphere occipito-sincipital electroencephalogram; b - right hem-
isphere temporal electroencephalogram; c - left hemisphere occipito-sincipital
electroencephalogram; d - left hemisphere temporal
electroencephalogram.
-138-
-------
Data showing the effect of 5.0 - 0.6
mg/m3 concentrations of S02 on the
EEG are presented in Table 1. Such
13
data show that 0.9 mgjm of S02
elicited desynchronization in 4 of
6 persons tested. K. A. Bushtueva
showed previously that the threshold
of S02 reflex effect on the reflexo-
genic zone of respiratory organs, as
determined by the adaptometrio method
was also at 0.9 mg/m3 concentration.
Therefore, it can be assumed that the electroencephalographio method herein
described yielded results approximately analogous to those obtained by the
adaptometric method.
The second substance investigated was H2SO4 aerosol. It was shown that
this substance possessed highly irritating properties in the zone of trigeminal
innervation. The specific effect of this substance on the central nervous
system indicated that concentrations which elicited a feeling of irritation,
changes in light sensitivity, and in optical chronaxy coincided with, or
actually were, at the 0.6 - 0.85 mg/m3 level. In this connection the question
arose whether at the time of the isolated application of H2S04 aerosol the
cerebral electrical activity had changed in the subthreshold conoentration as
indicated by verbal accounts or by the above enumerated methods. Studies in-
dicated that the isolated application of H2S04 aerosol in subthreshold con-
centrations elicited no desynchronization recordable by the electroencephalo-
gram. However, desynchronization was
noted when threshold concentrations of
TABLE
1.
Presence (+) or absence (-) of
desynchronization of a-rhythm
upon 802 inhalation.
Subject'si
initials: 5-3
N.N. + + +
S.G. + + +
)(.L. + + +
G.V. + + +
D.F. + + +
S.N. ++ + +
+
+
+
+
IfA:BLE
2.
Presence (+) or absence (-) of
desynchronization UpOD H2S04
aerosol inhalation.
Subject's:mg/mJ of H2S04 aerosol
initials i 0.15-0.6 0.5-0.4
N.N.
G. V.
L.K.
S.N.
S.G.
+
+
+
+
+
H2SO4 aerosol were applied. The effect
lasted only 1 - 2 seconds. Desynchroniza-
tion became manifest at the beginning of
H2S04 aerosol inhalation, as well as after
the inhalation of this substance was dis-
continued.
Data of the tests under dis-
CUSSiOD are listed in Table 2. Thus, de~
synchronization of the a-rhythm appeared
-139-
-------
upon the inhalation of H2S04 aerosol concentrations which elicited a feeling
of irritation and altered the course of other reflex reactions. In other
words, the present modified method of electroencephalography possessed no
advantages over methods previously used for the determination of threshold
reflex effect produced by air pollutants.
The second modification of the electroencephalographic method for the de-
termination of threshold reflex effect was then tested. It consisted in de-
veloping conditioned "electrocortical" reflexes associated with the inhalation
of the substances under study. It has been known that a sudden and sharp in-
crease in illumination acted as a conditioned stimulator and elicited desyn-
chronization or a-rhythm depression. By combining the effect of a given stimu-
lator, sound for instanoe, which alone had no effect on the electroencephalo-
gram, with light, it Was possible to create conditions for a temporary associa-
tion between the two stimulators. Such temporary association manifested itself
as desynchronization recorded on the electroencephalogram before responding to
any other stimulant which may combine temporarily with the light. Such an
association reaction recorded on the electroencephalogram was called "electro-
cortical" reflex.
In developing conditioned "electrocortical" reflexes, S02 and H2S04 aero-
sol were chosen as the conditioned stimulators and unbroken light as the un-
conditioned stimulator. The association of S02 or of H2S04 aerosol with light
was tested at intermittent intervals; this was done for the purpose of prevent-
ing the development of a time-conditioned reflex. Such a modification of the
method offered the possibility of objectively establishing central nervous
system stimulation or stimulability to the applioation of chemical substances
in low ooncentrations, particularly when the stimulation process, due to its
low magnitude, did not reflect on the "upper" electroencephalogram during
testing of the 'isolated effect of a chemical stimulant. Thus, the tests de-
scribed presented a basis for a reply to the question whether or not a chemi-
cal stimulator, which by itself had no effect on the electroencephalogram, was
able to elicit stimulation of the central nervous system. The method of
"electrocortical" conditioned reflexes thus presented the possibility to de-
termine stimulation by chemical agents which, according to the law of tempo-
rary association, can or may change the stimulability of cortical cells of the
optical and other analyzerso
-140-
-------
TA:8LE
3.
Electrocortioa1 conditioned
reflex upon 502 inhalation.
: Reflex appearanoe
Subject's: at mg/mJ of SO,
. :
lnitia1s :1.5 -: ° 9 : 0 6 ;:8e10w
: 1 i . ! . ! 0.6
N.N.
S.G.
)(.L.
G.V.
D.F.
6
5
6
9
+
15
12
12
14
12
5
9
9
+
Note: Data in the table show the
combination at which conditioned
reflex appeared. Dash denotes
no appearance of reflex.
I
I
a ~...-~_...... a ..',..~.
S02 gas effect on the electroencepha-
logram was studied by this association
modifioation in the concentration range
of 1.5 - 0.3 mg/m3. Data of this investi-
gation are shown in Table 3. Data in that
table show that in 0.6 mg/m3 oonoentration
S02 e1ioited reaction response in 4 of 5
persons tested. The conditioned reaction
to S02 oan be developed in 1 day in tests
of 6 - 15 associations with light. De-
synchronization arose with the lowest latent
period of response and was manifest through-
out the entire time of S02 effect. The
conditioned reflex changes in the cerebral
z
u
J
I
.....
- ~............~
-...
b
c
d-
~
- ----
Time in seconds
Fig. 2. Conditioned reflex des.ynohronization on the 8th oombination of 502
effect at 0.6 mg/m3 and uninterrupted light.
Upper line: 1 - moment of gas inflow; 2 - gas flow discontinued.
a - right hemisphere occipita-sincipital eleotroencephalogram; b - right hem-
isphere temporal electroencephalogram;. 0 - left hemisphere occipito-sincipita1
electroencephalogram; d - left hemisphere temporal
electroencephalogram.
electrical aotivity are graphioally shown in Fig. 2, from which it can be seen
that a-rhythm depression occurred at the moment of exposure to S02 gas in 0.6
mg/m3 concentration, and persisted to the time when it was reinforced with un-
broken light, indicating that an lIelectrocortioal" conditioned reflex had been
developed. Results of the present investigation indicated that "electrocortical"
-141-
-------
conditioned reflex studies constituted a most sensitive method for the deter-
Tests
mination of threshold reflex activity for odor-emanating substances.
made by these authors with substances affecting the trigeminal region, such,
for instance, as H2S04 aerosol, confirmed the high sensitivity of the method
herein described. Thus, as a conditioned
stimulator H2S04 aerosol was used in 0.4
mg/m3 concentration. The effect of the
aerosol alone continued over 10 seconds
TABLE
4.
Electrocortical conditioned reflex
upon H2S04 aerosol
inhalation.
Subject I S
initials
: Reflex appearance at
img/m3 of H?S04 aerosol
i 0.15-! 0.4 ! Below
: 0.6: : 0.4
N.N.
G. V.
S.N.
M.L.
8
16
12
6
21
19
23
and another 5 seconds in association with
unbroken light. Conditioned electrocortical
reflex was usually developed in the course
of 19 - 23 H2S04 aerosol and light associ-
ate~ effects. Results are presented in
Table 4. Investigations here reported
point to a high sensitivity of the method
of "electrocortical" conditioned reflexes as a procedure for the study of
threshold effect of irritating and odor-emanating substances on the reflexo-
genic zone of respiratory organs. The method is well adapted to the determi-
nation of practical maximal single limits of allowable concentrations of at-
mospheric air and is, accordingly, recommended for that purpose.
Bibliography.
I) e p H T 0 B 11., Bop 0 6 b e B A. TPY1!bI I1H-Ta ~H3H0J10nIH HM. oepIlTaWBHJ1H.
T6HJ1HCH, 1943, N~ 5, CTp. 369. - ill n H J1 b 6 e p r n. 11. 1)/oJ1J1. 3KcnepHM. 6HO,1. H MeD,.,
1947, T. 24. N~ 10, CTp. 271. - J asp e r H. H., S hag ass c., J Exper Psychol.. 1941,
v. 26, p. 373.- L 0 0 m i sA. L:, H a r v eyE. N., Hob art G., Ibid, 1936. v. 19, p. 249.-
T r a vis L. E., E g a n J. P., Ibid., 1938, v. 22, p. 524.
-142-
-------
Determination of Benzene, Toluene and Xylene Simultaneously Present in the Air.
E. G. Kachmar.
(From the F. F. Erisman Moscow Scientific-Research Institute of Sanitation
and Hygiene of the R.S.F.S.R. Ministry of Health).
Gigiena i Sanitariya, Vol. 25, No.5, 58-62, 1960.
Benzene, toluene and xylene are frequently found in mixed combinations
under industrial conditions; more often one of the compounds will contain an
admixture of another. Each of these components produce different toxic effects
or similar effects of different intensity. Sanitary control of industrial air
containing a combination of these pollutants must be based on the differential
determination of individual compounds. This cannot be accomplished by the
methods described in the literature. In addition, most methods described
earlier are not sufficiently sensit1vQ or require the use of special equipment
and highly trained laboratory personnel not available to all laboratories.
A method based on the Yanovskii reaction is in current use by sanitation
chemists for the determination of benzene and its homologues. This method was
first proposed by A. V. Stepanov in 1929, and was later improved and modified
by many investigators (M. V. Alekseyeva, 1940; M. K. Borezova, 1940; K. I.
KUz'mina, 1940; B. S. Boykina, 1950; M. S. Bokhovskaya, 1951; S. S. Gitis and
I. D. Chapala, 1954). The principle of the method consists in nitrating the
benzene (toluene or xylene), extracting the nitro-compounds with ether and
determining them calorimetrically in an alkalinized acetone or ether-acetone
medium. This method cannot be used when benzene, toluene and xylene are
present simultaneously, since the mixture of the different component colors
interferes with the qualitative and especially the quantitative determination.
The present author undertook to develop methods for the determination of
benzene, toluene and xylene present in the air simultaneously and avoiding
the use of different solvents if possible. The new methods were based on the
formation of azo-compounds.
Benzene was nitrified with a 10% nitration mixture to the dinitro form,
which was then reduced with metallic zinc, diazotized in the presence of con-
centrated hydrochloric acid by a 1% solution of sodium nitrite, and combined
with m-phenylenediamine. This author pictures the course of this reaction
as follows:
-143-
-------
o
H,SO.
-------
TA:BLE
2.
Results of benzene determinations under
plant conditions.
Technologi- !Determined by reaction! Error
cal process iYanovskiizAzo-compound!
Column color
Head color
Screen coat
:Base coat
0.015
0.05
0.05
0.006
0.08
0.06
0.04
0.006
+0.005
+0.01
-0.01
o
TA:BLE
3.
Effect of toluene admixture on
benzene determination by the azo-
compound reaction, in mg.
:Benzene
taken
Toluene
added
i :Benzene
s determined
0.01
0.02
0.04
0.01
0.02
0.04
0.01
0.02
0.04
0.005
0.01
0.02
0.0015
0.015
0.03
0.01
0.02
0.04
0.05 mg in 6.5 mI.
0.01
0.02
0.04
0.01
0.02
0.04
0.01
0.02
0.04
trinitro-compound and reduced
with metallic zino, after which
the reduction products were com-
bined with diazotized sulfanilic
acid. A yellow azo-oompound was
obtained. The sensitivity of
the reaction was 0.01 mg of
toluene in the colorimetric
volume.
For this determination
TA:BLE
4.
Effect of xylene admixture on
benzene determination by the azo-
compound reaction, in mg.
:Benzene Xylene s :Benzene
taken addea i determined
0.01 0.005 0.01
0.02 0.01 0.02
0.04 0.02 0.04
0.01 0.006 0.01
0.02 0.012 0.02
0.04 0.024 0.04
a standard scale was prepared with a
toluene content ranging from 0.01 to
checking of this scale showed a direct
-145-
correlation between color intensity and the azo-compound concentration in solu-
tion. Results of parallel tests made under laborator,y conditions by the Yan-
ovskii and the proposed method are listed in Table 50
While similar parallel check tests were made under industrial production
conditions, it was found that the toluene used in the plant contained an ad-
mixture of xylene, which seriously interfered with the determination of toluene
by the Yanovskii reaotion, while samples analyzed by the proposed method de-
veloped a color identical with the one of the scale, fit for quantitative de-
termination. Additional control tests showed that the presence of an equal
Photocolorimetric
concentration of xylene and of half the equivalent volume of benzene did not
interfere with the determination. Some results are listed in Tables 6 and 1.
-------
TABLE
5.
Results of laboratory toluene
determinations in mg.
: Deter- :
:. d b :
:m~ne ,.:
Toluene:th Y :
: e an-:
taken: kit:
: ova :
: t.:
:reac ~on:
Error
: Deter- :
:. d by:
:m~ne :
: .
:the azo-!
icompoundl
: :
:reaction:
Error
0.016 0.02 +0.004 0.02 -0.004
0.024 0.023 -0.001 0.022 -0.002
0.032 0.03 -0.002 0.03 -0.002
0.04 0.04 0.04
0.05 0.05 0.052 +0.002
TABLE
60
Effect of benzene admixture on
toluene determination by the azo-
compound reaction, in mg.
Toluene
taken
i
:
Benzene
added
i Toluene
i determined
0.01
0.02
0.04
0.005
0.01
0.02
0.01
0.02
0.04
In addition to benzene and its
homologues air of the industrial
production premises contained es-
ters of acetic acid (acetates) and
acetone, as components of the sol-
vents, lacquers, etc. A stu~ was
made of their effect on the deter-
mination of benzene and toluene by
the method of the azo-compound re-
action. Ethyl and amyl acetates
were tested as the most widel,. and
frequently used components.
It
TABLE
7.
Ef'fect of xylene admixture on
toluene determination by the azo-
compound reaction, in mg.
Toluene . Xylene i Toluene
i
taken : added : determined
0.01 0.005 0.01
0.02 0.01 0.02
0.04 0.02 0.04
0.01 0.0015 0.01
0.02 0.15 0.02
0.04 0.03 0.04
was found that ethyl and amyl ace-
tates interfered with the determina-
tion in amounts above 0.05 mg and acetone in amounts greater than 0.1 mg.
No suitable basis was thus far found for the development of a method for
xylene determination in the presence of toluene; for this reason xylene was
separated from benzene and toluene. This separation was attained chromato-
graphioal1,. . Methods for chromatographic and thermographic analysis of
aromatio hydrocarbons were described by I. )(0 Turkel'taub and L. S. Chemoda-
nova (1951) and Ye. Sh. Gronsberg (1958). Benzene, toluene and xylene were
passed through a silicagel column, accompanied by
temperature as a means of increasing differential
silicagel was used which had been washed with hot
at 150 - 160°. The following studies were made:
-146-
changing the adsorbent
adsorption effects. ASK
water and dried for 4 hours
1) conditions of benzene,
-------
toluene and xylene adsorption on silicagel; 2) conditions of desorption such
as effects of temperature and air volume passed through the silicagel in order
to displace the benzene, toluene and xylene.
Experiments were performed as follows: vapors of the three components
(benzene, toluene and xylene) were adsorbed in a V-shaped tube filled with
silioagel, after which pure air was passed through the tube. The velocity
and volume of air forced through varied. The adsorbent temperature was also
varied. In heating the adsorbent the tube with the silicagel was placed in a
chemotte cl~ oven of the Reberg type. A constant temperature of the oven was
maintained by a type RNSh-55 regulator. A Zaitsev absorber with 2 ml of nitra-
tion mixture was placed directly behind the tube to absorb the benzene, toluene
and xylene desorbed from the silicagel.
The desorbed hydrocarbons were determined by the Yanovskii reaction and
by the proposed methods. Results showed that at 8 - 100 there was little de-
sorption of xylene (6 - 8%). At the same time, benzene was desorbed completely
at this temperature when 9 li of air was passed through the silicagel. At 8 -
o
10 , toluene began to desorb when 10 li of air had been passed through the
silicagel, i.e., by passing the 11th Ii of air. To obtain complete toluene
desorption it was necessary to pass another 18 Ii of air. Desorption of xylene
from the silicagel was completed when 10 - 12 Ii of air had been passed at 800.
On the basis of the above results the following conditions for the separa-
tion of xylene from benzene and toluene are recommended: 1) pass the vapors
of benzene, toluene and xylene through a V-shaped tube filled with 4 g of ASK
silicagel, which has been processed beforehand at a rate of 10 - 12 li/hr;
2) force through the V-shaped silicagel column air heated to 8 - 100 at the
rate of 10 - 12 li/hr; the first 9 li of air will desorb the benzene, then
18 li will desorb the toluene. Then plac~ the tube in a Reberg type oven
heated to 800 and pass another 10 - 12 li of air to desorb the xylene. 3)
Pass the desorbed hydrocarbon vapors through freshly and consecutively changed
Zaitsev absorbers containing 2 ml of nitration mixture; 4) after the separa-
tion determine the benzene, toluene and xylene by the Yanovskii reaction or by
the proposed new method.
Bibliography.
A.1 e K c t' e B a M. B. 3aBOJl. .la6oparOpH5I, 1940, N~ 5, erp. 632. -.- 50 ii K H
H a 5. C. T a ~I iK e, 1950, N~ 9, crp. 1400. - r p 0 H C 6 e prE. W. CaH. H rHr., 1958,
N~ I, cr.p. 77. - K y 3 b M II H a E. H. B KH.: C60pHHK pa60r no caHHrapHo-npOMhlw.1eH-
HOjj XH~IHH. JI., 1940, crp. 36 H 50. - C r e n a HOB A B. CYJle6Ha51 XHMH5I. M.-JI.,
1939, crp. 74. - T y P K e.1 bra y 6 H .III\., lj eM 0 Jl a HOB a JI. C. 3aBOJl. Jla6oparopl!5I,
1956, N~ 12, crp 140{)
-141-
-------
Gas-Liquid Radiochromatograph.
M. I. Yanovskii and G. A. Gaznev.
Vestnik Akademii Nauk S.S.S.R., Vol. 30, No.5, 27-31, 1960.
The use of labeled atoms has become a firmly established procedure in
physico-chemical investigations. By introducing into the reaction zone a
substance which contained C14, for example, and then by determining the com-
position and the specific activity of the individual reaction products, it
was possible to arrive at an understanding of changes which the labeled sub-
stance had undergone, this frequently enabled the investigator to obtain a
clear picture of the order in which chemical changes or transformations take
place. Such a procedure enabled investigators to secure valuable information
in a short time regarding such catalytic reactions as, cracking, oxidation of
propylene and acrolein, dehydrogenation and dehydration of alcohols, and other
reactions. The anticipated wide utilization of labeled atoms in many branches
of chemistry was held back by the lack of convenient and efficient methods for
the isolation of individual reaction components from the mixture and of rapid
and reliable methods for determining their specific radioactivity. Procedures
previously used for the analysis of complex hydrocarbons by the C14 labeled
method consisted of the following steps: isolation of individual components
with the use of highly effective refining columns, combusting the isolated
compounds to 01402' converting the latter to BaC1403' preparing and measuring
of targets for specific activity determination. Such an analytical procedure
possessed the shortcomings of complexity, difficulty of execution, required
highly qualified and specialized scientific personnel and lacked precision.
Attempts were made at the Institute of Physical Chemistry of the Acade~
of Sciences of the U.S.S.R. to obviate the enumerated shortcomings by combining
the method of chromatographic analysis, normally completed in 15 to 30 minutes,
with the method of determining specific radioactivity in flow. A combination
of the 2 methods made possible to determine the chemical composition and the
radioactivity of substances under study, that is, a complete radiochemical
analysis was made within the period of time required for the performance of
the chromatographic analysis only. This was accomplished by passing the flow
coming from the chromatographic column through two detector analyzers, one
recording the component concentration in flow and the other the corresponding
-148-
-------
specific radioactivity. The ratio between the 2 detector analyzer indexes
characterized (determined) the component's specific radioactivity.
Based on this principle the Institute developed, built and tested several
types of radiochromatographs which combined the operations of partitioning and
identification of the components with the recording of the components' specific
radioactivity Ll]. Most suitable was the type in which concentration of vapors
emerging from the chromatographic column was determined by an ionization detec-
tor Pm141, and specific radioactivity was determined by a flow counter which
recorded gas flow intensification L2]. Such a device is of high sensitivity,
simple to operate, yields dependable and stable indexes, and makes possible
the determination of radiochemical composition of
tures within 20 - 30 minutes.
With the procedure
was possible to make physico-chemical measurements
complex polycomponent mix-
and equipment indicated it
(determinations) under dif-
ferent experimental conditions:
follow the course of homo- and heterogeneous
reactions at different temperatures, stu~ radiation of the reaction mixture,
the mechanism of isotope exchange, etc. The gaseous system of the radio-
chromatograph is schematically illustrated in Fig. 1. The mixture of gases
--- --- - -----
6 7
21
lD-
,g I
16
17
o <:tec-16
tor Ij
ther- '*
mostat/J
11
--.-.--'
I
I
t! .
. I
~ - -.-1
Setup for gas Column
supply and con- thermo-
sumption control stat
11
Freezing setup
A
5
Fig. 1. Plan of gas radiochromatograph.
1 - fine regulator valve; 2 - fluid relay; 3 -
reducer PDV-5; 4 - throttle; 5 - clamp; 6 - flow-
meter; 1 - drier; 8 - manometer; 9 - injector;
10 - chromatographic column; 11 - fan; 12 - ab-
sorber; 13 - collector; 14 - freezing trap; 15 -
stopcock of faucet; 16 - collector; 11 - by-pass;
18 - ionizing detectors; 19 - proportional counter;
20 - electromagnetic valve; 21 - three-way stop-
cock; 22 - safety device.
-149-
or liquids to be analyzed
is delivered into the up-
per part of the chromato-
graphic column by a dos-
ing device (10). Before
initiating the experi-
ment, the column is
flushed with a carrier
gas, usually Ar, He, H2'
N2' etc., from gas tank
B through flow regulator
(1). After having been
partitioned the mixture
components enter the
ionization detector (18)
and proportional counter
(19).
The signal from
the ionization deteotor
-------
passing ~ the electrometric amplifier reaches the poly pointed potentiometer
EPP-09; the signal of the proportional counter, passing ~ a separate channel,
reaches the same poly pointed potentiometer by an integrating system of a
"TyuPpan" (tulip) type count recorder. The performance (operation) of the
counter in the gas intensification system is adjusted to the gas flow coming
from the ionization chamber by the addition of methane from gas tank (A). The
radiochromatograph can be adjusted to operate under isothermic conditions or
under conditions of previously planned gradual temperature rise. Chromato-
graphic partitioning should be done under isothermic conditions when working
with a mixture the components of which have a boiling point difference of a
o
narrow range, such for instance as 20 - 30. In partitioning a mixture of BUb-
stances having a wide range of boiling point differences considerable time will
be saved by performing the chromatographic partitioning under conditions of a
previously determined graduated increase in temperature. Temperatures of
chromatographic columns are controlled by an air thermostat for the maintenance
of any desired constant temperature; temperatures of the ionization detector
and of the proportional flow counter are controlled by a detector thermostat.
When partitioning is done under conditions of gradually rising temperature,
the thermostats are set accordingly. The column thermostat temperature can be
elevated according to a previously set plan determined by the rate of movement
of a small vial along the scale of an automatically recording potentiometer
EPp-09 equipped with a triple position electric thermoregulator.
The gas flow emerges from the proportional oounter, enters the freezing
out partitioning system equipped with magnetic valves (20); these valves are
switched in automatically according to a previously set plan by an electro-
pneumatic control device KEP-12u. It should be noted that the chromatographio
partitioning s,ystem here described. yielded a variety of chemically pure sub-
stances; by means of catalytic group synthesis combined with the use of labeled
atoms and subsequent chromatograp~, as here described, it was possible to
isolate pure radioactive divinyl, a- and ~-butylene and other ~drocarbons,
the purity of which was established by the method of spectroscopic infrared
light absorption. All steps of the procedure were directed and operated from
an eleotric control board.
An ionization detector has been described in the literature the basic in-
gredient of whioh was Sr90. In this case the source of ionizing radiation was
-150-
-------
Fig. 2. An ionizing
detector compartment.
1 - Pm147 ionization
source; 2 - collecting
electrode; 3 - Teflon
heater.
Pm147 which was deposited electrolytically in a
thin layer of the oxide measuring 2 cm2 and having
a specific radioactivity 2.5 mcurie/cm2. The half-
life of Pm147 is 2.7 years and maximum energy of the
~-particles is only 0.22 Mev. With regard to its
differential scheme the ionization detector is made
up of 2 cylindrical compartments one of which is
visible in Fig. 2.
Pure carrier gas is run into the
comparative compartment, and the gas coming from the
chromatographic column flows into the measuring or
gaging compartment. The ionization source Pm147 is
isolated from the working space of the compartment
by a terilene film 5 ~ thick.
Under the influence
of the ~-particles the gas undergoes ionization in both compartments.
The
ionization flows are opposite in their direction and, therefore, are mutually
compensating when the carrier gas is flushed through the two compartments. As
a component enters the measuring compartment the magnitude of the ionization
current is altered and resistance tension drops in the order of 1.5 x 109 ohm.
This signal is transmitted to the grid of the amplifier EMU-3 lamp and there-
from to EPP-09. The use of noble gases, such as argon, as carriers enhances
the sensitivity by 50 - 100 times as the result of increase in the ionization
probability of the organic molecules while colliding with the exciting argon
molecules formed in large amounts under the influence of ~-radiation coming
from source Pm147. Maximum detector sensitivity amounts to 1 x 10-~% per mv
at 2000 v tension fed into the compartment. As compared with the heat con-
ducting type of detector, the ionization detector is considerably more sensi-
tive and more stable at variable flow temperature and velocity.
For the determination of radioactivity of substances in flow coming from
the detector use was made of a proportional flow counter (Fig. 3), which in-
sured 100% effective counts and the possibility of working with soft ~-emanators,
such as tritium, which has a maximal ~-spectral energy of 0.0179 Mev. Sensi-
tivity of the proportional counter is 0.001 - 0.0005 mcurie. Use of the pro-
portional counter lowers considerably the amount of radioactive substance
necessary for the completion of a kinetic experiment with an adequate degree
of precision.
-151-
-------
,
II
t
G,,5
inflow
J
Fig. 3. Proportional
flow counter.
1 - spring; 2 - body;
3 - Teflon heater; 4 -
thread; 5 - plug.
L
IfC)~
2
1
FractIon
nai r"
Fig. 4. Typical radio-
chromatograms of a poly-
component mixture inflow.
1 - concentration; 2 -
radioactivity.
CIH, t CzH.
An example of a typical radiogram of a mix-
ture of radioactive and non-radioactive gases and
vapors (Fig. 4) consists of 2 series of curves,
curve 1, recorded by the ionization detector and
curve 2, recorded by the proportional flow counter.
Under conditions of equal and constant time of the
detector and the proportional counter, each radio-
active peak on curve 1 has a corresponding peak on
curve 2. The ratio between the peak area of curve
2 and of curve 1 is in direct proportion to the
specific radioactivity of a given component. In the
field of kinetics and catalysis the character of the
relative change in radioactivity distribution is of
great importance. Therefore, there appears to be no
need for absolute calibration of the device.
However, where such calibration is required or
desirable, it can be accomplished by passing
through the column a carefully measured dose of
a substance having a known specific radioactivity.
The described radiochromatograph has been used in
the Institute of Physical Chemistry in a series
of investigations which proved the utility of
radiochromatography and of chromatography in
general in studying problems related to kinetics
and catalysis. Thus, it was found by the radio-
chromatographic procedure that butylene formation
in the catalytic synthesis of divinyls, according
to Lebedev, was attainable by 2 processes - dehydration, formed in the process
of butyl alcohol in the presence of a non-coked catalyzer, and by hydrogen re-
distribution between the coke and divinyl in the presence of a coke catalyzer.
Predominance of the second process increases as the quantity of coke increases.
By this device and the new chromatographic procedure important information
was obtained in the study of isothermio adsorption of individual substances and
their mixtures, of catalytic reactions in flow and in the adsorbed layer of the
fractional distribution in relation to adsorption temperature, etc. Temperature
-152-
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curves offer a basis for the oaloulation of adsorption heat at the surface of
catalyzers and adsorbents. It is hoped that the radiographic method here
described will make possible the determination of relative adsorption co-
efficients of individual products in the actual course of a catalytic re-
action. This and much more information will undoubtedly be obtained with the
aid of this analytical procedure by other investigators.
Bibliography.
1. M.~. HHOBCRMH, ~. C. KanycTMH, B. A. HoroTRoB-PIDTMH. B c6.
ITpo6~e~I RMHeTMRM M RaTa~M3a. ~3~. AH CCCP, 1957, CTp. 391.
2. C. H. 03MpaHep, r. A. ra3MeB, M. ~. HHOBCRMM, B. C. KOPHRROB.
3aBo~cRaR ~a6opaTopMR. 1959, m 6.
Quantitative Determination of Low 3,4-Benzpyrene Concentrations with Fine
Structure Fluorescent Spectrum.
P. P. Dikun.
(Laboratory of Experimental Oncology, Oncological Institute, Academy
of Medical Sciences, U.S.S.R.).
Voprosy Onkologii, Vol. 7, No.7, 42-53, 1961.
In a previous publication [7J this author described a method for the de-
tection of 3,4-benzpyrene in different complex substances and an approximate
spectrophotometric method for the determination of 3,4-benzpyrene concentra-
tions [6J. In the first method the produots had to be partitioned ohromato-
graphically, which increased considerably the reliability and sensitivity of
the method as compared with the method described by A. A. Il'ina C9, 10J. The
second method was an improvement over the first in that it enabled to make more
accurate quantitative determinations of 3,4-benzpyrene. By the use of the 2
methods qualitative studies were made of many substances: an extensive in-
vestigation of air pollution (llJ; an investigation of 3,4-benzpyrene content
-153-
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in smoked products processed by different technological procedures (1, 2, 4,
5J; tobacco smoke [8J; etc. However, results of such investigations clearly
pointed to the need for the development of a more sensitive method for the
determination of 3,4-benzpyrene. Minimal quantity of 3,4-benzpyrene in sam-
ples determined by the second method was 10 y. Securing samples which con-
tained 10 y of 3,4-benzpyrene with any degree of accuracy proved in some in-
vestigations a difficult task, and impossible in other cases. As was shown
in a previous publication [llJ, the aspiration method was successfully applied
to the collection of air samples with such low 3,4-benzpyrene concentrations
in only a few instances. In another report [3J, it was shown that 3,4-benz-
pyrene determination in the lungs of city dwellers yielded reasonably satis-
factory "summary" results of 11 persons; however, it was not feasible to
establish the presence of 3,4-benzpyrene in the lungs of individual test sub-
jects, which was the purpose of the investigation. A new method is described
in this report which enabled the determination of lower 3,4-benzpyrene con-
centrations than with any previous tests.
General principles and basis of the method. The above mentioned "approxi-
mate" spectrophotometric method was based on the assumption that the light ab-
sorption by admixtures present in the benzpyrene fraction was in linear rela-
tion to the wave length; a similar assumption formed the basis of R. Cooper's
method, used by many investigators abroad. Quantitative 3,4-benzpyrene deter-
minations were made by establishing or measuring the absorption by 3,4-benz-
pyrene fractions of light of different wave lengths. In the present method
fluoresoence intensity was used as the index of 3,4-benzpyrene concentration.
The possibility of using a fluorometr1c method for the quantitative determina-
tion of 3,4-benzpyrene was indicated in a previous publication [1J. Several
circumstances prevented this author from making full use of the fluorometr1c
method at that time: it was difficult to isolate 3,4-benzpyrene in its pure
form from the investigated complex products; extensive distortion in the
quantitative results due to the presence of other fluorescent admixtures.
In the present method the above enumerated difficulties were obviated by com-
bining the principle of spectrofluorometry with the fine structure spectral
fluorescence phenomenon recently described by E. V. Shpol'skii and his co-
workers [12, l3J. E. V. Shpol'skii and collaborators noted that oompound
spectra of 3,4-benzpyrene, and other substances, dissolved in normal paraffin
-154-
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hydrocarbons, such as hexane, n-heptane and n-octane, had changed markedly
upon freezing. The comparatively broad bands, observed at room or low tem-
peratures but dissolved in other solvents, broke up upon freezing into a sys-
tern of narrow bands approximating lines of atomic spectra.
These fine lines
can be used in simultaneously measuring the relative fluorescence intensity of
two or more compounds in solution even when the spectra of such compounds are
mutually superimposed under normal conditions. To make such measurement it is
only necessary to be able to select one line in each of the compounds which is
not in a superimposed position with regard to corresponding lines of the other
substances in the solution. When the system of fine lines can be effected, the
selection of such a free line presented no difficulties. The method of quan-
titative 3,4-benzpyrene determination presently described is based on measuring
or establishing the comparative intensity of two spectrofluorescent lines: the
o
3,4-benzpyrene line of A = 4021 A wave length (see Fig. I-a) and l,12-benzo-
o
perilene line of A = 4060 A (see Fig. I-b); the substances are dissolved in
-- --
. .. ".."~"~-.. >:.::,::~':~~':;::;'::
a
I
~.
':: . . ..."-: -:. :~.:=~.c:=~:.~,.t :-'.,~~':F~.,
. Jr. ." ~. -:&-~ -..: ..:t;f"',r- ~ .,. "'1'",."", Jr' . ,
,-", . ,. 4.: A;;':~~~--'" 'J'::'~:~-:!o'j.~;~ .a-. .: :.~~.. .. -.~ ~~t
. -...:.'.. ~~.- -v~'~~-J .::--;Y~.:':~'~:=~~~~--i~~~-~'-;:~~
b
:"'.;~ - -':",' ...:::-.~~- ' -~'-); -~~~~:.~.....
. -- ........ ..~."t.",-.. '.~H' J~~'.». "'.. .
..-.,., """''',,: :,'~".t ... '1a"'~... "'-..; ~..t .
. ;'a :-~~~'.f. '. '. :"~ -- r . '.:'~ :=~: .' ~'. . . :t;;
c
Fig. 10 Fluorescent spectra of
hexane solutions of substances
frozen with liquid nitrogen taken
by means of a gradual clearing agent.
a - pure 3,4-benzpyrene; b - pure
1,12-benzoperilene; c - typical
picture of a benzpyrene fraction
to which 1,12-benzoperilene was
added.
Arrows.point to two lines the
intensities of which are used in
determining concentrations.
n-hexane and frozen in liquid ni-
trogen.
These lines are so arranged that
the slightest illumination of one com-
pound affected the corresponding line
of the other compound. At the same
time they were arranged in cloBe
proximity to one another. As a re-
sult the background intensity ef-
fected by the fluorescence of the ad-
mixtures of structureless spectra dif-
fered only slightly at such points.
Therefore, it is possible to dis-
regard differences in sensitivity of
photographic films at such points.
Determination of fluorescence in-
tensity ratios of the two lines was
derived by the usual photographic
method.
As was previously indicated,
it was possible to find the relative
-155-
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intensity of the 2 lines by this method; in other words, it was possible to
determine to what extent the intensity of one line exceeded that of the other,
and on the basis of such data to establish the concentration correlation of the
2 substances in the solution under study. Determination of the absolute con-
centration of one of the substances in the solution necessitated a knowledge
of the concentration of the other. However, absolute concentrations can be
determined even when no quantitative information is available for either of
the substances. This can be done by changing the concentration of one of the
substances by adding a known quantity of this substance and determining the
change in the intensity relationship of the two lines. Data thus obtained can
be used for the determination, by a simple calculation, of the original concen-
tration of either compound. Concentration determination based on intensity
measurements is naturally possible only when, there existed in the solution,
a proportionality between concentration and fluorescent intensity for each of
the substances. Consideration was given the fact that the nature of fin~
spectral structure used in this study had been inadequately defined and its
properiies insufficiently studied; therefore, it was regarded expedient to
establish first whether such proportionality actually existed. This was
established as follows: a mixture was prepared of 3,4-benzpyrene and 1,12-
benzoperilene to be used as the stock solution; by diluting it with n-hexane,
a series of work solutions were prepared. The ratio between 3,4-benzpyrene
and l,12-benzoperilene was the same in all the dilutions, but the concentra-
tions differed, and the 3,4-benzpyrene concentrations ranged between 0.025 and
10 y/ml. The spectra of all such solutions were photographed by a gradual
clarifier and the intensity ratios between the two lines were determined.
Data in Table 1 show that the ratio between the fluorescence intensity
of the 2 lines remained constant only in the range of low concentrations.
Beginning with 3,4-benzpyrene concentrations of 0.5 - 1.0 y/ml the value of
the ratio diminished as the concentration increased, i.e., the fluorescence
intensity of the 3,4-benzpyrene line beoame weaker as compared with the fluo-
rescence intensity of the 1,12-benzoperilene line. Of importance in this oon-
nection was the fact that the rate of fluorescence intensity loss by the 3,4-
benzpyrene line with the increase in concentration followed the course of an
ascending curve.
The data lead to an important and practical conclusion, namely, that
proportionalit,y between fluorescence intensity of the lines and concentration
-156-
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TABLE
1.
Ratios between intensities of fluorescent spectral line of 3,4-benzpyrene
and of 1,12-benzoperi1ene at constant ratio in their concentrations
in relation to degree of solution dilution.
y/ml of 3,4-benzpyrene : : . . : : .
: 10 5 . 2.5 . 1 . 0.5 iO.25 0.1 :0.025
. i : !
: . :
. :
At thick solution layer...... 1.02 1.07 1.45 1.62 1.66 1.70 1.74 1.70
At fine solution layer....... 1.41 1.70
of substances under study prevailed only in the region of low concentrations,
indicating that concentration determination on the basis of fluorescence in-
tensity ratios was possible only in the low concentration region. Data of the
basic determination series are presented in Table 1. The determinations were
obtained by placing the solutions into tubes 12 - 14 mm in diameter and freez-
ing them so that absorption and light emission occurred in a thick layero
However, this author also made 2 light e~citation determinations in fine layers.
In this instance the solution was placed in the space between the walls of the
2 tubes one inserted in the other. The thickness of the frozen layer did not
exceed 1 mm.
Data in Table 1 show that the nature of the results remained
practically the same. Thus, the previously discussed concentration effect
was not the result of layer thickness. This indicated that in practice it
was possible to freeze the solution for analysis in comparatively wide tubes.
This presented an advantage, since under such conditions the luminescence in-
tensity was greater than in fine layers.
Final selection of the most suitable concentration range for analysis was
made as follows: the functional relation between line intensity ratios and
concentration of 1,12-benzoperilene was determined at constant 3,4-benzpyrene
concentration; this was done by preparing 2 series of solutions. In the first
series of 5 solutions the 3,4-benzpyrene concentration was 0.5 y/ml, the 1,12-
benzoperilene concentrations were varied to give ratios of 3,4-benzpyrene to
1,12-banzoperilene of 1:1, 1:2, 1:5, 1:10 and 1:20. Intensity ratios between
the selected lines were determined from the speotrum of each solution. Having
established these values, intensity ratios of 3,4-benzpyrene line to intensity
of 1,12-benzoperilene line were determined for same concentrations of these
substances.
Based on proportionality between lines of intensity and substanc6
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concentrations in all 5 tubes identical values for the ratios should have been
obtained. Aotually, however, the ratio values gradually rose with the inorease
in 1,12-benzoperilene ooncentration, pointing to the faot that under given oon-
ditions proportionality between line intensities and substanoe concentrations
in solution did not prevail.
In a seoond series of 10 solutions 3,4-benzpyrene concentration was 0.1
y/ml and ratio between that and 1,12-benzoperilene concentration ranged be-
tween 1:1 and 1:25, at intervals shown in Table 2.
TABLE
2.
Ratios between 3,4-benzpyrene and 1,12-
benzoperilene line intensities at con-
stant 0.1 y/ml 3,4-benzpyrene ooncen-
tration and varying 1,12-benzoperilene
concentration.
3,4-benzpyrene and iLogarithms of con-
1,12-benzoperilene icentration ratios
concentration ratios; (log Ibp/lbl)
1:1
1:2
1:3
1:5
1:7
1:10
1:13
1:16
1:20
1:25
0.64
0.72
0.72
0.72
0.67
0.70
0.69
0.67
0.72
0.62
Average 0.69
Data in Table 2 show that line
intensity ratio values at same 3,4-
benzpyrene concentration were the
same in all cases ~ allowable error,
even though the 1,12-benzoperilene
ooncentration varied. It can be oon-
eluded that at 3,4-benzpyrene 0.1 y/ml
and probably at lower concentrations,
a proportionality prevailed between
intensity of the selected lines and
the concentration of the substances
in solution.
This indicated that
analysis should be made with 3,4-
benzpyrene conoentration not exceed-
ing 0.1 y/ml.
Another important condition was
the following: it appeared that the
ratio between fluorescence intensities of 3,4-benzpyrene and 1,12-benzoperilene
lines of greatest interest to the analyst depended largely upon another factor,
namely, light excitation intensity. Increasing the light excitation intensity
enhanced the fluorescence intensity of 3,4-benzpyrene as compared with 1,12-
benzoperilene lines. Thus, by oonsiderably reducing the light exoitation in-
tensity with a metallic screen, the ratio between the 2 lines was reduced by
60%. Replacing an old lamp by a new one, the light of which was considerably
brighter, also changed the line ratios, so that as compared with the results
obtained by the old lamp, the concentration of 3,4-benzpyrene increased by 80%.
Thus, fluctuations in light exoitation intensity substantially distort the re-
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suIts, unless such fluctuations are properly accounted for. Means were taken
or recommended for the elimination, or reduction to a minimum, of errors
caused by factors just described, as discussed in the following section.
Technique of analytical procedure and required apparatus and reagents.
All preliminary analytical steps, including the isolation of the investigated
benzpyrene fraction, were conducted as described elsewhere. Only the actual
procedure for the determination of 3,4-benzpyrene concentration was new. For
the quantitative determination only n-hexane, liquid nitrogen and photographic
films are needed. The following apparatus is required: a setup for photo-
graphing spectra of frozen fluorescent solutions and a microphotometer, such,
for instance, as MF-2, for the determination of dark lines intensity on the
photographic film.
Fig. 2 is a schematic drawing of the setup. It consists
of ultraviolet light source, for which
~
7
8
5
L
I
I
Fig. 2. Plan of spectral setup
for the study of fluorescent
spectra of frozen solutions.
1 - mercury quartz lamp SVDSh-250
or PRK-4; 2 - quartz condenser;
3 - filter UFS-l which emits
(passes) ultraviolet rays; 4 -
quartz prism of complete inside
reflection; 5 - quartz or uviolar
~uarovsk vessel containing liq-
uid nitrogen; 6 - test tube with
solution under study; 7 - glass
condenser; 8 - spectrograph ISP-
51 with gradual clearing agent;
9 - photographic plate.
this author used a quartz lamp SVDSh-250-3
or PRK-4, provided with a special optical
device for the concentration of the lamp
light upon the test tube containing the
frozen solution.
The concentration of
the light is attained by proper arrange-
ment of transparent quartz prisms, con-
denser, etc.
The following are the analytical
steps:
the desiccated benzpyrene frac-
tion is dissolved in a known volume of
n-hexane; degree of dilution may vary
depending upon the quantity of 3,4-benz-
pyrene contained in the fraction. If it
is judged that the 3,4-benzpyrene concen-
tration was low, then it should be dis-
solved in not more than 10 - 15 ml of the
solvent; but the volume must remain fixed.
The solution thus prepared is then divided
into 2 or 3 even portions or 2 or 3 equivalent portions may be taken from it.
To each 3,4-benzpyrene portion 1,12-benzoperilene dissolved in n-hexane is added
by a pipette in accurately measured gradually increasing volumes, so that the
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first tube, for instance, will contain 1 y; the 2nd - 2 Y and the third - 3 y.
The dilutions are then poured into test tubes of 10 - 12 mm diameter and the
tubes, one after another, frozen in liquid nitrogen in a D,yuarovsk apparatus.
The tubes are inserted close to the inner wall of the Dyuarovsk receiver in
front of the spectrograph slit. After the solution in the tubes has frozen,
the fluorescent spectrum is photographed ~ the gradual clearing agent.
Pictures can be taken with the slits comparatively widely opened. In this
instance, using spectrograph ISP-51, pictures were taken with the slit opened
to 0.1 rom. Duration of exposure is usually 5 - 10 minutes.
Fractions which are judged to contain higher 3,4-benzpyrene concentrations
should be dissolved in larger solvent volumes, and only a portion of that should
be used in making the photographic spectrum. For instance, the sample can be
dissolved in 10 ml, and only 1 ml used and diluting it to 10 - 15 m1, proceed-
ing further as previously described. Fluorescent spectrographic photographs
were similar to those shown in Fig. I-b. The picture appeared as a series of
spectra of different intensity, one below the other. Different degrees of
spectral darkening were due to the fact that they were taken at different steps
of the gradual clearing agent. Comparing this picture with the ones in Fig. l-a
and I-b, it can be seen that it consists of 3,4-benzpyrene and 1,12-benzoperilene
lines. In the next stage of analysis determinations were made of the ratio in-
tensity of the spectral lines chosen for analysis, that is, 3,4-benzpyrene lines
o 0
with A - 4021 A and 1,12-benzoperi1ene lines with A - 4060 A. Such determina-
tion was made by measuring with microphotometer MF-2 the darkening intensity
on the logarithmio scale of these lines in all spectra obtained at different
clearing agent steps. After this, curves of darkening intensity are plotted
for each line. This is done by the usual method. A curve is constructed by
plotting darkening intensities along the ordinate, and degree of light passing
through the clarifying agent along the abscissa, using the logarithmic scale
on one of the ordinates. Each value of line darkening intensity is indicated
by a dot on the graph along the ordinate in terms of its absolute value and
along the abscissa in terms of logarithm of light intensity passing through the
steps of the clarifying agent by which the spectrum was obtained. By connect-
ing all dots of one line a plot is obtained of its changes in darkening in-
tensity; an analogous curve is plotted for the other line. In Fig. 3 curve I
-160-
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1,4 IJ
'2
1,0
08
06
q4 /
0.2
0,1 0,4 0,6 0,8 If}
Figo 3. Typical curves
of darkening.
I - darkening curve of 1,12-
benzoperilene; II - darken-
ing curve of 3,4-benzpyrene.
AB - distance between curves
which represent line
intensities ratio.
Abscissa - logarithms of
passing (filtration) through
clearing agent; ordinate -
logarithm of darkening
intensity.
represents darkening intensity of the 1,12-
benzoperilene line, and curve II the darkening
intensity of the 3,4-benzpyrene line. The
horizontal distance between the 2 lines, that
is, the distance between two points of equal
darkening (section AB in Fig. 3) represents
the logarithm of intensity ratio of the 2
lines. The prooedure is carried out for each
solution. If the dilution of the benzpyrene
fraction was appropriately prepared, then the
quantity of 3,4-benzpyrene can be established
by a simple calculation. For example: assume
that 'a' represents the logarithm of intensity
ratio between 3,4-benzpyrene and 1,12-benzo-
perilene lines, then the value of 'a' can be
expressed by the following equation:
xIbp
log nlbl .. a
(1)
in which Ibp represents the intensity of 3,4-
benzpyrene in a solution containing 1 y; x is
the quantity of 3,4-benzpyrene in y; Ibl is the
intensity of 1,12-benzoperilene line of a solu-
tion containing 1 y; and n is the quantity of
Generalization (1) can also be expressed as follows:
1,12-benxoperilene in y.
(2)
log x + log Ibp - log n - log lbl = a
from which the following generalization can be derived:
n lbp
log x - log lbl - a
(3)
Generalization (3) can be used in calculating 3,4-benzpyrene quantities used
in cases in which the original fractions contained no 1,12-benzoperilene. The
first part of the equation contains 2 values. As indicated above value 'a' is
determined from the curves of darkening. Expression log lbp/lel is the loga-
rithm of ratio of the line intensities of the 2 substances of equal concen-
trationso
condi tions.
As was previously indicated this value is determined under different
At 3,4-benzpyrene 0.1 y/ml or less and at large interval of
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1,12-benzoperilene concentrations this value was constant and equalled approxi-
mately 0.69. Therefore, formula (3) can be further simplified as follows:
log ~ - 0.69 - a
x
(4)
Letis now compute the quantity of 3,4-benzpyrene for a case shown in Fig. 3,
assuming that the benzpyrene fraction as such contained no 1,12-benzoperi1ene.
In that case value 'a' will be represented by section AB = 0.31; and, since
the curve of 1,12-benzoperi16ne darkening is above the 3,4-benzpyrene curve,
its values are negative and, henoe, AB - 0.31. According to formula (4)
log nix - 0.69 - (-0.31) - 1.0, and nix - 10. In other words, the quantity
of 1,12-benzoperilene in the solution was 10 times as great as the quantity
of 3,4-benzpyrene. In the case presented in the graph there was added to
the benzpyrene fraction 1 y of 1,12-benzoperilenej therefore, this fraction
would contain x - n/IO - 1/10 - 0.1 Y of 3,4-benzpyrene. Results of above
computation would, therefore, indicate that the analysis was conducted under
properly chosen conditions with regard to ratio of 3,4-benzpyrene and 1,12-
benzoperilene concentrations within the previously controlled limits of 1:10
and with 3,4-benzpyrene not exceeding 0.1 y/ml or 0.1 y/5 ml of the solution.
Had the conditions of the determination been chosen inappropriately, then
the resulting curves of darkening and values of n:x would have indicated that.
Assume that n:x . 0.5. This would indicate first that the range of concentra-
tion ratios was selected unfittingly; and second, if 1 Y of 1,12-benzoperilene
had been added to the sample it would then follow that the 3,4-benzpyrene con-
centration in the solution was high - about 0.4 y/ml on the basis of total
solution volume of 5 mI. Under such conditions it would have been necessary
to dilute the fraction 4 times and add another 4 or 5 y of 1,12-benzoperilene.
After having photographed the spectrum of the new solution and having completed
all determinations and calculations obtaining the correct values of 3,4-benz-
pyrene content should present no difficulties.
The above analysis represents a simple case, that is, one in which the
benzpyrene fraction contained no 1,12-benzoperilene. However, under practical
conditions benzpyrene fractions isolated from many studied products actually
contained 1,12-benzoperilene. Even under such conditions it should be possible
to make a quantitative determination of 3,4-benzpyrene and of 1,12-benzoperilene
without resorting to additional complex procedures of purifying the fraction.
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With such possibilities in mind, it was previously recommended that 2 or )
benzpyrene fraction dilutions be made to which different quantities of 1,12-
benzoperilene were to be added. Curves of darkening are then plotted from the
spectra of each solution as shown in Fig.). Logarithmic ratios between the
intensity lines of ),4-benzpyrene and 1,12-benzoperilene are then found on
the plots for each ),4-benzpyrene solution prepared. Computation of the ),4-
benzpyrene and 1,12-benzoperilene quantities present in the original fraction
are then made as followst three equations are derived from formula (4):
nl n2 n)
log ~ - 0.69 - &1; log x - 0.69 - &2; log ~ - 0.69 - 8.)
Now, assume that the following were obtained as the result of the computations:
nl n2 n)
~ - AI; x - ~; x - A)
Assume in addition that the original fr~ction contained nO of 1,12-benzo-
perilene in the sample volume placed into one tube, and that to each tube now
containing the same amount of the original solution nIl' n'2 and nt) of this
compound were added correspondingly. The equation can then be presented as:
nO + nIl nO + n'2 nO + n')
x - AI; x - ~; x - A)
Solving these equations in pairs, that is, 1 and 2, 2 and ), and) and 1, the
following) expressions are derived for x and nO:
x =
; x -
n') - n'2
A) - ~ ; x -
A)
nl - - n'
) ~ 2
A)
~ - 1
n') - nIl
A) - Al
(5)
no -
n'2 - nIl
~ - Al
A2
n' - - n'
2 ~ 1
A2
-- 1
Al
; nO -
; nO -
A)
n' - -n'
) Al 1
A)
--1
Al
(6)
Values of the) equations under (5) and under (6) are averaged to obtain
quantities of 3,4-benzpyrene and 1,12-benzoperilene found in each tube. The
averages are used in finding the quantity of 3,4-benzpyrene and 1,12-benzo-
perilene in the fraction by the usual routine procedure. Generalizations
under (5) and (6) are in essence formulas for the calculation of 3,4-benz-
pyrene and 1,12-benzoperilene amounts. The above outlined calculation pro-
cedure is intended for use in analysis employing) samples of the fraction
under investigation. It is possible to shorten the procedure by using only
-16)-
-------
2 dilutions, in whiCh case direot single values can be derived for x and nO'
Single answers only can be derived from solving single pairs of equations;
under such conditions no average values could be derived, and final results
m~ lack the desired precision. Therefore, it would be neoessar.y to repeat
the entire procedure should the final results indicate that the selection of
analytical conditions was not a fitting one. The above discussion dealt with
only one of many possible analytical variants encountered in 3,4-benzpyrene
determination. It should be added that a similar procedure of reasoning and
calculation can be applied to all varying cases.
It was shown in a preceding paragraph that line intensity ratios varied
with the intensity of light excitation. Changes in the intensity of light
excitation are accompanied by changes in coefficient 'a' and log Ibp/Ibl which
are components of formula (3). Possible errors which m~ arise in connection
with this phenomenon oan be avoided by adhering to the following procedure:
each time a lamp, as a source of light, is changed, or each time any other
type of change is introduced which may affect the intensity of light excita-
tion, such, for instance, as changing a light filter, changing a condenser,
changing a Dyuarovsk device, the value of log Ibp/Ibl, whioh was taken as -
0.69, should be carefully rechecked. In determining the 2 coefficients
mentioned and during making practical analyses, it is important to see that
the lamp operated under the same current intensity. As a general rule, values
of coefficient log Ibp/Ibl should be ohecked by means of specially prepared
solutions of pure compounds even under favorable conditions of analytical de-
terminations. In view of the above, it is essential that solution samples
used in checking the coefficients be preserved for future check tests. Should
the check test indicate that the coefficient value has shifted, the analysis
should be repeated. Results of analysis should not be regarded as final
unless and until an appropriate coefficient checking indioated that no note-
worthy changes had taken place in the coefficients under consideration.
Scrupulous observation of the above instructions will result in securing
correct analytical values. It should be noted at this point that fluctua-
tions in the light emanated by the electric bulb introduce no errors of con-
siderable magnitude. Thus, 0.5 amp. fluctuations in the current passing
through the lamp, such as 4.5 amp. and 4.0 amp., affected the results only
to the extent of 9 - 10%. In the light of the above mentioned cases the
-164-
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0.69 coefficient used in formula (4) can not and should not be applied in
analysis of a newly assembled installation; in such cases new and special
supplemental tests should be made.
Procedure for checking the method and a comparison with the approximate
spectrophotometrio method. The method was checked first by the following
procedure: several produots were selected which contained no 3,4-benzpyrene.
Dilutions were prepared to which known quantities of pure 3,4-benzpyrene and
1,12-benzoperilene were added. Quantitative determinations were then made
for 3,4-benzpyrene; the results are listed in Table 3. A comparison of the
results obtained with actual amounts added showed that 3,4-benzpyrene could
be determined by this method with a high degree of precision; averages of 15
sample analyses showed that the limit of error averaged * 8%. It is generally
conceded that for a photographic method such results are highly satisfactory.
The range of error was also comparatively insignificant. In only 3 of 15
analyses did the difference exceed 10%, with 13% being the highest. Data in
Table 3 are obtained with 5 3,4-benzpyrene-free fractions. They indicate
that none of the products used had any substantial effect on the results.
TABLE
3.
Checking the new method's precision.
Experiment i
number i
:
Fraction
number
: y of added: y of added: y of 3,4- i Percent
il,12-benzo- i 3,4-benz- .= benzpyrene ...
.. deviation
i perilene i pyrene i found i
1 1 2 0.4 0.31 -8
2 1 4 0.8 0.12 -10
3 1 8 0.8 0.9 +12.5
4 2 1 0.25 0.23 -8
5 2 2 0.25 0.282 +12.8
6 2 3 0.25 0.269 +8
1 2 2 0.5 0.45 -10
8 2 3 0.5 0.5 0
9 2 6 0.5 0.54 +8
10 3 2 0.5 0.5 0
11 3 5 0.5 0.46 -8
12 4 2 0.5 0.50 0
13 4 5 0.5 0.56 +12
14 5 2 0.5 0.51 +2
15 5 5 0.5 0.46 -8
Aver es. . . . . . . . '. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 8
-165-
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Therefore, it is concluded that foreign substances present in the fractions,
and in particular fluorescent substances, had no notable effect on the ana-
lytical results.
The next stage was a comparative evaluation of results obtained by the
new method herein described and by the old method of "approximate" spectro-
photometry. Twenty, thirty or more benzpyrene fractions, derived from dif-
ferent products, were tested by both methods. In evaluating the results the
following must be considered: first, all analyzed fractions containing 1,12-
benzoperilene should be separated from those free from that compound. This
is essential, since the absorption spectrum of 1,12-benzoperilene closely
approximates the absorption spectrum of 3,4-benzpyrene. Hence, in analyzing
the samples by the old method the 1,12-benzoperilene fraction imparts to 3,4-
benzpyrene determinations excessive values. Presence in the fraction of 4.5 y
of 1,12-benzoperilene, as determined by the "approximate" spectrophotometric
method, is equivalent to 1 y of 3,4-benzpyrene. (See note at end of paper).
Secondly, the results obtained should be combined into 2 groups: group 1
should contain results of samples which by the "approximate" method yielded
comparatively small errors, that is, fractions containing more than 10 y of
3,4-benzpyrene per sample; and group 2, results of samples which by the "ap-
proximate" spectrophotometric method contained less than 10 y per sample, in
which case the accuracy of the old method is not high. The comparative study
of the 2 methods led to the following conclusions: in analyzing fractions
free from 1,12-benzoperilene containing greater 3,4-benzpyrene concentrations
the 2 methods yielded practically coincident values. In the presence of
1,12-benxoperilene the new method yielded lower 3,4-benzpyrene value's than
did the "approximate" spectrophotometric method, the difference on occasion
ranging between 30 - 40%. However, if in using the new procedure the amount
of determined 1,12-benzoperilene is computed as 3,4-benzpyrene equivalent
and the two values are added, then the old and new procedures will yield close
to equal values in most cases.
In some instances the summary values may ex-
ceed the old values by 10 - 20%, and at most 30%.
In samples of low 3,4-
benzpyrene concentration the total picture remained generally the same, but
the magnitude of differences was somewhat greater, due to the inferior ac-
curacy of the old method analyzing low 3,4-benzpyrene-containing samples.
Thus, results indicated that values yielded by the 2 methods were within
-166-
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reasonable agreement and that results obtained by one method may be regarded
as a confirmation of the results obtained by the other method. A comparison
of the values yielded by the 2 methods leads to 2 conclusions which give
preference to the new procedure.
The preceding discussion clearly indicated that the new method had ad-
vantages in analyzing fraotions containing l,12-benzoperilene, a substance
which is found in many products. Its separation from 3,4-benzpyrene presents
difficulties even in chromatographic partitioning, and complete separation of
the two oan not always be attained. Admixtures of 1,12-benzoperilene con-
siderably distorted the analytical results yielded by the old method. The
presence of 1,12-benzoperilene was no obstacle to the correct analytical de-
terminations by the new method, thereby eliminating the need of thorough
partitioning of the 2 substances.
Another even more essential advantage possessed by the new method is
its higher sensitivity. By the new method 0.05 - 0.01 Y of 3,4-benzpyrene
per sample and in some cases, even lower quantities were determined with
reasonable accuraoy, whereas the old method was reasonably accurate only in
the presence of 10 y or more of the 3,4-benzpyrene. It has been estimated
that the new method was 100 times as sensitive as the "approximate" spectro-
photometric method. It is hoped that such increase in sensitivity might
prove of value in establishing the presence of this cancerogenic substance.
It is also hoped that supplemental studies of the new procedure will make
possible its application to analysis of other fluorescent substances.
Conclusions.
10 Results of a special investigation showed that fine structure spectral
fluoresoence can be used for qualitative and quantitative determination of
3,4-benzpyrene. Quantitative determination is based on ratio between 3,4-
benzpyrene and l,12-benzoperilene absorption intensity lines. The 1,12-
benzoperilene is added specially to the fraction under quantitative study
in known quantities.
2.
The new method is highly sensitive.
By the fine structure spectral
fluorescent method determinations oan be made comparatively easily of 0.05 -
0.10 Y or less of 3,4-benzpyrene per sample with a high degree of acouracy.
Average deviation of 15 control tests was only ~ 8%. Deviations exceeding
10% ocourred in 3 of the 15 control tests, and none exceeded 13%.
-161-
-------
30 The method here described for the determination of 3,4-benzpyrene
concentration based on the fine structure spectral fluorescent principle
manifested many advantages over previously recommended spectrophotometric
procedures. The primary and most basic advantage was in the fact that the
new method made possible the determination of minimum 3,4-benzpyrene concen-
trations 100 times lower than the minimum concentrations required by the
previously described methods, retaining the previously mentioned high degree
of precision. The second advantage resides in the fact that the presence of
slight amounts of 1,12-benzoperilene, the absolute removal of which at times
presented great difficulties, did not interfere with the accuracy of 3,4-
benzpyrene determination. The presence of 1,12-benzoperilene seriously dis-
torted determination results by previous procedures of this author as well as
by any determination procedure based on the principle of light absorption.
4. Principally the presently outlined method can be employed not only
in the determination of 3,4-benzpyrene, but equally effectively in the deter-
mination of any other substance characterized by fine structure spectral
fluorescence. Another advantage is presented by the fact that substances
other than 1,12-benzoperilene can be added in making quantitative determina-
tions. It must be borne in mind, however, that in applying this method to
the determination of substances other than 3,4-benzpyrene and in using addi-
tives other than 1,12-benzoperilene a thorough preliminary study must be made
to find the most suitable set of determination conditions.
5. Values yielded by the new analytical procedures were checked on a
control basis against values obtained by the previously described "approxi-
mate" procedure; results were within the range of statistically satisfactory
agreement.
Note: To avoid misunderstanding regarding the old method, it should be
borne in mind that 1,12-benzoperilene in -the fraction exists only as an ad-
mixture to 3,4-benzpyrene and that it can distort the outcome of quantitative
determinations; it is for this reason that the old procedure has been referred
to as the "approximate" photospectrometric method. On the other hand, the
assumption that the fraction contained only 1,12-benzoperilene and no 3,4-
benzpyrene and that the old method recorded total 1,12-benzoperilene as 3,4-
benzpyrene must be excluded by preliminary qualitative testing of the samples
for the presence of 3,4-benzpyrene.
-168-
-------
Bibliography.
1. r 0 p e JJ 0 B a H. 11., 11 H /{ Y H D. D. BOllp. OH/{OJJ., 1958, IV, 4, 398-405.
2. r 0 p e JJ 0 B a H. 11., .a H /{ Y H D. D. TaM >Ke, 1958, IV, 4, 405-408.
3. r 0 p e JJ 0 B a H. 11.. 11 H K Y H D. D. TaM >Ke, 1959, V, 8, 161-164.
4 r 0 p e JJ 0 B a H. 11. 11 H K Y H D. D., J1 a II [!J H H H. 11. TaM >Ke 1959 V g
341, 345. ' '"
5. r 0 p e JJ 0 B a H. 11., 11 H I{ Y H D. D., Co JJ H " e K B. A., EM [!J a HOB a A. B.
TaM >Ke, 1960, VI. 1, 33-37.
6. 11 H K Y H D. D. TaM >Ke, 1955, I, 4, 34-38.
7. 11 H K Y H D. D. TaM >Ke, 1955, 1,5,24-29.
8. 11 H K Y Ii D. D., q Y l1J K II H C. r TaM >Ke, 1959, V. 7, 34-38.
9. 11 JJ b H H a A. A. )}(ypH. aHaJJ. XHMHH, 1950, 5, 2, 90.
10. 11 JJ b H H a A. A. 113B. AH CCCP. C. q>H3HlJeCK 1951 15 6 771
II. ill a 6 aA J1. M., 11 H K Y H D. D. 3arp5l3HeHHe' aTMo~q>e;JH~ro B~3Ayxa Kalil\epOreH-
HblM Bell(ecTBoM 3.4-6eH3I1HpeHo~!. MeArH3, 1959.
12. ill II 0 JJ b C K H Ii 3. B., H JJ b H H a A. ;\., K ,1 HMO B a J1 A 110KJI AH CCCP
1952,87, 935. ". ,
13. ill II 0 JJ b C K H Ii 3. B., K J1 HMO B a J1. A. I-13B. AH CCCP. C. "'H3HlJecK., 1956,
20, 471. 'I'
14. Coo per R., Analist, 1954,573-579.
Collecting Air Samples for the Determination of Nitrogen Dioxide.
E. V. Alekseeva.
Gigiena i Sanitariya, Vol. 25, No.6, 50-51, 1960.
Accuracy of air sample analysis for content of any particular gas depends
on the method of air sample collecting to the same extent as it depends upon
the precision of the analytical methods used. Air samples for the analysis
of nitrogen dioxide concentration are usually collected by one of three meth.
ods: 1) by aspiration of the air through a liquid absorber; 2) by the vacuum
method; and 3) by the exchange method. Solutions of NaOH, of sulfanilic acid,
of XI and the Griess-Ilosvey reagent have been used as absorbers of nitrogen
dioxide. In the exchange method the air is aspirated through a bottle or a
gas pipette until the original air in those containers is completely replaced
by the air to be tested, which can be accomplished by aspirating through the
containers a volume of the air 6 to 10 times the capacity of the bottle or of
the gas pipette. The purpose of this study was to make a comparative evalua-
tion of the 3 methods of air sample collection for the determination of ni-
trogen dioxide concentrations.
The experimental procedure was as follows:
a known concentration of nitrogen dioxide was prepared inside a glass flask
-169-
-------
equipped with a ground-to-fit stopper having two fused-in glass tubes, one
extending down to the bottom of the flask, the otner protruding only slightly
below the lower end of the glass stopper. This served as the source of ex-
perimental air containing a known constant concentration of nitrogen dioxide
for use in any one of the methods investigated. The gas pipettes or the
bottle, as the case m~ have been, were first thoroughly washed, tested for
the presence of oxides of nitrogen and vacuumated (by a water pump). Simul-
taneously with the collection of a sample by aspiration through liquid ab-
sorbers, three samples were collected by the vacuum method. In all tests
nitrogen dioxide was determined by the Griess-Ilosvey reagent. Tests were
made with air samples containing quantities of nitrogen dioxide in the order
of hundredths or thousandths of mg per lie The absorber apparatus was V-
shaped and was equipped with a porous filter No.1. Over 200 tests were made
under identical conditions. Results are listed in the table below. The data
show that the NaOH solution manifested the lowest absorption of nitrogen
dioxide; the solution of sulfanilic acid, which is a constituent of the
Griess reagent, was only slightly better. Nitrogen dioxide reacted with
sulfanilic acid to form a diazo-compound; however, in the course of air sam-
ple aspiration the diazo-compound decomposed because of its high instability.
This explains the limited 20% absorption of the nitrogen dioxide. This was
verified as follows: air samples were aspirated through the Griess reagent
which was accompanied by a rapid diazotization reaction; however the final
determination results, though higher than in the case of sulfanilic acid,
still amounted to only .45%. The diazo-compounds formed in the Griess re-
agent reacted with a-naphthyl amine to form a dye compound; however, the latter
Summary table of average results of nitrogen dioxide determinations
in air samples collected by different methods.
Collection method
Found
in
percent
Vacuum method........... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
NaOH solution..................................................
Sulfanilic acid solution.......................................
Potassium iodide solution......................................
Griess-Ilosvey reagent.........................................
Exchange method, slow aspiration rate..........................
Excha~e method, at the rate of 5 - 6 Ii/min...................
100
17.9
20
43.6
45
131.5
95 - 100
-110-
-------
reaction proceeded at a rate considerably slower than the first reaction, and
much of the diazo-compound decomposed before reacting with the a-naphthylamine.
Hence, the lower results. The KI absorber solution absorbed only 43.6% of the
nitrogen dioxide.
Results of testa by the exchange method showed that aspiration of the air
at the rate of 5 Ii/min. recorded only 95% of the nitrogen dioxide present in
the air sample, and at the rate of 6 Ii/min. recorded 100%; from this it can
be ooncluded that the rate of air aspiration affected the determination re-
suIts. On the other hand, when the rate of air aspiration was too low (0.5 -
1.0 Ii/min.) the final result was 131%. This may be the result of nitrogen
dioxide adsorption to the surface of the glass container. Aspirating the air
through the gas pipette at the rate of 5 - 6 Ii/min. yielded analytical re-
sults approximating those yielded by the vacuum collection method.
The results presented indicated that nitrogen dioxide was incompletely
absorbed by the liquid absorber used and that air samples for the determina-
tion of nitrogen dioxide had best be oollected by the bottle or gas pipette
vacuumation method, or by the exchange method, aspirating the air through the
containers at the rate of 5 - 6 Ii/min.
-111-
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Hydrogen Sulfide Oxidation in the Organism.
A. I. Gunina.
Trudy Vsesoyuznoi Konferentsii po Meditsinskoi Radiologii, Eksperimental'naya
Meditsinsk~a Radiologiya, Kedgiz, 1951, 280-283.
.Discussions on the mechanism of hydrogen sulfide baths are based on the
assumption that upon entering the organism hydrogen sulfide enhanced the number
of sulfhydryl bonds accompanied by an increase in the concentrations of gluta-
thione and cysteine. It was also assumed that sulfur accumulated in the organs
and that hydrogen sulfide persisted in the circulation for a long time. The
purpose of this study was to check the correctness of the above assumptions
and to establish, if possible, the course of hydrogen sulfide oxidation in
the organism. Studies were conducted by the method of labeled hydrogen sul-
fide. Four series of investigations were conducted based on different routes
of H2S administration. Tests were made for H2S concentration in the blood and
percent of labeled S incorporated into proteins of different organs.
In the first series six dogs were injected intravenously with Na2S at
the rate of 10 up to 600 y, with specific activities ranging between 500,000
up to 14 x 106 imp. per kg of body weight. Injection took 10 - 20 minutes.
Blood was taken for analysis from the artery and vein opposite the injected
side after 1, 3, 5, 7, 8, 9, 10, 11, 13, 15, 20, 30, 45 and 60 minutes. No
H2S was detected in either the venous or arterial blood samples. One hour
after the injection of the Na2S solution the urine contained 11.4% of the in-
jected dose, 60% of which was in the form of inorganic sulfates, 3% in the
form of S esters, and the rest in the form of neutral sulfur. No H2S was
found in the urine.
Hydrogen sulfide and products of its oxidation in the organs were in-
vestigated as follows: dogs were killed 30 and 60 minutes after the Na2S
injection, the organs removed and tested for specific activity. Results are
listed in Table 1. Highest specific activity was found in the kidneys,
testicles, lungs, liver, pancreas, and lowest in skeletal muscles.
Experiments of the second series were performed with 26 rats. Animals
were injected subcutaneously with a solution of Na2S35 once or daily over 4 -
6 days at the rate of 1 - 8 y per g of body weight. Specific activity of the
injections ranged between 3000 and 6000 imp/min. Simultaneous determinations
for the presence of H2S and intensity of specific activity were made 24 and
-172-
-------
TABLE
1.
Specific activity of organs one hour after intravenous injeotion
of Na2S35 equivalent to 6.6 mg of H2s35 of 157 x 106 imp/min.
Organ
S mg/g of
tissue
i Imp/min. per i .p~rctendt of i
: f t' : 1nJec e ac-:
i g 0 1ssue :tivity x 10-2 i
Speoifio
activity
x 10-2
Lungs............ 1.21 24,807 1.57 13
Kidneys.......... 1.10 33,360 2.12 19
Liver............ 1.57 24,829 1.57 10
Heart............ 0.82 10,566 0.67 8
Spleen........... 1.04 13,368 0.85 8
Pancreas......... 0.79 12,435 0.79 10
Testicles........ 0.55 13,480 0.86 16
Skeletal muscles. 0.93 8,819 0.56 6
48 hours after the Na2S35 injection. No H2S was found in the blood of any
rats. Results of studies on the elimination of S35 via the urine are listed
in Table 2. Data indicate that 24 hours after the Na2S35 subcutaneous in-
jection the urine showed specific activity of high intensity, and that 92 -
99% of the eliminated S35 was in the form of inorganic sulfates.
TABLE
2.
Sulfur elimination via urine following subcutaneous administration
of Na2S35 equivalent to 220 g of H2S35 of 7.4 x 105 imp/min.
: :
Days iMl of urinei
. .
: :
Sulfur per 1 ml : Imp/min/ml : Percent
Total i Inorganic i Total: Inorganic i of total
: : S x 10-2 : S x 10-2 : sulfur
1
2
5
6
5.7
3.8
6.0
1.2
1.15
1.23
1.88
0.65
1.29
1.08
1.65
717
106
18
702
98
10
10
99
92
55
Determinations were then made of total and radioactive S in different
organs 24 hours and six days after the subcutaneous Na2S35 injection. Data
indicate that 24 hours after the injection highest specific activity was
found in the liver, lungs, kidneys and spleen; six days after the injection
the intensity of specific activity sharply fell in the liver and remained un-
changed in the liver and kidneys. Data obtained with rats repeatedly injected
with the Na2S35 are also listed in Table 3. The data indicate that following
the injection of large H2S35 doses, such as 495 y on four successive days,
-173-
-------
specific activity was registered by all protein fractions of all organs; fol-
lowing the injection of small doses, such as 39 y on four successive days no
specific activity was registered by any of the organ proteins.
TABLE
3.
S35 distribution in organs following subcutaneous injection of sodium sulfide,
:Injected 3~3.6 y H2S35 ! Injected 220 y H2SJ5
i 1. 7 x 10 imp/min. i-L..1- x 105 imp/min.
: ~ ! ~ Q) : rd! ! t(): :~ :
: Q) ";:1 : Q)' i Q): t()Q) fQ) io~
: J.1 ;:I ! ~ en : ~ ~ ! 0 ~ . J.1;:1 :';:1 .~ ~ "M+»
: (I) fQ :'M co i o+» :.....+» i Q) co : s:: co :o+» ~.~
: P. co i 8 'M . Q)'rl:\J i ~.~. P. co :'M co : Q) 'MN :'M > I
: 'M .,+» : .,,>, ..,-i >,: .,-i: 8'M :.,,> , :o.,-iO
: U') +» : P. : ~.,-i 0 : O'M 0 : (J) +» :........... +» : s:::.,-i 0 : Q) +> r-f
: : 8 Ct-4 : .ri~rl : Q)~,...-i : : p. JTt+=t r-i : PIt>
: t()~ : H 0 : 0 : PlO : t()~ i e ~ 0 :en as H
: ::Ii 0 i i''b'it ct! ~ :Cf) ~ H : ::iI 0 : H 0 ~ oj H :
Organs
: Injeoted I Injected
i495 y H2S35i37 Y H2s3g
: 11 x 106 :0.39 x 10
i imp/min. i imp/min,
: s::.s:::~: ~.~S:::
: CD""': 'M""'iCD"'" :'rl.rl
: >8: (1)&.>8 i(l)a
: 'M'.' +»,:....., ..p"""
! +» P.. 0 P.!+» P. ! 0 Pt
. aS8. J.18.a!8 .J.18
: IZ<""'! Po.""':IZ<'M illl.;..j
Brain
Lungs
Kidney s
Liver
Heart
Spleen
Muscles
0.69 425 2.5
0.93 740 4.3
1.04 720 4.2
1.18 1100 6.5
1.67 561 3.3
1.15 810 4.8
1. 26 140 0.8
counted 24 hrs.
injection
36
46
40
55
20
41
6
after
95
344
230
28
93
169
1.3
4.6
3.1
0.4
1.2
2.3
16
39
26
3
6
18
34 74
67 94
170 185
21 29
28 33
101 76
10 29
4 days
injection
6 0
3 0
3 3
1 1
3 0
3 0
1 4
5 days
injection
The third series of experiments was conducted with 23 rats and 2 dogs by
inhalation of sublethal H2s35 doses. Inhalation time, including the post-
inhalation interval, ranged between 10 minutes and 2 hours. Blood samples
were taken during inhalation to oheck on the presenoe of ~s35, none of it
was deteoted in any of the blood samples.
Results of blood and organ tests for 535 disclosed that following in-
halation the specific activity intensity was reduced, especially in the blood
and lungs and to a lesser degree in the liver and spleen, while it rose in the
kidneys. Results of urine tests made 10 minutes following H2S35 inhalation
in the gaseous form indioated that in the oourse of the first day after in-
halation exposure more than 10% of the total S appeared in the urine in the
0.19
1.18
1.18
1.32
2.00
1.24
0.98
oounted 6 days after
injeotion
form of inorganic sulfates.
The rate of total 5 elimination via the urine
in the course of the seoond day after inhalation exposure fell to considerably
lower levels, with the percent of inorganic sulfates increasing.
thus indicated that the predominant amount of oxidized H2S35 was
~ the urine in the course of the first two days.
-114-
Results
eliminated
-------
The following was observed in dogs with exposed ureters after 20 minutes
H2s35 inhalation: 5 to 10 minutes after beginning inhalation S35 appeared in
the urine, with maximum S35 elimination recorded 2 - 3 hours later; after 8 -
10 hours the rate of S35 elimination through the urine had considerably sub-
sided. No H2S was detected in the urine; 30 minutes following the H2S35 in-
halation inorganic sulfates constituted 70 - 90% of the total eliminated S.
Experiments of the fourth series were done with 15 rats kept in baths
containing 100 - 200 mg/li of hydrogen sulfide at 36° for 10 minutes. Radio-
active H2s35 was added at the rate of 1200 - 1600 y, the radioactivity of which
registered 3 x 107 to 6 x 107 imp/min. per 800 mI. Some rats received single
treatments and some 4, 5 and 10 treatments. Animals were examined 10 and 30
minutes, and 24, 48 and 72 hours after bath treatment. Results of tests in-
dicated that H2S35 became rapidly oxidized in the organism and that the prod-
ucts of its oxidation appeared in the urine mostly as inorganic sulfates and
partly as 5-esters. Data listed in Table 4 show that the sum of urine elimi-
nated S compounds constituted 80% of the S contained in the urine. Most of
the oxidation products of H2S35 were eliminated through the urine within 24
hours after the bath treatment, as in all cases of hydrogen sulfide adminis-
tration by the other methods. No S35 was found in any organ proteins of rats
administered H2S35 by the bath submerging method. Therein lies the difference
of H2S effect on the organism administered by the bath treatment as compared
with the injection administration.
TABLE
4.
Sulfur in urine of rats after hydrogen sulfide bath.
:
!
Rat i Hours
N : after
o. I bath
! Activity
! !Im I. !Imp/min.! !Imp/min.! :p rcent
. Im I. . p m~n.... . P t.. S . P t: e
: p m~n.:. t t l:~n ~nor-: ercen : ~n : ercen: f
: f: ~n 0 a: . S: f 1 : t : f t t 1 : 0
: g 0 :s l:gan~o:o tota: es ers:o 0 a: t 1
: . : per m : 1: If: 1: If : neu ra
: ur~ne : f . : per m : su ur: per m : su ur: If
: :0 ur~ne: .: : f .: : su ur
: : :of ur~ne: :0 ur~ne: :
5
5
6
6
12
12
24
48
24
48
24
48
19,430 20,610 19,814 96 966 4.7
1,970 2,814 2,218 79 213 7.6 13.4
6,070 6,569 3,617 55.0 306 4.6 40.4
4,670 5,615 3,769 67.0 360 6.4 26.6
4,220 4,239 3,554 83.8 107 2.5 13.7
690 819 544 66.6 24 2.9 30.5
-175-
-------
Conclusions.
1. H2S became rapidly oxidized and eliminated regardless of the method
or route of its administration. No H2S was detected in the blood.
2. Products of H2S oxidation appeared in the blood, urine, and organs
within 5 - 10 minutes after its administration. At that time 50% of the S
appearing in the urine was of the inorganic sulfate and sulfur ester type,
30 minutes later the concentration of inorganic sulfates in the urine con-
siderably increased.
3. Most of the products of H2S oxidation were eliminated by the organism
within the first 24 hours. This was true of all methods of H2S administration.
4. S35 appeared in organ proteins only in instances of massive intra-
venous, subcutaneous and inhalation administration. No S35 was detected in
the organ proteins following the bath-type of administration.
5. No positive evidence was elicited which might have indicated that S
accumulated in the organism as the result of H2S or Na2S administration in
any of the above described experiments.
Benzene and Its Homologues as Poisons in Electrical Winding
and Insulation Plants.
A. P. Rusinova.
(From the Department of Labor Hygiene of the Leningrad Institute
of Post-Graduate Medicine).
Gig1ena Truda i Professional'nye Zabolevaniya, Vol. 1, No.1, 20-24, 1951.
The production of winding and insulation materials is an important funo-
tion in plants of the electrical industry. Workers connected with the pro-
duction of winding and insulation materials are constantly exposed to the
effects of benzene, toluol, and xylol. In this connection, the prevailing
significance of sanitary labor conditions has been investigated insufficiently.
The investigation conducted by the present author was directed into two
channels: 1) a study of the sanitary-hygienic labor conditions, and 2) a stud1
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of the workers' health.
Production of insulation material such as micatape,
synthetic tape, micanite, etc. and of different types of winding materials
required the use of adhesive substances, coating lacquers, enamels and tars,
which have to be mixed with or dissolved in benzene, toluol, xylol, white
spirit and ethylol. Application of the lacquers is done by machine, the roll-
ers of which are submerged in a small vat containing the above-mentioned
treatment materials. Nevertheless, most steps performed in this industry are
accomplished manually using a brush or similar means of application. Part of
the treated tape and other materials are placed into special drying ovens;
however, much of it is dried in the open air within the working premises.
Many other operations, though partly mechanized, are performed manually in
the open, so that vapors of the above-mentioned solvents and admixtures satu-
rate the surrounding air. Such pollutants are removed by combined forced and
exhaust ventilation systems installed in only part of the working premises.
Many of the plants' departments have no ventilation facilities.
Inspection of the plant in 1953, prior to the initiation of this inves-
tigation, showed that benzene has been used as the solvent and in many cases
also as the diluent, so that it constituted 30 - 85% of the material used in
the plant.
Benzene was also used in some of the washing operations.
In 1953 -
1955 toluol replaced benzene in all except 2 departments, so that toluol in-
stead of benzene constituted 30 - 85% of the solvents used. Toluol, xylol and
white spirit were used most frequently in the washing department. Many work-
ers preferred to use xylol.
The use of lacquer has been stepped up consider-
ably during the last few years. Thus, silica-organic lacquer, containing up
to 85% of toluol, was used in 12 times as many operations in 1955 as in 1952.
In the production of clear lacquer glyfuoro-oil lacquer was used mostly; it
contained 55% toluol instead of the previously used benzene; the coating lac-
quers and gray enamel also contained 55% of toluol and xylol. Replacement
of benzene by xylol, toluol and white spirit was adopted for the protection
of working space air against pollution, without previous investigation or
standardization, so that no information existed regarding prevailing concen-
trations of volatile ingredients in the surrounding air. Studies conducted
in 1954 - 1955 showed that concentrations of benzene and its homologues in
the air exceeded the limits of allowable concentration, as shown in Table 1.
Data in Table 1 show that in 1954 - 1955, when benzene was still pre-
dominantly in use, its concentration in the air exceeded the allowable 0.05
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TABLE
1.
Content of benzene and its homologues toluol and xylol.
:
Toxio !
substance i
.
i
Number of
analyses
: Limits of :
: .
: concentration i
! fluctuation i
: . /1' :
: ~n mg ~ :
Average
ooncentration
in mg/li
:Number of analyses
i exceeding limits
:
: of allowable
: concentrations
Benzene
Toluol
Xylol
Total
110
110
256
536
0.002 - 0.5
0.01 - 2.5
0.03 - 2.0
0.15
0.32
0.17
121 (11.1%)
62 (55.9%)
108 (4g!)
291 (54..:.1!L
mg/li limit in 15% of the tests. Toluol concentration exceeded the official
limit in 50% of the tests, and xylol exceeded the limit of 0.1 mg/li in 40%
of the tests. The most unpleasant operation with regard to benzene air pollu-
tion was the manual brush application of gray enamel to pole coils, placing
the micanite into the dr,ying ovens, and application of adhesive micanite.
Average toluol concentrations in the air were 2.5 - 4.0 times as high as
average benzene concentrations at points where these production functions were
performed. Concentrations of xylol in the washing processes ranged between
0.05 - 2.6 mg/li, with an average of 0.41 mg/li. Finishing of coil ends by
the brush method and the newly introduced process of insulation removing were
not accompanied by xylol evaporation; therefore, no such vapor was found in
the air of premises where these and similar operations were performed. Gen-
erally, the concentration of benzene and its homologue vapors in the air
depended upon their content in the lacquer, the air temperature and the ex-
haust ventilation operationo
The volume of work in the plant has considerably increased of late with-
out introducing additional health protecting measures. As a consequence,
concentrations of benzene and of its replacing homologues, toluol and xylol,
were high. Above described labor conditions were the cause of many chronio
benzene and its homologues intoxications among workers, symptoms of whioh
were leukopenia, thrombopenia, anemia, nose and gum bleeding, in women ex-
cessive menstruation, neurotic syndromes accompanied by vegetative dysfuno-
tion on the basis of asthenia, etc. In workers who continued their ocoupa-
tion despite the above symptoms,
ressed to a point where they had
then the toxic effects persisted
the gravity of benzene intoxication prog-
to be assigned to different jobs. Even
for a long time. Most clear-cut forms of
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intoxication arising in a comparatively short work period as 2 years were ob-
served among women working at the preparation of the insulation tape, the lac-
quer, and those performing the washing function. In studying the general rate
of morbidity and loss of work capacity and work days during 1952 - 1954 it
was noted that more than 50% of the women workers of the department studied
manifested symptoms of a variety of illnesses. This was particularly true
of women with long work records. An attempt was made to establish the role
played by benzene and its homologues in the so-called "non-occupational mor-
bidity" among women employed in the winding-insulation department. For this
purpose a control group was selected from among women workers of the winding-
insulation department who showed no signs of intoxication. Rate of "non-
occupational morbidity" of this group was investigated on a parallel basis
with "non-occupational morbidity" rate among a group of women working in the
same department who manifested symptoms of intoxication. Age and work records
of the non-toxic controls and the toxic group were nearly the same. Each
group consisted of 86 women workers. Results of the investigation are shown
in Table 2. Data in Table 2 show that the so-called "non-occupational mor-
bidtty" among the women of the toxic group was 1.5 times as high as in the
control group. A study of 28 types of "non-occupational" illnesses indioated
that 19 occurred in the toxic group at greater frequency than among the wamen
of the control group who had no intoxication symptoms. The greater part of
TABLE
2.
Comparative data on total morbidity among workers suffering of intoxication
with benzene and its homologues and among the control group during 1953-1954.
(Data represent absolu~e numbers among 84 workers in each group).
Number
:of :>i ck
: women
: Morbidity indexe:> of al I
: diseases, occupational
intoxication excepted
: : Work:
; Number: days: Number
: of :Iost due:of sick
::>ick in-I to : women
:stances ::>ickness:
. M or bi d i ty indexes of
achronic benzene intoxica- :
:tion and of toxic vegeta- :
tive polyneuritis
: : Work
: Number: days: Number
, of :Iost due:of sick
,sick in-: to ,women
,stances :sickness:
Total morbidity
: : Work
. Number. days
. f .
: . o. : f ost due
.slck In-. to
. stances' . k
:SIC ness
G ro up of women
Women with clear-cut 88 584 6,331
benzene intoxication, 81 396 3,190
(116.0) (157.0) (155.0) 58 Iti8 3,144 (118.5) (232.0) (309.0)
o~ with symptoms sus-
piciou:> of same 70 252 2,052
70 252 2,052
Control group (100.0) (100.0) (100.0) (100.0) (100.0) (100.0)
Data in parenthesi:> are in relation to control group assigned the value of 100.
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the increased morbidity indexes in the toxic group as compared with the con-
trol group were of "non-benzene etiology". Thus, morbidity indexes on days
when women of the toxic group felt incapable of working exceeded similar in-
dexes of the control group as shown below:
Grippe............................................ 4 times as high
Acute catarrh of upper respiratory tract.......... 3 times as high
Cardiac muscle disease.......................... 2.8 times as high
Radiculitis..................................... 2.1 times as high
Purulent skin diseases.......................... 2.0 times as high
A considerable number of women with intoxication symptoms were sick up
to 18 times in 2 years. Forty women of the toxic group were sick more than
4 times as compared with 11 women of the control group, i.e., 2.4 as many.
Thus, results of the investigation indicated that women workers employed in
the department under study had typical benzene and its homologues intoxica-
tion symptoms and in addition had so-called "non-occupational" diseases of
sufficient severity to cause their abstention from work for reasons of work
incapacity.
Conclusions.
1.
The air of winding and insulation departments of the plant investi-
gated contained benzene and its homologues in concentrations exceeding the
allowable limits. In percent of samples investigated the results were as fol-
lows:
benzene in 71.1%, toluol in 55.9% and xylol in 42%.
2. Most unfavorable operations from the viewpoint of benzene and homo-
logues evaporation were: application of adhesives to micanite on tables
manually and their loading into the drying ovens; insulation and lacquering
of windings; brush coating of pole coils; and finally, washing and cleaning
various finished products.
3. Unsatisfactory labor conditions produced occupational poisoning with
aromatic hydrocarbons among the women workers, with symptoms of typical blood
picture changes and nervous system disturbances.
4. Continuous and systematic exposure to benzene and its homologues ap-
peared to have created a state of susceptibility on the part of the organism
to some cormnon "non-occupational" diseases, as was shown by increase in the
morbidity of such diseases in women with toxic symptoms as compared with the
control women.
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5. Most effective means of health condition improvement are the following:
a) replacing toluol and xylol by less toxic solvents; b) hygienic standardiza-
tion of lacquer, solvent and diluent composition; mechanization to the highest
possible degree of now prevailing manual operations, and hermetization of
operations which eliminated deleterious vapors.
Installation of effectively operating mechanical ventilation, improve-
ment and insulation of steam pi~es, drying chambers and systematic check of
compliance with all sanitary-hygienic regulations.
Hygienic Evaluation of Hydrogenated Coal Gasoline.
Z. E. Grigor'yev.
(From the Toxicological Laboratory of the Leningrad Institute
of Labor Hygiene and Occupational Diseases).
Gigiena Truda i Professional'nye Zabolevaniya, Vol. 1, No.2, 34-37, 1957.
Gasoline obtained by hydrogenation of Cheremkhovsk coal is a transparent
liquid of sp. gr. 0.7288. It begins to boil at 44°, 10% is distilled off at
750 and 90% at 155°; its maximum boiling point is 182°. Its composition in-
cludes the following in percent by weight: unsaturated hydrocarbons 0.3;
aromatic hydrocarbons 2.2; naphthenes 59.2; and paraffins 38.3; it evaporates
103 times slower than ethyl ether and 10 times slower than "Galosha" petroleum
gasoline.
The toxic properties of the gasoline were tested on white mice,
white rats and rabbits.
For purposes of comparison, parallel experiments
were performed with I1Galosha" petroleum gasoline, the toxicity of which has
been studied by N. V. Lazarev, E. N. Levina, Ie. I. Lyublina, I. S. Tsitovich,
G. I. Tsobkallo, and others.
Resorptive properties of the gasoline vapor were tested by 2-hour ex-
posure of white mice in a sealed exposure chamber. Each concentration (with
intervals of 10 mg/li) was tested on 10 animals. The gasoline vapor concen-
tration in the chamber was produced and maintained as per calculations. In
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view of the fact that the volatility of the gasoline obtained by coal hyarogena-
tion was lower than that of gasoline "Galosha", its calculated concentration
was checked by chemical analyses.
Results of the experiments showed that hydrogenated coal gasoline had a
higher resorptive rate than gasoline "Galosha". Thus, the minimum concentra-
tion causing lateral decubitus in white mice was 24.5 mg/li for the hydrogen-
ated coal gasoline, as determined chemically, and 30 mg/li for gasoline "Galo-
sha". Minimum lethal concentration was 21.8 mg/li for the hydrogenated coal
gasoline and 60 mg/li for gasoline "Galosha". Absolute lethal concentration
was 100 mg/li for gasoline "Galosha"; it could not be determined for hydrogen-
ated coal gasoline since maximum air saturation with vapor of this gasoline
amounted to 44.51 mg/li. Maximum number of dead mice at this concentration
did not exceed 70%. The resorptive power of the hydrogenated coal gasoline
vapor was closer to gasoline "Gudri" obtained by catalytic cracking; according
to E. N. Levina's 1952 findings, the narcotic concentration of the latter was
16 mg/li and the lethal concentration 30 mg/li.
The clinical picture of acute poisoning of animals by the vapor of the
gasoline under study was different. Animals poisoned with gasoline "Galosha"
manifested excitation, and death usually occurred suddenly during the excita-
tion period, accompanied by severe tetanic spasms of the extremities and of
the occipital muscles. On the other hand, exposure to hydrogenated coal gaso-
line rendered animals relatively immobile, they sat quietly and huddled to-
gether. Narcosis set in while the animals were in this state. The animals
usually died lying in a lateral position, in a few isolated instances death
occurred before the state of narcosis set in.
Hydrogenated coal gasoline evaporated more slowly and the concentration
of its vapor in the exposure chamber rose gradually, which was reflected in a
delayed onset of the toxic condition. For example, animals exposed to the
action of gasoline "Galosha" began to show evidence of narcosis within an
average of 45 minutes, whereas animals exposed to the hydrogenated coal gaso-
line began to manifest narcotic effect within 75 minutes. The narcotic ef-
fect of gasoline "Galosha" lasted an average of 43.7 minutes, while the nar-
cotic effect of the hydrogenated coal gasoline lasted on the average 81
minutes. )4ice exposed to the action of gasoline "Galosha" died on the
average after 55 minutes, while animals exposed to the hydrogenated gaso-
line died on the average after 89 minutes. The slower onset of narcosis,
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the more persistent the narcotic state, and the difference in time of death
could be explained not only by the slow saturation of the animalst blood with
the hydrogenated coal gasoline and its delayed elimination from the organism,
but also by the chemical nature of the component parts of this gasoline.
The threshold concentration of gasoline effect on the central nervous
system was established in white rats by the conditioned reflex method.
Ex-
periments were performed on animals with well-fixed conditioned reflexes to
visual and auditory stimuli accompanied by food reinforcement.
Chamber gaso-
line vapor concentrations were first calculated and in the case of the hydro-
genated coal gasoline the concentration was checked chemically. Tests with
the gasoline were performed with each rat individually 2 - 3 times a week to
check their original neuro-pattern. Each test lasted 55 minutes. The ef-
fects of individual concentrations were checked 2 - 3 times on the same ani-
mals.
Nine animals were used in the investigation, and 75 experiments were
performed with each of the tested gasolines.
Data obtained with the animals
preliminarily to the actual testing and data obtained during actual testing
prior to exposure to the gasoline were used for control purposes.
Results
of numerous control experiments showed that the latent period of response
ranged between 0.4 and 0.6 seconds, with an average of 0.5 seconds, while
reaction time from beginning of the motor reaction to the time of the animalts
running to the feed box averaged 0.9 seconds.
Results of the experiments showed that hydrogenated coal gasoline vapor
in 0.2 mg/li concentration had no disturbing effect on the conditioned reflexes
of the animals. In 0.4 mg/li concentration the gasoline brought about a
lengthening of the reaction time, especially at the end of the test period
from 0.7 to 1.5 seconds; in 4 of the 60 cases or 6.6% the differential in-
hibition reflex response to the buzzer sound was disturbed, indicating an
impairment in the cerebral cortex function of these animals. An increase in
the gasoline concentration to 0.75 mg/li caused a lengthening of the reaction
time from 0.7 to 1.1 seconds, and in 8 cases (13.3%) differentiation inhibi-
tion was disturbed. A 2.62 mg/li concentration caused impairment of differ-
entiation inhibition in 33 cases (55%). Collapse of positive conditioned re-
flexes was not observed. The hydrogenated coal gasoline left no after-effects,
upon exposure to a concentration of 8 mg/li, the conditioned reflexes returned
to normal the following day. Accordingly, the threshold concentration effect
on the central nervous system in the animals ranged between 0.4 - 0.75 mg/li.
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Experiments with gasoline "Galosha" showed that its threshold concentration
ranged between 0.1 - 1.0 mg/li.
One hundred and eight persons participated in the determination of the
character and intensity of the odor of the gasoline. Test subjects were most~
healthy persons 18 to 20 years old. In the determination of the odor intensity
of the hydrogenated coal gasoline, 27% of the tested persons stated that the
gasoline possessed a weak odor, 26% characterized it as moderate, and 47% as
strong; 50% of the test subjects identified the odor of the gasoline as such,
and 50% as the odor of kerosene. Gasoline "Galosha" was evaluated differ-
ently: 5.7% of the subjects evaluated its odor as weak, 59.1% as moderate,
and 34.8% as strong. The character of the odor was identified by 92.3% of the
test subjects as gasoline and 7.7% as the odor of kerosene. Consequently, the
odor of hydrogenated coal gasoline, as compared with that of gasoline "Galosha",
was predominantly similar to that of kerosene. It would appear from this that
the odor of hydrogenated coal gasoline could not cause any unpleasant odor
sensations even under industrial working conditions.
The irritating action of gasoline on intact skin was tested on the tails
of white mice and rabbits' ear pinnae. Results of experiments with the tails
of white mice (64 animals) showed that hydrogenated coal gasoline caused less
pronounced local reactions than did gasoline "Galosha". Thus, 30-minute
application of hydrogenated coal gasoline gave rise to an appreciable dila-
tation of the caudal vessels, which returned to normal within 24 hours ex-
cept for slight residual exfoliation; gasoline "Galosha" in similar experi-
ments gave rise to marked dilatation of the vessels of the entire tail and in
24 hours to caudal edema and exfoliation. A similar picture of tail inflamma-
tion was produced in 100% of the animals after a 60-minute exposure.
Results of experiments with rabbits' ear pinnae showed that 30-minute
applioation of hydrogenated coal gasoline gave rise to a severe inflammatory
reaction in the ear in every case. A 1.80 temperature rise and a 33% swelling
appeared at the end of 24 hours.
The inside surface of the external ear re-
vealed fissures and small purulent uloers. Seven d~s later the size of the
external ear began to normalize but alopecia began to develop. Not until the
12th day did the external ear return to its original size, and by the 18th
day the fur began to regenerate. Wi th similar exposure, gasoline "Galosha"
gave rise to a marked hyperemia of the entire ear lobe and a 15% increase in
its size; by the 4th day it returned to normal. No sheeding of fur was noted.
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The effect of the gasoline on human .skin was tested on 60 males and 15
females 19 to 33 years of age; all had voluntarily expressed their desire to
participate in the experiments. Skin tests were made by the Bo-called "com-
press" method. Pieces of gauze measuring 10 x 10 mm, folded into 4 layers,
were soaked in gasoline and applied to the external aspect of the forearm,
covered with wax paper, held in place with a bandage, and left thus for 24
hours. Results showed that hydrogenated coal gasoline produced more marked
local effects than gasoline "Galosha". When the hydrogenated coal gasoline
tests had been applied to the skin for 24 hours, a positive reaction was ob-
served in 10 of 15 women and in 9 of 60 men; after 48 hours in 14 females
and 21 males; and after 72 hours in 12 females and 21 males. The positive
reaction appeared in the form of erythemas, edemas, and the presence of
vesicular papules. Gasoline "Galosha" produced considerably less pronounced
reactions. At the site of applic~tion only a slight erythema remained in 5
females and 2 males.
Conclusions.
1. Hydrogenated coal gasoline is of relatively low volatility and of
broad fraction composition, with a predominance of naphthene hydrocarbons.
2. In its resportive action hydrogenated coal benzine proved more toxic
than gasoline tlGalosha" of petroleum origin; its toxicity was similar to the
"Gudri" brand of petroleum gasoline.
3. The threshold concentration of hydrogenated coal gasoline gave rise
to functional impairment of the central nervous system in white rats similar
to that of gasoline "Galosha".
4. The local aotion of hydrogenated coal gasoline on intact rabbit and
human skin Was greater than that of gasoline "Galosha".
5. Hydrogenated coal gasoline possessed physico-chemical properties use-
ful to industrial exploitation on par with petroleum gasoline.
6. The adopted maximum permissible concentrations of petroleum gasoline
in air of working quarters must also be extended to hydrogenated coal gasoline
(N 101-54).
7. Existing sanitary-hygienic regulations applioable to work with
petroleum gasoline must extend over work with hydrogenated coal gasoline.
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~I
Olfactory and Taste Analyzer Changes in Chronic Carbon Disulfide Intoxication.
V. G. Osipova.
(Institute of Labor Hygiene and Occupational Diseases, A.K.S., U.S.S.R.).
Gigiena Truda i Professional'nye Zabolevaniya, Vol. 1, No.3, 44-48, 1957.
The toxicity of carbon disulfide as an occupational poison has been known
sinoe its introduotion into the manufacture of artificial fibers, the rubber
industry, and many other industries. A review of the extensive literature on
carbon disulfide intoxioation indicated that its effect was principally on the
nervous system. Lately some investigators attempted to explain the toxic action
of carbon disulfide by neuro-vascular changes, with selective blocking of
certain zones of the central and peripheral nervous systems. According to
U.S.S.R. literature carbon disulfide poisoning presented a clinioal picture
of mild chronic forms of intoxication, in which functional disturbanoes of the
nervous system predominated. Pathomorpholegical findings obtained under chronic
experimental conditions oonfirmed the faot that oarbon disulfide brought about
diffuse changes in the oentral nervous system.
The purpose of this investigation was to study changes in the olfactory
and taste analyzers as indexes of the functional condition of the central nervous
system in chronic carbon disulfide poisoning. A thorough study of oortical
ohanges was made through an investigation of the organism's conditioned reflex
activity. Reports of such an investigation will be presented at some future
time.
The method. The olfactory analyzer was studied by the Elsberg-Levi method,
using rosemary, thymol, tar and oamphor as olfactory stimuli and 3 to 10 ml as
the normal threshold of olfactory sensitivity to all 4 substances. In cases in
which the threshold of olfactory senstivity could not be determined, test
persons were offered a choice of odor-emanating substances, among which were
purely olfactory odors and some which gave rise to trigeminal stimulation. If
no odor was perceived from the flask upon active inhalation, it was considered
that the subject was anosmic.
Taste sensitivity was determined by the drop stimulation method. In aC-
cordance with the topography of the taste zones, drops of different strengths
of hydrochloric acid, salt, quinine ohloride and refined sugar solutions were
plaoed on the tongue. Normal taste sensitivity was finally recorded as followsl
sweet, 0.25 - 1%; sour and salty, 0.13 - 1%; bitter, 0.00025 - 0.003%.
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This report deals with data obtained under field conditions in mass surveys
of working personnel in 2 plants, and also with a dynamic investigation of pa-
tients under treatment or observation of Dr. M. A. Kazakevich in the Institute's
clinic for chronic carbon disulfide intoxication.
Otorhinolaryngological ex-
aminations were made by Dr. L. A. Kozlov.
Persons who had inflammation of the
nasal accessory sinuses, hypertrophic rhinitis, deviated nasal septi were not
included in the statistical evaluation. The 108 workers studied under indus-
trial conditions consisted largely of women spinners from 20 to 30 years of
age. Neurological examination revealed that some workers had incipient and
pronounced symptoms of chronic carbon disulfide intoxication. A correlative
study of results of all examinations indicated that symptoms of chronic carbon
disulfide intoxication were accompanied by lowered taste sensitivity to bitter
and sweet stimuli and by a lowered olfactory sensitivity to the 4 odor-emanating
substances used as stimulating agents.
Curves in Fig. 1 show the condition of the thresholds of olfactory (A) and
taste (B) sensitivity in examined healthy workers (I) and persons with chronic
CS2 intoxication (II - III). It was noted that among the practically healthy
workers there were many with relatively low rosemary odor perception thresh-
olds. Among workers who were under identical industrial conditions but did
not have contact with carbon disulfide, the thresholds of olfactory and taste
perception were within normal limits. More ~ronounced changes in the state of
the olfactory and taste analyzers were observed among patients under clinical
Most of these were women spinners
observation for chronic CS2 intoxication.
E 28
c: Z5
.- 24
~ 22
~ 20
~ 18
~ 15
+'
14
c:
~ 12
~ 10,
~ 8
~ 6
Q. "
L-
o 2
-0
o
A
Tdr
Thy mo I
[ D m
- _.- Camphor '---
Rosemary -
O,o'o'J
c: 3,0
-0 0, 0,0,4
~ 2,0,
" +'
~ c: 0. 0,0,3
.c ~ 1,5
+' L-
c: ~ 0.0,0,2
.~ c: 1,0,
~.~ 0.0,0,1
~ j 0.5
~ "0 0.0,0,0,5
0.. '" 0. 25
~ a, 0,0,0,25
~ 0,13
I-
/
/
/
/
/
I/'
r
6
[
!l
ill
~.eet ---
Sour -
8itter-
S"I ty - -
Figure 1.
-187-
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and washers from 20 to 55 years of age. Fifty-five percent of the patients
exhibited olfactory damage in the form of pronounced hyposmia, and 20% in the
form of total anosmia. Lowered taste perception was noted with respect to all
stimuli used, especially to sweetness (in 50%) and to bitterness (in 30%).
(Fig. 1, II).
A comparison of threshold values for olfactory and gustatory perception
with the severity of chronic carbon disulfide intoxication disclosed a correla-
tion between the gravity of intoxication and the rise in odor and taste percep-
tion threshold. However, no correlation was noted between the change in odor
and taste perception acuity and the work duration record.
Dynamic observation of the state of olfactory and taste analyzers in
hospital patients was performed in the course of complete clinical and eserine
therapy.
Despite improvement in the patients' general condition under complex
therapy, consisting essentially of intravenous glucose administration, use of
vitamins, brewer's yeast, hydrotherapy, no sensitivity restoration was observed
in cases of anosmia and hyposmia. Complex treatment effected a lowering of the
olfactory and taste sensitivity in patients whose perception thresholds rose
only slightly. Best effect was obtained by eserine therapy, which restored
the olfactory function in anosmia and completely normalized olfactory sensi-
tivity. A lasting improvement in olfactory sensitivity was noted after 9
10 eserine injections. Two to 3 weeks after eserine therapy, and in some cases
after 3 and 9 months, olfactory sensitivity was still within normal limits.
Parallel studies of taste sensitivity in patients who were under eserine therapy
showed the same trend, but restoration of taste sensitivity was less pronounced.
Records were made of the status of olfactory and taste sensitivity in pa-
tients receiving single eserine injections in doses of 0.4 - 0.5 ml (1:1000).
In contrast to effects of repeated eserine therapy, single eserine injections
had no beneficial effect on the manifestations of anosmia.
Favorable eserine
effect was noted only in hyposmia, and the maximum lowering of the thresholds
for all the olfactory stimuli was observed 60 - 10 minutes after eserine in-
jection. However, after 3 - 4 hours the initial threshold perception returned.
Determinations of threshold perceptions of taste sensitivity after a single
eserine injection revealed no regularity.
To clarify specificity of eserine action in restoring olfactory sensi-
tivity, a study was made of the results of oral administration of caffeine in
doses of 0.03 - 0.9 ml, since the latter induced increased excitability of the
-188-
-------
cortical cells. Experiments with caffeine were performed before eserine therapy
was initiated, with single eserine injection, and in the course of eserine
therapy. Like the single eserine injection, caffeine had no effect in anosmia.
In the case of hyposmia, caffeine lowered the thresholds of olfactory sensitivity,
but by comparison with eserine this lowering was less effective, both as to the
degree of threshold lowering and as to the duration of the effect. The greatest
lowering was observed after 40 - 50 minutes, and the time of return to initial
sensitivity was 1 - 1.5 hours (Fig. 2). Results of caffeine use with a back-
ground of eserine therapy, i.e., when the patient took caffeine 5 - 10 minutes
after the eserine injection, indicated that this combination brought about a
more marked restoration of the 01-
Ca Heine
e
Eserine
factory function than did caffeine
alone or a single eserine injection.
.!:. 24
" Z2
"0 20
i 18
..
~ 16
.c
." 14
g 12
:;; 10
~ 8
~ 6
~ "
~ Z
o
"
o
.= Z6
" 24 " ".
on \ \
-i 20 \. \
f 18 \ \
~ \
.... I~ \ \
g 14 \ \'
:; 12 \ \
;- 10 \.
~ 8 \
..
C>. 6
... "
o
204060 80fOOfZOf40fOO g 2 20406[180 1001Z0f40 160
Changes observed in differences of
caffeine and eserine effects given
as a single dose or as a course of
th~rapy, and changes noted in the
I I, I ,I
course of combined therapy, in-
dicated that eserine apparently
(0 JO 5070 gO ffO fJOf50 170
fO 3050 70 gO If 0 130150170
Figure 2.
played a therapeutic role in the
restoration of olfactory sensitivity.
A review of the literature on
Tar
Time in minutes
- -, Camphor -- - Thy mo 1- Rosemary --
the specific anticholinesterase activity of eserine and its stimulating effect
on the synaptic apparatus gave rise to the assumption that hyposmia and anosmia
resulting from chronic carbon disulfide intoxication were largely connected
with the impairment of nerve excitation transmission in the synaptic apparatuses
of the olfactory analyzer. The favorable effect of caffeine discovered by this
writer apparently was connected with the fact that functional changes which oc-
curred during CS2 poisoning in the cortical part of the analyzer pl~ed a part
in the lowering of the olfactory analyzer activity. Evidence of the existence
of changes in the cortex was obtained through investigations of cortical dynamics
by studying the blinking and vascular conditioned reflexes. In agreement with
the findings of A. A. Vodel and L. P. Chepka, results of the present investiga-
tion showed that chronic carbon disulfide intoxication was accompanied by changes
in cortical activity, which were also reflected as changes in the functional
-189-
-------
state of the cortical part of the olfactory and other analyzers.
agreement with previous findings of A. A. Model and L. P. Chepka.
This was in
Concl usions.
10
Effect of oarbon disulfide vapor on the human organism was accompanied
by functional changes in the olfactory and taste analyzers. Changes in the
olfactory analzyer appeared in the form of 2 phases: a) a lowering of rosemary
odor threshold perception in the absence of clinical symptoms of intoxication;
b) a rise in the odor intensity thresholds for all the odor-emanating substances
in the clinical study of chronic carbon disulfide intoxication.
Changes in the taste analyzer were noted in chronic carbon disulfide in-
toxication, which appeared as lowered sensitivity, largely with respect to
sweet and bitter stimuli.
2.
Anosmia caused by the action of carbon disulfide on the organism was
reversible.
3. Restoration of olfactory sensitivity during eserine and oaffeine treat-
ment offered a basis for the assumption that the mechanism of olfaotory function
disturbanoe was connected with functional changes originating in the synaptio
apparatuses of the olfactory analyzer and also in its cortical section.
4. Results of analyzer studies together with clinical findings, may be
used as an early diagnosis of chronic carbon disulfide intoxication.
Bibliography.
K a.1 a K e B H 4 M. A. K KnHHHKe XrOHH4eCKOH IIHTOKCIIKaUHH cepoyrJlepO.QOM.
B .c6.: TpY.QbI AMH CCCP, T. XXXI, I954.-K e BOp K b 51 H A. A. flpo
-------
Effect of Benzanthrone Poisoning on Liver Function.
L. I. Slutskii.
(From the Ukrainian Central Scientific-Research Institute
of Labor Hygiene and Occupational Diseases).
Gigiena Truda i Professional'nye Zabolevaniya, Vol. 1, No.4, 40-46, 1957.
The textile industry has recently presented the chemical industry with
a request to increase variety of dyestuffs. This increase referred largely
to light and fast vat dyes, among which the benzanthrone derivatives stood out
prominently. For this reason benzanthrone production has been rising steadily.
Production of benzanthrone, originally regarded as a relatively non-toxic sub-
stance, was first started in one of the chemical plants in 1950. It was found
soon that benzanthrone possessed strongly toxic properties, giving rise to a
peculiar and complex picture of intoxication in workers employed in the dye
industry. This led to a study of the occupational toxicological effect of
benzanthrone. The work was initiated by the Ukrainian Central Scientific-
Research Institute for Labor Hygiene and Occupational Diseases (V. G. Pisku-
nova and co-workers). The clinical picture of occupational benzanthrone in-
toxication was described with particular reference to symptoms indicative of
liver function disturbances.
A combination of methods was used in the study of the liver function,
including an investigation of liver detoxification function, its participa-
tion in carbohydrate, protein and pigment metabolism, and in the formation of
the colloidal-chemical properties of blood. Under investigation were 53 persons
diagnosed as having benzanthrone intoxication. The subjects included 43 males
and 10 females, among whom there were machine operators and their helpers,
mechanics, electricians, workers in the shop laboratory, auxiliary workers,
and engineering-technical personnel. On the basis of employment duration the
patients were grouped as follows: up to 1 year, 4 persons; 1 to 2 years, 3
persons; up to 3 years, 43 persons; more than 3 years, 3 persons. Clinical
symptoms of liver changes, such as enlargement of the liver, tenderness on
palpation, intolerance of fatty food, pain in the right hypochondrium, were
noted in 29 of the 53 individuals. Persons with benzanthrone intoxication
were divided into 3 groups according to V. G. Piskunova:
1.
In the first group were placed persons with pronounced clinical pic-
tures of intoxication based on characteristic pigmentation and trophic changes
-191-
-------
of the skin, anorexia, emaciation, muscular weakness, enlargement and tender-
ness of the liver, pain in the right hypochondrium; this group included 21
persons.
2. The second group included persons with symptoms of early intoxication,
such as complaints of general weakness, loss of appetite, emaciation, pain in
the right hypochondrium, burning of normally exposed skin, especially in sun-
light, but without changes in skin coloring; this group consisted of 21 persons.
30 The third group included persons with residual manifestations from
previous intoxications; this group consisted of 18 persons. 1/
Factual data obtained in this investigation of benzanthrone poisoning ef-
fect on different phases of liver function revealed many pathological devia-
tions from the normal indexes, the frequency with which such shifts occurred
and the gravity of the clinical symptomatology. An attempt was also made to
establish a correlation between shifts in liver function indexes and the nature
of morphologic changes.
In this study the Quick test was regarded as positive when the excretion
of hippuric acid, calculated as sodium benzoate, was less than 0.15 g. The
following were regarded as pathological blood sugar curves: curves of the
"diabetic" type, depressed curves, and curves with an initial hypoglycemic
level. A total blood serum protein concentration less than 6.5% was regarded
as hypoproteinemia, and an albumin/globulin ratio of less than 1.2 was regarded
as pathological. 0.10 - 1.25 g% was set as the limit of normal y-globulin
content of blood serum and 0.35 - 1.0 mg% was taken as the normal limit for
bilirubin. The above-indicated values were taken after a study of pertinent
data in the literature. Thymol turbidity tests were negative in all 28 cases
tested. The cadmium test manifested low sensitivity in this form of pathology.
Hence, no further mention will be made of these tests.
Patients were re-examined at intervals of 1 to 11-1/2 months. The entire
complex of the liver function tests was performed only on some of the patients.
Of those fully tested only 2 cases (patients G-ov and K-ko) were fre~from
indications of liver function pathology; both were in the ini~~al stage of
benzanthrone intoxication.
In all other cases, functional involvement of the
liver manifested itself in one form or another.
The number of pathological
1/ Upon re-examinaticn some of the patients were assigned to different groups
which caused them to be mentioned twice.
-192-
-------
shifts in liver function values was as high as 5, or 6 in some cases (Sh-va,
Ch, Sh-ko and S-ov).
Benzanthrone intoxication was accompanied by different
disturbances in the functional state of the liver.
Results of individual
functional tests showed discrepancies in some cases; N. D. Strazhesko insisted
that this indicated the need for performing the entire battery of liver func-
tion tests on all cases. Nevertheless, it can be said that benzanthrone
poisoning was commonly accompanied by a disturbance of the liver function,
as shown by the cephalin-cholesterol emulsion test (in 48 of 59 subjects)
and protein synthesis function. Disturbances in the latter were of a peculiar
character: they appeared in the form of hypoproteinemia (in 50 of 63 sub-
jects), frequently of considerable gravity (below 5.5 g%). In some liver
diseases hypoproteinemia was accompanied by lowered albumin/globulin ratio;
in benzanthrone intoxication the A/G ratio was below normal in less than 50%
of the cases (15 of 32). This fact was apparently related to another charac-
teristic of liver function pathology in benzanthrone intoxication, namely,
the tendency toward a lowered concentration of serum V-globulin. Hyper-y-
globulinemia, usually described in liver diseases, was found in only 14 of
68 determinations. Aside from this, the serum V-globulin level approached
the lower normal limit in 17 patients, and in 26 cases it fell to less than
0.70 g%. Disturbances in the carbohydrate function of the liver were less
common and appeared in the form of pathological blood sugar curves ("diabetic"
curves, "depressed" curves, initially hypoglycemic curves) in 42 of 74 tests.
Disturbances in the detoxifying liver function (hippuric acid synthesis cal-
culated as sodium benzoate) appeared in 30 of 74 tests. Of striking interest
was the absence of hyperbilirubinemia in benzanthrone poisoning, although it
often accompanied other forms of toxic-chemical liver damage (B. Ya. Agrano-
vich). In 11 of 20 determinations, the bilirubin content was below the con-
trol level (0.13 - 0.09 mg%).
The thymol turbidity test was regularly negative, which further differen-
tiated benzanthrone intoxication from other forms of liver poisoning, such
as CC14' trinitrotoluene. The tests failed to discern any correlation between
intensity of functional liver impairment and the presence or absence of clini-
cal symptoms indicative of liver pathology. Extensive functional impairment
according to certain tests, was noted in cases which showed no clinical symp-
toms of liver damage, e.g., a reduction of the hippuric acid excretion to
0.35 g in patient V-uk. There were also cases with an inverse relationship.
-193-
-------
Generally, the sensitivity of the battery of functional liver tests was con-
siderably higher in benzanthrone intoxication than were clinical observa-
tions. Therefore, a correct evaluation of the state of health of persons
working with benzanthrone should be made with liver function tests.
Functional liver damage has been encountered so often and with manifesta-
tions 60 serious that it can scarcely be regarded as secondary to the intoxica-
tion. It undoubtedly plays a definite role in the pathogenesis of intoxication
as such. The nature and extent of shifts in liver functional indexes reflect
the stage and gravity of the organism's intoxication. The stage of pronounced
intoxication is characterized by a very deep suppression in the liver detoxify-
ing function (in 5 studies the hippuric acid excretion waS less than 0.40 g),
frequent impairment of the carbohydrate function, and frequent hypoproteinemia.
In the initial stage, the cephalin-cholesterol flocculation test was strongly
(+++) positive, and this, together with the less common disturbances of the
glycemic curve, distinguished this stage from the subsequent stages. In the
stage of residual manifestations, lowered hippuric acid excretion was en-
countered more rarely than in the first 2 stages, and in only one case was
the excretion less than 0.60 g; in all other cases, the lowering of the ex-
cretion rate was slight.
It must be assumed that changes in the functional state of the liver were
among the factors responsible f~r the cyclic course of the intoxication proc-
ess. It is possible that the transition from the initial stage to the pro-
nounced stage, the chief manifestation of which ~as melanin hyperpigmentation
of the cutaneous integument, was the result of liver function worsening. As
is generally known, functional insufficiency of the liver (estrogen detoxifica-
tion) was connected with melanin hyperpigmentation observed in hepatic cir-
rhosis (Whitlock). It is possible that disappearance of pathologic pigmenta-
tion was connected with a normalization of liver detoxifying function observed
in the stage of residual manifestations. It should be noted that in spite of
this normalization, the stage of residual manifestations retained profound
disturbances, such as prpnounced hypoproteinemia, strongly positive cephalin-
cholesterol flocculation test, pathologic glycemic curves. Despite the gen-
eral improvement of the patient's subjective and objective stages, this con-
dition must be evaluated as a stage in which serious pathology persisted.
Thus, re-examination of persons with intoxication in this phase revealed pro-
gressive hypoproteinemia.
The findings show that in the treatment of patients
-194-
-------
in different stages of benzanthrone intoxication it is necessary to apply
measures directed to an improvement of liver function. On the olinical side
of benzanthrone intoxication, emphasis should be placed on symptoms indicating
functional impairment of the vegetative nervous system. In order to clarify
the possible connection between these disorders and the above-described dis-
orders of liver function, or the role of innervation disturbances, studies
were conducted in which liver functional tests were used against the back-
ground of the pharmacological action of drugs on the vegetative nervous system
TAB L E 10 (its parasympathetic region).
N : p: of
ame !
abbre-:
. t d:Control
VJ.a e :
:
E-k'IH
B-YK
B-Ka
r-KO
r-k'IH
r-OB
r-KO
.IJ:-k'IH
K-KO
K-k'IH
K-KO
K-YH
JI-KO
M-OB
M-aJi
o-KO
TI-eB
P-k'IB
P-OH
P-Ba
C-Ba
C-OB
C-k'IH
C-OB
T-KO
'I-k'IH
ill-aK
hippuric acid excretion:
: After !Difference
testsi carbocholine i in g
: administration:
0.37
0.35
1.10
0.95
1.02
0.97
0.52
0.61
0.84
0.94
0.73
0.68
0.68
1.20
0.70
0.95
0.99
0.98
0.14
1.01
0.29
0.14
1.08
0.40
0.86
1.00
0.17
0.63
0.18
0.90
1.10
1.02
1.12
0.51
loll
0.98
1.28
0.93
1.18
0.16
1.19
1.08
1.25
1.09
1.11
0.91
1.06
0.36
0.82
1.22
0.52
1.00
1.71
0.78
+0.15
+0.05
+0.50
+0.14
+0.34
+0.20
+0.50
+0.08
-0.01
+0.38
+0.30
+0.10
+0.19
+0.11
+0.05
+0.01
+0.08
+0.14
+0.12
+0.14
+0.71
+0.01
+0.26
+0.46
-0.20
+0.15
-195-
These studies, made with
the background of the action
of the vagomimetic drug carbo-
choline (a single administra-
tion of a therapeutic dose,
1 ml of an 0.01% solution
subcutaneously) showed that
under the influence of ex-
citation of the vagus nerve,
hippuric acid synthesis regu-
larly increased, and in 8
cases returned to normal.
The most noted increase in
hippuric acid synthesis ap-
peared in the initial stage
of intoxication (0.30 g, on
the average), in the manifest
stage of intoxication, 0.15
g, and in intoxication in the
stage of residual phenomena,
0.08 g.
Administration of
carbo choline gave rise to an
elevation of the total protein
content of the blood serum
(Table 2) and albumins just
as regularly (in 9 of 10
cases).
-------
TABLE
2.
N : P5> of
ame :
abbre-i
. t d:Contro1
v~a e :
:
total serum protein:
: After iDifference
tests; carbocho1ine iin peroent
£administrationi
K-YH 5.34 5.46 +0.12
K-KO 5.98 5.46 -0.52
JI-KO 5.38 5.80 +0.42
o-KO 5.84 6.44 +0.60
IT-eB 6.60 6.80 +0.20
P-JlIB 6.80 6.94 +0.14
C-JlIH 6.26 1.54 +1. 28
C-OB 6.14 6.62 -0.12
C-OB 6.42 6.78 +0.36
T-KO 5.66 6.20 +0.54
q-JlI~ 6.56 1.80 +1. 24
III-aK 5.58 5.60 +0.02
TABLE
3.
N : g of
ame :
.
abbre-:
. t d:Control
v~a e £
hippuric acid excretion:
: After : Difference
tests; atropine; in g
!administration!
A-eB 1.07 0.65 -0.42
E-JlIM 1.42 0.85 -0.51
E-YK 0.98 0.70 -0.28
f-KO 0.53 0.43 -0.10
f-KO 1.15 0.65 -0.50
E-KO 0.10 0.15 +0.05
M-KO 1.20 1.14 -0.06
M-a.R: 0.91 0.67 -0.30
C-OB 0.11 0.49 -0.28
C-JlIH 1.09 0.88 -0.21
T-KO 0.58 0.49 -0.09
Y-JlI~ 1.21 0.90 -0.31
Q-OB 1.09 0.65 -0.44
III- II a 0.94 0.11 -0.11
Shifts in blood sugar
curves under the influence of
carbocholine (23 studies) were
insignificant and irregular.
Generally, the effect of
carbocholine (and consequently
that of excitation of the
parasympathetic system) on
the liver in benzanthrone in-
toxication may be regarded as
favorable. Studies performed
in a similar experimental set-
up with a pharmacologic an-
tagonist of carbocholine,
namely, the parasympathetic
drug atropine (1 ml of 1:1000
solution subcutaneously) ~p-
ported this view.
As a rule,
hippuric acid synthesis de-
creased against the back-
ground of atropine action
(Table 3). There was also
a regular decrease in the
total blood serum protein
concentration (Table 4); in
9 cases of 14, albumin con-
cent rat ion also dropped.
The pronounced shifts
in the functional indexes of
the liver in benzanthrone
intoxication under the in-
fluence of vegetotropic drugs
indicated that the functional
liver disorders in this form of pathology were closely associated with dis-
turbances of the regulatory functions of the vegetative nervous system. This
-196-
-------
TABLE
4.
Name i g% of total serum protein:
: : After !Difference
abbre-: . .
. t d:Control tests: atropine :in percent
v~a e : : dIn. . t t . :
: :a lnlS ra ~on:
A-eB
E-HH
E-PL
B-YK
r-KO
E-KO
r-KO
K-KO
M-a.fI
C-OB
C-HH
T-KO
Y-HM
lX-oB
III-rra
6.00
5.98
6.02
7.20
6.00
7.10
6.04
5.44
6.00
5.74
6.08
5.98
6.42
5.78
5.98
5.64
5.78
5.98
5.38
5.98
5.38
5.24
5.68
5.68
5.18
5.80
5.60
5.80
5.36
5.25
-0.J6
-0.20
-0.04
-1.82
-0.02
-0.72
-0.80
+0.24
-0.32
-0.56
-0.28
-0.38
-0.62
-0.42
-0.46
indicated that promising re-
sults may be obtained from
trials of vegetotropic drugs
as therapeutic agents in
benzanthrone intoxication.
Shifts observed in liver
function tests under the in-
fluence of vegetotropic phar-
macologic agents were directly
opposite to those observed in
similar studies in epidemic
hepatitis by A. L. Myasnikov
and co-workers. This dif-
ference was apparently con-
nected with the peculiarities
of disturbances in the fune-
tional state of the vegetative
nervous system in various
pathological conditions. It is possible that, unlike parenchymatous hepatitis,
characterized by hyperfunction of the parasympathetic region of the vegetative
nervous system, the tonicity of this region was lowered in benzanthrone intoxi-
cation. S. R. Frenkel showed earlier that benzanthrone lowered the tonicity of
the sympathetico-adrenal system.
By elevating the tonicity of the parasympathetic region of the vegetative
nervous system, it was possible to improve some of the liver function indexes
in benzanthrone intoxication, but this cannot serve as a basis for denying the
direct action of the toxic principle upon the liver. Benzanthrone can be dis-
covered in the blood by the method of S. R. Frenkel, which can detect 0.2 y/ml
of the toxic agent. Benzanthrone was found in the blood of 14.3% of the cases
indicating that it was circulating in the blood in some changed form and that
its circulation in unchanged form in the blood was not an essential condition
for the development of the intoxication process.
1.
Conclusions.
Benzanthrone intoxication was accompanied by a disturbance of liver
function detectable by a combination of liver functional tests.
-197-
-------
2. Disturbances of liver function in benzanthrone poisoning were con-
nected to a degree with a functional disorder of the vegetative nervous system.
3. Liver function studies proved of considerable value in diagnosing
benzanthrone intoxication and in evaluating the state of health of workers,
especially in the stage of residual intoxication.
4. Treatment of benzanthrone intoxication should be aimed at the normal i-
zation of liver functions.
50
Benzanthrone was rarely found in the blood of persons with benzanthrone
intoxication.
Bibliography.
A r p a HOB H 'I 6. 51. I(JIHHHKa H naTOJIOrl!5I TOKCHKO-XHMH'IeCKHX nOBpe>KJl.eHHA
,.e'leHH. M., 1948. - Mil C H H K 0 BAlI. TPYJl.bI BoeHHo-MoPCKOii MeJl.HltHHCKOii aKaJl.eMHH
.12,11.,1949, CTp. 159-164.-nHCIIIYHoBa B. r., AHaToBcKali B. C., I(OPOT~
K 0 Bar. 11., H e p Y 6 e H K 0 A. B., .n: a H H JI' 0 B B. H., 3 P M a H M Ii E P e M H'
H a 3. 11. rHrHeHa H caHHTapHII, 1956, No 7, cTp. 22-26. - P e H K e JI b' C., P MeTO,It
onpeJl.eJIeHHII MaJlblX KOJIH'IecTB 6eHs3HTpoHa B KpoBH. B KH.: ¥KpaHHcKHii UeHTpaJIbHblA
HBCTHT rHmeHbI. TPY~3 H ~p&lp3a60JleBaHHii. I(Heo, 1955, CTp. 42-43. - W h i t-
10 C k . A. Melanm PigmentatIOn and Hepatic Disease. Arch. dermat a syph.'l 1951
v. 64, p. 23-34. " ., ,
Hygienic Characteristics of Tantalaum and Niobium (Rare Metals) Dusts.
Yu. L. Yegorov.
(Department of Labor Hygiene of the First Moscow Order of Lenin
Medical Institute, 1m. I. M. Sechenov).
Gigiena Truda i Professionaltnye Zabolevaniya, Vol. 1, No.6, 16-22, 1957.
Present-day technology is associated with widespread use of rare elements,
among them tantalum and niobium, highly refractory metals, are readily proc-
essed by cold methods, such as rolling, drawing, etc. In their remarkable
resistance to corrosion, they are close to the noble metals and in some re-
spects even superior to platinum. Tantalum and niobium are used in the manu-
facture of vacuum (generator, electron, etc.) tubes and as acid-proof materials.
Tantalum is also widely used in plastic surgery as screws, screens, powder,
etc. The Directives of the XX Session of the CPSS on the Five-Year-Plan em-
-198-
-------
phasize the need for a considerable expansion in the production of tantalum and
niobium.
Not much is known of the toxicology of tantalum.
lished in the U.S.A. results of investigations on the
oxide that entered the respiratory organs (Shepards).
In 1955 there were pub-
action of tantalum pent-
The author found that
intratracheal introduction gave rise to temporary bronchitis, interstitial
pneumonia; after a year residual symptoms appeared as focal emphysema and
penumonia in the area of the metallic deposits.
No fibrosis was observed.
This author undertook to investigate conditions prevailing in the manufacture
and processing of these metals and with a view to proposing measures for the
sanitization of working conditions, to survey the state of workers health in
this industry, and to determine experimentally the character and degree of
toxic action of tantalum and niobium as a basis for arriving at hygienic
standards in the manufacture of these metals.
Metallic tantalum and niobium
are prepared by the metallurgical powder process, electrolytically or by the
reduction of their respective compounds.
This author studied working conditions in plants where tantalum was ob-
tained by reduction of potassium fluorotantalate with the aid of metallic
sodium. The metallic powder thus obtained was washed, dried, ground in ball
mills, sifted through vibrating screens and pressed into bars at 2.1 ton/cm2.
The bars were then fused at temperatures just below the melting point of
tantalum (m.p. of tantalum is 2800 - 30000; bars were fused at 23000). In
this form the tantalum bars had undergone further cold treatment. Tantalum
became suspended in the air of working premises in the form of disintegration
aerosol.
The heat treatment of tantalum was done in vacuum; any vapor created
in the process was drawn off and became precipitated on the conduit inner
walls. On the other hand, tantalum dust was found in the working premises at
points where different operators were stationed. It was found that at the
breathing level of workers who cleaned the exhaust conduits tantalum dust con-
centration ranged from a few milligrams to 10 mg/m3; in the unloading of the
ball mills and the sifting of the metallic powder, dust concentration ranged
from tenths of a milligram to 120 mg/m3; in weighing the potassium fluoro-
tantalate and loading into the crucible the dust concentration ranged from
15 to 114 mg/m3, or in excess of the maximum permissible concentration for
hydrofluoric acid salts as established by N 101-54.
-199-
-------
The above indicated operations were all of short duration and were re-
peated 3 - 4 times during each shift. At intervals between operations and at
2 meters from the operator's position during the operation itself, the dust
concentration dropped to 3 - 0 mg/m3. This rapid fall in dustiness can be
explained by the high specific gravity of tantalum and by the existence of
adequate ventilation at the operatoris positions. In addition to tantalum,
welders of the tantalum bars may be exposed to the effect of mercury vapor
coming from the mercury pumps and the manometers. Women working on all other
processes were subjected to the effect of potassium fluorotantalate; the latter
is a strong irritant of the upper respiratory tract; the women used hand-made
protective respiration masks.
The number of workers in this industry was
limited; 22 workers, among them 12 welders, were examined medically.
All male
welders, 26 to 54 years of age, had work records of 3 to 24 years. Chemical
operations were performed by women 25 to 56 years of age, with work records
of 5 to 25 years.
No pathologic changes were found in the welders internal
organs.
Urine and blood analyses were also normal.
However, all welders
manifested changes in the vegetative nervous system, probably caused by the
mercury vapor; the word probably is here used advisedly, since the mercury
vapor concentration in the air of the shop was low. Mercury was found in the
urine in 10 of 12 persons examined in amounts of 0.002 to 0.02 mg/li. Chest
films of 2 welders and a shop foreman, with work records of 5, 14 and 24 years
revealed changes indicative of incipient pneumosclerosis. Neither the female
or male welders manifested any changes with respect to the internal organs
ascribable to their occupation. X-ray films of female workers revealed no
pneumosclerotic changes, despite their many years of work with potassium fluo-
rotantalate (in one case, 24 years). Dental or oral mucosa changes were not
indicative of HF effects. Only 2 women workers had chronic hypertrophic rhi-
nitis.
Results of observations under practical production conditions did not
permit drawing definite conclusions with regard to the sanitary-hygienic con-
ditions effect on the health of the workers; it became necessary to resort to
experimental study on a chronic basiso Accordingly, an experimental study was
made of the following: a) the course tantalum followed after it entered the
organism through the respiratory and digestive tracts; b) the solubility of
some tantalum and niooium compounds in media approximating fluids of the or-
ganism; c) the possibility of generalized tantalum action on the organiBm,
-200-
-------
and also the fibrogenic action of tantalum and niobium on lung tissue. The
study was conducted by mea.ns of labeled radioactive substances.
It has been generally established that the course followed by a substance
after it entered the system determined to a considerable extent the degree of
its deleterious effect on the organism.
The information contained in the
literature on the distribution, deposition and elimination of labeled tan-
talum and niobium from the organism was inadequate. It was known that Nb95
had the tendency to accumulate in the skeleton. On the lOth day after ad-
ministration of a soluble NO compound, up to 15% of it was deposited in the
skeleton. NQ95 was also found in the parenchymal organs; 65% of the initially
administered N095 was eliminated with the urine and feces within 20 days of
its administration.
Tantalum pent oxide was used in studying the fate of
gansim, because it occurred most frequently industrially
in the pent oxide form was used as the labeled indicator
tantalum in the or-
in that form. Ta182
in tracing the dust
particles of its compounds. Dust of the active and the inactive part of the
mixture employed was highly dispersed (up to 82% of the particles measuring
less than 2 m~). The dust was administered to white rats intratracheally,
suspended in physiological saline solution (0.5 ml or 50 mg). Animals were
sacrificed variously, after 4 hours to 14 days, and radioactivity determina-
tions were made in sections of the different organs using apparatus "B". It
was demonstrated that when tantalum pent oxide was introduced into the lungs,
it did not pass from there into other organs, or it did so extremely slowly,
remaining unchanged in the lungs almost indefinitely. Tantalum administered
orally had not been assimilated by the organism even at the end of 14 days.
Approximately 100% of the labeled tantalum pentoxide was eliminated with the
feces during the first 4 days, and no tantalum pentoxide was found in the
urine.
No sufficiently sensitive test for tantalum was found in the literature;
therefore, the solubility of tantalum pent oxide in the gastric fluids, blood
serum, and other liquid media with a pH close to that of the physiological
media of the organism was studied by the labeled atom method. Two hundred g
of active and inactive tantalum pent oxide was placed into flasks containing
100 ml of the solvent; the mixture was filtered and activity determined using
the "B" apparatus. Tantalum pent oxide did not dissolve in any of the media,
even after 3 months standing. Niobium pent oxide was relatively more soluble
-201-
-------
in strong bases than in concentrated acids; it dissolved only in 0.22% of
sodium bicarbonate at pH 8.1. After 24 hours 100 ml of the solution contained
0.004 mg from 200 mg of the suspended solid phase, between 10 days and 6
months the level remained at 0.02 mg per 100 ml of sodium bicarbonate. Anal-
yses were performed by the method of Professor I. P. Alimarin. Experimental
data obtained on insolubility of tantalum pentoxide and on the slight solu-
bility of niobium pent oxide in biological fluids of the organism in animal
experiments and ~ vitro, were in agreement with the results of chemical in-
vestigations of the extremely slight solubility of compounds and the metals
themselves in strong acids and bases. The extremely low solubility of the 2
metals and of their compounds in body fluids gave reason to believe that no
marked toxic effects might be produced by chronic experiments.
In a way of preliminary orientation this author used effects produced by
such related compounds as vanadium as the guide in his experimental work. As
the first step, a study was made of the penetrability of tissue barriers and
of tissue metabolism in the presence of invading tantalum compounds.
For this
18 white rats were kept under identical conditions of general maintenance and
nutrition. Six of the rats inhaled a highly dispersed tantalum pent oxide dust
in concentration of 130 mg/m3 for 2 hours daily over 6 months. In exactly the
same manner, another 6 rats inhaled potassium fluorotantalate dust in 130.2
mg/m3 concentration. The remaining 6 rats served as controls. Inhalations
were made in a V. B. Latushkina exposure chamber. Upon completion of the ex-
posures all animals received 7.5 m~ of methionine S35 and 10 ~cu of N~504.
(Probably a misprint. B.S.L.). Animals were killed 45 minutes, 1.5, 3, 6,
12 and 24 hours after administration of the labeled radioactive compounds.
Study preparations were made from blood plasma, liver, kidneys, spleen, brain,
muscles, and lungs. Activity of tissues and of extracted proteins was evalu-
ated for each isotope, according to the following indexes: 1) "relative tissue
activity"; 2) "relative activity of protein contained in 1 g of tissue", ex-
pressed as percent of activity introduced per g of animals weight, and 3)
"the relative specific activity of the protein expressed in percent", repre-
senting the ratio of the second value to the first. Unlike the first two, the
last value reflected degree of labeled compound incorporation into tissue
proteins; account was taken of the amount of labeled substance contained in
these tissues; on that basis it was possible to determine extent and estimate
the rate of methionine and phosphate metabolism in these tissues.
-202-
-------
!>.
,p
~ 8
~ G ;' '?~---~::::.::.:.:.:::.:::?
Q) :' f '
,~ :' Ii
,p 'I
cd 4 'i
~ ,('
Q)
o Ol.........
~ 8.75 1.5 J
Q)
Il-I
6
,
12
,
U
Hours
Fig. 1. Changes in the rate of radio-
phosphorus incorporation into lung
proteins following dust inhalation of:
1 - control; 2 - potassium flu oro-
tantalate; 3 - tantalum pent oxide.
:>a
~ 50
>
IH'M
o+>
o
+> cd JO
s=
Q) 0>
o >
~ 'M
Q),p
Il-I cd
r-i
0>
~
"'"
/ ' -------- 3
I J ' ;,," - :..:.. -: -=.=.. ~
,,o-"""'':'~.:'_.--O-''_.--. 2
"
,O~
f) .
0.75/,5 J
12
Hours
Fig. 2. Changes in the rate of radio-
phosphorus incorporation into muscle
tissue following dust inhalation of:
1 - control; 2 - potassium fluoro-
tantalate; 3 - tantalum pentoxide.
5
From the data thus obtained and
graphically presented in Fig. 1, it
might have been conoluded that the
rate of labeled compounds entry into
pulmonary tissues of animals exposed
to potassium fluorotantalate dust in-
halation, and to a lesser extent, of
tantalum pentoxide, was below that of
the controls. Actually, the rate of
incorporation of these substances in-
to pulmonary tissue proteins was
greater than in the controls. These
findings indicated a decrease in
permeability barriers of the "blood-
pulmonary tissue" and some increase
in the rate of methionine and phos-
phate metabolism in the lungs fol-
lowing inhalation of the dust of
tantalum compounds under study.
.
?~
Different effects were noted in
other organs, as shown in Fig. 2.
These findings are in agreement
with changes in the general condi-
tion of the animals, such as reduced
rate of gain in weight in the exposed
animals compared with the controls.
Morphological changes in the lungs and other organs were studied in ani-
mals exposed to potassium fluorotantalate and to tantalum pent oxide for 4
months, and in animals injected intratracheally with metallic tantalum, its
compounds, and niobium pentoxide, once or twice at the rate of 50 mg of dust
per dose.
Animals were killed after 3, 6 and 9 months.
Tissue and section
studies were made by Professor P. P. Dvizhkov. Animals treated with potassium
fluorotantalate manifested pulmonary tissue changes as diffuse interstitial
processes with clearly defined thickening of the interalveolar septi, multi-
plication of histiocytic elements, and the appearance of collagen fibers
(Fig. 3).
-203-
-------
Fig. 3. Four months exposure to
pgtassium fluorotantalate dust in-
halation. Lungs: thickening of
interalveolar septi; histiocytic
element proliferation; thickening of
blood vessel walls. Microphoto BOX.
- - -- -
-,-----~~
, ,
Fig. 4. Nine months of intra-
tracheal administration of tantalum
metal dust. Lungs: thickening of
interalveolar septi at foci of dust
deposition; dust-filled lymphatic
vessel. Microphoto 100X.
endothelium in the marginal sinuses.
Tissues of the thymus glands revealed a slight hyperplasia of the reticulo-
Pulmonary tissue reaction in animals ex-
posed to tantalum pentoxide increased with the time elapsed from the moment of
dust administration; it remained moderate even after 9 months; thickening of
the lnteralveolar septi, small histiocytic infiltrates, and a slight increase
in the number of connective fibers, largely in the places where dust was
deposited, made their appearance.
in the thymus glands.
The reaction of the pumonary tissue to metallic tanta-
No special reaction to the dust was noted
lum was similar to but less pronounced than the reaction produced by tantalum
pentoxide (Fig. 4). Pulmonary tissues of animals exposed to niobium pent oxide
reacted by slight intermediate fibrotic changes in the areas where dust was
deposited. No specific changes were found in the internal organs.
Conclusions.
10 Dusts of tantalum and niobium and of their respective compounds found
in the metallurgical powder industry are highly dispersed and insoluble (tan-
talum) or nearly insoluble (niobium) in liquid media of pH close to that of
biological fluids.
-204-
-------
2.
Tantalum was eliminated almost entirely from the gastro-intestinal
tract within the first few days.
not been noted.
Its resorption through the intestine had
J.
The general toxic action of tantalum and niobium compounds was
slight, probably due to the extremely low solubility of tantalum compounds.
4. The effects of dusts of niobium and tantalum compOunds on pulmonary
tissue following inhalation or intratracheal injection varied largely depend-
ing on the form of the dust.
Results of some observations pointed to the fact that a
might develop in the lungs upon inhalation of dusts of these
5. Measures related to the elimination of tantalum and
dusts should be based on the use of dust-abating equipment.
fibrotic process
compounds.
niobium compound
Existing sani-
tary-hygienic standards for fluorine and fluorides may serve as the basis for
sanitary-hygienic standards for dusts and vapors of fluorotantalate. Niobium
and tantalum and their compounds showed signs of possessing pronounced fibro-
genic properties; this should be given serious consideration in establishing
appropriate sanitary-hygienic standards for the Nb and Ta metallurgical in-
dustries.
Bibliography.
I. A.II H M II. P H H Ii. n., no Jl B a.ll b H 3 R P. n. )Kypa311 3H811HTHQecKOA XHMIIH,
I. 1. 30, 1'946.-2. B 0 rOM 011 0 B II. O. P., 11 e 6 e Jl e B a H. C., C II. B Q e H K 0 E. JI..,
I\.plO'IKOBII. r. C. XHpyprHR,3 (32), 1956, CTp. 69-72.-3. Bpe.nHloIe BeJ.UeeTB8 B "PO-
MbllIlJleHHOCTR. nOJl pe.ll. Ii. B. 11a3apeB3. 1.1. 2, n., 1954, crp. 466-467.- 4. Me e p-
COR f. A., 3 e 11 H K M aHA. H. MeTallnypnll1 peJUUlx MeT3nJlOB. M., 1955,
CTp. 184-255.-5. HH06HA H T3HT3.11. C6. nep~BOAo8 BOA peA. KOII'I1IH8. M., 1954.-
6. fipOItOneHKO T. A. Te3Helol cef(!J.HOIfHYX Jl0KJl3.11OB BceCOI03ROA KOHcllepeHIUIJJI DO
MeJlHIUllICJ[oA p8JlH01l0l"HH, CeKIUlIl !tKenepllNeHTa.llbROI p3J111OJ1orHH. M., 1956, CTp. 122.-
7. T. P f COB B. H. B e6.: BHOJIOrH'IecKDe Jl.eAcr8Be H!tJIY'IeHd H KJlHHHK3 ny'leBoA
(iOJle3HH. M., 1954, crp. 67-11.--8. n.ll T y W K H H 8 B.' 5. fHr. H eaH., 8, 1956,
t.Tp. 18-23.-9. n 11 aT 0 HOB M. C., K. p H B 0 m n 101 K 0 B H. C!J. B KH.: Tp. BeeeOI03H.
""ORt. no 3HaJIHT. XHMHR, T. II, M. - n., 1943. CTp. ~.
-205-
-------
Pathogenic Properties of Some Dusts Occurring in
Ferrous Metallurgy Production Plants.
B. A. Katsnel'son.
(From the Institute of Labor Hygiene and Occupational
Diseases, A.M.S., U.S.S.R.).
Gigiena Truda i Professional'nye Zabolevaniya, Vol. 1, No.2, 24-30, 1951.
Charging blast
frequently reaching
in this respect are
furnaces pollutes the air of some working areas with dust
concentrations of several grams per m3. Most dust-creating
sinter and coke. Iron ore sinter is a product of fused
ore. Sinter usually contains about 50% of iron in the form of ferrous and
ferric oxides: calculated on the basis of Fe203 oxides of iron constitute
15 - 80% of the entire material. Content of silicon dioxide mostly ranges
between 8 - 10%, occasionally going up as high as 15 - 16%, but the percent of
silicon dioxide for any one agglo-plant is fairly constant as a rule. Results
of analyses made by this author indicated that free silicon dioxide did not
exceed 5%.
Most investigators who studied the effect of dust consisting of oxides of
iron alone found that such dust was deposited in the lungs without producing
pneumosclerotic changes (S. V. Miller, H. M. Carleton, C. Nasslund, H. E.
Harding, and others). Other investigators, such as A. J. McLaughlin, Perry,
and others expressed the guarded opinion that iron oxides could elicit pneumo-
coniotic fibrosis even in the complete absence of silicon dioxide.
It has
been known that pneumoconiosis, or so-called sidero-silicosis, can be elicited
by dust which contained oxides of iron and a varying percent of quartz. With
regard to this, reports in the literature indicate that the mild form of
coniosis, as distinct from the typical form, may be the result of a compara-
tively low concentration of Si02' as well -as the result of the assumed pro-
tective action of iron oxides. Such opinion was expressed by N. M. Demidenko,
P. P. Dvizhkov, E. H. Kettle, C. Nasslund, and others. In the light of such
evidence no clear-cut conclusion can be drawn regarding the importance of low
silicon dioxide concentrations, especially in the presence of high concentra-
tion of iron oxides, in the development of pulmonary processes. Therefore,
this author undertook to make a direct study of the problem under considera-
tion. The study included a parallel investigation of the effect of coke dust
on the lungs. Coke, used as fuel in the metallurgical industry, is a product
-206-
-------
of coal pyrolysis and is composed approximately of 90% elemental carbon and
9 - 11% ash, half of which is silicon dioxide in the form of silicates. Ac-
cording to analyses of the Institute of Labor Hygiene and Occupational Diseases
of the Academy of Medical Sciences, U.S.S.R. performed by E. I. Vorontsova,
neither coke nor its free dust contained free silicon dioxide.
As compared
with the importance of the etiology and pathogenesis of anthracosis, coke
pneumoconiosis is of mere theoretical interest. N. A. Vigdorchik, E. King,
C. V. Harrison, S. C. Ray, M. Landwehr, E. Bruckman, and others are of the
opinion that silicon dioxide contained in coal and not the carbon or any other
combustible component was the primary etiological factor in the development
of anthracosis.
In this connection a study of the effect of coke on lungs is
regarded by this author of value, since coke contained no free Si02' On the
other hand, many investigators uphold the hypothesis of Hart and Haselette who
believe that a connection existed between the aggressiveness of coal dust of
different mines and the degree of coal-fixation.
The geochemical process of
coal fixation is characterized by a gradual increase of free carbon and a re-
duction in the volatile components. From the viewpoint of this hypothesis
coke presents itself as an interesting study subject, since it contains more
free carbon and less volatile substances than anthracite, which is the most
highly geofixed, and, judged from the frequency of anthracosis, the most ag-
gresive of all mined coals.
This author employed the most widely used bloodless method of intra-
tracheal dust suspension injection into white rats at the rate of 1.0 ml of
isotonic solution containing 50 mg of the coke dust. Studies were conducted
with 2 types of agglomerates (sinters): Bakal, containing 16.6% of Si02 of
which 5.4% was of the free type, and Magnitogorsk, which contained 8.8% of
total and 0.7% free 8i02' Experiments were also conducted with coke of Kuz-
netsk coal produced by the Chelyabinsk coke department of the metallurgical
plant. The coke contained 10.9% of ash, i.e., approximately 5% of total Si02
and no free 8i02. Animals were sacrificed by rapid decapitation 15, 30, 91,
183, 274, 365 and 548 days after injection of the dust suspension.
Results of the investigation.
Agglomerate (sinter). Fig. 1 represents typical changes produced in the
lungs three months after intratracheal injection of Bakal sinter dust. The.
section shows a considerable amount of brown pigmentation which yielded a re-
-207-
-------
Fig. 1. Diffuse dust distribution of dust in
lungs with the formation of dust-cell foci of
irregular configuration after 3 months of
Bakal agglomerate dust.
action characteristic of
iron; the pigmented material
was distributed in a diffuse
manner in the thickened al-
veolar septi and partly in
the lumens of the alveoli
and bronchi; the pigmented
material also appeared in
the form of characteristi-
cally pigmented cellular
foci consisting of dust cells
and histiocytes.
Such a
focus was of irregular,
poorly delineated shape
almost indistinguishable
from the surrounding tissue, had none of the characteristic concentric dis-
tribution of cellular elements; van Giesen stain failed to show development
of collagen fibers either within or around the focus; silver stain brought out
a moderate amount of reticular fibers and their hardening. It is thus seen
that the focus did not resemble a typical silicotic node; rather it resembled
the formations described in experimental "pure" siderosis.
The admixture of
silicon dioxide to the dust failed to change the histologic picture.
Beginning with the ninth month following the intratracheal injection of
Bakal sinter dust the dust cells began to assume a different character. They
appeared as foci of miliar and submiliar dimension, located at points of pre-
vious alveoli and interstitially. They appeared distinctly unlike the pre-
viously observed small foci by having a typically round shape sharply deline-
ated from the surrounding tissue, as shown in Fig. 2. Unlike the small foci
of the simple dust cells, these formations appeared as nodes in the sense in
which this term is used to denote a characteristic morphologic picture ob-
served in processes of pneumoconiosis. And yet, these small nodes differed
substantially from typical silicotic foci by their extremely slow rate of
development, having appeared on the ninth month, after which they remained in
that stage of development to the end of the first yearo The collagen fiber
developed generally only as narrow rim around the node; unlike in typical
-208-
-------
r ~~'~,.- .
. ~.O.' ..,fl.
... Cf '.~
~' . J 1.
... -rta .......~
-.---.y ..
.'
Fig. 2. Lung sections: miliary and submiliary
dust cell nodes 12 months after Bakal
agglomerate dust administration.
~~.''''''~'~'''~'~~~.' .'t'
I iIt:~.;' ~~~.
'it" " . ~~
.. ' .'
~. .
"
.
p
<.
Fig. 3. Formation of collagen fibers
peripherally and in the thick of dust cell
nodes 18 months after Bakal agglomerate
dust administration.
,
\:..
silicosis, no thick retes of
argerophilic fibers were 00-
served histologically even
12 months after the dust
injection.
Nevertheless,
sclerosis of the focus
(node) developed slowly and
gradually, 80 that after 18
months the development of
coarse collagen fibers could
be seen within the node as
well as around it, as can
be seen in Fig. 3.
Development of the type
of foci or nodes similar to
the ones described above was
not observed in the lungs of
-i
rats injected intratracheally
with Magnitogorsk sinter dust
even 18 months from the begin-
ning of the experiments.
How-
ever, a slight development of
connective tissue fibers was
observed at points of dust
accumulation in the later
experimental periods.
A com-
parison of the organism's re-
actions to the 2 types of in-
jected sinter dust shows that
the pneumoconiotic node developed or failed to develop depending upon the Si02
content in the sinter dust. Therefore, it can be concluded that an increase
in the content of free Si02 to 5% in the presence of 15 - 16% of total Si02
affected the character of the iron dust effect on the organism. It is possible
that in this case an important part was played by the fact that at the 15000
of the sinter formation a part of the quartz may have become converted into
-209-
-------
cristobalite and tridymite which, acoording to ,some authorities, possessed
higher biologically aggressive properties than quartz. The above results
present a positive answer to the question posed regarding the significance
of different concentrations of Si02 found in agglomerates (sinters) produced
by different plants. This fact, along with any other, must be taken into
account in attempting to evaluate the possibilities of pneumoconiosis devel-
opment at one plant or another.
The present author is of the opinion that even low concentrations of Si02
found in the Bakalsk agglomerate (sinter) are reason sufficient to regard their
effect on the organism not as of the nature of "simple siderosis", but as
siderosilicosis. On the other hand, the present writer finds himself at dis-
agreement with those who fail to see basic differences between silicosis and
pneumoconiosis elicited by dust having no or only a slight content of Si02.
It should be re-emphasized that the changes herein reported showed a degree
of benigness in their slow rate of development and in the fact that they bore
no resemblance to changes observed in typical experimental silicosis.
E. I. Makovskaya and E. D. Bakalinsk~a in their experiments in 1955 in-
jected rats intratracheally with sinter dust containing 15% of total Si02;
however, they limited their observations to 6 months. They reported finding
"isolated nodules and diffuse processes consisting of scar tissue! (exclama-
tion mark is by original author, B.S.L.) and oonnective tissue". No such
phenomena were observed in the experiments here described even in the con-
siderably later stages of the experiments.
Coke. Three months after the intratraoheal injection into white rats
of coke dust the histologic changes in the lungs presented a less clearly
expressed cell proliferation reaction, a les8 exte~sive polymorphism of cel-
lular elements than in the sinter dust experiments at the same period of time.
Characteristically in this case the dust formed agglomerated conglutinated
clumps in spots where dust accumulation was high.
These conglutinated masses
were not atifarcts, i.e., they did not exist prior to the coke dust injeotion,
but developed in~, which was shown by the fact that the phenomenon prog-
ressed with time, as can be seen in Fig. 4, and by the fact that whole fields
of conglutinated black pigmented material were seen also in the regional bi-
furcate lymphatic nodes to which the dust is naturally brought by individual
coniophagss, or into which the free dust may find its w~. Recently reports
appeared in which special importance was ascribed to the phenomenon of dust
-210-
-------
Blocking lymphatic passages by coke dust was seen in many histologio
preparations. It is true that coke dust contained no Si02' yet the fact must
not be overlooked that prolonged lymphostasis in itself may become an etio-
logical factor in the development of diffuse sclerotic changes in the lungs,
as was shown by A. I. Abrikosov and by V. D. Davydovskii. Therefore, it is
not surprising that in thickened interalveolar septi, and particularly at
points of coke dust accumula-
tion, a slow but unmistakable
development of collagen fibers
took place, which became par-
ticularly pronounced 18 months
after the dust injection, as
Figo 4. Lung tissue. Conglutination of
coke dust into dust foci 12 months
after administration.
8i02 in connection with coal dust.
- -~...---ro...-
...
".'
tv. .
J
.:~ ~
Fig. 5. Lungs. Formation of collagen
fibers around the dust foci 18 months
after injection of coke dust.
-211-
conglutination.
Landwehr and
Bruckman, for instance, express
the opinion that the property
to conglutinate caused block-
ing of the lymphatic pulmo-
nary passages, thereby im-
peding the elimination of
quartz dust.
King also as-
cribed considerable signifi-
cance to this type of block-
ing of pulmonary lymphatio
passages; in his opinion this
blocking explained the en-
hanced fibrogenic effect of
can be seen in Fig. 5.
On
the basis of such histologic
changes the following as-
sumptions are made: a) coke
dust can cause the develop-
ment of pneumoconiosis of
anthracosis type following
its prolonged inhalation in
-------
high concentrations; b) coal containing coke dust can elicit pneumoconiosis
even in the complete absence of 5i02.
Conclusions.
10
Two components of modern fuel used in blast furnaces, agglomerate
(sinter) and coke, create dust which can elicit true pneumoconiotic pulmonary
changes; judged from the results of experiments such pulmonary changes are of
a benign character as compared with silicotic pulmonary changes; they develop
after a considerably longer exposure time.
2. Coal dust (coke) and agglomerate (sinter) dust in the presence of
5i02 concentrations not exceeding 1%, or in its complete absence, can elicit
pulmonary changes in the form of poorly expressed fibrotic processes; it is
hypothecated that blocking of pulmonary lymphatic passages by the dust may
have a noteworthy auxiliary effect on the development of this type of patholo-
gy.
3. The practically negligible concentration of 5i02 in agglomerate
(sinter) dust can affect the normal lung tissue reaction imparting to it the
characteristics of pneumoconiosis and sidero-silicosis.
40 In evaluating the dangerous aspect for workers in contact with ag-
glomerate (sinter) dust the concentration of the dust, the duration of ex-
posure, etc. should be given dup. consideration; it should be emphasized,
however, that equal consideration should be given the 5i02 concentration in
the agglomerate.
:Bibliography.
B .n:~I\01.n:-~IIK_() H. M. fHr. i'i c~~. 1954, N9 II, CTp. 26--29.--J!BII);I(KOB n. n
KH.. uopb6a C d/JiIlK030M. M. 1955 T 2 cTp ~18-322 M ~ .
II 6 a K 8 JI E J1. B' ,. '. .. ~ .-" J( 0 1\ C K 2! R E 11
HIICK3H ., . p"t;..lI.e.~o. 19:j5.N2 .2,c"/'p.1'203-1206.-K OJ1bH',n'
M II J!I~:OP ~. 86 Tp~.lI. II 3'10pC!'JI>€ CBaprUHKOI3 BOJlb'rDIIOn JIYro~. C60P'tIIK ~T8Te~. Xapl::
J{HolJ. . ,1.:,0. . - ~ a r! e ton H. M. JD.JT!l. of hyg. 1927 v 26 N 2 " 227 234
.8 r ri 111 go }I. E. Brit. jotirn. uf indo med. 1945 v' 2 N J' . 3?' i; ,f" -....-
JO!Jm. of pathol. a bact 1932 v 35 ... 39'"' ~"5' . It.: ,PE' ---3. .--1( e t tIe E. H.
H - c: V. N,' ,. . . II", ..:>--.~ .-"If1g . J., Moh.\Jnty G P
arjlg()~ .~. .. a~el~chml.dt G. Bn~. jOll(':J. 01 ir.d. rhed. Ige3 . IO~
p. 9-1!.-K.!ng E., HarrIson C. V., Rav S. C. The PToceedm ~ r th' ~'th
intern"atlooaJ con~ress of industrial medicirJe: Lr:ndor.. 1949. p. 66t~75 -~ I :i: d.
w.eh l,~:. B~uckmann E. Untersuchungei1 fiber. aM Ve-rhaUen ::Ier . iclJt!
~~;h~sJ:~:~bE'LO m~~5?t1c.hend L.~ngfn unter Beriicksicht;g1J\!g ihrer ch~mISC~-krjsf::t:
Ekl(!1l11J, ~g . _lceNt~ ~ a ~n ~II I AesJAiJGft..'l-te~~ .ntl Ger t.ergmannischEn Bcarbeitung.
IO~ J" . u g n . . . Bnt. Journ. of tuoelcul 1951 v 45 1\' ~
P: 43t:~ ':3 = N ~ ~ s l.tI,n d C. JourI'!: of indo hyg. toxleo!. 1938, .;. 20. 'N.' 6:
~omhU/i. 'Boc~I;~.~~t&~ ~: s:' S~ 1~~~4~~ 8 t h Ii B KH.: Eeitrllge 1:'E S1\ik~
-212-
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The Blastomagenic Effect of Polyvinyl Chloride.
A. Kh. Kogan and V. N. Tugarinova.
(Department of Pathologic Physiology of the First Moscow Order of
Lenin I. M. Sechenov Medical Institute).
Voprosy Onkologii, Vol. 5, No.5, 540-545, 1959.
Many writers C5 - l4J presented data pointing to the cancerogenic effects
of cellophane and of many plastic materials, including polyvinyl chloride, im-
planted into rats in the form of films. H. Nothdurft C1 - 9J implanted the
following materials into rats intraperitoneally and subcutaneously: polyvinyl
chloride, cellulose hydrate, polystyrol in the form of small perforated discs,
powder, etc. He also injected silver, gold and platinum plates into mice in a
similar manner. Results of his experiments indicated that cancerogenic effects
of implanted materials were not the result of any particular chemical structure
only, but were connected with the shape and possibly with the condition of tis-
sue hypoxy produced by the disturbed blood circulation.
Contrary to the findings of Nothdurft, B. S. Oppenheimer and his collabo-
rators [13J expressed their opinion regarding the chemical effects of implanted
materials on cancerogenesis.
Results of experiments conducted by these authors
indicated that smooth platelets made from materials of different chemical nature
produced different effects. Thus, cellophane AB produced tumors (cancers) in
35.7 - 46.1%, polyvinyl chloride in 38.6%, polyethylene in 12.5% and glass in
only 2%. Following the implantation into rats of labeled polymers of polystyrene,
polyethylene and polymethylmetacrylate radioactive substances appeared in their
urine indicating that the implanted materials were in some way absorbed by the
system and may have reacted with the body tissues.
In previous tests performed by this author and his collaborator C4J, poly-
vinyl chloride injected in the shape of cylindrical bodies elicited no cancer
tissue growth. The purpose of this investigation was to determine more specifi-
cally the cancerogenic effect (properties) of polyvinyl chloride and to establish
the possible effect of the shape of implanted material on cancerogenesis. For
this purpose 6 series of experiments were performed with polyvinyl chloride of
different shapes (see Fig. 1) implanted into white rats. Tests were performed
with 139 white rats of both sexes weighing 120 - 150 g which were obtained from
the Animal Breeding Institute of the Academy of Medical Sciences of the U.S.S.R.
Rats were maintained on the usual diet.
-213-
-------
---
Fig. 1. Different shapes of polyvinyl
chloride used in the experimental
implantation.
1 - kidney superimposed capsular; 2 -
non-perforated platelet; 3 - perforated
platelet; 4 - "package-shaped" platelet;
5 - comminuted platelet.
1. Experiments with polyvinyl
chloride capsules plated over the
kidney. Tests were performed with
sheets of polyvinyl chloride such
as are used for medical and domestic
purposes. The polyvinyl chloride
material was first sterilized in 76°
alcohol for 4 days or longer.
Plac-
ing the polyvinyl chloride capsules
over the right kidney was accomplished
by a modified procedure previously
developed for the production of kidney
hypertonicity in rats [lJ which was
also used in previous studies of
cancerogenic properties of cellophane
[2 - 4J. Tests were made with 37
rats.
Sixteen of the rats survived
over periods exceeding 7 months;
cancers developed in 5 of these, in 4 the malignancies appeared between the
7th and 11.5th months, and in one 19 months after the capsule application.
The (malignant) tumors were of the size of pigeon and in some cases chicken
but never penetrated into the organs.
eggs, were nodular and fused with the surrouding organs by mesenteric tissue
The malignant tissue presented the ap-
pearance of fish meat on cross sectioning.
The cancer tissue was capsule-
shaped and was surrounded by a wall 1 - 3.5 cm thick located around the poly-
vinyl chloride film-enclosed kidney. The latter was of reduced size, indurated
to the feel and showed no differentiation between the cortical and medullary sub-
stance upon sectioning.
The cancers were connected with the kidney by a thin
protusion in 2 cases. The cancer measured 1 x 0.7 em in one rat and was located
within the wall of a thick connective tissue capsule formed around the polyvinyl
chloride-enclosed kidney. The capsule showed foci of purulent fusion or liqui-
faction. Foci of metasteses were found in the mesentery of one rat. Histologic
sections were then made of the malignant tissues which were stained with hemo-
toxyline-eosin.
Microscopic examination showed the presence of fibrosarcomas in
Polymorphism, atypical cells, and frequent irregular mitoses were
all cases.
also observed.
-214-
-------
Ip
Micro section of a fibrosarcomatous
Hemotoxylin-eosin stain 5 x 20.
Fig. 3. Sarcoma developed 1605 months after
implantation of a solid polyvinyl chloride
platelet close to the right kidney.
2.
Experiments with
polyvinyl chloride implanta-
tion around the kidneys in
the form of solid platelets.
Polyvinyl chloride im-
plantations at the right kid-
ney were made with solid plate-
lets 0.1 em thick and 1.6 x 1.6
em in area.
Seven of the 20
rats thus implanted survived
for periods of 11 months and
longer.
Of 5 animals surviving
16 - 18 months, 2 developed
malignancies in the vicinity
of the implantation on the 11th
month (Fig. 3). One of the
malignancies was of the size of
a goose egg.
As in the case of
malignancies developed in the
first series, this tumor was in-
dura ted, nodular, fused to sur-
rounding tissues as shown in
Fig. 3, enclosing in its center
the polyvinyl chloride platelet.
The second malignancy appeared.
in the form of a nodule and was
1.5 x 0.5 em in size; the nodule
protruded from the inner surface
of the connective tissue capillary
wall which became distributed
around the illiplanted polyvinyl chloride platelet. Upon sectioning the nodule
looked like fish meat and the capsule cavity was filled with a caseous-purulent
fluid.
The capsule wall was 1 - 2 mm thick.
As in the case of series 1 these
malignancies were of the fibrosarcomatous type having characteristic cellular
atypism.
-215-
-------
3.
Experiments with implantation of perforated polyvinyl chloride plate-
lets at the kidney proximity.
The polyvinyl chloride platelets were of the same measurements as in the
preceding 2 series and had 35 - 40 needle perforations. Experiments were per-
formed with 15 rats of which 8 survived 12 months or longer. A malignancy
developed on the 18th month after implantation in one of 4 rats which survived
17 - 18 months. The malignancy was of the size of a hen's egg, surrounded the
polyvinyl platelet and grew through the platelet perforations; no cavity was
observed at any point near the polyvinyl platelet. The malignancy was nodular,
indurated, fused to the kidney, the mesentery, the intestines, and the liver.
Like the others, this malignancy was a fibrosarcoma.
4.
Experiments with implantation around the kidney of "package-shaped"
polyvinyl chloride.
"Package-shaped" polyvinyl chloride specimens were prepared in the shape
of tightly-rolled polyvinyl chloride platelets, measuring 0.4 x 0.6 x 0.2 em.
Experiments were performed with 15 rats of which 13 survived 7.5 months or
longer; of these 9 survived 12 months or longer, and 6 li.ved between 17 - 18
months. None of the rats developed malignancies. In all cases the rolled
polyvinyl chloride implanted in the vicinity of the kidneys was surrounded by
thin~walled fibrose capsules.
5.
Experiments with fragmented polyvinyl chloride implanted in the kidney
proximity.
Polyvinyl chloride platelets twice the size used in the previous experi-
ments were cut with scissors into pieces of approximately 0.1 x 0.2 em and
implanted in the kidney proximity. Experiments were made with 20 rats of which
14 remained under observation for 3 period of 5 months and 4 survived for periods
of 11 - 17 months. Autopsy results in all cases showed the formation of compact
induration 2 x 1 em consisting of polyvinyl chloride fragments surrounded by
connective tissue. These fragments were fused in spots with the spinal muscles
and with the kidneys. Malignant formations had not been observed. The poly-
vinyl ~hloride fragments were examined and found to have undergone changes such
as the loss of the characteristic gloss, and they acquired a dull milky ap-
pearance.
6.
Experiments with ground cellophane implanted in the proximity of the
kidney 0
-216-
-------
Cellophane platelets were first cut into small pieces with scissors and
then ground in a mortar until the fragments measured 0.05 x 0.01 cm and 0.01 x
0.02 cm. The comminuted cellophane was sterilized as previously described in
76° of alcohol. Amounts of cellophane equivalent to that of the polyvinyl
chloride were implanted in these experiments into 32 rats of which 6 survived
over periods of 10 - 15 months.
Autopsies were performed on all rats; solid
lumps measuring I - 2 cm were found in all cases at the point of implantation
in the proximity of the right kidney. These lumps consisted of cellophane
pieces fused by connective tissue. No malignant formations were observed. The
nature of the cellophane was changed in a manner similar to the one described
for changes in the polyvinyl chloride fragments.
Discussion of results. The results obtained confirmed data presented in
the literature regarding the nature of cancerogenic effects produced by poly-
vinyl chloride [1 - 13J. The superimposition of polyvinyl chloride over one
of the kidneys resulted in the appearance of malignancies in 4 of 16 rats which
survived 1 - 11 months and in 1 rat which survived 19 months.
Free implantation of non-perforated polyvinyl chloride platelets into the
kidney proximity elicited malignant growths in 2 of 5 rats which survived 11 -
18 months. The malignancies appeared on the 11th month of survival.
One of 5 rats surviving over a period exceeding 18 months developed a
malignancy on the 18th month after implantation of perforated polyvinyl chlo-
ride platelets into kidney proximity.
It was considered essential to confirm the malignant nature of t~e tumors
formed as the result of polyvinyl chloride platelet implantation. Therefore,
a specimen of one such malignant tissue was implanted into a normal control
rat.
This was done by a subcutaneous injection into the control rat of a 25%
suspension of the tested malignant tissue.
At the moment of writing the trans-
plantation has been carried over 1 generations. Histologically all neoplastic
formations proved to be fibrosarcomas. The malignant nature of the neoplasms
was confirmed by their properties of transplantation. Metasteses were observed
in only one case into the mesentery. The neoplastic localization always oc-
curred at the point of original polyvinyl chloride implantation.
In 5 cases in which polyvinyl chloride capsules were placed over the kid-
ney the malignancies were formed outside the polyvinyl chloride capsules. No
neoplastic growth was observed within the kidney location. The new growth was
connected to the kidney by means of a thin pedicle in 2 cases. The above data
-211-
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are not in agreement of Zollinger's affirmation that primary malignant nodes
resulting from kidney superimplantation of plastic material formed in the kid-
ney capsule. According to the results of the present authors malignant nodes
formed in the connective tissue capsule developing around the point of the
plastic implantation, whether the implanted plastic material was in direct
contact with the kidney or separate from it. No malignancies developed in any
of the animals implanted with either "package-shaped" or powdered polyvinyl
chloride even after 10 - 15 months observation; on the other hand, cellophane
platelets implanted in the proximity of the kidney or subcutaneously elicited
the development of malignant formations in similar time intervals, and, in
some instances, in considerably shorter periods of time. This was previously
noted and reported on by the present authors elsewhere [2, 4J. Such results
appear to indicate that the physical shape or form of the implanted synthetio
material was a factor of direct importance or significance, as was previously
shown by Nothdurft. These authors implanted polyvinyl chloride in the shape
of sticks in previous experiments L4J and found no malignant growth development
in any of the animals, which can serve as additional indication of the fact
that the shape of implanted synthetic plastic was a factor of considerable
significance. Results of the present investigation confirm the above asser-
tion, namely that implantation of the polyvinyl material in the form of a
capsule superimposed upon the kidney produced a more intensive blastomagenic
reaction that did, so-called, "free" implantation in the kidney proximity.
This niay be due to the known effect which kidney compression and its isochemi-
zation resulting from capsular superimposition had on malignancy genesis. On
the other hand, results of the present experiments pointed equally emphatically
to the role played by total surface contact between the implanted material and
the tissue surrounding it. Nevertheless, it must be admitted that the real
significance of the shape of implanted material in relation to malignancy de-
velopment remains unanswered. Equally unexplained remains the question whether
the chemical, physico-chemical, or the purely mechanical factors play the pri-
mary role in effecting neoplastic formation, although there exists some evidence
indicating that the effect of the implant was in no way the result of intensive
mechanical irritation. This was also substantiated by the present results (and
results of others) of comminuted and powdered polyvinyl chloride and cellophane
implantation, which in the presence of a maximum surface area contact produced
-218-
-------
no malignant developments. Further confirmation of the above expressed opinion
was presented by results of other experiments reported on by these authors [4J:
experimental animals were implanted with glass wool, admittedly a high degree
mechanical irritant, and yet no malignancies were produced in any of the ani-
mals after 12 months observation.
Results of all previous and present studies
point to the most probable explanation that blastomagenesis was the result of
the complex effect of chemical, physico-chemical and mechanical factors under
the conditions of the described experiments, and only future studies may show
which of the enumerated factors was of primary significance.
Conclusions.
1. Implantation of polyvinyl chloride capsules over the kidney, or of
polyvinyl chloride perforated or non-perforated platelets in the kidney prox-
imity, but not in direct contact with it, in many instances resulted in sarcoma
development. Polyvinyl chloride capsules superimposed over the kidneys, as a
rule, elicited malignancy growth in a shorter time than implantation by the
other method mentioned above.
2.
Some of the experimental results indicated that the shape or form of
the synthetic implant was a factor of significance in the malignancy develop-
manto
Bibliography.
I. K 0 r aHA. X. Apx. naTOJ!., M 2, 63-69, 1952.
2 K 0 r aHA. X., 4 e 'I Y JI H H A. C. H A JI H e B. Apx. naTOJl. N2 5, 65-6n. 19:'.0,.
3. K 0 r aHA. X., 4 e 'I Y JI H H A. C. naTOJl., IjJl.l3H0J1. II 3!\CnepHM. TepanliH. N2 .1. 39-44,
1957.
4. KoraH A. X., 4e'lYJlHH A. C. H D.p. Apx. naTO.1., N2 I, 1958.
5. Be r in g E. A., Jr., M c La u r i lJ H. L., L 0 i rl J. B. "nd In g r a ham G 0
Cancer Research, v. 15, N2 5, 300-301, 1955. . .
6. 0 rue k r e Y H. und S c h m ii hiD. Zeitschr. N,lturforsch 7 353 1952
7. Not h d u r f t H. Archlv ~. Geschwulstforsch, Bd. IX, H. j', 1(JI-i02, 1055.
8. Not h d u r f t H. Na turwlssenschaften, 42, 4, ] 06, 1955.
9. Not h d u r f t H. Strahlentherapic, 100/2, 19'2-'210, 1956.
10. 0 P pen he i mer B. S., 0 P pen he i mer r:. T. Proceed Soc Exper Bioi
and Med., v. 67, M I, 33--34, 1948. ... . .
11. 0 P pen he i mer B. S., 0 p pen h e i mer E. T. and S to utA. P. Proceed.
Soc. Exper. BioI. and Med., v. 79, N2 3, 3G6-3G9, 195'2.
12. O.p pen h e i mer B. S., 0 P pen he i mer E. T., S t 0 utA. P. and 0 a-
n 1 she f sky J. Science, v. 118, M 3063,305 -306, 1953.
13. 0 p pen he i mer B. S., 0 P pen h e i mer E. T. Dan ish e f 5 k y J
S to u.t A. P. and E i r .i c h F. R. Cancer Research, v: 15, l','Q 5, 333 --340, 1955:
14. Z 011 1 n g e r H. Exp~nmentel.Ie Erzeugung maligner NierenkapsC'ltumoren bel
der Ratt~ durch DruC'~relz. (Plastic ,Kapseln). Schweizcrische Zschrift flir allgemeine
Pathologle und Bactenologle, 15/5,666-671, 1952; Excerpta medica, Cancer, ~ection
XVI, v. I, N2 3, 162, 1953.
-219-
-------
Effect of Metallurgical Plants Emissions on Children's Health.
D. N. Kalyuzhnyi.
(From the Ukrainian Institute of Community Hygiene).
Gigiena i Sanitariya, Vol. 24, No.2, 3-7, 1959.
Ferrous metallurgical plants constitute a potent source of atmospheric
air pollution with dust and with a variety of gaseous components. Most inten-
sive air pollution of metallurgical origin comes from blast furnaces, coke-
chemical departments, central electric heat and power stations (TsES) and from
a variety of metallurgical by-product plants. Results of numerous investiga-
tions established highly intensive atmospheric air pollution within a radius of
2 - 3 meters from metallurgical plants by dust, sulfur dioxide, hydrogen sul-
fide, carbon monoxide and other gaseous air pollutants. The purpose of this
investigation was to determine the effect of such air pollutants on the health
of inhabitants of two cities which housed within their confines two extensive
metallurgical production and processing plants (points 1 and 2); similar in-
vestigations were conducted for control purposes in two other cities which had
no industrial production or manufacturing plants (points 3 and 4). Simulta-
neously, a special study was conducted to determine the state of health of
children residing at the same 4 points. Such a study was suggested by M. S.
Gol'dberg in 1949; the ages of children covered by the investigation ranged
between 8 and 14 years. Data on the degree of atmospheric air pollution of
each of the 4 inhabited points are listed in Table 1.
TABLE
10
Inhabited i
section i:
Maximal
Dust
: Minimal
Concentration in mg/m3
: Sulfur dioxide
: Average i Maximal: Minimal: Average
1
2
3 (control)
:1- (control)
6
4.83
0.35
0.37
0.24
0.7
0.1
0.14
L81
2.06
0.21
0.25
0.8
0.91
0.05
0.27
0.1
0.19
o
0.01
0.25
0.52
0.05
0.05
Data in the table show the following: dust concentration in the air at
point 2 reached a maximum of 4.83 mg/m3 and at point 1 - 6 mg/m3, both in ex-
cess of the maximum permissible concentration. Maximum air dust concentrations
at control points 3 and 4 ranged between 0.35 - 0.37 mg/m3 and average con-
-220-
-------
centrations between 0.021 and 0.25 mg/m3. It should also be menticned at this
point that the air dust at the industrial points contained 15% of silicon di-
oxide. According to analyses of M. S. Gol'dberg the ash coming from the elec-
tric heat and power station contained 24% of free silicon dioxide, and accord-
ing to analyses made by N. Ya. Yanysheva 15.8% of free Si02. Excessive con-
centrations of sulfur compounds were also found in the air within a 2 - 3 m
radius from the ferro-metallurgical plants.
Complaints presented by residents
at points I and 2 in the proximity of the metallurgical plant had reference to
radius of
unfavorable sanitary-hygienic conditions of every-day living over a
3 m from the ferro-metallurgical plants. Clinical roentgenological
were made of children living in workers villages located within a 6
studies
m radius
belt surrounding the plants; similar studies were made of children living at
control point 3 located 20 m from the plants; the socio-economic pattern of
residents of the 2 localities were practically identical. Six-hundred and
thirty children residing in control point 3 over a period of not less than 3
years were Pirquet and Mantu negative. Three-hundred and fifty-five children
residing in villages at points I and 4 (control ?oint) were examined similarly.
Based on the results of the exauinations the children were divided into 4
groups: group I with normal roentgenograms, i.e., with no visible pathologic
changes in the chest, lungs, roots and in the pleural folii; group II with
changes limited to the roots of the lungs and with symptoms of indurated and
petrified glands; group III in addition to hylus and gland induration there were
changes in pleura, interlobal and pleural adhesions, tissue changes in the form
of exaggerated vascular and connective tissue picture, linear and alveolar fi-
brosis and foci; group IV with most clearly expressed roentgenological changes
in the roots and in the lung tissue characteristic of early stages of coniosis.
Results of the roentgenological examinations are listed in Table 2.
TABLE
2.
I : Groups
nhabited; I + II : III + IV
section iNumber: % iNumber: %
.
.
~Total
I 365
3 (control) 18
2 124
4 (control) 111
II Group III only,
this category fell
68.6
8101
13.0
95.1
532
98
110
185
161
20
46
8
31.4
18.3
21 . ~, /
4.Jli
none of the children in
into group IV.
-221-
For purposes of greater
clarity results of children's
examinations were divided into
2 groups by combining groups I
and II into one group and
groups III and IV into another
group.
A careful study of the
roentgenograms showed that
children residing in sections
-------
1 and 2, belonging to the combined I and II group constituted correspondingly
only 68.6 and 73%, while percentages in the case of children residing in the
non-industrial production sections 3 and 4 were correspondingly 8107 and 95.7%.
On th~ other hand the percent of children belonging to the combined groups
III and IV and who lived in the industrial sections 1 and 2 was correspondingly
31.4 and 27.0%, while children of control point 3 classed as the III-IV com-
bined group constituted only 18.3%; in the case of children residing in control
section 4 the percentage of children classed as group III constituted only 4.3%
of the total of examined children; no children of control section 4 had to be
classed as group IV.
Comparative analysis of the roentgenological results pointed to the fact
that school children residing in the areas having polluted atmospheric air, i.e.,
in the proximity of the ferro-metallurgical plants, showed signs of pulmonary
pathology of a more profound type and in greater numbers than did the children
residing in control sections 3 and 4, i.e., in localities where the atmospheric
air was comparatively free from pollution by the discharges coming from the
ferro-metallurgical plants. This is in conformity with M. S. Gol'dberg's find-
ings of 1949-1952 and with the more recent findings of N. Ya. Yanysheva and
K. L. Moskovskaya. M. S. Gol'dberg also established a correlation between
residence duration in localities with polluted atmospheric air and intensity
of pulmonary fibrosis.
No olear-cut correlation of this type could be deduced on the basis of
results of the present investigation. This may be due to the fact that the
present study covered children who lived within the confines of districts 1,
2, 3 and 4 over periods of not less than 3 years, and that the ferrous metal-
lurgical plants located at points 1 and 2 had been working at full capacity
only during the past 4 years, and as a consequence all examined children of
the industrial districts I and 2 had been exposed to the effects of the at-
mospheric air pollution over equal periods of time. However, with respect to
conditions within the plants this phase of the problem requires further study.
It became important to establish or to exclude the possibility that past
infectious diseases among the children might have been responsible for some
of the pathological roentgenological findings. Data presented in Table 3
show that frequency of occurrence of infectious diseases among the children
of industrial section 2 and the control section 4 was practically the same
among all the 4 groups per child, indicating that there was no correlation
-222-
-------
TABLE
3.
between the rate of pathologic pulmonary
findings and past infectious diseases.
Results of special laryngological examina-
tion given the children residing in the
industrial section 2 and the control sec-
.
Point i
Group
I II : III I IV
: Aver-
i age
I
2
..J
3.3
3.5
3.3
3.5
3.4
3.4
3
3.1
3.4
TABLE
4.
tion 4 are listed in Table 4.
Data in Table 4 show
Diseases of the upper respiratory tract in
relation to at~ospheric air pollution.
. : Point 4
Types of diseases . Point 2
. i (control)
.
.
.
Chronic catarrhal rhinitis 31 10
Chronic hypertrophic rhinitis 13 3
Chronic atrophic rhinitis 3 10
Acute rhinitis 3
Chronic rhinopharyngitis 1 1
Chronic catarrhal pharyngitis 6 1
Chronic granular pharyngitis 10
Atrophic pharyngitis 11
Hypertrophic pharyngitis 2
Catarrhal tonsillitis 33 5
Hypertrophic tonsillitis 3
Tonsillar hypertrophy 3
Total of diseases 112 55
Total of examined children 116 185
Average of disease per child 0.63 0.3
that diseases of the upper
respiratory tract among the
examined school children
residing in industrial sec-
tion 2 were twice as numer-
ous as among children resid-
ing in control section 4.
Anthropometric measure-
ments showed a general nor-
mal physical development of
all the tested school chi1-
dren, i.e., of all children
residing in the 4 investi-
gated sections or points,
although the chest measure-
ments and weight of the
children living in industrial sections 1 and 2 were somewhat below the corre-
sponding indexes of the children residing in control sections 3 and 4.
Conclusions.
1. Industrial discharges into the atmospheric air by ferro-metallurgical
plants located in close proximity to residential areas may exert an unfavorable
effect on health and on the sanitary living conditions of inhabitants over a 3
2.
meter radius belt surrounding the production or processing plant.
The approved 1 meter wide sanitary clearance protection zone for metal-
lurgica1 plants fails to secure the required sanitary conditions of residential
areas located immediately beyond the 1 kilometer sanitary protection zone. It
follows that the adopted scheme of sanitary clearance or protection zones should
-223-
-------
be revised in the direction of appropriate widening to at least 2 kilometers
insofar as ferro-metallurgical plants are concerned.
3. The amount of pollutants emitted into the atmospheric air should be
reduced by the following means: a) thorough hermetization of technological
processes accompanied by the emission of deleterious gases and dust; b) maxi-
mum recovery and utilization of industrial by- and waste-products; c) forbid
the discharge into atmospneric air of blast furnace and other gases not puri-
fied prior to discharge; d) replace presently used hard fuel by gas fuel in
all heat and power electric stations; e) electrify intra-plant means of trans-
portation; f) increase the efficiency of the technical utilization of produc-
tion complexes which emitted deleterious substances into the atmospheric air.
Bibliography.
f 0 JI b II 6 e p r M. C. B KH.: npelleJlbHO llonycrKMble KOHueHTpauKK arMoccpepKhI"t
3arpH3HeHKH. M., 1952, ~. I. CTp. 40-49.-0 H >K e. fHr. K caK., 1957, Nt 4,
crp. 9-15. - M 0 C K 0 B C K aRK. A. B KK.: HOBbie llaKHble no rHrKellC lleTeH H nOll-
pOCTKOB. M.,-JI., 1956, crp. 36-40.- 51 H hi weB a H. 51. fKr. H caH., 1957, Nt 8,
crp. 15-21.
Effect of City Air Pollution on the Population's Health.
R. A. Babayants.
Vestnik Akademii Meditsinskikh Nauk S.S.S.R., Vol. 14, No. 12, 3-12, 1959.
Hygienic literature is replete with data concerning the effect of indus-
trial air pollution on workers health. Many occupational diseases and indus-
trial intoxications caused by dust and gaseous pollutions of the air in produc-
tion premises have also been known for a long time. Industrial air pollution
has reached considerable proportions. Therefore, plants and factories of the
U.S.S.R. have been systematically installing modern sanitary-technical equip-
ment for the elimination of dust from the air.
In comparison with industrial air, city air is polluted to a lesser degree
and, therefore, its harmful effect on population's health attracted no special
attention for a long time, and what is worse, authentic protests of sanitation
-224-
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specialists and of western European workers against air pollution by indus-
trial discharges during the last century were rejected as the result of in-
vestigations of some hygienists. Using primitive methods and tests, the in-
vestigating hygienists considered the dust and gas concentrations in the city
air as neutral agents of the environment.
Reports appeared in the hygienic
literature which repudiated the opinions expressed about the harmful effects
of city air pollutions. Such tolerant and, indeed, indifferent attitude of
physicians towards city air pollution is strangely paradoxical. It is well
known that natural atmospherio air containing oxygen "in statu nascendi", ozone
admixtures and hydrogen peroxide, as well as negative ions, possessed oxidizing,
sterilizing and health restoring properties, and constituted factors of impor-
tance in guarding the population's health against many widely spread diseases.
It would be logical to consider as credible the opinion expressed regarding the
possible harm caused to health by the spread of diseases and the worsening of
sanitary living conditions in localities in which the air was polluted with
dust and harmful gaseso
The first investigation related to air pollution was conducted 50 years
ago by the German hygienist Ascher. However, the inadequate number of Ascher's
experiments and his statistical interpretations raised numerous justified ob-
jections. Ascher's attempt was followed by other authors whose attempts to
establish a relation between city population mortality and air pollution failed
for lack of scientifically verifiable results. In those days workers were ex-
ploited by the rising industrialists and morbidity and mortality rates were
largely the results of low level living and work conditions. In comparison
with such basic factors other environmental factors, including air pollution,
were of comparatively minor significance in relation to rates of morbidity
and mortality.
The first attempt to study the effect of community air pollution on the
population's health was made in the U.S.S.R. in 1933 by v. P. Tsvetkov, R. A.
Tsibul'skii and A. P. Sapozhnikov. X-rays of 19 children living near the
Kashirskaya electric power station showed shadows in the lung films. The
inadequate number of observations failed to provide a convincing basis for
conclusions; but the method of approach to the problem of harmful air pollu-
tion effects was a basic one because of its objectivity. M. S. Gol'dberg used
this method more extensively 15 years later in his study of the effect of
mineral pollutants discharged by the same electric power station, on the health
-225-
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of school children.
After a preliminary examination Gol'dberg selected 285
school children, 8 - 13 years old, who were born and permanently resided in
the vicinity of the station. X-ray examinations indicated no changes in the
lungs of 41% of the children. Among the remaining 59% changes were seen at
roots of the lungs in 24%, at the roots of lungs and in the lungs proper in
18%, and manifest changes in the roots and lung tissue in 11%. In 1939 the
Leningrad Medical Institute of Sanitation and Hygiene made a study of the ef-
fect on the health of the surrounding population and their living conditions
of air pollutants discharged by three large industrial plants.
Residents were
interrogated as the first step of the investigation.
The answers contained
complaints of indisposition, headaches, damage to house plants, early mortality
of domestic animals, damage to trees in parks and gardens; signs of the latter
were visible at a distance of 1000 m from the source of pollution.
The first extensive study of the effect of air pollution on the popula-
tion's health was conducted on a cooperative basis in 1948 - 1949. The in-
vestigation began with a study of clinical histories of patients visiting
several polyclinics serving the population of the area where air pollution was
2 - 3 times greater than in the peripheral control zone. The study was con-
ducted simultaneously in three cities nearest to Leningrad: Kolpino, an in-
dustrial city, and Zelenogorsk and Pushkin, resort cities with practically
identical air pollution. The number of cases studied offered a reli~ble volume
of data which covered 10% of the Leningrad population. In the peripheral con-
trol zone the public residences and general living conditions of the population
were lagging considerably behind those prevailing in the other air polluted
regions. Despite that, the population of the latter areas requested medical
TABLE
10
Average coefficients of population morbidity of air polluted Leningrad regions
compared with those of the control region in 1948 - 1949.
Disease
Polyclinic Number
10 18 11 16
1.5 1.6 2.2 2.1
4.0 3.5 2.3 2.5
2.6 2.3 1.8
4.5 2.5 3.3
8.1 1.4 1.1
4.2 2.1 2.2
Angina. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Bronchitis................................
P .
,J.. neumonla. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Pleuritis..............o..................
Tuberculosis..............................
Diseases of the pharynx and tonsils.......
-226-
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help in regard to diseases of the lungs, pharynx and tonsils (Table 1) up to
8 times as frequently as did the control section.
A similar ratio was established between Kolpino and Zelenogorsk.
A. L.
Iorish determined a direct connection between street eye traumas and air aero-
sol concentration. Thus, when the air in the vicinity of polyclinic No.9 was
highly polluted (612 g/m2 taken as 100%), the number of eye traumas amounted
to 248 (also taken as 100%); and in localities with air pollution of 75 and
34%, eye traumas amounted to 70 and 34% correspondingly. Results yielded by
the study of clinical histories ran roughly parallel with results of street
eye trauma studies. K. Kiyanov used the question method in studying the ef-
fect of air pollution caused by emissions from the Syas'sk Cellulose-Paper
Combine on the health of the population; his results showed that 25 - 81% of
the near-by population complained of headaches, cough, shortness of breath,
eye diseases, palpitation of the heart, fatigue, lack of appetite and sweating.
Similar complaints coming from the population of the control settlement located
at a considerable distance from the Combine, amounted to 6 - 38%, that is 205
to 5.0 times less frequently. Similar complaints came from 9% of the children
of the control area and from 24 - 59% of the children residing in the vicinity
of the industrial plants.
Next, medically selected persons were divided into
two groups:
group 1 included persons exposed to the effect of air pollution;
the other group served as a control.
Results of this study indicated that
changes in the upper respiratory tract, lungs, heart, digestive tract, eyes
and oral cavity in the first group ranged between 34 and 56%, while in the con-
trol group the highest figure was 28%.
A comparison of population morbidity in the Syas'stroi settlement, the
air of which was intensely polluted, and in Novaya Ladoga where the air was
pure, indicated that the Syasistroi population received more medical help than
did the population of Novaya Ladoga: diseases of respiratory organs occurred
twice as frequently; bronchitis and laryngotracheitis occurred 9 times as fre-
quently; tuberculosis of the respiratory organs occurred 2.5 times as frequent-
ly; and other diseases 1.5 - 2.0 times as frequently. In this connection it
should be mentioned that home and economic conditions of the Syas'stroi popula-
tion were of a higher level than of the Novaya Ladoga population.
Results obtained in the study of the effect of air pollution on the health
of children compelled special attention.
In 1953, K. A. Moskovskaya conducted
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a study of the pollution of air surrounding two schools in an industrial area
and in a peripheral section with relatively pure air (Leningrad); simultaneously,
films were made of the school children's chests. Results showed that suspended
aerosol concentration was 3.5 times as high and S02' 25 times as high in the air
of the industrial region. Correspondingly, changes in lungs of school children
residing in the industrial zone occurred 5 times as frequently as among the
children of the control area.
M. A. Pinigin attempted to coordinate 4-year morbidity data with the ef-
fect of the Lesogorskaya Viscose Plant discharges on the health of children.
He, too, found increased morbidity among children living close to the plant, as
compared with the morbidity of control groups living approximately one km away
from the factory. Thus, catarrh of upper respiratory tract occurred twice as
frequently, angina 1.5 times as frequently, and bronchitis 108 times as fre-
quently, among the children living in the vicinity of the plant as among the
control children. This study was followed up in a more thorough manner by
Van Tszun-tsyuan. In this instance 4 schools were selected: No. 146, at the
edge of the city, where the air was relatively pure; two other schools, Nos.
165 and 173, were located in the central industrial zone of Smolvninsk at 500 -
1000 m from a group of 15 enterprises which intensely polluted the city air
with sulfur dioxide and aerosols.
The air was even more intensely polluted
near the fourth school, No. 180, situated in the industrial Kalininsk zone,
surrounded by many large plants.
The degree of air pollution surrounding these schools was investigated
through a full year. Air samples were collected as follows: precipitating
aerosols 72; dust 127; sulfur dioxide 132; and classroom air 47 samples. Re-
suIts of these investigations indicated that the air surrounding the schools
in the industrial zones was much more polluted than the air surrounding the
school of the control area; with aerosol pollution being 3 times and S02 pollu-
tion 3 - 4 times as intense. Investigation of the effect of air pollution on
the children's health included a study of the over-all living conditions of
2500 pupils from the 4 schools.
Four-hundred and fifty-one children were
selected who were of similar age and who resided in the given section for not
2
less than 5 years, with living space of not less than 5 m per member of
family, same satisfactory housing conditions, no pulmonary patients in the
family, annual vacation spent in the country, monthly income per each member
-228-
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of the family not below 300 rubles.
The state of health of the selected school
children was studied from records of systematic examinations made by the school
physicians over a period of 5 years and from X-ray films and fluorographic ex-
aminations; these were supplemented by examinations at the request of the in-
vestigators by the Institute's Department of Otolaryngology and Roentgenoscopy.
Table 2 indicates that morbidity rate among the school childre~ in rela-
tion to air pollution was higher and more frequent in the schools located in
polluted air areas than in the pure air control area. Average data indicated
that grippe occurred 3 times, bronchitis 6 times, angina and catarrh of the
upper respiratory tract 7 times, broncho-adenitis and pneumonia 10 times as
frequently among the school children of the polluted air areas as among the
school children of the control area.
At the same time infectious disease
morbidity not related to air pollution, such as measles, scarlet fever, diph-
theria and rheumatism, was higher in the control zone.
TAB L E
20
Percent of pulmonary and pharyngeal
morbidity among school children in 1958
according to Van Tszun-tsyuan.
Diseases
.
i 146
School number
165 173: 180
Angina 4 33 28 15
The grippe 18 43 33 29
Catarrh of upper 2 17 10 14
respiratory tract
Bronchitis 4 10 13 10
Pneumonia 1 11 13 8
Broncho-adenitis 1 6 6 8
Pleuritis 0 2 3 2
TABLE 3.
Percent of rhinitis among school
children in 1958, according to
Van Tszun-tsyuan.
: Hyper-
School numberi Simple i tonic iAtrophiC
146 (control) 9 2 4
165 2 3 6
173 3 6 10
180 1 7 16
-229-
Results of the otolaryngo-
logical examination of school
children (Table 3) showed that
hypertrophic and atrophic changes
of the upper respiratory tract oc-
curred 3 - 4 times as frequently
among the school children residing
in the polluted air area as among
the school children of the con-
trol area; the common cold (rhinitis
occurred 3 - 4 times as frequently
among the children of the control
area due to unbalanced conditions
of residential heating. X-ray and
fluorographic data demonstrated (Fig.
1) that pulmonary changes in the
roots and tissues of the lungs oc-
curred approximately four times as
frequently among the school children
in the polluted air area as among
the children of the control area.
The effect of city air pollution on
-------
~
/00
90 7j
80
70 6/
60 JJ
,f0
40
JO
20
10
0
"'6
Control
1 . 2 J
Dim f1/!1I
Fig. 10 Pulmonary condition of
school children of the schools
under study as shown by roent-
genoscopy and fluoroscopy in
percent in 1958, according to
Van Tszun-tsyuan.
1 - Normal; 2 - changes in
roots of lungs; 3 - changes in
lung roots and tissues.
IlJ
1M
150
the population's health was investigated by
many U.S.S.R. scientists during the past 5
years. The local Baku investigation con-
ducted by M. M. Efendi-Zade and D. M. Stein-
grad in 1955 deserves first mention. Re-
sults of this investigation disclosed a clear-
cut relationship between the occurrence of
bronchitis and laryngotracheitis and air pollu-
tion with aerosols. D. N. Kalyuzbny's in-
vestigations in 1954 - 1955 in the Ukraine
yielded similar results.
Diseases of the
upper respiratory tract in percent of total
morbidity ranged between 40 - 71% among people
living 500 - 1500 m away from a cement plant;
it never exceeded 26% among persons living
beyond the 1500 m zone. Results also indicated that complaints of cough, head-
aches, nausea, worsening of sanitary living conditions, came in considerably
greater percentages from persons living within the 0.5 km zone from the plant
than from those living 2 km from the plant. In 1958, N. Ya. Yanysheva published
the results of her study of population morbidity in an industrial settlement
with highly polluted air (up to 15 mg/m3 aerosols). Her data showed that rhi-
nitis, rhinolaryngopharyngitis, tonsillitis and adenitis were found in 60% of
the examinees with 18% atrophic forms. These diseases occurred only among 17%
of the control persons with no atrophic conditions.
Next of importance in this study was the effect of the particular type of
pollution present in the air on the population's health. In this connection
particular consideration should be accorded data accumulated on localities the
air of which was polluted with sulfur compounds, CO and fluorine. The effect
on the organism of city air polluted with carbon monoxide was studied in Lenin-
grad by A. S. Lykova in 1953 and A. F. Sorokina in 1957. In the first investi-
gation 650 air samples were collected at designated points of Leningrad streets
and plazas, where the CO pollution was caused by motorized traffic. It was
shown elsewhere that the CO concentration in the street air of Leningrad,
Moscow, Khar'kov, Chelyabinsk, Saratov, L'vov, Makeevka and Rustavi reached
an average of 30, and a maximum of 200 - 360 mg/m3. These concentrations were
-230-
-------
considerably below the concentration of this gas in the air of 20 West European
and U.S.A. cities, where the CO concentration ranged between 180 - 750 mg/m3
Nevertheless, carbon monoxide concentrations in the air of Leningrad and other
U.S.S.R. cities were approaching toxic levels and were considerably higher than
the maximum permissible concentrations of CO in the air of sanitary protection
zones. Investigation of the effect of these carbon monoxide concentrations on
135 traffic directors, showed that the latter were subject to a very noticeable
carbon monoxide intoxication.
Data in Table 4 indicate that specific complaints connected with carbon
monoxide intoxication and carboxyhemoglobin in the blood of the examined was
as follows: when the CO concentration in places of heavy traffic averaged 25
3
mg/m , complaints amounted to 68%, while CORb in the blood averaged 11%; in
places with medium traffic, where CO concentration averaged 15 mg/m3, complaints
amounted correspondingly to 42%, and CORb averaged 8%; while in places with
light traffic, where CO concentration averaged 5.7 mg/m3, complaints amounted
TABLE
4.
Blood carboxyhemoglobin and complaints of traffic directors in relation to CO
air pollution in 1953, according to A. S. Lykova.
mg/m3 of CO
Air sampling points
.
.
.
.
.
.
.
.
.
iAverage
iMinimal
iMaximal
Heavy auto traffic
Average auto traffic
Light auto traffic
128.0
54.0
19.0
4.1
3.2
0.2
25.3
14.9
5.7
TABLE
5.
Average magnitude of sensory, optical and motor
chronaxy in 0 in traffic directors stationed at
highest CO-polluted main highways in relation
to work record.
Work !Sensory chronaxy £0 tical £ Motor chronaxy
iForearm :Forearm : p :Forearm :Forearm
record : : chronaxy: :
: flexor :extensor: : flexor :extensor
1-2
3-8
10
Control
0.31
0.52
0.65
O.~
1.6
1.65
2.40
1.50
0.31
0.38
0.50
0.26
0.67
0.76
0.93
0.69
0.33
0.36
0.45
0.23
-231-
.
: CORb in percent
.
.
iAVerage ~Maximal
:Percent of
: persons
i with
icomplaints
10.9
7.9
4.2
68.0
42.0
19.0
22.1
14.2
8.06
to only 19%, and the CORb
in the blood averaged 4%.
The effect of these con-
centrations on the entire
organism of the traffic
directing personnel ac-
cording to the data of
sensory, optical and
motor chronaxy, are in-
dicated in Table 5;
values of the corre-
-------
sponding indexes rose by 50 - lOO~. ~n ~~)~ ~. ~'. ~oro~na investigated the
CO concentration in the air of 160 rooms in 42 gas-equipped apartments by
analyzing 800 air samples. Carbon monoxide concentrations in the air of these
3
rooms ranged between 4 - 214 mg/m and in the air of the control non-gas-equipped
apartments the concentration did not exceed 6.5 mg/m3. Detailed investigation
and questioning of III housewives living in these apartments showed that 80
complained of carbon monoxide intoxication which was distributed as follows:
headaches 41%, dizziness and tinnitus 26%, pain in the heart region 13.5%,
nausea and vomiting 11%, and other complaints 8.5%. The CORb concentration
in the blood of tenants of gas-equipped apartments reached 21% as compared with
1.8 - 505% of the controls.
N. N. Skvortsova made a study of CO concentrations in the air of several
areas in the vicinity of 2 metallurgical plants, consisting of 35 investiga-
tions with 151 determinations of CO concentrations in the air of near-by dwell-
ings. Average CO concentrations in the air surrounding the plants within a
radius of 1200 m ranged between 53 - 113, with 190 mg/m3 as the maximum con-
centration. The CO concentration within the zone of 500 m radius ranged be-
tween 21 - 31 mg/m3 in the air of dwellings, or 3.5 - 6.0 times above the per-
missible concentration limit for this gas in the sanitary protection zone.
Children living near the plants manifested symptoms of erythrocytosis. In 28%
of the children the erythrocyte count was as high as 6,000,000. In the 50 and
100 m radius zones no carboxyhemoglobin was found in the blood of 62% of the
tested children. In the remaining 38% the CORb concentration in the blood
ranged between trace and 24%.
~.
Maximum CORb concentration in the controls was
Effect of small concentrations of sulfur dioxide on the organism was
studied experimentally by N. V. Volkova in 1955. She used the chronic exposure
method of intoxication and its effect on the conditioned reflex reaction as the
indicator.
Results listed in Fig. 2 indicated that the latent period of the
conditioned motor-nutritional reflex response was delayed considerably by ex-
posure to 20 mg/m3 of S02; it was still affected but to a lesser degree by ex-
posure to 3 - 1 mg/m3; exposure to 2.5 mg/m3 had practically no effect. Ex-
posure of animals to low concentrations of S02 markedly affected the animals'
respiration.
A. M. Yusupov investigated the effect of air polluted with discharges
from the Volkhovo aluminum plant. His results demonstrated that aerosols, S02
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aJ
-------
with dust from asphalt and tar-paved roads and streets. L. S. Serebryannikov
in his thesis and F. G. Uglov in his recently published monograph presented
interesting statistical data which lead to the assumption that increase in
lung cancer morbidity and mortality paralleled the increase in pollution of
atmospheric air of large cities. Table 7 compiled by F. G. Uglov shows th2.t
lung cancer morbidity in the cities has been increasing during the past decades
at a steadily rising rate and that it constituted approxiDately 12% of all
Cancer types.
TAELE
7.
Lung cancers in relation to all cancers.
City Year Percent Authors
Moscow............ 1909 2.2 A. V. Govorov
Moscow............ 1946 14.5 P. P. Dvizhkov
Petersburg........ 1880 - 1909 3.04 A. V. Govorov
Leningrad......... 1932 12.24 N. N. Anichkov, S. s. Veil
Rostov-on-Don..... 1901 - 1920 2.54 S. M. Derizhanov
Rostov-on-Don..... 1921 - 1929 16.9 S. M. Derizhanov
Kursk. . . . . . . . . . . . . 1927 - 1936 11.22 N. S. Kozlov
Kursk. . .y. . . . . . . . 1937 - 1938 14.65 M. V. Mokshina
Tbilisi 1 ........ 1923 1946 12.8 A. N. Sharashidze
Khabarovsk........ 1938 - 1947 12.8 A. A. Zelenko
Petrozavodsk...... 1 0 - 1 11. V. A. Samsonov
1 Formerly THlis.
Studies of L. S. Serebryannikov and of F. G. Uglov and their conclusions
bring into sharp focus the importance of improving the sanitary conditions of
the environment, and in this instance, the sanitary condition of the at~ospheric
and indoor airo
Data of the American Cancer Society indicate that during the
period of 1930 - 1950 lung cancer in the U.S.A. rose from the last plQce in
1930 (less than 4 per 100,000 persons) to the first place (20 per 100,000 per-
sons), which is a five-fold rise. In this connection it should be pointed out
that during the same 20 years stomacfi and skin cancers (per 100,000 persons)
decreased, cancer of prostate gland and liver increased only slightly, and T.B.,
the grippe and pneumonia morbidity declined by 50 - 80%. Lung cancer mortality
in cities of highly polluted air is greater than in localities having relatively
pure air; for example, it is 33 per 100,000 persons in Vienna, 18.4 per 100,000
in Austria's small towns and 10 per 100,000 in that country's resort places.
-234-
-------
Evaluating lung cancer mortality in London as 100, lung cancer mortality in
localities with higher air pollution will be: 162 for Liverpool, 233 for the
Ruhr, while in rural agricultural regions it will be 89.
The steadily increasing use of radioactive substances in practical medicine,
in scientific research and in different fields of national economy presents a
potential danger of environmental pollution, particularly of the atmospheric
air, with these substances.
Lowering the standards of specific prophylactic
protective sanitation will undoubtedly lead to pollution of the air with dan-
gerous ionizing substances.
Results of past experiments indicated that under
the influence of ionizing radiation unusual biochemical and biophysical changes
take place in many organs, systems, tissues and cells of the organism which
inhibit enzyme activity, induce degenerative phenomena, disorganize the immuno-
logical mechanism rendering the organism more susceptible to infection; parallel
with this the body elimination system will break down so that the organism will
become poisoned by the accumulation of tissue and organ decomposition products.
As the result of air polluted with radioactive substances, disturbances may
originate in the neuro-regulation processes, and the normally regulated func-
tioning of the organism may come to a stopo
The discussion of the effect of air pollution, in particular of outdoor
air pollution was limited up to this point to its direct influence on man as
an individual. It must be borne in mind, however, that air pollution has many
other aspects of equal importance to man: destruction of plant life of economic,
decorative and general aesthetic value; corrosion of articles of utility and of
art; shortening the life of farm and pet animals; pollution of soil and of
water basins. These are only a few of the air pollution phases which create
problems requiring immediate and rational solutions.
The above discussed results of air pollution investigations, the effects
of sporadically occurring "toxic fogs" or "smogs" and the steadily increasing
S02 concentration in the air leave no doubt that pollution of the atmospheric
air of cities is a factor most harmful to the health of the present day city
~opulation. Solution of the air pollution problem is the concern of the entire
citizenry young and old.
In 1949 the Council of U.S.S.R. Ministers issued a decree entitled "Con-
trol Measures Against Atmospheric Air Pollution and Improvement of Sanitary-
Hygienic Conditions in Populated Areas". This decree required all enterprises
-235-
-------
to purify the waste discharges before their emission into the air via smoke-
stacks. Since then thousands of purifying installations were set up for the
removal of ashes and dust. According to this decree all sanitary organs of
the U.S.S.R. must carryon an incessant fight against all types of air pollu-
tion to insure clean air in the populated areas.
Health agencies, factory
and plant administrators, power station operators and all others concerned
must strive towards further practical realization of the complex of preventive
sanitation as applied to the elimination of air pollution in accordance with
modern hygienic standards.
The complex for the improvement of sanitary air protection should consist
of the following: 1) increase the use of smokeless fuel; gasification of resi-
dences and public buildings using only pure natural gas and closed combustion
systems. Other types of gas, containing large quantities of carbon monoxide,
sulfur and other harmful admixtures should be used only in furnaces of factories,
plants and electric power stations; 2) changes and improvements in all techno-
logical processes of production leading to complete recovery and utilization of
waste products; 3) study of effects and determination of maximum permissible
concentrations of aerosols and harmful gases in discharged smoke, ventilation
exhaust air and other discharges emitted into the atmospheric air; 4) further
development of standards of maximum permissible concentrations of harmful air
pollutants in sanitary protection zones, when occurring singly or in combina-
tion; 5) continuous strict sanitary and technical supervision of all existing
and potential sources of air pollution and effecting all sanitary-technical
measures for the elimination and liquidation of air pollutions in populated
areas.
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1953. - M 0 C K ° B C K a SI K. A. B KH.: ~HoBbie Jl.aHHble 110 mrHeHe Jl.eTerl Ii noap1JCTKOBJ>.
M.-JI., 1956, T. :::'1, CTp. 36.-11 H H II r Ii H M. A. l-I3Y4eHlle 30Ha:ibHoro JarpSl.JHeIfHH aT-
Mocq,epHoro B03J1.yxa Bbl6pocaMII BHCK03HOH It>aGpHKu Ii ero BJlHfI~He Ha Hace.leHI.H'. ABTO-
pe<\J. aHCC. JI~ 1959.-CKBoPuoBa P.. H fur. Ii caH., 195',.r-.Q 12, ~TP..3. -Yr-
,lOB <1>. f' PaK JlerKoro. JI., 1958.-UBeTI\oB B. n.. Ubl6YJlbCKHH 5. .\., Ca.
IIO)/(HHKOB A. n. KJlHH.-MeJl.., 19,)3,]>,29-10, CTp. 458.-3(j>eHJl.H-3aJl.I' M. M..
W T I' Ii H rap JI. JJ.. M. A3ep6aHJI.)/(aH. MeJl.. )/(VpH., 1955, N'Q I, ('1'p. 67. - A 5 C her L
Dtsch. med. Wschr., 1903, Bd. 29, S. 1012. - 0 H )to; e. Dtsch. med.. WsdJr., 19U3-
Bd ;,5, S. 58!); 63.1.
-236-
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Hygienic Properties of Murmansk Ultraviolet Radiation.
N. M. Kaikov.
Gigiena i Sanitariya, Vol. 24, No.3, 76-78, 1959.
The northern regions of the U.S.S.R. are being developed rapidly economi-
cally and culturally. There is no longer a desert zone at the polar circle,
but a region with a population numbering in the thousands. Therefore, medical
and hygienic workers are greatly interested in the living conditions of those
who inhabit the polar circleo
The problem of ultraviolet radiation adequacy in the polar regions is a
very acute one, in addition to factors of outer atmosphere, which affect men
under ordinary conditions such as humidity, temperature, precipitation, wind,
etc., there are also specific factors, not encountered in other regions of the
U.S.S.R.
Such factors as the polar night and the polar day are phenomena of
high intensity; they must be dealt with effectively hygienically and medically.
This author's evaluation of the climatic conditions of the north deals
only with data related to the number of sun ray hours.
Up to recent years there
has been no quantitative and qualitative rating of the solar radiation. At
69 - 70° the continuous polar day lasts 55 - 60 days; however, the possibility
of using solar radiation during that period is not great, since the sun is low
even during mid-day; in the summer many days are foggy, cloudy and windy, and
the climatic conditions change sharply. During the polar night, which is just
as long as the day, the inhabitants of the polar areas are deprived not only
of ultraviolet radiation, but also of natural light.
The author began his observations in 1953 and continued through 1955.
The photochemical oxalic acid method, modified by A. N. Boiko and Z. N. Kulich-
kov was used in the study. In this case the .opportunity presented itself to
study the effect of ultraviolet rays with a wave length of 435 to 290 megacycles
long; that is, practically the entire ultraviolet spectrum which passes through
the thick atmosphere of the earth and meets its surface. Observations were
carried on around the clock regardless of weather and temperature conditions.
The test tube with the solution was heated when necessary.
Data gathered during the 3 years observation are listed in Table 1. In-
formation gathered on climatic conditions around Murmansk during the observa-
tion period is shown in the same table.
-231-
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TABLE
10
Combined annual observation results of ultraviolet radiation
and climatic characteristics.
1\1 ontl>
: Max i lOa 1 ,
CI ear cays
,h" i':)ht :
,of :>un : per month
,at 690 :
,1955 , i'lL in :1953:1954:1955
,degrees:
'Percent of yearly'mg/cm2/month of ae- '~ercent of year-: Eryt""mabus
:hO'Jrs of sunshine'composed oxalic acid: Iy oxalic ..cio : doses ~er month
: decompos it ion
,1953 : 1954 : 1955 : 1953 : 1954 I 1955 : 1953: 1954 : 1955 : 1953 : 1954
Janua rj 0.15 0.12 3.2 0 2
February 2.07 5.76 2.& 81.86 2.58 - 20.5 12.7 2 6 3
ilia rch 8.7 10.04 13.8 199.34 - 6.29 49.8 24.9 0 0 4
Apr II 1 1.6 20 17.8 323.16 481 .98 371.2 13.5 15.1 17.24 80.8 120.5 92.d 35.4 I I 3
May 14 12 13.7 381 .23 536.9 35d.83 1:>.9 15.9 16.5 95.2 134.2 88.5 42.8 0 I I
June 26 16.1 11.7 569.3 409.05 442.05 23.8 12.9 20.3 142.5 102.2 110.5 44.3 5 0 0
Ju Iy IG .26 21.9 15.5 506.65 855.27 4~4.37 21.2 27.18 22.7 126.7 213.7 123.7 39.5 2 5 O.
A u3 u s t 9.06 &.82 15.8 339.08 411.9 319.8 14.2 13 14.7 &4.7 103 80 29.';1 2 I
Sep~ember 7.8 4.08 4.9 196.31 123 .65 123.26 &.2 3.9 5.66 49.2 31 31 le.6 1 0 0
October 4.29 1.3 2.ea 75.82 68.31 65.11 3.2 2.15 2.9 19 17 16.3 7.2 3 I 0
November 0.07 0.9 0 2 0
December I 0 0
Analysis of the data indicated that the yearly ultraviolet radiation dis-
persion in Murmansk varied greatly. Of the total ultraviolet rays emitted during
the period of February to September, 60% was emitted during May to July, repre-
senting 60 - 65% of the total number of annual solar radiation hours. Maximum
exposure intensity occurred in 1953 in June, and in 1954 - 1955 in July, coin-
ciiental with the maximum number of sunshine hours.
Conversion of the decomposed oxalic acid into equivalents of erythematous
doses (illnount of ultraviolet rays which decompose 3.7 - 4.1 mg/cm2 of oxalic
acid were regarded as equivalent to one erythematous dose) indicated that during
the months of maximum illumination the ultraviolet radiation equalled 123 - 213
erythematous dcses per month, or 4 erythematous doses per day.
It is ccnsidered
that the least amount of ultraviolet radiation which a man must be exposed to
in order to prevent "light starvation" equals 1/8 erythermatous dose. Conse-
quently, the necessary "light starvation" prophylactic effect can be obtained
under Uurmansk conditions by exposure to less than the total ultraviolet radia-
tion.
Comparing the data here presented with the data of other authors (N. F.
Galanin, Sviderskaya, Z. N. Kulichkova, G. S. Yatsula) (Table 2), it appeared
that the annual amount of erythematous doses in Murmansk was considerable. The
data in Table 2 appear paradoxical.
Actually 1954 was more favorable with regard
to the amount of ultraviolet radiation in Murmansk than in Leningrad, and very
-238-
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TABLE
2.
close to that of Kiev.
On the
A comparison of Murmansk, Leningrad and
Kiev ultraviolet radiation.
.
basis of the above data one might
suppose that during the northerly
summer months we would encounter
Observation; Year
point ~ observed
: Total of :~rthema-
: :.u..t...:r
:decomposed :tous doses
;oxalic acid; per year
no "light starvation" cases.
Ac-
Leningrad
1953
1954
1955
1945-1948
and 1953
(average)
2391. 4
3168.3
2177.6
598.1
791.9
542.8
tually, this was not so, probably
due to the northern summer round-
Murmanak
Murmansk
Murmansk
the-clock radiation.
Ultraviolet
2529
646
radiation can be utilized in the
polar region much the same as in
the south during the waking hours.
Kiev 1952 3645 911 During the severe polar months
precipitation lasts 10 - 20 days each month, the wind velocity reaches 1 - 6
m/sec., average monthly temperature does not go above 130, cloudiness reaches
4 - 9 balls and there are only 10 - 20 clear days during the whole year; the in-
habitants wear closely woven, light colored, impermeable clothing, and practically
no ultraviolet rays can reach them according to N. F. Galanin and D. M. Tyukov.
As a result of all this, polar region population is experiencing a lack of ultra-
violet radiation throughout the year, despite apparently favorable ultraviolet
rays conditions during the summer months.
However, "light starvation" can be prevented by properly utilizing what
little ultraviolet radiation might be available. During the summer months chil-
dren should be kept out in the open in all kinds of weather. During the winter
months, that is, during the months of December to March, children should be ex-
posed for calculated periods of time to the effect of artificially created ultra-
violet rayso
Bibliography.
f 8 n a H H H H. 4!., T 10 K 0 II .n. M. OTHOWeHHe TK8HeA OAeJKJUII K ynbTpacllROJleTO-
IILlN JlyqaN. fHf. H cn., 1954, Nt 2, CTp. 3-9. - f 8 JI 8 H.H H H. CII. npo6neMa KOMneH-
caUHH npHpOllHOIl YJlbTpacllHoJleTolIoll HeAOCTaTO'IHOCTH Ha ceBepe. Cu. H fHf., 1955, HI 5,
np. 54-56. - fHrHeHH'IeCK8S1 oueHKa YJlbTj)acllHOJIeT08ol1 pallHIUHH .6onbworo fopOAa.
nOA. peA. H. CII. fa.UHHHa. 11., 1949. - H U Y JI a r. C. fJlbTpacJIHOJIt!T088S1 paAHaQHII
8 KHeBe H ee rHrBeHJI1IetK811 XapaKTepHCTlUta. fHr. H CaR., 1955, Nt 8, CTp. 46-48.
-239-
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Vitamin C in the Organism in Connection with Atmospheric Pollution by
Discharges from Synthetic Chloroprene Rubber Manufacture.
M. Ko Khachatryan.
(From the Department of Community Hygiene of the Erevan Medical Institute).
Gigiena i Sanitariya, Vol. 24, No. 12, 3-6, 1959.
Synthetic chloroprene rubber, widely used in different departments of the
domestic economy, is synthesized from acetylene prepared from calcium carbide
in plants investigated by this author.
Recently acetylene has been obtained
from natural gas.
Acetylene was converted to monovinylacetylene by dimerization
and monovinylacetylene was converted to chloroprene by hydrochloridation and
isomerization.
The latter was then polymerized and converted into a clear
plastic mass of rubber.
Many haTInful substances are formed at different stages
of this manufacturing process which are discharged into the atmospheric air by
the ventilation systems and also by the so-called unorganized routes; among such
substances are monovinylacetylene, divinylacetylene, tetrameracetylene, chloro-
prene (2-chlorobutadiene-l,3), dichlorides (dichlorobutene), dimers, and chloro-
prene polymers, acetylene, and so forth. They find their way into the air as
a result of imperfect hermetization of eQuipment employed in loading and un-
loading of the raw materials and in the production and processing of the rubber
latex, etc. The atmospheric air is also polluted by discharges from out-plant
departments, such as the steam boiler room, the manufacture of calcium carbide,
chlorine, hydrogen chloride, etc. Such discharges are rich in chlorine, hydrogen
chloride, carbide, coal dust, lime dust, soot, carbon lilonoxide, and S02. The
dust contains compounds of calcium, iron, sulfur, phosphorus, aluminum, arsenic,
silicon, etc.
Average single chloroprene concentration in the air was 8.9 mg/m3 250 m
from the plant; 3.3 mg/m3 at 500 m, 6.4 ITlg/m3 at 1,000 m, and 4.8 mg/m3 at
2,000 m from the plant; average daily concentrations were correspondingly 1.81,
1.94, 1.04, and 0.62 mg/m3 (A. V. Mnatsakanyan, 1955). Prolonged experimental
exposure to chloroprene concentrations of 0.3 - 8 mg/li produced a decrease in
vitamin C content of the organs, tissues and blood of white rats, guinea pigs,
rabbits and dogs.
Workers engaged in the manufacture of chloroprene rubber
for a long time also Inanifested a lowered vitamin C content in the organism and
particularly in the blood (G. I. Mirzabekyan, V. G. Mkhitaryan, and others).
-240-
-------
Functional liver disorders caused by chloroprene intoxication resulted in dis-
turbed ascorbic acid metabolism, as was shown by V. M. Avakyan, Ye. I. Gasparyan,
et al., V. Vel 'kovich, N. O. Avetisyan, A. M. Troitskaya-Andreyeva, M. K.
Khachatryan, and T. A. Asmangulyan, V. G. Ettingen, and others. Chloroprene
oxidized vitamin C directly forming unstable peroxides which oxidized many vitul
compounds (V. G. Mkhitaryan). Therefore, an investigation was made of t~e popu-
lation residing in the vicinity of a plant manufacturing chloroprene rubber; the
purpose of the investigation was to determine the degree of possible vitamin C
deficiency among t~e human and animal populations, and use it as an index of the
unfavorable effects of the plantis discharges on the health of residents and ani-
mals.
Domestic cats were taken from dwellings located within 2 kID from the plant,
brought to the laboratory and sacrificed, immediately dissected, and the organs,
especially the liver, spleen, kidneys and heart quickly removed and examined.
Specimens were washed free of blood and tested for ascorbic acid content by
v. S. Asatian's method.
A similar study was made with animals of a control
group obtained from a region outside the zone of industrial discharge effects.
Ascorbic acid was extracted from the thoroughly ground tissues, using a mixture
of equal volumes of 8% metaphosphoric and 16% trichloracetic acid, followed by
3 times repeated extraction with 5% acetic acid. The extract solution was then
titrated with a solution of dichlorophenolindophenol.
Table 1.
Results are listed in
TABLE
1.
Mg% of vitamin C in organs of cats.
Organs
Index
Region
Spleen
Liver
~ Kidneys
Heart
Averages of 7 cats Control group 50.7 30.2 18.8 8.3
Fluctuation limits Control group 36.4-60 19.8-34.9 14-27 4.4-11
Averages of 9 cats Effect of plant 39.1 22.3 15 7.3
discharges
Fluctuation limit s Ditt 0 30.6-56.3 15.4-28 11-18.8 6.2-9.1
Average deficiency
in percent in rela- Ditto 22.9 26.2 20 12
tion to control
-241-
-------
A comparison of averages showed that the ascorbic acid content of all organs
under study was considerably lower in animals exposed 1 - 6 years to the air
polluted by the chloroprene synthetic rubber discharges.
The possibility that
vitamin C deficiency might ~lso prevail among those residing in the vicinity of
the plant was investigated.
For this purpose children of a kindergarten located
at 500 m from the plant who lived within a 2 kID radius around the plant were ex-
amined medically. The control group consisted of children of another kinder-
garten, located outside the effects of the industrial discharges. Diets in the
2 kindergartens were practically identica1 as to caloric values and vitamin C
content (25 - 45 mg).
Vitamin C deficiency can be detected in the organism in the following ways:
1) by determining ascorbic acid concentration in the blood; and 2) by the rate
of ascorbic acid excretion via the urine after the organism has been saturated
with vitamin C. The latter procedure was employed in this investigation, using
the method developed by I. I. Matusis ~nd checked by V. V. Yefremov, G. G.
Nikogosyan, S. O. Badalyan, and others. In accordance with the procedure, con-
trol curves of urinary vitamin C excretion were plotted over periods of 3 - 4
days; the children were then administered 300 mg of ascorbic acid orally and
its urinary secretion rate plotted for periods of 4 and 7 hours. Children hav-
ing no vitamin C deficiency eliminated 14 - 15 mg% of the vitamin with the 2
urinary portions.
If ascorbic acid concentration was below this level, the
child was administered the same vitamin saturation dose each day, with subse-
quent analysis of the urine, until the 14 - 15 mg% excretion level was reached.
Absence of the 14 - 15 mg% urinary excretion level during the initial testing
period was regarded as symptomatic of vitamin C deficiency in the organism.
Under observation were 151 children, 48 belonging to the control group. Ascor-
bic acid content of the urine was determined on 3 successive days before ad-
ministering the saturation dose and for 6 days following. Determination was
made by titration with dichlorophenolindophenol. Results are presented in
Table 2.
Data in Table 2, and the curves, show that children of both groups mani-
fested a more or less pronounced vitamin C deficiency in the spring.
Vitamin C
deficiency was considerably more pronounced in children who lived in close
proximity of the synthetic rubber plant. Percentage of children manifesting
a rise in the urinary ascorbic acid secretion of 14 - 15 mg% or more after 3
-242-
-------
TABLE
2.
Percent of children with increased rate of urinary ascorbic acid elimination
of 14 - 15 mg% or higher, following supplemental administration of 300 mg of
vitamin C during the spring season.
Children
residing
Within a 2 km
radius around
the synthetic
rubber plant
Average
Control group
~ lon~
"u 8
c: c:
~ 'ji c: 7
~ ~.~ 6
.- .- +"
~ > ~ S
...]~~
o 1/1 II>
III " J
+' II> S
; ~ " z
~ .~ 1
II>
0..
,
:Chil- :Number: First day: Third day £ Fifth day: Sixth day
:dren's: of : After: After: After: After
iage inichil- i 4 : 7 i 4 : 1 i 4 : 7 i 4 : 1
iyears i dren ihoursihoursihoursihoursihoursihours;hoursEhours
4 31 9.1 9.1 25.8 25.8 64.5 11 96.1 96.1
5 33 9 6 24.2 27.3 48.5 54.5 90.9 94
6 25 8 4 16 16 44 60 80 84
1 14 0 0 14.4 14.4 42.8 48.8 64.4 71.4
6.1 4.9 20.1 20.9 49.9 58.8 83 86.5
4-1 48 16.6 12.5 80.2 83.3 85.4 81.5 89.6 91.1
days vitamin C administration was only 20.1 -
(j
--
II
/l /.
. I.
/J/
/ (/
/
/.
/.-
~~
Z 3
4.
,
.5-
Days of supplemental intake of
300 mij of lIitaroin C per day.
Curlles of da i Iy increase in ur i nary
II i tam in C e t i m i nat ion.
Aft - Chi Idren of control group; A - 4
hours after administration; a - 7 hours
after administration; Bb - chi Idren re-
siding in the plant region; B - 4 hours
after administration; b - 7 hours after
administration.
.
Ii
2009 among those who lived in the vicinity of
the plant and 80.2 - 83.3 among children of
the control group. On the fourth day of vita-
min C saturation, the percentages of children
with urinary vitamin C elimination of 14 - 15
mg% increased to 37.1 - 37.5 and 83.3 - 85.4
respectively; on the fifth day to 49.9 - 58.8
and 85.4 - 87.5; and on the sixth day to 83 -
86.5 and 89.6 - 91.7%. Results indicate that
children who lived within a radius of 2 kID
from the plant and attended the kindergarten
located at 500 m from the source of pollution
manifested a definite vitamin C deficiency,
which was corrected gradually by daily intake
of 300 mg of ascorbic acid. Vitamin C deficiency was more pronounced in children
6 - 7 years old than in children 4 - 5 years old. Aside from other causes this
can be attributed to the fact that the older children had been exposed to the
action of the polluted air for a longer time.
In the autumn and summer the same
children manifested no symptoms of vitamin C deficiency; this was a normal find-
ing for the Erevan region and was the result of vegetable and fruit availability
and also of the fact that the children were sent to camp for 2 months.
-243-
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As an immediate measure for the correction of the ascorbic acid deficienoy
among children residing in the vicinity of a chloroprene rubber plant, it is
recommended that during the winter-spring months the children's ration be sup-
plemented by 100 mg of vitamin C daily. This is 2 to 2.5 times the amount pro-
posed by G. G. Nikogosyan and S. O. Badalyan as the optimum ascorbic acid in-
take (40 - 45 mg per day) for children of pre-school age under Erevan cond1-
tions.
Volume discharge by the synthetic chloroprene rubber plant into the at-
mospheric air should be reduced and purifying devices should be installed for
the removal of unsaturated chlorinated hydrocarbons from the exhaust gases
emitted by the ventilation system.
The 500 m wide sanitary-protection zone provided for in Statue N 101-54
for the synthetic rubber industry must be regarded as insufficient and should
be increased to 900 - 1000 m.
Bibliography.
A B 3 K 51 H B. M., r 3 <: n J p 5111 E. 11. H .llf1. B KH.: ll-laTepHa;lbl 16-ii Bble3.ll'HOH lIa-
Y'IHOH ceCCHH EPOO3H(,K. Mell. HII-Ta. EpeIJa'fl, 1 !:JS7, CTp. 85. - A B l' T II C 51 H H. O. Ta'.\
JIo.e, crp. 105. - A C 3 T II a H H B. C. ME:TO.llbl GHOxHMH1leClwx HCCJleD,OB3HHii. M., 1956.-
B e JI b K 0 B H 4 B. r. TpY.llbl 106HJleii11 oii !laY'IHoii ceCCHH j111-Ta fllrJ1ell b! TpY.lla 11 npo-
~t'CCHOH3JlbHb!X 33G0J1eB3HHH. JI., 1940, CTf1. R7.-MaTycHC H. H. K.1HH. MeD,., ]938,
T. 16, N~ I, crp. 50..- M II P 3 aGe K 51 H r. H. B K'H.: MaTepHa.%! I b-il IJble3.llHOH HaY4-
HOH ceCCHU EpeBallcK. Mch. HH-Ta. EpeBJII, 1 %7, CTp. '27. - H II K 0 roc 51 H r. r., 6 a-
II a JI 51 H C. O. TpY.llbl EpCIJaHcK. Me.ll. HII-T;]. EpenaH, 1956, B. 8, crp. 83. - T p 0 H u-
K a R-A H.ll pee BaA. M. B KH.: 3KcnepHMCIITaJlbHble IIcc.~eD,OBaHH51 110 npOMbIUIJleHHb!\f
RllaM. JI., 1936, 13. 25, CTp. 1'26.- 0 e it tin g e n W., Dc i C h man n-G r ii b I e r W.,
J, Indus!. Hyg., 1936, v. 18, p. 271.
Effect of Non-Occupational Factors on the Course of Carbon Bisulfide Poisoning.
B. E. Saf'yan.
Gigiena i Sanitariya, Vol. 25, No.1, 69-72, 1960.
Carbon bisulfide is the most important harmful industrial substance dis-
charged into the air by synthetic artificial fiber plants; its concentration in
1956 - 1958 was 2 - 3 times in excess of the permissible maximum. In additiob
to carbon bisulfide, some plant departments also emit low concentrations of
-244-
-------
hydrogen sulfide. Such air pollution becomes aggravated by high humidity, un-
favorable temperature conditions, and evaporation of acids and bases. Examina-
tion of persons having chronic carbon bisulfide poisoning convinced the present
author that the course of intoxication and its outcome depended not only on the
presence of so-called unfavorable industri~l or occupational factors, but on
other factors as well. Practically no references were found in the literature
on the significance of non-occupational factors in the development of chronic
intoxication by industrial poisons. There was only general mention of such
factors, and yet such knowledge is of unquestionable importance not only to
investigators, but also to practicing physicians for a better understanding of
individual sensitivity and of reasons why intoxications caused by industrial
conditions followed different courses of development. In a dissertation by
I. D. Makulova, entitled "Dynamic Observations on the Course and Long-Range
Sequelae of Several Kinds of Industrial Intoxication", mention was made of the
fact that intoxication was aggravated by contact with other toxic substances
and by the fact that the patient had dystrophy or physical and mental traumas
in the past. Intoxication follows a graver course in women and especially in
young women. Delpech expressed the opinion that thin, nervous persons, women
and youngsters manifested greatest predisposition to carbon bisulfide poisoning.
Zangger showed that alcohol created susceptibility to carbon bisulfide poisoning.
Seventy persons with chronic carbon bisulfide intoxication, or suspected of
having same, came under clinical observation in the synthetic fiber plant during
1956 - 1958. Most of them were women (66) 26 to 50 years of age, 31 of whom
were 31 years old; 19 had work records of 5 years, the others of more than 5
years. On the basis of the clinical picture and the gravity of the chronic
carbon bisulfide intoxication the workers under observation were divided into
2 groups: group 1 included those having pronounced and lasting forms of chronic
carbon bisulfide intoxication; to group 2 belonged those having initial forms
of chronic carbon bisulfide intoxication and those suspected of having carbon
bisulfide poisoning. Each group consisted of 35 individuals of approximately
same numbers of men and women of equivalent ages and work records. Vost cases
were examined and diagnosed by specialists of the Leningrad Institute of Labor
Hygiene and Occupational Diseases. Diagnoses were made on a differential basis
as follows: vegeto-asthenic syndrome, neurasthenic syndrome with vegetative
dysfunction, and toxic encephalopathy.
As a rule, these forms were accompanied
-245-
-------
by mild manifestations of toxic polyneuritis of the upper limbs.
tial distribution is shown in the following table.
The differen-
Group
I
.
.
i
II
Type of intoxication
Vegeto-asthenic syndrome............................
Neurasthenic syndrome with vegetative dysfunction...
Toxic encephalopathy................................
Toxic polyneuritis (beginning form).................
Residual intoxication phenomena.....................
Concomitant diseases
Female diseases.....................................
Diseases of the cardiovascular system...............
Chronic gastritis...................................
Other diseases......................................
11
10
10
15
13
3
21
8
25
9
6
10
4
6
2
Data in the table show that the first group included the more pronounced
forms of intoxication (toxic encephalopathy, neurasthenic syndrome with vege-
tative dysfunction) and also cases of the graver and persistent vegeto-asthenic
syndrome of toxic origin. An examination of residences and of daily living con-
ditions of workers of both groups showed the following: workers lived in 2
sections of a workers' settlement 1.5 - 2.0 km apart.
One area, nearest the
plant had finer residences equipped with running water, sewers, hot-water heat.
However, it was located within a radius of harmful effect of the plant wastes,
while the other section had poorer residences, most of which had water cisterns,
outdoor privies, and stove heating, but the section was located farther from
the plant and was free from the effects of the industrial wastes. Workers of
both groups were approximately equally distributed through both sections. The
economic status and state of nutrition of the working families under study
were satisfactory; all plant workers received the same food rations consisting
of bread, meat, butter, milk, vegetables, fruit, sugar and so forth. Most
workers had hot meals 2 - 3 times a day; they ate at different and irregular
times because of shift work.
A special study was made of workers with unfavorable habits and home and
family conditions, such as systematic use of alcohol by the members of the fami-
ly, frequent conflicts, difficult living conditions, which led to psychic traumas
-246-
-------
of the subjects under study, serious infectious diseases, and with mental and
psychic traumas recorded in the medical history. Such persons represented 72.7%
of the first group and 20.3% of the second. A comparative study of pertinent
factors recorded in the medical histories with the frequency and severity of
carbon bisulfide poisoning indicated unmistakably that unfavorable home and
family conditions constituted a potent primary non-occupational factor which
elicited in the workers enhanced susceptibility to carbon bisulfide poisoning
as the result of mental and psychic traumatism. This was corroborated by women
workers who stated that they were more seriously affected by their husbands'
alcoholism, by quarrels between husband and wife, and by conflicts with chil-
dren, or by serious illness of a member of the family. Experiences of such
type generally produce lasting effects with the result that when poisoning sets
in each of the unfavorable factors aggravates the condition of the others, so
that susceptibility and irritability become enhanced.
Severe psychic traumas in the medical history, especially in combination
with infections, were also reflected in the course of the chronic carbon bisul-
fide intoxications often giving rise to peculiar symptoms of progressing in-
toxication.
Thus, a pronounced neurotic state, such as reactive neurosis,
developed in a female worker after a severe psychic trauma caused by the fact
that her only daughter nearly drowned; over a period of 3 - 4 years against
this background she developed chronic carbon bisulfide intoxication in the form
of a manifest neurotic syndrome with hysteroid reactions according to the In-
stitute specialists, who kept the woman under medical surveillance. T~ere were
also secondary effects, such as weakening of the organism, lowering of its immuno-
logical and mental stability resulting from prolonged contact with carbon bi-
sulfide, all of which made the workers more susceptible to psychic trauma and
infection. During the latent period of progressing carbon bisulfide intoxica-
tion psychic traumas or infection may also elicit decompensation effects, a
"patent" intoxication or relapse. .After an influenza attack one worker developed
a pronounced and lasting asthenia with vegetative disturbances. The patient, a
woman, was referred to the Institute, where it was found that she had symptoms
of chronic carbon bisulfide intoxication aggravated by previous influenza in-
fection.
Observation showed that indications of infectious disease in the medical
history, independent of psychic traumas, did not necessarily imply an enhanced
sensitivity to carbon bisulfide poisoning nor an increase in the intoxication
-247-
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gravity.
As an illustration, one of the female workers manifested a chronic
benign intoxication, even though she had malaria in 1939 and typhus and typhoid
fever in 1945 - 1947.
Two patients were seen with pronounced and persisting manifestations of
chronic carbon bisulfide poisoning who had previously had alimentary dystrop~
at the time of the blockade. Three patients were observed who had overindulged
in alcohol periodically over many years. In these patients chronic carbon bi-
sulfide intoxication progressed in a serious form with toxic encephalopathy in
2 instances; they were transferred to different work but the symptoms of poison- , ,
ing persisted for many years. In four of six patients under observations, who
had symptoms of cerebral traumas, carbon ~isulfide intoxication was severe and
protracted. As a rule, the unfavorable vital factors herein described were
interconnected, and in their plurality a non-occupational factor played a pri-
mar.y or secondar.y role.
Conclusions.
1.
Several non-occupational factors such as psychic trauma, unfavorable
living conditions, infeotious diseases, etc. can elicit the appearance of car-
bon bisulfide poisoning or they can aggravate the course of chronic carbon bi-
sulfide intoxication.
2. Most frequent among non-occupational factors are unfavorable family or
home conditions, and these have manifested the most damaging effects on the
workers' health.
3. Non-occupational factors must be considered by physicians called upon
to recommend therapeutic procedures, to establish prognosis in persons with
chronic carbon bisulfide poisoning, and to prescribe temporar.y vacation or
change to another type of occupation.
Bibliography.
Lan den h elm e r, ({HT. no E. Harmsen. Vierteljahrsschr. f. ger. Med., 1905.
Bd. 30, S. 149; S. 422. - Que rei i i G. rHrHeHa, (5e30nacHocTb H n8TonorHII TPYA8.,
1931, Nt 1, CTp. 90.
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Ionic State of Air in Living Quarters and Its Hygienic Significance.
A. A. Kinkh.
(Department of Hygiene, Moscow Medical Stomatological Institute).
Gigiena i Sanitariya, Vol. 25, No.1, 78-83, 1960.
The problem of air ionization in its application in medicine is attracting
increasing attention, but the hygienic significance of ionized air has not been
studied sufficiently. At present the interest in air ionization as a hygienic
factor has grown noticeably with attention focused basically on the physiological
significance of the ionic state of indoor air. The so-called electro-hygienic
air problem appeared at the end of the last century. I. P. Skvortsov pointed
out that a certain degree of atmospheric saturation with electricity was neces-
sary for the organism's normal existence. In his opinion the basic cause of
ill effect from bad indoor air was caused by the diminution of electrical prop-
erties in the air, and he believed that such a state of air was more harmful
than the accumulation of carbonic acid and of other chemical ingredients. I. P.
Skvortsov's views were not accepted at that time for lack of supporting experi-
mental evidence. However, his views attracted the attention of SOkolov, Domo,
Iaglou, A. A. Minkh, E. E. Lesgaft, S. P. Speranskii and others, who made special
studies, the results of which proved. that a lowered air electrical conductivity
and a reduction in the number of light ions could be detected in living quarters.
~ring these studies research was also conducted on the effect of individual
factors on air ionization in living quarters; the results were compared with the
sanitary condition of the indoor air by usually employed methods. Thus, attempts
were made to arrive at an evaluation of the physiological significance of the
changes produced in air ionization of living quarters and of public buildings.
Results obtained and their nature are described below.
The state of indoor air ionization changed considerably under the influence
of many factors. To a degree the changes were determined by daily and seasonal
fluctuations in atmospheric air ionization; however, under specific conditions,
and principally when people were congregated under conditio~s of bad ventila-
tion, the atmospheric effec~ became insignificant as compared with the inde-
pendent movement of a number of light and heavy ions. During the warm season
the number of light ions in outdoor air was higher than indoors; the reverse
was true in cold weather; this was reflected in the difference in ventilation
-249-
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effect on the indoor concentration of light ions at different times of the yearo
The effect of ventilation on the concentration of heavy ions has not been thor-
oughly followed up; however, it can be assumed that when outdoor air has not
been polluted, ventilation lowered the indoor concentration of heavy ions.
Basic changes in the ionization state of air in a room crowded with people were
affected by life processes which lowered the number of light ions and increased
the number of heavy ions. In atmospheric air concentration of light ions was
10CO/cm3 or more, while in indoor air it frequently dropped to 200 - 100/em3.
This drastic drop in ionization occurred in crowded rooms during the first hour;
thereafter it decreased at a considerably reduced rate until a constant minimum
had been reached (100 - 50 light ions); such irreducible minimum was maintained
by the compensating effect of radioactive emanations coming from the building
materials. Concentration of heavy ions in indoor air increased to some tens
of thousands per cm3, while their concentration in pure air had been estimated
in thousands.
Variations in ionic polarity indoors showed no regularity. As a rule,
approximately the same low concentration of positive ions had been found in in-
door air as in atmospheric air and only in rare cases did the coefficient of
unipolarity in indoor air exceed notably that of atmospheric air. Loss in the
numbp,r of indoor light ions was the result of ion consumption in the process
of breathing, contact with the body surface, adsorption to wearing apparel and
by settling out with dust particles suspended in the air. The number of large
ions increased as the light ions fell out from the air, with settling dust
particles or other condensation nuclei, a process which was conducive to the
formation of heavy ions; heavy ions also came with exhaled air.
The index which
expressed numerical changes of heavy and light ions in indoor air Can be ex-
pressed as N/n. In pure atmospheric air the ratio of heavy to light ions is
only 50:1; in indoor air this ratio is considerably higher. This relationship
between concentrations of heavy and light ions in the air can, therefore, be
used as a criterion in judging the sanitary-hygienic purity of air. The degree
of heavy ion predominance over the light ions offers itself as a sensitive,
reliable and constant "electrical" index of good air.
Results of hygienic tests established that a definite connection existed
between ionization of indoor air and its hygienic state; it strengthened the
assumption that changes in the ionic state of indoor air affected man's organ-
ism. Special attention was paid to fluctuations in light ion concentrations,
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since it was thought that the electric interchange between the organism and
the atmosphere was effected ~ the light atmospheric ions. Dorno (1927) called
attention to this interchange. Recently, Winsor and Beckett (1958) proved ex-
perimentally that the human body was the absorber of atmospheric ions. Hutchin-
son, Spolverini, Beckett and others linked the reduction in number of light ions
with the loss by air of its refreshing quality, its lowered physiological and
chemical activity, which, in their opinion, was the cause of unfavorable ef-
fects of bad indoor air. The question of changes in the number of heavy ions
had been treated differently: Wait was of the opinion that increase in the
number of heavy ions was the cause of feeling of "heaviness" sensed in a crowded
room, while Birman and Loeb attached to it no physiological significance.
The assumptions that fluctuations in the degree of indoor air ionization
was of sanitary-hygienic significance has been refuted by such investigators
as D. I. Kagan and V. N. Kovalenko, Loeb, Kunow, Bodien, Liese, and others.
D. I. Kagan pointed out that changes in the number of light ions not exceeding
100 - 200/cm3 exerted no special physiological action, and that changes in
degree and type of atmospheric air fluctuated within considerably wider limits,
to which the human organism has fully adapted ~tself biologically. This opinion
is supported by the fact that highly ionized air employed in medical practice
did not essentially affect the organism of healthy people (Harrington, L. L.
Vasil'av and others). At the Vienna Conferenca of the Association on Resort-
ology and Climatology in 1939 it was agreed that natural air ionization should
be regarded only as a factor of purely theoretical significance.
Thus, the question of the hygienic significance of indoor air ionization
becomes a debatable subject which required further physiological studies to ob-
tain information as to whether changes taking place in the absolute numbers and
in the ratios between different ions in indoor air had any effect on the organ-
ism of man and animals.
At the present time it is possible to refer only to
single attempts in this direction. For example, Japanese authors under the lead-
ership of S. Kimoura (1933 - 1939) claimed that, despite former concepts, main-
tenance of animals in a de-ionized atmosphere was not endangering their life;
this has been subsequently confirmed, by Kornblush, and in the U.S.A. by Nedzel
(1955). At the same time other Japanese scientists obtained results which in-
dicated that prolonged keeping of animals in artificially de-ionized air arrested
their growth, decreased the concentration of inorganic blood phosphorus and ac-
celerated the development of experimental rickets. The studies indicated that
-251-
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people living in rooms from which light ions have been removed developed symptoms
of indisposition, headache, perspiration, etc., even though all other air con-
ditions remained undisturbed. The above indicated symptoms largely disappeared
when 500 - 2000/cm3 negative ions were introduced into the room air. Experi-
ments conducted by D. A. Lapitsky with animals supported the concept that the
introduction of artificial negative aero-ionization into closed spaces prolonged
the stay of persons in a room having a limited supply of oxygen.
The data presented cannot be regarded as adequate for the solution of this
controversial subject. The data should be broadened and confirmed by more ad-
vanced experimental and analytical procedures. If such research should produce
scientifie evidence of the physiological significance of ionization of indoor
air, then the next step will be to establish optimum concentrations of light
ions necessary to artificially introduce into hospitals, schools, offices, etc.
The creation of an artificial ionic indoor air atmosphere may prove intrinsically
beneficial whether or not natural reduction in their concentration may be dele-
terious. Increased concentrations of light ions at a given predominance of ionic
polarity can be beneficial to the general state of health of normal persons,
stimulating their activity and enhancing their mental and physical efficiency.
Despite the above conjectures, the expediency of creating a constantly increased
level of air ionization in rooms has been doubted. Kornblush (1959) showed that
the periodic effect of ionized air was more beneficial to health than its con-
tinuous effect. Beckett (1959) stated that a condition of physical comfort did
not indicate that all factors of the surrounding atmosphere had to be maintained
at a specific level; periodical effects, in particular of such a dynamic factor
as electrical properties of air can act as intensive physical stimuli.
At the present state of air ionization research attention should be focused
on the question of supplemental indoor air ionization, and investigations in the
field of developing means for freeing indoor air from heavy ions (Wait) can be
postponed. However, the problem of enriching air with light ions must be in-
vestigated not only from the purely physical, but also from the chemical point
of view. The process of ion formation is closely connected with the chemical
composition of the atmosphere in which ionization takes place.
It was observed
that indoor air contained different concentrations of ionized molecules of oxygen,
nitrogen, carbonic acid, etc. According to E. A. Chernyavskii, Pontani, and
others, this fact is of substantial physiological significance. In all proba-
bility this may be true, but, according to results obtained by L. Lo Vasil'ev,
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ions of dissimilar chemical composition which carried identical electric charges
acted on the functional indexes generally in like manner. This subject calla
for greater precision, even though it is difficult to solve it owing to the in-
sufficient knowledge concerning the relationship between the atom and the elec-
tron, which varied for different gases present in the atmosphere. There are
reasons for the assumption that persistent negative ions represent to a greater
degree molecules of oxygen and water vapor (P. N. Tversky). This fact deserves
attention, since it bears closely on the possible favorable effect of negative
ions.
Many phases of this problem must be solved before the application of arti-
ficial air ionization into practical life can be recommended. However, there is
a trend in that direction, especially on the part of sanitary engineers whose
opinions are based on ~ priori physiological assumptions and faulty primitive
notions that, in the process of conditioning and ventilation exchange, air was
losing the greater part of its light ions (Currier, 1928). Subsequent studies
by Yaglu and other American hygienists established that the assumed diffusion
and adsorption of ions upon metallic surfaces did not exceed 30% of their origi-
nal concentration and that such loss was fully compensated by air warming. Air
condensation lowered the degree of ionization, air washing and filtration re-
moved the light ions of mobility exceeding 0.9 em/sec. and increased the con-
centration of heavy negative ions at the expense of the total air electric ef-
fecto Tests made by P. F. Afanasyeva in one of the Moscow cinema theaters,
which had an air-conditioning system, showed that the number of light ions in
the air of the theater decreased by 30 - 45% one half hour after the air-con-
ditioning system began to operate; after an hour the loss in air ions amounted
to only 5%, and ultimately the original concentration of light ions was restored
almost completely.
For the past 30 years, artificial air ionization has been applied experi-
mentally in sChools, hospitals, and other public buildings in America and other
foreign countries; but such experimental application has remained limited, and
individual American scientists have expressed themselves categorically against
the incorporation of aero-ionization into air-conditioners (Loeb, Harrington).
Despite the fact that the question of the significance of air ionization was
first raised in the U.S.A., unanimity of opinion on that subject is lacking in
that country. Murphy (1954) regards light ions as a necessary quality in the
state of air and believes that only artificial production of negative ions
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could create a sufficient density of ions in conditioned air. Specialists in
the field of air-conditioning, such as Hutchinson, Beckett, and others, manifest
a positive interest in the question of artificial aero-ionization as a matter
of principle, but stress the fact that knowledge of its aspects was of an em-
pirical character and the basic scientific-physiological principles for the ap-
plication of aero-ionization were still lacking (1954 - 1959).
American scientists were paying considerable attention also to purely physi-
cal aspects of this question. Serious studies were in progress with a view to
working out methods for the generation of ions which might assure uniform air
ionization throughout an entire residence or building, which would be safe to
operate and easy to service and be free from any danger to the occupants. Pro-
duction of light ions by high tension current has been rejected in the U.S.A.,
using instead radioactive sources and thermo-ionizers, based on the utilization
of thermo-electronic emission from red hot metals (Beckett, Hicks, Skilling).
Successful studies in this field are now conducted in the U.S.S.R. (Ia. Iu.
Reinet, P. K. Pr.yuller, E. A. Chernyavskii, and others).
Attention should again be directed to the new points of view which recently
appeared concerning the physiological significance of continuous and brief
periodic actions of aero-ions. Such views are of practical significance: if
brief periods of inhalation of artificially ionized air should prove more ef-
fective, the installation of uninterruptedly working aero-ionization equipment
in rooms and in ventilation systems would be superfluous. It should be mentioned
here that M. P. Davidov and T. A. Trambitskaya favored periodic air ioniza-
tion in hospital wards by radioactive ionizers. Study of sportsmen during periods
of intensive training conducted by M. A. Vytchikov and A. A. Minkh indicated that
daily brief periodic effects of light air had advantages over continous ion
effect and, therefore, should be preferredo
Artificial ionization of indoor air appears to be of some physiological
significance; in addition attention should be directed to the need for freeing
air of dust and microorganisms (0. N. Nitchkevich and N. G. Ivanchenko, E. Yu.
Zuikova, A. I. Franch, A. L. Chizhevsky). In this respect the direct bacteri-
cidal action of aero-ions comes into play. E. A. Chernyavskii observed a de-
crease of bacteriological infections in cotton plants exposed to the effect of
artificial aero-ionization. L. K. Dobrolet established the cidal effect of
negative ionization on microflora of skin wounds. Krueger and co-authors ex-
perimented with staphylococci suspended in droplets of water and found that high
-254-
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oonoentrations of positive and negative ions acoelerated the destruction of
microbes by aoting direotly on the cells and increased the rate of the droplets
evaporation. According to Pollard's data, negative ions decreased the toxic
effects of air bacteria and viruses.
It can be stated in conclusion that the question of the type of air present
in living quarters and in public buildings is of vital interest and of practical
significance. This assertion can not be refuted despite the fact that many
aspects of this problem are still in a debatable stage. On the other hand,
reasons are still lacking for asoribing to air ionization any universal sani-
tar,y-hygienic qualities. It can be stated merely that air ionization is one
of many factors in atmospheric air the action of which manifests itself in its
interplay and interrelation with other physical and chemical factors prevailing
in the air. Therefore, the question of the physiological signifioance of air
ionization in living quarters must be solved as an aspect of the general problem
of air hygiene and should not be treated abstractedly as "aero-ionization for
aero-ionization's sake".
Overestimation of the significance of the air ioniza-
tion factor may perhaps be tolerated in popular scientific magazines; in prac-
tical sanitation and hygiene it can lead to unnecessary costs and efforts and
may discredit the true degree of the hygienic significance of the electrical
properties of airo
Bibliography.
D a p a HOB a E. r. H IIp. MeTOllH'IeCKHe YKa3aHHR K Jle'EHHIO HOHH3Hp08aHHblN 803-
llYXOM M., 1957. - B a C H JI be B JI. JI. TeopHR H npaKTHKa Jle'leHHR HOHH3Hp08aHHblM B03-
llYXOM. JI., 1953.- 0 H )K e. HaYKa H )KH3Hb, 1940, N~ 10, CTp. 29.- B bI T 'I H K 08 a M. A.
rHr. H caH., 1959, N~ I, CTp. 82. - B bI T 'I H K 0 8 a M. A., M H H X A. A. TeopHR H
npaKTHKa (jm3KYJlbTYPbl, 1959, N! 5, CTp. 444. - Bonpocbl KypopTOJlOrHH. PHra, 1959, T. 5.-
LI. a 8 bill 08 a M. n., T paM 6 H II. K aRT. A. B KH.: DpOHXHaJlbHaR aCTMa. n., 1959,
CTp. 322. - K a r a H .It 11., K 0 B a JI e H K 0 B. H. DIOJlJI. HHcpopMall.HoH. MOCK08CK.
HaY'IHO-HCCJlell. HH-Ta HM. 3pHcMaHa, 1957, N~ 6-7, CTp. 57.- JI a n H II. K H if 11.. A. TPYllbi
I1H-Ta no H3Y'IeHHIO M03ra. JI., 1947, T. 18, CTp. 76. - M H H X A. A. l1oHH3all.HR B03llyxa II
ee rHrHeHH'IeCKOe 3Ha'leHHe. M., 1958,- Bod i e n K., Beliiftung, Beleuchtung und lonisa-
lion yon Raiimen und ihre Bedeutung fUr die Hygiene. Diss. Frankfurt a. M., 1939. -
Cur r i e r W. H., J. Am. Soc. Heat. a. Ventilat. Engineers, 1928, v. 34, p. 145.-
Hi C k s W. W., J. Frank. Inst., 1956, v. 261, p. 209.- H u r chi n son F. W., Heat. a. Ven-
tilat., 1944, v. 41, p. 76. - K rue g erA. P. a. of h., J. Gen. Physiol., 1957, v. 41, p. 359;
J. Frank. Inst., 1958, v. 266, p. 9.- L 0 e b L. B., Heat., Piping a. Air Condit., 1934, v. 6,
p. 437.- M u r p h y H. C., Heat., Piping a. Air Condit., 1954, v. 26, p. 120.- Pol-
I a r d E. c., Scient. Am., 1954, v. 191. - P 0 n tan i U., Ann. Igiena, Roma, 1950, v. 60,
p. 3.- S pol v e r in i L. M., Ann. Sanita Pub!., 1950, v. 11, p. 1411.- Win so r T.,
Be C k e t t I. C., Am. J. Phys. Med., 1958, v. 37, p. 83.- Jag Iou C. P. a. oth., Helt..
Piping a. Air. Condit., 1934, v. 6, 25; J. Industr. Hyg., 1935, v. 17, p. 280.
-255-
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Sanitization of Gumbrin Clay Processing.
E. O. Kossovskii.
(From the Shaumyanov Regional Sanitary-Epidemiological Station, Baku).
Gigiena i Sanitariya, Vol. 25, No.8, 68-71, 1960.
Subbentonite and bentonite clays, trade named gumbrin and askonite, found
in the Caucasus possess high adsorption properties and are widely employed in
purifying and clarifying crude oil products and mineral oils. Gumbrin thus
used is first dried and ground. Transportation, drying and grinding of gumbrin
is accompanied by intense dust elimination. The sanitary-hygienic labor con-
ditions during gumbrin processing at the Baku Crude Oil Refining Plant basically
reflected the technology and equipment involved. Gumbrin is obtained in the
vicinity of village Gumbrin (hence its name) and is delivered to the Baku plant
in open railroad gondolas. Gumbrin 1s unloaded from the gondolas and stored in
a special building from which it is loaded into hand wheelbarrows and dumped
onto conveyors, which in turn, deliver the material onto other means of con-
veyance which bring them to the grinding and drying departments. In the dry-
ing department the gumbrin cl~ is loaded into a drying drum heated by flue
gas. As gumbrin passes through the drying drum, rotating at an angle, it is
automatically delivered into a bucket elevator which delivers it to an upper
located conveyor which, in turn, delivers it to the mill bunkers and from there,
by means of rotating dosers, it is delivered into the grinder. A disk equipped
with a cutting blade similar to one used in plows delivers the clay into rollers
equipped with a retaining ring. The rollers force the cl~ into the ring and
grind it to a powder. Simultaneously, hot air is drawn into the mill from a
furnace heated to 4800. The dried and powdered clay and the hot air enter an
upper located separator in which larger particles are removed and returned to
the grinder. The powdered sifted clay is delivered by air vacuum suction into
cyclones where it is precipitated and by means of special valves is then de-
livered into collecting bunkers. It can be seen from this brief description
that the process of gumbrin grinding lacked appropriate hermetization and neces-
sary mechanization. As a result, the air of the production premises contained
gumbrin dust concentrations exceeding by far the allowable limit of dust con-
centration in working premises. Air pollution with gumbrin dust also extended
into the atmospheric air.
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TABLE
1.
Chemical composition of
gumbrin after calcining
at 8000, in percent.
The basic part of gumbrin, an alumo-
silicate, consists of silicon dioxide whioh
causes silicosis even in its combined form.
Grind
iSi02
(See Table 1). Medical examinations were
made of 48 workers employed as gumbrin
grinders; 10 of these manifested symptoms
Kutansk 70.02 15.05 1.68 7 of silicosis, stages I and II, and 3 had
Local 71.8 17.8 2.52 4.67 symptoms of silico-tuberculosis, while 2
showed signs of pre-silicosis. Twelve of the workers affected with silicosis
iA1203iFe203~ CaO
had long time work records. Gumbrin dust concentrations sharply exceeded the
limits of allowable concentration mostly because of inadequate hermetization of
the technological processes; concentrations varied with the time of the year.
During the cold months of the year, when gumbrin contained more moisture, gum-
brin dust concentrations in the air were considerably lower (see Table 2). How-
TAB L E
2.
Gumbrin dust concentrations in the air of working premises, in mg/m3.
Place and conditions of
sample taking
Silo section
Including:
Mixer building
Moving the bulldozer
Mill section
Including:
At bucket elevator
At slanted mill platform
. .
. .
. .
. .
; Concentration;
Ifluctuations I
I Average
'\ Maximal
Minimal
{Average
Maximal
Minimal
Average
{ Maximal
Minimal
{Average
Maximal
Minimal
{Average
Maximal
Minimal
{Average
Maximal
Minimal
~ During throwing down ground gumbrin.
Near the Fuller pump.
Gumbrin dust concentrations
February-
March ~ April-May i June-July
Working space air temperature
9-110 17-200 26-310
105
199
42.6
136.5
199
126
49.3
54.2
42.6
43.9
52
33.6
49.4
52
46.4
39.7
44.6
33.6
206.6
286.6
130
269.8
286.6
252
143.3
160.6
130
138.7
152.7
126
146.2
152.4
138.4
131.2
136.4
126
507
668.4
320
356.2
386
320
657.91/
668.4
646 .
598.211
684
506
-257-
-------
ever, increasing the moisture content of gumbrin prior to grinding i~ proved
imprac:ical, due to the fact that raising the gumbrin moisture content lowered
sharply its technological properties and reduced its effectiveness in the puri-
fication of the mineral oil. Therefore, it was suggested that the dust suspended
in the air of the grinding rooms be removed by dry type dust catchers in order
to eliminate the possibility of the gumbrin dust finding its way into the at-
mospheric air and into workers' premises.
Raw clay lumps
from the
dry i ng drum
7
"
""
"
5
8
Fig. 1. Plan of mill operation without
dust catchers.
1 - Bunker; 2 - mill; 3 - mill separator;
4 - cyclone; 5 - silo; 6 - cupola vent; 1 -
doser; 8 - ventilation (fan).
The Baku Crude Oil Processing
Plant has been operating on such
a basis.
Prior to the installa-
tion of dust catchers, the raw
clay lumps were delivered from the
drying drums .Y!!. the bunkers into
the mills or grinders together with
hot air coming from the air heat-
ing ovens, into the mill or grinder,
and from there .tl!. the mill sepa-
rator into the ventilator which
delivered it into a cyclone and
therefrom into a collecting pit or
silo. A part of the steam. formed
in this prooess, the hot air with suspended gumbrin dust, were discharged into
the atmosphere, polluting same. The clay was removed from the collecting or
storage silo as needed with the aid of a pneumatic dose feeder into the appro-
priate section of lubricating oil purification. The cupola vent shown in Fig.
2 was stopped up and vapors, hot air and clay dust found their way into the
ventilator and therefrom into the dust catcher in which the dust was directed
downward by a special partition system finally falling upon a layer of lubri-
cating oil which was automatically maintained at a constant level. The air
purified in the dust catchers was then discharged into the atmosphere. The
dust-saturated oil was removed at definite time intervals and replaced by fresh
oil. From the doser the clay was directed into the final installation.
Preliminary data obtained in checking the improved procedure indicated a
high degree of atmospherio air purification and a dust concentration not exceed-
ing the allowable sanitary limits. Nevertheless, in such sections as the store-
room and the pit or silo and in the loading and unloading room, high gumbrin
-258-
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choke
v-
,
,
,
,
air
air
5
6
8
. to the instal-
lation
Into the at-
III os ph ere
lQ
9
oi I into the
dust catcher
oi I froll the
dust catchers
Fig. 2. Plan of cl~ grinder operation after
dust catcher installation.
1 - Bunker for raw cl~; 2 - mill or grinder; 3 -
mill separator; 4 - cyclone; 5 - siloi 6 - cupola
vent; 7 - doser; 8 - fan (ventilator); 9 - dust
catcher; 10 - pump.
2.
dust concentrations in the
air persisted presenting a
danger source for the de-
velopment of silicosis among
the workers employed at such
points. New appropriate
purification means must be
adopted to improve the labor
conditions; loading and un-
loading should be done me-
chanioally and under her-
metical conditions; the same
is true of the milling proc-
esses.
Conclusions.
10 Gumbrin el~ grind-
ing was accOlllpanied by in-
tense pollution of the air
of working premises.
Cases of pneumoconiosis have been uncovered among workers assigned to
the gumbrin milling department.
3. Workers employed at processing and application of gumbrin cl~ in crude
oil refining plants should be medically examined prior to their assignment and
at definite time intervals in the course of their employment.
4. Steps in gumbrin processing, its transportation, loading and reloading,
drying and grinding should be mechanized as much as possible and all means ap-
plied to secure hermetization which should reduce if not completely eliminate,
gumbrin dust in the surrounding air.
-259-
-------
Hand Lead Contamination of Workers in Contact with Ethyl Lead Gasoline.
I. 10 Brekhman, V. A. Matyukhin and N. K. Fruentov.
Gigiena i Sanitariya, Vol. 25, No.1, 91-98, 1960.
A study was made of lead quantity found on the hands of automobile drivers,
workers in automobile garages, auto repair shops, etc. This was done as follows:
at mid-day and at the end of the work day washings were obtained from the work-
ers8 hands, from steering wheels and from other automobile surfaces. The wash-
ing was done with gasoline B-10 which was previously tested and found to con-
tain no tetraethyl lead. The method used for the determination of small amounts
of lead in the washings was based on the decomposition of tetraethyl lead by a
hot alcoholic iodine solution followed by a nephelometric determination of total
lead by the potassium bichromate method. (Since no differential organic and in-
organic lead determinations were made in the washings the total results m~ ap-
pear slightly exaggerated. Editor's Note).
Results of 300 tested washings are presented in the table below in percent-
ages of the total number of tests. The data show that 3.6% of automobile drivers
and 4% of auto station, auto repair shop and other similar workers' hands were
free from tetraethyl lead; no such free cases were found among 50 workers en-
gaged in the aviation industry. The average tetraethyl lead found on the hands
of automobile drivers amounted to 0.125 mg and on the hands of workers in auto-
mobile garages and automobile repair shops amounted to 0.115 mg, while on the
hands of the technical workers in the aviation industry the amount of lead found
was 0.249 mg.
Such high hand contamination of the technical aviation personnel
Mg of lead in hand washings of different specialists in percent
of total number investigated.
Content of
tetraethyl lead
Automobile
drivers
!Workers in garages,!
! repair shops, !
! filling stations, !
: and the like :
Technical
aviation
personnel
0.5 - 0.41
0.4 - 0.31
0.3 - 0.21
0.2 - 0.11
0.1 - 0.01
o
1.2
1.2
14
33
41
3.6
54
42
4
11.5
65
11.5
5
-260-
-------
with tetraethyl lead is easily explained by the fact that aviation gasoline con-
tained 2 - 3 times as much ethyl fluid as did automobile gasoline.
It was also shown that a considerable amount of tetraethyl lead was de-
posited on the steering wheels. In 89% of the cases it ranged between 0.1 -
0.2 mg and in 11% it amounted to 0.3 mg or more. About the same amount of
tetraethyl lead was found on the automobile handles and hand operated trans-
mission parts and on the outside of the automobile. Tetraethyl lead was also
found on many objects in the airplane cabins, in amounts of 0.4 - 0.5 mg. Simi-
lar results were obtained with washings of servicing personnel which contained
up to 0.3 mg of the tetraethyl lead. Of particular interest was the fact that
auto traffic directing and other personnel not having direct contact with tetra-
ethyl lead also showed the presence of tetraethyl lead in their hand washings,
to a considerable extento Washings of the hands of other workers connected with
different types of automotive and aviation driving, piloting, servicing, etc.
functions contained tetraethyl lead in quantities ranging between 0.1 - 0.5 mg.
Results indicated that despite existing instructions regarding personal hygiene,
contamination of hands and possibly other parts of the body of above enumerated
personnel has not been eliminated or reduced. Chronic intoxication with tetra-
ethyl lead, therefore, appears as a possibility. This can only be eliminated
by strict observation of personal hygiene as outlined in sanitary-hygienic in-
structions, by a thorough consistent and persistent cleaning of contaminated
machine parts and surfaces with kerosene, soap and water, etc. to the point of
almost complete elimination of tetraethyl lead. It may be desirable to instruct
auto drivers, airplane pilots and other workers connected with functions im-
mediately related t~ the operation of automobiles and airplanes to carry with
them jugs containing kerosene or soap and water and towels so that they can wash
their hands free of tetraethyl lead at every possible opportunity.
-261-
-------
Duration of Carbon Monoxide Excretion from the Body.
L. A. Tiunov, T. I. Sokolova and V. P. Paribok.
Farmakol. i Toksikol., Vol. 20, No.4, 76-78, 1957.
Data presented in literature on the rate of carbon monoxide excretion from
the body are contradictory. According to Roughton and Root half of the carbon
monoxide is excreted within 20 minutes after it has been inhaled; according to
Pace, Strajman and Walker (cited by Lilienthal, 1950) the CO elimination period
is between 34 - 84 minutes. Data in the literature indicate that after pro-
longed inhalation of low carbon monoxide concentrations under industrial condi-
tions it remained in the body for a long time (Kohn-Abrest, 1948). It is pos-
sible that carbon monoxide reacting with tissue enzymes (N. S. Pravdin) m~
linger not only in the blood, but also in the tissues. In this study, using
the labeled atoms method, these authors investigated the rate of carbon monoxide
excretion from the blood and the possibility of its being retained by the tis-
sues.
Methods used.
Use was made of C14 in the form of carbonate.
14
C was 0"0-
tained according to the method of Bernstein and Taylor (1947); carbon dioxide,
C140 was obtained from barium carbonate and converted to Cl40 in a zinc reduc-
2
ing column heated to 400 - 500°. Experiments were conducted on cats in an ex-
posure room of 90 liters capacity. Soda lime absorbed the exhaled C02 and the
partial vacuum created as the result of absorbed C02 was automatically replaced
by oxygen, thus retaining a constant atmospheric pressure. This enabled the
authors to expose the animals to any carbon monoxide concentration desired for
h d d.t' f f . CO The concentrat;on of C140
many ours un er con 1. 1.ons ree rom exceSS1.ve 2. ~
was determined with the aid of TM-20 radiation end-counter, fed ~ a high volt-
age cable by a liB" type installation.
Blood containing Cl40 was injected intravenously into the animals in some
tests. Samples of the catst blood were taken from the marginal ear vein at
one hour intervals after exposure was completed. Blood activity was determined
by the end-counter as mentioned above. Count precision equalled 0.25. After
the C140 had been completely eliminated from the blood, the animals were killed,
the brain, liver, heart and muscles were removed, finely cut up with scissors
and ground in a mortar with dry ice and acetone. The homogenized tissues were
spread in even layers and 2 cm2 portions placed into foil cups, using an end-
type radiation counter and the specific activity of the samples was determined.
-262-
-------
TABLE
1.
Time of 0140 elimination from the blood of experimental animals after
different type and duration of 00 administration.
.
Test:
.
No. :
:
Means of 00
administration
1
2
3
4
5
6
7
8
9
10
11
Intravenous
Intravenous
Intravenous
Inhalation chamber
Inhalation chamber
Inhalation chamber
Inhalation chamber
Inhalation chamber
Inhalation chamber
Inhalation chamber
Inhalation chamber
: Duration of
! inhalation
i exposure
395 minutes
350 minutes
366 minutes
23.5 hours
24 hours
47 hours
49 hours
49 hours
2.
0140 content in organs.
Test:CO concentration in :Imp/min. in: : Imp/min.
NQ. :chamber and duration:blood prior:vrgans:in organs
of exposure :to exposure:
2
3
4
5
6
TABLE
0.024 mg/li
48 hours
None
Brain
Heart
Liver
Tissue
Brain
Heart
li ver
Tissue
Brain
Heart
Liver
Tissue
4
Brain
Heart
li 'jer
Tissue
I
8
9
I
I
2
3
2
8
7
4
7
8
4
6
5
I
2
5
I
3
4
2
0.07 m9/ I i
48 nours
0.147 mg/ I i
24 hours
0.063 m3/ Ii
6 hou rs
(J.078 mg/ Ii
6 hours
Intravenous
inJection of
C 40-s
-------
monoxide had been excreted from the blood completely (Table 2). Results in
Table 2 indicate that carbon monoxide or any Cl4-containing product of its con-
version in the body was retained in the organs in extremely small amounts,
practically traces. If allowance is made for the fact that residual blood in
the tissues may contain more significant amounts of C140 at the time of tissue
examination than did the peripheral blood, then the content of C14 in the tissues
must be considered as near zero.
Experimental Study of Working Conditions and Atmospheric Air Pollution with
Ethylmercuric Chloride During Treatment of Cereal Grains in the Omsk Oblast.
Z. Z. Bruskin.
(From the Regional Sanitary-Epidemiological Station and the Department
of Labor Hygiene of the Medical Institute).
Gigiena Truda i Professional'nye Zabolevaniya, Vol. 2, No.5, 20-24, 1958.
Granosan has been used for the disinfection of cereal grains from spores
and microorganisms. Granosan, NIUIF-2, is a 2% mixture of ethylmercuric chlo-
ride, EKC, (C2H5HgCl) and talc. According to L. I. Medved, N. S. Pravdin,
S. N. Kremneva, and others, EKC is more toxic than vapors of mercury and of
mercuric chloride, and according to L. I. Medved, and I. K. Trakhtenbergt.and
others, it is also cumulative. E. A. Drigichina, A. K. Karimova, E. I. Yaro-
slavskii, and others described cases of acute and chronic poisoning with EKC
in which the predominant symptom was disturbance of the central nervous system.
L. I. Medved and others made a hygienio evaluation of working conditions on
farms of the Ukraine and Belorusiya using granosan. The present author made a
similar study in the Omsk oblast, where climatic conditions and other local
characteristics were different from those prevailing in the Ukraine or in
Belorusiya. The study was conducted during May in 1956 and 1951 in the ~avri-
chesk and Kalachinsk regions in three kolkhozes, where the seed or grain treat-
ment was done manually by shovel mixing and by machine PU-l in an apparatus
PSP-0.5. The EMC was used at the rate of 100 g per C of seeds or grain; mixing
-264-
-------
was done with shovels in the open air. Machine PU-l has a grain bunker equipped
with a worm gear for the del;ver.y of the grain and a special slit and a sliding
control shutter; there is also a small bunker for dry grain treatment by means
of a special mixer, which also serves as the granosan deliverer, the rate of
which is controlled by a sliding shutter as in the case of the grain delivery;
the machine is also equipped with a small tank and a special arrangement for
wet treatment of grain. In the dry treatment the seeds and the granosan are
delivered into a special mixing compartment by means of a worm gear conveyor.
The machine is brought into operation by mechanically engaging a special driv-
ing gear. Apparatus PSP-0.5 consists of a metallic drum; 50 g of the grain and
a desired dose of the granosan are placed into the drum which i8 then rotated
for 5 minutes, and the treated grain is removed from the apparatus.
Fifty-seven air samples were collected for the determination of EKC in the
dust, and another 57 air samples for the determination of EMC vapor; 102 wash
water samples were collected from the hands of the working personnel, their
clothes, protecting respirators and of surrounding objects; records were kept
of the duration of work. EKC determinations were made by the method recommended
by the Kiev Institute of Labor Hygiene and Occupational Diseases, which is based
on the colorimetric estimation of a resulting precipitate of CuIHgI2' Analyti-
cal results of air samples taken at the workers' breathing level are listed in
Table 1.
Lowest concentration of EMC was found in the air at the point of grain treat-
ment by machine PU-l manually operated; concentrations of EMC in air samples col-
lected during operation of apparatus PSP-0.5 were, on the average, five times as
great as in the case of machine PU-l hand operated; the mechanically operated
machine PU-l produced a dust concentration 14 times as intense, and the shovel
mixing process produced an EMC air concentration 41 times as intense. Among the
air samples collected at the manually operated machine PU-l only one had a con-
centration exceeding the allowable limit in a 1.4 ratio. GOST specifies no limit
for allowable concentration of EMC in air of working zones, but there is one for
Hg; therefore, results here dealt with are with reference to limits of Hg con-
centration. It should be noted at this point that in dealing with organic mer-
cury compounds, such as ethylmercuric chloride, a concentration of 0.00001 mg/li
in the air at the level of workers' breathing should not be regarded as the
permissible limit, as was indicated by I. K. Trakhtenberg in Gigiena i Sanitariya,
1950, No.6, p. 17.
-265-
-------
s=
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at
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s= ~
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~ ..-1
'd
Q)
r-I 'd
Q) ..-1
> ~
Q) 0
r-I . r-I
rQ .J:I
~'d 0
s= 0
'rl.J:I
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at a
Q)
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r-I .0 s=
Q)
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at Q)
IZ1 ft-! .J:I
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Lt"\ 0 0 r-I
at
~ 0 0 0 0
Q) 0 0 0 0
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o 0 0 0
..
co ..... Lt"\ Lt"\
\D co N r-
at \D 0 0 N
~ r-I 0 8 0
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Lt"\ 0 r-
at 0 0 0 0
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o 0 0 0
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N Lt"\ .....
~ co 8 Lt"\ Lt"\
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o 0 0 0
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co 0 0 (\J
a; ~ 0 0 (\J
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o 0 0 0
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s= 0 0
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. . . .
o 0 0 0
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r-I \D 0'\
~ r-I \D 0 ~
~ 0 0 0
at
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Q) 8 0 0
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. . . .
o 0 0 0
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co 0'\ (\J Lt"\
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cd r-I 0 0 0
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o 0 0 0
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cd 0 0 0
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.-I 0 8 0 8
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.-I 0 0 0
. . .
o 0 0
..
I
:-4 s=
Q) '" .rl
Q) .J:I 0
.J:I ~ s:I ~..... .. ~
~ M'.-I..-I s= ~.....
s= at '" at cd
s:I ..-1 ::S.. .J:I..-I
..-1 1:1 t1() s= 0 ~ s:I
'" oS s:I Q) Q) oS ~
.. Lt"\ 81..-1 PtEl~
r-I . ~ 0 0 0
ats=o~..", ..~
~~I r-I~Q)r-I Q)
s:I oSP4 oS I O.J:I I 1>a.Q
"'PU].o~~~::>r-I~
:::iI P4 P4
<21
r-I
r-I
at
~.
o
8::::ii1
r-I
;:II
<21
r-i
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«
r-I
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o
cd
>=a
r-I
::::iiI
-266-
During one hour collection of an
air sample, cereal seed was treated
and discharged onto an open platform
over a period of six minutes; another
six minutes was required for shovel-
ing the treated seed into bags, and
an additional 12 minutes for weighing
and transporting the filled bagso
In another instance it took 15 min-
utes to treat the seed and pour it
into the bags, and 9 minutes to
empty the machine onto the open plat-
fo~. The concentration of EKC in
the air amounted to 0.0000007 mg/li.
In another instance, in which the
air dust concentration was only
0.000003 mg/li, the air sample was
negative for EMC vapor.
In the latter
case the entire process of machine
grain treatment took 18 minutes and
the treated grain was emptied into
bags tightly attached to the dis-
charge opening. Such an arrangement
could not be secured in the case of
the manual grain treatment, which
has now been abolished by special
sanitary regulation. Machine PU-l,
operated by mechanical gear meshing,
discharged the treated grain with
considerable force, so that at the
point where the grain was discharged
directly onto the open ground, the
air became permeated with a heavy
concentration of EKC dust.
Where
the grain was mechanically filled
into bags, the process was 80 rapid
-------
that before the workers were able to remove the bag, the grain overflowed onto
the ground. Attaching a hose of heavy but soft material directly and tightly
to the discharge opening of the machine reduced considerably the air pollution
with the dust and vapor of EKC. Grain treatment by means of apparatus PSP-O.5
created considerably less dust, but created considerably higher EMC vapor con-
centrations. This was due to the fact that the treated grain was discharged
onto an open surface of considerable area which was accompanied by the vaporiza-
tion of the EMC; and since the treatment was conducted inside a closed barn, the
EYC vapor concentration tended to accumulate. Another important observation in-
dicated that in the treatment of grain with EKC by machine, it was important to
insure smooth and uninterrupted operation.
The next step in this investigation dealt with the determination of EYC air
pollution concentrations in relation to distance from the point of grain treat-
TABLE
2.
Ethylmercuric chloride in the air at x distance from point of
treatment by manual rotating machine PU-l.
:mg/li ethyl-: Ratio of ethy1mer- : : : ,
Meters: ,:, hI 'd i th: Ai :Percent of:A1r current
f : mercur1C : Cur1C C or1 e n e: r : 1 t' : 1 it i
rom: , : , ,: t: re a 1 ve : ve oc y n
hi :ch1or1de in :a1r of working p01nt :tempera ure: h 'd't: /
Mac ne: ,:,. ,: : um1 1 y: m sec
: the a1r tat 1nd1cated d1stance: : :
1 0.000 019 1:1.4
5 0.000 01 1:0.8
10 0.000 004 1:0.4
25 0.000 009 1:0.7
50 0.000 022 1:1.2
100 0.000 005 1:0.3
TABLE 3.
20 - 21
25 - 26
27 - 28
27 - 28
27
24
53 - 74
53
22
18 - 22
21
26
0.8 - 1.2
0.9 - 1.8
0.9 - 1.8
1.6 - 4.1
3.9 - 5.5
2.1
10
30
60
100
150
200
0.000 024
0.000 02
0.000 02
0.000 02
0.000 021
0.000 026
mente The study was conducted in the
vicinity of grain treatment barns located
along a straight line; air samples were
collected on the lee side of the barns.
Results are presented in Tables 2 and 3.
Data in the tables show that EKC was pres-
ent in all air samples collected at all the
Ethylmercuric chloride concentra-
tion in the air at x distance
from the storage barn.
Meters from:mg/li of ethylmercuric
the barn i chloride in the air
distances indicated, up to 200 meters; the
same was true of tests made on wash waters
from objects at same distances from the
points of grain granosan treatment up to
-261-
-------
200 meters which is the regulation width of the sanitary clearance zone for
plants engaged in the treatment of seeds with disinfecting poisonous chemicals.
Results of analyses are listed in Table 4. Wind velocity had a determining ef-
fect on the spread of air pollu-
tion with EKC over the treatment-
0.000 18
0.000 16
0.000 1 less evident. At wind velocity up
of 50 m from the source of origin (PU-l machine)
to 0.000022 mg/li. Data listed in Table 3 were
TABLE
4.
Ethylmercuric chloride in washings from
surfaces of environmental
objects per 100 cm2.
Washings from -
: :Average of
!Number of!ethylmer-
:washings: curic
i i chloride
Inside treatment barns
Outside surface of
barn walls
At distance of:
up to 50 m
up to 150 m
up to 200 m
to 5.5 m/sec and at a
10
6
0.000 5
0.000 24
17
11
2
distance
the EKC air concentration rose
surrounding territory, as is
shown in Table 2. At wind veloci-
ty of 0.8 - 1.8 m/sec, the concen-
tration of EKC in the air rapidly
diminished as the distance from
the points of treatment increased;
however, beyond a certain high
velocity the relation between EKC
air concentration and distance
from the source of origin became
obtained under weather conditions characteristic of the month of May changes in
Western Siberia, with prevailing sharp turns to low temperatures accompanied by
northern winds. In such instances the EKC concentration in the air at 200 m
from the source was twice as high as the limit of its allowable concentration.
The data thus show that the prescribed 200 m sanitary protection zone may be
inadequate for granosan treatment plants under weather conditions prevailing in
the steppe and forest belt of Omsk oblast.
Concentration of EKC in air samples taken 152 m from the point of grain
treatment with granosan by means of PSP-0.5 apparatus ranged between 0.000008
and 0.00002 mg/li. Samples of air collected at the kolkhoz yard surrounded by
different buildings 1 m from the barn housing the operating apparatus showed a
concentration of EMC of 0.000008 mg/li, while the air sample collected at the
center of the yard had ~l EMC concentration of 0.00002 mg/li. On the basis of
such findings it seems logical to recommend that seed treatment with granosan
be done at a point where natural ventilation was most favorable.
Temperature is another factor of importance. Observations made during the
present investigation showed that at +4 to +60 the air contained twice as high a
granosan dust as EMC vapor concentration.
-268-
As temperature rose, rate of EKC
-------
~porization became enhanced so that at 280 the concentration of EMC vapor be-
C~e the predominant air pollutant. The results justify recommending that grain
treatment with granosan be done preferably, if not exclusively, at time when low
temperature prevailed, that is during the early morning or late evening hours
of the month of April.
V. A. Russkikh and A. Ya. Tubina found that EMC remained suspended in the air
.for a long time and that EMC settled upon different objects became easily redis-
persed with air currents; therefore, it appears rational to suggest that during
the seasons of grain or seed treatment with granosan, when the poison is constant-
ly present in the air, and especially during the working hours of the day, workers
should be forbidden to be exposed to the effects of EMC for more than 4 hours.
A study was also made of the effectiveness of protective devices. Samples
of wash water from 7 semi-mask type of respirators KB-2 were analyzed. The outer
surface of the respirator masks showed a deposit of 0.0003 mg of EYC and the in-
side surface 0.00005 mg of the chemical, indicating that this type of protecting
respirator failed to adequately perform the protective function for which it had
been designed; in other words, the cotton and gauze padding proved ineffective.
L. I. Medved showed that gauze and cotton combined pads placed over the nose and
mouth had only a slight protective effect, and analyses made by the present au-
thor indicated that an area of 100 cm of a gauze-cotton mask contained 0.002
~/li of EYC on either side of the mask. V. A. Russkikh and A. Ya. Tubina rec-
ommended that mercury vapor absorber liAS" be used to protect the workers' respir-
atory organs; this absorber operated over 7 days without letting through any of
the poisonous vapor. It is here recommended that kolkhozes and sovkhozes be sup-
plied with adequate numbers of "AS" mercury vapor absorbers. Observations made
by the present author clearly indicated that the use of rubber gloves during
grain or seed treatment with granosan should be made mandatory, since tested
samples of hand wash-water from women who worked with bare hands, showed the
presence of 0.00035 to 0.0006 mg of EMC.
Supplemental tests showed that a 100 cm2 area of the coverall had deposited
Upon it 0.0007 - 0.0002 mg of EKC. Therefore, it is imperative that the working
clothes should not be carried out or worn outside the granosan treatment premises.
As previously indicated, most, if not all, workers engaged in the process
of grain or seed treatment with granosan were women. They were asked questions
pertaining to their occupation in relation to health. Most of the women com-
Plained of loss of appetite, sweet taste in the mouth, and 3 of the women workers
-269-
-------
complained of persistently frequent nose bleeding. One month after the grain
treatment with granosan was concluded, 8 of the women workers were again ques-
tioned concerning their health. Of the 8 only 2 presented no complaints of
affected health. The remaining 6, while still in condition to work, complained
of head-aches, especially of frontal head-aches, loss of or reduced appetite,
insomnia, and 2 women complained of somnolence. On woman experienced vomiting
spells at the end of the fourth work d~, which recurred at some intervals over
a period of 3 days. It could be assumed that all complaints and apisodes may
have been the result of light poisoning with EMC.
Conclusions.
10 Process hermetization and complete elimination of EKC dust or vapor
discharge into the air should bring about a decided sanitary-hygienic improve-
ment in the prooess of grain and seed treatment with granosan. The manual meth-
od of treatment, forbidden by sanitary regulations, should be abolished totally.
Machine PU-l and apparatus PSP-o.5 may be used, provided they were in good op-
erating condition and are intelligently exploited.
2. Air analyses showed that with increase in wind velocity during open air
grain treatment with granosan EMC dust and vapor concentrations frequently were
in excess of the recommended limit of allowable concentration at distances as
great as 200 m from the point of treatment.
This is particularly true in in-
stances of improper machine operation.
Therefore, it is recommended that the
presently adopted sanitary clearance zones be widened for the Omsk oblast in
accordance with its local meteorological characteristics.
3. Grain treatment with granosan should be carried out in the open at 10.
temperatures, preferably in the early morning or late evening hours.
4. It is essential that all sanitary-hygienic regulations applicable to
this type of work be observed strictly and faithfully. Workers should be limited
to a four hour work day.
5. Protective respirators of the gauze-cotton semi-mask type without mer-
cury vapor absorbers proved ineffective for the protection of the workers' or-
gans of respiration against the deleterious effect of EYC dust, and especially
vapor.
6. Practice of personal hygiene in accordance with regulations prescribed
for workers employed in the treatment of grains and seeds with granosan or other
disinfecting poisons must be strictly and scrupulously enforced for the effec-
tive protection of the workers' health.
-210-
-------
Bibliography.
JJ.porH'IHH8 3. A., KapHMoBa A. K" fHr. H caH., 1956, N2 4, CTp. 31-
:i' - M e II Bell b JI. 11., 8 KII.. BonpoCbI 3.L!paROOXpaHeHHH Ha cl.'Jle. M., 1955, CTp. 83-
.-0 I! )f( e H liP., 8 KI!.: TelHcbl .L!OKJI. 13.ro 8C£'COI0311. C'be3l1a mrHellHCTOB :;nH.L!eMHO-
noroB, MHKp06HOJlOrOB H HItq,rKllIlOItHCTOB. M., 19')6, CTp. 434-438.-0 P 8 B ~ H 11 H c.,
K p eM I! e B a C. H.. <1>apM8KOJl. H TOKCHKOJl., 1939, N2 3, T. 2, CTp. 3-7. - P y c-
C K H X 8. A" T y 6 H I! 8 A. ~., fHrHeHa TpY.L!a B npOH3BO.L!CTBe rp811038Ha. B KI!.:
MaTepHaJlbl no BonpocaM rHrHeHhl TPY!l8 H KJlHHHKH npoq,eCCHOHaJlbllbJX 60Jle3Heii C6 5
fOPbKHH, 1956, CTp. 73-80.- T p 8 X Tell (') e p r 11. M., fHr. H caH., 1950, N2 6, c~p. 1'3-'-:
17.-011 )f( e, <1>apMaKon. H TOKCHKOJl., 1951, N2 I, CTp. 48-51.-~ P 0 C naB C K H ii E 11
BecTI!. OTOpHIIOJlapHllr., 1956, N2 5, CTp. 28-33. . .,
Carbon Monoxide in Typical Auto-Tractor Machine Shops.
N. K. Val'chuk.
(Department of General Hygiene, Vinita Medical Institute).
Gigiena i Sanitariya, Vol. 24, No.5, 80-82, 1959.
Carbon monoxide is formed in auto-tractor machine shops by agricultural
machines coming in for repairs, by tractors being checked, and particularly dur-
ing electric welding and other processes of machine repairing. Project MTK No.
1662 developed by the agricultural trust in 1954 provided that tractors and other
machines coming in for check-up or repairs should be brought in by so-called uni-
versal stands to reduce the concentration of carbon monoxide in the air of the
machine shops by cutting down on the amount of exhaust gases.
This author in-
spected tractor machine shops of the Vinits region and found that the precau-
tionary measures provided for in Project KTK No. 1662 had not been taken ad-
vantage of and that practically all machines were coming in and going out on
their own power. The reason for that was, in the first place, the insufficient
number of universal moving stands in the MrK, and, second, the poorly designed
and unstable moving stands which presented some danger to the machines being
moved in and to the workers.
This author studied the pollution of motor transport station air with car-
bon monoxide, using the microtitrimetric method. Samples were taken at the level
.
of workers I breathing. Two hundred air samples were analyzed. Resul ts are
listed in the following table. Data in the table show that carbon monoxide
-271-
-------
Carbon monoxide concentration in the air of MTS repair shops, built according to Project No. 1662.
: :Limits of CO:
: . .
:N b f: concentra- :
: um er 0:. 1 :
: : t~on f uc- :
:analyses : t t" " :
: : ua ~on ~n :
: lair in m~/li:
Outside gates were widely
opened periodically
.
.
.
Section or i
.
department !
!
.
.
.
Disassembly and
washroom
Ditto
Testing station
Ditto
I Ditto
I\)
--:!
I\)
I
Ditto
Copper casting
Conditions and place of air
sample collecting
Heating the caustic solution in vats in
machine washing section
Heating the caustic solution at differ-
ent points on the premises
So-called cold motor burnishing near
moving stand
Ditto, near second stand
So-called hot motor burnishing near
the stand
After so-called hot motor burnishing
near the second stand
Bushing casting, preliminary heating of
bearings on the forge, smelting of bear-
ing alloys - position of smelter
Mechanical Id" During operation of one forge -
we ~ng position of smith
Ditto
Assembly in cen-
tral part of shop
Smith and
mechanical shop
During operation - at the position
of electric welder
During tractor rolling into shop - at
different points of the central track
Starting tractor motor in assembly divi-
sion for a period of 2-3 min. at differ-
ent points of assembly section
Repair and testing After regulating of fuel atomizer - at
of liquid fuel different points of the premises
apparatus
4
0.03-0.05
6
0.02-0.03
16
0.058-0.012
4
0.02-0.045
6
0.023-0.257
4
0.09-0.1
26
0.045-0.2
Remarks
Ditto
Samples were taken with
fan in operation
Ditto
Ditto
Ventilation was in opera-
tion only periodically
Ventilator in continuous
36 0.028-0.168 operation, door leading to
street open occasionally
26 0.02-0.23
13 0.02-0.15 Outside gate wide open
6 0.02-0.05
13 0.03-0.095
-------
concentration at the level of workers' breathing in most instances exceeded
considerably the limit of allowable carbon monoxide concentration in the air
of working premises. Lowest carbon monoxide concentrations were found in the
disassembly and cleaning sections and in the mechanical machine shops; during
testing and "cold burnishing" of the motors, vapors of heavy hydrocarbons and
of carbon monoxide were discharged into the air of the testing station, so that
even with the exhuast fan in operation the concentration of these pollutants
exceeded the allowable concentration by 2.0 to 11.5 times. Particularly high
concentrations of carbon monoxide were created in the air of the testing station
when the motors were tested under heavy loads or so-called "hot burnishing".
Such concentrations of carbon monoxide were 6 to 9 times as high as the allow-
able limits at the point of testing and 3 times as high 2 m away.
A few hours
after the "hot burnishing" of the motors the carbon monoxide concentration in
the air of the test room was still in the neighborhood of 0.82 mg/li with the
exhaust fans in operation.
The cause
of air pollution with carbon monoxide
especially during the so-called "hot motor
the connections between the outdoor-leading
in the premises of the test station,
burnishing" was due to the fact that
exhaust pipes and those of the tested motors were leaking and, therefore, did not
serve the purpose originally designed for, namely, the direct exhaust of the gases
into the atmospheric air. The low efficiency of the ventilation installed in the
motor tractor shops (MTM) was clearly indicated by high carbon monoxide concen-
trations in the air of the copper casting and general welding sections, where
the pollution concentration was twice as high as the limit of allowable concen-
tration, with the exhaust fan in operation. In the copper casting department
of the Strizhev Motor Tractor Station (MTS), the operation of the electric fan
created a vibration and noise of high intensity (up to 82 - 86 db.); this was
due to the technically faulty installation of the fan and caused the workers to
switoh the fan off and carry on their work under conditions of air highly pol-
luted with carbon monoxide, which rose to 0.2 mg/li. The exhaust fan installed
in the mechanical welding department which, according to the provisions made in
the typical plans, was supposed to take adequate care of the air of the working
spaoe, housing a double forge and an electric welding installation, proved in-
adequate and was not able to insure the complete removal of gaseous products
from the working premises housing only one forge and an electro-welding installa-
tion, as can be seen from the data shown in the table. The exhaust hood over
the position of the electric welder was installed above 2.5 m; this was too high
-273-
-------
a position and the dust and gaseous products formed during electric welding
passed into the exhaust hood only partially. The greater part of them remained
at the point of origin and became disseminated by the prevailing air currents
over the entire section. When welded materials were covered with dirty crude
oil residuals the CO concentration in the air at the level of workersi breathing
rose to 0.218 - 0.30 mg/li. Thus, it can be seen that the location of these
two work operations, not technologically related to one another, in one and the
same room, served no good purpose since it increased through summation the dele-
terious aspects of air which affected the mechanic (smith) and the electric weld-
ero The CO concentration of the air at the workers' breathing level reached
0.15 mg/li in the assembly department occupying the central part of the shop
during the tractors incoming, as can be seen from the data in the table; such
a concentration exceeded the limit of allowable CO concentration in the air of
working premises 5 times. Thus, workers in the tractor repair shops, built ac-
cording to the new plan No. 1662, were subjected to the continuous effects of
high concentrations of carbon monoxide. In the course of the above investiga-
tion workers frequently complained of headaches, heavy feeling in the head, which
are characteristic complaints in chronic carbon monoxide poisoning.
Conclusions.
1.
The air of premises housing motor tractor shops
built according to plan
the working period which
and which usually led to
No. 1662 contained carbon monoxide concentrations during
exceeded the hygienically allowable concentration limits
chronic CO intoxication.
2. The presence of high carbon monoxide concentrations in the air of such
typical tractor repair shops indicated the following: a) the need for more favor- ,
able technological solution of bringing tractors and other agricultural machinery
into the repair shop; b) the fan, installed according to the provision of project
No. 1662, worked in the motor test station, in the copper casting and in the
machine welding departments at low efficiency, calling for imperative changes in
the original ventilation provisions.
30 Formation of high carbon monoxide concentrations in the air during so-
called "hot burnishing' inside the testing station premises resulted primarily
from the careless way in which the motor exhaust pipes were connected to the out-
door-leading pipes; this inadequacy should be resolved immediately.
4. Housing of the smith and the electric welding funotions in
considered inappropriate, since the two functions are of completely
one room is
independent
-274-
-------
nature, and when operating in the same room caused accentuated air pollution.
5. Rate of artificial ventilation in the mechanical welding shop should
be considerably enhanced and, in addition, the exhaust hood over the work table
of the electric welder should be lowered to enable the dU3t and gaseous products
formed during electric welding to be caught and carried off by the exhaust air.
6. Mechanical ventilation should be installed in the room housing liquid
fuel testing apparatus, and provision should be made for the removal of low dis-
persed particles of crude oil distillation products from the point of their forma-
tion.
City Street Air Pollution by Autotransport Using Ethylated Gasoline.
F. 10 Dubrovskaya.
Gigiena i Sanitariya, Vol. 25, No.4, 15-18, 1960.
In connection with the growing autotransport, hygienists are faced with the
serious problem of safeguarding the air of populated areas against pollution by
exhaust gas, in particular from pollution caused by burning ethylated gasoline.
During ethylated gasoline combustion part of the lead compounds remain within the
engine and part are discharged into the air. According to data of foreign in-
vestigators (Preis, Hirschler and their collaborators), an automobile burning
ethylated gasoline discharged 70 - 80% lead into the air. Increase in speed
proportionately increased the rate of lead discharge. Tests made at the F. F.
Erisman Moscow Scientific-Research Institute of Sanitation and Hygiene of the
U.S.S.R. Ministry of Health established that an idling GAZ-51 motor vehicle dis-
charged into the air 0.3 g of lead for each kg of combusted ethylated gasoline,
0.87 g of lead per same amount of combusted gasoline when running at the rate of
15 km/hour, and 0.9 g of lead when running at the rate of 40 km/hour. According
to Witt's 1957 report the air in the U.S.A. urban streets contained up to 30 - 40
v/m3 lead compounds. Jacklin reported that the yearly lead discharged by the
autotransport in Switzerland amounted to 165,000 kg. Preis presented the fol-
lowing data regarding the lead content in the streets of Zurich.
-275-
-------
TABLE
10
Pollution of Zurich region
in 1948 - 1955.
Sample collecting
point
:Number of:
. .
! auto!
:machines i
: :
:per hour:
City center
City center
At city outskirts
At city outskirts
240
350
650
800
v/m3
of
lead
0.8
1.3
0.9
1.7
According to Jacklin's 1956 data,
the lead content in the air of Basel was
4.8 - 7 v/m3. A search of the U.S.S.R.
literature indicated that M. Ko Nagib-
chenko's 1958 report was the only one on
the subject under consideration. The
present paper is a report of a study on
air pollution by non-organic lead compounds
coming from autotransport operating on
ethylated gasoline. Air samples were co1-
.5
$
Fig. 10
Setup for air sample collection.
lected by the aspiration method, using a motor vehicle engine GAZ-51 and a setup
shown in Fig. 10 The motor vehicle was installed at any desired point of a street
or courtyard. A metal elbow (1) was attached to the suction opening of the car-
buretor and a rubber hose (2) 1.5 m long was connected to the free end of the
elbow; a rubber tube (3) 8 - 10 mm in diameter was connected to the free end of
the hose and the joint made leakproof with adhesive tape. If four or more samples
were to be collected at the same time, a three-way metal pipe (4) was attached to
the open end of the hose to connect it with three rubber tubes. Special holding
devices (5) and adapters (6) containing special filters were attached to the
rubber tubes; the filters consisted of analytical filter paper FPP-15 or ab-
sorbent cotton dipped in nitric acid, washed with hot water, and dried. Filter
paper FPP-15 proved best for the purpose. The rate of aspiration in either case
was 20 - 25 Ii/min. and was regulated by a flowmeter (7). It was possible to
oollect 4 - 6 samples at one time. Samples were collected at pedestrian's breath-
ing level.
-216-
-------
The described method was used for collecting air samples on sidewalks among
pedestrians during heavy traffic. No industrial establishments were located in
the immediate vicinity where the air samples were collected. Tests were made
during the spring and summer seasons. Only winter samples were collected in
Perm in 1957- Lead determinations were made on the basis of 24-hour averages;
but air samples were collected 4 times a day between 0 and 3 o'clock, 6 and 9
o'clock, 12 and 15 o'clock and 15 and 21 o'clock. 14.4 - 18 m3 of air was
aspirated for each air sample. Lead determinations were made by the potassium
chromate method. Filtered samples were treated with sulfuric acid converting
the lead to lead sulfate; filters were then ashed at 500 - 550°; the lead sulfate
dissolved in 3% solution of ammonium acetate followed by treatment with potassium
chromate, and the lead ion determined accordingly.
Air was tested in Tula, Chelyabinsk, Perm, Kuibyshev and Gor'kii. Studies
in Tula were conducted by members of the F. F. Erisman Moscow Scientific-Research
Institute of Sanitation and Hygiene in cooperation with Tula9s District Sanitary-
Epidemiological Station. In other cities the work was conducted by local munici-
pal sanitary-epidemiological stations. Final interpretation of results was made
at the F. F. Erisman Moscow Institute. Samples totalled 157. Results of analyses
are presented in Table 2.
TABLE
2.
Average daily lead concentrations in city air in v/m3.
City
.
.
!Number of:
. .
i air :
! samples i
1957
Concentration
Maximal i Average
.
.
lNumber of:
: :
. air .
i :
: samples:
1958
Concentration
Maximal i Average
Tula
Chelyabinsk
Iui byshev
Perm
Gor'kii
19
20
20
10
6.94
15.00
0.62
3.10
1.40
3.86
0.36
1.90
55
0.50
0.24
20
10
3
1000 0.68
Below the method's
sensitivity
0.08 0.03
Results indicated that in 1957 the air was heavily polluted with lead. De-
creases in street air lead pollution noted in some of the cities in 1958 was due
to the reduced amount of lead added to the gasoline at the time. In 1958 non-
ethylated gasoline only was used in Perm, hence the absence of lead pollution in
the street air. In 1958 both ethy1ated and non-ethylated gasoline was used in
Tulao Data in Table 2 show that heaviest concentrations of lead were found in
-277-
-------
the air of Chelyabinsk streets. Average 24-hour lead concentrations in the air
of all cities except Kuibyshev during 1957 exceeded the 0.7 v/m3 limit of allow-
able atmospheric air concentration for community air. Lead concentration in the
air of city streets varied throughout the d~. The lead concentration was higher
during the day than during the night. Fig. 2 shows that increase in lead air
pollution ran parallel to the increase in motorized traffic. Jacklin (1956) was
of the opinion that city dwellers were being subjected to lead poisoning.
1!I,58
I!lS 7
If)
'"
D,<#.
I"") IJ,40
a 0,:1
~ o.JO
:g, 0.25
0.20
>- 0.'5
0)0
o
1000 '"
'"
400 "0
...,
: r,4
Q) 10
1=1.'
>- 0.5
.-
18(}0 -g
E
o
1200 -<:;
'"
800 .~
o
E
1 500 .$
:>
..
800
~
o
..
200 :;
E
:>
z
0.2
(}
..
..
400 ~
:>
z
24-]
8-9
11-75 18-21
24-! 8-10 13-15 '8'200
Time in hours
Time in hours
Fig. 2. Lead concentration in atmospheric air in relation to
automotive traffic intensity.
1 - Number of automobiles; 2 - lead concentration
Members of the F. F. Erisman Moscow Scientific-Research Institute of Hygiene
and Sanitation conducted supplemental polyclinical and hematological studies on
street traffic directing personnel of Tula posted at points of heaviest motor
traffico The study covered 41 traffic directors posted within the city and 44
outside the city limits. The entire traffic directing personnel consisted of
males close to 40 years old; all appeared to be in good physical and nutritional
condition; all had work records of over 6 years; all were subjected to rigid
medical examination in 1957 - 1958. Some manifested deviations in the nervous
system (vegetative dysfunction), in the cardiovascular system (dystrophic and
hypertonic or hypotonic). Blood pictures showed the presence of reticulocytes
and erythrocytes with basophylic granules; basophylic erythrocYtes with granules
were also found in traffic directors of Chelyabinsko Deviations from the normal
functioning of individual organs were found less frequently among men stationed
at city outskirts than among those in the oi ty proper. Two traffic men were ex-
amined while in the hospital; lead poisoning was discovered in one, despite the
fact that he had never been in contact with leado
-278-
-------
Conclusions.
1. The air tested in city streets was heavily polluted with lead exhausted
by the autotranaport; the deleterious effect of the lead was demonstrated.
2. It was recommended that the use of ethyl lead gasoline be discontinued.
Bibliography.
He,l10rK611eHKO M. K. rHr. H caH., 1958, N2 8, CTJ>. 6.-Hirsch1er D. A..
G i I be r t L. F., L ,a rn b F. W., N i e by ski L. M., Indust. a. Eng. Chern., 1957,
\" 49 p. 1131.-J e c k Ii n L., Schweiz. rned. Wschr., 1955, Bd. 85, S. 685. - Ide m..
Arch.' Gewerbepath. u. Gewerbehyg., 1956, Bd. 14, S. 626. - Pre isH., Automobiltecnhi-
sche. Ztschr., 1957, Bd. 59, S. 304. - Wit t H., Zbl. Arbeitsrned., 1957, Bd. 7, N. 2, S. 43.
A Study of Automotive Exhaust Gases.
M. V. Alekseyeva and V. A. Khrustaleva.
(From the F. F. Erisman Scientific-Research Institute of Sanitation and
Hygiene of the R.S.F.S.R. Ministry of Health).
Gigiena i Sanitariya, Vol. 25, No.5, 10-14, 1960.
Fuel undergoes many physical, thermodynamic and chemical changes in the in-
ternal combustion engine. Incomplete combustion of liquid fuel in the automobile
engines results in the formation of toxic compounds, which are discharged into
the surrounding atmosphere with the exhaust fumes. The composition of automotive
exhaust gases depends upon the technical condition of the engine, the manner in
which it is used, and on many other factors. The composition of exhaust gases
has been studied by many investigators, but certainty and finality in this respect
are still lacking.
The present authors undertook to determine the organic substances in the at-
mospheric air in the immediate proximity of automobile exhaust gases on the street
sidewalks during heavy automobile traffic. Quantitative determinations were made
of formaldehyde, acrolein, ketones, unsaturated and aromatic hydrocarbons, and
also of the total amounts of carbon and carbon monoxide. Hydrocarbons and carbon
monoxide were determined using a gas analyzer in which the organic substances
were combusted on a platinum spiral to carbonic acid; the latter was absorbed by
-219-
-------
barium hydroxide and titrated with acid. Formaldehyde was determined by the
sensitive and specific method of chromotropic acid. Acrolein was determined
colorimetrically by the color reaction with tr,yptophan. Unsaturated hydro-
carbons were determined by the bromination method and calculated on the pentose
basis. Aromatic hydrocarbons were determined by the Yanovskii reaction, and
the results calculated as benzene. Ketones were determined by two nephelometric
methods: with demidon (demeton1 B.S.L.) and by the iodoform method and the
results expressed as acetone. Samples were collected by the vacuum method into
special pipettes of 0.5 - 1 Ii capacity at a distance of 0.5 m from the exhaust
pipes of small "Volga", ZIL-110 and "Pobeda" types of automobiles burning high
octane gasoline; GAZ-51 trucks burning low octane gasoline, and ZIL busses burn-
ing Diesel oil. Results of more than 100 analyses are listed in Table 1.
TAB LEI.
Total organic carbon and CO in g/m3 in automachine exhaust.
Type of automachine
Index "Volga" ZIL-110 "Pobeda" i Autobus ZIL
Total organic carbon 15.4 - 20.1 9 - 20.4 3.3 - 2102 0.2 - 1.4
Amount of CO 202 - 4.5 1.1 - 3.2 1.1 - 5.0 0.13 - 0.34
Table 1 shows that exhaust gases contained considerable concentrations of
carbon monoxide and of total carbon.
Of considerable interest is the fact that
engines burning Diesel fuel produced gases which contained lower concentrations
of carbon monoxide and less total carbon. Formaldehyde, acrolein, ketones, un-
saturated and aromatic hydrocarbons were determined in 40 air samples each. Some
of the results are listed in Table 20
A study of the data in Table 2 shows that automotive exhaust fumes polluted
atmospheric air with formaldehyde, acrolein, ketones, unsaturated and aromatic
hydrocarbons. Formaldehyde was present in proximity of almost all engines
studied; its concentration reached 2 mg/m3. Acrolein in concentrations up to
20 mg/m3 was found only near the exhaust pipe of GAZ-51 truck, which was burn-
ing low-grade gasoline. No ketones were found in the exhaust gases of light
"Volga" and "Pobeda" automobiles which were burning high-grade fuel. Ketones
were found in concentrations of 6 - 20 mg/m3 in the exhaust gases coming from
engines of GAZ-5l truck and ZIL bus, which were burning low-grade gasoline or
Diesel fuel. Unsaturated hydrocarbons were found in the exhausts of all auto-
-280-
-------
TABLE
2.
Organic substances in the air 0.5 m from the automobile exhaust in mg/m3.
.
.
Automobile i
. .
make i
.
. .
. .
Formal- i i Ketone
dehyde ! Acrolein !(acetone)
:Unsaturat-:
! ed hydro- !
~ carbons ~
Aromatio :
hydro- ~
carbons i
:
Fuel type
. . i :(pentene) i(benzene) .
. .
. . .
0.08 None found None found 20 5
None found None found None found None found 4
"Volga" None found None found None found 30 10 High octane
0.24 None found None found 40 16 gasoline
0.68 None found None found 40 None found
None found None found None found 40 26
0.04 None found None found 5 16
0.06 None found None found. 12 20
"Pobeda" 0.12 None found None found 26 24 High octane
0.24 None found None found 68 32 gasoline
0.32 None found None found 200 60
0.4 None found None found 410 30
None found 4 2 20 8
0.1 12 6 50 24
GAZ-5l None found 16 8 90 32 Low octane
None found None found 10 100 40 gasoline
0.04 20 12 120 80
None found None found. 13 130 120
0.16 None found 8 5 None found
Autobus 0.2 None found 14 50 None found
ZIL 0.4 None found 16 60 None found Diesel fuel
2.0 None found 18 80 None found
2.0 None found 20 140 None found
motive vehicles, while aromatic hydrocarbons were present only in the exhausts
of machines burning gasoline.
Air samples were collected on sidewalks at pedestrian breathing levels dur-
ing heavy automobile traffic; while vehicles were in motion and while they
stopped for traffic light changes on avenues, and in narrow side streets which
had no traffic lights. The above mentioned substances were present in 31.3% of
the tested air samples. Some of the results are shown in Table 3.
Data listed in Tables 1, 2 and 3 show that incomplete fuel combustion in
motor vehicles was a potent source of atmospheric air pollution with organic
compounds injurious to the popu1ation8s health. Automotive exhaust gases should
be rendered harmless by oxidative catalytic complete combustion of automotive
fuels. In this respect use can be made of palladium, hopcalite, oxides of man-
-281-
-------
TABLE
3.
3
Harmful substances in street air in mg/m .
.
: Carbon
Street ~ monoxide
Formal-
dehyde
.
.
i Acrolein
.
.
.
.
.
.
.
.
.
.
Ketone
:Unsaturated: Aromatic
. .
! hydro- ! hydro-
: carbons: carbons
4 10.0 None found 0.2 16 None found
22 10.0 None found 1.0 20 None found
Wide 25 None found None found None found None found None found
70 None found None found None found None found None found
80 0.6 None found 2.0 30 None found
80 10.0 None found 2.0 160 None found
14 0.04 0.001 0.10 None found None found
30 0.016 0.002 0.10 Trace None found
Narrow 47 0.12 0.004 0.16 None found Trace
50 0.2 0.004 0.80 None found Trace
50 0.6 None found None found None found Trace
50 0.8 None found None found None found Trace
ganese, vanadium, cobalt, iron, chromium, or mixtures of same.
The best cata-
lyst, platinum, was recommended by Gudry in 1950 and used in France as a "com-
bustion completer", called by the author "oksicat" (short for oxy-catalyzer).
The active principle of "oksicat" is a combination of platinum and aluminum,
which converts atmospheric oxygen into the monatomic form, which accelerates
the oxidative process. One of the favorable aspects of this catalyst is its
o
ability to react at 250 .
In collaboration with the Scientific-Research Institute of Automotive Motor
Designing the present authors tested the ''Moskvich-407'' engine to which Gudry's
combustion device was attached in the place of the muffler. At the time of the
test determinations were made for concentrations of oxygen, carbon dioxide,
carbon monoxide and the above enumerated organic substances.
Air samples were
collected near vehicles with motor running at different speeds, carrying loads
of different weight. Samples were collected by the aspiration method with and
without the catalytic oxidizing deviceo Results of the tests are listed in
Table 4.
Data in Table 4 show that without the Gudry device the exhaust gases con-
tained 1 - 8% of carbon monoxide, which was reduced to 0.5% when the Gudry devioe
was attached; the organic compounds underwent complete combustion.
-282-
-------
TABLE
4.
Analysis of exhaust gases of automobile "Moskvich-401" with
and without catalytic oxidation.
.
:
i
i
.
r.p. i Run-
m. i ning
.
.
.
.
.
.
.
.
. . . .
. . . .
: : : :
. . . .
i :Fuel: Gas i
: : : : : : t
:Pow-:con- :con-: : : :
. . . . . . .
: er :sump-isump-:Per-:Form-iA iA
:. :. :. : : : cro-: ce-
: ~n :t~on :t~on :cent:alde-:l' :t
: :. :. : : : e1n : one
:l.s.: ~n : ~n : of :hyde : :
. . : . . : .
: ikg/hr:m3/hr: CO i : i
. . . . . . .
. . . . . . .
No catalytic oxidation
iWith catalytic
i oxidizer
:
: : : : Formalde-
: : : :
: : : : hyde,
.p .B :p . 1.
i en-i en-i er- iacro e~n,
iteneizeneicent iacetone,
i i iof COipentene,
: i i :benzene~
i . . . . . . iin mg/m
. . . . In mg/mJ .
. : . . : :
. . .
580 Idling 0.1 6.0 5.5 1.0 100 None 250 90 0.5 None
- found found
1,430 1.5 4.3 34.8 1.8 None 80 Ditto 8 Ditto
- found - -
1,420 12.5 2.9 39.8 1.1 Ditto 400 Ditto 30 None Ditto
- -
found
2,620 - 5.1 2.9 38.0 2.2 3.0 - Ditto 35 100 Ditto Ditto
1,400 - 1.0 2.0 28.3 1.8 1.0 60 Ditto - 50 0.25 Ditto
1,400 3.1 1.1 20.0 2.6 0.5 30 Ditto 20 20 None Ditto
- found
2,600 - 14.6 4.1 55.5 1.3 0.2 90 Ditto 8 40 Ditto Ditto
2.600 - 10.4 3.'5 '50.0 2.3 0.2 90 Ditto 7 30 Ditto Ditto
Conclusions.
10
Air of cities with heavy automotive traffic is contaminated by exhaust
gases containing considerable amounts of toxic compounds.
2. Vehicles burning Diesel fuel discharged considerably larger amounts of
formaldehyde into the air than vehicles burning gasoline.
3.
Acrolein and acetone were found in the exhaust fumes of vehicles burn-
ing low-grade fuel.
4.
High concentrations of aromatic hydrocarbons were found in exhaust fumes
of vehicles burning gasoline.
5. Unsaturated hydrocarbons
vehicles.
6. Supplementary catalytic combustion of exhaust gases can be effective
in abating atmospheric air pollution by automotive exhaust gases.
were found in samples collected near all motor
-283-
-------
7. Data listed in the tables point to the need for systematic sanitary
inspection of automobiles and examination of city air for concentrations of
carbon monoxide and such organic substances as formaldehyde, acrolein, satu-
rated and unsaturated hydrocarbons and other substances.
:Bibliography.
MeJleXlflia B. n. fHf. H CaH., 1958, N9 8, CTp. 1O.-He.aofH6'1eHKo M. K.
TaM )f(e, CTp. 6.-nJlOTHHKOBa M. M. TaM )f(e, 1957, N2 6,. CTp. 10.-lllHMaHo-
. H 'I A. M. OronJleHHe H BeHTHJlJlLlHJI fapa)f(eii. M., 1952. -.c 0 m m ins B. T.,
Wall erR. E., Law the f P. J., Brit. J. Indust. Med., 1957, v. 14, p. 232.
Effect of Superphosphate Production Discharges on Children's Health.
z. Ya. Lindberg.
(Department of Hygiene of the Riga Medical Institute).
Gigiena i Sanitariya, Vol. 25, No.5, 89-96, 1960.
Parallel with a stuqy of the effect of superphosphate production discharges
on the health of the population this author, in cooperation with physicians of
local children's institutions, carried out a thorough and systematic medical ex-
amination of the children residing within the region of a large superphosphate
producing plant in the winter of 1953 - 1954. Medical examinations included
general examinations with emphasis on chest X-rays and results of tuberculin
tests. The study covered 2,053 individuals of whom 1,375 were children residing
in the superphosphate plant district and 67~ control children. The factory dis-
trict consisted of 2 settlements: the southern, located at 0.5 - 1.7 km south
of the plant; and the western, located 0.5 - 3 km west of it. The settlements'
atmospheric air was intensely polluted by the harmful components of disoharges
coming from the superphosphate plant (Z. Ya. Lindberg). Air samples colleoted
in the inhabited zone 500 m from the plant yielded the following analytical re-
sults in terms of limits of allowable concentrations in community air: fluorine
oompounds 16.2 times as high; sulfur dioxide 9.5 times as high; H2SO4 aerosol
27.9 times as high; and oxides of nitrogen 33.9 times as high. The analytioal
-284-
-------
results were as follows at 3000 m from the. plant: concentration of fluorine
compounds 3.3 times as high as the limit of allowable concentration; sulfur di-
oxide 1.7 times as high; H2S04 aerosol 3 times as high; and oxides of nitrogen
3.2 times as high. Such intense air pollution was the result of inefficient
exhaust pipes (18 - 34 m) of the plant.
The control district was located more than 10 km from the superphosphate
plant and had no industrial establishments on its territory. In this district
no harmful substances were detected in the atmospheric air. The character of
buildings, the population's social-economic status were approximately on the
same levels as in the factory district. Medical examination of children from
the factory district disclosed that a high percentage had enlarged lymphatic
glands and a catarrhal condition of the upper respiratory ~assages, the frequency
of which could be ascribed to the irritating effect of the plant discharges.
(Table I). Distribution according to ages is shown in Table 2.
TABLE
10
Catarrh frequency of upper respiratory tract and
lymphatic gland enlargement as compared
with the control region.
Settlement
: Number examined
! With i With
: catarrh: 1 d
: : en arge
: of upper:l h t"
i respira- i ymp a 1C
: : glands
:tory tract:
: In percent
Total
Southern village
Western
Control region
164
249
100
318
1,058
662
1,740
1,040
100
TABLE
2.
Frequenqy of catarrhal
conditions of upper respira-
tory passages in children
of the factory district in
relation to residence dura-
tion is shown in Table 30
This table contains no data
on the control district since
the frequency of catarrhal
conditions in the upper re-
spiratory passages had no
relation to residence dura-
hon.
Catarrh frequency of upper respiratory tract according to age groups.
Number examined
Settlement
.
.
.
.
.
.
iUpper age:Pr h 1:
: : esc 00 :
:of creche: :
. . age .
: nurse~ : :
School
age
Southern village
Western village
Control region
46
58
60
272
967
541
33
61
-285-
:Percent of frequency
: tion to the control
iUpper age: :
: :Preschool:
:of creche: :
. . age .
: nursery: :
in rela-
region
School
age
222
100
1,563
621
100
2,052
1,318
100
-------
TABLE
30
Catarrh frequency of upper respiratory tract in relation to
length of residence in the plant region.
Southern
village
92
225
Western
village
216
809
:Percent frequency in relation
: to children of less than
i 3 years residence
: Southern Western
~ village village
.
.
.
.
.
.
Residence duration i
:
:
i
Number examined
Up to 3 years
Longer than 3 years
100
122
100
199
Data in Table 3 show that frequency of catarrhal conditions of the upper
respiratory passages in children living in the southern settlement was 11.4
times as high and in the western settlement 10.4 times as high as in children
living in the control district; the frequency increased noticeably with chil-
dren's age and length of residence in the factory district. Children living in
the settlements of the factory district showed an increasing frequency of lym-
phatic gland enlargement, especially of the neck. A wider occurrence of some
p~thological conditions in children living in the factory district can be regard-
ed as the result of the harmful effect of the plantRs discharges on the child's
organismo X-r~ examinations were made of most of the children included in the
study plan. Children living in the southern settlement were examined in the
district's tuberculo-preventive clinic by an X-ray of the chest, and those liv-
ing in the western settlement were examined fluoroscopically on the spot by
the physicians of the same clinic.
Children of the control district were given
X-ray examinations of the chest in the district's polyclinic. Medical special-
ists of the tuberculo-preventive clinic regarded +he fluoroscopic examination
TAB L E 4. diagnostically on par with
that of chest X-ray ex-
amination. Changes de-
tected in the lungs were
grouped as of tubercular
and of non-tubercular
origin; at the recommenda-
Results of roentgenologic examinations
of children of all ages.
Settlement
: : Percent frequency of pul-
~Number~monary changes in relation
: ex-: to the control region
~aminediOf non-tuber-:Of tubercular
i £cular origin i origin
Southern village
Western village
Control region
300
985
618
663
1,212
100
316
268
100
tion of the specialists
the non-tubercular changes
were classed as broncho-
-286-
-------
adenites and as changes at the roots of the lungs.
Results of examinations are
listed in Table 4. Frequency of lung changes of tubercular origin ran parallel
to the length of residence in the factory district, as shown in Table 5.
TABLE
5.
Frequency of pulmonary changes of tubercular origin.
Southern
village
Western
village
:Percent frequency in relation
: to children of less than
i 3 years residence
: Southern Western
i village village
i
Residence duration i
I
Number examined
Up to 3 years
Longer than 3 years
19
221
164
188
100
238
100
318
According to the X-r~ findings pulmonary changes of a presumably tubercular
origin were noted among children of all groups in the following ratios in rela-
tion to positive changes seen among the children of the control group: 3.16
times as many among the children living in southern village and 2.68 as many in
the western village; correspondingly pulmonary changes of non-tubercular origin
were numerically 6.63 and 12.12 times as many. In this connection it should be
noted that in terms of absolute numbers, cases with pulmonary changes of tuber-
cular origin predominated. All children were also given the Pirquet tuberculin
skin test. Children reacting negatively to the Pirquet test were given a supple-
mental intradermal Mantu test, and children reacting to either of the tests were
regarded as tuberculin positive. Results of the tests are listed in Table 6.
TABLE
6.
Data indicating the effect of resi-
dence duration on frequency of tubercular
infection are listed in Table 1. Data in
Table 1 show that the number of children
Tubercular infection among
children of all ages.
i . Percent from the factory district who had been
.
.
ifrequency infected with tuberculosis was in the
i iin rela-
Settlement : Number i tion to southern settlement 1.85 times
i and in the
. i control
i western settlement 1.63 times as high as
: region
in the control district, and it increased
Southern village 300 185 with the length of the
Western village 1,002 168 residence in the
Control region 616 100 air polluted district.
-281-
-------
TABLE
1.
Tubercular infection among children in relation to residence duration
in the plant region.
Southern
village
Western
village
:Percent of infection in rela-
!tion to children of less than
! 3 years residence
:
: Southern Western
! village village
.
.
i
Residence duration i
~
Number examined
Up to 3 years
Longer than 3 years
85
215
183
186
100
314
100
573
Analysis of the results of medical examinations, including the X-ray and
tuberculin tests of children residing in the 2 villages of the industrial district
and of those residing in the control district brought out a clear-cut relation-
ship between the frequency of pathological conditions and the intensity of at-
mospheric air pollution with harmful substances.
Results of this study were used by bodies of the Sanitary Inspection in
their presentation of a request for the imperative intensification of the fight
against atmospheric air pollution by dis~harges from the superphosphate plant.
As the result of such a request the following corrective measures had been io-
stituted:
an additional electrostatic sulfuric acid precipitator had been in-
stalled, the device for the recovery and utilization of fluorine compounds had
been rebuilt, new equipment was installed for the recovery and utilization of
oxides of nitrogen, and a 100 m vapor and fumes exhaust pipe had been erected
for the wider dispersion of the plant's exhaust gases.
Bibliography.
K a JI 1O)f( H bI Ii J],. H. Bpa'!. Jl.eJIO, 1954, N2 4, cT6. 337. - JI H H Jl.6 e p r 3. 51.
B KH.: C60PHH'K HaY'!HblX pa60T Pu)f(CK. MeJl.. IIIH-Ta. PHra, 1956, '8. 6, CTp. 205. - 0 H )f( e.
TaM )f(e, B. 5, CTp. 99. - P II 3 a HOB B. A. CaHHTapHall oxpaHa aTMoclj>epHoro B03J1.yxa.
M., 1954, C1'p. 45.
-288-
-------
Two Cases of Acute Carbon Monoxide Poisoning.
N. V. Grin and Zh. I. Pokrovenko.
(From the Stalinsk Medical Institute and Stalinsk Municipal
Sanitary-Epidemiological Station).
Gigiena i Sanitariya, Vol. 25, No.8, 63-63, 1960.
Sanitary inspectors of gas-equipped buildings frequently encounter cases
of gas seeping into living quarters as a result of improper exhaust conduits or
due to defects in the gas mains. The two cases of gas poisoning here described
occurred in living quarters which used coke gas for domestic purposes; the
coke gas contained 4.5% of carbon monoxide.
In the first instance a family of 5 were affected who lived on the second
floor of a gas-equipped house; all were hospitalized as a result of symptoms of
acute poisoning, such as loss of consciousness, convulsions, rigidity of the
nape of the neck, vomiting, etc. Tests for possible food poisoning were all
negative. A few hours after the application of appropriate therapeutic means
patients were discharged from the hospital in a favorable condition. Results of
air analysis in the apartment showed the presence of carbon monoxide concentra-
tions ranging between 0.09 - 0.25 mg/li. Higher concentrations were found at
the grate of sub-floor ventilation. Air samples were collected in different
apartments located on the first floor directly beneath this particular apart-
mento
Results showed that the outlet for the combusted gas was damaged and
partly clogged, as a result of which products of gas combustion penetrated into
the upper floor apartmento
Instance number two. Seventeen persons were brought to the hospital with
symptoms of acute gas poisoning. All patients lived on the first floor of a
gas-equipped house. Analyses of air samples collected in different apartments
of the first floor showed the presence of carbon monoxide in concentrations
ranging between 0.15 - 0.5 mg/li, and as high as 0.25 mg/li in basement samples.
Careful inspection disclosed that 2 gas mains were passing underground 6 m away
from the house, both of medium pressure. A leak developed in one of the con-
duits and the escaping gas found its way into the house through the foundation
into the basement and from the basement to the apartments on the first flooro
-289-
-------
Carboxyhemoglobin in the Blood of Persons Directing City Traffic. 1/
A. A. Vasil'eva and M. D. Manita.
(Moscow City Sanitary Epidemiological Station).
Gigiena i Sanitariya, Vol. 25, No. 12, 77-80, 1960.
z. G. Vol'fson, A. S. Lykova, V. Z. Martynyuk, Z. V. Babayan, and others,
previously reported that carboxyhemoglobin concentration in the blood of persons
directing city street traffic was higher than in the blood of control persons.
The following is a preliminary report of a study conducted by the present authors
on the carboxyhemoglobin content in the blood of persons directing street traffic
in the city of Moscow. The authors employed a spectrophotometric method based
on the property of different hemoglobin forms to absorb light rays in different
spectral regions. For the particular purpose at hand COHb in the blood was de-
termined by a V. V. Popov modified procedure; Popov employed an automatically
recording spectrophotometer SF-2M. The principle of the modification is as fol-
lows: use was made of the difference in light absorption by COHb and reduced
hemoglobin, PHb, in the 534 m~ wavelength spectral region. In this region the
difference in light absorption by COHb and PHb is at its maximum, and follows
the law of Bear. At this wavelength reading magnitudes characterize the degree
of blood saturation with CO. At wavelength 563 m~ there appeared no difference
between light absorption by COHb and PHb; the quantity of hemoglobin is deter-
mined at this point and converted to COHb with the aid of a special formula.
(Authors fail to present the formula. B.S.L.).
The procedure proposed by Popov was used in this study in a somewhat dif-
ferent way. Instead of diluting the blood 1:75 in 0.005 ml of N NaOH, £I the
present authors used a 1:100 dilution of the blood, and for the following rea-
sons: the optical density scale on spectrophotometer SF-4, which was at the
authors' disposal, was graduated up to 2. Optical densities of 1:75 blood dilu-
tions were close to the limiting 2 calibration point of the instrument, and
readings at such points were not accurate to the degree desired.
Therefore,
the present authors used the blood in a 1:100 dilution; this raised the degree
of reading accuracy to the maximal level, beoause the values fell within the cen-
1/ The original title translated literally would read: "Concerning the Problem
of Carboxycarbon Content in the Blood of Street Traffic Directors". B.S.L.
Y This is an obvious error: it should have been "with 0.005 N NaOH". B.S.L.
-290-
-------
tral part of the reading scale. In mass analyses of blood for GOHb concentra-
tions, 0.1 ml of blood was taken by finger puncture, prepared for the spectro-
metric reading, and the optical density determined accordingly.
The technic is as follows: with the aid of a blood micro-pipette take 0.1
ml of finger blood; the pipette should be first moistened with 5% solution of
Na-citrate; blow the blood out into a 10 ml volumetric flask; rinse the pipette
several times with 0.005 N solution of NaOH and blowout into the volumetric
flask; now bring the volume up to the 10 ml mark with the 0.005 N NaOH; mix and
pour the entire solution into a test tube with a ground-to-fit glass stopper;
the tube volume should be such that the diluted blood will be in contact with
the glass stopper.
Bring the tube with its content to the laboratory and begin
the spectrophotometric determination not later than 1.5 - 2.0 hours after the
blood specimen has been obtained. Remove 5 ml of the clear diluted blood into
a tube and add 1 mg of Na-digitonine as the reducing agent. Make spectrophoto-
metric determinations for optical density of the diluted blood in spectral re-
gions of 534 and 563 m~. Use formula and convert to COHb in the blood. Deter-
mination time should not exceed 5 minutes.
For comparison purposes blood of street traffic directors was studied on
a parallel basis with the blood of suitably selected control persons residing in
Moscow, none of whom were engaged in city traffic directing at any time. However,
one of the control persons was a chauffeur, and his GORb concentration was 8.0%.
On days when CORb was determined in the blood of city traffic directing personnel,
the time was set close to 9:00 a.m. when traffic was at its highest, and when
the CO concentration in the air ranged between 15 - 16 mg/m3. Seventy-six blood
specimens were tested for COHb concentration covering two shifts of traffic di-
recting personnel numbering 16; 50 blood specimens were collected and analyzed
in the summer and 26 blood specimens in the winter of 1959; blood specimens were
taken at 7:00 o'clock, before duty performance and at 17 o'clock at end of tour
of duty. Test subjects ranged between 31 and 47 years of age; 4 of 16 did not
~oke; 10 lived in gas-equipped residences and 6 in non-gas-equipped residences.
Results are presented in Table 1.
Results listed in Table 1 show that COHb concentration in the blood prior
,to assuming tour of duty ranged between 7 - 30.2%; at the conclusion of the work
day the blood COHb concentration rose by 50 - 100% in 23 of 39 persons; in 8
persons morning and evening GORb blood concentrations were nearly identical; in
another 8 persons the morning values were higher than the evening values. The
-291-
-------
TABLE
1.
Results in percent of COHb determinations in the blood of
city street traffic directing personnel.
: Summer
So! First investigation: Second investigation
m ker!Before tour:After tour :Before tour:After tour
i of duty i of duty i of duty; of duty
Yes
Yes
Yes
Yes
No
No
No
Yes
Yes
Yes
Yes
Yes
No
Yes
Yes
Yes
12.0
20.0
18.0
29.0
18.6
16.2
30.2
17.0
23.0
20.0
26.0
12.0
12.0
11.0
16.4
25.6
12.5
20.9
14.0
24.4
22.0
28.4
40.0
14.4
17.0
21.6
20.0
25.1
15.0
Not tested
Not tested
12.5
1l.6
17.0
9.4
12.7
19.5
15.5
9.0
Not tested
12.0
17.2
18.4
Not tested
14.0
Fall
.
.
.
~Before touriAfter tour
~ of duty ~ of duty
Not tested
Not tested
25.0
30.0
25.0
Not tested
19.0
23.0
12.4
19.0
Not tested
34.5
20.6
17.5
Not tested
35.0
Not tested
17.6
11.5
18.0
14.8
23.0
7.0
9.8
Not tested
20.0
22.4
13.0
17.3
18.0
Not tested
11.5
Not tested
16.0
28.0
25.5
23.3
24.0
30.2
22.8
Not tested
20.0
32.0
18.0
16.0
16.0
Not tested
12.0
reason for the above seemingly paradoxical results has not been determined. No
differences were observed in the COHb blood concentration among workers residing
in gas-equipped and those residing in non-gas-equipped homes. Results of the
study of Moscow residing controls compared with those of the traffic directing
personnel are listed in Table 2.
Results in Table 2 show the following: blood samples of 28 controls were
free from COHb, which included 25 of 44 tested in the summer and 3 of 58 tested
in the fall; 34 of 102 had a blood COHb concentration ranging between 0.0 - 6.0%,
and 37 between 7.0 - 12.0%, and in only 3 cases did it range between 13.0 - 18.0%.
Thus, data in Table 2 show that COHb concentration in the blood of city street
traffic directing personnel in the summer and in the fall was at higher levels
than in the blood of Moscow residing control persons. This is in agreement with
the results obtained by Z. V. Babayan in a similar study made in Leningrad. No
differences were noted between the blood COHb concentration of smokers and non-
smokers in any of the groups studied.
Information obtained from the polyclinic of the Ministry of Internal Affairs
concerning morbidity of the studied city street traffic directing personnel for
-292-
-------
TABLE
2.
Data from comparative parallel determinations of blood CORb content
in the fall of 1959 in Moscow residing control persons and in
city street traffic directing personnel.
Percent of
CORb
0.0
0.0 - 3.0
4.0 - 6.0
7.0 - 9.0
10.0 - 12.0
13.0 - 15.0
16.0 - 18.0
19.0 - 21.0
22.0 - 24.0
25.0 - 27.0
28.0 - 30.0
30.0
Totals
.
i
~MOSCOW
:
~ Males
Summer
.
.
: Traffic i
controls: di t :Moscow
: rec ors :
: iBefore : After i
;Females;tour or;tour ofi Males
: : : :
: : duty: duty:
Fall
: Traffic
controls: d' t
: ~rec ors
: :Before : After
iFemalesitour of it our of
. . .
: : duty: duty
1
2
3
3
3
1
1
24
3
3
1
3
5
7
4
2
1
2
14
30
25
44 visited the polyclinic; of these 23 complained of
19
39
13
1959 showed the following:
4
2
3
5
3
4
2
2
25
7
8
4
3
3
13
5
14
1
1
1
3
2
4
1
2
4
1
3
1
2
1
13
headaches; one visited the clinic 5 times, 3 four times each, and 1 came twice.
In reply to questions ma~ of the traffic directing personnel complained of ver-
tigo toward the end of the day. The above is a report on a preliminary study;
it is being continued by the Moscow City Sanitary-Epidemiological Station.
Conclusions.
1. Sixteen Moscow city street traffic directing workers were examined for
CORb blood concentration as described in the text. Results of analyses of 76
blood specimens showed a higher level of CORb blood content than in appropriately
selected controls.
2. CORb blood concentration among the Moscow residing controls ranged be-
tween 0.0 - 6.0% in the summer and 0.0 - 12.0% in the fall; CORb concentration
in the blood of Moscow traffic directing personnel ranged between 12.0 - 40.0%.
Bibliography.
5 a 6 a H H 3. B. Te3HcbI .llOKJI. KOHepeHIJ.HH JIeHHHrpa.llCK. HH-Ta ycoBepllJeHCTBOBa-
HH!! Bpa'leii. CaHHTapHo-rHrHeHH'IecKHii aKYJlbTeT. JI., 1956, CTp. 3. - B 0 JI b.p-
co H 3. r. BJIHHHHe BblXJIOnHblX ra30B aBToTpaHcnopTa Ha 3.ll0pOBbe HaCeJIeHHH H npo-
IIJIaKTH'IeCKHe MepOnpHSITIlH, M., 1950. - JI bI K 0 BaA. C. 3arpH3HeHHe B03.llyxa ro-
pO.llCKIIX YJIHIJ. OKIICblO yrJIepo.lla H ee Bpe.llHoe BJIIIHHHe. .aHCC. KaH.ll. 11., 1953. - M a p-
I bI H 10 K B. 3. (pe.ll.). XpOHH'IeCKHe oKcHyrJIepO.llHble HHTOKCHKaIJ.HH. JIbBOB, 1957.
-293-
-------
Effect of Poisoning with Some Phospho-Organic Insecticides.
Yu. S. Kagan and Ye. I. Makovskaya.
(From the Kiev Scientific-Research Institute of Labor Hygiene
and Occupational Diseases).
Arkhiv. Patologii, Vol. 22, No.9, 44-49, 1961.
Among chemical poisons used to control insects harmful to farm crops, an
increasingly great importance should be ascribed to the phospho-organic insecti-
cides (POI), and in particular to mercaptofos (sistoks) and substances of the M
group (M-74, M-8l, M-82). These insecticides are similar in their chemical
structure, physico-chemical properties, and in the character of their biological
action. The general formulas for these compounds are:
x
II
P
\
yCH2CH2SR1;
mercaptofos (thione isomer) - R - C2H5' X z S, y - 0, Rl =
mercaptofos (thiole isomer) ~ R = C2H5; x - 0, y = S, Rl -
M-74 (disiston) - R - C2H5' x = y = S, Rl = C2H5;
M-8l (ekatin) - R = CH3' x = Y = S, Rl = C2H5;
M-82 - R - CH3' x = y - S, Rl = CH3.
(RO)2
C2H5;
C2H5;
The enumerated insecticides are liquids of low volatility with unpleasant
odors, relatively insoluble in water and readily soluble in organic solvents
(M. I. Kabachnik, et al, 1956; N. N. Mel'nikov, et al., 1958); they are used in
the form of emulsions. Studies of the toxicity of mercaptofos (Wirth, 1953;
Diehamann and Rakoczy, 1955; Yu. S. Kagan, 1956, 1957; and others) and of the
compounds of group M (Yu. S. Kagan, 1956, 1957; G. L. Taranovich, 1956; K. S.
Shadurskii and co-authors, 1957) showed their high toxicity to animals and their
ability to penetrate into different organs not only when introduced internally
but also when coming in contact with intact skin or mucosa, and also to bring
about an intoxication characterized by the stimulation of the choline-reactive
systems of the organism. There have been descriptions of serious and fatal
mcrcaptofos poisonings in human beings (Kaiser, 1953; Naeve, 1957; Maresch, 1957;
Metcaef, 1957) and of changes in cholinesterase activity as the result of agri-
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cultural use of this insecticide (Yu. S. Kagan, 1956, 1957; v. A. Kryu, chkova
1957; M. Ye. Machabeli, 1957; and others). Literature contains only scanty data
regarding morphologic changes in cases of poisoning with these insecticides and
particular~ regarding the connection between these changes and the clinical
aspects of the intoxication and the biochemical shifts. Thus, Naeve performed
an autopsy on a man who died of mercaptofos poisoning and found hemorrhages in
the gastric and duodenal mucosae and also parenchymal dystrophy of the liver.
The present authors obtained data (1957) regarding the morphological changes in
the cerebrum in experimental animals poisoned with mercaptofos. There are no
data in the literature related to the morphological changes in animals poisoned
with insecticides M-74, M-81 and M-82.
This paper presents findings in the clinical course of poisoning by mer-
captofos and its analogues and the blood cholinesterase and pseudocholinesterase
activity paralleled by morphological changes noted in aniffials treated with POI
by various routes, such as oral administration, cutaneous administration, inhala-
tion, and intravenous injection. The effecGs of a single and repeated toxic doses
of the insecticides in different concentrations were investigated.
Methods of investigation.
The toxic preparations were injected into white
rats, mice and cats in the form of emulsions prepared by mixing the substances
with OP-7 (polyethylene glycol esters) and then diluting with water to 0.1 -
1.0%. The test preparations were administered intragastrically; cutaneously to
a shaved portion of the skin of the rabbitts back, and by inhalation in a special
chamber. Changes in the animals' behavior, in their weight and in the cholin-
esterase and pseudocholinesterase activity of the blood served as indexes of
pOisoning. All dead animals (280) were autopsied, and the organs of 189 (58 cats,
30 rabbits, 28 mice and 73 rats) examined histologically. The organs studied
were the cerebrum, the heart, the liver, the lungs, the spleen, the thyroid and
pancreas, the adrenals, and the testes. Celloidin sections were stained with
hematoxylin-eosin, van Gieson, sudan III, and silver nitrate impregnation accord-
ing to Foote. The brain sections were stained with toluidine biue and also by
the Beletskii-Shtern method. Following the organic phosphorus insecticide ad-
ministration, the time of intoxication picture appearance, its severity, and the
survival time of the animals, differed with each poison, the dose, the route of
entry into the organism, and the animal species.
Two hundred and sixty mice were administered single toxic and lethal doses
of the POI compounds. The LD50 doses for mice were as follows: 8 mg/kg for mer-
-295-
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captofos; 4.8 mg/kg for M-74; 37 mg/kg for M-82, and 23.mg/kg for M-82.
~ri~
the first 10 minutes to 2 hours the animals were somewhat lifeless, depending
on the dose and the compound used, then they developed dyspnea, twitching of
individual muscles and fibrillation of the muscles of the entire body, saliva-
tion, and tremor. Some mice exhibited ataxia and tension of the caudal muscles.
As a rule, a brief spasmodic period ensued before the animal died. All such
manifestations appeared considerably more rapidly with mercaptofos and M-14
poisoning (death within the first few hours) than with M-81 and M-82 poisoning
(death within 10 days). The intoxication picture in 158 rats (LD50 for mer-
captofos - 3.5 mg/kg; for M-14 - 3.4 mg/kg; for M-81 - 14 mg/kg; and for M-82 -
75 mg/kg) did not differ greatly from the one described above. Rats exhitibed
a more pronounced tremor and at times clonic spasms. The rats exuded a charac-
teristic reddish secretion from the lacrimal glands, which was connected with
the production of the pigment protoporphyrin (Burgen, 1951).
Nine of 18 cats receiving fatal doses (meroaptofos - 3 mg/kg; M-74 - 3 mg/kg;
M-81 - 20 mg/kg) showed a degree of depression and decreased activity; after 30 -
60 minutes the animals became excitable and aggressive and flung themselves about
the cage. Motor excitation symptoms were more pronounced with mercaptofos in-
toxication and less with the oompounds of the M group. Voluminous salivation
appeared next; it progressively rose in intensity to the stage of continuous flow
from the mouth.
Rasping respiration developed, dyspnea increased followed by
the appearance of fibrillar twitches of the muscles, tremor in the paws, and
periodic attacks of clonic spasms.
The animal's condition gradually worsened,
respiration became weaker, involuntary defecation and urination appeared, and
coma set in. The cats died in a state of increasing respiratory weakness. In
12 of the poisoned rabbits no pronounced symptoms of motor excitation were noted;
instead a state of depression prevailed. There was considerable salivation,
muscular fibrillation, and bradycardia. Pupils of most animals were somewhat
constricted, in other animals the pupils remained dilated.
The POI compounds were then applied to rabbits cutaneously (lethal dose of
mercaptofos, 10 - 20 mg/kg; M-74, 3 - 5 mg/kg; M-81 and M-82, 50 - 150 mg/kg).
Symptoms similar to the ones previously described appeared slowly in 36 rabbits.
Mercaptofos or M-14 applied cutaneously caused the animals death during the first
day of the experiment; M-81 or M-82 similar applied killed the animals on the
2nd - 3rd day.
-296-
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Rats and cats were exposed once for 4 hours to POI vapors, the lethal con-
centrations of which were 0.015 - 0.02 mg/li for mercaptofos, 0.01 - 0.014 mg/li
for »-14, and 0.02 - 0.025 mg/li for M-8l and M-82. Most animals died after
several hours or on the 2nd - 3rd day after exposure.
During exposure the ani-
mals exhibited pronounced pupilary contraction, salivation, muscular fibrilla-
tion and tremor. Cutaneous administration of POI compounds to cats produced
less severe effects than did oral administration.
In chronic experiments in which various routes of POI administration were
employed the animals exhibited no aigns of poisoning for 5 - 6 days to 6 months,
depending on the dose; salivation, muscular fibrillation, and other signs char-
acteristic of the previously described single administration of toxic doses of
the poisons appeared during 2 or 3 days, and at times only on the day of death.
Repeated administration of POI lowered the intensity of the convulsive component.
Blood cholinesterase and pseudocholinesterase activity was reduced by more than
50% in all the animals administered toxic doses of POI,; this symptom appeared
before the other signs of intoxication during the period of progressive intoxi-
cation, blood cholinesterase activity was reduced to 20 - 10% or it was com-
pletely depressedo Regardless of the route of POI administration autopsies of
animals that died within 1 hour to 15 days of a single exposure to a lethal dose
revealed different degrees of venous plethora of the internal organs and of the
cerebrum. Many animals exhibited microfocal and even macrofocal pulmonary hem-
orrhageso Examination of the cerebrum and internal organs one hour after ad-
ministration of the poison revealed extensive vascular dilatation, di~tension
of the smaller vessels and laceration of individual cells of the endothelium
and looseness and edema of the walls.
Most pronounced changes in the vessels
were noted when the animals were poisoned with M-14. The cerebral cortex, cau-
date nucleus, and optic thalamus exhibited dystrophic changes in the individual
nerve cells during the early days of the intoxication, manifested as swelling,
eccentric position of the nuclei, pulverization of the NiseI bodies, and partial,
rarely total chromatolY3is. In rare instances and particularly in the cerebral
cortex and subcortical nuclei, individual nerve cells were seen in a state of
karyolysis and karyocytolysis after 15 days of exposure to the POI. Hearts of
all the animals showed changes in the form of turbid swelling of the muscle
fibers, accompanied by clearly manifested venous engorgement and occasional
microfocal hemorrhages (in 30 of 15 animals). Intermediate microfocal infil-
trates composed of lymphoid cells and histiocytes were seen less frequently.
-291-
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In addition to engorgement, the liver exhibited a turbid distension of the
cells, and the nuclei of many cells had undergone pyknosis. An enlargement of
the Nisel spaces occasionally was noted, which resulted from the accumulation
of a liquid and which stained a pale color by eosin. Widely scattered foci of
tissue necrosis were seen in 2 animals which died 15 days after POI administra-
tion. Kidneys revealed dilated lumens of the convoluted tubules; in each case,
the lumen was filled with small lumps of eosinophilic protein masses interspersed
with individual epithelial cells. The epithelium of the canaliculi was dis-
tended; the cells were poorly outlined and the nuclei of many cells had under-
gone lysis. The lumens of the glomerular capsule were free or contained eosin-
stained liquid. Many nuclei of the cubic epithelium which lined the straight
canaliculi had undergone pyknosis. Stroma capillaries were dilated and showed
signs of stasis. Pulmonary vessels of the septi were markedly dilated, and many
exhibited stasis and hermorrhages extending into the perivascular tissue. Scat-
tered focal hermorrhages were observed containing varying amounts of hemosiderin.
Fifteen animals exhibited focal inflammatory changes. The argyrophilic fibers
in the myocardium, liver, kidneys and lungs were thickened or fused; this change
was noted during the day following the mercaptofos administration. The spleen
revealed venous engorgement and medullar hyperplasia; cells of the testicular
germinal epithelium and of the adrenal cortex manifested dystrophic phenomena;
in 10 animals, the cortical and medullary substance of the adrenals revealed
hemorrhages.
Autopsies of 82 animals, dead after repeated administration of mercaptofos,
(the deaths occurred after 2 weeks to 6 months), revealed distension of the myo-
cardium, of the renal canalicular epithelium, and of the hepatic tissue, in addi-
tion to very pronounced engorgement; fatty dystrophy of the liver was noted early
in cats. Numerous hemorrhagic foci were visible in the lungs; 12 of 82 animals
developed small airless grayish-red foci. Microscopic examination of brains of
all animals revealed engorgement of the membranes and tissue of the brain; walls
of many small vessels were loose and edematous; their endothelium was distended;
the nuclei of the endothelium were enlarged and markedly hyperchromic. Prolifera-
tion of the endothelium and adventitial cells were seen in the animals dead after
3 - 6 months.
Swelling
and ectopia of the nucleus and total chromatolysis were observed
cells of the cerebral cortex; in addition, groups of nerve cells
karyolysis, karyocytolysis, and cirrhosis were seen frequently.
in most nerve
in a state of
-298-
-------
pronounced.
Similar changes were seen in the subcortical nuclei, but they were much less
a diffuse manner.
Nerve cells of the caudate nucleus were shrunken and stained in
Similar changes were observed in the nerve cells of the
medulla oblongata and in the ganglionic layer of the cerebellum. Many of the
nerve cells had undergone total chromatolysis, karyolysis, or karyocytolysis.
In addition, the ganglionic layer of the cerebellum revealed prolapse foci situ-
ated at different distances, and groups of cells in a state of cirrhosis, ac-
companied by nuclear PYKnosis and protoplasmic hyperchromatosis; the latter was
stained intensely by toluidine blue. The myocardia of all autopsied animals
revealed engorgement, focal hemorrhages, and distention of the muscle fibers.
In 28 of 82 animals, micro- and macrofocal accumulations of histiocytes and
lymphoid cells were observed among the muscle fibers (Fig. 1). These changes
were accompanied by fatty infiltration of the myocardium in some of the aniffials.
Liver of all animals revealed distention
Figo 10 Lymphoid type and
histiocyte cells infiltra-
tion in eat's cardiac mus-
cleso Exposure to mercap-
tofos vaporso Died after
6 months. Hematoxylene-
eosin stain x 400.
and inflammatory changes; intertrabecular
spaces and interlobular connective tissue showed
serous exudate accumulation or infiltration com-
posed of lymphoid and histiocyte cellso Fatty
dystrophy with necroses of individual groups of
cells was seen in 35 of 82 aniffials, vacuolar
dystrophy in 18 of the animals.
Kidney changes appeared as engorgement phe-
nomena and as granular and vacuolar cellular dys-
trophy of the convoluted tubules epithelium.
Lumens of the capsules of many hyperemic glom-
eruli in 26 animals revealed a serous fluid with
a large number of epithelial cells lining the in-
side surface of the external capsular leaf. The
following changes were seen in the lungs:
en-
gorgement of the capillaries, stasis with intra-
vascular breakdown of erythrocytes, plasmorrhagia,
and hermorrhagic foci with large amounts of
hemosiderin. Argyrophilic fibers in the myocardium, liver, kidneys and lungs
were thickened and acquired a lilac tinge upon silver impregnation. The lungs
of animals revealed intraalveolar fibrillar development (Fig. 2). The spleen
was engorged, its pulp was hyperplasic, and there were signs of hemosiderosis.
-299-
-------
Fig. 2. Thickening and in-
teralveolar development of
argyrophilic fibers in cat is
lungs. Exposure to mercap-
tofos. Died after 6 months.
Silver nitrate impregnation
x 200.
Cells of the germinal epithelium of the tes-
ticular canaliculi revealed dystrophic changes,
the adrenal cortex cells had a lowered lipid con-
tent, and the thyroid gland contained less
colloid.
Conclusions.
1. Administration of organic phosphorus in-
secticides (mercaptofos, M-74 , M-81, M-82) to
mice, rats, cats and rabbits by several routes
in toxic and lethal doses brought about marked
vascular disturbances and extensive dystrophic
and focal necrobiotic changes in the brain and
internal organs.
2.
Intoxication with POI compounds first
gave rise to vascular disturbances, dystrophic
changes in the nerve cells of the brain, par-
ticularly the cortex and subcortical nuclei,
and also condensation and liquefaction of the
basic ar5Yrophilic substances. These were followed by the development of dys-
trophic granular, vacuolar, fatty, and less often, inflammatory and necrobiotic
changes, with lethal doses, in the liver, kidneys, myocardium and glands of
internal secretion.
3.
Morphological changes discovered in the experimental animals were not
specific for the action of organic phosphorus insecticides and were apparently
dependent not only on changes in the acetylcholine metabolism but also on dis-
turbances in other aspects of metabolism and on hypoxia, which is especially
characteristic of the administration of toxic and lethal POI doses.
Bibliography.
I( a 6 a:: HH,K ,\1. H, .\1 aCT p 10 K 0 BaT., A H ;J.p. 1.!.OK.l. AH CCCP, 1956, T. 109
N~ 4, CTp. 7 /7; J~g 5, CTp. 947.-1( a r a H 10. C. npoepeHUH'H no rHrHe-
He 'If TOKCHKOJIOrHH HHceKTocj>yIirHUIIJ10B. KHeB, j 957, crp. 66.- M a 4 a 6 e JI H M. E., T 3-
peHKo M. J.1., raM6alliHJ13e r. M. TaM JKe, crp. 90.--Me.lbHlfKOB H. H.,
M aH.LJ. C J; ~ 6 a y M 51. A~ B KH.: Opr:1HH4ecKHe HHceKTocj>YHrJIIlH.LJ.bI If repOOUHJ1b1. M., 1958,
CTp. 7.- ill a.LJ. y p C K If If K. c., I( 0 M H C cap 0 B J.1. B., J.1 JI b IO 4 e H 0 K T. 10. B KH.:
MaTepHa.lb1 HaY,:H. ceCCHH MHIICK. MeJl,. HH-Ta, nOCBHlU. 40-JIeTHIO BeJIHKOii OKTH'6pbCKOH
COU'HaJIHCTH4eCKOH peBO.lIOUH'H. MHHcK, 1957, 4. I" CTp. 402.- Bur g e n A. S. V., Brit.
J. Pharmacol., 1949, v. 4, p. 185.- Dei C h man n W. B., R a k 0 C z yR., Arch. Indust.
IIyg., 1955, v.)I, p'. 324.:-Kaiser H., Ang-ew. Chemie., 1953, Bd. 65, S. 165.-Ma-
res c h W., Wlen. klm: W~hr., 1957, Bd. 69, S. 774.- N a eve W., Arch. Toxikol., 1955,
Bd. 15, S. 167.- S c bel n e r H., Compt. rend. Soc. bioI., 1939, v. 130, p. 74B.-
Wi rt h W., Arch. Ex p-e r. Pa!h.u. Pharmakol., 1953, Bd. 217, S. 144.
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Modern Approach to Air Dustiness in Workshops.
E. V. Khukhrin.
Gigiena i Sanitariya, Vol. 24, No.7, 50-55, 1959.
Normalization of environmental conditions is the task of hygiene.
During
recent years scientific research institutions and institutions dealing with
practical problems of health protection, labor unions and different industries,
gathered new data on the effect of harmful air pollutants; this led ot a revi-
sion of limits of existing maximum permissible air pollutant concentrations and
to an extension of the list of standardized harmful air admixtures.
In accordance with sanitary standards for industrial enterprise planning
(N 101-54), industrial dusts were divided into "toxic" and "non-toxic"; a con-
siderable number of different dust types was included into the "non-toxic" group
3
for which only 2 concentration limits were recommended: up to 2 and 10 mg/m .
Included in the non-toxic group was also a considerable number of dust types
containing quartz, asbestos and different metallic dust combinations.
The standardization principle recently became the subject of considerable
discussion.
Thus, at the symposium on pneumoconiosis, conducted in Moscow in
May 1957, the question was raised about basing pollution standardization not
on hygienically arrived at concentration levels, but on concentrations techni-
cally attainable industrially (P. N. Torskii, Z. G. Linkin). Similar opinions
were voiced at the meetings of the Commission on Silicosis Control at the Academy
of Sciences, U.S.S.R.
Such opinions met with sharp opposition from hygienists
and a majority of engineers and technicians.
The development of U.S.S.R. tech-
nique and technology has been progressing so rapidly that elimination of dust
in industrial processes presented no great difficulty.
Work on silicosis con-
trol in the mining industry indicated that mining engineers were able to solve
complex technical problems of dust control in the mines; in a number of mines
in Krivorozh8e, the Ural, Uzbekistan, etc., air dustiness was reduced to 2 mg/m3,
and in some cases to 1 mg/m3. The system of dust elimination in the mines was
developed sufficiently well for a variety of work conditions, and the problem
was only one of consistent application of measures developed and of a systematic
control of their effective operation. There are also definite systems for the
elimination of dust formation in coal concentration (enrichment) plants, in
drying-grinding shops, in foundries, and in building material plants. Therefore,
there is no need to be guided by levels of outdated technology accompanied by
-301-
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considerable dust formation. Planning organizations, technicians and builders
of different industry branches should be urged to create new dust-free techno-
logical processes. Scientifically proven sanitary norms must urge engineering
departments to devise more perfect industrial technological sanitizing instal-
lations.
Lately tbe question has also been raised regarding the appropriateness of
standardizing air dustiness by the gravimetric metbod. At tbe Jubilee Session
of the Institute of Hygiene and Occupational Diseases, A.M.S., U.S.S.R., in
1953, participants of the Committee on Silicosis Control again raised the ques-
tion of changing to the particle count method widely used abroad. In this con-
nection studies related to the hygienic importance of mass versus number of
polydispersed dust particles and fractions of different degrees of dispersion
conducted experimentally demonstrated conclusively the preeminent significance
of the dust mass effect. Experimental data coincided to a considerable degree
with the information gathered on lowered morbidity in pneumoconiosis which ran
parallel to the mass of suspended dust. Previous data on lower morbidity rate
in silicosis among sandblast operators also ran parallel to gravimetric dust
concentration; analogous results were obtained by A. S. Plakhin in foundries;
investigations of labor conditions and silicosis morbidity in the mining in-
dustry yielded similar results. Attempts to compare air dust counts with rate
of morbidity among workers showed no clear connection between the two, as might
have been expected theoretically. Data presented by foreign authors and ex-
change of experience with them indicated that the count method was used mainly
because it was simpler and not necessarily most reliable.
It appeared that in conducting scientific research in the field of air dust
pollution by the gravimetric method use was made of dry and liquid filters, elec-
tric precipitators, etc. No legislation exists in foreign countries controlling
maximum permissible dust concentrations in the air, and such recommendations
proposed by individual counties or states of the U.S.A. up to the present had
no legal status. At first these recommendations were made in gravimetric terms
(Lehman, Mavrogordato); later they were expressed in terms of number of particles
per 1 cm3. However, recently the hygienic importance of dust mass has been
recognized in foreign countries. Thus, at the 1956 U.S.A. Convention, physicians
specializing in industrial sanitation recommended that in addition to the count
method the gravimetric method should be used in connection with certain types
of dust, mainly of toxic nature. In 1957 the International Labor Organization
-302-
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(110) recommended that dust concentration be expressed in gravimetric terms.
The importance of the gravimetric method of determining air dust concentration
for hygienic purposes has been established.
Next in importance is the principle on which to base the determination of
the limits of allowable dust concentration. This, indeed, constitutes a complex
and difficult problem. Unfortunately, so far no clear and incontestable data
have been presented establishing safe threshold of aerosol inhalation, because
methods for the study of the effect on man of harmful substances still lack the
required precision. Data obtained regarding the state of health of those work-
ing in the presence of certain concentrations of different active aerosols could
not be used as criteria in this study, since the disease effected far advanced
(irLjurieS beyond the initial forms of the effect on the organism. For toxic air-
I
!suspended aerosols, created in industries newly introduced into the national
economy, limits of allowable concentrations must be arrived at experimentally
as early as possible without waiting for the development of symptoms of occupa-
tional diseases. However, such experimental data must be regarded as tentative,
subject to revision on the basis of results of future clinical observations and
supplemental experiments.
Thus far it was not possible to verify the necessity of establishing separate
norms for maximum single and mean work day concentrations, due to the fact that
in the majority of aerosols existing research methods enable the determination only
of average concentrations for a more or less prolonged time period.
However,
despite these limitations, extensive data were accumulated during recent years
on the study of the effect of different types of industrial aerosols. Based on
the summary and evaluation of new data obtained from work of institutes, university
departments and practicing physicians a list was prepared of maximum permissible
concentrations; it was presented at the 1957 Symposium on the Problem of Pneumo-
coniosis, and published later in the journal "Labor Hygiene and Occupational
Diseases" (1957, No.4). The list presented concentrations of 34 individual
I aerosols. It was discussed at the Symposium, at the meeting of Labor Hygiene
'Section of the Scientific Society of Hygienists, and at the meeting of the Com-
mittee on Hygiene of the Scientific Medical Council of the Ministry of Health,
:U.S.S.R. Together with a list of maximum permissible concentrations of vapors
and gases the list of dust concentrations was sent to all institutes of hygiene
and labor protection and planning, to all technological chemical institute~, and
to the National Committee on Chemistry of the Council of Ministers of the
-303-
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U.S.S.R.
More exact definitions were suggested and additions to a number of
concentration values of toxic aerosols were introduced in the course of discus-
sion; these were taken into consideration and discussed at the meeting of the
Committee on Hygiene of the Scientific Medical Council at the Ministry of Health,
U.S.S.R., as a result of which the following list was prepared.
Dust and other aerosols. in mg/m3.
a) Mineral and organic dust
1. Dust containing over 10% free Si02 in its crystalline
modifications (quartz, crystabalite, tridymite).............
20 Dust containing over 10% and up to 10% free Si02"..""'..'
3. Asbestos dust and mixed dust containing over 10% of
11.
180
19.
20.
2l.
22.
23.
a s be s i 0 B. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.
5.
Dust of glass and mineral wool..............................
Dust of other silicates (talcum, olivine, etc.), containing
under 10% of free SiO 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.
Dust of baryte apatite, phosphorite, cement (containing
under 10% 8102 ~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Dust of artificial abrasives (corundum, carborundum)........
Dust of cement, clays, minerals and their mixtures
containing no free Si02.....................................
1.
8.
90
10.
11.
12.
13.
Coal and coal-rock dust, containing over 10% free Si02......
Coal dust containing under 10% free Si02....'...'.""....'.
Coal dust containing no free Si02."..'.......'.".......... 10
Tobacco and tea dust........................................ 3
140
Dust of vegetable and animal origin (cotton, flax, flour,
grain, wood, down, etc.), containing 10% and more free 8i02.
Dust of vegetable and animal origin containing under
10% of free Si02............................................
150
Dust of pressed powders (phenolic aldehyde and amino-
plastics). ........................... ........ .. .............
160
Organic and other non-toxic dust............................ 10
Hexachlorane. . . . . . . . e 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.1
Hexachlorbenzene............................................
Hexachlorcyclohexane (y-isomer).............................
Heptachlor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Dinitrothiocyanogenbenzene..................................
Octamethyl (octamethyltetram1dopyrophosphoric acid).........
Pentachlornitrobenzene......................................
-304-
1
2
2
3
4
5
5
6
2
4
2
4
6
0.9
0.05
0.01 (1)
2
0.2
0.5
-------
24.
25.
26.
27.
28.
29.
(dinitrofluorocresol type).......................
Compound 125
(thiophosphate).....................
Thiophos
Chlorindin (pyrimethamine)..............
.................
......................
ChI art en. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Ethy Imercuric
Ethylmercuric
phosphate.........
...... ........ ....... .........
chloride. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
b) Aerosols of metals,
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
metalloids and their compounds
30.
31-
32.
Aluminum,
aluminum oxide,
aluminum alloys.....................
Beryllium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Vanadium and its compounds:
a) &noke
b) Dust of vanadium pent oxide.................................
c) Ferrovanadium...............................................
of vanadium pentoxide................................
33.
34.
Tungsten,
tungsten carbide....................................
Ferric oxide with admixture of fluorine or manganese
compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Cadm.ium oxide.................................................
Cobalt
(cobalt
oxide) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mangan e s e. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Molybdenum
Molybdenum
(soluble compounds).......................
.........
(non-soluble
compounds)...................
.........
Arseneous acid anhydride and arseneous oxide..................
Nickel,
Lead and
ni eke 1 icon de. . . . . . . . . . . . . . . . . d . . . . . . . . . . . . . . . . . . . . . .
its non-organic compounds...................
.........
Selenium
amorphi c . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mercuric
chloride. . . . 0 e. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Tantalum. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Tellurium. . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Ti tanium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . .
Thorium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Trichloropheno1ate of copper..................................
Uranium
(soluble compounds)...................................
(non-soluble compounds)...............................
Uranium
Chromic anhydride,
(as Cr203)..........
chromates,
bichromates
Zinc oxide............... 0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Zirconium.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alkaline aerosols
(as caustic soda).
......... ........ .........
-305-
3
0.05
0.1
0.2
0.005
0.005
2
0.002
0.1
0.5
1
6
4
0.1
0.5
0.3
4
8
0.3
0.5
0.01
2
1
10
0.01
10
0.05
0.1
0.15
0.75
0.1
5
5
0.5
-------
Note: Departures from the above values can be made with the permission of
the State Sanitary Inspection where workers remain on production premises a short
time only.
This project 1/ has certain shortcomings as pointed out during the discus-
sion. However, arriving at more precise values or adding new substances would
require consiaerable time; the Committee on Hygiene concluded to approve the
list of values as presented, believing that additions could be introduced upon
future revision of the list within the next 3 - 4 years.
Taking into consideration the importance of hygienic norms and the need
for a comprehensive development of research work, attention should be given first
to the development of methods for the study of aerosols and their properties and
of the effect of aerosols on the organism. It is also necessary to equip the
laboratories with facilities for micro-gravimetric analysis for the performance
of rapid and precise study of air dustiness.
During recent years the importance of degree of dust dispersion has been
receiving wider recognition. Experimental research conducted by this author
earlier (1952 - 1955) enabled him to discern a slight biological activity of dust
particles up to 2 ~ in diameter only in the presence of certain total mass values.
Experimental research conducted at the Institute of Labor Hygiene and Occupational
Diseases, Academy of Medical Sciences, U.S.S.R. in 1951 - 1958 (T. A. Kochetkova,
T. T. Lubova and E. V. Kbukbrina) indicated that small quartz particles numbering
millions produced no pronounced experimental silicosis if the total mass was
small. At the same time, a greater mass of such highly dispersed dust could
produce a sharp reaction with symptoms of acute emphysema, etc. The importance
of-high dispersion aerosols was also demonstrated in the Sverdlovsk Institute
of Labor Hygiene (V. T. Velichkovskii and others) in studies of aerosol condensa-
tion.
Results of the above studies emphasize the need for more rigid limits for
the density in the air of dust particles less than 2 ~ in diameter. However,
when speaking of dust dispersion degree, the hygienists should have in mind not
microscopic determination of dispersion degree. The microscopic method yields
a "dust formula" only according to the number of particles without regard to
1/ At present this project has been approved by the Chief State Sanitary
tion as a regulation on maximum permissible concentrations. Editor.
Inspec-
-306-
-------
mass. Nevertheless, determination of dust dispersion according to particle di-
ameter fractions must be used when conducting hygienic research. This should
be made
tically
mandatory because the methods are well developed theoretically and prac-
(N. A. Figurovskii, N. N. Tsyurupe) and can be used even with very small
(2 - 3 mg) of dust.
samples
The need is urgent for the development of methods for the determination of
dust properties and their chemical composition.
Most industrial aerosols are
of complex composition; in addition new unstudied chemical compounds might per-
meate into the organism which might considerably complicate the final effect.
Thus, it was shown that the presence of small admixtures of fluorine compounds
in phosphorite dust affected mineral metabolism, reduced the rate of calcifica-
tpon of tuberculosis nuclei, thereby increasing T .B. morbidity. Complete analy-
sis of the chemical and mineralogical composition of aerosols should be made by
latest research methods, with emphasis on spectrography, X-ray, electronography,
etc. Study of biological activity of a number of a~rosols presents considerable
~ifficulties in the choice of research methods.
In the majority of cases suggested levels of maximum permissible concentra-
tions were arrived at on the basis of data obtained from a study of workers'
morbidity paralleled by experimental data. However, it is known that many occu-
pational diseases caused by aerosol inhalation may persist for years without
manifesting clear symptoms and may be diagnosed only after the worker has left
his occupation, as, for example "late" silicosis. Some diseases, such as chronic
bronchitis and emphysema in textile women workers, are still not classed as occu-
pational diseases, even though the effect of the textile dust is of importance
in the etiology. There is no doubt that the diseases of respiratory organs caused
by the effect of dust of some metal oxides may persist, diagnosed as non-occupa-
tional diseases. Most early disease forms are difficult to diagnose. As a rule,
it is difficult to establish the effect of the general state of morbidity on the
organism's reactivity to low dust concentrations which cause no clearly expressed
symptoms of occupational disease, but may have a so-called diffused general ef-
fect on the organism.
Animal experiments are conducted to define more accurately the character
of a disease, peculiarities of its course and dates of its origin. Micro-pathol-
ogy of pulmonary tissue and of lymph node and weight change records are used as
indicators in studying the effect of different aerosols. In some cases conditioned
reflexes, gas metabolism, condition of individual organs and systems, such as the
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-------
functions of respiration, blood circulation, etc. are studied specifically. A
single intratracheal introduction to white rats of 50 mg of dust suspension in
physiological solution, followed by examinations of pulmonar.y and lymph node
preparations at different intervals is used extensively, and has become an almost
standard procedure. This method permits making a comparative evaluation of bio-
logical activity of some dust varieties, containing silicon dioxide (dust of var-
ious ores, silicates, abrasives, etc.). However: it should be pointed out, that
the use of a single intratracheal injection of dust suspension is not always ex-
pedient, particularly in studying dusts of weak biological activity.
Large dust
doses have a marked mechanical, sometimes acute effect, unlike the chronic ef-
fect of dust on humans. Studies should not be limited to morphological changes
characteristic of diseases in their later stages. It is necessary to develop
physiological, biochemical and immunological investigation procedures. These
investigations should aid in disclosing early symptoms of aerosol effect and
serve as more positive bases for the determination of new maximum permissible
concentration levelso
Bibliography.
11 cae R H... c., C M e JI !! H C K H ii 3 5, X 0 II, 51 HOB JI. K. H .1I.p. fHr. TpYJla H
IIpUljJ. 3aro.~(,BaHHH. (<)57. N~ 4, CTp. 1-(I.-n JI a K x H HAC. Tp. HaY'IHO-TeXHH'IeCKOH
cerellH MoeKoBeK. OTJI.. Beee. HaY'IHO-HHaiE'HepHOro TeXHWfeeKoro OO-Ba JlHTeiiWHKOB no
T€'XII. 6£'3on. H OXpaHE' TpY.lla B JlHTellHoM npOll3fJO.lleTlJe. M., 1953, CTp. 13-46.-P II 3 a-
He IJ . B. A. CaHHTapHaH oxpaHa anlOeljJepHoro B03.llyxa. M., 1954. - C Me JI 51 H.
( /( II H 1. r; fHr. TpY.lla H npo. 3aO(),1eRilflllll, 1957, No 5. eTp. 55-57.- To p-
C Kiln n H. 'Of Hr. II eaM., 1<)51, N~ B, CTf]. 33-34. - <1> H r y p 0 B C K H H H. A. Ce.llIlMeH-
TOMeTI'H'Ir~'''Hli
-------
Present-Day Status and Future Problems in Sanitary Protection of
Community Atmospheric Air in the U.S.S.R.
Yu. D. Lebedevo
(U.S.S.R. State Sanitary Inspeotion, Moscow).
Gigiena i Sanitariya, Vol. 25, No.1, 5-11, 1960.
In fulfillment of the resolutions adopted at the XXI Conference of the
I.P.S.S. (Communist Party of the Soviet Union) means are now being instituted
for the gasification of cities and workersl villages, for the electrification
of railway transportation, etc. For the past ten years large scale sanitization
.means have been introduced throughout the land, and the functions of the state
s~~nitary control organizations have been broadened and their authority reinforced.
Such organizations are now keeping careful watch over the protection of atmos-
pheric air purity, development of scientific research in that field, determina-
tion of appropriate limits of allowable air pollutant concentrations, and methods
and devices for the purification of industrial discharges before their emission
into the atmospheric air.
In this connection particular attention has been given
to sources of air pollution and their effect on the health of workers, children,
and general population. Among organizations participating in such work are re-
search institutes of hygiene, sanitation, clinical medicine and regional sanitary-
epidemiological stations, etc. Morbidity studies among populations related to
industrial atmospheric air pollution are now being conducted in 40 cities and
workers I villages. Results of correlated statistical studies clearly point to
the etiological connection between certain types of morbidity and industrial and
other atmospheric air pollution. Morbidity studies must constitute a mandatory
part of any investigative and corrective system of atmospheric air protection.
Such studies should be participated in by local and regional hospitals and clin-
ics and the results should be verified and analyzed by appropriate statistical
analysis. Such a method of morbidity study has proved its value in health in-
vestigations conducted in heavily industrially and otherwise heavily air pol-
luted areas.
For instance, a study was made of general morbidity, types of diseases of
a population residing in a region where the aluminum chloride department of a
metallurgical plant emitted into the air pollutants containing components dele-
terious to human and animal healtho
A medical survey of the population and a
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statistical investigation of clinical histories kept in the files of the region-
al clinic indicated that the population morbidity was considerably higher when
the plant was operating; this was particularly true of conjunctivitis, acute in-
flammat~ry processes of the upper respiratory tract, tracheobronchitis, bronchi-
tis, etc. Results of such investigations place in the hands of appropriate au-
thorities scientifio data on the basis of whioh requirements can be formulated
for the correction of the local unsanitary conditions by plant management and
regional sanitary authorities. During the last ten years atmospheric air has
been investigated for the oontent of cancerogenic hydrocarbons of the 3,4-benz-
pyrene type caused by industrial discharges and automotive vehicles exhaust gases.
The presence in the air of such substances and the rise in cancer morbidity among
urban residents gave rise to a number of urgent sanitary hygienic problems.
The urgency of the fight against oancer was first discussed in June of 1956
at the All-Union Conference of Hygienists, Epidemiologists, Microbiologists and
Infectionists. In December of the same year the All-Union Conference was held
on problems related to cancerogenic substances prevailing in the surrounding en-
vironment; the discussion was centered mostly on means to be used in the fight
against cancer. It was mentioned that U.S.S.R., as well as foreign investigators,
as a result of their studies, felt that there existed a connection between the
presence of cancerogenic substances in industrially polluted air and the increase
in frequency of cancer occurrence among urban populations. As a result of such
findings the State Sanitary Inspection of the U.S.S.R. organized a committee in
March of 1957 which was endowed with the responsibility to investigate the pres-
ence of cancerogenic substances in the external environment and to study means
of combatting same. The committee was assigned the task of coordinating such
work by engaging the planned cooperation of pertinent scientifio eduoational
institutions, industrial research laboratories, etc. It is to be regretted that
even as of this date, many authorities and scientists fail to recognize the im-
portance of this hygienic problem. It is suggested that immediate priority be
given the following studies: a broad investigation of cancer morbidity among
inhabitants of industrial cities and towns; a parallel study of the degree of
air pollution of such looalities with 3,4-benzpyrene and other cancerogenio
substances; a determination of sources at which oancerogenic air pollutants
originated, such as industrial enterprises, autotransport, etc.; development of
cancer preventing means and methods.
-310-
-------
The problem of sanitar,y protection of atmospheric air against pollution in
the U.S.S.R. is closely bound with some economic problems of national importance
Lack of means for the proper purification of certain industrial emissions before
they are thrown into the atmospheric air results in tremendous losses of certain
valuable substances in the form of waste products. For example, it has been
estimated that the cement industry lost 16 - 20% of its production with the
emission gase$; it should be added that the lost cement oonsists mostly of the
most finely ground and, therefore, most valuable part of the cement.
Air po11u-
tion and great national economic losses are also caused by the fact that many
of the gas purifying dust catching installations are inefficiently operated, as,
for instance, in the Riga Superphosphate Plant. "Maardu" Chemical Combine, Ster-
litamask Soda-Cement Combine, Slavseda and Donsoda combines, the Volkhovsk Alu-
minum Plant, etc. The inspection office of the Technical Supervision over the
Operation and Correct Utilization of Gas Purifying Installations inspected 2000
gas purifying installations in 540 enterprises of different industrial branches,
On the basis of the inspection results and taking into consideration that there
existed 2000 enterprises which had gas purifying installations, an estimate was
made of the technical condition of the gas purifying installations and of the
grand total of valuable materials lost due to inefficient operation of gas puri-
fying equipment. Greatest offenders in this respect were the cement, the non-
ferrous metallurgical, and the chemical industries, the Sverdlovsk, Kemerov,
Gor'kii, Stalin, Krasnoyarsk and several other sovnarkhozes (Soviet communal
enterprises). Organizations of the State Sanitary Supervision and research
sanitary-hygienic institutes have been devoting much of their efforts to the
control of means and methods used in the sanitary-protection of atmospheric air.
In this connection they have urged that future scientific investigations in the
field of air pollution abatement and prevention be regarded as one of the prac-
tical and basic means of attaining and maintaining air purity. They also urged
that greater emphasis be placed on the determination of limits of allowable con-
centrations of air pollutants, on the development of more sensitive and more
specific means for the qualitative and quantitative determination of poisonous
substances in the air, on the broader application of toxicological and pharma-
cological studies of all types of air pollutants, on the effect of atmospheric
air pollutants on health of populations and general living conditions, includ-
ing the effect on animal and plant life, and on monuments and other esthetic
and decorative objects; particular stress is laid on broader and more inclusive
-311-
-------
checking and evaluating and re-evaluating the effectiveness of existing and
of proposed means for the protection of atmospherio and indoor air.
As of this d~ limits of allowable air pollutant concentrations have been
established for over 30 toxic substances; this attainment has substantially im-
proved the sanitary condition of community air in previously badly polluted lo-
calities, but also accumulated a vast store of practical and theoretioal ex-
perience which can now be applied with ever greater expediency to the improve-
ment of indoor and outdoor air sanitation in the future. Proposed limits of
allowable air concentrations are presented to the Office of the State Sanitary
Inspection where they are discussed and finally incorporated as mandatory
regulations into the National Sanitary Code, which means that all Union produc-
tion industries, their branches and plants must comply with such regulations.
As new types of finished products are being manufactured, such as organo-
synthetic products, new air pollutant and new toxic waste products develop which
necessitate new sanitary, toxicological and general pharmacological investiga-
tions, new determinations of limits of allowable concentrations, and new equip-
ment and installations for their removal from the final discharge gases or ven-
tilation air. Then, there is the problem of determining limits of allowable con-
centration of toxic substances when two or more such pollutants are present in
the air; in such cases either synergism or antagonism come into pl~, or possibly
both, to some extent. The solution of air pollution problems of this type pre-
sents many difficulties and calls for the cooperation of the physical chemist,
pharmacologist-toxicologist, chemical analyst and sanitary hygienist. There are
also air pollution problems which baffle the physician-sanitary-hygienist (in-
dustrial physician in the U.S.A. B.S.L.). One such problem is presented by
oxides of nitrogen as air pollutants. Previous studies indicated that between
5 - 10 tons of oxides of nitrogen had been discharged daily by a given industrial
plant and that population complaints were frequent, persistent and seriousJ de-
spite that laboratory studies failed to find actual pathologic conditions which
might indicate any need for extreme and stringent demands for a lowered nitrogen
oxides concentration in the air.
This m~ be due to imperfection of the meth-
ods used in determining the limit of allowable nitrogen oxides concentration
in community and indoor air. Consideration must also be given the fact that 0%-
ides of nitrogen, as a rule, occur simultaneously with sulfuric anhydride (503)
and sulfuric acid aerosol.
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Data obtained for limits of allowable community air pollutants can and
should be used in efforts to determine the degree of purification industrial
waste gases must undergo before they are discharged into the atmospheric air.
Computation formulas should be derived which the sanitary personnel of any
pertinent establishment could use for the practical determination of degree of
gas purity at any phase of industrial production, or at any time or rate (in-
tensity) of production. Studies must be intensified also along the lines of
air pollution with radioactive substances; unfortunately this phase of air
pollution has received insufficient attention on the part of air pollution
scientists. (To ~ knowledge this is not true; such studies have been conducted
mostly by classified agencies and to some degree by general scientists, but the
results have been designated as classified. B.S.L.).
Increase in state sanitary control over the purity of community atmospheric
air development of the science of hygiene in this field stimulated a rise of work
in developing technical means for the purification of industrial emissions into
the atmospherio air. Thus, in 1949 thirteen research projects related to the
purification of industrial emissions discharged into the atmospheric air were
studied in 5 institutes; in 1950 - 1951 projects of such character were under
study in 66 institutes affiliated with such industries as the non-ferrous met-
allurgical, machine building, construction material processing, chemical and
similar industries. Despite that, progress along the development of methods
for the purification 6f discharge gases from oxides of nitrogen and hydrogen
sulfide in plants producing artificial fibers (meaning the synthetic products
industries, B.S.L.) has been far from satisfactory. From the viewpoint of
production the supp~ fell lamentably short of the demand and from the view-
point of information seeking, scientific institutions failed to provide timely,
numerically sufficient and at times scientifically or practically adequate
replies to inquiries. As of this date 15% of the inquiries still remain un-
answered. Scientific research institutes have developed many methods (in-
cluding equipment, installations and procedures) for the purification of dis-
charge gases fram oxides of nitrogen, hydrogen sulfide and carbon bisulfide
in plants producing artificial fibers, for the purification of gases of blast
furnaces and boiler operated plants of 500 - 1900 tonE of steam per hour capac-
ity, for the purification of metallurgical industry gases emitted by new proo-
esses, and for gas purifioation in a variety of other industries. However, the
problem of complete automation of gas purif.ying installations remains unsolved.
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New methods of industry management opened up possibilities for governmental
sanitary agenoies to inspect and control oonditions, means and facilities in the
protection of atmospheric air against industrial pollution. Such inspection,
supervisory and corrective experience has been growing in depth and extent. Ac-
cumulation of such experience over the past 10 - 15 years is now being applied
by the All-State and other national and regional planning organizations in the
preparation of plans for the construction of new and rebuilding old industrial
production plants. It is now possible to incorporate into new construction
plans provisions for sanitary-hygienic purifying installations, ventilation
facilities and other types of sanitizing equipment. This in essence is the
principle of prophylaxis, and upon such a principle all scientific researoh
pertaining to sanitation and hygiene, especially in the realm of air pollution
prevention, should be organized and conducted. This should also be the guiding
principle of sanitary inspectors, supervisors and similar authoritative personnel,
whether All-Union or regional. The industrial sanitary-hygienic physician should
consult statistical morbidity data wherever available on a current basis, so that
upon the suspicion of unfavorable trends, preventive means and measures could be
instituted at the earliest possible moment; wherever such statistical informa-
tion is not available the physician should by his own effort secure same. Suoh
a procedure is the very core of preventive industrial medicine, hygiene and
sanitation.
With the above viewpoint as the basic principle, the Office of the State
Sanitary Inspection of the U.S.S.R. cooperated with the U.S.S.R. Gosplan (State
planning) in preparing plans for future development and realization of the
Seven-Year-Plan. This viewpoint also constituted the basic guiding principle
of work conducted by State Sanitary Inspection bodies of the R.S.F.S.R. (Russian
Socialist Federated Soviet Republio, which was the original nucleus of the pres-
ent U.S.S.R., and the entity of which had been retained for reasons of political
and economic dominance, B.S.L.), the Ukrainian, Kazakh, Lithuania~, and other
Socialist Soviet Republics, which participated in the preparation of state plans
of various Soviet republics, and which developed means for the abatement of at-
mospheric air pollution. As a result, air dust intensity has been reduced and
atmospheric air pollution has been notably abated in the cities of Moscow,
Saratove, Gor'kii, Baku, Kashir and other industrial cities.
Future developments in the line of sanitary protection of atmospheric air
depend to a large extent upon the organizational intensification of the work of
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supervising and inspection governmental bodies, and incorporation and intensifi-
cation of regional sanitary-epidemiological station activities in the field of
atmospheric air pollution control. The time is now ripe for a revision of the
methodological specifications for the study of community air pollution. Now is
the time to end the old controversy which began in 1938, namely, what method
should be preferred, the aspiration or the sedimentation. All data on limits
of allowable community and indoor air pollutants have been cbtained by the as-
piration method and expressed in terms of weight units per unit of air volume;
for this reason alone, if for no other, the aspiration method of air sample
collecting should become the standard official one.
The resolutions adopted at the XXI Congress of the K.P.S,S. (Communist
) Party of the Soviet Union) regarding "The Key Figures for the Development of
the U.S.S.R. National Economy for the Period of 1959 - 1965" provided for further
expansion of atmospheric air protection based on the expectation that progress
will be made in the technology of different types of industrial production, tech-
nical and technological means of gas emission purification, general industrial
automation, high specialization and cooperation among different national in-
dustries. New types of production, manufacture and processing which came into
being as a result of experimental research and semi-practical tests have brought
with them heretofore unknown sanitary-hygienic problems which required immediate
solution from the viewpoint of atmospheric air pollution with new types of toxic
raw materials and waste products. In this way research scientists, sanitarians
and industrial physicians have been faced with urgent and challenging demands
which, it is hoped, they will be able to meet within a reasonably short time.
Improvement in production technology obviating the emission of dele-
terious substances into the atmosphere coupled with a rational solution of sani-
tary protection of atmospheric air should effect large scale economies in that,
on the one hand, many valuable raw and by-products now discharged into the air
will be conserved, and, on the other hand, initial production gases contain im-
measurably less of a waste product load, so that the cost of their purification
will fall to lower figures. Once such a state of sanitation in atmospheric air
will have been attained, it will be possible to turn the present sanitary clear-
ance zones into special types of residential areas. In this connection it should
be borne in mind that many production plants and combines are not surrounded by
any type of sanitary clearance zones, and that residents in the proximity of such
plants and combines are frequently exposed to the harmful effect of the industrial
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discharges. Improvement in production and processing teohnologies, by lessening
the amount of gas or ventilation air contained pollutants, will reduce the ex-
tent of community air pollution to the limits of allowable concentrations, and
in some instances even below suoh limits.
During the May 1958 Plenum of the Central Committee of the Communist Party
of the Soviet Union it has been resolved that greatest emphasis should be placed
on the development of the chemical industry. The first impetus of this will be
felt in the production of polymer materials, the use of raw materials and semi-
processed products applicable to such production. A search will be instituted
for cheaper and more easily available usable raw materials, such as crude oil
gases (natural gas), gases eliminated during crude oil processing, products of
the coke-chemical industry, gases from the turf and shale industries, waste
products created by the lignine plant processing and agricultural by- and waste
products. The manufacture of artificial and synthetic fibers, plastic masses,
synthetic resins, synthetic rubber, synthetic alcohols, and the like is accom-
panied by the oreation or emission of substances possessing toxic properties.
At practically every stage of such materials production large quantities of
gases, vapors and dust are eliminated which are being thrown into the atmospheric
air via the ventilation systems. In this connection the following will be among
the problems which will urgently require solutions during the next "semiletka"
(seven-year economic progress plan): a study of new technological processes on
an experimental semi-industrial scale; the effect of complex mixtures of new
pollutants discharged into the atmosphere by the modern type of production and
manufacturing plants on the health of populations and on general living condi-
e
tions; expanding and extending scientific research for the determination of limits
of allowable concentrations of the new pollutants; determination of widths of
sanitary clearance zones surrounding the new types of production plants and com-
bines; determination of
given earliest possible
year economic plan).
Sanitary-hygienic studies and development of sanitary-hygienic standards
should not only be in step with progress made in general industry, they should
in fact, run a few steps ahead of industrial developments, and, so to speak,
anticipate the sanitary-hygienic needs of the steadily progressing industrial
developments. The fact is that all necessary conditions for such action on the
part of the researoh investigators are in existence, most basic among which are
smokestack heights; etc. All such problems should be
priority in the oourse of the current "semiletka" (seven-
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experimental semi-industrial installations of a great variety. It is noted
with regret that sanitary-epidemiological stations have participated in such
advanced scientific industrial studies only to a slight degree, despite the
recognition that only through the participation of such stations on the broad-
est possible scale can such scientific studies attain the wide application
essential to success under the anticipat'ed "semiletka" conditions. The public
health ministries of the individual Soviet republics should endeavor without
delay to expand the activities and responsibilities of the regional sanitary-
epidemiological stations, enlarge their laboratories, equip them with all nec-
essary modern apparatus (and library facilities) and staff them with well-trained
competent technicians and technologists.
In connection with what has been stated and outlined above the following
initial steps should be instituted without del~:
a) Speed up the development and production of means, methods and installa-
tions for the purification of gases and other industrial emissions so as to meet
the rising demand for such equipment by the newly constructed industrial produc-
tion plants as a step toward preventing the air from becoming polluted at the
very outset;
b) Improve the efficiency in the utilization of gas and air purifying in-
stallations by instituting a strict inspection and supervision system of the
condition of installations, and the duty performance by the operating personnel;
c) Effort should be unsparingly exerted in the direction of increasing the
tempo of scientific research and of the practical utilization of results at-
tained.
No effort should be spared to keep scientific research several steps
in advance of actual industrial developments.
State sanitary inspection organizations on their part should concentrate
their time and activities on problems related to the location of new and re-
construction and possibly relocation of old industrial production and manufactur-
ing enterprises; they must increase strict enforcement of existing sanitary-
hygienic regulations prescribed by the sanitary code adopted for the purpose of
liquidating community air pollution; they must cooperate with sanitary authori-
ties of individual republics, regions and sovnarkhozes (soviet peoples economic
bOdies) in planning means for the protection of atmospheric air, and see that
such plans were in accord with the state sanitary code for the protection of at-
mospheric air; they should keep careful records of their experiences in the realm
of air pollution abatement, so that such records may be of use and value in plan-
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ning sanitary means of air protection at some future time. In order that dif-
ferent educational institutions may effectively cooperate in the work of pre-
venting community air pollution by the newly arising types of production,
manufacture and processing, the Office of the State Sanitary Inspector of the
U.S.S.R. should help such institutions to acquire an adequate amount of modern
apparatus and equipment needed for air pollution research in any specific phase
of study.
Proposals for methods and procedures, as well as for development of equip-
ment, apparatus and installations connected with air protection against pollu-
tion, should be approved by the special Committee on Air Sanitation mentioned
in one of the preceeding paragraphs.
Sanitary Protection of Atmospheric Air in Poland.
Ya. YUste
Gigiena i Sanitariya, Vol. 25, No.1, 84-85, 1960.
Problems related to the sanitary protection
insufficiently investigated in Poland, and means
lution are still in the stage of organization.
protection of atmospheric air has been under the
of atmospheric air have been
for the protection
Supervision over the
jurisdiction of the
of air pol-
sanitar,y
Office of
the Chief Sanitary Inspector, Ministry of Public Health, and controlling agencies
were assigned to sanitary-epidemiological stations. Actual systematic inspec-
tion and investigation has not been undertaken as of the present, except in
response to local complaints presented by a village or a city section where air
pollution became intolerable, and in instances where choice had to be made for
the location of a new village. In such cases the method of Owens (see U.S.S.R.
Literature Survey, Vol. 3, Department of Commerce, O.T.S. No. 60-21475) has been
used in connection with the sedimentation method, including 502 and occasionally
F determinations. No regulation requiring determination of limits of allowable
air pollutant concentrations and no methods to eliminate air pollution are in
existence in Poland at present. The Polish Ministry of Public Health is now
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considering the formulation of such a sanitary regulation.
In view of the fact
that Polish authorities had no experience with methods for the determination of
effective combat against air pollution, they centered their attention on the
appropriate localization of newly arising industrial enterprises. New plants,
and some old ones, are being equipped with dust-catching installations, but
gas purifying installations are still rare. Only few sanitary scientific in-
vestigations have been conducted in the field of atmospheric air. Studies in
the field of finding connection between the state of the population's health
and air pollutiop are still in the initial developmental stages in Poland. The
Polish Ministry of Public Health receives reports from different sections of
the country where metallurgical industrial plants prevail; such reports indicate
that the state of health of children living in close proximity to metallurgical
plants has been worsening steadily.
regards air pollution as the primary,
deterioration of children's health.
The problem of automotive exhaust gas on the organism has received atten-
tion prior to the last war, and it was natural that no exhaust gas concentra-
The Institute of Motherhood and Childhood
if not the only important factor in such
tions deleterious to human health should have been found in the air at that
time. The Presidium of Acade~ of Sciences appointed a special Commission whose
responsibility it was to organize studies of atmospheric air pollution and means
for combatting same. This work has been conducted by medical organizations and
institutes in cooperation with the Central Institute of Labor Protection, the
Department of Heat Technique of the Mining Acade~, the Institute of Non-Ferrous
Metals, etc. Consultation connected with problems of the sanitary protection
of atmospheric air has been assigned to different planning organizations and to
institutes associated with certain branches of different industries. Significant
systematic studies of atmospheric air pollution are now being conducted at only
two points, namely, at the Katovits region and in Warsaw. Such studies are con-
ducted at the Katovits region by the Geographic Institute of Yagellonsk Univer-
sity in Krakow in cooperation with the State Hydro-Meteorological Institute which
has been investigating the climatologic characteristics of the Gorno-Silezsk
industrial region known by the initials as GPO (a mining district), and by the
Department of Climatology of Vrotslavsk University in cooperation with the Labo-
ratory of Climatology of the Geographic Institute, Polish Acade~ of Science;
studies are centered on the determination of atmospheric air dust pollution and
intensity of solar radiation in the territory of GPO. The Institute of Labor
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Medicine in Rokitnits has been studying GPO atmospheric air pollution with 302'
In addition the Regional Sanitary-Epidemiological Station of Katovits city has
initiated a general sanitary-epidemiological investigation. Studies made thus
far by the method of Owens indicated that maximal dust intensity in some regions
was 4,000 particulates per ml, with an average of 2,853 particulates per ml
during the months of January and June. Results of sedimentation tests made
of the GPO air were as follows: maxima ranging between 12.0 - 17.1 t/km2/24 hrs.,
and averages of approximately 11 t/km2/24 hrs.; however, in some regions only
105 t/km2/24 hrs. were found. 302 concentration in the air of GPO ranged be-
tween 0.025 - 1.206 mg/m3, rising on occasion to 5.45 mg/m3. Intensity of solar
radiation in regions of highest air dust concentration was reduced by 30 - 37%.
Warsaw air has been investigated by the Department of Community Hygiene of
the State Institute of Hygiene. The purpose of such investigation has been the
determination of boiler-operated heat and power electric stations discharges on
the sanitary condition of the cityts atmospheric air.
In June of 1957 a seminar
was conducted at the State Institute of Hygiene located in Warsaw in which sani-
tarians and other pertinent workers participated; the purpose of the seminar
was to convery information and stimulate attempts to place the work of atmos-
pheric air pollution protection on a broader basis.
The problem of sanitary atmospheric air protection should be approached
the same as any other important social problem from the viewpoint of health and
national economy.
In this connection attention is called to the following urgent
sanitary-hygienic problems related to the protection of air pollution:
a) Data should be obtained to show the extent of loss to national economy
caused by inappropriate fuel combustion, discharge into the atmospheric air of
valuable raw products and similar phases;
b) Determine the mechanism of deleterious effect of air pollution in any
given territory in relation to predominating meteorological conditions;
c) Establish limits of allowable concentrations of deleterious substances
in atmospheric air;
d) Institute appropriate and mandatory regulations for the control of newly
constructed villages and different industrial production plants;
e) Exert pressure in the direction of purifying equipment installation in
newly erected industrial production plants. Sanitary-epidemiological authorities
should insist that provision be made for purifying dust and gas equipment in the
preliminary and final plans made for such plants;
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f) Institute systematic check of the sanitary condition of atmospheric air
using a standardized procedure;
g) Initiate systematic investigation of the deleterious air pollution ef-
fect on human health, and develop means for its elimination which would simul-
taneously and automatically protect the air against pollution.
Third All-Union Conference on Methods for Air Dust Pollution Studies.
P. N. Torskii.
Gigiena i Sanitariya, Vol. 25, No.2, 95-96, 19600
On May 19 - 21, 1959, a Conference was held in the Institute of Labor Hygiene
and Occupational Diseases of the U.S.S.R. Academy of Medical Sciences on research
methods for air dust pollution; the Conference was organized by the Silicosis
Prevention Commission of the U.S.S.R. Academy of Sciences. Ninety specialists
of the engineering and sanitary-hygienic profession attended the Conference, at
which 20 reports were presented.
E. V. Khukhrina talked about "Methods for the Study of Air Dust Pollution
in Relation to New Data on the Hygienic Significance of Pollutants Concentra-
tions". She enumerated the following basic requisites:
a) Dust control must be aimed to determine the dust mass which affected the
organism and to establish weight indexes for its concentration in the air;
b) Collection of air samples must be conducted to enable the simultaneous
determination of average and highest concentrations even in cases where their
effect was of short duration;
c) The picture of fractional particulate dispersion should take into ac-
count differential gravimetric values;
d) Parallel with the above, studies should be made of the physico-chemical
properties of dust, its electrical characteristics and biological effects.
The Conferees manifested considerable interest in the presentation of A. I.
Frank of the Institute for Labor Hygiene and Occupational Diseases, A.M.N.,
U.S.S.R., who recommended that in making gravimetric dust determinations filter
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cloth trade-marked FPP-15 be used. Experiments confirmed that this cloth pos-
sessed many advantages: low pressure drop and high filtration efficien9Y,
high dust retention capacity, non-hygroscopicity; light weight which was of
value in weighing small quantities of dust with a high degree of accuracy.
Prof. Ya. B. Reznik of the Odessa Institute of Medicine in his report entitled,
"Determination of Air Dust by the Use of Membrane Filters", demonstrated that
it was possible to introduce the membrane filter into the study of air dust
under practical conditions.
Parallel with reports presented on improvements made in existing devices,
such as the VDK ultramicroscope, the field meter for ultramicroscopy in aerosols,
designed by the Leningrad Institute of Labor Hygiene and Occupational Diseases,
(LIGTPZ), G. Y. Vlasenko and G. S. Berezhyk described new devices which were in
the process of completion and final testing in their application in mines. The
following devices were mentioned as examples:
A device for the visual determination of low coal dust concentrations in
mines, IMP-I, developed by the Makeev Institute of Scientific Research (MakNII)
and the Institute of Hypercoalautomatization and presented by V. T. Malikov
(MakNII); a solar-reflectoscopic device for the determination of settled coal
dust thickness (POTOP-3), developed by MakNII and reported on by M. D. Krivitskii;
an electrostatic preoipitator designed by the Mining Institute of the Kazakh
S.S.R. Aoademy of Sciences and reported on by M. 10 Volokhov.
Many devices required construotional improvement and adaptation for use
under coal mine conditions; among such were:
an acoustical dust gauge, de-
veloped by the Central Laboratory of Scientifio Research Gostekhnadzor R.S.F.S.R.
and reported on by S. S. Anisimov; an automatic dust collector for deteoting
air dust by the gravimetric method, developed by the Mining and Metallurgical
Institute of the Armenian Sovnarkhoz and reported on by A. N. Zhamkochyan; a
device for the rapid collection of dust samples, essential to the determina-
tion of degree of dust dispersion (electrostatic dust precipitator), developed
by the Khar'kov Institute of Labor Hygiene and Occupational Diseases, based
on the utilization of charges in dust particles and reported on by A. I. Kos-
enko; a device for the determination of concentrations and electrioal charges
of dust by the ultramicroscopic method, developed by the Khar'kov Institute
of Labor Hygiene and Occupational Diseases and reported on by A. I, Kosenko.
Mention should be made of the portable micro-projection camera AN, U.S.S.R.
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reported on by V. I. Uskov, a description of which was published earlier. V. V.
Kudryashev, in his report entitled, "Concerning Indireot Methods of Dust Con-
trol", analyzed oauses of errors made in utilizing visual methods in aerosol
studies in mines. P. N. Torskii, in his report entitled, "Concerning Methods
and Apparatus Employed in Dust Control in Czeohoslovakia", cited facts col-
leoted during a trip to Czechoslovakia by a group of Soviet specialists to
study and exchange experiences in the fight against mine dust. A. Io Frank of
the Institute of Labor Hygiene and Occupational Diseases, A.M.N., U.S.S.R. in
his reported entitled, "Determination of the Composition of Dispersed Dust by
Microgravity Sedimentation Analysis", proposed the utilization of sensitive
quartz spirals for micro-weighing in connection with the analytical computa-
tion method developed by N. N. Tsyurup. The report by N. I. Smetanin of the
Tashkent Institute of Medicine entitled, "Device for the Determination of Dust
Dispersion Based on Fractional Weight", called for the use of a device found
of little practical value. V. V. Skobunov presented a report entitled, "Con-
cerning the Method of Gas Dust Control in the Mining Shafts"; he based his
method on a theoretical assumption regarding gas and dust distribution by ven-
tilation currents.
The Conference noted that since the 1953 (Second) Conference on Dust Con-
trol Methods, considerable progress has been made in the development and con-
structionof new dust determining devices and in the study of new types of
filtering materials. However, during these years only one device, the AER,
of the many demonstrated at the Conference in 1953, had received wide practical
application. Very little attention has been paid to the study of physico-
chemical characteristics of dust, which delayed considerably the development
and acceptances of the new dust measuring apparatus.
Reports were discussed at considerable length after which the Conference
resolved to pursue the following essential aims:
10
To direct attention of practical workers in dust creating occupations
and in sanitary-epidemiological institutions engaged in designing and making
dust-measuring apparatus and in developing methods for dust control, to the
importance of solving these problems in accordance with the specifications
formulated by E. V. Khukhrina in her report.
2. To apply greater effort to the development of rapid methods for the
determination of dust intensity and to the development of methods and apparatus
for remote and automatic dust intensity determinations.
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3. To institute systems of comparative evaluation of the practicability
and efficiency of the following: a) cloth filters FPP-15; b) membrane filters;
c) device for the determination of small coal dust concentrations (MakNII); d)
radiation-reflecting device for measuring the thickness of settled coal dust
(POTOP-3, MakNII); e) portable counter for ultramicroscopic aerosol measuring
(LIGTPZ); f) ultramicroscope VDK; g) photoelectrocolorimeter IGD AN, U.S.S.R.;
h) automatic dust catcher of the Armenian Sovnarkhoz; i) device for the deter-
mination of dust concentration designed by the Khar8kov Institute of Labor Hy-
giene and Occupational Diseases; j) electrostatic precipitator IGD AN of the
Kazakh S.S.R.; k) electroconimeter EK-4 IGD AN of the Kazakh S.S.R.
4. To create a special committee headed by E. V. Khukhrina who would be
responsible for the realization of the above objectives during the first quarter
of 1960. Headquarters of the Committee shall be in the Institute of Labor Hy-
giene and Occupational Diseases of the U.S.S.R. Academy of Medical Sciences.
5. To expedite the development of the newly proposed methods for weighing
dust samples collected by filters made of FPP-15, proposed by the Institute of
Labor Hygiene and Occupational Diseases, and by membrane filters as proposed by
the Odessa Institute of Medicine, with a view to applying such methods to the
microgravimetric and dispersometric methods of dust determinations. Hopes were
expressed for the possible use of material FPP-15 under practical conditions.
6.
To note with interest the initiative of institutes which volunteered
to undertake the development of rapid methods for the determination of air dust
intensity and of equipment required for the purpose; to recommend that the
above mentioned equipment and apparatus be modified, so as to increase their
sensitivity and precision, and to establish the effects of humidity and aerosols
which develop during the work with spray devices on the composition of dispersed
dust.
7. To regard as imperative, in evaluating hygienic working conditions and
the effectiveness of sanitary-technical measures, the adherence to the recom-
mendations stipulated in the "Provisional Directives for Methods in Collecting
Air Dust Samples", by the Committee on Fight Against Silicosis affiliated with
the Academy of Sciences, U.S.S.R.
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Third All-Union Conference on Sanitary Protection of Atmospheric Air.
Lo F. Glebova and S. I. Murovannaya.
Gigiena i Sanitariya, Vol. 25, No.1, 101-109, 1960.
The Third All-Union Conference on problems of the sanitary protection of
atmospheric air was held in Kiev, May 26 - 30, 1959. It was called qy the A. N.
Sysin Institute of General and Community Hygiene, A.M.N., U.S.S.R., by the
Ukrainian Institute of General Hygiene of the Ukrainian S.S.R. Ministry of
Health, and by the Committee on the Sanitary Protection of Atmospheric Air of
the U.S.S.R., representing the State Sanitary Inspectorate. Approximately 250
delegates attended the Conference, representing 14 Union republics, workers of
institutes of scientific research and sanitary hygiene, professors of hygiene
in medical institutes, workers of sanitary-epidemiological stations, of technical
planning and scientific research institutes, of factories, sovnarkhozea, of the
Ukrainian S.S.R. Gosplan, and of many other organizations.
The Conference was opened by Profo N. N. Litvinov, Director of the A. N.
Sysin Institute of General and Community Hygiene, A.M.N., U.S.S.R. Sixty-two
reports were presented covering the most important questions of the day. Lively
discussions by 400 participants of the Conference followed the presentations
of the reports. A report on "The Present Condition of Atmospheric Air in Cit-
ies", was presented by Yu. D. Lebedev, Deputy Chief of the State Sanitary In-
spectorate of the U.S.S.R. The report consisted of a critical analysis of
work accomplished and outlined concretely the needs of future scientific re-
search, the problems of practical and effective measures required for the pro-
tection of atmospheric air raised by the vast growth of production in existing
industrial establishments and by development of new industrial areas in the
U.S.S.R.
Prof~ D. N. Kalyuzhnii, Director of the Ukrainian Scientific-Research In-
stitute of Community Hygiene, summarized the principal results attained in the
field of atmospheric air hygiene in the Ukraine and outlined the next perspec-
tive for scientific research in that field. Prof. V. A. Ryazanov, Chairman of
the Committee on Sanitary Protection of Atmospheric Air, affiliated with the
State Sanitary Inspectorate of the U.S.S.R., reported on future plans for sci-
entific research into the protection of atmospheric air from newly created in-
dustrial emissions. He stated that the most important present problem concerned
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the universal broadening of research in hygienic standardization of atmospheric
pollutants as individual ingredients and as co-existing factors. The high
tempo development of industry, and especially of the synthetic chemical in-
dustry, necessitated an intensified rate of endeavor in this field. M. S.
Gol'dberg and L. F. Glebova, Candidates for Medical Sciences, presented a
report entitled, liThe Hygienic Reason for Sanitary-Protective Zones Between
Industrial Enterprises and Residential Areas", and suggested a plan for a new
sanitary classification of industries and of sanitary-protective zones, based
on an analysis of research materials collected during a study of atmospheric
air pollution in cities and workers' settlements in areas allocated to indus-
trial production, manufacturing and processing.
M. F. Skatchko, Manager of trust "Gazoochistka" (Gas purification) reported
on the present state of purification of industrial discharges which polluted
the atmospheric airo
He noted that a considerable amount of work had been con-
ducted through the years 1955 - 1958, along the lines of planning, assembling
and technical assistance, in the field of gas purification. Since 1959, 66
departments of institutes have been working on 199 assigned projects in the
field of gas purification; the Institute "Giprogazoochistka" (Gas hyperpurifica-
tion) has developed many gas purification projects for dust-catching devices.
However, the techniques of gas purification and dust collecting were still far
behind the growing demands of industry. Prof. A. I. Pakhomychev and his col-
laborators, E. A. Sarkisyansk and I. K. Atyakina, reported on the results of
their study on the organism's reaction to the effects of small concentrations
of toxic substances.
Many reports were devoted to the problems of determining
limits of allowable concentrations of to~ic substances in atmospheric air.
Chao Chen-Ii and B. A. Gofmekler of the Department of Municipal Hygiene of the
Central Institute of Post-Graduate Medicine reported on their experimental
findings in the determination of limits of allowable concentrations of methanol
and acetates in atmospheric air; A. V. Mnat, sakanyan Senior Scientific Asso-
ciate of the Armenian Institute of Epidemiology and Hygiene reported on con-
centrations of chloroprene; R. S. Gildenskjold, Scientific Associate of the
F. F. Erisman Moscow Scientific-Research Institute of Sanitation and Hygiene
reported on concentrations of carbon bisulfide; V. N. Kurnosov, Scientific As-
sociate at the A. N. Sysin Institute of General and Community Hygiene, A.M.N.,
U.S.S.R., reported on concentrations of mercury. Considerable interest was
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roused by the reports of K. A. Bushtueva entitled, "New Data on the Combined
Action of Sulfuric Acid Aerosol and of Sulfur Dioxide Gas"; of M. I. Gusev en-
titled, "Effect of Small Lead Concentrations in the Air on the Organism of Man
and Animals"; of A. A. Shmakov entitled, "Powder Dust of Snake Weed and of As-
bestos as Pathogenic Factors in City Air"; of M. K. Khachatryan entitled,
"Vitamin C in the Organism in Relation to Atmospheric Air Pollution by the
Emissions from Synthetic Rubber Manufacture"; of A. S. Lykova entitlted, "Con-
cerning the Toxic Effect of Oxides of Nitrogen". These reports stressed the
pathohistological, biochemical and physiological methods of research for the
determination of the harmful effect of low concentrations of toxic substances
in chronic experiments.
Considerable time was devoted to the question of the hygienic evaluation
of atmospheric air pollution in cities and industrial centers by discharges
coming from leading branches of the national industry. More than 20 reports
were devoted to this problem in relation to non-ferrous metallurgical plants
(Prof. I. S. Koryakin and co-workers, N. R. Pakhotina, A. V. Mnatsakanyan and
M. I. Nikosyan, and others); in relation to ferrous metallurgy (V. F. Dokuchaeva
and N. N. Skvortsova); in relation to the chemical industry (Z. Ya. Lindberg,
N. P. Gordynya, A. M. Ibragimov and A. N. Melkumwan, and others); in relation
to the building material industry (M. V. Kryzhanovskaya and T. K. Ignatyeva,
S. A. Davydov and collaborators, and others); in relation to cellulose-cotton
combines (K. K. Kiyamov, E. Chapkevichene and V. Songailo); and many others.
New data on atmospheric air pollution by fumes from solvents were presented
by N. F. Izmerov.
A special session was devoted to the question of atmospheric air pollu-
tion with cancerogenic substances (reports by V. S. Serebrennikov, L. M. Shabad,
Ya. M. Grushko, P. P. Dikun, N. N. Volkov and T. K. Mosolnikov, and others).
The reporters and discussants stressed the need for intensifying research to
determine the nature and sources of atmospheric cancerogenic pollutants, the
need for prophylactic measures and for attracting clinical oncologists to co-
operate in the efforts to solve this problem.
Mention should be made of reports dealing with problems of atmospheric
air pollution with exhaust gases from automotive vehicles and problems dealing
with measures for its prevention (F. I. Dubrovskaya, M. V. Alekseyeva, V. A.
Khrustaleva, I. V. Datsenko, D. P. Partsef, M. D. Garbarenko). Studies of
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atmospheric air in city main streets disclosed the presence of 3,4-benzpyrene,
high concentrations of carbon monoxide, oxides of nitrogen and in the presence
of automotive vehicles using ethylated gasoline, high lead concentrations.
Two reports were devoted to results of experimental sanitary control of at-
mospheric air in cities by Zh. L. Gabinova of Moscow and Z. Ya. Rudchik of
Stalin District, Donbass. New devices and methods for research in atmospheric
air pollution were described in reports by L. F. Kachor, E. V. Rychter and
Ya. G. Kiskho. The reports were accompanied by work demonstrations of the
apparatus.
All reports stimulated animated discussions. Hygienists and physiologists
(Prof. Babayants, Prof. Ya. M. Grushko, Prof. I. S. Kandror, Prof. L. M. Shabad,
Prof. L. I. Los, M. S. Sokolovskii, and others), engineers, representatives of
planning and economic bodies - all participated actively in the discussion.
At the closing session of the Conference a far-reaching resolution was
passed, which outlined the need for intensification of the fight for clean
atmospheric air in cities by improving the technology of production, of means
for gas purification and dust collection and by general improvement in the
domestic production technology and economw. The Conference resolved to rec-
ommend that the U.S.S.R. Ministry of Health submit to the Government a special
report on the present state of atmospheric air pollution in cities and indus-
trial centers in relation to diseases among city populations, accompanied by
suggestions of basic relief measures to be instituted without delay in the fight
against atmospheric air pollution. The Conference recognized that in deter-
mining limits of allowable concentrations of atmospheric air pollutants and in
establishing sanitary pro"Gection zones, additional experimental studies were
required, first to find a basis for limits of allowable concentrations for
each of the toxic substances emitted by industrial enterprises manufacturing
raw materials, intermediate products, materials used in the preparation of
plastics, synthetic resins and fibers, rubber, etc., and to find a formula or
method for the determination of limits of allowable concentrations of harmful
pollutants simultaneously occurring in the air. The Conference emphasized
the urgent need for extending experimental methods for the study of effect
of cancerogenic air pollutants on animals and the need for determining the
connection between frequency of cancer occurrence among a population and the
presence in the surrounding air of different concentrations of 3,4-benzpyrene
(benzo-phenanthrene) or of other cancerogenic substances.
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Resolutions were passed to intensify the fight against automotive vehicles
exhaust gases.
The Conferees recognized and emphasized the following pressing needs: 1)
to organize a systematic serialized production of gas-purifying and dust-col-
lecting apparatuses by specialized plants in quantities adequate to meet the
domestic requirements; 2) to make research studies in development of apparatuses
for the automatic control of gas concentrations emitted into the atmosphere by
industrial plants before and after purification a part of scientific institutes'
regular program; 3) to fom an inspection body within the trust "Gazoochistka"
whose duty it shall be to supervise the operation of gas-dust-collecting in-
stallations and the personnel in control of instruments for the determination
of the coefficient of effective operation of gas-cinders-dust collecting in-
stallations; 4) to organize the affiliates of the Scientific-Research Institute
for Industrial and Sanitary Purification of Gases (NIIOGAZ) in Siberia which
covers enterprises of the Ural Mountains, of Kazakhstan and of Central Asia, in
the Ukraine, which included the Transcaucasion Republics; 5) to create in one
of the country's higher technical institutes a center for the training of spe-
cialists in the field of gas purification, dust collection and waste products
recovery.
To intensify the control over the sanitary protection of atmospheric air,
the Conference requested that the U.S.S.R. Ministry of Health undertake the
following:
1) create responsible positions in air protection for sanitary
physicians in sanitary-epidemiological stations of districts planning to erect
new industrial production enterprises; 2) organize, beginning with the F. F.
Erisman Moscow Central Institute of Post-Graduate Medicine, courses for train-
ing chemists for laboratories of sanitary-epidemiological stations which con-
duct research in atmospheric pollutions; 3) improve facilities in sanitary-
epidemiological stations, in institutes of hygiene and in departments of labo-
ratory equipment and apparatus development for research in atmospheric air pol-
lution and its effect on the organism.
The Committee for Sanitary Control of Atmospheric Air of the U.S.S.R.,
affiliated with the St~te Sanitary Inspection, was delegated to organize at
the A. N. Sysin Institute for General and Community Hygiene a permanent ex-
hibition of equipment and instruments for the study of atmospheric air pollu-
tion, displ~ing foreign and domestic models of installations, equipment and
technological procedureso
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The Conference appealed to hygienists and technicians at large to cooperate
in every way possible to make its resolutions a reality in the field of general
air pollution abatement and prevention.
Some Problems Connected with Sanitary Conditions in Cement Producing Plants.
A. Ko Belevitskii.
Gigiena i Sanitariya, Vol. 25, No.8, 63-68, 1960.
The rapid growth of cement manufacture anticipated by the Seven-Year-Plan
of U.S.S.R. national economy planners presents authorities of the cement indus-
try with a number of responsibilities from the viewpoint of workers' health;
foremost among such responsibilities is the one associated with the demand to
improve sanitary conditions in cement plants.
In cement production workers
deal with masses of raw and semi-processed materials, and with final products,
all of which eliminate high dust concentrations. An average capacity cement
plant has a daily turnover of 100 tons of materials to be treated by different
mechanical processes; some of the materials have to be transported over long
distances or be replaced from upper to lower positions, etc.
Such conditions
create dense concentrations of highly dispersed dust of rapid motility and
penetrability into all sections of the cement plant.
Cement is produced by two different processes: the wet, and the dry proc-
esses. In the case of the former the raw materials to be treated go through
most stages of production as wet masses, or in the form of a slurry which is
dust-free. In the second method the raw materials go through completely dry,
or almost completely dry, treatment processes. In the case of the wet method
dust appearance begins with the calcining stage. In the second case dust
appears at the first stage of the work.
In the production of cement by the
wet process, as can be judged from the above statement, the problem of dust
creation is not completely obviated. In the production of cement by the dry
method the problem of dust creation not only exists but is of such gravity
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that it overshadows all other existing sanitary problems, and no satisfactory
solution has been either found or proposed thus far.
The dry method for the production of cement requires no consumption of fuel
for slurry drying and from this viewpoint it is a highly economical one. It
can be easily understood, therefore, why foreign countries, and in particular
Germany, have used mostly the dry process of cement production. A similar
tendency has been noted of late in the U.S.S.R. It is fitting, therefore, that
before the dry process becomes widely accepted in the U.S.S.R., methods should
be found for the elimination of cement dust from the air of production premises.
It should be noted in this connection that much work has been done in the
U.S.S.R. in that direction of late, chiefly by adopting electrostatic precipi-
tators built by the Moscow and Leningrad Institutes of "Giprogazoochistka"
(Gas Purification). These installations have not solved the problem of dust
elimination completely, since they have no bearing on the reduction of dust
concentration prevailing at points of servicing personnel employment. This is
due to the fact that directors and administrators of cement producing plants
have paid no attention to problems related to the sanitary condition of dif-
ferent departments of cement producing plants. Furthermore, even high authori-
ties responsible for development of newly planned industrial, in this case
cement producing plants, failed to make provision for the sanitization of the
plants' individual departments. As an example of the above, mention can be
made of the Krivoi Rog dry cement producing plant, which was built according
to a plan proposed by the "Yuzhgiprotsement" Institute and which was set into
operation as recently as the latter part of 1955.
All intradepartmental suc-
tion installations of this plant proved deficient or entirely inoperative,
while dust creation resulting particularly from interdepartmental material
transportation reached unheard of high concentrations. Data obtained by the
Krivoi Rog Municipal Sanitary Inspection Office indicated that at many work
positions dust concentration exceeded the allowable limits by thousands of
percent. Due to such deficiency in sanitary safety provisions the plant had
to be closed for the reconstruction of the dust catchers and of the general
ventilation system.
500 million rubles.
The corrective measures cost the government more than
In addition, the unfavorable working conditions resulted
in a rapid turnover of the workers, which lowered the productivity and effi-
ciency of the work. In the long run the plant fell behind its assignment.
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It must be admitted in this connection that past experience had indicated
that the problem of dust elimination, especially in such industries as cement
production presents many difficulties.
On the other hand, the same experience
also showed that the solution of the problem required no new special discover-
ies; it was only necessary to apply the present engineering knowledge and ex-
perience to the problem in a common-sense way. An unfortunate and harmful mis-
conception has become rooted in the minds of industrial directors and plant
administrators: they believe that dust abatement means consisted of the in-
stallation of exhaust equipment of sufficient force and capacity to remove or
precipitate the dust completely, regardless of the amount generated at certain
production points. The causes which generate the dust failed to interest them,
and all their efforts have been exerted in the direction of improving the ex-
haust and aspiration ventilation systems.
This is an inexcusable error, since
factory experience has indicated that most effective means for dust elimination
or abatement must begin not with the installation of dust catchers, but with
the elimination of sources of dust generation as such.
Where this can be suc-
cessfully accomplished dust-catching installations and exhaust ventilation can
be kept ready for operation in emergency cases. In the case of cement plants
the selection and construction of dust removing installations should be based
not only on the specific characteristics of the production functions since the
nature of cement production does not lend itself to easy hermetization. It
is also necessary to take into consideration the steps of raw materials deliv-
ery to various points and of the intertransportation of the final product,
steps which are accompanied by intense air dust generation. The Krivoi Rog
Cement Plant can be taken as an example of careless attitude on the part of
pertinent authorities to such problems of sanitation and hygiene as dust abate-
ment and dust elimination.
In that plant all dust-emanating raw, semi-proc-
essed and processed products are conveyed from point to point by open belt
conveyor systems, the total length of which exceeds 1 km; the conveyor system
as such requires numerous transfers of the material from one conveyor belt to
another.
After the conveyors have been in operation for a time the dust in
the conveyor passages was so heavy that one had to pass through them by "feel-
ing" his way blindly. Such were the conditions the personnel servicing the
conveyors had to work under. Subsequently, the plant had introduced certain
corrective measures: about 40% of the conveyors were dismantled without any
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loss in productivity; the remainder of the conveyor system was reorganized in
a way which reduced the intensity of dust generation. However, even a basic
reconstruction of the aspiration and exhaust systems did not prove adequate
for the catching, precipitation and removal of the tons of dust generated at
practically every meter length of the conveyor system.
General plant experience indicated that, wherever possible, use should be
made not of mechanical but of pneumatic conveyor
systems which had the ad-
vantages of complete hermetization and required no special means of efficient
maintenance.
The pneumatic conveyor system is more certain and more convenient
in every respect.
It can be easily incorporated into any type of plant premises,
it is simple in construction and utilization and requires no extensive initial
financial outlay.
Among objections frequently raised against the installation of pneumatic
conveyor systems is the fact that its operation consumes a considerable amount
of electric energy and that it frequently wears out as a result of destructive
properties of certain abrasive components used in the cement industry.
It is
true that planners of pneumatic conveyor systems have not had sufficient ex-
perience to be able to design compact and economical conveyor systems which,
incidentally, is the main reason for high electric energy consumption by such
systems. However, it should be known by now that the above difficulties have
been resolved. In 1955 - 1956 Engineer Yu. N. Mikoltskii, in cooperation with
the present writer, developed
tion at the Krivoi Rog Cement
which consumed less than half
a revised pneumatic conveyor system, now in opera-
Plant (Tsement, 1956, No.4), the operation of
of the electric energy previously consumed, and
considerably reduced the number of servicing personnel. Another cause of high
energy consumption by the pneumatic conveyor system was found in the lack of
required construction specifics. As a rule the operation of pneumatic helical
pumps used in cement plants has found no application as basic equipment. This
is the cause of excess power consumption and of complicated and cumbersome
conveyor systems.
The production of pneumatic conveyor system equipment and
parts should be put on a broad scale without delay.
The wear and tear of the pneumatic conveyor main channels is not a techni-
cal problem but rather one of organization. The Belgorod Cement Plant changed
the construction of individual parts of the pneumo-conduits in 1954 and applied
a special protective lining at points of highest wear.
The application of such
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simple means reduced the wear of the main conveyor lines to less than 10%. This
resulted in an annual econo~ of 194,000 rubles. However, the primary advantage
was not so much the economic savings as the fact that wear of main conduits was
practically stopped, thereby obviating work stoppages for repair and at the
same time considerably improving sanitary working conditions. There is a woe-
ful lack of information or knowledge bearing on the problem of abatement or
elimination of dust emitted by basic and auxiliary technological equipment in-
side of many departments especially in the hearth departments. In this case
the leading role must be pl~ed not by dust aspirators or mechanics, but by
technologists whose primary responsibility shall be to so organize the process
of dust conveyance so that the existence of negative pressure be insured at all
zones or sections of the furnace aggregate under all conditions of its opera-
tion. In the case of the usual rotating kilns this problem can be resolved
comparatively easily. The problem becomes more complex in connection with
furnaces equipped with conveyor calcinators, so frequently used in the dry
system of cement production. For example, when the calcinators of the Krivoi
Rog Cement Plant were put into operation, it appeared during the first few
days that their actual method of operation differed sharply from the one pro-
vided by the plan, as was shown by the fact that furnace gases and dust were
being emitted systematically from the furnaces into the department premises.
Supplementary dust installations were being installed one after another, and
even then only a slight amount of the dust and gases were removed from the
working premises. Experience indicated that the operation of furnaces with
conveyor type of calcinators largely depended upon gas permeability through
the ~alcinating screen, and this in turn was connected with the quality of raw
material granules loaded into the furnace. Studies indicated that it was nec-
essary to secure better knowledge of the raw material granulation, specifically
to secure highly stable and heat-resistant granules from raw materials of any
composition. B. A. Petrov of the Leningrad Giprotsement Institute tried to
investigate new original methods of consolidating the granules. Such investi-
gation progressed slowly, and the results thus far obtained in the laboratory
experiments have thrown no light on the situation under practical conditions.
Aspiration or exhaust ventilation systems in operation in different de-
partments of the cement plant up to the present failed to satisfy the manage-
ment in many respects and are very often being reoonstructed and rearranged
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in the process of actual utilization. As a result such exhaust ventilation
systems frequently become complicated, cumbersome, regulated with difficulty,
and in relation to the original purpose operated highly inefficiently. Under
such conditions cases have been seen in which the resulting complicated and
cumbersome exhaust ventilation system itself became a source of dust distribu-
tion within the working premises.
It is the opinion of the present writer that
the time has come when new types of inside exhaust systems should be devised
specifically for cement plants. It should be noted in this connection that in
the case of cement plants, specifications for each department should be differ-
ent, since the type of materials used and many other circumstances or condi-
tions differ with each department. This means that a careful study should be
made of the suitability of scrubber type for any particular production depart-
mente
The same is true of dry dust catchers.
Existing scientific research
laboratories dealing with problems of dust sanitization of the cement industry
have not been able to cope with the magnitude of the problem, and have not been
in a position to satisfy the rising demand for installations and equipment.
For instance, the exhaust ventilation and aspiration laboratory of the Leningrad
Giprotsement Institute, which by the way is the largest research institute
taking care of the sanitarY-hYgienic needs of the cement industry, has a staff
of not more than 15 or 60 workers, and it occupies several small rooms. The
Institute has no semi-industrial facilities, on the one hand, while, on the
other hand, it is not able to test the effectiveness of certain designed equip-
ment under factory conditions, due to the fact that its scientific and technical
personnel which, as previously indicated counts only 15, have considerable dif-
ficulty in coping with the accumulated demands for general information and in-
stallations.
Under the present conditions it appears most appropriate to enlarge the
facilities and services of the existing laboratory, basically reorganize the
methods of approach to problems and their execution, or else to create one
single central laboratory dealing with the problem of dust abatement and elimi-
nation a6 applied to all industries. Organization of a central laboratory,
had such action been agreed upon by all concerned, would enable the investi-
gators to conduct intensive and extensive research along the lines of perfect-
ing existing and designing new dust-catching equipment and installations. It
is recognized that in the total problem of dust elimination the cement industry
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might appear as a minor factor. Nevertheless, a factor it is, and in addition,
some basic principles of the problem it creates and which call for urgent solu-
tion are different from problems of the same general nature in other industries.
Then, there is the problem of electrostatic gas purification which in
princip~e is intended for the liquidation of dust discharged into the atmos-
pheric air. In this connection it can be stated that dust elimination from
the air of indoor premises cannot be completely solved by electrostatic pre-
cipitators. The problem must also be approached from the viewpoint of protec-
tion of exhaust or aspiration equipment and installations against the effect
of abrasive dusts, of developing high quality U.S.S.R. filtering cloth for use
in bag filters, improvement in the hermetization of transport and conveyor con-
duits, etc. Such problems are at present given little attention, while others
are entirely neglected. By creating a central dust elimination laboratory these
problems might receive greater attention. (Note by B.S.L. - It is frankly
recognized that this paper contains nothing of intrinsic value insofar as
specific scientific and practical information is concerned. However, it does
clearly indicate how short the U.S.S.R. is of reaching the desired sanitary-
hygienic goals, how poorly some of their so-called research and applied in-
stitutes are, and how inadequate are some of the equipment, installations,
and materials used in gas purification and dust catching and abatement. The
last paragraph herein translated is not the end of the original paper; how-
ever, enough has been said to present a reasonably clear idea of certain in-
dustrial sanitary-hygienic situations in the U.S.S.R. And since the remainder
of this paper was judged ~o be repetitive of inadequacies and shortcomings and
of proposals for improvement, the translation was stopped).
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-tru.s. GOVERNMENT PRINTING OFFICE: 1962 0 -63Z6os
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