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U.S.S.R. LITERATURE ON AIR POLLUTION
AND RELATED OCCUPATIONAL
DISEASES
Volume 4
A SURVEY
by
B. S. Levine, Ph. D.
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-------
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U.S.S.R. LITERATURE ON AIR POLLUTION
AND RELATED OCCUPATIONAL
DISEASES
Volume 4
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.
AUGUST 1960
-------
Other books and surveys dealing with U.S.S.R. air pollution
and related occu~tional diseases available from U. S. Depart-
ment of Commerce, Office of Technical Services, Washington 25,
D. C.
Sanitary Protection of Atmospheric Air,
Purification of Industrial Discharge
Gases from Suspended Substances. 59-21092 $3.00
Limits of Allowable Concentrations of
A tmospheric Pollutants, Book 1. 59-21173 $2.75
Limits of Allowable Concentrations of
Atmospheric Pollutants, Book 2. 59-21174 $3.00
"
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U.S.S.R. Literature on Air Pollution
and Related Occupational Diseases.
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U.S.S.R. Literature on Air Pollution
and Related Occupational Diseases.
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U.S.S.R. Literature on Air Pollution
and Related Occupational Diseases. $4.00
A SurVey. Volume 3. 60-21475
The following is available from Academic Press, Inc., 111 Fifth
Ave~ue, New York 3, N. Y.
Russian-Eng1ish Medical Dictionary.
By Stanley Jablonski. Edited by
B. S. Levine.
$n.oo
-11-
-------
FOREWORD
The organization of the material in Volume 4 is based on the same principles
as in Volume 3, a brief statement of which was presented in the Foreword to that
Volume (O.T.S. No. 60-21415). Papers which appeared in Zhurnal Prikladnoi Khimii
and similar journals, which in the opinion of the undersigned had a direct and
in some cases indirect relation to some phases of air pollution, were given
greater representation in Volume 4.
The reader's attention is called to Section VI - Sanitary Clearance Zones,
and to Section VIII - Bactericidal Substances Emitted by Living Plants. In
connection with the material presented in Section VI it is interesting to note
the following: In the introduction to the second edition of his book "Atmos-
pherio Air Pollution, Its Origin and Prevention", A. R. Meetham states: "An-
other fruitless effort to rid London of smoke was made b.y the philanthropist
John Evelyn in the reign of Charles II. He proposed that the factories of
brewers, dyers, lime burners, salt and soap boilers, and others of the same
class, should be moved lower down the Thames; and that Central London. as we
know it. should be surrounded by a green belt thickly planted with trees and
.
scented flowers." This, in essence, is the idea and principle of the Sanitary
Clearance Zones.
The papers presented in Section VI, though few in number, will neverthe-
less enable the English readers to form a basic picture of how the U.S.S.R.
sanitary-hygienic authorities are endeavoring to put the principle of Sanitary
Clearance Zones, or Sanitary Green Belt Zones, into practice on a national scale.
It is to be noted in this connection that all sanitary codes in the U.S.S.R.
are fluid and are subject to revision in accordance with pertinent developments.
This also applies to the prescribed widths of Sanitary Clearance Zones. The
classification presented b.y M. S. Goldberg. in the first paper of Section VI
appeared in 1948. At the time this volume was completed, the undersigned re-
ceived a copy of the 1953 compendium of U.S.S.R. sanitary codes which shows
that the sanitary clearance zone classification has been revised. The revised
list will appear in Volume 5.
The material in Section VIII-was selected from a book entitled "Pbytoncides
and Their Role in Nature". The undersigned .selected from its content papers
which had a bearing on natural air purification from bacteria. It is hoped
-111-
-------
that it will prove of interest t_o AmeriQan and- E11g~i~h_:read~rs, and that it
will prompt some investigators to make studies of their own in the field of
"Phytcncides".
B. S. Levine, Ph. D.
3312 Northampton Street, N. W.
Washington 15, D. C.
Note: By way of grateful acknowledgement each item in this collection is
headed by the original title (in translation), the name of the author or authors,
institutional affiliation and periodical or book from which item was selected.
The volume, issue number, year of publication and inclusive pages are indicated
for the convenience of those who m~ wish to consult the Russian original or
make full reference to same.
B. S. Levine.
4J
-iv-
-------
Contents.
Foreword.
Section I.
Methods and Deterreinations Analytical.
Rapid Determination of Small Quantities of Dimethylaniline in the
Air. N. I. Fomicheva and P. A. Mel'nikova.
The Polarographic Method in Sanitary-Hygienic Investigations.
M. S. Bykhovskaya and M. I. Poletaev.
Spectrographic Determination of Manganese in Animal Organs and
Tissues. L. V. Kuznetsova.
Determination of Paratoluidine Vapors in the Air of Industrial
Premises. V. A. Vinogradova.
Spectra and Spectrophotometric Analysis of Chlorinated Organic
Compounds. Report. The Determination of Chlorex in Dichlorethane.
Ts. N. Rogi.nskaya and A. I. Finkelshtein.
Titrimetric Method for the Determination of Ionic Chlorine, Bromine
and Iodine in Mixture. A. S. Vorob'ev.
Improved Experimental Toxicological Met~od of Ani~al Inhalation
Exposure. G. N. Kotov.
Calculating "Physical" Toxicity for the Preliminary Determination
of Maxi~1 Permissible Concentrations. E. I. Lyublina.
Determination of the Direct and Indirect Effects of Pharmacalogical
Preparations on Blood Vessels. V. M. Kh~~tin.
Section II.
Apparatus, Devices and Equipment.
An Apparatus for the Determination of Dispersed Polyelementa1 Air
Pollution. P. N. Matveev.
An Apparatus for Work with HYdrogen Sulfide in the Open.
V. P. 1likhailov. .
A Continuously Operating Stationar,y Water Aspirator.
P. G. Kil'kovskii.
A Device for the Evaluation of the Dust Collecting Property of
Wetting Agents. S. A. Nikitina and A. B. Taubman.
The Use of Battery Combustion Chambers in the Purification of
Industrial Emissions into Atmospheric Air. S. P. Belousov,
A. S. Dun and I. I. Nikberg.
Rapid Determination of Nitrogen Oxides in the Air of Industrial
Premises by Special Tubular Indicators. L. A. MOkhov,
Yu. F. Udalovand V. S. Khalturin.
-v-
i11
1
5
11
15
16
21
24
30
37
42
43
45
48
54
56
-------
Section III.
Absorption of Gaseous Pollutants.
I. G. Plit and
Carbon Dioxide Absorption by Potash Solution Foam.
K. N. Shishkin.
Purification of Exhaust Gases of a Sulfuric Acid Tower Plant by a
Flowmeter Pipe Type of Apparatus. M. L. Var1, amov G. A. Manakin
and Ya. I. Starose1skii. .
Scrubber Application to Carbon Dioxide Absorption by Potassium
Carbonate Solution. I. G. Plit.
Coke Gas Purification from Hydrogen Sulfide in High Speed Rotar,y
_.J\'o~()~bers. S. N. Ganz and M. A. Likshin.
Oxidation of Ammonium Sulfite-Bisulfite Solutions in the Recover,y of
S02 from Smoke Gases. B. A. Chertkov.
Carbon Dioxide Absorption by Sodium Hydroxide Foam. M. E. Posin,
B. A. Kopy1ev and E. Ya. Tarat.
Section IV.
Poisoning, Acute, Chronic and Other.
Hygienic Aspects of Industrial Vanadium Aerosol. I. V. Roshchin.
Effect of Vitami.ns C, PP and B2 on the Course of Acute Poisoning
by Orthonitroch1orobenzene. Yu. S. Grosman and Z. A. Nazarova.
The Peculiar Relationship between Air Concentrations of Some Volatile
Substances and the Development of Pu1monar,y Edema. A. A. Go1ubev.
Acute Dich10rethane Poisoning. G. N. Morozov.
The Toxicity of Highly Dispersed Cadmium Oxide Aerosol.
E. A. Melinikova.
Section V.
Hygienic Evaluation and Lindts of Air Pollutants.
Hygienic Evaluation of Atmospheric Air in the Vicinity of an Abrasive
Plant. M. Karimov.
Determination of Limit of Allowable Concentration of Hydrochloric
Acid Aerosol (Hydrogen Chloride) in Atmospheric Air. E. V. Elfimova.
The Determination of Limits of Allowable Concentration of Lead
Sulfide in Atmospheric Air. Yu. P. Sha1amberdize.
Effect of Garages and Filling Stations Located in Residential
Sections on Health and Living Conditions. F. F. Lampert.
-vi-
60
68
78
85
93
100
109
115
122
128
133
141
144
154
161
-------
Section VI.
Sanitary Clearance Zones.
The Sanitary Protection of Air. The Sanitary Classification of
Industrial Plants and Sanitary Clearance Zones. M~ S. Gol'dberg.
Effectiveness of Sanitary Clearance Zones between Industrial
Enterprises and Residential Quarters. D. N. Kalyuzhnyi,
Ya. I. Kostovetskii, S. A. Davydov and M. B. Aksel'rod.
Planning and Effecting San~tary Clearance Zones in the Ukraine.
D. N. Kalyuzhnyi and Ya. I! Kostovetskii.
Sanitary Clearance Zones between Residential Sections and Flaces
of Fuel Storage in Sovkhozes of Saratovsk (Oblast) Territory.
V. A. Kononova.
Section VII.
Effect of Meteorological Conditions; Ventilation.
Ratio of Sulfur Dioxide and Sulfuric Acid Aerosol in Atmospheric Air,
in Relation to Meteorological Conditions. K. A. Eushtuyeva.
Effect of High Air Temperature on Biochemical Processes in Vivo.
G. Kh. Shakhbazyan and F. M. b'hleifman. - -
Selection of Air Intake Points for Ventilation of Premises in
Petroleum ITocessing Plants. B. E. Stankevich and M. I. Isaeva.
Purification of Ventilation Air from Tetraethyl Lead. A. S. Arkhipov,
P. I. Bogatkov, I. V. Oreshkevich and N. V. Seredinina.
165
179
183
187
193
196
202
209
Section VIII.
Bacterioidal Substanoes Emitted by LivinR Plants (Phytonoides).
Disinfection of Air by Dispersion or Evaporation of Lactic Acid.
V. I. Vashkov, A. K. Astraf'ieva and R. M. Ginzburg.
Effect of Atmospheric Pollution on the Bactericidal Effectiveness of
Solar Radiation. A. P. Krupina, D. M. Tyukov and A. M. Ponomareva.
An Investigation of the Pbytoncidal Action of Live Plants.
B. C. Drabkin and A. M. Dumova.
Emission of Pbytoncidal Substances by Cereal Grains.
N. V. Novotel'nov and I. S. Ezhov.
An Experimental Investigation of Baotericidal Substances of Plant
Origin (Phytoncides) and Their Use in Disinfecting the Air.
M. A. Komarova.
-vi i-
216
220
224
232
239
-------
Section IX.
Dustiness Investigations.
Effect of Mixed Industrial Dust on the Organism. 11. M. Demidenko.
Investigation of Air Dustiness in Agriculture. S. I. Sosnovskii
and D. Kh. Khakimov.
Dustiness and Meteorological Conditions in Seed Houses and in Some
Sections of Cottonseed Oil Mills. S. I. Sosnovskii.
Dust Concentration in Residential Districts of Asbest City and Its
Effect on the Children's Health. A. T. Bobyleva, R. M. Bukhantseva,
S. E. Lovtsova and M. S. Sadilova.
A Device for the Evaluation of the Dust Collecting Property of
Wetting Agents. S. A. Nikitina and A. B. Taubman.
Experimental Determination of Air Dustiness in Kiev. G. E. Tsapko.
The Organization and Methods of Fluoroscopic Examination of
Workers in Dust Generating Industries. A. G. Shumakov.
Section X.
Fuel and Gas Combustion Studies.
The Effect of Combustion fuethod and of Fuel Type on the Content
of 3.4-Benzpyrene in Smoke Gases. B. P. Gurinov.
Purification of Cupola Furnace Gases Discharged into the Atmosphere.
Discussed at the Moscow City Council of National Economy.
L. S. Rozanov.
Section XI.
Street Noise Abatement.
Street Noise Abatement Qy Proper Allocation of Tree and Shrub
Plantings in City Blocks. P. I. Leushin and M. Ya. Nikitin.
Section XII.
Administrative and Semipopular.
A Compendium of Official Materials Related to Problems of Sanitation
a~d Prophylaxis.
-viii-
243
248
249
251
48
254
257
260
264
268
216
-------
Rapid Determination of Small Quantities of Dimetbylaniline in the Air.
By
N. I. Fomicheva and P. A. Mel'nikova.
(All-Union Scientific-Research Institute of Labor Protection, VTsSPS).
Gigiena i Sanitariya, No.5, 49-52, 1952.
Dimetbylaniline (C6H5N(CH3)2] is a liquid of 0.962 specific gravity at 150
and boiling point of 1930 at 760 mm pressure; it has an unpleasant odor. The
vapor tension of dimetbylaniline at 400 is about 2.5 mm of mercury, and the va-
por is 4.2 times as heavy as air. DimethylaniJine is used in t~e aniUn~e
industry, the pharmaceutical and rubber industries. Its effect on the organism
is similar to that of aniline; it is predominantly a blood poison; intoxication
results from inhalation of its vapor and from contact with the skin.
Of the several reagents which produced color with dimethylaniline, only one
has been used for its colorimetric d~term1nation, as suggested by A. S. Zhitkova
in 1927. This determination was based on the reaction of dimethylaniline with
nitrous acid in hydrochloric acid solution, in which hydrogen in tho para posi-
tion was substituted b.Y a nitrose group, forming a water soluble paranitroso-
basic .salt, according to the scheme shown below:
<=> (CH3h + Na~O, + IIC! -+ ~O
\JI
1
<-> N (CHah + NaCI + H20 -+
- I
H
1;1
. /=', I
-+HON=,,=/ = N (CHah.
The resulting compound imparts to the solution a yellow color the intensity of
which can be determined colorimetrically. Dimethylaniline can be absorbed from
the air b.Y hydrochloric acid. This method requires the aspiration of large air
volumes and, therefore, considerable time and bulky equipment. The same reaction
forms the basis of the recently proposed determination of dimethylaniline and
of other tertiary amines in the presence of primary and secondary amines with
the aid of photoelectric absorptiometer.
On the basis of data found in the literature a rapid colorimetric method
-1-
-------
was developed for the detexmination of dimetby1aniline in the air, by applying
the above _~~n~~on~d ~olor reaction of paranitrosobasic salt in hydrochloric ac-
id solution. In testing hydrochloric acid concentrations of 10%, 5% and 1% for
use in the preparation of a standard solution of dimethylaniline it was noted
that during the formation of paranitrosobasic salt deepest yellow color was ob-
tained with 1% hydrochloric acid. It was also noted that dimethylani1ine was
fully retained in the first 1% HOI absorber.
The possibility of the colorimetric determination of dimetbylani1ine in
small volume air samples was established first; this was followed b,y the devel-
opment of precise methods for the preparation of low concentration standard
scales. Standard solution was prepared with 1% hydrochloric acid containing
0.01 mg dimetbylaniline per 1 ml, from which was prepared a standard scale con-
taining corresp~ndingly 0, 0.001, 0.002, 0.004, 0.006, 0.008 and 0.01 mg dimeth-
ylani1ine per 1 mI. Into each test tube of the scale 0.2 m1 of 10% sodium ni-
trite solution was added. The maximum color intensity developed within 5 min-
utes and no color fading could be detected after 3 days. Differences in the
color intensity in the tube were easily perceptible. Smaller amounts of sodium
nitrite produced unstable colors.
A permanent artificial standard scale was prepared from 0.05% aqueous so-
lution of sodium dichromate, as shown in Table 1.
TA:BLE
1.
Artifioial 80a1e for the determination of dimetbylaniline.
)(l of 0.05% ~Cr04 I 0.1 I 0.2 I 0.4 I 0.6 I 0.8 I 1.2
solution .: 0.0 . I : : I
1 i . I I I
I : . i . . .
1.2 1.1 . 1.0 0.8 i 0.6 i 0.4 . 0.0
Kl of water .
: . .
. i .
: : I .
I . I . I 0.0061.0.0081 0.01
Kg of dimetbylan11ine I 0.0 i 0.0011" 0.002: 0.0041
: :- :: ..
. .. .
The artificial scale was first checked against the natural 3cale prepared
as previously described and errors and deviations were correct~d accordingly.
Several lots of K2Cr04 were tried; all were found satisfactor,y. The color in-
tensity of artificial scales kept in tightly stoppered tubes did not change
with time.
-2-
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The determination can be speeded up by absorbing the dimetbylaniline into
a combined hydrochloric acid and sodium nitrite solution so that the color may
develop directly in the absorber while the air is -being aspirated.
It was established that the aspiration of pure air through two absorbers
containing the combined reagents mentioned above at a temperature of 18 - 400
and an aspiration rate of 2 - 15 Ii/hour did not produce any color in the so-
lution due to the formation of nitrogen oxides which tended to persist in the
absorbers. Aspirating air containing dimetbylaniline through absorbers with a
mixture of acid and sodium nitrite and through absorbers containing only acid
(sodium nitrite was added to the absorbers after the end of absorption) pro-
duced similar results under otherwise identical conditions. It was noted that
after standing for 24 hours the mixture of acid with sodium nitrite lost some
nitrous acid; ~ence, the absorber should not be filled with this mixture in ad-
vance.
Air containing 0.114 - 0.002 mg/li of dimethylaniline was aspirated through
the consecutively arranged absorbers, each filled with a mixture of 1 ml of 1%
bydrochloricacid and 0.2 ml of 10% sodium nitrite; 70 to 200 ml of air was as-
pirated at the rate of 10 to 100 ml/min until a pale yellow color appeared in
the first absorber. Five minutes after the collection of the sample was com-
pleted the color intensities developed in the absorbers were compared with the
permanent standard scale. No dimetbylaniline was detected in the second ab-
sorber.
Known concentrations of dimetbylaniline were determined colorimetrically
using the natural and the permanent artificial standard scales. As seen in
Table 2 in either case the results were satisfactory.
TABLE
2.
Checking the method of dimetbylaniline determination'with known
concentrations in mg.
,
Kg metbyl- ,
aniline'
taken
Mg dimetbylaniline
found
Batural ,Artificial
,.
scale , scale
i Kg met~l-
: aniline
! taken
0.0005
0.001
0.002
0.002
0.003
0.001
0.002
0.003
0.0005
0.001
0.002
0.002
0.003
0.004
0.004
0.005
0.006
0.008
-3-
.
~
i
.
i
Mg dimethylaniline
found
Batural : Artificial
scale i scale
0.004
0.004
0.005
0.006
0.008
0.004
0.004
0.007
0.008
-------
The rapid method for the determination of dimethylaniline was checked at
a pharmaceutical plant and in a workshop which used dimethylaniline. The air
was drawn with the aid of a 200 ml microaspirator through a single microabsorber
containing 1 ml of 1% hydrochloric acid and 0.2 m1 of 10% sodium nitrite solu-
tion until a pale yellow color appeared. After five minutes colorimetric de-
terminations were made on the location using the artificial standard scale.
Conditions under which samples were collected and the results of dimethylani-
line determinations are presented in Table 3.
TABLE
3.
Dimethylaniline in the air of working premises.
" :Minutes of: : :Mg/li of di- :
Air vol.: 1 :Rate in:Temper-: thy1 i1": Place of sampling
: samp e : I": ame an J.ne:
in ml : taldn :ml mJ.n.: ature : i th . :
: r R: : : n e aJ.r :
360 At place ot dimetbylaniline
2,000 23 87 0.002 distillation at beginning
ot work
1,000 11 91 310 0.004 At dimethylaniline drum
1,000 10.5 95 310 0.003 At dimethy1aniline drum
310 Near dimethy1aniline and
1,000 10 100 0.0025 toluol distillation
apparatus
1,000 10 100 32.50 0.004 In the center ot the
department
800 8 100 32.50 0.0025 In the center ot the
department
Near open apparatus tor the
600 5 120 32.50 0.017 treatment of dimetbYl-
aniline-toluol mixture with
alkali
400 3 130 330 0.01 Ditto, during pumping into
sedimentation tank
600 7 86 300 0.0033 On the work bench
370 Near dimethy1aniline
400 4 100 0.012 distillation apparatus in
the middle of dq
800 11 73 34.50 0.005 In the center ot the
department
-4-
-------
Toluol, methanol and dichlorethane vapors did not interfere with the di-
methylaniline determinations. The same was true of the presence in the air of
aniline, monomethylaniline, ether or benzene. Diethylaniline produced an iden-
tical color.
Conclusions.
1. A rapid colorimetric method was developed for the determination of
small quantities of dimethylaniline in the air, based on the formation of a
yellow colored paranitrosobasic salt; the air aspiration and the colorimetric
estimation with the aid of an artificial scale can consume approximately 15 to
20 minutes; the dimethylaniline content per 1 ml of the air must be within
0.001 - 0.01 mg.
2. The method suggested is simple, requires no complex equipment and is
suitable for dimethylaniline determination in the air of indus~rial premises
at concentrations in the order of hundredths and thousandths of a milligram
per liter.
The Polarographic Method in Sanitar,y-HYgienic Investigations.
~
M. S. Bykhovskaya and M. I. Poletaev.
(Institute of Labor Hygiene ~~d Occupational Diseases of the Acade~ of
Medical Sciences, U.S.S.R.).
Gigiena i Sanitariya, No. 12, 41-50, 1952.
The purpose of the investigations was to establish optimum conditions for
the polarographic determination of small ~uantities of lead, zinc, copper and
cadmium. The study was made with the aid of a recording polarograph of the
Odessa Institute of Rare Metals, employing model No.5 with a mirror galvano-
meter of 3.1 x lO-9A sensitivity, having a capillar,y with a constant mercur,y
-~
-------
droppine rate of 10 drops per 15 seconds. Polarographic determinations were
made using an interior anode, as well as an outer calomel electrode, connected
with the analyzed solution through a salt-agar bridge. Temperature fluctua-
tions did not exceed 10.
Determination of lead. Regardless of the method qy which lead was ab-
sorbed from the air and of its subsequent separation from the absorber, the
stu~ dealt with the problem of minimal determinable lead quantities in dif-
ferent solutions used as basic electrolytes.
In the first step of the investigations the oxygen present in the solu-
tion under stu~ was removed by blowing through it pure hydrogen for 20 - 30
minutes. A few drops of 1% glue or agar were added to the solution to prevent
excessive foaming. In the study 2 - 5 ml of the solution were used contained
in an electrolyzer.
For the absorption of lead from the air under field condHions, industrial
sanitary laboratories have been using solid absorbers, such as absorbent cot-
ton, glass wool, filter paper, and the like, subsequently leaching the lead
out with 5% solution of nitric or acetio acid. Accordingly nitric and acetic
aoids were used as basic eleotrolyzers. Solutions of these acids containine
2 to 50 mg of lead per liter were tested first. The results indicated that a
5% EN03 solution was the most suitable medium for the pola.rographic detemina-
tion of lead, since in the presence in the soluti~n of 2 mg or more of lead
the maximum diffusion current, as reflected by the amplitude of the wave, was
proportional to the lead concentration in solution.
Fig. 1 is a curve of the fUnctional relation between the amplitude of
polarographic waves and the lead concentration in a 5% nitric acid solution.
Minimum determinable lead concentrations amounted to 2 - 3 mg/li; which corre-
sponds to 0.01 - 0.015 mg of lead per 5 m1 of the solution. Half-wave poten-
tial of a nitric acid lead solution in relation to a standard calomel electrode
was equal to 0.47 V. Working in the region of highest galvanometer sensitivity
it is best to use agar to prevent foaming, since glue is frequently contaminat-
ed with substances which interfere with the examination of the soluti~n under
investigation.
Having established the possibility of determining lead content in the
presence of ni"tric acid, additional tests were made for the polarographic de-
termination of lead in acetic and hydrochloric acid. Such tests also yielded
-6-
-------
clear-cut polarographic waves with half-wave potentials in relation to a stan-
dard calomel electrode, in an acetic acid solution equal to 0.36 V and in hy-
drochloric acid solution equal to 0.45 V. In Fi~. 2 are presented curves of
the functional relation between wave amplitudes and lead concentrations in 5%
acetic and hydrochloric acid solutions as basic electrolytes. The curves in-
dicate that a linear relation existed between the lead concentration in solu-
tion and the wave amplitude.
lj
II
CD
rd 20
~m
~ 15
Pt'~
9"" 10
E 5
JJ:
.-/
Q
2.5 '0 15 20 2 5 10 15 10
Lea d 0 0 n 0 e n t r a ti 0 n sin mg/11
Fig. 1. Galvanometrio I - Hydroohlorio aoid ~
sensitivity: II - Aoetic aoid 5%
I - 1/10, II,- 1/5. Fig. 2.
Analysis of the results lead to the conclusion that all the acids tested
could be used as basic electrolytes for the polarographic determination of
small quantities of lead.
However, experiments in the recovery of the lead from the absorbers with
acids and its subsequent polarographic detennination demonstrated that best
results were obtained with 5% nitric acid solution. If the quantity of lead
in the sample is no less than 0.1 - o.? mg and the volume of nitric acid after
recovery does not exceed 20 - 30 ml, the polarographic determination can be
carried out directly in this solution, after the removal of suspended admix-
tures by centrifugation. Acetic acid in 5% concentration can be used as a ba-
sic electrolyte for the determination of lead content in skin or work clothes
wash water.
It must be pointed out that in attempting to determine the lead content
in the air approximating the maximum permissible concentration of 0.00001 mg/1i,
the described polarographic method of direct lead content determination fol-
lowing its recovery from the absorber 1fy means of acids proved to be inadequate.
-7-
-------
In such cases the sample should be first concentrated by evaporation to dr,yness
and the residue redissolved in a suitable small volume of the basic electrolyte.
Lead nitrate was dissolved in a buffer solution consisting of 30% acetate
of ammonium and 1% acetate of sodium dissolved in 1% acetic acid solution; this
buffer solution is generally used in the determination 'of small quantities of
lead in samples containing lead chromate. Polarograms obtained indicated that
both solutions could be used in the polarographic determination of lead. Most
clear-cut polarographic waves were obtained with 30% ammonium acetate solution
at pH = 6.6 - 1.0. The half-wave potential in relation to the standard calo-
mel electrode in a 30% ammonium acetate solution was 0.58 V and in 1% sodium
acetate 0.41 V.
In Fig. 3 are presented curves of the functional relation between dif-
fusion curren~ and lead concentration in 30% acmonium acetate solution and
in 1% sodium acetate solution in 1% acetic acid.
Supplemental tests were made to determine the effect of copper and zinc
on the determination of lead. Analyses of solutions in which lead, zinc and
copper were present simultaneously indicated that copper and zinc in concen-
trations exceeding the content of lead by two or more times did not interfere
with the polarographic determination of lead. It was also established that
separate determinations of copper, lead and zinc were possible only in a 30%
ammonium acetate solution and in 1% sodium acetate solution in 1% acetic acid.
As seen from Fig. 4, polarographic waves of copper, lead and zinc were distinct,
and no shifting on the half-wave potential nor fluctuations in the polarographic
wave amplitudes were noted. In 5% solutions of nitric and acetic acid, copper
and zinc could not be determined; only the lead wave was clearly expressed in
the polarogram. Data contained in the literature on the possibility of deter-
mining lead presented some interesting facts.
According to Teisinger lead albuminate was destroyed in the blood by the
addition of hydrochloric acid. In this way Teisinger was able to determine
polarographically lead recovered from the blood. In checking this method only
faintly expressed lead waves were noted. Blood analyses of animals which re-
ceived lead chronically revealed no lead either in the whole blood or in the
plasma after the separation of the erythrocytes. Thus, Teisinger's results
could not be confirmed. Only after the destruction of organic substrate were
-8-
-------
15
m ]0
m
. a
-0./ -0.4 -0,6 -0,8 -',6 ',~/ -1,4.
V () 1 t a.B e.
Fig. 4
-(' .41
I=:
-r 25
CD
J 20
....
riot IJ
i '0
~ s
Ii 0
2 J 10 15
Pb oonoentration in-mg/11
Fig. 3. I - Ammonium ace-
tate 3~J II - 1% sodium
acetate in 1% acetic acid soln.
s::
or!
" CD
'Id
~
or!
rot
~
as
~.
,
2.0
characteristic lead waves obtained. This was done with a mixture of sulfuric
and nitric acids and using 30% ammonium acetate as the basic electrolyte medi-
um.
Determination of zinc. copper and cadmium. For the polarographic deter-
mination of zinc and cadmium a solution of ammonium was used as the basic
electrolyte medium in accordance with recommendations found in literature.
Zinc and cadmium compounds were absorbed from the air onto solid absorbers
from which they were removed with the aid of acids. In the polarographic de-
termination of these metals the basic electrolyte medium consisted of 20% by-
dorchloric acid neutralized to a slight excess qy strong ammonia. The oxygen
present in the solution was bound to a small amount of added dry sodium sul-
fide; two drops of 1% agar were added to prevent excessive foaming. The half-
wave potential in relation to the standard calomel element in the test solution
was 0.6 V for cadmium and 1.2 V for zinc. The lowest determinable quantity of
cadmium was I mg/li and 2 mg/li for zinc. At lower concentrations the func-
tional relation between concentration and diffusion current became irregular.
The results demonstrated that under above described conditions small
quantities of copper and zinc could be reliably determined when present simul-
taneously. In the usual chemical analytical procedures their separation pre-
sents difficulties. Polarograms presented in Fig. 5 manifest distinct and
easily measured waves.
-9-
-------
m
~
.1"4
Q)
-g
~
;q .5' VIae"
!I
~,
==
On the basis of the results obtained it is
recommended that in the determination of zinc,
copper and cadmium absorbed from the air onto
the solid absorbers should be removed with 20%
hydrochloric acid solution; the solution should
then be filtered; neutralized with concentrated
ammonia to slight excess and the polarographic
determination made after the addition of a few
atD.4 0.6 -0.8' .~a -'.2 ." -II drops of 1% agar solution. In cases of low con-
Vol t &-g_..- centrations of the isolated metals, the hydro-
Fis.. 5.ch1.orlc acid should be evaporated to dryness and
the residue dissolved in 1 - 2 ml of hydrochloric acid and neutralized with
ammonium.
Conclusions.
1. It was demonstrated that polarographic determinations of small quan-
tities of lead in the air can be made b.Y using 5% nitric acid solution, 30%
ammonium acetate solution and 1% sodium acetate in 1% acetic acid as the basic
electrolyte medium. Zinc and copper did not interfere with the polarographic
determination of lead.
2. It is recommended that 30% ammonium acetate be used as the basic elec-
trolytic medium at pH of 6.6 - 1.0 in the separate determination of lead, zinc
and copper.
3. A 5% acetic acid solution is recommended for obtaining test wash sam-
ples from the skin or from working clothes.
4. Lead in blood can be determined only after the destruction of the or-
ganic substrate to which it is bound; a 30% ammonium acetate solution is rec-
ommended as the best basic electrolyte medium.
5. Small quantities of zinc, copper and cadmium can be determined polaro-
graphically in ammonia solution of ammonium chloride when present individual~
or simultaneously.
-10-
-------
Spectrographic Determination of Manganese in Animal Organs and Tissues.
By
L. V. Kuznetsova.
(Department of General Hygiene, 1st Moscow Order of Lenin' Medical Institute).
Gigiena i Sani tariya, No. 10, 48-50, 1954.
In this paper are presented data obtained by the spectrographic method in
the determination of manganese in organs and tissues of animals suffering of
manganese intoxication. Tests were conducted with three groups of rabbits:
the firs~ group, consisting of 6 rabbits, was not treated, and served as the
control group. Four rabbits of the 2nd group were injected hypodermically with
small doses of manganous chloride over a period of one month to a total of ap-
proximately 60 ID8/kg of body weight. Some of the rabbits died during the in-
jections; the organs .and tissues of these animals were examined to establish
the distribution of manganese in the organism when introduced parenterally in
solution. Four rabbits of a 3rd group were exposed for 6 months to the inhala-
tion of oxide of manganese in the form of highly dispersed aerosols obtained by
vaporization of manganese dioxide by an eleotric arc; the rabbits were exposed
daily for one hour to 0.05 mg/li concentration of manganese in the experimental
ohamber. At the end of the experiment the rabbits were killed and their organs
analyzed for the oontent of manganese. Table 1 presents averages of 8 - 12
analyses for each organ.
The results indioated that chronically inhaled manganese aerosol accumulat-
ed in the blood and in the cerebrum and that manganese passed from the lungs,
where it is retained in the insoluble form, into the blood. This fact is par-
ticular~ significant since under actual conditions intoxication is caused b,y
the inhalation of the insoluble manganese dust.
Accumulation and. distribution of manganese in tissues and organs was studied
by the spectral method. The Hilger type of spectrograph was used in this inves-
tigation, equipped with a quartz lens of 10 cm focal length. The electric arc
image was projected on a background with a rectangular aperture faciDg the col-
limator slit located 3 cm fram it, so that the points of carbon electrodes would
not run into the slit. This was necessitated by the fact that the radiation
coming ?rom the incandescent electrode points is replete with molecular spectral
-11-
~
-------
TABLE
1.
Manganese oontent in mg% in organs and tissues of rabbits.
! . Subcutaneous s Chronio
i Controls, i manganese ! inhalation
Organs . .
: :
i first group : injeotion, I exposure,
I . S
: i second grOUP I third groUP
Heart 0.4 1.5 0.4
Lungs 0.2 1 0.43
Kidneys 0.225 3 0.248
Spleen 0.18 1.5 0.2
Liver 0.512 5.6 0.6
Cerebella 0.2 5.4 0.3
Dienoephalon 0.029 8 0.03
Medulla oblongata 0.3 5 0.3
Spinal oord 0.4 4.5 0.4
Blood 0.05 29.8 0.3
bands which seriously hamper the analysis of the spectrum. The illuminating
condenser lens is provided with a diaphragmal iris for the control of degree of
illuoination coming tr~ough the spectrogTaph slit. Tee position of the elee-
~rodc points, set at 4 rom distance between them, were indicated on the back-
ground. This facilitated the control of distances between the electrode on a
constant standardized basis.
The distance between the arc flame and the 001-
limator slit was about 20 em. The arc was fed by an alternating current a.nd
supplemental activation. The arc intensity was kept constant at an 8 A level.
A slit 0.02 rom wide was used for qualitative analysis, and a slit 0.1 mm wide
for quantitative analysis. In most cases the analytical bands were selected
from the ~ost intensive spectral bands, or, the so-called, end lines. Spectral
000
bands 2576.lA, 2593.7A, 2605.A are recommended for use in manganese determina-
tions.
In the study of manganese distribution in the organism an 0.02 g per 0.02
ml solution of BeS04 was used as the standard. The work was carried out by the
method of triple standard of comparison. Such a procedure records on one plate
the spectrum of the substance tested together with spectra of each of three
standard solutions of different strength. Solutions of MnS04 were used in the
preparation of the standard. The ranse of standard concentrations was chosen
in relation to the expected manganese concentration in the material investigated.
-12-
-------
conditions.
The standard curve is prepared as
follows: the relative darkening of
2 duplicate bands of standards were de-
termined microphotometrically and the
dl
Calibrated graph. logari thm of ~ was recorded, where ~ ..
microphotometer position of the bar,rl1ium band and ~ = microphotometer posi-
tion of the manganese band. The value thus detern:i.ned, called the extinction
difference (blackening), was plotted on A S ordinate; logarithms of standard
concentrations (logO) were plotted on the abscissa.
All calculations for the calibrated graph are presented in Table 2.
dS
2
-I
1..5
I
lie
D,S
u
-0,5
The spectra of standards were used in
plotting a standard curve of comparison.
It is of utmost importance that the
standard and tested Mn concentrations
be burned and photographed under identical
TABLE 2.
Data for the construction of the graph.
! ~ . ,
: i Mn. conan. : LogC
i As. l~ .
"-l i ~ i in y i
, . , :
, ,
0.15 2.05 100 2
16.8 1.63 50 1.1
14.9 0.35
0.8 1.2 10 1
12.1 2.3 0.81 5 0.1
11 0.5 -0.3
16 10.8 0.11
For spectra of unknown manganese concentrations photographed on the same
plate, the difference in the darkening (extinction) of the analytical pair was
determined as described, and their values were plotted on the axis of extinction.
The corresponding point w~s established on the standard curve; the values of
the unknown concentrations were determined with the aid of this point.
This stu~ was made with spectrally pure carbon electrodes 6 mm in diame-
ter. A hole was drilled in each carbon 3.5 mm in diameter and 4 mm deep.
-13-
-------
Hygroscopicity of the carbons was eliminated by the use of cupferron and other
suitable substances, and of collodion in particular. Solution of the standard
was poured into the drilled hole and the carbons were dried. The carbon elec-
trodes thus prepared were then filled with the ash of the organ under investi-
gation and used in the quantitative analysis. Preliminary tests indicated that
complete vaporization of the test samples from the drilled carbon electrode
opening occurred in 6 minutes. Positive films of 2 - 3 X-D sensitivity were
used. These photofilms had a conGtant contrast range within 2500 - 3100 A.
Hilger's microphotometer was used in the determination of the intensity of
spectral line extinction (darkening).
Samples for analyses were ashed in the usual w~, and the weight of the
ash determined in relation to the original weight of the raw tissue. A weighed
portion of the ashes was then used in the final spectral ana~sis as described
above.
Conclusions.
1. Manganese was found in all tissues and organs of "rabbits living under
normal environmental and nutritional conditions.
2. The subcutaneous administration i~to rabbits of soluble Mn salts brought
about Mn accumulation in the kidneys, liver, cerebrum and, particularly, in the
blood.
3. Following the inhalation of aerosolized manganese dioxide the manganese
content increases in the tissues of the lungs, the cerebrum and, particularly,
in the blood.
-14-
-------
Determination of Para toluidine Vapors in the Air of Industrial Premises.
By
V. A. Vinogradova.
(Gas-Analysis Laborator,y of the Novosibirsk Scientific-Research
Sanitation Institute).
Gigiena i Sanitariya, No. 11, p. 48, 1954.
Paratoluidine is used widely in the production of dyes, liquid fuel, phar-
maceuticals, etc'. It is a white crystalline substance which melts at 450 and
boils at 200.40; its specific gravity i8 1.058. The maximum permissible con-
centration of paratoluidine vapor concentration in the air of industrial prem-
ises was set at 0.005 mg/li. Paratoluidine reacts with bichromate of potassium
in sulfuric acid medium, with paranitrophe~ldiazonium and with ferric chloride.
Experiments were conducted to establish the suitability of some of the above
reactions for the quantitative determination of paratoluidine in the air; the
results were as follows:
1. Potassium bichromate in sulfuric acid produced a yellow color not spe-
cific for paratoluidine; the reaction proved to have a low sensitivity.
2. In the presence of paranitrophe~ldiazonium paratoluidine produced a
yellowish-pink azo dye; the reaction's sensitivity was 0.001 mg in 5 ml; the
reaction was not specific and the presence of aniline and of other aromatic
amines interfered with it.
3. In the presence of ferric chloride in hydrochloric acid medium para-
toluidine produced a brown to pink-red color; the sensitivity of this reaction
was on the level with the one above.
A quantitative colorimetric method for the determination of paratoluidine
in the air waS developed based on this reaction. The only advantage of this
method was the low cost and easy availability of the reagents; as was the case
with the previous reaction, the presence of aromatic amines caused some inter-
ference.
The paratoluidine vapors are aspirated through two consecutively connected
Petri absorbers, each containing 10 m1 of 0.1 N hydrochloric acid solution.
The air is drawn through the absorbers at the rate of 30 Ii/hour. For the de-
tection of 0.005 mg/li of air, which is the maximum permissible concentration,
-15-
-------
it is necessary to draw through the absorber no less than 10 liters of air.
For the determination of paratoluidine content in each of the two absorb-
ers 5 ml are taken from each absorber and placed into a test tube. A standard
scale is prepared simultaneously. Into a series of colorimetric test tubes.
are placed 0.1, 0.2, 0.4, 0.6, 0.8 and 1 ml of a standard solution containing
0.1 mg of paratoluidine per 1 ml; the volume of fluid in all test tubes is
brought up to 5 ml with 0.1 N solution of hydrochloric acid.
5 ml of 0.1 N hydrochloric acid solution is poured into the first, or
control, test tube. Thus, a scale is obtained with a paratoluidine content
ranging from zero to 0.1 mg per 5 mI.
Then, into each of the test tubes of the standard scale and of the samples
are added 0.1 ml of a 20% ferric chloride solution; the content is stirred with
a glass rod or shaken, heated to boiling and cooled to room temperature by sub-
merging into cold water. Colorimetric determinations are made as usual after
the full development of brown to brown-red color.
Spectra and Spectrophotometric Analysis of Chlorinated Organic Compounds.
Report. The Determination of Chlorex in Dichlorethane.
~
Ts. N. Roginskaya and A. I. Finkelshtein.
Zhur. Anal. Khtm., Vol. XI, No.5, 602-605, 1956.
Analysis of a mixture of chlorex, i.e., ~,~-dichloroethyl ester, and of
dichlorethane by chemical methods is a complex problem. The fractional dis-
tillation of the mixture by Engler's method m~ produce only approximate re-
sults. A more elaborate distillation is time consuming, and, therefore, not
suited for use in production control. On the basis of the marked difference
in the molecular structure of chlorex and dichlorethane, it can be
that one of the methods of molecular spectral analysis might offer
to the given problem. In this connection a detailed investigation
expected
the solution
of the
-16-
-------
spectral properties of chlorex was undertaken; the results of this investigation
are presented in this report.
Among all the reports found in the literature on~ one [lJ, dealt with
the ultraviolet spectrum absorption band of chlorex dissolved in hexane. In
the work described ch10rex was used which had a boiling point of 1750;. d20i.200;
n 1.4562; according to literature the data are: d~O 1.220 - 1.222; n 1.4560 -
1.4570; boiling point 178.50. A quartz photoeleotric spectrophotometer SF-4
was used for the analysis of the absorption spectra, and the analytical work
in the ultraviolet region. A detailed description of the instrument, as well
as the descriptions of other domestic spectrophotometers used in the present
work are described in Prokofiev's [2J and Khrashanovskii's reports [3J. The
absorption spectra of ch10rex in ethyl alcohol and in dichlorethane, as well
as the absorption spectrum of dichlorethane, are shown in Fig. 1.
" It is seen from Fig. 1 that the ab-
to
dichlorethane produces no noteworthy ab-
sorption in this region the above wave
length can be conveniently used for ana-
lytical purposes. The calibration curve
shown in Fig. 2 was constructed with the
aid of artificial mixtures.
The results of the analyses of artifi-
cial mixtures shown in Table 1, indicate
that the mean relative error amounted to
4.0%. The analysis can be completed in 3
to 5 minutes, and the sensitivity, using an
absorbing layer of 1 cm thick, is 0~2%.
This method is not suited for the analysis of substances containing res-
ins, tars or rubber. Removal of the interfering admixtures by activated char-
coal yielded no desired results. Therefore, a new method was developed for the
analysis of substances containing the above mentioned constituents, based on
the absorption spectra in the infra-red region. In the development of this
method spectrophotometer IKS-ll was used, which is equipped with a rocksalt
prism and a 0.1 mm thick potassium bromide cell. The temperature at the source
119
114
111
116
llJ
Il.
4J
IlZ
41
Fig. 1. Absarptio~ spectra in
the ultra violet region.
1 - Chlorex in etbylol; 2 - di-
chlorethane in alcohol; 3 - chlor-
ex in dichlorethane
sorption of the chlorex solution in dichlor-
ethane has its maximum at 261.5 mmc.
Since
-11-
-------
of radiation ranged between 1600 to 17000.
The chlorex absorption spectrum in the infra-
red region is shown in Fig. 3.
The spectrum plot was constructed b,y
consecutive recording of the absorption
curve of the empty cell and of the same cell
filled with the analyzeu substance. The
width of the slit was regulated manually.
A comparison of the chlorex spectrum with
that of dichlorethane indicated that for the
analysis under discussion the 8.50 mc ab-
sorption band was the most suitable. The
Qalibration curve constructed on the basis
of mixtures of chlorex and dichlorethane is
shown in Fig. 2. Resins, tars and dissolved
rubber produced no appreciable effect on the
results of analyses.
A single analysis was made in 15 to 20
the sensitivity was 0.3%, and the mean relative arithmetical error
Ana~tical results of the artificial mixtures are shown in Table 2.
'lABLE
1.
Taken
I Error %
I
. I Abs~ i Re1a-
I Found I lute i tive
Chlorex %
4.00
13.30
8.40
7.40
2.50
1.20
1.62
3.36
4.63
5.57
7.95
9.32
12.12
1.96
3.98
4.05
13.0
8.20
7.25
2.50
1.30
1.70
3.20
4.35
5.30
7.75
9.45
15.75
1.90
3.85
+0.05
-0.30
-0.20
-0.15
o .
+0.10
+0.08
-0.16
-0.38
-0.27
-0.20
-0.37
-0.37
-0.06
-0.13
1.25
2.26
2.38
2.03
o
8.35
4.95
4.75
8.2
4.85
2.52
3.77
3.06
3.06
3.26
Average relative error 4.0.
minutes,
N5.5%.
o
fOO'
go
60
70
60
j(J
*0
30
zo
10
6 9 fO If
IZ
fJ
f*
f5
fOIL
6 to 12 1+ fIi
Fig. 2- Fig. ~ .
Fil$. 2. Calibrated curves I
1 - Absorption in the ultra violet region, ~ ~ 2~1!2 ~Pi-
2- Absorption in the infrared region, ~-- 8.50~.
Flg~ 3. Chlorex absorption spectrum in infrared region.
-18-.
-------
TABLE 2.
Chlorex % s Error %
s
s
: s Abse- : Rela-
Taken i Found i lute i t1ve
9.74 9.72 -0.02 0.20
3.98 3.90 -0.08 2.01
12.48 12.35 ~.13-- 1.0
1.65 1.75 +0.10 1.31
1.73 1.55 -0.18 10.4
6.02 6.02 0 0
12.96 12.90 -o~06 4.64
7.65 6.90 -0.75 0.98
6.65 6.80 +0.15 2.26
8.50 8.44 -0.06 0.70
4.90 4.92 +0.02 0.41
0~92 0.68 -0.24 26.0
3.81 4.25 +0.44 11.55
3.85 4.41 +0.62 16.1
9.31 9.72 +0.41 4.4
Average relative error 5.5.
In the course of the investigation spec-
tra were obtained of combined dispersion and
of absorption in the near infra-red region.
Combined dispersion spectra were obtained
with the aid of a three-prism glass spectro-
graph ~SP-5l with a single bulb source of
light and a standard light filter which brought
out the Hg 4358 line, used in eliciting the
spectrum. A comparison of the di~hlorethane
spectrum with that of chlorex, shown in Table
3, indicated that the spectra of combined
dispersion, in principle, could be used in
the analysis.
A universal monochrometer UM-2 with two
lead sulfite photoresisters, type F5-A-l,
connected to an unbalanced bridge hookup, was
used for the study of chlorex and dichlorethane
absorption spectra. Notwithstanding the small
TABLE
3.
Chlorex
Speotrum of combination dispersed light
Dichlorethane 4
242 an-I (1)
295 an-I (1)
671 an-I (10)
157 em-I (3)
192 em-I (I)
1219 em-I (10)
1258 em-I (1/2)
1460 em-I
2817 em-I (2)
2916 em-I (2)
2968 em-I (7)
3017 em-I (2)
I
124 em-I (5)
264 em-I (4)
301 em-I (10)
410 em-I (5)
653 em-I (12)
616 em-I (5)
753 em-I (15)
881 em-I (3)
943 em-I (5)
991 em-I (0)
1032 om-I (2)
1054 em-I (3)
1143 em-I (I)
1207 em-I (5)
1263 em-I (2)
1302 em-I (6)
1428 em-I (5)
1442 em-I (4)
2845 em-I (2)
2956 em-I (10)
3002 em-I (6)
-19-
-------
dispersing power of the instrument in this particular region of the spectrum,
the results obtained, as shown in Fig. 4, were definitely of value to the de-
velopment of a stmplified method of spectral analysis of a mixture of ch10rex
and of dich1orethane.
Bibliograp~.
Mohler, H., Sorge, F. Helv. Chtm. Acta, 23, 1200, (1940).
Prokof.yev, V. K. Transactions of the All-Union Conference on Analytical
Chemistr,y, t. 2, Izd. AN 5.S.S.R., M., 1943, str. 115-181.
Khrashanovakiy, S. A. Herald of Leningrad University, No.3, L., 1950.
Kolraush, K. Spectra of Combined Dispersion, IL, M., 1952.
70
6fJ
50
'ill
JO
"
:0
to/!
10UO
, IZ/JU
I~OO
1500 mp
Fig 4. Absorption spectra in the nearest
infrared regions
1 - Clorex, 2 - dichlorethane, pure sub-
stances; absorption 1qer 3.0 em.
1.
2.
3.
4~
Conclusions.
10
Methods are described for
obtaining absorption spectra of
ch10rex in the ultraviolet, infra-
red and the near ultra-red spectral
regions and the combined dispersion
spectrum.
2. A techni~~~ is described
for the determination'of ch10rex in
mixture with dichlorethane, based
on light absorption in the ultra-
violet and infra-red regions.
-20-
-------
Titrimetric Method ~or the Determination of Ionic Chlorine, Bromine
and Iodine in Mixture.
By
A. S. Vorob'ev.
(Udcurt State Pedagogical Institute, Izhevsk).
Zhur. Anal. Khi~., Vol. XII, No.3, 395-391, 1957.
There are two widespread methods for the determination of large quantities
of halides in mixtures: the titrimetric ~nd the gravimetric. Beck (lJ devel-
oped a gr~vimetric method based on the precipitation of halides by the Ag+ ion.
Freedheim and Meyer [2], following preliminary processing of the solution,
deteluined I- and Br- by Na2S203 titration; the Cl- ion was precipitated by
Ag+ and then determined gravimetrically. .
Berg (3, 4J described a titrimetric method for the determination of the
three halides in mixture. The I- ion was titrated with potassium iodate in
tho presence of acetone in a solution acidified b,y H2S04. The precipitating
ion reacting with the acetone formed an iodoacetone. The Br - a.."ld C1-- ionsuwere
determinad simultaneously by titration according to Folgard. The C1- ion was
deter.~inAd in a separate sample containing C1-, Br- and I-; for this purpose
ions of 1- and Br- were oxidized with potassium bromate, and, after binding the
free 12 and Br2 by acetone the Cl- ion was deter.mined according to Folgard. In
c~ses of small amounts of 01- it was determined nephelometrically. The amount
of B~- ~as determined by difference. Using this method Mitchel and Ward [3J
obt~ined higher yields for ions 1- and Br-. Alpine [6J ascribed the higher
yield in determining 01- to the hydrolysis of bro~o- and iodoacetone. Accord-
ing to the data furnished by Berg (4J the lOGS of 01- ion due to oxidation by
bromate m~ range from 2% to 40% depending upon the duration of the reaction
and the halide concentration. All the indirect ~ethods mentioned consist of a
large nuzber of operations, are complex, time-consuming and are insufficiently
accu:::-ate [5J.
The titrimetric method of R. Berg for the determination of large amounts
of halide ions in mixture was improved as the result of experiments carried out
by the present author in the direotion of simplification, precision and rapid-
ity.
-21-
-------
Chlorine, bromine and iodine were determined in one sample. The procedure
to be followed in the modified method is as follows: into an Erlenmeyer flask
of 100 - 200 ml capacity place 5 or 10 ml of 0.01 or 0.10 N XI solution, 0.02
or 0.10 N KCl solution and 0.20 N KBr solution. Add 15 ml of acetone and 3 to
5 ml of 1:3 colorless H2S04 solution. The iodide concentration in the final
solution should be respectively 0.001 or 0.01 N, and the concentration of H2S04
should be respectively 0.8 to 1.3 N. The I- is titrated with 0.01 or 0.10 N of
a KI03 solution. The liberated free iodine reacts with the acetone. The solu-
tion containing 0.001 N KI becomes colorless intermittently, while the solution
containing 0.01 XI retains its color and becomes colorless only toward the end
of titration. Further titration should be carried out gradually adding two to
three drops of the KI03 solution at a time. In both cases th~ change from yel-
low to colorless, or ~ versa. is very distinct. At the point of equivalent
ionic I- oxiiation the solution remains colorless to the last drop of the KI03'
To assure full oxidation of the I- ion, it is enough to add a one or two drop
excess of KI03' At H2S04 concentration range of 0.8 to 1.3 N only the I- ion
becomes oxidized, while the 01- and Br- ions remain in the solution.
For the determination of the Br- ion, 15 ml of 2:1 H2S04 is added to the
solution while stirring. The total H2S04 concentration in the solution will be
6.7 - 7.30 N, and the concentration of bromide will be 0.018 N. The solution
temperature will rise due to the addition of the H2S04f in this warm solution
the Br- ion is determined by titration with an 0.40 N solution of KI03' which
is added a drop at a time. Under the above conditions only the Br- ion becomes
oxidizedf the latter together with the iodine formed in the process of iodate
reduction will turn the solution yellow; this color will rapidly disappear as
the result of the reaction between the halogens and the acetone. At the point
of equivalent Br- ion oxidation the last drop of the KI03 will no more color
the solution. To assure complete oxidation of the Br- ion, add a one or two
drop excess of iodate.
For the determination of the Cl- ion the solution is cooled to room tem-
perature.
The lowest initial chloride concentration which can be determined
"b,1titration is 0.0017 N. In solutions of such or higher chloride conoentra-
tions the 01- ion is determined according to Folgard; at lower concentrations
it is determined nephelometrically. Determination results are shown in Tables
1 and 2.
-22-
-------
TA.BLE
1.
The 1- 10n was t1trated with 0.01 11 1I0) solution and Br- 10n
with O.~ Jl 1I0) soluUon.
Taken in ml : Pound in 811
:
:
0.01 11 II I 0.20 11 Dr I 0.20 If XC1 : : 0.20 If XBr I 0.20 Il XC:r
: 0.01 Il II I
: . I - .
5.0 5.0 5.0 4.95 4.90 4.85
5.0 5.0 5.0 5.00 4.92 4.94
5.0 5.0 5.0 5.00 5.00 5.00
10.0 10.0 10.0 9.94 9.95 9.85
10.0 10.0 10.0 10.00 10.00 10.00
10.0 10.0 10.0 10.05 10.00 . 10.05
TABLE 2.
The 1- ion was U trated .i th 0.10 B' 1I0) solution and Br - ion
with 0.40 B' 1I0) solution.
Taken in m1 Found in ml
0.10 Ii II I 0.20 Il Dr I I 0.10 Il XI I I 0.10 B' XC1
i 0.10 B' XC1 I 0.20 11 Dr I
. . I :
5.0 5.0 5.0 4.96 5.00 5.09
5.0 5.0 5.0 5.00 5.10 4.98
5.0 5.0 5.0 5.05 5.08 5.10
10.0 . 10.0 10.0 10.05 9.80 10.14
10.0 10.0 10.0 10.15 10.12 10.01
10.0 10.0 10.0 10.20 10.00 9.91
Cono1usions.
1. A titrimetrio method was developed for the determination of r-, Br-
and C1- ions simultaneously present in solution. The r- and ~r~ 10ns are ti-
trated with oalcium iodate, C1- ion is titrated according to Fo1gard.
The determination of the three halogens is made in one sample. The deter--
mination requires 12 - 15 minutes. The method is simple ~~d aoourate.
2. Optimum initial H2S04 oonoentrations were established for the separate
titration of the r- and C12 ion8 with potassium iodate.
3. Lowest initial conoentrations that oan be determined by titration of
mixtures of the three were found to be 0.0014 N for r-, 0.0180 N for Br - and
0.00170 N for 01-.
-23-
-------
:Bibliography.
1. Gillerbrandt, V. F. and Lendel', G. E. Practical Manual for Inorganio
Analysis. aNTI, 1937, str. 636.
2. Bilts, G. and Bilts, V. Quantitative Analysis, ONTI,1933, str. 184.
3. Mitchel, A. D. and Uord, A. I. A New Method of Quantitative Chemical Analy-
sis. Goskhimizdat, 1933, str. 45.
4. Berg, R. Z.Anal. Chem., 69, 342, 368, (1926).
Vorob'yev, A. S. Zh. Anal. Khim., 2, 96, (1947).
Alpine, Me. J. Am. Chem. Soc., 51, 4, (1929).
5.
6.
Improved Experimental Toxicological Method of Animal Inhalation Exposure.
By
G. N. Kotov.
People's Republic of Bulgaria (Sofia).
Farmakologiya i Toksikologiya, Vol. 20, No.2, 70-73, 1957.
The exposure of laboratory animals to dust inhalation is a basic method
employed ,in the investigation of effects of harmful dusts, gases and vapors
on the living organism. Inhalation exposure of test animals is carried out in
special chambers such as the dynamic exposure chamber, in which concentrations
of harmful substances in the air can be varied automatically in the course of
the experiment.
In the existing experimental toxicological practice complete examination
of test animals is made before and after the exposure of the animals, that is,
before placing them into the exposure chamber and after removing them from it,
thereb.y interrupting the process of the experimental exposure. This constitutes
a great shortcoming in present-day toxicological experimentation. Until re-
cently only a most general and cursor:; examination of the condition and beha-
-24-
-------
vior of the experimental animals was possible without interrupting the active
experimental inhalation, i.e., without removing the test animal from the ex-
perimental exposure chamber. This was due to the lack of appropriate d,ynamic
toxicological methods and procedures for the intimate observation and recording
of changes occurring in the physiological and behavior indexes of the test ani-
mals. This was and still is particularly true of the so-called chronic toxico-
logical exposures.
The present article presents an account of a preliminary experiment in
improving presently existing experimental toxicological procedures. The meth-
od developed enables automatic kymographic recording of changes in respiration,
pulse beat, blood pressure, and to obtainvitograms under active exposure con-
ditions,inS1.de the treatment chamber. By the new experimental procedure it
was possible to take blood samples from the femoral and common carotid arteries
for blood pictures, biochemical and chemical investigations under active condi-
tions of acute intoxication, thereby enabling a more thorough examination of
the organism during a prolonged uninterrupted action of harmful substances en-
tering the organism ~ the respiratory tract.
This procedure m~ prove of value in the study of pathological and clinical
problems and in experimental therapy of acute intoxication caused by high~
active paralyzing or. lethal poisons.
The following laboratory equipment is employed in the suggested procedure:
1) exhaust hood; 2) set-up for the dynamic exposure of laboratory animals to
vapors of the substance under study, or exposure chamber (250 - 500 Ii capaci t;r);
3) universal stanchion built 'to order; 4) laboratory animal (medium size dog);
5) kymograph, Ludvig manometer and time recorder; 6) fine rubber tubing and
glass connections; 7) Hofman, Moore and Diefenbach clamps; 8) 30% sodium citrate
solution (500 ml); 9) set of surgical instruments for exposure of arteries, .
arterial cannulae, rubber gloves; 10) 30 - 50 ml toxic substance under investi-
gation in a spray apparatus.
With the exception of the universal stanchion, description of the rest of
laboratory equipment and of the set of instruments can be found in any handbook
of physiology or toxicology.
The universal stanchion consists of a regular wood or metal frame into
which the test animal is fixed to maintain a standing position; attachments for
the kymographic recording of respiration and blood pressure of the animal are
-25-
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arranged. The stanchion with the animal in fixed position is then wheeled into
the experimental exposure chamber which contains other equipment or apparatus
required for performance of the experiments. The stanchion, illustrated by
Fig. 1 and Pig. 2, is essentially a modification of the Pavlov frame, and can
be built to accommodate work with laboratory animals of any size. Supplemental
attachments or contrivances can be introduced for the performance of special
studies.
12
•s.
Fig, 1. Universal stand for doge under study during
their (dynamic) exposure to a poisonous gas or dust.
1 - Perforated steel floor for retension of feoes;
2 - steel funnel, connected with 3 - glass urine col-
lector? 4 - moving wheels} 5 - wooden platform con-
nected with device recording aovament of front legs;
6 - rubber cushioned steel chains for holding dogs in
place; 7 - upper adjustable fra»s; 8 - adjustable head
holder; 9 - animal entrance door; 10 - adjustable hind
leg holder; 11 - adjustable front leg holder; 12 - res-
piration recording connection; 13 - Ludwig nanometer
connection; 14 - general actogram connection
The procedure. For kymographio records of respiration and blood pressure
under conditions of dynamic exposure to vapors of harmful substances, medium
size dogs weighing 6.8 and 10 kg are the most appropriate laboratory animals.
The test animal is secured to the operating table and prepared for the
operation; the femoral or carotid artery is bared and the cannula inserted,
fastened to the animal's hip with 2-3 skin sutures, and the artery shut off
with a Diefenbach clamp; the animal is then taken carefully off the operating
-26-
-------
table and secured in the universal stanchion in a standing position, as shown
in Fig. 2.
. ~ '; I
11:111:'.1 . ;':-; I. .1
-- ---- -----_._------....-
: I"
, I
Fig. 2. General plan of apparatus for recording blood
pressure and respiration in the course o~ animals' e~
po sure to the poisonous gas or dust
1 - Exhaust hood and fan, 2 - exposure chamber, 3 - act-
ivated charooal air purifier, 4 - activated charooal
and oalcium chloride air drier, 5 - flow meter, 6 - test
substance disperser, 7 - fan; 8 - universal animal stand,
9 - glass and rubber oonnections, 10 - kymograph.
With the help of four iron rings, soldered to the base of the stanchion
(the front rings are immobile and the rear ones mobile), the dog's paws are
fastened firmly to the base of the stand. In preparing the dog for kymographic
recording of respiration and of blood pressure all four legs should be securely
fastened, and in preparation for the vitogram record only the rear legs, allow~
ing the front legs to move freely. When the dog is highly irritated, or stimu-
,-'
lated, which usually occurs during the reflex period of intoxication by the
tested substance, the animal will struggle in an attempt to break loose from
,the stanchion which will cause the free legs to exert some pressure on the
movable disc in the middle part of the stand. The pressure on the disc will
transmit itself to the rubber balloon and from it, along a closed air pressure
system through narrow rubber tubi21g to the second IImareevskaii drum"; changes
in the-latter will be recorded on the kymographic tape. Sharp deflections in
the actogram, or vi togram reflect the degree and duration of the animal' 6 agi-
tation. Agitation will be followed by inhibition of the animal's nervous system,
and the actogram deflections will become ipfrequent and of low amplitude.
-27-
-------
In addition to fastening the feet to the base of the stand, the test ani-
mals are also held by foUr rubber rings. The dog's body is fastened to the
stand with two wide canvas belts at the origin of the front and hind legs. The
dog's head remains free during the test. Held in this position the test ani-
mal maintains a relatively normal physiological balance when it is calm. The
chest movements (inhalation and exhalation) are normal, and the blood circula-
tion and respiration can be recorded in a natural standing position. The dog,
fas.tened to the frame, remains composed and can be held in this position up to
10 - 12 hours; frequently the animal will fall asleep. Recording of respiration
movements is done with the help of the rubber cuff fastened around the animal's
chest. The cuff is connected by means of fine rubber tubing with the first
"mareevskaya kapsullt. The blood pressure is recorded ~ the cannula inserted
into the femoral or carotid artery, and connected by means of fine rubber tubing
filled with a 30% sodium citrate solution to a graduated Ludvig manometer.
Application of the method durin~ the test. By means of the special univer-
sal stanchion it is possible to record respiration, blood pressure and the
vi'togram or actogram under conditions of dynamic exposure of the animal to Va-
porsof a harmful substance (Fig. 2). The stand with the laboratory animal
fastened in it is placed inside the exposure chamber. During the dynamic ex-
posure of animals, air containing known concentrations of the harmful substances
is aspirated through the chamber at a constant rate. Special provision is made
to prevent the escape of the poison-saturated air into the external air medium.
Details of the construction and operation of universal stanchion inside the ex-
posure chamber are shown in Figs. 1 and 2.
[Note: Electrocardiographic studies can be carried out in a similar manner
b,y making appropriate provisions for the extension of the leads and extra con-
nections.]
The tubes connecting the arterial cannula with the Ludvig manometer must
be absolutely clean, washed with a 30% sodium citrate solution immediately
before the test; the7 ought to be as short as possible to avoid blood coagulation
in the cannula.
. Thus prepared, the system is ready for operation. First, a thorough in-
spection is made of all recording parts of the qrnograph and of their connec-
tions. The Diefenbach clamp on the artery is then released allowing automatic
-28-
-------
recording of blood pressure. Appropriate connections are then made for the
recording of the respiratory movements. The door of the treatment chamber is
then tightly closed. During 1 - 2 minutes "normal" or "control" records are
made. Then, without stopping the movement of the kymograph, the dynamic ex-
posure set-up is plugged in. Vap
-------
Calculating "Physical" ToxicitY' for the Prelimina17 Detemination of )(A.TilllllDl
Permissible Concentrations.
~
E. I. ~blina.
'Toxtc~olo~~~1. Laboratory, State Scientific-Research Institute of Industrial
HYgiene and Occupational Diseases.
Gigiena Truda i Prof. Zabolev., Vol. 2, No.2, 41-47, 1958.
New substances are being steadilY' introduced into the production industry,
same of which possess properties deleterious to health. It is imperative that
methods be found for the rapid determination of maximum allowable concentrations
in the air of such substances before their production and industrial utilization
assume extensive proportions. Clinical, statistical and animal experimental
data frequently proved inadequate for this purpose. The rapid determination
of limits of allowable concentrations of air pollutants should,be based on
general principles derived from a study of the action of a significant number
of different substances. Some of the general principles which detemine the
properties of organic sUbstances, chiefly volatile organic fluids, are now well
mown.
In 1944 N. V.~-I.a.zarev summarized the information available on the relation
between the narcotic potenqy of organic substances and their physiochemical
properties. He presented formulas for the estimation of narcotic concentrations
of such substances. Lazarev called the biological action of nonelectrolytes,
gS determined b.r their physiochemical properties, nonelectrolytic or non-specific
in distinction from the specific action of a poison as a function of its active
chemical properties. Similarly, foreign scientists speak of "physical" toxicity,
when referring to the nonelectr()J.~~~ effect, or of "chemical" toxicity when
the poison acts on the organism through special chemical reactions.
Ferguson concluded that concentrations producing identical biological ef-
fect (death of insects after seyeraihours) were within relatively narrow 11m-
its; his conclusion was based on calculations of the concentration intensitY' of
the deleterious substances present in the animal's environment. Ferguson found
this to be true of liquid and gaseous solutions or suspensions. In the oase of
the gaseous or air phase Ferguson expressed active concentrations as percentages
-30-
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of gas buoyancy or vapor pressure, and called them "thermodynamic" concentra-
tions.
Results of experimental studies by the Toxicological Laborator,y of the
Leningrad Institute of Industrial Hygiene and Occupational Diseases established
the existence of a relationship between the potency of none1ectrolytes and
their physiochemical properties by showing that lethal, narcotic and threshold
concentrations, which affected the flexor reflex in rabbits after 40 minutes
exposure, varied with solubility of the substance in water and with the distri-
bution ratio between oil and water. Threshold concentrations of various organic
substances for rabbits were compared with official maximum permissible concen-
trations and those determined by this author. Results indicated that where
organic solvents have no marked "chemical" toxicity, the ratio between the two
series of values fluctuated within comparatively narrow limits. On the basis
of the data the following empirical formulas were derived for the presumptive
estimation of maximum permissible concentrations of substances with nonelectro-
lytic action:
log C = 0.92 log S +' log M - 10gA - 3.15
log C a -0.81 log K + log M - 10gA - 0.35
where S = solubility of the substance in water in millimols per liter;
M = molecular weight;
A = factor of vapor solubility in water;
K = distribution ratio between oil and water.
Data derived from formulas (1) and (2) are expressed in milligrams per
liter.
In 1955'MacGowan proposed two other formulas for the determination of
(1)
(2)
maximum permissible concentrations of substances free from "chemical" toxicity.
For preliminary estimation MacGowan used formulas he advanced for the
computations of average lethal concentrations of insecticides and dividing the
final result by 25, or qy subtracting 1.4 from the logarithm of the concentra-
tions.
log C = (3.12 + log P - log L + O.COln) - 1.4
where C = maximum permissible concentration;
(3)
P = vapor pressure in mm mercury;
L = a fraction, the nume=ator of which is the density (in practice the
specific gravity) multiplied by 1000, and the denominator is equal
-31-
-------
to the molecular weight;
n = parachor (a constant related to molecular volume).
MacGowan introduced additional values for the computation of 0.0014 w.
It is pointed out that this formula was derived on the basis of an assumption
of equal thermodynamic poison effects of "physically" toxic substances.. The
formula is based on extensive experimental data and is useful for the calcula-
tion of the toxicity of vaporized liquids.
MacGowan's second formula is a simple one:
log C =I:f - 1.4 (4)
The total of factors (~f) is taken from a special table of ~ f values for
ethane, cyclohexane, benzene and naphthalene. Corrections in the totals are
introduced where definite groups consisting of carbon and hydrogen elements are
substituted qy groups which contain different numbers of carbon and hydrogen
atoms, and those in which hydrogen was replaced by Cl, N02' CH3' CN and other
groups. :By the gradual substitution of groups most closely simulating the ex-
ternal structural formula by other suitable groups it is possible to arrive at .
homologues; in the course of this process values corresponding to each substitu-
tion are added to or subtracted from the original total of factors, ~ f.
The calculation is simple and is based on the knowledge of the structural
formula of the substance. Factors for the original compounds and the correc-
tions are obtained experimentally. It has been established that each succeeding
member of -a homologous series is two to three times more toxic than the pre-
ceding member. Accordingly, substitution of G-CH3CH for the CH group decreases
the logarithm of the sum of the factors by 0.34, which is equivalent to the
division of the toxic concentration by 2.2. To~city intensification by sub-
stituting CCI for the CH group, according to this Table, requires that the con-
ceritratJon~logarithm be decreased b,y 0.14 or the absolute concentration divided
b,y 5.5, etc. Both MacGowan's formulas yield results in parts per million.
For the evaluation of the different methods of calculating maximum permds-
sible concentrations, the values derived were compared with the maximum permis-
sible concentrations fixed by law or suggested b,y Soviet industrial toxicologists.
This was done for 53 organic substances. In addition to checking the above four
formulas, calculations were made on the basis of average threshold concentrations
. for rabbits, divided by ten:
-32-
-------
.
GI
k 0
j ~j' I
i
1~'~-09'~
19'1-0~ '~
It" ,~'I
10'1- 0.'1
'9'0-00'(
1~'O-09'l1
6I'O-0~'O ,
6g'O-O~'O-
66 '0-09'0-
6£'1-00"-
ilL "-0."-
I-
I
~!
. PI
~o
j;1
01:)
j::1G1
8~
k I::
,\.tort
Jo III 00
s= GI
o III
orto
- ~ PI
NaSO
d8 k k
. ,~ PI
roIGlk
00
1Ig
'.0
.
J-- -g
~
rot
~
. I
I ~ I ~ I ~ I
::-: I:'" I'. I
-I--
I -~ I ,
I
,
-~i,
---I
L1:>
-CO') I <'::<0 ~L1:>
---
°1
~. '
L1:>
- C'I
where C
log C = log C1 - 1 (5)
= maximum permissible concen-
tration;
.,.
Cl = average threshold
tion using flexor
action eff~cts in
concentra-
reflex re-
rabbi ts,
It)
-::-!
after a 4o-minute exposure,
as the indicator.
Hence, formula (5) is based not on
physiochemical constants, but on ex-
perimental data.
Fig. 1 presents distribution curves
of logarithm deviations of calculated
concentrations from the logarithms of
~I
~ '"
L1:> ~
------
-""
- '"
---- ---
CD!:; ,', CD ~ 0> 00
"i--
~~=~ ~g
.r-
-CO')
.~ ;;;
L1:><'::
"':?
It)
-'~
=.
~
--
to-~
.00 C~ 0>.
~ -=-:"I-=-
Ll':.. I
- L"') ... aD - C'I
.;::
---
I I
~I
--
I I
-~
'"
-~
r- to-
U.S.S.R. regulatory concentrations.
The curves also show that according to
MacGowan's formulas the limits of al-
lowable concentrations for most sub-
-::-..
stances were too high. However, the
point of importance in this case is not
the poor correlation between the calcu-
lated values and the physical toxicity
of the sUbstances, but the excessively
high limits of permissible concentra-
tions in U.S. industries. It is only
natural that MacGowan's formulas should
cover a range of maximum allowable con-
centrations accepted in the United States
.
--
""
.' ,
. ,
. I
6 .......... .
....' N, i-f
. .
as' ,as' r-4
,-4, ,-4' I.
if: if, - .
~, .~ .' ~ . ~.
CH CH . .
O. ,0, ,J! . I!::
""...., o. o.
\.t CH,
fW)' H~ O.
t::', "I:: ..... 0, 0 "
.... '" ..... .......
'2', ~. 'G. ~. I:~ -, '
8' Ig. b . 0,' ~o I' :
~:c: ~ ~': I~ ~i,~,,",I~ ~Q"
,..-.; , laS ' ,
,-4' rot"
.. i::J . 6
r-4 ,a.
I' J4 '
........ :0'"
. fH . ,
'fiGi
~8
..1118
~31k0ortPl
kio1i~g
GI~,:ort~~
1.o6:::~
.goGi
Olk
. "
r-4 "
too
:H
~
and not in the U.S.S.R. For our ptU'-
poses it is important that there be a
good correlation with physical toxicity;
correction factors for lowering the con-
centrations can be easily introduced.
Correlation coefficients calculated
for values derived from different for-
-33-
-------
'td
44
i 40 .
\ \ J6 Ii \\
:-1 J2 , "
I s:l1 , ,
128 I \ \
, CD I' i
; 01 24 I ~ ,:
! ; E q
i !20 I.' \ i
: f.4' /'
i 1/6 /.' \ .
. CD, / . .
:P4!/2 ,.'
I. / .
! ! I ,:,
/ /
" ,.'
1,/ '....~ ,"
o ...
-1.4 -1.0 -0.6 to,2 D.6
Fig. 1. Distribution curves of limits of allow-
able concentra:t.iOXl deviations arrived at b.1 ditf-
e~J1f methods trom those adopted b,y or proposed
'.. to the U. S. S. R.
'Solid. line - distribution of experimental con-
centration deviations, heavy dash line - bas'"
'on solubility in water; light dash line -basec1
'on coefficient of distribution between oil aD4
water, dash and dots line - according to Mac
.Gowan's simple formula; solid fine line - aco.
ording to MaoGowan' s complex formula
mulas in relation to ad-
opted limits of allowable
concentrations, yielded the
highest correlation (82%)
with values obtained ex-
perimentally. Calculations
based on the coefficient of
distribution between oil
and water and on MacGowan's
complex formula, yielded a
correlation of 68%. Solu-
bility in water, according
to our calculations, was
60%; according to MacGowan's
simple formula, it was only
41%. The curves in Fig. 1
show that the spread of data
calculated by the American
formulas was considerably
greater than of the data
calculated according to our
formulas.
The value distribution curve derived from threshold concentrations for
rabbits has a median tending toward overestimation. In determining the cor-
relation of such data with adopted U.S.S.R. limits of allowable concentrations
and in deriving the correlation equations the need to decrease the values by
subtracting not 1 but 1.1 from the concentration logarithm became apparent.
If the v~lues obtained from MacGowan's formulas are to be brought into closer
agreement with the Soviet maximum permissible concentrations, their logarithms
must be reduced by at least 1.1. MacGowan's formula log C co ~f - 1.4 will
then appear as:
log C = ~f - 2.5
The limits of allowable concentrations established in the U.S. are based
on t~e assumption that it was safe to work at a pollutant concentration 1/25th
of the one lethal for insects. In the U.S.S.R., the lethal concentration for
-34-
-------
insects must be divided not by 25, but by 316 the antilog of 1.4 being 25 and
of 2.5 - 316.
Fig. 2 presents distribution curves obtained after making appropriate cor-
rectionsr i.e., after subtracting 0.1 fram formula (5) and 2.5 instead of 1.4
from MacGowan's formulas (3) and (4). Following such corrections the distri-
bution curves fell more in line with the maximum of data for each curve with a
deviation of : 0.2. The greater part of the data calculated accqrding to each
formula were within: 0.6 of the logarithm of the maximum permissible concen-
tration required by the Soviet regulation or within a range of values 4 times
higher or lower.
stances have strong irri-
tating effects related to
their chemical activity,
and it is not surprising
that a formula, based on the
assumption that a substance
hg. 2. DistributiOJ) C\lnes Qt li!J!i~~ S'f allow-
able concentration. de:'Q.ationsarrived at by diff- possessed only "physical"
eren~ methods trom those adopted by or proposed toxicity should yield in-
to the 1). s. a.-li., after the introduction of cor- '
- -recUoDs a8 indicated in the text congruent values. The maxi-
(Rest of legend 1s the same as in Fig. 1) mum permissible concentra-
tions for aldehydes were not calculated by MacGowan's second formula for lack
of certain constants. Results of calculations by this would place vinyl buty-
rate, vinyl proprionate and vinyl acetate, i.e., irritants with marked chemical
activity and "chemical" toxicity at the extreme'right end of the list.
It was not possible to calculate the maximum permissible concentrations
for aldehydes either by their solubility in water or b.Y the ratio of distribu-
I !.16
II....
, 32
: 23'
I ~ ul
, k 2(J
.
15
Pt
12
I
'8~
Most overestimated val-
ues according to MacGowan's
simple formula were obtained
for the following chemical
compounds: formaldehyde,
acetaldehyde, propionic al-
dehyde, vinyl acetate, butyl-
aldehyde, and vinylidenedi-
chloride. All these sub-
52
48
r ;44
; : 40
4
"
, 0 ", ,
-1.6 -1.4 -W -0.5 x0.2
". ,
". .""
-35-
-------
tion between oil and water because the coefficients of their fume solubility
in water, necessary for such calculations, were not known. Van Ventyan obtained
experimental data for formaldehyde and butylaldehyde. Values obtained for both
substances had a deviation range of ! 0.2.
Lowest deviations were obtained in calculations based on results of ex-
periments with effects of vapor threshold concentrations of the flexor reflex
response in rabbits. Only for 2 or 41 poisons (methyl alcohol and cyclohexanone)
did the calculations yield fourfold overestimated concentrations.
The specific action of methyl alcohol caused by its chemical transforma-
tions in the organism is well understood. In addition vapor of methyl alcohol,
like vapor of c,yclohexanone, is highly soluble in water and slowly saturates
the organism upon inhalation. The action of these substances is augmented by
increase in concentration and by exposure time. Naturally, correct results
cannot be obtained for such poisons with 40-minute exposure tests as the basis.
The data of A. P. Voronin derived from 8-hour experiments on rabbits were taken
as indexes of threshold concentrations.
If the threshold concentrations of
cyclohexanone at 8-hour exposure are t~en as the basis, the maximum permissible
concentration of cyclohexanone will be only twice the one proposed by the writer
on the basis of his experimental results. It can be concluded that all the for-
mulas cited were generally useful for the preliminary estimate of limits of al-
lowable concentrations of substances free from marked "chemical" toxicity, and
that appropriate correction factors must be introduced into MacGowan's formulas.
. .
The fact that MacGowan's simple formula produced the highest deviations must
also be kept in mind. For "chemically" toxic substances calculation by the for-
mulas determined upper limits; m~~imum allowable concentrations should be estab-
lished at levels below such upper limits.
In practice it is useful to make preliminary determinations of maximum
permissible concentrations by all methods applicable to each specific case.
Since limits of allowable concentrations were established for a comparatively
small number of ha~nful organic substances, preliminary calculation of an ap-
proximate maximum concentration would be valuable fer newly introduced sub-
stances as well as for substances currently employed in industry but little in-
vestigated.
-36-
-------
References.
Lazarev, N. V. Non-Electrolytes, Leningrad, 1944.
Lyublina, Ye. I. Farmakol. i Toksikol., No.6, 10-15, 1951.
Idem in the book: Jubilee Scientific Session, 30th Anniversary of the Lenin-
grad Institute of Industrial Hygiene and Occupational Diseases (1924 -
1954). SummarJ of Proceedings, Leningrad, 150-152, 1957.
Determination of the Direct and Indirect Effects of Pharmacological
Preparations on the Blood Vessels.
By
V. M. Khayutin.
(Institute of Normal and Pathological Physiology, A.M.S., U.S.S.R.).
Farmakologiya i Toksikologiya, Vol. 21, No.3, 78-81, 1958.
In measuring the resistance of blood vessels by the method of minute b.1
minute autoperfusion by regulated blood volumes, there appear two conditions
which make it possible to immediately determine the nature of the direct or
1
indirect effect of pharmacological preparations on the vessels of a~ organ.
The determination of the blood vessel resistance is based on the following
principle (Fig. 1). A perfusion pump (a - d), equipped with outside electro-
magnetic valves (e', ell) draws blood from the central end of the artery (f),
1 By direct effect is meant the change in tonus of the vessels of an organ due
to the action of a substance within the given organ, i.e., on the smooth muscles
of its vessels, or on the elements'of the peripheral nervous system found therein.
By indirect effect is meant the change in the lumen of the vessels due to the
action of the substance on the elements of the nervous system found outside
the organ in question, or due to reflex reactions to the vessels of this organ
arising after the introduction of the give~ substance.
-37-
-------
which supplies the given organ, and forces it into the peripheral end of the
same arter,y (g) in constant minute by minute amounts. Constriction of the
vessels forces part of the blood into a manometer (h), the pressure between
the outflow valve of the pump (ell) and the vessels of the organ rises, reach-
ing a new level needed to pass the desired minute by minute constant amount
of blood through the constricted vessels. Contrariwise, when the vessels are
dilated, their resistance to the blood flow falls and consequently the pres-
sure caused by the minute to minute constant blood flow through the organ also
falls. Variations in pressure are proportional to the type and degree of
change in the vessel lumen and, therefore, to the resistance by the blood ves-
sel to the blood flow.
.9'. t \ .i~
:" "I~\-
..' I ~,.\ ~J
.,' ';>.
,.1
, :~
Fig. 1. Plan illustrating the deterudnation of vascular re-
,'sistance by the autopertusion method on the minute inter-
, val basis.
a - Syringe; b -rigid conneoting tube; 0 - pumphead chamber;
d - an elasti c" finger valve" which separates the working
liquid (water) from the blood; e' and et' -outside electro-
:magnetic valves; t and g - cannulas inserted into the cent~
a1 and peripheral arterial termini] h - merour.r manometer.
..:..
-------........ ~.
a',
The apparatus here proposed was described in 1951 by V. M. Xh~tin,
V. ¥. Danchakov and V. L. Tsaturov. In this apparatus use is made of indepen-
dently ~e~~ated electromagnetic valves which Sttparate the organ vessels from
the animal's arterial system and the use of a constant wate~drive system.
The construction of the apparatus is such that the minute-by-minute discharge
of ~lood and perfusion pressure remain constant despite fluctuations in the
animal's arterial pressure.
-38-
-------
This is the first condition which makes possible the differential obser-
vation of the direct and indirect effects of pharmacological preparations on
the vessels of an organ under ~tudy. The second condition is created by in-
corporating into the arterial system of the organ an auxiliar,y artificial cir-
culator,y system consisting of cannulas, connecting tubes, and elastic "finger"
of the ?!~usion pump, (Fig. ld). Accordingly, to the blood circulation time
T (e.g., from the.femoral vein to the arterioles of the organ under study)
additional time t is added, equal to the time required for the blood to pass
through the artificial system. Time t can be determined by dividing the amount
of blood contained in the system (V ml) by the volume of the blood per second
(Q ml/sec) forced through by the perfusion pump:
V~
Q ~/sec = t see
Take for example the effect of intravenous injection of adrenaline It
enters into the arterioles of the major circle causing their constriction and
increasing the cardiac output per minute. The result is a rise in the arterial
blood pressure. As noted above, suCh pressure has no direct effect on the per-
fusion pressure; therefore, it remains unchanged at first. It begins to rise
only after a lapse of time equal to T + t, i.e., only after the adrenal in has
entered the vessels of the organ. The marked time interval between changes in
the arterial and perfusion pressures is the manifestation of the direct effect
of the substance in question. This is confirmed by the kymogram shown in Fig.
2a which is a record of the reactions of the arterial pressure and of the pres-
sure of the hind leg vessels of a cat after intravenous adrenalin injection.
The interval between the pressor reaction of the arterial pressure and the
beginning of leg vessels constriction, as revealed by a rise in the perfusion
pressure, equalled 22 seconds. With a blood inflow of about 18 ml per minute,
(as roughly determined from the scale on the pump) and pulse beats of 120 per
minute, the amount of blood perfused is 0.3 ml per second. In this case the
capacity of the perfusion system was about 6 mI. Consequently, the adrenal in
could not reach the vessels of the leg earlier than 6 ml: 0.3 ml/sec - 20
seconds.
This statement applies
get into the vessels except
lateral vessels. Different
only if the substance under investigation cannot
through th~ perfusion pump, i.e., through the col-
time relations develop between the reactions of
-39-
-------
I a --,
2'0 '
~m
arterial and perfusion
pressures in instances
where the injected sub-
stance affected the
central nervous system
or the elements of the
peripheral nervous sy&-
tem outs~de the perfused
organ.
Fig. 2b is a reoord
of the effeots noted
lP"
,.-
after intravenous in-
jeotion of niootine.
The pressor reaotions
. 1 I I'. I I I
Fig.' 2. Cat's hind leg vascular reaction to the
intrajugular injection of (a) 25 mgjqHofadren-
al1n and ('b) 4 -/kg of nicotine. Records from
top down. ,perfusion pressure. ill th~paroUd arte17
(mercu17 mauometer, zero (base) 1i~ of perfusion
and arterial pressure, respi~~tlon mark showillg
the injection of test subst~oe .intrajugular17;
time-30 seo. Dotted line - latentreaotion period.
of arterial and perfusion
pressure ocour almost
simultaneously due to
the well known stimula-
tion of the sympathetio
,ganglion by J'~:i.~iI~in~ a and b of Fig. 3 illustrate the time oorrelations fol-
lowing the injeotion of vasodilators papaverine and tetamon.
In the first instanoe vasoular dilation, in the extremity began 9 seoonds
after the arterial pressure fell; in the second instance the reaotions oocurred
simul taneously. The oapaoi ty of the, perfusion system in these experiments was
3 ml, whioh at a rate of blood flow of 0.4 ml per second, delayed the entranoe
of the substance into the extremity vessel by 7 1/2 seconds. Suoh delay didn't
appear when ganglioblooking tetamon was used; it appeared atter the injeotion
of papaverine, which aots directly on the vessels.
Fig. 4 presents a reoord of the r~actions to adrenalin, substantially dif-
ferent from those shown in a of :li'i$.2. The perfusion pressure fell the moment
the arterial pressure rose; but not as a result of the direct effect of adrenal in
on the vessels of the extremity. The vasooconstriction phase actually began 28
seconds after the injection of the adrenalin (perfusion system capacity 6 ml).
Evidently the initial dilatation phase was due to the reflex elioited by the
rise in the arterial pressure, or to some other effects of adrenalin on elements,
-40-
-------
of the nervous system located outside the
perfused extremity. The experiment s of
D6rner (1956) and of several others were
more in line with the first possibility.
Thus, by registering the resistance
of vessels in autoperfusion tests as here-
in described, it was possible to make a
quantitative evaluation of the degree to
which the resistance of vessels changed
after the action of pharmacological agents,
as well as to elucidate the direct and in-
direct effects of the preparations on the
---
~---Lj
-~-'
1- b
~7fi-
loo \~
I
I
I
I
I
I
/20 .;-
1,1/
I I
I I
I I
I I
/00 ':
I
1,0
~
L~Q"
~~
--=--- ~I
3* :--~---~J' 30" - b --~
I I I I I I I I I ~ I I I I I I I I I I. I I I I I ' I I . I
Fig. 3. Cat's hind leg vascular -
reaction to int~a ~1--"r__injQct;----1
ion- (f~ ot ~"p~r1n~
and b 5 DIg of tetamone. Reo-
ords from top down same
as in Fig. 2;
!,\
j
blood vessels. The latter ~ be determined ex-
actly by enlarging the capacity of the perfusion
system. The panCipar-inerit of the method is
that it permits to differentiate between the
hemodynamio and striotly vascular factors whioh
,determine the level of blood supplied to the
organs.
Referenoes.
IChayut in , V. N.
1957.
:Byull. Eksperim. :Bio1. i Med.,
D8rner, J.
Pflftg. Arch., 262, 265, 1956.
-41-
I'D
~'
.
, I
I
I
6~-~
~
r KI'~MHJ'1r1 tfl'''''
. :-..-.-
. I I I
. . . .
Pig. 4. Two-phase eat's
hind 1eg-.vascular reaot-
iOl1 to- intrajugu1ar in-
jection of 20 mg/kg of
adrenaline First phase
is indireot, second phase
is ~ direct vascular adre~
al1n effeot.-
Records from top down S&88
as in F1g. 2. .
(.) - 20 - mtljkB ot &dreD&l1u I
-- intrajUPlarlT
-------
/
An Apparatus for~ the Determination of Dispersed Polyelemental Air Pollution.
:By
P. N. Matveev.
(Institute of General and Community Hygienet Academy of Medical
Sciences, U.S.S.R., Moscow).
Lab. Delo, Vol. 3, No.1, 47-48.
The air of populated areas ~ be polluted b.Y dust, gases and microorgan-
isms. Prior to proposing measures for the prevention of air pollution it is
necessary to determine the degree and the deleterious effects of the pollution.
M~ methods have been proposed and are now in use for the determination of
the degree of pol!ution with inorganic substances and for the determination of
~~~Q~~~~~~~~~nthe air; however, none of the methods have been completely
satisfactory. The colorimetric method using Petri dishes and solid media fails
to register the degree of air pollution at the v~ry time of the experiment;
furthermore, the developed bacterial colonies do not present the true air pol-
lution picture, sinoe the open surfaoe of the dish is in a stationar,y position
in relation to air current changes caused b.Y turbulent conditions.
The apparatus herein described allows the simultaneous collection of air
samples for the determination of air dustiness, configuration and chemical
composition of the dust particles and for the identification of the microbial
population. It consists of four parts: a collecting chamber with two micro-
scope slides forming an angle of 900 for the quantitative, morphological, and
qualitative chemical analyses of the particles; depressions at an angle of 450
to hold Petri dishes with appropriate media for the stu~ of the airborne micro-
.... --
organisms; a wind vane which keeps the 'open part of the collecting chamber and
the Petri dishes exposed to the blowing wind, and a supporting stand.
The apparatus can be used under all conditions. It requires no source of
power for its operation, it. is portable and can be used undercomp~loa.tea.-con-
ditions of atmospheric air investigations of inclosed spaces.
The apparatus was used in the stu~ of the degree of pollution and the
bacterial population of atmospheric air under a variety of conditions at tam-
o 0
peratures as low as -40 and as high as +50 .
-42-
-------
Fig. 1. Assembly side viaw
(Support not shown)
1 - Trapping devicej 2 - Pat-
ri dish holdari 3 - wind vane
devicei a - Tana wing} to hol-
low tuba fitting aver support
rod
fig. 2. Swinging part of
assembly at 3/4 turn. Sup-
port not shown
1 - Holders for grease co-
vered microscope slides;
2 - hollow tube, fitting
over support rod
An Apparatus for Work with Hydrogen Sulfide in the Open.
V. P. Mikhailov.
Lab. Delo, Vol. 4, No. 3, 55-56, 1958.
In laboratory procedures such as the determination of vitamin C, the
quantitative separation of metals, etc., hydrogen sulfide is used as the basic
test reagent. The Kipp apparatus used in such cases is bulky, costly to oper-
ate and the H_S must be generated under a hood. This author developed an ELS
generator which can be operated on the laboratory table without the use of a
hood.
-43-
-------
The unit is assembled as shown in the
drawing. It consists of three heavy-walled
test tubes (A, B, C) 2 - 2.5 cm in diameter;
a calcium chloride tube (l), glass T-joints
(2, 3, 4), screw type clamps (5, 6), Mohr
pipette (7) which is shortened at both ends,
rubber stoppers and connection tubes.
The apparatus is operated as follows:
the absorber tube (C) is filled with a
20 - 30$ solution of caustic soda; snail
pieces of iron sulfide are placed into gas
Apparatus for work with hydrogen generator (A) over a rubber fitting (ll);
sulfide in the open.
it is then gradually lowered to the bottom
of the generator tube. The fitting can be made of a rubber stopper having two
or three notches along its circumference. Clamp (5) is tightened and tube (3)
is 2/3 filled with dilute hydrochloric acid; the top opening of tube (l) is
immediately closed with a tightly fitting rubber stopper through which tube
(10) passes, thereby connecting tube (l) with tubes A, B, and C through T-joint
(4), as shown in the drawing. The test liquid, through which the H^S is to
pass, is poured into test tube (B). At this point openings (8, 9) of T-joints
(2, 3) must be sealed by clamps or glass rods. The flow rate of hydrogen sul-
fide can be controlled with the aid of a screw clamp (5). Excess of the gener-
ated gas forces the HC1 back into the calcium chloride tube (l), thus deceler-
ating or stopping further gas generation; isolated H2S bubbles forced in tube
(l) from fine fragments of iron sulfide carried into the tube with the rising
acid, pass through tube (10) into the alkali containing absorber.
Hydrogen sulfide remaining in the analyzed liquid is forced out by carbon
dioxide coming in through tube (8) from a separate CO. generator or some other
suitable source. Prior to this, clamp (5) must be securely tightened to com-
pletely stop any further flow of HpS. To ascertain that H-S was completely
replaced by the CO the clamp at (9) is released very cautiously and a lead
acetate moistened filter paper brought close to it to test for the presence of
K?S; if the hydrogen sulfide has been removed completely the paper will show
no color formation.
Clamps (5, 6) should be tightly closed when test tubes with the analyzed
-44-
-------
liquid are replaced or the charged unit is stored between analyses.
If all connections are airtight and the changes of the absorbing alkali
solution are well timed, there will be no escape of hYdrogen sulfide.
The removal of spent reagents and washing of the gas generator should be
done outside of the laboratory.
The proposed unit is sin~le in construction, easily installed in any labo-
ratory and can be used in routine or training work.
A Contir.uously Operating Stationary Water Aspirator.
:By
P. G. Kil'kovskii.
Sofia Transport Medical Laboratory (Bulgaria).
Gigiena i Sanitariya, Vol. 23, No. 12, 69-11, 1958.
Sulfurous anhydride is an important sanitary-hygienic atmospheric air pol-
lutant. This laboratory had the task of determining the presence of S02 in the
air surrounding large railroad terminals of Bulgaria.
Investigations of sulfurous ~dride require the aspiration of relatively
large volumes of air. To obtain a correct picture of the average daily concen-
tration of sulfurous anhydride it is necessary to sample the air continuously
over a 24-hour period, or at definite time intel~als. This can be accomplished
only with the aid of an appropriately designed aspirator. Tbe comcon water
aspirators of 5 - 10 Ii capacity were found unsuitable for this investigation
due to their small volume capacity which required three work shifts for their
operation. For the present investigation a stationary water aspirator was
needed which provided uninterrupted air aspiration at a steady rate without
requiring constant human attendance; its installation, operation, and servicing
had to be simple and easy and the apparatus had to be of a wide range of versa-
tility.
-45-
-------
.:?"'
In designing a new aspirator, oonsideration was given to the following:
it is known that ohanges in the height of the water column determined the rate
of water flow. Therefore, it was neoessary to provide a oonstant hydrographio
pressure under constant conditions to obtain a water stream flow of a constant
rate. The new aspirator__~~_~_1n Fig. 1 consists of the following parts: a
5 - 10 Ii capaoity cylindrical vessel labeled 3, with.metallic pipes of 10 mm
diameter, labeled 2, 8 and 9, attached to it. Pipe labeled 8 is connected to
a wate~ supply faucet by means of a rubber pipe of same diameter, through
which water continuously flows into vessel 3. Pipe 9 is connected with a
hydrostatic pump, 10, through which the water is discharged. Overflow pipe 2
extends 5 - 8 em short of the level of the vessel and serves for elimination
of excess water. The water inflow rate is slightly greater than the outflow
rate whioh helps to maintain a water column at a constant level. This assures
a constant hydrostatic pressure for the operation of the pump which, as a con-
sequence, aspirates the air at a constant rate. To compensate for any lessen-
ing or stoppage of the water flow, a simple automatically recording installation
is attached to the aspirator. A float 4 is plaoed in vessel 3. The float is
provided with an axis 5, shaped as seen in Fig. 1. The axis terminates with a
stylus 6 whioh records on a bearer 7. 'The automatio recording device operates
as follows: when the water column is maintained at a constant level, float 4
remains on the water surface. The stylus registers this initial position on
paper placed over the bearer~ Any reduction in the rate of the water flow or
its stoppage lowers the water level in tank 3 and causes the float to drop down,
whioh is recorded by the stylus on the paper as a straight line. This registers
the stoppage of water flow. Pipe 9 extends 5 om above the bottom of tank 3, so
that the water in the tank retains.that level when the water flow stops; this
is recorded by the float. If pipe 9 had terminated flush with the bottom of
tank 3, the water would flow out without being automatically recorded. To ac-
count not only for the stoppage of the water flow, but also for the duration
of suoh stoppage, it is essential that the stylus retain its reoording contaot
with a drum revolving around its axis over a 24-hour period.
The aspirator is calibrated as follows: the aspirator is
tion, i.e., the water level reaches the level of overflow pipe
excess water flows out through it. The order of connecting the installation
when air samples are taken is shown in Fig. ~.
set into opera- ,
2 (Fig. 1) and
-46-
'-
..
\
,
-------
-
-
-5
'-r-...-:"."-'-"
, .
, .
. ,
, ,
: I
~ . i
: i : i
i; !!
"5
1
z
rig. ..2.SQh8J!1!t. of. .~~l~ ~()~~e~:t~1".~~t~P.
\
Aspirated air p_~sses through absorbers 1 (in
this case two successively connected absorbers)
charged with 5 ml of 5% KCI03 solution; the air
passes through the fl~wmeter 2 which determines
the volume of aspirated air, and through water
manometer 3, which measures the pressure drop.
The speed of the air current is regulated by means
of clamp 1 shown in Fig. 1. For more precise cali-
bration the rate of air flow is measured with a flowmeter as shown in Fig. 2
for a period of 5 - 6 hours. The volume of air is calculated on the basis of
the gas meter reading. The volume of air passed through the gas meter is
divided by the time of aspiration, giving the rate of air flow expressed in
liters per hour or per minute. After that the flowmeter is removed. The pres-
sure drop of the air flow is regulated with the help of a manometer after which,
as in the case of gas meter calibration, the manometer is also removed. This
concludes the calibration process.
The aspirator runs uninterruptedly. The absorber should .be recharged with
fresh absorbing solution once ever.y 24 hours, an operation which takes 5 - 10
minutes. Depending on the character of the investigation recharging of ab-
sorbers can be done ever.y 2 - 3 hours, which facilitates the carr.ying out of
dynamic investigations. Usually the aspirator is installed on premises fitted
out with water supply and canalization (sewer system). This prevents freezing
of the aspirator in the winter. Suction of atmospheric air for investigation
is done through an air probe. For this purpose rubber or glass pipes with a
10 mm diameter were used. Knowing the time of aspiration, it is easy to find
the volume of air passing through the absorbing solution. The absorbing solu-
tion is poured into the test tubes, the absorbers are washed several times with
disti~ledwater, recharged with the absorbing solution and then attached to the
Pig 1. StaU0D&r7
oont1nuousq oper-
ating water aspirator.
I
{
-47-
-------
aspirator for future studies. The aspirator is presently widely utilized in
practice and yields reliable results.
Conclusions.
1. The stationary continuously operating water aspirator described is
applicable to sanitary-hygienic investigations of air polluted with gases,
mainly with sulfurous anhydride.
2. The aspirator permits carrying out of dynamic investigations without
requiring continuous presence of a human observer.
3. The aspirator is easy to install and to service.
4. The water consumption does not exceed more than 10 times the volume
of the aspirated air.
Bibliography.
A..aeltcee.a It\. B., ABAPOR08 6. E., fYPBHU C. C. HAp. Oupuene.e
apq1lKx 8elUecT8 8 B03J1yxe npoH3BOACTBeRHblX DOyelIttHHI. M., 1954. - 6 Y P m.
Te IRA. H. MeTOAbi caHHTapHO-rHrHeHHqecKHx HCCJleAOBaHHA. KHeB. 1950. - 0 R )I( e.
MeroJUI 1ICC.IIeJ(00aBHA SanWJIeRHOCTR R S8JI.blMJleRHoCTH I03AYxa. Kae8, 195:'. - P . . a.
.. o. B. A. CaHHTapHa8 oxpaHa aTwoc4lePRoro 803J1yxa. M., 1954.
A Device for the Evaluation of the Dust Collecting Property of
Wetting Agents.
By
S. A. Nikitina and A. B. Taubman.
Institute of Physical Chemistry, Acade~ of Sciences, U.S.S.R.
Gigiena i Sanitariya, Vol. 23, No. 12, 71-74, 1958.
Results of physiochemical investigations of wetting agents used in the
abatement of silicosis-causing dusts indicated that the fundamental mechanism
of their dust-collecting action was based on physiochemical laws. The effective-
ness of their action was found to be specifically cor~ected with the molecular
structure of the colloidal-chemical characteristics of the surface active sub-
-48-
-------
stanoes. This makes the experimental evaluation of the properties of water so-
lutions of wettil18 agents more important and interestin8. In this connection
the inoreasing produotion of synthetio surfaoe-active substanoes offers the
possibility of their wide use in the next years for the control of si1icosis-
causing dusts as cheap and easi~ obtainable wettir18 agents. Under suoh con-
ditions the utilization of wettil18 agents represents-one of the simplest and
highly effective means for the increase of dust collecting properties of water
used in drilling blast holes or in bringing down air-suspended dust. In this
paper a device is described_f~r_the evaluation of the effectiveness of dust
collecting properties of wetting solutions. This device is in effect an im-
provement of an apparatus formerly used in the Institute of Physical Chemistr.y
of the Academw of _Sciences~ U.S.S.R.; with the present device reliable and
easily reproducible results can be easily obtained. The principle of the de-
vice is the same as of a water spr~ wet scrubber.
In the studies here described dust collecting with water and wi~h wetting
solution spr~s was done simultaneously in air having the same degree of dust
concentration. Such a procedure made reproducibility of results easier and
more precise. In addition it enabled a more precise comparative nephelometric
evaluation of the dust sedimentation results obtained by water sp~ and wet-
ting agent solutions.
It is important to note that "static" conditions of aerosols formation in
the ~bsenceof air currents insure a uniform distribution of dust particle
clouds throughout the entire dust chamber and at the same time make possible
the fractional determination of polydisperaed dust within the device. The
desired degree of dispersion can be attained and regulated on the basis of
precipitation t~e calculated b,y Stokes formula (on the assumption that the
particles were spherical) and the subsequent checking of particle size micro-
scopically. Such fractional dust determination obviates any effect of dust
"age" or its tendency to agglomerate, etc.
The device (see picture) consists of a dust chamber which has a diffuser
(1), three burettes - one for water and two for the wetting solution (2), and
small beakers (3), one of which is for the collection of freely (normally)
precipitating dust. The beakers are placed on a platform suspended from the
cover of the chamber (4) and are covered with metallic lids; with the help of
,
,
-49-
-------
an electromagnet, placed outside the device, the lids can
be removed before the start of the tests.
The dust chamber is a large bottomless cylinder having
a diameter of about 25 em, a height of about 60 em and a
volume of approximately 25 - 30 li. An ebonite cover fitted
. with a rubber gasket to an ebonite ring, placed on the upper
part of the cylinder, hermetically clos8s it and prevents
. the dust from escaping into the atmosphere and diverts it
through a special pipe into the exhaust ventilation.
. The diffuser, in the shape of a bent tube 10 - 12 rom
. -- ~ i.']. diameter, is set into a rubber stopper in the covering
of the device. A weighed amount of dust (0.1 - 0.2 g) ~s
" ;
;1 " I placed into the straight part of the tube which is connected
;( with the air under 0.3 - 0.4 atm. pressure. Inside the
i'; J~ diffuser are projections which diffuse the dust uniformly
i':'~
". it: ::,,::t withO;:e"::~~l~:g;~rst dried at 105 -= 1000,-sifted-through
.' j a 5000 - 6000 mesh sieve and is kept in closed boxes in a
,;a
~~ desiccator. To prevent moisture from entering the devioe
and to prevent dust particles froe adhering to each other,
the air is dried in a 50 em long calcium chloride tube before
it enters the diffusion tube.
Burettes for the water and for the wetting solution, of
25 rom capacity, are placed into special holders attached to
. the cover of the device in such a way that their lower parts
~;,~~~ protrude 8 -10 mm into the chamber. Each burette is fitted
:;' 4i ',,/ ,w.
, . !' wi th one ordinary and one micro stopcock which permit fonna-
,
. .~~ . .~..- ..~>.~ tion of droplets of a wide range of sizes.
The distance which the droplets fall must be not less than 40 - 50 em to
enable them to gather a sufficient quantity of dust particles. In the lower
part of the dust chamber, on a special platfonn suspended from the cover (4),
glass receptacles are placed for the collection of the dust and droplets. For
this purpose it is convenient to utilize standard 22 - 25 ml capacity penicillin
flasks, having a 12 - 14 mm diameter at the top. With a greater diameter a
greater quantity of free precipitating dust enters the receptacle, thus increas-
-50-
-------
ing the magnitude of the correotion faotor (see below) and lowering somewhat
the preoision of the determination values. As mentioned above, to reduce the
quanti ty of free (spontaneously) precipitating dust during the dusting of the
ohamber, the colleoting glasses are kept oovered with light lids while the dust
is admitted into the chamber. The lids are joined so that both oan be lifted
or placed in position in one operation. Before the test begins, the lids are
-automati~~I1i--removed with the aid of an electromagnet. To prevent the dust
collected on the lids from falling inside the collecting glasses the covers
are fitted with a flange oovered with a thin layer of glue. The devioe is in-
stalled in a true vertio~l position so that droplets separating from the tips
of the burettes fall through the neck to the receptacles.
With this device evaluations can be made of the general effectiveness of
the wetting agents in relation to droplet size, the hydrophilic action of their
adsorption layers, as well as the adsorption effect alone by separating it from
the total effect. For the comparative stu~ of the general effectiveness of
the wetting solution use is made of equal volumes of water and of wetting solu-
tion, working with oapillary pipet_tes havinB' tip openings of equal diameter, so
that the number of droplets of water and of solution is different due to dif-
ferences in their surface tension. For the determination of the adsorption ef-
fect alone use is made of burettes with different cross-seotion tips so chosen
that the droplets of water and of the wetting solution are equal in size.
It is easy to select t~~-right opening cross section if the tapering part
of it is conical by gradually grinding the tips down and counting the number of
droplets coming per unit volume. In all measurements the volume of liquid used
must be 10 mI.
The test proper is performed as follows: the oover of the dust chamber is
removed. The burettes are plaoed into the holders and filled correspondingly
with water and with wetting solution. The micro stopcocks are then opened to a
point which would permit a flow of droplets at a constant rate; such for example
as 10 ml in 3 minutes. Then the two glass containers are covered with the
double lid, described just above. The c,ylindrical dust chamber is tightly
closed, a weighed quantity of dust placed into the diffusor tube which is then
connected through a caloium chloride tube to a source of compressed air and the
actual comparative tests are begun.
Diffusion of the dust in the dust chamber takes one minute, after which the
-51-
-------
comp~essed air is shut off. With the aid of the electromagnet the double lid
is r~noved from the two receptacles; simultaneous~y the regular burette stop-
cocks are opened; the micro stopcocks have been set previously to a regulated
position. After exactly 10 ml of liquid will have run out from the burettes,
the stopcocks are closed and receptacles 1, 2 and 3, containing the dust sus-
pension, and receptacle 4, containing dry dust, are removed from the dust cham-
ber. The test is repeated 15 - 20 times and the final result calculated as
the mean of the total of determinations. The test precision is ~ 10%.
The quantity of dust collected by the liquid droplets is determined by
nephelometer l~. The pure water suspension of dust particles may partially
agglomerate, ther~by, affecting the true turbidity value; to prevent this,
some wetting solutio.., ~sed in the study, is added to the conc~ntrated water
suspension, used in the ~~st. The same wetting solution is used in making a
suspension of the dust freely precipitated in receptacle 4. The turbidity of
this supension is subtracted from each of the other three nephelometric readings.
Turbidity (T) in the nephelometer used is the ratio between the reading (R)
of the tested suspension and the reaqing (Ro) of the standard which is a clout\1
glass prism of unit value. Hence, T = R/R. As an example the dust collecting
. 0
ability of t~e 0.1% solution of a wetting agent DB is evaluated herein on the
basis of experimental data.
After conclusion of the test, the content of each of the four receptacles
were diluted to a final volume of 25 ml as follows: into the first receptacle
containing 10 rnl of dust suspension in water 10 m1 of 0.1% DB solution and 5
ml of distilled water were added, making a volume of 25 ml; into the second and
third receptacles, each containing a dust suspension in 10 ml of 0.1% DB solu-
tion, 15 ml of distilled water were added; into the fourth receptacle, with the
'free settled dust, 10 ml of 0.1% DB solution and 15 ml of distilled water were
added. The turbidities were then determined as described, and mean values of
each set of 15 - 20 tests were calculated.
The following symbols were used in formulating generalizations: E = total
or general effectiveness of dust collecting; Ead = adsorption effectiveness of
dust collection; rl' r2 and r) = cross-section radii of burette outlets used
for water and for wetting agent determinations of E and Ead; Rl' R2 and R3 =
corresponding radii of droplets flowing out of the burettes; T~ = relative
value of dust-water suspension turbidity; TO = relative value of turbidity of
c
-52-
-------
.dust-wetting solution suspension turbidity (rl '" r2' I1. '" R2); ~~-ad '" relative
value of dust-wetting solution 'suspension turbidity (rl = ry Rl 1:1 R2h T~::a
relative value of freely settled dust suspension.
The turbidity of dispersion medium enters into all values of T. Relative
o 0
values of turbidity will equall for wetting agents To = Tc - TA and for water
T '" TO - T~.
w w -
Dust collecting ability of the wetting agents:
Tc Tc-ad
E . r and Ead = T
.W w
ErAfl\Pl&: T: - 0.39; T~ '" 0.47; T~-ad '" 0.45; T,& = 0.34.
From this the following corrected turbidity values are derived: T '" 0.05;
w
T '" 0.13; T d . 0.11, E a 0.13/0.05 '" 2.60; E d '" 0.11/0.05 1:1 2.20.
c c-a . a
Extensive' experimental material accumulated indicated that the described
device yielded precise and'reproducible results in the investigation of the
relation between dust collecting properties of wetting agents and their chemical
composition, molecular constitution, solution concentration, etc. All this
constitutes information of value to the proper selection of the -most suitable
wetting agents and most appropriate concentrations.
Bibliography.
P e (5 II H A e p n. A., C e p (5 . C e p (5 H H a H. H.,K 0 PAlO K 0 B a C. A B KH'
6opb6a C C:H.lHKOJO... M., 1953, T. I, CTp. 57-68.-TaYO,,'aH A. 5., HRX.TH':
. . a . C. A. B KH.: 50pb(5a c: CHJlHK030... M., 1955, T. 2, CTp. 61-70.-.01111 . e
l!oU. AH CCCP, 1956, T. 110, Hi 4, C:Tp. 600-603. .
nOCTyDU8 IIIX 1068 r.
-53-
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~he Use of Battery Combustion Chambers in the Purification of Industrial
Emissions into Atmospheric Air.
~
S. P. Belousov, A. S. Dun, and I. I. Nikberg.
Gigicna i Sanitariya, Vol. 24, No.4, 10-11, 1959.
The selection of effective measures for the purification of industrial
emissions prior to their discharge into the atmospheric air plays an important
part in the problem of sanitary protection of atmospheric air. Ma~ different
methods have been proposed and tried for the purification of waste gases from
suspended substances, such as the dry methods by the use of cyclones, battery
cyclones, etc.; wet gas purification by different types of scrubbers, filtra-
tion through porous materials and electrostatic precipitators. As a general
rule these installations are used where only partial sanitary purification of
the waste gases io required and the utilization of such gas purifyine equipment
to the full extent of their efficiency may not be imperative for the attainment
of the prescribed sanitary conditions of the industrial plant. Certain secon-
dary factors m~ be frequently responsible for the lowered efficiency of the
acove mentioned gas purifying insta1lation~. As an example of such factors
mention can be made of the frequently arising difficulty of removing and util-
izing of the gas purification products, which may result in the complete shut-
ting off of their operation.
In this connection the use of gas purifying installations in an industrial
plant is of considerable interest due to the fact that the nature of the plant's
production made the continuous and efficient operation of the gas purifying
installation an absolute prerequisite.
The gas purifYing installation was of the type used in one of the Donbass
(Don basin) coke-pitch plants of the coke-chemical industry. The coke waS
roasted in batteries of open flame furnaces of the "Yuzhkokremont" system;
each battery consisted of 10 - 15 open flame furnaces.
Prior to this experimental stu~ the plant had no gas purifying equipment;
all the uncombusted products of pitch coking and the suspended particulate mat-
ter were discharged directly into the atmospheric air, hoavily polluting it
with dust, soot and gaseso According to estimates the daily emission of sus-
pended substances amounted to no less than 250 m (?). Fig. 1 is a schematic
-54-
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nologica1 process preclud-
ed the use of purification
installations of the usual
type. Therefore, reconstruction of the batter.y furnaces was carried out which
consisted in rebuilding part of the furnace into purification installations of
the supplemental combustion
chaI!1ber type. Thus, the
exhaust gases coming. from
the furnace flues were
J .
F1g. -1. Gas flow path in pitoh-coke ovens before
the installation of oomplete combustion ohambers.
1 - Smokestack; 2 - firebrick lining; 3 - flue for
gas colleotion, 4 - subfloor channel,- 5 - furnace
i .. chambert 6 - p~ outflow channels.
z
+ . uutw&rd gas movement
. J IJlW&~ gas movement
~
.;
Fig. 2. Gas flow path in pitch-coke,ovens after th~
..-hsta'-1I8:tlon of comPlete combus.t1on chambers.
1 - :Dinas brick lining, 2 - smokestaCk, 3 - 3 -"-4
meters smoke stack extension, 4 - firebrick lining,
5 - gas oombustion chamber, 6 - &1.r hole; 7 - oven
ohamber, 8 - gas outflow ohannels;
9 - flue for gas oolleotion.
-55-
illustration of the course
of emission of ~aste gases
before the introduction of
the change.
In compliance with
the demands of the State
Sanitar.y Inspection Agency,
the coking batteries were
rebuilt to insure their
more efficient combustion
and a reduction in the at-
mospheric air pollution.
Peculia.ri ties of the tech-
passed through the supple-
mental combustion chambers
before entering the seoke-
stacks, as schematically
illustrated in Fig. 2. The
supplemental combustion of
pitch-coke waste products
is accomplished at 1150 -
1500°. This high tempera-
. ture is attained by sucking.
in extra air through spe-
cial openings in the supple-
mental combustion chamber.
-------
The important feature of the structural and procedural changes introduced
is the fact that the original basic plants in the pitch-coking plant remained
undisturbed; another important feature of the modification was the fact that
the normal operation of the supplemental combustion chamber assured the nomal
'operation of the battery furnaces. Results of ten months experience with the
supplemental combustion chamber proved its effectiveness with regard to the
complete combustion or the pitch coking waste products, and demonstrated that
pollution of the surrounding air was considerably reduced.
Rapid Determination of Nitrogen Oxides in the Air of Industrial Premises
by Special Tubular Iridicators.
By
L. A. Mokhov, Yu. F. Udalov and V. S. Khalturin.
Zhurn. Prikl. Khim., Vol. 32, No.2, 452-453, 1959.
The detection and ~~antitative determination of nitrogen oxides in plants
which produce nitric and sulfuric acids, various types of nitrated organic
compounds, azo dyes, etc., is of great importance from the sanitary, hygienic
and technical viewpoints. Tests for the qualitative and quantitative presence
of nitrogen oxides for the above mentioned purposes are made frequently; hence,
there is need for a simple and rapid method which can be performed by persons
of average education and of no special training.
Many of the existing methods for the determination of nitrogen oxides by
the use of the Griss-Illosvay reagent were discussed in recent reports [1 - 3J.
Determinations of nitrogen oxides by the method above referred to are made in
the liquid phase; other methods use carriers which absorb oxides of nitrogen,
and, in so doing, undergo change in color. Some authors [4J proposed the use
of filter paper saturated with an alcoholic solution of benzidine as the ab-
sorbing material. Other authors proposed the use of silicagel onto which the
Griss-Illosvay reagent has been adsorbed [5J. As the tested air passes over
-56-
-------
the treated silicagel, the oxides of nitrogen are adsorbed and the color of the
indicator changes. Quantitative estimations are made on the basis of the color
intensity developed or on the ~epth of its penetration into the silicagel [6].
Fillipychev and Petrov [1] studied the action of nitrogen oxides on amino-
compounds; their results indicated that the aromatic amines were easily diazo-
tized in the presence in the air of dry nitrogen oxides. This observation lead
to the development of a method for the determination of nitrogen oxides and n-
aminobenzoic acid [8]. The determination of nitrogen oxides [2] was based on
the following: when air containing oxides of nitrogen is aspirated through a
solution of amino-benzoic acid, the latter becomes diazotized. Subsequent
combining of the diazotized n-aminobenzoic acid with H-acid produces a perma-
nent4Y~~t~~f of a crimson-red color, the intensity of which is proportional
to the concentration of nitrogen oxides present in the air.
This reaction has certain advantages over the generally used Griss-Illosv~
method; however, like the latter, it is a liquid phase method which hinders its
wide usage. Using this reaction and taking into consideration all the requisites
[1] published in recent reports, these authors developed a new method for the
rapid determination of nitrogen oxides by means of a tubular indicator L9J.
The method is as follows: H-acid, n-aminobenzoic acid, and nickel chloride
were adsorbed upon silicagel. The gel indicator thus obtained gradually changed
its initial color from light pink to a brown-red in the presence of nitrogen
oxides; the different shades of color depend upon the concentration of nitrogen
oxides. As the result of the reaction between the oxides of nitrogen and the
n-aminobenzoic acid diazonium salt is formed. The diazonium salt then combines
with the H-acid which is the nitrogenous component in this reaction, while the
nickel chloride acts as the catalytic agent to form the dyestuff.
The gel indicator is prepared in the following manner: 20 ml of a saturated
alcoholic solution of H-acid was added to 1 g of sific~~~and mixed for 2 min-
utes; the alcohol is evaporated while stirring; 20 ml of 0.5% alcoholic solution
of n-aminobenzoic acid is then added; the indicator is dried with continuous
stirring, and 0.5 ml of 0.1% of alcoholic solution of nickel chloride is added;
the indicator is dried while stirring, until it becomes granular.
The tube indicators are prepared as follows: one end of a glass tube, 80
to 100 mm long and of 3 to 5 mm inside diameter, is drawn out and sealed. A
'~}ass wool or cotton wad is inserted through the open end as far as the cone-
-51-
-------
shaped end, and the pad is gently packed; this is followed by a 3 mm. layer of
dried quartz sand or silicagel, and bya 2 mm layer of the silicagel indicator;
the latter is overlayed by a 2 mm. layer of dr.y quartz sand or silicagel; a pad
ot glass wool or of cotton is then placed over the sand, gently packed by means
of a glass rod and sealed. The tube indicators can be stored indefinitely.
In making nitrogen oxide determination in the air, both ends of the tube
are opened, and 100 ml of the air to be tested is aspirated through the tube
from the wide end in the direction of the cone-shaped end; the coloring of the
indicator is compared with that of a standard scale, and the amount of nitrogen
oxides expressed in mg/li.
The standard scale is prepared by passing looml of air through a series
of tube indioators; the air contains progressively increased concentration of
nitrogen oxides. The tubes are then sealed and stored. The respeotive shades
of oolor can be reoorded on paper by a color sensitive person.
The sensitivity of the proposed tubular indioators was determined by cheok-
ingagainst the standard Griss-Illosvay method; it was found to be 0.0005 melli.
Check determinations were made by the tube and Griss-Illosvay methods. The
results are listed in the Table below.
Results of oxides of nitrogen determinations by the indicator
tube method of Gr1s~I1osvai.
. I Colorimetric determina- I Concentration determined
Calculated capacit7 COD-'ition by the Gr1ss-Ilosva1i by the ii1d1cator tube
centrat10n in mgfl1: lDethod 1n mgfl1 i method in mRIl1
0.00056
0.0028
0.0034
0.0053
0.0055
0.087
0.09
0.095
0.1
0.1
0.00055
0.0028
0.0033
0.0051
0.0053
0.1
0.093
0.097
0.098
0.12
0.0005
0.003
0.003
0.005
0.005
0.085
0.9
0.1
0.1
0.1
Note: Nitrogen oxides in the cubic oontent was obtained by means of a reaction
,/
of sodium nitrite and hydrochloric acid.
-58-,
-------
The data i~ the Table show that the tube indicator method for the deter-
mination of nitrogen oxides in the air was accurate and reliable. ,Its use is,
therefore, recommended.
The specificity of the reaction was tested by aspirating through a tubular
indicator vapors of ether, hydrochloric acid, mercur,y, carbon bisulfide, nitro-
gen, ammonia and carbon monoxide. No changes in the coloring of the tube in-
dicators were noted.
Temperature changes from 10 to 250 recorded in industrial establishments,
or changes in the relative humidity of the air within the range 40 - 90% had no
effect on the determination results.
Bibliograp~.
1.' A. Zhitkova. Express Methods for Determining the Noxious Gases in the Air
of Industrial Establishments. Goskhimizdat, M.-L. (1946).
2. I. N. Xuzminykh. Control of Nitrous Gases. Goskhimlzdat. M. (1945).
3. A. Te. Por~-Koshits and A. V. Chorvinskaya. AKP, 3, 8, 339 (1933).
4. W. Arnold u. N. Mondel. Ber., 35, 1324 (1902).
5. M. G. Lukina. Instruction for the Express Determination of Nitrogen Oxides
in the Air-of a Mine after an Explosion. Inst. ekhrany truda. Sverdlovsk
(1949).
6. -T. G. Platonov, Te. D. Filyanskqa.
26 XI, 1953.
1. S. F. Filippychev and P. P. Petrov. AlP, 3, 8, 351 (1933).
8. L. A. Mokhov and Tu. F. Udalov. Laboratornoye Delo, 4, 19 (1955).
9. L. A. Mokhov and Tu. F. ~dalov, V. S. IOl1turin. Avt. avid. No. 110041 ct
1 XI, 1951.
Avt. svid. No. 99812/449, 189/3165 ct
-59-
-------
Carbon Dioxide Absorption b7 Pot~ Solution Foam.
.4 .
B,.
I. G. Plit and K. N. Shishkin.
Dnepropetrovsk Chemical-Technological Institute.
Zhur. Priklad. Xhimii, Vol. 29, No. 10, 1323-1329, 1956.
PUt and. Shishkin [1] showed that poorlT soluble gases were absorbed at a
comparative~ rapid rate in foam scrubbers. On the basis of that an experimen-
tal stu~ was undertaken of the process or carbon dioxide absorption b7 a solu-
tion of potassium carbonate. PUt [2] established that the mechanism of such
process followed the principles of chemical absorption associated with a revers-
ible chemical reaction in the liquid phase, when the constant Kp of the rate of
the chemical reaction exceeded respectivelT the values of the coefficient Dl .
of carbon dioxide diffusion IpUl the ooefficient D2 of the chemicallT active part
of the absorbent in liquid film; this was in agreement with Posin's classifioa-
tion [3].
The
rate of the prooess can be determined fram equation
G
r . Ief . Ct
t
where the coefficient of absorption Kt depends on the site of the reaction zone,
and consequentlT, on the concentrations of tlie reacting substanoes. '!'he lIIpel-
lent tactor Ct ot the process, which is the mean logarithmic value of the solu-
tion volume, is determined more easilT from equation (1) than fram the equations
proposed b7 Pozin [3]. Therefore, equation (1) was used in prooessing the ex-
perimental data. '!'he stu~ of the course of the absorption process in toam
sorubbers is complicated by the fact that the contaot surface of the phases is
unlmown. On the other hand, the application of a stud.y method inwhioh the
prooess rate, or the absorption coefficients, are functions of the absorption
volume of the appara tus ~ present an erroneous pioture of the course ot the
process, due to the fact that with the use of a foam head the ooeffioient of ab-
sorption and the t11le of the foam head, that is, the specifio surfaces, ars
functions of common parameters. '!'he present experiments were carried out with
the aid of an apparatus which enabled the stu~ of absorption on the basis of
individual bubbles and whioh made possible the computation of the oontaot sur-
(1)
-60-
-------
faoe of the phases. Suoh a prooedure ma,y not be in exaot oorrespondence with
the charaoteristice of a sorubber in praotioe, but the qualitative charaoter-
istics remain preserved, so that it becomes possible to stu~ the effects of -
ditferent factors and to evaluate them on a oomparative basis.
The apparatus oonsists of an absorption tube
1, and the absorbent solution container 2. The
upper end of the absorption tube 1s oonneoted
with spherical vessel 3, having a tused-in burette
4; the lower end ot the absorption tube 1s eD-
larged in a conical formation and is submerged
below the .surface of the absorbent solution. A
carbon dioxide-air mixture enters through nozzle
5; simultaneousl7 foam bubbles were created in a
weak saponin solution. Through the cone-shaped
end of tube 1 the bubbles asoended into the ab-
h denotes the average height of the small bubble
cp
the course of the experiment;
w denotes the rate of the cylinder movement;
r( denotes the duration of the experiment;
n denotes the total DUmber of a,ylinders.
The phase contact surface was computed according to
d2
, . (2 _4 + wdh ) x n
cp
Upon leaving the absorption tube and entering the spherical container the vol-
ume of the bubbles changes. This destroys the bubble, and the liquid acoumu-
lates in burette 4 where it can be measured aocurate17.
The first set of experiments was devoted to the stu~ of the effect of the
surface-active admixture ooncentration upon the oourse of the absorption proc-
ess. The experiments were conducted with mixtures containing respective17 7.16%
~g. 1: EJ;perimental apparatus
(Se8 text for description)
lowing formula:
where
sorption tube and moved along as short equa1l7
sized oylinders. The number ot bubbles during
the experiment was computed according to the f01-
h
~ naatT
... -\.
(2)
cylinders measured in
the tollowing tormula:
(3)
-61-
-------
and 21.8% of carbon dioxide by volume and 150 g/U of K2CO)" The saponin con-
centration ranged from 0 to 4 g/li. The data of the experiments are plotted
in-Figs. 2 and 3. Curves in Fig. 2 show the functional relation between ab-
A
1)13 \0 ~3
I)fl '-/
o
0.09
o
o
o
2
f
sorption rate and the saponin con-
G
oentration, expressed as: i.
Curves in Fig. 3 show the func-
tional relation between the ab-
sorption coefficient and saponin
concentration. It is apparent that
both sets. of curves are of a simi-
lar type, indicating that a decrease
in the absorption rate and in the
absorption coefficient occurred at
low saponin conoentrations such as
0.6 g/li; at concentrations ranging
within the limits 0.6 to 1 g(li the
absorption rate and the absorption
coefficient rose to certain mRTimal values.
0.03
11010 f 2 3 . 5 Fig. 2.
Effect of saponine concentration on
absorption rate 2
Ordinate - Absorption rate in kg/m Ihr
Abscissa - Saponin. concentration in
gfl1 .t soluticm
Carbon dioxide % and Co correspondingly:
1 - 7 and 14, ?- -168.nd 18, .3 -21.8 and 14
A
3
Q
2
o
0.020
b
3
6
1
Fig. 3. Effect of saponine concentr-
ation on the absorption coefficient
Ordinate - Abs,0iP.tion coefficient
111 ,k8!r/Ar/m01/1i
Abscissa - Saponine concentration
in gjl1 of solution
Gas % and CO correspondingly'.
1 - 7 and 14, 2 - 16 and 18;
3 - 21.8 and 14
Further increase in the saponin conoen-
tration showed no appreciable effects upon
the rate or coefficient of absorption.
The similarity of the ourves points to
the existenoe of a definite relationship
between the diffusion resistance and the
respeotive saponin conoentration in the
solution. Concentration of saponin with-
in the limits of 1 to 1.1 gfli resulted
in the formation of a saturated adsorp-
tion l~er which characteristioally man-
ifested a minimal diffusion resistanoe.
The me."(imal resistanoe appears in the range of unsaturated l~ers with a
concentration olose to 0.6 gfli. The latter is in accord with the results of
. other investigators, in particular of Pokhil [4], who showed that maximum vis-
00s1 ty e110i ted by the islet structure of an unsaturated l~er oocurred in the
region of the saturated f1lm. As conoentration increased the film density also
-62-
-------
increased accompanied bT a rapid destruction of the islets which resulted in a
sharp drop in the film viscositT at the point nearing saturation.
It i8 known that the ratio between diffusion resistance and viscosity i8
of the order ot 1/6 and that the absorption coefficient was inversely propor-
tional to the viscosity in a 5/6 ratio. For this reason the curves obtained
olosely followed the law of the viscosity changes in an unsaturated adsorption
layer. After the adsorption layer became saturated, no further changes were
caused in the absorption coeffioient b,y increase in saponin concentration; the
coefficient acquired a constant value, approximately corresponding to the ab-
sorption by a solution with 0.1 gfli saponin concentration. Of the above dis-
cussed two possible concentrations with maximum absorption coefficients the 1
to 1.1 gfli concentration should be regarded as the optimal, because of the
greater firmness of its adsorption films which form the foam bubbles, and con-
sequently the scrubber foam head. According to the theory advanced by Tolmud
the firmness of the adsorption layers reached its II'I:::I.Ti IIIIIDI before a saturated
adsorption layer was formed, in the case of saponin solutions this holds true
only for freshly prepared solutions. Tolmud, Sukhoval' sltaya and Lubman [5J
showed that the firmness of a saponin film increased with "aging", and that the
fimness of an "aged" film increased with the concentration. Accordingly the
rate of gas flow through the scrubber process in each particular case constitutes
the factor determining the saponin concentration most appropriately, even though
ocoasionally it may be greater than 1.1 g/li. However, the usual absorption co-
efficient which corresponds to the optimal concentration for diffusion resis-
tances, i.e., 1 - 1.1 glli, may be used in the computations.
Another factor of equal importance is the effect of the adsorption layer
at the oontact surface of the phases on the rate of the absorption process. Data
available on the subject, particularly with reference to the usual film absorp-
tion, are highlT contradictory. According to some data a decrease in surface
tension resulted in a greater absorption coefficient; in connection with this,
it is recommended that special surface-active admixtures be introduced into the
solution. [6]. However, Ternavskii and Belopol'skii stated [1J that, contrar,r
to the above, the mass-transfer coefficient was greatly reduced by the addition
of even small doses of surface aotive agents. For this reason, and in order to
compare absorption rates, experiments were oonducted with 1200) solutions con-
taining no saponin and 16% gas-air mixtures. The dotted extensions to the zero
-63-
-------
point of curves in Figs. 2 and 3 present the results of such experiments. It
can be seen that the presence of an adsorption layer at the phase contact led
to a considerable increase in the absorption coefficient and, con8equentl~, to
an acceleration of the absorption process, the rate of which was doubled. The
adsorption layer lowered the surface tension of the solution at the surface of
phase separation; however, it also enhanced the diffusion of the gas into the
liquid thereby enhancing the absorption rate.
A Fig. 4 shows the ratios between
2
the volume of the gas (w) that passed
through, and the volume of the solution
(u) collected in the burette during the
experiment and at different saponin oon-
603 centrations. The wju ratios reflected
o f 2 J * 5 6 the capabilit~ of the adsorption films,
Fig. 4. Effect of saponine concentrat- which formed the bubbles, to entrap a
ion of the amount of solution per foam definite amount of solution. The greater
. . bUbble.
Ordinate - u/w ratio; abscissa - sapon- the value of wju, the lower was the amount
ine gjli. Gas %: 1 - 18, 2 - 14. of solution retained by a bubble, and
.:!!.2!. versa. An increase in the ooncentration of saponin reduced the value of
wju, and consequently increased the quantity of the entrapped solution. The in-
crease persisted up to the formation of a saturated adsorption l~er. There-
after, the ratio w/u remained constant. Under the conditions of the experiment
the value of the ratio at 18.50 was 19.6 and at 140 it was 18.3. The thickness
of the film forming bubbles, computed on the basis of above data, ranged between
0.1 - 0.15 mm.
Fig. 5 shows the results of experiments conducted in the stu~ of the ef-
fect of absorbent solution oonoentration upon the absorption ooefficient. The
experiments were conducted with 7% and 16% gas at 14°, an optimal saponin con-
centration of 1.0 slli. The concentration of the absorbent solution varied be-
tween 50 to 200 g/ll of K2C03.
Increase in the absorption solution ooncentration reduoed the absorption
coeffioient. Nevertheless, it does not follow that the solution concentration
should be made as low as possible. A higher solution concentration has a greater
chemical capacit~; hence, where the larger capacity, consequent to a greater con-
centration, rose faster than the corresponding reduction of the absorption co-
o
0.05
I
0.04
-64-
-------
fO
fOO
150
200
o
efficient~ the use of concentrated so-
lutions may be more profitable. The
IllATill'n1m rate of the process for the
system under oonsideration was obtained
at 150 gjlio Up to this maximum the
rate of the process increased with the
conoentration. At higher concentra-
tions the absorption coeffioient de-
creased faster than the rise in the
. chemical capaoi t1' of the solution,
oonsequently, the rate of the process
decreased~ It can be ooncluded that
A
::~
o
Fig. 5. Effect of saponine concentration
on the absorption coefficient
Ordinnte - Abe~~tion coefficient
in k8/m2/hr/mol/li
Abscissa - K2CO in 8/1i
Gas percent: 1 ~ 7.2, 2 - 16
the optimal concentration for the absorption of carbon dioxide by a foam head
corresponded approximately to the molar concentration or, more precisely, to
1.09.
The rate of the absorption coefficient change ~ be expressed b.1 the fol-
lowing empirical formula:
x .. X 150
t 0 a
a denotes the concentration of solution in g/li;
K denotes the absorption coeffioient at solution ooncentration of 150
o
gin.
The reaction zone position is determined by the concentration of the ab-
sorbing solution and by the concentration of the gas to be absorbed; this points
to the existence of an absorption coefficient which depended upon the concentra-
tion of the gas to be absorbed. Suoh an assumption was substantiated by ex-
periments with gas conoentrations ranging fram 5% to 38% by volume, at 18.50.
The concentration of the absorbing solution was 150 gill of 12C03 and 1 g/li of
(4)
where
saponin.
Fig. 6 shows that an inorease in gas oonoentration increased the absorption
coeffioient according to the following empirical rule:
_1 1.23
r = p
(5)
absorption coefficient at 18.50 expressed
where ~ stands for the value of the
in kg/m2 x hour. mOl/Ii;
p denotes the gas concentration
expressed in fractions of unity.
-65-
-------
A
Unlike the concentration of the
absorbing solution, the rate of the
absorption steadily increased with the
128
o
increase in gas concentration.
This was
Of
oz
03
~5
04
due to the fact that with the increase
in the absorption coefficient the
checical capacity of the solution also
a fO
001
Fig. 6. Effect of gaB concentration on
the absorption coefficient
Ordinate - Absorption coefficient
in kgfm2fhr/mol/11 .
Abscissa - Gas concentration in frac-
tion of a unit
increased.
Because of the specific nature of
the experiments, studies of temperature
effect upon the rate of absorption were
limited to the range of 140 to 20°.
The effect of temperature upon the ab-
Of5
sorption coefficient is shown in Fig.
7.
(120
o fO
The curve shows that the absorp-
tion coefficient diminished with the
rise in temperature. Absorption co-
efficient values within the limits of
140 to 180 can be dete~ined by the
o 14 f5 ffj 17 f8 f!1 ZO 5
Fig. 7. Effect of temperat~re at 16% of
Rae on. the absorption coefficient.
Ordinate - Absorption coefficient
in kgjm2/hr/mol/li
Abscissa - Temperature in Co.
followir~ formula:
l~
Kt .. K t1.9
(6)
where t denotes temperature in degrees Centigrade;
~ denotes the value of the absorption coefficient at 18.50.
While the mean logarithmic value of the solution capacity increased slightly
with a rise in temperature, the rate of the absorption process diminished. Thus,
absorption by the foam bubble was more intense at lower temperatures.
The effects of basic factors on absorption rate of gases by discrete bubbles
was investigated. The optimal concentration of K2C03 and saponin solutions, the
absorption coefficient at a given gas concentration can be computed with the aid
of fo~la (5), and later correcting for temperature according to formula (6).
If for any reason the absorbing solution concentration exceeds or falls below
150 8/11 of X2C03' then a correction for concentration can be introduced with
the aid of formula (4). The absorption coefficient determined in this w~ holds
-66-
-------
true only within the conditions of the conducted experiments. In this case the
conditions were: absorption by discrete bubbles which moved at en average rate
of 3.8 em/see, a rate which was maintained throughout all the experiments.
In group of intimately close multibubble, or foam formation, the
absorption coefficient largely depends on the rate of the foam moveroent. At
higher rates of foam movement the phenomenon of solution entrappping increases
at the moment of bubble foam formation, due to the fact that the qUantit~ of
liquid retained in the film increased markedly. An analogous phenomenon was ob-
served with the movement of a discrete bubble; as soon a6 its diameter became
greater than the diameter of the absorption tube, its movement became impeded,
accompanied by greater solution entrapping.
From the viewpoint of the course of adsorption the fact just mentioned is
of considerable importance. This was proven b,y the experiments conducted at
different rates of gas movement. As the rate of gas movement increased, the
ratio w/u, i.e., the ratio of gas phase to the liquid phase diminished and,
therefore~ the amount of the solution retained by each bubble increased. This
brought about a sharply increased turbulence in the movement of the film liquid
particles which formed the bUbbles, thereby lowering the diffusion resistance.
The absorption coefficient and the rate of absorption increased.
In the case of foam scrubbers, this factor can not be accounted for with
the aid of any coefficient, due to the fact that the "crowding" conditions in
the course of bubble group movement through
the absorption tube differ greatly. The
needed correction must be determined ex-
perimentally with the foam scrubber in
A
~
az
af
o
J
~
5
~
Fig. 8. Effect of velocity of bubble
movement on absorption coefficient.
Ordinate - Abso~tion coefficient
in kg/m2fhr/mil/li
Abscissa - Velocity of bubble move-
ment in cm/seco-
Gas %: 1 - 19.5, 2 - 27.2
operation.
Conclusions.
A stu~ of the effects of different
factors on the course of carbon dioxide
absorption b.y discrete K2C03 solution
bubbles indicated that absorption by foam
bubbles proceeded in accordance with spe-
cial ~drod1namio conditions which lowered
diffusion resistance and enhanced the
kinetics of the process.
-67-
-------
-'
Bi'bl1ographtr.
[1J H. r. nJIBT n IC II. IIIHIIII{JIH. Tp. :l.'-TIf,!j (1(56).-12) H. r. TlnHT
Tp. JlXTIl. 4 (1955).~[:1I M. I;. IIO;:UII,. iI\I,lX, XIX, 1y~t1 (1946).~
[4) n. (]'I. TloxHn, Ihl1>X, Xl" (19(1)). --I"') ,l.,;1. 1 OJlMY!\, C. ;(. CyxoBalJl.-
CKIIJI H H. T. Jly6Mlln. mq..\:, J/, I (1!J:I1),-'16) B. ~L PaMM. A6copU/tHOIIHIJl>
"pO/tet'CI.! II xH!ofll'leCKOii npoMhllII.leIlHocTu. rOCXHMH:J;WT (H)51). -171 A. II. T e pHil R-
CKall Ii A. rt. r.eJlono.lbc"lIii. il,'D.\:, XXI'I (1952).
Purification of Exhaust Gases of a Sulfuric Acid Tower Plant by a Flowmeter
Pipe Type of Apparatus.
By
M. L. Varlamov9 Go Ao Manakin and 1a. I. Starosel'skii.
(The Odessa Po~technica1 Institute).
Zhurna1 Prikladnoy Khimii, Vol. 31, No.2, 178-186, 1958.
The purpose of this investigation was to test the flowmeter pipe, or
Venturi pipe type, of apparatus for the recover,y of spray, sulfuric acid fog
(aerosol) and nitrogen oxides from the exhaust gases of a sulfuric acid tower
plant. The experimental apparatus was treated in one of the tower system plants
of the H2SO4 industry. It was hoped that in addition to the sanit817 purifica-
tion such an arrangement might reduce the consumption of nitric acid and cut
down the sulfuric acid wasteo
The acidity of the exhaust gases in plants
depends principally on the presence of nitrogen
gBli°3
or 6 T 10 3 ) accompanied by a 10.. rate of NO oxidation, which complicates
nul of gas .
the process of purification to a considerable degree. Furthermore, the gases
.' - ~SO
contained spray and fog of sulfuric aoid (1.5 .;. 3 2 ) and sulfUr dioxide
nm3 of gas
[1, 2]. The acidity of the exhaust gases also depends on the rate of the sys-
tem's operation, type of oonstruction, technological p:J;ocess parameters, the
condition of the equipment, methods of acid distribl.1tion, etc. The f01'lll8t1on
operated by the tower system
oxides (,,-,,0.2 : 0.35% NO, N02
-68-
-------
of H2S04 spr~ and of fog m~ take place in the wet electrostatic precipitators
installed at the end of the system; however, such filters do not collect such
gaseous components as nitrogen oxides and S02. These electrostatic precipita-
tors do not attain a sufficiently high degree of gas purification at all times
[3].
The use of ooncentrated H2S04 spray in the last absorption tower of the
nitrose system reduced the H2S04 in the exhaust gases by approximately 50% [4],
and the loss of nitrQgen oxides by 30 to 35% [5J. The use of commercially de-
livered acid proved costly and, therefore, inexpedient. High exhaust staoks
improved the sanitar,y conditions only in the immediate production surroundings,
but failed to be of help in the purification of the exhaust gases or in the
recovery of eoonomically valuable components.
Apparatus of the type of flowmeter pipes have been used successfully b.y
many plants for exhaust gas purification [6 - 8J. However, such apparatus has
not been used in plants producing H2S04 b.y nitrose installations of the tower
type. .
The experimental set-up used in the present experiments consisted of two
units: ~ small assembly, producing up to 50 m3/hour, and a larger one producing
up to 500 m3/hour.
In tube No.1, shown in Fig. 1, the fluid entered the main channel of the
apparatus at an angle; in tube No.2, the fluid entered tangentially and became
distributed evenly over the perimeter of the diffuser. In this type of tube the
gap between the colleotor (konfuzor) and diffuse~' is controlled by rotating the
head of the apparatus.
Apparatus No.3, shown in Fig.
its main axis. The separator walls
ly, whioh foroed the passing gas to
3, had a radial fluid feed in relation to
of the small unit were arranged ooncentrioal-
impinge upon the surface of the liquid twioe
in sucoession.
The type of tube shown in Fig. 4 was tested in connection with the large
unit. This tube had two radial fluid feeds set at 900, and a separator of the
type of abbreviated cyclone TsKTI. No oontrol fluid feed was used in the ex-
periments described.
Water was used as the absorbing fluid. It could also be fed into the re-
action zone of the tower system in pla~e of technological water whioh contained
absorbed nitrogen oxide and sulfuric aoid. The exhaust gases were purified in
paoked sorubbers in a similar manner [9, 10].
-69-
-------
.130
~fOO
.58
~
?"z-z '",
section
48. :. .17
~
z"
"
<:>
~
.50
I
.JO
/ ~
/
W.!1_~her
16 -30-2
'"
~ TSRMMit1
Section ,,1-1"
Fig. 1. Apparatus No.1 with water inf?ow at an
angle to the-aat:i-a ef'-t-he tube.
(Dimensions in Figs. 1, 2, 3 and 4 are in mm)
A soda solution in a concentration ot 5 .;. 30 g/l1 was also used as the ab-
sorbing tluido Because ot the complex! ty ot analyzing gaseous and liquid phases,
ditferent assembly types were tested at the experimental installation shown in
Fig. 5. Gas tor the tests was taken from the conduit which connected the last
-70-
-------
- -
----I
I,
Section thru
A-A
Fig. 2. Apparatus No.2 with water int ow tangential to
mixing chamber.
tower of the system with the exhaust gas cyclone, and was drawn through the
installation b.Y the force of partial air vacuum caused by the exhaust fan.
[The following persons participated in the analytical work: 11.)1. Kaza-
kova, M. Yu. Viner,1\(. S. Gutman, V. Kosovets and R. Varvarslcqa. J
The gas which passed through apparatus No.4 w.as measured b.Y a Venturi
tube; the gas which passed through the small unit was determined diaphragmatical-
ly. Fluid consumption was measured by flowmeters. Control me,asurements were
made by diverting the fluid flow into graduated containers. Content of H2S04
spray and of nitrogen oxides was determined with the aid of glass wool or
~groscopic cotton and vacuum containers of 20 liters capacity. Glass filters
No.4 and colorimetric tubes were also used. Results of ana:qses were calcu-
lated in the usual way [l1J. Under the experimental conditions S02 concentra-
tion in the exhaust gases was negligible, amounting approximately to 0.1%. The
concentration of nitrogen oxides was also relatively low, so that the 502 oxi-
dation during the gas aspiration could be disregarded. The ratio of gas volume
to the fluid volume was taken as one of the basic parameters. This ratio is
designated as g:f and is an immeasurable quantity; the gas volume was reduced
-71-
-------
with the widening of the
opening between the col-
lector (konfuzor) and the
diffuser. For apparatus
No. 4, ~p depended on
the consumption of gas as shown in curves of Fig. 7. For values of gaf ~1000,
.6P was practically independent of this ratio, and was equivalent 40 .;- 120 mm
of water column, it depended upon the construction of the apparatus, the rate
of gas flow in the orifice of the tube, the fluid consumption, and the angle of
inflow.
~130
4>100
.....
-
4, :4>17
c::,
~
50
....,
'"
4>50 ~
We
'ee
ea
16-30-Z
cal
one
r
'--' '<")
'" -
..., -&
38
"'"
~
section'" 1- 1 "
"f'
....
.....
....
I"
..
"
-- I
Fig. 3. Apparatus No.3 with water inflow
radial to the axis of the tube.
to standard temperature
and pressure. The lat-
ter determines the grav-
ity force of the gas flow
andthe~o~~icco~
d1 tions of the apparatuso
The specific fluid con-
sumption expressed in
11/nm3, is determined as
the reciprocal of the
ratio g/f.
An investigation of
the hydrodyn~ics of the
gas and fluid flow in the
tubes described showed
- that a fluid inflow at an
angle to the main axle of
the tube considerably low-
ered the pressure drop of
the apparatus (Ap) as
compared with the radial
inflow as shown by curves
in Fig. 6. Ap increased
in the case of tube No.2
The mechanism of absorption of the acid components from the exhaust gases
V'.
-72-
-------
-0014>1
fil~-f
~f: ~I ,
~r -.. - -t---- './'
"'
..,.
....
.:,~ .
1.
""
'" .
f
I
t
-: +i- ~I
':;?
I
rl1 ! i
rI.i ,.
~ ~ II
N
,g .
''''.r ,
- .
~: t
;:;:
...
°1 -----~---~
~
u~-- --
-I
II:
o
~
!f+-I
s::
.....
F-i
-------
Parameter A as a function of g/f ratio.
.
.
Pipe!
No. i
Pipe
diameter
in ram
: Parameter A at g/f ratio
i equal to
i 250 I 500 i 700 i
.
i
i
1000 :
:
Liquid
Indicator
1
2
3
4
4
20
11
20
48
48
1.05
3.3
2.8
5.5
3.3
0.9
3.05
2.5
4.6
3.15
0.73
2.7
2.1
3.85
3.0
0.52
2.5
1.80
3.1
2.8
Water
Water
Water
Soda soln.
Soda soln.
Methyl orange
Phenolphthalein
Phenolphthalein
Phenolphthalein
Mixed indicator
1
- --
---
~
~
- ---
---
- --
1Z
'5
----
-- -
---
, To tower No.2.
Tower No.3
Fig. No.5. Operational and technological plan of the large installation
1 - Apparatus No.4; 2 - separator; 3 - device connecting the last absorpt-
ion tower with the cyclone of the exhaust gas system; 4 - small pressure
tank; 5 - small circulation tank; 6 - vacuum pump, RMK; 7 - centrifugal
pump; 8 - sp~ catcher, RMK; 9 - Venturi meter; 10 - water meter; 11 -
flow meter for liquid entering apparatus; 12 - colorimetric tubes; 13 -
line (level) of taking samples of gas upon entrance into the apparatus;
14 - ditto at gas exit; 15 - sample taking of liquid upon entrance into
the apparatus; 16 - ditto at liquid exit.
-74-
-------
Values of ~ for different pipes.
Pi i Pipe i
peidiameteri
No.: . :
: J.n mID :
: :
Gas used
nm3/hour
iGas velooity i
! at throat i
i in m/sec i
. .
Absorber
! Value of ~ at g/f ratio
I equal
i 250 i 500 I 700 i 1000
1
2
3
4
33 - 60 29.4 - 52.9
23 - 58 67.3 - 170.0
27 - 59 23.7 - 52.0
220 - 490 33.8 - 74.5
Water
Water
Water
Soda soln.
20
11
20
48
4
,
'l
,3
2no
100
------
(I
jO
tOf!
150
35.0
26.5
38.5
31.5
27.2
34.0
39.0
27.5
28.0
28.0
39.5
24.0
29.0
22.0
10.0
The curve in Fig. 6 in-
dicates that the value of ~ was
practically independent of the
ratio g:f, and that a value for
~ approximately equal to 40%
was attained in apparatus No.
4 with a soda solution. The
average content of acid compo-
nents of the gas entering the
tubes amounted approximately to
8 + 10 gfnm3 and consisted
principally of oxides of nitro-
. gen. The rate of spray and of
sulfurio acid fog absorption in
the tube was determined individ-
Fig. 6; Comparison of hydrolio resistanoe
(pressure drop) of apparatus No. 1 and No~' 3
having the same throat diameters at differ-
rent rates of gas flow, .
Ordinate - Hydrolic resistanoe (pressure ually. Numerous experiments in-
drop) p in DIm of water column, abscissa - dicated that for tube No.4,
water cqnsumption in li/hr.
Gas flow in ~ /hr: 1 - 20, 2 - 30; 3 - 40. with a 3 consumption of gas rv
a - Apparatus No.1, b - apparatus No.3. 400 nm /hour, an average sprq
3
and ~S04 content at the entrance/V'1.4 gfnm , ~ was equal approximately to 80%
and that it was practioally independent of the g:f ratio. In packed towers the
absorption was considerably lower [9, 10J, despite the greater spray and tog
concentration and the considera.bly lOJ188r stay in the apparatus. The rate of
spray and fog absorption in the tubes can be still higher, as is shown in pre-
viously published reports [12, 13J. A comparison of the degree of absorption
of low conoentrations of oxides of nitrogen (T) from nitrose gases in apparatus
-75-
-------
A
\
of different construction in-
dicated that the values of ~
attained in the experiments
100
under discussion were of the
same order as those ootained
by other investigators [5, 10,
6
400 14 - 11J. However, the rate
Fig. 7. Hydrolic resistance (pressure drop) of absorption in the flowmeter
of tube No.4 as the. function of v?lume flow tubes was considerably higher
rate of gas at llquid consumptlon of '
145 - 160 li/hr. . . while the overall dimensions
Ordinate- ~drolic resistance (:~res~re drop) of the apparatus were smaller.
p; absclssa - gas flow rate In m /hr.
Ratio of gas to liquid (g/f): The comparatively low values
1 - 660; 2 - 1330; 3 - 2100. obtained for ~ can be explained
principally by the fact that the nitrogen oxides were not proper~ conditioned
for most favorable absorption. Technological conditions which prevail in a
tower system with a slight peroxidation of NO toward the end of the system, en-
hance the absorption of oxides of nitrogen from exhaust gases by alkaline solu-
tions.
o
A stu~ was made of the operational characteristics of the flowmeter tube
type ot apparatus along with a comparison of their ettioienc,r with that ot
packed towers. This was done as follows: the coefficients of volume rate ab-
sorption were oomputed according to formula Nul.. .,(Re, Pr) for apparatus work-
ing on the principle of spray dispersion of the reaction fluid [18J, and also
by the tOl'mUla of Nukiyama and Tanasava [19J used in computing average drop
diameters.
The volume rate coefficiont of absorption of N203 in relation to the tube
k8W203
orifice was 1"V400,000 3 . For the apparatus as a whole the value of
m hour atm
this coefficient was considerably lower.
. kg!l203
eftioient were 50,000 3 ' whioh is approximately 80 to 100 times greater
m houratm
than tor packed towers.
The total consumption of electric energy per 1 t H2S04 was 5 to 6 ki1owatt-
hours, or 10 to 12%.0£ the total electric power used in the production of 1 t
at sulfuric acid by the tower system.
The g:t ratio in these computations was taken as equal to 1000 + 1200 and
The experimental val]1~s at this co-
-76-
-------
A
b'C' 0 c
00 0 I>-
40 00 n,... 0
: 0 o:J 'gO' 0 0'0
20
a 6
/000 2000 3000 4000
Fig..8.
No.4 on
Effect of ratio g/f in apparatua
- --
the degree of exhaust gas purif-
ication 1).
- Ordinate - degree of absorption 1) in %.
Abscissa - ratio g/f.
A p . 250 mm of water column,
plus an allowance for resistance
of the communication and separator
systems.
Conclusions.
1.
In cases of linear rate
of gas flow at the tube orifice
ranging between 30 : 75 m/sec,
gaf of 750 to 250, and water as
the absorber, the pressure drop (6p) ranged between 40 and 120 DID of water.
The value of A p is less for a tube with an angle fluid flow.
2. Using flowmeter tubes in alkaline absorption of H2S04 spray or fog
and of nitrogen oxides of average initial concentration equal approximate~ to
g H2S04
to 10 3 ' the absorption rate was~4O% as determined by provisional ca1-
nm gas
culation of H2S04 acidity.
3. The comparatively low degree of total exhaust gas purification ma-Y be
explained by the lack of preparation (conditioning) of nitrogen oxides to a~
sorption. The acidity of the exhaust gases depended basically on the oxides
of nitrogen.
4. The power consumed in the operation of the flowmeter t~~e type of ap-
paratus in the purification of exhaust gases emi Ued by the tower ni trose sys-
tem ranged between 5 - 6 kilowatt-hours per ton of H2S04' or 10 to 12% ot the
total power used in the production of one ton of sulfuric acid by the nitrose
method.
Bibliograp~.
III II. 1'1. eM 101 ('.1 () B, 11. II. BY;I 1.1 r 11 H, M8TCpUaJ/1.1 110 UUMCII) OI1I.1TUM,
HID,ill. C. \1 a p 0 H. IIpH'
MeHeuuc HOBOH allnapaTypr.l A;IH npoMldBKH cepHIlCTOj'O raaa. YllllXHM (1954).-
[13] B. II. B 0:1 r n H, $. C. ~1 a po H H Ap. lIpllMeHl~HHc ROBon annapaTypbl Will
npOMI.1BKIJ cepUIlCTOf'O r8aa. YHHXI1M, (1952-1953). - [14] H. H. K Y 3 b M 8-
BI.1X, }f{Xll, 3 (1953).-[I:.J H. M. t!{aBopOHnOB, IKXII, 7 (1954).-
[16] n. H. AT P 0 111 e H K O. TI'XHOJIOI'UIl a30THOn KIIC:IOTbi. fOCxHMu3AaT (1949). --
[17J C. H. r a'/J ;1, C. B. n p a B t( II U C Ii a R, IKIlX, XXVI/I, 2, 145 (1955).--
[18J 13. 1\1. PaM M. A6copUl1110HHIoIe npol1l'CCLI B XBMII'IeCKOD npOMl.1ll1neHIIOC1'IJ.
rOCXIJMH3A3T (1951). - - [191 II. I. (' wis. Ed war II s, Inil. Ellg. Ch., 1 (1948).
-77-
-------
Scrubber Applioation to Carbon Dioxide Absorption by
Potassium Carbonate Solution.
B7
I. G. PUt.
(DnepropetrovSk Chemical and Technical Instit~te).
Zhurnal Pr1k1adnoy Ehimii, Vol. 31, !lo. 2, 186-191, 1958.
Absorption of carbon dioxide by a solution of potash is widel1' used in
praotice [1]. ]Jevertheless, the process has not been thoroughl1' investigated;
it needs to be studied in greater detail as a step toward the solution of other
praotical problems.
Acoordingto the present c1ass~fioation [2, 3] the meohanism of C02 ab-
sorption by ~C03 solution is one of chamosorption with a reversible chemical
reaction in the liquid phase. The course followed by such a reaotion is sohe-
matically presented in Fig. 1. The conoentration of the absorbing gas within
,the limits of the gas diffusion lqer d changes from P to P or gas equilibrium.
g g
]Jeutralization of the mono-moleoular lqer occurs at the interphase surface,
that is at points of contaot between the gas and the J.iquid. Immediately there-
after, the zone of reaction is shifted deeper into the liquid diffusion layer
df until a d3namic equilibrium is reaohed, as graphicalq illustrated in Fig. 1.
In this wq it is possible to atta.in a reaction zone of equivalent amounts 'of
the gas to be absorbed and of the chemically active absorber. In this oase the
. j" re~ction zone divides the_dif~sion layer
~I into a neutralized part (4df) and a non-
'a neutralized part (l-4)df; at the same time
, G) the concentration of the dissolved gas in
s:t
i the neutralized part of "the lqer oh&l188s
from xl at the interphase to equilibrium
x in the reaction zone.
p
?
c=o
6'., ,ocoJo( (t-«JoJo(
. ,- no ...,...,---- ,- - ,-...
, !JK J
'~g~' ''1~ --S-chemaiti,o presentation
-of~ablJor:P't1on--meC1iamsm- , ,-
Ip
Pozin proposed a kinetic equation ex-
pressing the oourse of scrubber absorption
for similar systems, which is based 011 val-
ues the praotioal determination of which
, presents certain ditficul ties. Therefore,
-78-
-------
the experimental data were processed according to the following equationl
G
., x1" . I: x em (1)
'!'he iJDpellent ~c factor e in this equation is the mean logarithmic
II
differenoe of the solution oapaci ty expressed in 1101/11. It should be noted
that chaD8es in the ohemical capacity of the solution at the depth of'the non-
neutralized fi1m occur within the 'limits of e on the inner boundar,y of the
film surface and e . ° in the reaction zone. With such a concept of the 1m-
pellent or ~c factor, the absorption coefficient has the value of K -
D2
~ which depends on the posi Uon of the reaction zone.
Theoretioally the location of the reaction zone in its turn depends upon
the parameters of both phases. accordiDgly, the mapi tudes of this dependency
can be determined by assigning to coeffioient x: suitable values, whioh should
exolude the effeot of one respeotive phase.
1
I: - 1 + 1
a.Xg K;
When the sorubber i. operated on the cotmter flow principle the coefficients
for all conditions of scrubber operation shQuld be (4]:
(2)
x . oonst
(i) 1/2 . [- (1 - ¥ )r.15.
dO.25 0.75
. Yg
ul/2 . y~6
Xf . oonst (t) 1/2 . 1)r6
0.25
Yg
(3)
(4)
where 1 is the height of the packing in meters,
d the diameter of the packing in meters,
U the migration rate of the absorbent in ra!hour,
Y the specifio gran ty in k8fm3,
1) the viscosity expressed in poises,
a Hel117's constant at atm mol/11,
W the rate of gas flow in m/hour.'
-79-
-------
'he oonstant Ii was oomputed from the value of the equilibrium oonstant of
the reaotion ~C03 + CO2 + H20 ~ 2XHC03' as the ratio between the partial car-.
bon dioxide tension in the gas and its equilibrium ooncentration in the solu-
tion.
The purpose of this stu~ was to determine the proportionali t7 constants
in equations (3) and (4), and to determine the effect of ditterent taotors on
the kinetics ot the absorption process. The experimental installation consisted
ot an absorption oolumn 25.5 mID in diameter and a packing consistiD& ot 8 % 8 %
2 Raschig riDgB.The packing was 465 JIIII high. In the detemination ot the
nominal coefficient Xt the eftect ot the. gaseous phase was excluded by' a loa.( .
absorption ot carbon dioxide. The experiments were mad~ within a considerable
raD88 ot tluid tlow, ranging betW8. 1.83 to 18.7 m/haur, in relation to the
sorubber cross section at temperatures ranging trom 16 to 300 C. The capacit7
ot the absorbent varied trom 1.45 to 2.8 mOl/lie
8
Fig.~~; Effect ot liquid phase flow rate on
the oondi tional coefficient ,KIa.
. Ordinate - oondi tional coetticient
Klq in k8/Ji!/hr. : .
Solution congentration (normality) and temp-
erature in C oorrespondingly: 1 - 1.8 and 16,
2 - 2 and 30, 3 - 2.85 and 20
Curves in Fig. 2 present
the functional relationship
(U) between coefticient Xt
and the average rate ot linear
tlow ot the liquid phase.
Computed on the basis ot
equation ~4) Xt - Ul/2, this
is fully confirmed by' the
curves in Fig. 2. The eftect
ot the absorbent's p~sioal
properties are acooUDted tor
yY6
by' the equation Xt - -:3l6'
Yt
this is substantiated by' the faot that the plots ot all the experiments follow
the course ot a straight line whioh passes through the origin ot the ooordinahs,
as i8 shown in lPig. 3. This proves again that equation (4) holds true for the
nominal coettioient Xt and that the proportionalit7 constant was of a permanent
value. The numerical value ot the oonstant is equal to that ot the tangent ot
the angle which the straight line curve tomed with the abscissa, and amounted
to 6.28 % 10-5. Consequently, the tinal equation iSI
!
~
A
-80-
-------
2 . br ~ "Ol/l~)
This equation establiShes the conneotion between the basio parameters of
the liquid phase with the nominal ooeffioient of absorption.
Coeffioient X can be
I c. - . /.. " c_tod ee tOll"~' the
--~ value of X is first deter-
t /- '. . mined experimentally for a
diluted gas, and the value
~u,c~~~~~." :eK~~:e~~' :::"::~:ed
- . from equation f2).
Fig. 3. Effect of l~quid phase parameter on
the oonditional par~i~l absorption Xf . X
ooeff~c~ent Klq Kg . H(Kf-- K)
Ordinate - oonditiona1 partial ooefficient Klk The s stem under inves-
in kg/Df/hr - mol/Ii. y.
- 1/2 1/6!J(1)1/2. 5/6 tigation does not operate
Abscissa - vale of I U . Y f l' d . '1f aooording to Henry t slaw, and
in this oonnection the oonstant H ohanges with ohar188s in ooncentrations of the
reacting substance, accordingly, R varies with the height of the apparatus. All
other conditions being the same, the nature of H changes with the height of the
apparatus is such that their course belongs to a family of monotype curvesJ
this makes it possible to obtain a suffioiently olose definition of this JDaB-
ni tude fraa an analysis of one scrubber cross section. The most oonvenient
cross section for this purpose is at the bottau of the scrubber, where the oon-
centrations of the incoming gas and outgoing liquid are known. Prom the data
thus obtained the value of oonstant H can be oomputed.
The functional relation between the conditional coefficient X along the
g
gas film and the determinant parameters are shown as a straight line curve in
Fig. 4. In the experiments the rate of gas flow (W) varied between 100 and
900 m/hour in relation to the free oross section of the apparatus; the ooncen-
trations of the absorbed carbon dioxide varied from 10 to 50 peroent ~ volume,
and the absorption temperature varied from 20 to 300. The fact that the curve
in Fig. 4 is a straight line Shows that the functional relationship between co-
effioient K and its parameters was independent of the above mentioned factors.
g
Xf . 6.28 .
(5)
-81-
-------
The tangent of the slope of the straight line represents the mean value of the
-6
proportionality constant 2.55 x 10 . The effect of the gas phase upon the ab-
sorption coefficient can be determined by the following equation:
1 0.5 ( U)~O. 75. 0.25
-6 d w ,1 - i IJ Y f t ICG )
Kg . 2.55 . 10 dO. 25 0.75 2 hr tm' (6)
.t) m. .a
g
. The absorption coefficient K can not be determined exactly without the
knowledge of the nature of changes in the constant B as effected by the deter-
minant parameters. Results of theoretical analysis indicated that the para-
meters referred to were the concentration of the gas which was being absorbed,
A the temperature, the relative rate of
J~' phase migration and the ooncentration
0/
/. ",-,:-' of the absorbing solution.
Curves in Fig. 5 show the tuno-
-,'
tional relationship between the con-
stant B and the concentration of car-
--~B
Fig. 4. Effect of gaseous phase para-
meter on the conditiona partial a~-
sorption coefficient Kg.
Ordinate - conditional partial coef-
ficient in kg/m2/hr/atm.,'
Abscissa - value of
(~t5 ~ ~ - ¥ w. 75 . T~.25/dO.25 . ~~. 75
A
1
/
/-
[lOlj
0014
.rJ.OI]
00'2
00/1
O,'I.'0(J I(J 12 14
8
16 IfJ 20 .
Fig. 5. Effect. of gas--concentration
at 211- potassium oarbonate solution'
at 25° on the constant of Henri.
-_Ordinate-~ -const.. -Ii in atm/mol/li.-
Absc~sa.~-percent-of . C02 lnthe-ga_~.-
Relatl.ve vj:ll"oi ti~e w/TJ; 1-80; 2-62'.4
bon dioxide absorbed from the gas. . It
can be seen that the absorption of a
highly concentrated gas was accompanied
by a corresponding increase in the val-
ue of constant Ii and an increase in the
absorption, coefficient. (The negligible
yO.25
changes in magnitude of ~ of equation
. g
(6) caused by increased concentration
were disregarded). It should also be
kept in mind that, as a rule, a rise
in the gas concentration automatically
increased the gas absorption capacity
of the solution. The simultaneous in-
crease in the indicated parameters in-
variably enhanced the intensity of the
process.
The effect of temperature was
-82-
-------
..... . .
o ZO 25
Fig. 6. Effect of temperature at
23% carbon dioxide in the gas on the
constant of Henri.
Ordinate - constant of Henri
H in atm./mol./li. 0
Abscissa - temperature in C .
Relat! ve velocity wju and potassium
oarbonate concentration (normality)
correspondingly: 1 - 50 & 1.8, 2 -
6.8 and 2.5.
somewhat unique.
1/6
Yf
ot :376 the viscosity of which diminished faster than the specific gravity.
11f
The value of It decreased insignificantly while constant H increased (see Fig.
g
6) and, as a consequence, the absorption coefficient increased.
On the other hand, with the rise
in temperature the equilibrium constant
of the absorption reaction increased,
and. the absorbing capacity of the solu-
tion decreased. Therefore, when the
increase in the absorption coefficient
was greater than the decrease in the
solution absorption capacity, the rate
of absorption increased, and..!12.! versa.
It follows that the effect of temperature
on the absorption rate is different for
different intervals of carbon dioxide
concentrations in the gaseous phase, and
of the salts in the liquid phase. The
latter can be computed by the methods previously described for the determination
of constant H, and by using the equations for the determination of the condi-
tional fractional coefficients Xf and Xg. The absorbing capacity of the solu-
tion is computed 8S suggested by Pozin (5]. Within the ranges of concentration
and temperature of the present experiments, a rise in the temperature was ac-
companied by an increase in the absorption rate. Data obtained by these authors
at higher temperatures showed that the m$l.Thmuu occurred at temperatures of the
order of 500, and that at h1gher temperatures the absorption'rate decreased.
An increase in concentration of the chemosorbent lowered the value of con-
With a rise in the temperature, Xf increased as the £"unction
/I"
OOS
004
0.03
0.02
aOt
~
. 30 8
starit H, as indicated by the curve in Fig. 7. At the same time, due to the
rapid increase in the nscosi ty of the solution, the values of Itf and of the
absorption coefficient X decreased. However, a decrease in the absorption co-
efficient does not necessarily mean that the abscrption rate decreased. Since
an increase in the chemosorbent concentration automatically resulted in an iD-
crease of the solution absorbing capacity, it follows that the resultant rate
of the process was determined by the combined effects of the specified factors.
-83-
-------
sorbing solution co~cent~tion approximating
150 gjli; higher concentrations markedJ.,' de-
creased the absorption rate.
The value of constant H is also appreci-
abJ.,' affected by the relative migration rate
of phases Wju, as is shown in Fig. 8. The
value of H increased with an increase in W/U.
At the same time, under conditions of a con-
stant flow of the liquid, K increased; as a
g
consequence the absorption coeffioient K also
increased. This increase continued until the
1
value of iiK bec8U!e negligible as compared with
the resistance t-, and a further increase in the
f
rate of gas flow has no appreciable effect on
coefficient K. Nevertheless, the value of K ~
be further increased by increasi1:lg the rate of
liquid flow. Such a combination of the para-
meters makes possible the final selection of an
optimal value for the absorption ooefficient,
by taking into consideration the cost of the ab-
sorbent and the limits beyond which scrubbers
may become flooded.
In addition to increasing the value of K an increase in W/U enhanced the
absorbing capacity of the solution by increasing the amount of gas in contact
with a unit volume of the liquid phase. In fact, under above conditions absorp-
tion followed the same course as under the condi tiOfi of a llhighly concentrated
gas". . Simultaneous increase in the absorption coefficient and in the absorption
capaci ty of the solution leads to the assumption that the W/U factor is highly
effeotive in enhancing the course of the absorption process. This applies par-
ticularly to gases of high solubility. Because of their low liquid film resis-
tance such gases create conditions for more effective utilization of the favor-
able increases in W/U.
A
0.05
~.
00.1;
0.0.3
0.0.2
aJ)t
B
a
2
Fig. 7. Effect of potassium
carbonate conoentrationat W/U=
88.5, temp. 25c and 25% carbon
dioxide in the gas on the con-
stant of Henri.
Ordinate - ccnstant H in atm/
/'4101/11
Abscissa - soluticn concentra-
tion (normality).
A
0.0.5
00.4
0.0.3
11.02
aUf
----
2
~
8
0. 20. 30. ,0. 5D 60. 70. 80. 90.
Fig. 8. ~ffeo~ of relative
udgration velocity of phases
w/U on the constant of Henri.
Ordinate- constant of Henri
in atm./mol./11
Abscissa - relative
velocity W/U.
'!'his 18 substantiated by the experimental
data, the plotted curve of which shows a
conspicuous m::ly;ul11m corresponding to ab-
-84-
-------
Bibliograpq .
(I) ~~C H K B H H. ¥l'.'IeKUCJlOT8. JJumcllpoMU3A8T (194U). -- 12) M. E. II 0-
.8&. mn . XIX, 10-11 (1946).-13111. r. nJIHT, Tp. l\XTl1, IV (1955).-
(4) M. E. 03 B H. mnx. XX. 3 (1947) - (5) M,.. 110 a U H ".vlIX XXI
8 (1948) . '" . . m . . .
Coke Gas Purification from ~drogen Sulfide in High Speed Rotar,y Absorbers.
B7
S. N. Ganz and M. A. Likshin.
(The Dzerzhinskii Chemical and Technological Institute, Dnepropetrovsk).
Zburnal Prikladnoy Khimii, Vol. 31, No.2, 191-197, 1958.
The sodium arsenite method for the purification of coke gas from h1"drcgen
sulfide is now widely used. This stu~ was undertaken fer the purpose of in-
tensifYing the processes of h1"drcgen sulfide absorption.and of sodium arsenite
solution regeneration in high speed horizontally rotating absorbers. The ex-
periments were carried out in a labcratoX7 equipped with a large gas pur1f7ing
installation using cODlllercial coke gas intended for ammonia synthesizing plants.
Experimental part. The shaft of the horizontal absorber was equipped with
stationary discs, each of which had 12 paddles set at an angle. The absorber
shaft was connected directly with a motcr, the speed of which was controlled by
a slide rheostat. The experimental installation is shown in Fig. 1.
Sodium arsen! te solution from container 1 was fed into absorber 2 by grav-
1 ty. The level of the liquid was maintained at 0.25 the height of the absorber
diameter. !he spent solution was run into receiving tank 3. Coke gas from
c.ylinder 4 entered absorber 2 at the lower part of its end wall and came out
at the other end of the absorber through an outflow pipe connected with a drop
separator 5, equipped with an overflow pipe 6 which in turn was connected with
the absorber. From the drop separator 5 the gas entered absorbers 7 connected
in series; the absorbers 7 were partiall;y filled with a 3% solution of zinc
-85-
-------
- 11
8
I
7
Fig. 1. Plan of the experimental setup
1 - Small pressure tank, 2 ~ mechanical absorber, 3 - ass-
embler, 4 - collector, 5 - drip drain, 6 - overflow pipe,
1 - glass absorbers; 8 - flow meter, 9 - gas meter, 10 -
manometer; 11 - monostat (level control?), 12 - motor,
13 - sliding flow meter.
acetate which absorbed the residual coke gas. The series was made of a number
of absorbers sufficient to absorb the entire residual coke gas. Additional
two flasks served as controls. The rate of gas flowing into the horizontal
rotary absorber was controlled by flowmeter 8 and gas recorder 9. The gas
pressure at the points of entrance and exit was indicated by manometers 10,
and pressure constancy was maintained by monostat 11. The H2S content was
determined by the zinc acetate method. The zinc aoetate solution was treated
with a 0.1 ]i iodine solution to the appearance of an or~ color, followed
by starch, which turned the solution black, U was then titrated. with an 0.1
]i solution of byposulfate.
Studies were made of the effect of the bydrodynamic, 88we11 as the
pbysico-chem1cal conditions on the absorption rate. The effect of the h7dro-
dynamic factors was studied with reference to the construction of the discs,
their peripheral velocity, the volume rate of the gas flow, and the height
(volume) of the liquid in the horizontal absorber, and the rate of the hori-
zontal movement of the liquid in the absorber. The effect of the pbysico-
chemical factors was studied with reference to temperature, chemical absorp-
tion capacity of the solution and the H2S concentration in the gas. The
greater number of experiments was carried out with a sodium arsenite solution
containing 8.4gfli AS203' and the solution pH - 1.9 - 8.1. The effect of
"203 concentration on the absorption rate "as studied in a special series of
experiments.
-86-
-------
The effect of peripheral veloci t7 and the construction of discs upon the
rate of absorption. Results of the experiments indicated that the construc-
tion of the discs plqed an impcrtant part in the creation of optimal ~d.ro-
dynamic conditicns. Three different shapes of paddles marked respective~ a,
b and c, shown in Fig. 2 were studied. All the a-type disc paddles were bent
in the same direction at an angle of 15°. The b-type disc paddles were bent
toward one another in an alternate fashion.
a
c
All c-type disc paddles
were bent toward one another,
and the discs were fastened
to the shaft so that the COD-
cave sides of the paddles
faced each other. Results
showed conclusive~ that the
Fig. 2. Disc construction. c-type discs produoed ~dro-
a - all blades at unidirectional angles; dynamic conditicns most favor-
b - every other pair of blades at cpposing
c - each succeesi ve pair of blades at OPP- able to the highest rate of
ceing angles. absorption.
The peripheral velooity of the discs plqed the principal part in the
intermixing of the liquid and the gas. With the increase to the optimal periph-
eral velocity of the diso rotation, the absorption rate steadily increased.
A peripheral velocity exceeding the optimal lowered the absorption rate. Re-
sults obtained from an investigation of the effects of peripheral velocity
and of the disc construction on the absorption rate are shown in Fig. 3. The
data show that with an increase in the number of revolutions of the shaft to
2000 per minute and with Vg . 8.6 m/sec, the rate of H2S absorption increased
,rapi~ due to the disruption of the diffusion films and the convection move-
ment of the materials. At n . 1700- 2300 revolutions per minute the rate of
the process became stabilized, indicatin6 the presence of most favorable hydro-
~amic conditions in ~he apparatus. Further increase in the number of revo-
lutions of the discs increased the centrifugal force and threw the liquid
against the walls of the apparatus; simultaneously, the gas concentration in
the liquid became lowered as a result of which the contact surface between the
two phases was diminished; together these two phenomena brought about a reduc-
tion in the absorption rate.
Experimental results also indicated that irrespective of the peripheral
-87-
-------
2
. .~l
1000 2000 3(JOO
Fig. 3. Effect of peripheral disc velocity (num-
ber of shaft revolutions) and of disc construct-
ion on the absorption coefficient Kg
w = 400 m/m3Jhr; . .. VI/Va. 0.25; t. ~4-26°;
Clq . 8.4 gfli; pH .8.0. 3
A - coefficient of absorption Kg in kg H2S/m /atm..
B - Peripheral disc velocity; C . No. of shaft rpm.
Disc construction. l-c; 2-b; 3-a; (see Fig. 2).
10001
~l
velocity of the discs,
the absorption rate de-
peDded to a considerable
enent on the construo-
tion of the discs. The
highest -absorption rate
was attained with discs
A 2 6 C
. -.
ZOOO
1500
of type c. In this case
foam and sprq were formed
between the discs; a
thick lqer of active
foam with bubbles of I
to 2 mID in diameter was
formed over the liquid;
at optimal peripheral disc velocity a gas-liquid emulsion was formed in the
apparatus. The highest absorption rate was attained under the latter condi-
tions.
The effect of the volume of liQuid in the apparatus. Strict maintenance
of a constant volume of liquid in the apparatus was an iJDportant condition for
the normal operation of the installation. The amount of liquid in the appara-
tus was one of the basic }qdrocQrnam1c factors affecting the rate of the pro()ooo
ess.
An investigation of the effect of volume of the liquid in the apparatus
was Jlade under the following constant conditions. w . 263 m3/m3 Ihour, t ..
sr
25 - 260, Ceg. 8.4 slli, pH . 8.1, ~ . 1.51 - 1.58% H2S in the gas. Discs
type c and type a, at 2175 and 2900 revolutions per minute respectively, were
used in this investigation. The results of these experiments are plotted in
Fig. 4.
~he curves show that the highest absorption rate corresponded to a volae
of liquid tilling 25 - 30,t; of the absorber capacity. A lower level of the
liquid resulted in a lower concentration of gas in the liquid aDd a reduced
contact surface between the two phases. Filling of the apparatus with the
liquid above 3o.r; of 1ts capac1t7 coaplete17 disrupted the operational 87st-
of the apparatus and lowered considerab17 the rate of gas absorption.
The effect of volume rate _s flow. The volume rate gas flow deteminecl
the efficieDC7 of the apparatus aDd was one of the most illportant factors
-88-
-------
controlling its ~o~o
ooDdi tions, and conaequentq,
the absorption rate. lit-
vestigatione of the effeot
ot volume rate gas flow were
oarried out under the fol-
101ri.Dg oonstant conditional
Vf - O.28Va' pH . 7.9 - 8.1,
St . 8.4 gfli ot solution,
and ~ . 1.3 - 1.4% H2S.
f1pe a and type 0 discs
were used in the experiments,
with n . 2175 revolutions
per minute. The time required for the liquid to pass through the apparatus
A
100
90
//~z
~/
'f/-
7:1
~I az oj a4 0.5 0.6 B
Fig. 4. Effect of absorber load (tp=VlqjVa)
on the amount of H2S absorbed (<1).
For oonditions of the experiment see text above.
A - <1 in peroent, B - values of ., C- absorber
load.
Type of disc and n.shaft r.p.m. oorrespondingql
1 - diso c, --n.2115, 2 - disc a, ~2900.
was one minute.
The volume rate of gas flow ranged between 100 and 700 m3/m3 per hour and
o
temperature between 25 and 42. Plots ot the results ot this investigation
are ahown in Pig. 5 and Fig. 6.
The curves indioate that the rate of H2S absorption in the apparatus
equipped with diec8 of type a rapidq decreased with an increase in the volUlDe
31. 3
rate of gas flow. WUh w . 400 . ,m hour the absorption rate was onq 66%.
With discs of type c arJT increased voluae rate ot gas flow gradualq deoreased
the absorption rate.
60 200 1,00 500
Fig. 5. Effect of gas volume velocity (w) on
the degree of qdrogen sulfide absorption (a).
n . 2115; , . 0.25 - 0.30, t . 240, solution
concentration-. 8.4 gfli, pH . 8.l~
Oxdinat.e .... " in %, absoissa - w in m3/~/hr.
1 - 1;.240. disc a, 2 - ~240-, disc 0' 3 - t.
300, disc c, 4 - t-420, disc c.
(For disc types see Fig. 2).
5
'fhe experimental data
ahowed that at a temperature
ot 400 to 420 discs of type
o eftected a180st complete
H2S absorption with w ranging
between 400 and 500 m3/m3
hour. The effeot of the vol-
ume rate of gas flow on the
absorption ooefficient simu-
lated that of the peripheral
velocity of the disos.
Gradual increase in the
volume rate of the gas flow
so
. t
~J
. ~~2
80
70
-89-
-------
II
.000
JOOtJ
J
Z
0'
,
500
'5
100
~oc
Fig. 6. Effect of gas volume ve10citl (w) on the
absorption coefficient (X J.
n . 2175; cp .. 0.25 - 0.80; t .. 24°; g solution con-
, centration . 2.i g/li; pH .. 8.1. 3 3
Ordinate-X in kg H2S0 /m /hr. Abscissa-w in m 1m /hr.
g 4 °
Temperature in C and disc type:
1 - 24°, a; 2 - 24°, c; 3 - 300t 0; 4 - 420, c.
(For disc types see Fig. 2).
to the point of optimum
rapid~ increased the
absorption rate until
it reached a definite
maximum. An increase
in the volume rate of
the gas flow was ao-
companied by- an in-
creased rate of the
linear gas flow in ac-
oordance with the fo1-
lowiDg equation.
w . V
a
6J.in .. 3600 . f
sv
where fsv is the free cross section of the apparatus, and Va is the volume of
the absorber.
A reduced linear rate of gas flow lowered the turbulenoe effect of the
87st-. Acoording to available data, the optimal linear rate of gas flow re-
mained within the limits of 0.8 and 2.5 m/sec, at which the absorption rate
was highest.
!he effect of PMsica1 and chemical factors upon the rate of absorption.
The basic physical and chemical factors which determined the rate of absorp-
tion were temperature, .A.s203 concentration in the sol~tion, and ~S concen-
I
tration in the gas.
The stu~ of the effect of teDiperature upon the absorption rate was cu-
. 3t 3
rled out under the following constant oonditions: w - 400 . ,. hour, n -
2200 revolutions per minute, ooncentration of H2S in gaseous phase x - 1.26 -
2.26% and a concentration of As203 - 8.4 gfli. The pH value ef the operating
solution before H2S absorption W&8 wi'thin the limits 7.9 and 8.1, but the pH
after absorption decreased and was within the limits of 7.5 and 7.55. The ex-
perimental data are shown in Fig. 7 and Fig. 8.
o
The curves show that temperature rise up to 40 or 42 increased the ab-
sorption rate, which mq have been due to an aoceleration in the reaotion be-
tween H2S and oq-su1fo-arseno-sod1um salt, accordiDg to the following equatiolu
Ba4.A.s2S502 + H2S - Ba4As2S60 + H20
-90-
-------
~
100
'~
zeY.
J
.' ~~~~-
90
20 3(1 ~O 50
Fig. 7. Effect of temperature (t) on the
gen sulfide absorption (aj.
V ." 9.4 m/sec.; n .. 2200; w .. 400 m3/m Ihr; cP - VI IVa a
.g - 0.30, Cl a soln. concn. - 8.4 gIll; pH - 8.o~
Ordr~te - a in %; abscissa - t in Co.
Hydrogen sulfide concentration in tbe gas as it entera
the absorber, in % a Xl' 1 - 1.82 - 2.26, 2 - 1.57,
3 - 1.26 - 1.32.
!l°fO
606
degree of ~dro-
o
A temperature rise above 42 .
lowered the rate of absorption
consequent to an increase in the
H2S tension and an accomp~ de-
crease of the absorption motive
20 40 6'06 foroe. The experimental dda shew
Fig. 8. Effect of temperature (t) on the that the optimal t.perature for
coefficient of absorption (Kg).
~~l 3, I the proceS8 ranged between 40 and
Ordinate - K in ~m Qhr atm. 0
Abscisel - t in C . 42 .
XJ as in Fig. 7: 1-1.82-2.26; 2-1.58;
3-1.2622-1.3208.
J
GOI/III
,~l;,701
I
zooor
,nr,,? ~
01
~
The next important fact ~-
fecting the rate of the process was
the conoentration of As203 in the solution. The experimental results showing
absorption rate of H2S b.1 a sodium arsenite solution containing 17.38 &/li of
As203 are listed in the Table below.
Degree of H2S absorption at liquid saturation Q 17.38 Blli AS203
using b-type discs.
i i
Gas vol.: :
velocityi n j
3; 3/hrir.p.m.1
m m i i
v
g
periper.
velocity
m/sec. -
I Ratio of :
: absorber:
i sOl/vol. i
. .
: ot drum !
i Vlf/Vldr i
Temper.
t
in CO
i % of H2S in gas
: :
i xl at I %2 at
i intake i outflow
.
i
:
: a
i % of
iabsorption
:
421
525
630
720
1850
2000
2000
2000
7.9
8.6
8.6
8.6
0.30 -
0.30
0.30
0.30
30 - 32
30 - 32
30 - 32
30 - 32
1.2487
1.2487
1.2487
1.2487
0.0
0.0
0.0025
0.0037
100
100
99.8
99.7
-91-
-------
The listed data show that traces of R2S were present at volume rates of
gas flow above 600 m3/m3 hour, indicating that a content of As203 equalling
17 - 18 g/li brought about a high efficienoy and the complete absorption of
R2S at volume rates from 500 to 550 m3/m3 hour.
The effect of an H2S concentration in the gaseous phase upon the absorp-
tion rate was studied within the narrow limits of 1.26 to 2.26% of H2S. The
experiments were carried out under the following conditions: w.. 400 m3/m3
hour, v - 9.4 m/seo, absorber liquid, - 30% of capaoity and discs of type o.
g
The interpolated data are shown in Fig. 7. It follows that the absorption
rate increased with higher H2S concentrations in the gaseous phase. The dif-
ference for various absorption rates was particu1ar~ manifest at relatively
10. temperatures.
The technolo«ical and the economical aspects of the proposed method. A
comparison of the productivity of reaction volumes in paoked towers with the
rotar,y apparatus described, revealed that under similar conditions of operation
the rotar" apparatus was at least 25 to 27 times more efficient. It follows
that for similar productivity the required volume of the rotary apparatus oan
be 25 to 27 times smaller than that 'of the towers. The metal required for
the construction of a rot817 absorption apparatus is only 8 to 10% of that
required for tower construction.
In comparing the operational expenses of a tower system with those of a
rotar" apparatus, it should be noted that they are about the same except for
the consumption of electrio power. The electric power is used principally in
feeding of the absorbent solution into the apparatus and in aspirating the
gas. On the assumption that the required solution volume is' 350 m3 per t08er,
a four-tower system would require a m1nilllUDl motor power of 360 kilowatts for
its operation. The power necess817 for the gas aspiration through the towers
for removal of sulfur is determined by the pressure drop of the entire system:
in the existing tower installations the pressure drop is never les8 than 1000
mm of water requiring a power of 220 kilowatts. Accordingly, the total con-
sumption of electric power in the modern installations amounts to 570 kilowatts.
In the rotar,y absorbers the liquid is raised to a height not exceeding 5
meters, wherefrom it is fed by gravity. In this case the required motor power
does not exceed 4.5 kilowatts. The maximal pressure drop of a rotar,y absorber
sys~em varies between 100 to 200 II1II of water, therefore, the power required
for the gas aspiration is approximately 44 kilowatts. Rotation of the working
-92-
-------
parts ot the rotary apparatus requires an add.i.ticmal 40 kilowatts per appara-
tus [1].
Coneequentq, the total required electric power for the operation ot a
rotar;r apparatus amounts to 248.5 kilowatts, or about 2.5 times less than is
required tor the operation ot the tower system.
Conclusions.
1. The results ot the investigation indicated that the absorption rate
ot R2S by sodium arsenite solution 111 a hip speed rotary absorber was con-
siderabq greater than in tower s7st.S.
2. R2S absorption in a rotar,y apparatus requires considerab17 lower re-
aotion volumes, less metal, smaller capital investment and less eleotrio power
for its operation.
Bibliograpq.
1.
S. .. Gans aDd II. A. Lokshin.
Tr. DXhTI, 5 (1956).
Oxidation ot Ammoniwa Sulfite-Bisulfite Solutions in the Recover,y
ot 802 trca Smoke Gases.
By
B. A. Chertkov.
ZhurDal Prikladnoi Xhimii, Vol. 32, No.5, 960-965, 1959.
Previous reporte [1 - 3] dealt with the effect of' different factors, suoh
&8 the solution composition, temperature, etc., on the rate of ammonium sul-
fite-bisulfite oxidati.9B. Results showed that an increase in the relative
concentration of bisulfite ~B the solutiOB (S/C ratio), in the temperature,
and. in the partial ~gen tension in the gaseous phase increased the degree
of oxidation in the solution, and that at a detinite concentration of sultite-
bisulfite, oxidation attained a IllA.TiIllUJll rate which abated above or below that
opt1Jaal concentration. It was determined simul taneous:q that the oxidation
-93-
-------
reaction was notably accelerated under the cata~ic effect of added ammonium
thiosulfate, whioh in time accumulated 'in the solution, and that the introduo-
tion of an inhibitor, such as n-phelQ"lenediamine, stopped the aotion of thio-
sulfate and markedly arrested the oxidation reactiol1. However, the presenoe
of solid impurities in the solution partioularly of f:q-ash ooming from smoke-
stacks sharply oounteracted the effect of the inhibiting substance. Under
practical operating conditions of gas-purifying installation. hTdrcxQ'Damic
factors came into pls.J along with the above-enUllerated factors, so that the
total oxi4&tiol1 effect of the absorber solution became a oomplex fUnotion of
a series of variable values.
The experimental results and the theoretical relationships (ratios) de-
ri ved from them were compared with the actual oxidation process of ammonium
sulfite-bisulfite solution UDder industrial conditions. This was done il1 a
case of workiag solution orldation in an installation for the recover'7 of. 902
from smokestack gases by the 070lic ammonium process [4].
Ammonium sulfate [(04)2504]' the product of ammonium sulfite-bisulfite
oxidation was extracted from the solution and used as a fertilizer. The de-
tails of the technological prooess of 502 recover'7 from 8IIIission gases by the
cy-clic ammonium method will not be discussed in this paperJ however, it should
be pointed out that the removal of the aocumulated ammonium sulfate was ao-
complished by vacuum condensation of the wOrking solution, which caused the
falling out of solutions of the least soluble ammonium sulfateJ final removal
of the latter was attained by centrifugation.
In an. ideal cyolio procees the quantity- of cr;ystalline (BB4)2S04 obtained
during a given time interval can serve as an indicator of the reaction rat.
of the absorber solution oxidation. UDder conditions of aotual production
10s8es of solution occur which to some degree reduce the amount of ammonium
sulfate. Suoh 10sse8 can be determined with a high degree ot accuracy from
the amount of aDDOnia used by the installation. On the basis of the quantity
of o17sta11ine (04)2504 obtaiDSd and the quantity lost in the produotion 07cle,
and by ana:qtical:q detemining the change in the (04)2504 of the working so-
lution in a unit time, it is possible to deteDDine the total amount of ammOnium
sulfate tormed as a result of the absorber solution oxidation in the course of
. 502 absorption from the gas. Such quanUtative aocounts of ammonium sulfate
formation were computed for different operational stages of the purit.Jing in-
stallations. Results of one such computation are shown in the following '!sure.
-94-
-------
The curve in the Pisure
shows that the prooess ot
wOrld.DB soluUon oxidation
ot a given installation,
general17 speakiDB, tollowed
an even course. During long
time iutervals and specitio
oonditions ot absorber opera-
Ucm, the aver8B8 rate ot
(1B4)2S04 tormation waB COD-
staDt. ~anU tative data
on workiDB solution oxida-
tion and on the working con-
di UODB ot the absorberB at
all investigated periods are
presented in the tollowiDg
'fable. In addition to the
average (1B4)2S04 increase duriDB 24 hours, C0rr8SpondiDB17 equivalent rates
ot o~gen absorption 1>7 G are presented in g/m2/hour, in relaUon to the
02
BUrtaoe unit (area) ot the absorber pacJd.Dg.
'fhe data in the Table show that duriDB the tirst three work periods of
the sulfur-catching installation, oxidation proceeded at highest intenait7 and
the value ot G reached 1.1 B/m2/hour. ThiB was due to higher t8l1peratures
02
ot the absorber BoluUon as well as to the higher content ot t17-aah, which
counteracted the etteot ot the reaction inhibitor. Low oxidation rate duriDg
the tourth work period ot the installaUon .as due to the low thiosultate oon-
centration and low t17-ash content in the solution. !he tact that the saturat-
ed soluUon tlowiDB out ot the abscrber had a lower SIc ratio than during
other periods wa~ alBo ot importanoe. Increased rate ot solution oxidation
during the titth period, in addiUon to the above .entioned reuODB, was due
large17 to the taot that duriDB this period the absorber solution .a. satura..
ed to a higher SiC ratios than during the preceding periode. During sub-
sequent work periods ot the installaUon, the temperature solution in the ab-
sorbers was considerab17 lower, causiDB reduction in the OxidatiOD rate despite
the notable increase in the thiosulfate content of the .orking Bo1uUon. Dur1Dg
A
3800
Z400
ZOOO
1600
'zoo
800
II J.O Ill' 26 ;/8 J(J 1 J i 1 g If ,j 15 17 ,g !~ 1.3 25 27 ?15
.January 1957 February 1957
IncreasiD6 total amount ot &aImonium sultate
tormed in the s1'st....
A - 'fota1 amount of ammoniUm sulfate in the
system in ~ol f B - Number ot daTs
Anrase rate of ammonium sUlfate formation
acoording to periods in q-mol/dfql
I - 65.0, II - 49.5, III - 67.5
-95-
-------
I~
s: 0
.... ..
~8
'I"f
~~
'l"fr-4
k cO
GI+»
Pot.
I
\D
Y'
!O 16 I
11 311
12 22 n
Besul ts of working solution oxidation in the operation of the sulfur catching installation
Date.
1 25 III -13 V
2 15 IX -to XI 1952
3 29 X I - 7 I
4 30 VIII-12 IX 1953
5 12 IX -27 IX 1953
6 6 XI -13 Xl 1955
7 13 XI -30 Xl 1955
8 30 Xl -22 XII 1955
9 22 XII -28 XII 1955
-311
-22 II
- 2 III 1957
13 12 III - 3 IV 1957
, Properties of the working solution ~ ~ ~ f:
I ~_.....Jr-4 ~ NIlS J
IO+» .g k,
i Content in mOl/li ~ k ! f: I !1J ~ ~ ~! k
r-" --'-1"""--- . - ... r -..-"it - rl "eiit GI J I' ~ J I ~ ~ . ~ ~. ~ ~ ~(\J g
I.. ' ~ ~o r-4o ,.... m ' k I ~
JL"otal .u I N ~ r-4~ s~, ~.p I: e.~IJ t"'I.
'1fH UD3 i" I 0 v.. I r-i . Ii "'I g EI
I' 3 ef , ~~ i i ! ~:::: ~ i ~ g ~ ~ ~ k ~
/2i '.... 0 4:1'1"f'>"'lo
~ \ I - I i P=I, 0 +» ....~, ..
I
1952 .
7.25
8.25
1952
6.8
5.0-8.0 2.5-5
3.2
3.6
;'.0
0.06 - 0.25 8.3
0.03-0.10 3.5
0.03-0.10 4.5
0.01-0.04 1.1
2 -7.5
7.0-9.0 2.~-4;5 0.04-0.07 2.3
I -4.8 0.01-0.07 L05
0.79
0.79
(J:H8
(J.89
38-30 4LU
35-35 35..')
OJI(I
0.90
35-34 49.5
0.78-0.H2 0.83-0.90 28-40 22.5
0.78-0.82 0.87-0.96 2/j-38 ;)5.5
0.79-(l..~2 0.9 -0.92 11<-28 34.3
7.5-9.7 3.3-4.5 0.07-0.29 1.85 0.79-0.82 0.93--0.96 17-24 78.8
9.5
9.5-10
2.7-4.a 0.29-0.42 2.0
2.9-4.3 0.42-0.52 1.9
0.79-0.82 O.90-1I.9fJ 23-2H 63.7
0.79-0.82 0.91-0.96 23-26 70.0
1957
7.0-9.5 3.4-4.6 0.10-0.26 L94 0.79-0.82 0.92-0.95 2D-22 65.0
0.79-0.82 0.86-0.96 21-24 49.5
1957
9.5
9.5
9.0
3.7-4.6 0.26-0.35 2.0
3.6-4.2 0.35-0.34 3.12' 0.79-0.82 0.95-0.96 20-22 67.5
3.5-4.1 O.15-0.~7 2.03 0.79-0.82 0.93-0.97 20-22 72.4
0.50
.,
0.38
0.88
2
2
0.71
D.78
2
'J
0.72
0.55
')
2
0.75
0.80
2
Remarks
0.91
During all the periods
the linear veloci t,. of
the..sa. t~OUBh the
tO'\al d.rua oroS8-seot-
iOD~equa11ed 1.1 - 1.3
ra/ .eo. aoistu. 4ensi-
t,. - 4.0-4.5 -.3/m2/hr.
absorber packing area -
30000 m2. SO oontent
18 BIIokesta~ gas was
0.3 - O.~. 02 c~tent
ranp ,,&8 8 - 12%. in-
hibitor range in solut-
ion "a8 0.5 - 1.5 8111.
U.79
1.11
1.24
-------
the sirth period the reduoed oxidation rate was due to the low total salt oon-
centration in the solution at the beginning of the period (solution accumula-
tion) and to the low thiosulfate oontent. If this be temporarily excluded
from consideration, then it will be seen that in the following seven periods
the average rate of solution oxidation fluctuated within a limited range and
corresponded to an average o:qgen absorption rate of 0.75 gfm2/hour.
The absorber operating conditions listed in the preoeding Table for the
latter periods were specific for 802 recovery from BlDoke gases by the cyclio
ammonium method. If this be taken into consideration, then 0.75 gfm2/hour can
be reliably accepted as the specific rate of ammonium sulfite-bisulfite solu-
tion oxidation under industrial condi Uons. Changes 111 ~ of the condi tiODS
of 502 absorption from smokestack gases can affect the solution oxidation rate
in several ways. Changes in the percent content of 802 in the gases cannot
alone aftect the rate of the solution oxidation; however, in the cyclio proc-
ess each 802 concentration in the gas is accompanied by a specifio optimum
solution composition [5]; therefore, ohange in the percent 802 content in the
gases .ill automatically etfect a change in the solution's composition. Changes
in the percent oontent of o:qgen in the smokestack gases, for example, during
the change over to 802 absorption fram non-ferrous discharge gases, must re-
sult in a proportional chal188 in the G value [2]. The 0han8e in linear
- 02
veloci t7 of the gas in the absorber cannot affect the rate of solution oxida-
tion, due to the fact that in absorption of o:qgen, which is a poor17 soluble
gas, the basic role is played by the resistance of the fluid film, and the
resistance of the gaseous film can be ignored.
Increase in the absorber moisture density lowers the resistance of the
fluid film and enhances the o:qgen migrdion from the 111111 ting film into the
,de~per layers of fluid. On tne other haDd, since the general oxidation proo-
ess is oontrolled by the relatively:slow reaotion between sulfite-bisulfite
and dissolved o:qgen, the conoentration of the latter in the fluid phase is
apparently insipifioant, and the effeot of moisture densi t7 tor ~ case can
'be aooepte! &S similar to that preva1li~ in simple phTsical absorption. Ao-
oording to V. M. RaIla [6], t-he' c~e~tfb1ent of III&SS transmbsion in fluid fila
I ,"
(Xt) is an e~OJ1ent1al tUncti~;of the humid! t7 (i), the power of which caD
vary lroa 0.33 (in fila absorber) to 0.67 (in packed absorber). Thus, the
.tteot ot ~c factors oan be manitest8d only if the moisture cl8ns1 t7
-97-
-------
of ~he absorber is con8iderab17 increased. However, this condition 'lIJA7 not
artse where the solution in ~he absorber secUons is recirculated. The un-
1mporiaD~ role of h1dro~c factors i8 conf'irmed also by the fact that the
0.75 B/.2/hOur average ra~e of o~gen absorption in the absorber approximates
the value obtained in laborato17 studies of oxidation prooesses under statio
condiUons [3].
"
Change in salt concentraUon can have different effects on the prooess of
oxidation. Inoreas. in &3 sum and &3 .t ooncentrations above the values in-
dioa~ed in ~he fable will pertoroe increase the oxidation rate due to the
lowering of 0X7gen solubili~y in more concentra~ed salt solutions. A lowering
in 03 et c~ncentration will at first increase the rate of oxidation to a
III&%iJIum of 2.5 1101/11 of 03 et' after which it will sharp17 deor~ase due to
~he fact that t~e role of 0X7pn intake as the l1m1 ting factor will be taken
over by the reaction rate between sulfite-bisulfite and dissolved o:Q'gen [1].
However, in the cyolic proces8 of 602 recove17 from smokestack gases, the use
of low dilution is preoluded. Increase in ~he thiosulfate content of the so-
lution, tor e%&8ple to 0.5 1101/li, can b,y itself cause a sharp increase in the
rate of the solution oxidation (1]. However, in the presence of a suffioient
quaatity of 1Dh1bitor (1 gjl1), the catalytic action of thiosulfde i. sup-
pre8sed, 80 that this factor can be disregarded. lProm this viewpoint, the
increase in t17-ash oontent is undesirable, because it weakens the action ot
the added 1Dh1bi tors. .
Change in S/O ratio of the saturated solution can notioeably affeot the
speed of oxidation on17 when the variation range of this ratio i8 a wide one
[1]. In the normal cyol1c prooess the S/O ratio of saturated solution in the
case of ~ initial 802 concentration in the smokestack gaB approaohes the
theoretically possible liait (tor pure bisulfite sIc - Ih accordingly, the
etfect of this factor is 1181ted to a relatively narrow &rea in .wh1oh changes
in ~xidation rate plq a comparatively unimportant role. Rise in absorber so-
lution temperature must also have an aocelerating effect on the oxidation
proce8S [2].. SwIIdng up the above, it can be concluded that in ohanging the
cODditions of 802 absorptioD fram smokestack gases most potent effeots on the
o:.d.dation process will be produced b,y partial oX7gen pressure in the gas,
8IIIIDODium sulfite-bisulfite ooncentration in the solution, sIc ratio in the
resulting saturated solution and the temperature of the absorber solution.
-98-
-------
It was shown [1, 2] that the eftects of the enumerated factors can be de-
termined quantitative17 with the help of previous17 established functional
tactors; this should make possible the determination of the oxidation degree
in ~ case of 502 absorption froll smokestack gases b7 the C7cl1c aumonium
method under a:tJ¥ absorber operating conditions, by taking ae the initial value
the average rate of solution oxidation in the purification installation under
investigation. The quantity of sulfate formed as a result of reagent oxida-
tion in ~ method of 502 absorption from gases is usual17 compared with the
total amount of 502 absorbed during a unit time. The dsgree of oxidation thus
derived is a relative value which depends on the 802 concentration in the gas
and the total gas load in the absorber. It can be seen that, as the total
quantity of 502 absorbed in the absorber inoreased, the degree of oxidation
was lowered, provided. that other conditions remain the same. The ~dr~c
factors play no prominent role in the oxidation of the working solution, yet
the,r affect substantially the rate of 502 absorption; theretore, lowest degree
of oxidation will take place in the absorber under conditions of most intensive
502 absorption.
lProm this point of view intensive bubbling of the gas through a foam type
absorber should be preferred to the use of a packed abs~rber. Results ot
previous investigations indicated [7] that the speed of 502 absorption :trOll.
BDlokestack gas in an experimental bubble-foam absorber was 10 - 15 times as
effeotive as in the packed absorber and that the o~gen absorption rate rose
on17 2 - 3 times. As a result, the degree of oxidation was about 5 times lower
than under analogous conditions in a packed absorber. Thus, replacing packed
absorbers by bubbling foam absorbers, in addition to other advantages, will
make poss1 ble 502 recove~ fran gases with low 502 content b1' the cyclic am-
monium method; this will reduce the rate of (BB4)2S04 formation and will result
in a lower consumption of ammonia.
It ~ also make unnecessar.y the use of the relativel;y expensive oxidation
reaction inhibitor, n-phen;yldi8Ddne.
Conclusions.
General conoepts were derived trom practical data on oxidation of ammonium
sulti te-bisulfi te solutions in the process of 502 recovery from lIIII10kestack
gases in packed absorbers. The averase rate of o:q-gen absorption trea gas
(G ) was deteJ:m1.ned under specifio conditions of the c1'clio 8DID10mum method;
°2
-99-
-------
limits of possible value fluotuations were studied UDder changing absorber
operatiJ2g conditions. Attention was called to the p08sibllit7 to considerab17
decrease the degree of 502 oxidation by using a bubbling foam tns of absorber.
:Bibliograp~.
111.B. A. q e p Y K 0 B, HUIX, IIX, 10, tfie (1857). -12)B. A. q e p~1C 0 B,
HmX, IZIII, t, 78 (t9l8). - 13) B. A. q 8 P Y * 0 8, JRItX, zzzn, 5, 9SJ{t8l8). -
14J A. n. A's,."... 0 8, B. A. q 8 P Y K 0 8, JRXn, 'T, to (19M). - 15JB. A. q 8 py-
K 0" Tp. BHHOrA3a. rOCDDlllU8Y (t957). -181 B. ¥. P a 1111. Moap6~1UIIIjI
DpOQ8CC:U B UMB'I8CROi ~1IIIIIDI8IIII0Cft. focuuwy (t95t). ~ 17J B. A. q 8 P Y -
K 0 a, B8C1'II8R TexlDl'leclKli J( 8KOHOllB'leCKOi BH~pllaIt1lB fOCymtPCTBeBBOI'O KOlDITefa
DO DUB, I, 7 (t958). .
Carbon Dioxide Absorption b7 Sodium IQ-droxide 1'0811.
:B7
M. E. Posin, :B. A. KoWlev and E. Ta. Tarat.
(Lensovet Technological Institute, Leningrad).
Zhumal Prikladn07 lhiII1i, Vol. 3, 110. 5, 1011-1018, 1957.
Sodium ~dro%1ds solutions have been used .ide17 in low temperature cool-
ing of synthetic ammonia for its fine purification aDd in II8D7 other proc-
esses which require almost complete purification of gases from carbon dioxide.
The equipment used in such gas purification processes consists of either bu~
packed scrubbers or of foam tne gas purifiers. Previous reports on the ab-
sorption of carbon dioxide aDd other gases by 3 11 1IaOB solution at 600 [1] in
a foam apparatus [2 - 7], showed that absorption of carbon dioxide by aD al-
kaline solution was more effective in fOall apparatu8 than in a scrubber or
bubbliJ2g apparatus. In cormection with the above, it .as of interest to es-
tablish the optimal conditions for the absorption of C02 in a foam apparatus.
rnowledge of the chem1st17 and mechanism of the process and i is rate under
different conditions is still la-n1rl w,g.
The mechanism of the process depend8 on the condi. tions of the CO2 dif-
fusion in the gaseous or liquid phase, the reaction products at the contact
surface and at different depths of the thin mass of the liquid, and a180 on
-100-
-------
the ~~l1ons in the reaction zone [8]. The fomed oarbonate differs from
sodium ~droxide in its solubll1t;r in water, in the rate of its reaction with
CO2' the rate of its diffusion, etc. The poor solubilit;r of C02 in the surt'aoe
181'er of the liquid (carbonate) retards the diffusion of the absorbate CaR-
ponent from the gaseous phase. The available reports on C02 absorption b;y
IFaOH solutions [8 - 14] UDder difterent coDdi tions present cont1iotiDB re-
sults and otfer diverse explanationa for the mechanism of action. Therefore,
the reports oannot serve &8 reliable criteria in the seleotion ot optimal COD-
di tions of teaperature. and solution concentration tor use in the experimental
testiDg ot toam apparatus.
'!'he purpose of the. present work was to investigate the rate of C02 ab-
sorption b;r IFaell solution in a toam apparatus under different p~sioal, ohemi-
cal, and 1qdr~c oonditions, such as CO2 concentration in the gaseous
phase, BaOB oonoentration in the solution, temperature, linear rate ot gas
tlow, the rate of liquid flow, eto. The exper1aental data obtained related
to the rate and completeness of carbon dioxide absorption b7 a solution of
sodium ~drox1de in a foam apparatus under various condi Uons. The absorption
data presented below were obtained fram experimental absorption of carbon di-
oxide b7 a solution ot sodium ~x1d., in a prev1ous17 described t1P8 ot
foam apparatus [1]. Pig. 1 ShOW8 the functional relationship between absorp-
Uon ooeffioient (X) in the case ot 1 m2 of the apparatus shelf screen and also
ot the efticienc;r coetficient (ec) of it. siDgle shelt screen of the apparatus
(1) and the in! tial ooncentration of C02 in the gas (C in) . ~ethods tor the
. calculaUon of X and 1) were described on several previous occastions (1 - 7].
The condi tioDB under which the experiments were performed at aD1' stage of the
investigation are specified in the legends acoanp~Dg text Fi8ures 1 to 9,
inclusive.
It was demonstrated that all other oonditions beiDg the same, the value
ot X was independent of Cin within ohange limits 2 to 15%. This indicated that
under such oondiUons the rate of absorption was controlled b;r the resistance
of the gaseous phase. The value of 1) slightl;r increased with the increase in
Cin. 'fh1s mq be due to a decrease in the linear velooit;y (w) of the unab-
sorbed component of the gaseous mixture, as the value of Cin increased, since
the JD8BI11tude of (1) inoreased with the decrease in (w).
The functional.relationship between the indexes of oarbon dioxide in a
foam apparatus and IFaOll solution conosntration is shown in Pig. 2. The curve.
-101-
-------
15fiJl~
IZ5)
looof
&J,.
.
,r
show that an inorease in BaCH
oonoentration from 0.25 . to 2
. resulted in inoreased values
Fig. 1. Effeot of oarbon dioxide ooncentrat-
ion on Ie and TI. 2
A - AbjOrption coefficient (Ie) in ~m /hr x
x ks/m J E - degree of absorption (TI) in %J
C - original concentration of carbon dioxide
,in the gas (C 1) in volume %.
vo x
Soreen 5/2. Rate of gas flow w . 2.0 m/seo.,
intensity of liquid phase flow i . 5m31 m{ hr;
height of weir h - 100 mm; 3 . solution of
sodiumwbydroxide; t . 600.
of the absorption coefficient
and the rate of C02 absorption
effioiency coefficient. This
oan be explained by the fact
that in the oase of a compara-
it vely low .aOB solution oon-
centration the absorbing power
of the process was determined
by the conditions of the dif-
fusion in the gaseous and
liquid phases. It should be
noted that the magnitudes of
(Ie) and (TI) inoreased within
the concentration range of the
solution referred to, despite
the fact that an inorease in the .aOB concentration produced a thinner layer
of foam under similar conditions as a result of changes in the physical
properi1~. of the solutions, such as increased specific gravity, viscosity
and surfaoe tension.
Such a course of the curves representing the functional relationship be-
tween (X) and the lfaOB solution concentration was observed in all the examined
rates of gas flow in the apparatus, whioh ranged between 0.5 and 2 m/sec,
c108e17 agreeing with the results published on C02 absorption in the packed
absorber [13].
The effect of carbonization degree of the NaOB solution on the rate of
C02 absorption i8 shown in Pig. 3. Up to 25% carbonization values of (X) and
(TI) deoreased only slipt17; at a higher degree of carbonization the values
of (X) and (TI) sharply decreased. The 1es8 favorable oonditions aooomp~nc
a higher carboni.ation of the BaOB solution reeu1 tad from the decrease in the
chemical absorption capacity ot the "aOB solution. The above mentioned 188.
favorable conditions are also related to the greater diffusion resistanoe in
the liquid phase oaused by the foxmation of a carbonate layer in the liquid
:B
l5
7J
-~
~~~
::0
I
L______-~--- d_-_____J'5
. J 5 9 Ii /j C
-102-
-------
A
C
jjl'O
i
-- If I
--.
r
I
I
1j(}1J
. .
------ i
----:-12;,(/
1»
to
I
I
-
1000
-y;--~!
y---;'w
1)
0-1
.-z
.
2
OJ,
Fig. 2. Effect of NaOH concentrat1on on K, ~
2 3~d_H.
A - ~eL. ,hr.k&/m , Jr- oad or ~ in %, C - foam
crest H in l1li1; D - sodium hydroxide in gr. eqiv.
per liter.
Gas flow rate in apparatus in m/sec.s
1 - 0.5, 2 2 2.0.
Screen 5/2. i - 5 m m x hr, h - 100 mm
C ,- - 6%, t . 600.w
vo~
phase; the C02 solubilit7
in that lqer is consid-
erab17 less than in the
deeper lqers of the lIaOB
solution. This was sub-
stant~~ted b.1 results of
experiments on C02 ab-
sorption b7 dif'f'erent so-
lutions, all of' which con-
tained the same amount of
lfaOB but difterent amounts
of' ]Ia2C03' ~s shown in
Pig. 4.
After bicarbonisa-
Uon ot the soda solu-
tion inoreased trom 20
to 25%, the rate ot CO2
absorption began to in-
crease, due to the taI-
ling out of' the f'omed
bicarboDate which en-
hanced the carbon dioxide
solubi1it7 in the system
[4], as can be seen in Pig. 3.
The functional relationship between (x:) or (1) and temperature is shown
o 0
111 Pig. 5. Wi th a temperature rise from 20 to about 45 or 50 the C02 ab-
sorption increased clue to the f'avorab1e effect ot the higher temperature on
the rate of' chemical reactions paralleled b.r more favorable conditions tor
the ,f01'll8tioD ot toam. With further rise in temperature the values of' (K)
and' (q) remained practica117 constant, and even slightly decreased at 70 to
800 0
. According17, a ranee of' 50 to 70 is optimal for the process ot C02 ab-
sorption b.1 an alkaline solution.
Pig. 6 shows the effect of liquid flow rate (r) on (x:) and (q). The flow
rate (r) is expressed in m3/m/hours; its Dl88D1tude depends upon the size of
the outflow opening of the shelf' screen of the apparatus. Increase in the
value. of K and q with the increase in (r) is a functional consequence of the
-103-
-------
A
IjOO~
B
1'5
0-1
.-3
10
5
500
o ' 0
1.0 05 0 C
. .
0 05 D 1.0 0504 O. D
, .
o 0506 10 E
Fig.). Effect of solution carbonization on K
andT). 2. )
A - Absorption ooefficien~ K in k8/m .hr x k8/m
B - Degree of absorption cad or T) in percent.
C - NaOH in solution in g:-9quivalent per Ii.
D - Sodium carbonate in solution in g equiv/1i
E - WaHCO) in solution in g equivalent per Ii
Initial concentration of carbon dioxide in
the gas C Ix in volume %: 1 - 6, 2 - ~O.
Screen 5/2. vo w. 2.0 m/sec.; i . 5 /m I
/m 0 hr; h" . 100 mm, t . 18 .
6
A
t
'~t ~q-"
5"'[ ------.~ '
. . i
o
I B
Fig. 4. Effect of sodium carbonate in sod-
ium hydroxide solution on K and T).
A - Absorpt!on coefficient K in kgfm2 x
x hr . kslm; B - degree of absorption cad
or T) in %; C - sodium carbonate content "i.'i1
sodium hydroxide solution in g equiv./li.
Screen 5/2. w . 2.0 m/sec.; H. 220 mm;
3 N NaOH solution; C Ix. 6%; t . 180.
vo
increase in the thickness
or height (H) of the foam
lqer which enhance the
C02 absorption rate.
The functional rela-
tionship between (X) or
(T) and the linear gas flow
velocity is more complex
and more important, as
shown by an analysis of
curves in Fig. 7. An in-
orease in (w) causes the
foam lqer to rise in
height; this, in turn, ra-
suI t8 in a corresponding
increase in (X). However,
when the value of (w) ex-
oeeds 2.5 - 3 m/sec, the
rate of corresponding rise in
the values of (x:) becomes
retarded, due, perhaps, to the
reduced contact time between
the two phases which is no~
oompensated for b.J an inorease
in the interphase areas, all
of which lowers the efficiency
coefficient of the process [3].
Within a definite and a suf-
fioiently wide range for (w)
in practice, approximately up
to 2.5 m/sec, the absorption
coefficient increased in pro-
portion to the increase in the height of the f~ lqer.
The data plotted in Fig. 7 were obtained at oonstant flow rate
a constant threshold height (ht) i.e., for a constant height of the
-104-
(r) with
initial
-------
A
-. .1f
I
B
;.."~ --4-.-.- ~:........ ;
Iji7
/
//.
,,'
.:,: /'
l~
I
-' ---- --..L-. !20
.
\;0
)., 4:; :~j :-..-'0
Fig. 5. Effect of temperature on -K and 1}.
A - Coefficient of absor;]ion K in kg/m2 .
. hr . k8/m .
B - degree of absorption ~ or ~ in %J
C - temperature in Co. 3
Screen 5/2. w80 2.0 m/sec., 1 - 5 m /m . hr
h .. 100 rmn, 1 N.BaOH soln.; C ,-.. 6%.
n vo~
A
c
__A
':: ?-;
J,'
Z,5
B
10 2.5
5.0
7.5
liquid layer (ho) and a vari-
able height of the toam layer.
As a matter ot theoretical in-
tOl'lD&Uon and to elucidate the
ph7sical aspect of the etfect
of gas flow rate on the dit-
ferent aspects ot absorption,
it is desirable to establiSh
the (X) and (1}) functional
relationship to (w) at a con-
stant toam layer heisbt.
Curves in Figs. 8 and 9 repre-
sent data obtained tor (X) and
(1}), respective17, in accordance
with the following em-
pirical tormulae& K80
t(H) and 1} - .(H) [1].
The data indicate
that with a detinite
toam layer heisbt the
absorption coefficient
increased proportionatel7
to the increase ot gas
velooit7 in the appara-
tus, as shown in Fig. 8.
To a certain extent it
illustrates the true
Fig. 6. Effect of liquid flow intensit~ on K and 1})
A - Coefficient of absorption K in kg/m . hr x kg/m
B - degree of absorption (cBd) 1} in percent.
C - liquid flow intensity i in m3/m x hr.
Screen 5/2. w a 0.75 m/sec., h - 200 rmn. 1 B BaOH
solution; C ,- a 6%V t . 18°.
Vo.u.
functional relationship
between (X) and (w),
since it equally presupposes that other factors, aftecting X and depenc3i"8 on
the velocit7 ot the gas, would be automatical17 eliminated if H were constant.
It should be borne in mind, however, that conditions at which H - constant
are attainable by changing H , hence, by changing the structure ot the gas-
o
liquid s7stam at different (w).
The degree of C02 absorption fram gas, or the efficiena,y coetticient ot
a shelt screen (1» ot the apparatus, abrupt17 drops with the increase in (w),
-105-
-------
2
10
as shown in Fig. 9,
siDoe with the same foam
height and approx1mate~
the same phase contaot
-area, the contact time
between the gaseous and
liquid phases is reduced.
A stu~ of the proc-
ess of C02 absorption by
llaOH solution brought out
the oomplexi ty of the
meohanism and the depen-
denoe of the prooess on
the st~te of diffusion
1000
c
/1
. ' 3U{)
250
// If
20(1
..
:B
30
A
Joao
/600
15001
I
TOOOll .
soo
- '
20
Fig. 1. ,Effect of gas flow rate through the to-
tal apparatus cross-section on K, ~ and H.
A - Coefficient of absorption K in kg/m2.hr x kg/m3
B - degree of absorption (cad) ~ in peroent;
C - foam layer thickness H in mm; D - gas flow
rate (w) ineide 03 the apparatus in m/sec.
Screen 5/2. i - 5 m /m.hr, h - 100 mm, 3 N Na~H
tr
solution; C ,- - 6%, t - 600.
vo~
in the gaseous and liquid
phases, the rates of the
chemical reactions, the
oarbonate ion concentra-
tion in the solution and
the temperature. The re-
suIte of the experiments
showed that the intensit3' of the process as a whole, and consequentl3', of its
consti tuent stages sharply rose under conditions of highly turbulent foam
formation. According to published data [8, l3J C02 absorption coefficient by
NaOB in a packed absorption apparatus operating under ordinar,y film conditions,
did not excesd 1000 to 1250 kg/m3/hours/atmospheric pressure. At a linear gas
velocity through a total cross-section of a foam apparatus equal to 2 to 2.5
m/sec, with a distance between screen shelves of 0.5 m, the absorption coef-
ficient of a foam absorption apparatus is 4 to 5 times greater than of the most
generall3' used paoked scrubbers.
Conclusions.
1. The purpose of the stu~ was to determine the completeness and rate
of carbon dioxide absorption by a foam layer of sodium hydroxide solution,
under different conditions of C02 concentration and rate of flow, different
llaOH ooncentrations, degree of oarbonization of the alkaline solution and
topera ture.
-106-
-------
?(l(JO
1500
1000
I
'DOL
A
f
. . . . B
I 2 J
Fig. 8. Effect of gas flow rate through total appar-
atus cross-section at constant foam layer on the ab-
sorption of carbon dioxide. 2 3
A - Coeffioient of absorption (X) in kg/m x hr.kg/m ;
B - gas flow rate through the apparatus (w) in mfsec.
Height of foam layer H in mm: 1 - 100, 2 - 150, 3 -
- 200, 4 - 250, 5 - 300. 0
Screen 5/2. 3 N NaOH solution; Cvolx . 6%; t . 60 .
A.
5
1,0
J
30 '
;~
ZO
fO
B
2 J
Fig. 9. Effect of gas flow rate through the total
apparatus cross-section at constant thickness of
foam layer on the rate of C02 absorption (~) T).
A - Degree of absorption (cad) T) in %.
B - gas flow rate in apparatW3 (w) in m/sec.
Foam layer thickness H in mm:
1 - 100, 2 - 150, 3 - 200, 4 - 250, 5 - 300.
Screen 5/2. 3 N BaOH solution; C ,-. 6%; t . 600
. vo~
-107-
2.
It was demon-
strated that coefficient
(X) for carbon dioxide
absorption b1" 3 N NaOH .
at 600 was practical~
independent of the C02
concentration in the
gas wi thin 2 to 15%.
3. The functi onal
relationship between BaOH
concentration and coef-
ficient (X) and (T))
reached its maximum at
2 11 NaOH.
4. As the carboni-
zation of the sodium hy-
droxide solution pro-
gressed, the masnitudes
of (X) and (T)) sharply
diminished dur1!18 C02 ab-
sorption by Naoa solution;
these magnitudes were ap-
proximate~ four times as
great as during absorption
b1" a fully carbonized HaOH
solution. Results of ex-
periments showed that as
the rate of carbon dioxide
absorption by a sodium hy-
droxide solution of constant
conoentration decreased the
Na2C03 concentration in the
solution increased.
5. The values of the
tunctional relationship be-
tween temperature and coet-
-------
ficients (x) and (~) reached their mAyima at 45 - 500.
6. Within the range of 0.5 - 3.5 m/sec linear gas f'low velocit;y during
absorption of carbon dioxide b;y 3 If NaOB solution at 600, the lD88Ditude of
(Ie) increased approximatel;y from 700 to 2000 'm/hour, and the magnitude of (t)
decreased from approx1matel;y 34 to 1$.
7. On the basis of the above data it is possible to choose optimal con-
ditions under which different gases can be freed of carbon dioxide, or for
carbonization of alkaliDe solutioDs in the foam apparatus.
8. Under properl7 organized conditions of foam apparatus operation the
rate of C02 absorption 'b;y a solution of lfaOB can be increased to 4 - 5 times
the rate of the widel7 used scrubber type gas purifiers.
Bibl1ograpq.
(1) ~I. E. no a H H, B. .-\. H 0 n LI JI e B, a. H. l' a paT, mnx, XXXII, 5, 12~2
(1959) - [2) M. E. n 0 ;j \I H. II. n. ~I y x .'1 e a 0 B, ~. C. l' Y III a p K H ,
a H . l' art a T neHlIl.lH cnoco6 06pa6OTKH raaOB H >KIIAKOCTeH. ~ocxHIIIHaAaT (19~5). -
. '. . E -\ HonLlJIeB mnx XXX, 3, 362 (19;)7).-[4) M. E. Ilo-
(3) ~I. I... 0 ~ H H, .'" '''''fix xxx 5 674 (1957). - (5) M. E. n c-
aUIl r; A HOllhl.fCB, 3. H. TapaT, m, .,
, fi..'. L' 0 n LI '[ e D r. B. E e JI b q e a K 0, Tp. "lTU HllleHB J1eacoDeTa, BYn.
a H H." ..,.. n . . , B AU' B H A n e T-
XXXt'1 rOCXIIMHa~aT (l!ij6). - (6) M. E. no a H H, . . non hi JI ~' . . mnx
OBa 'mnx XXXI IWJ (1958).-[7) M. E. noaHa, a. H. lip a,!, '
~XXI: 1332 (1958). ..:.. ISI ~L E. no a H H, mnx, Xl!, 10-1,1, 12 (1\146); X~
3 (1947). - [~) 1. W. Pay n e, B. F. Do d.g e, Ind. Eng. Ch., 24, 6, 630(193~).
[10] S. H a tta, Techn. Reports Tohoku Imp. Umv., 8'J-n(lx928lXl [~1~~'(~94r) o~ il~i
mnx XX 4 145 (1947). - [12) a. H. l' Y P x a H, m, " . 14)
J B"T ' , B f' 1) 0 d g e Trans. Am. Inst. chern. Eng., 2, 255 (1943). - [
M.X. H~~e~H~B~KHi, M.'A. nepitHBapeHKo, mnx, XXIV, '>,42 (1951).
-108-
-------
Bt~eDic Aepects of Industrial Vanadium Aerosol.
By
I. V. Roshch1n.
(Department of Labor Btgiene of the 1st .osco. Order of
Lenin Medical Institute).
Gigiena i Sanitari1'a, 110. 11, 49-53, 1952.
Some reporh appeared in Soviet 11 terature whioh dealt with the problem
of sanitary labor conditions in industries producing or using vanadium; some
ot the reports dealt primarily with the toxicological aspects of vanadium.
This author undertook to examine the conditions and nature of possible
effects of vanadium compounds on the organism, to determine the type and
properties of vanadium compOUDds contained in the air, to obtain experimental
toxicological data necessar,y tor the ~gi8Dio evaluation of industrial plant
surroundings, and to arrive at a basis for ~gienic measures to be instituted
in industrial plants using vanadium.
Vanadium belongs to the group of rare elements. It is rarely found in
concentrated spots in the earth'. crust, and occurs mainly in the form of
oxides and salts in combination .i th iron, uranium and other metallio ores.
As a result vanadiUm oxides are contained in considerable quantities in blast
furnace and open hearth sl8BB. Investigations indicated that during crushing
ot these slags an aerosol was formed which contained lower oxides of vanadium,
oxides of silicon, calcium, iron, and in smaller quantities, titanium, chro-
mium and manganese. Formation of aerosols in the crushing process was caused
by insufficient proteoting devices, open dust-forming processes and by a lack
of on-the-spot ventilation. During slag caloining the air ~ become polluted
by its dust to 50 mgjm3 concentration. Suoh dust JIJlq contain soluble vanadium
salts, sodium vanadate, the air oonoentration of which can be as high as 5
mgjm3.
Vanadium pentoxide is derived trOll sodium vanadate. :Before the pent oxide
is used. in the production of ferro-vanadium it is melted in smelting fumaces,
a prooess which generates vapor of vanadium pent oxide , such vapor oondenses
into a vanadium pentoxide aerosol of high dispersion, the particles of whioh
have a diameter of less than 2 p. Data on vanadium pent oxide aerosol distri-
bution in the vioinity of smelters are presented in Table 1. Vanadiua pent-
-109-
-------
oxide was de'te1'l1ined b7 the me'thod of )I. Je. Beresova (G1g1eD& i San1tari7a,
Bo. 7, 1951).
TABLE
1.
Content of vanadium pent oxide in the air during smelting.
I I 3
Concentration in J1J8/m
Place of sample taking i Bumber of I
: samples: )(A.yim~l : Kinimal
I I i
0.5 m above the ingot mould 8 7.1 16.5
during the pouring
Over the tap hole of the 14 1.9 5.5
smelting furnace
Over the charging hole of the 11 4.8 7.2
smelting furnace
At working points 14 1.2 1.8
Some distanoe from working 12 Bon e found
point
,
ii
I'
)(olten vaDadium pent oxide is used in prod11ction of terro-vazaadiwa. Prior
1;0 its use in the preparation of ferro-vanadium the pentoxide is reduced to
its metallic form in electric furnaces. The reduction process is a gradual
one: pentoxide ~ tetroxide ~ trioxide ~ oxide ~ metallic vanadium. The
question of volatilit7 of the above vanadium compoUDds while in the electric
furnaces is of interest, and importance. Repeated ana~.es of air over the
surface of molten ferro-vanadium indicated that the latter was not the source
of vanadium vapor emission into the air. Particles of vanadium compounds were
carried off not from the a1107, but from the lqer of slag floating over the
top of the all07 mass in the electric furnace. Vanadium was present in the
slag in the form of calcium vanadate 4CaO.V205 (the ferro-vanadium 8IIeIting
o
temperature is 2000 , whioh is the 8ame a8 the temperature in the vanadiwa
pent oxide electrical red11cing furnace) and lower oxide. '204' V203' V202 and
'20. According to Po~akov the melting points of vanadium oxides are a. fol-
lows: V205 - 6580; V204 - 2000°, V203 - 19760 and '202 - 19700.
The above data show that the lower oxide. of vanadiWl have high melting
points, therefore, it can be assumed that their volaUlit7 at the electric
furnace temperature i. insignificant. The melting point of vanadiwa pentoxid8
-110-
-------
1. low aDd 1~. vaP0r1..~1OD can be expeo~8d ~o be h1Bh, as large II&SSe8 ot 1 ~
momen~ar1q 'Wl'D iD~o lower ondee, however, 1 ~ 18 rap1a.q reduoed ~o ~he lower
ondes in the eleotrio fU1"D&Oe. On the o~her baDd, under oon41 Uons ot ~he
eleotrio aro fl8118, the ~_pera~ur8 of which 1. 32000, the rate ot V&D&d1um
vaporisaUon IllUst be oonsiderable. Ana17s1s of the BUrroundhg air made during
~he 118~~1ng of terro-vanadium iDdioa~ed tha~ dust ooncentrations in the air
can be as high as 67.7 mgja3, and of vapors of lower vanadium oxides as h1Bh
a. 0.45 mg/m3. Thus, persons wor1d.ng at ferro-V&D&d1um smelting caD be ex-
posed 'to the effeot of aeroaols oonta1n1ng high17 dispersed pent oxide and lower
ondes of vaD&d.1um. Those working at orushing and SifUng ferro-v&D&d1wa IIJa7
be exposed to the effeot of ferro-vanadium dust.
!he aoute and chron10 effects and the qg1emo aspec~s of vanadium com-
pounds were 8~udied experiaental17. The chronic tests wer6 made with 20 white
.rats, animals were placed in the exposure ohamber ever'7 other d&7 for 2 hours
over a period of three aonths, the chamber air coDtained 0.003 - 0.005 mgfu
of v&D&d1um pent oxide aerosol which was obtained b7 burning vanadium pent oxide
in an electric aro flame. Fifte8D rats of a second series were exposed for
one hour daiq for a period of 4 months to 0.01 - 0.03 mg/li of vanadium pent-
oxide dust of high d1apersion. Thus, the vanadium dust entered the animals'
resp1rato17 pass888s b7 w&7 of natural 1nhalaUons. In the third series of
tests 15 white rats inhaled highly dispersed dust of crushed ferro-vanadium
eV817 other dq tor one hour, the dust concentration was 1 - 2 mg/li, and ex-
posure extended over a period of two months.
Duri ng the first and second months of exposure the weight and behavior of
the test animals were pract1cal17 identical with those of the control animals.
During the third month of exposure the gain in weight of the test animals showed
a retardation, toward the end of the exposures the test animals began to lOBe
weight s1mu1taneouB17 with the appearance of a b1oo~ nasal muOOUB diBcharge.
The general health conditions and behavior ot the animals exposed to vana-
dium dust inhalation appeared to be no different from those of the control
animals. Jlaorosoopio post-mortem examinations of the test animals showed no
signs of pathology other than qperem1a of the lungs.
Microsoopic examination showed the fo11owUlgc
1. Plethora and capillarostasis in the pulmonar,y tissue, particular17 in
peribronchial regiQn8, develop:Dent of perivascular edemas and l7mphostases.
-111-
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Exposure to. highly dispersed vanadium pentoxide aerosol produced hemorrhages
and focal pulmonary edemas pointiDg to the graver and more acutely expressed
toxic effect of this type of vanadium aerosol.
2. A manifest reaction of interstitial (coDnective) tissue of the lungs.
The character of the reaction was difterent in the difterent test seriesl in
some cases of ferro-vanadium aerosol intoxication this reaction resulted in
. the development of chronic peribronchitis and peria1veolitis characteristic
of chronic productive pneumonia. In animal s exposed to the inhalation of .
coarsely dispersed vanadium pentoxide, the intermediate productive pneumonia
was either weakly expressed or totally absent. In chronic intoxication,
caused by hiply dispersed vanadium aerosol, there were sisns of' di.sturbances
in the blood and qmph circulations, in the permeability of the pulmonary
blood vessels, also signs of serous desquamative panbronchitis. Sclerotic
foci were observed in the region of peribronchial infiltrates. The chronic
tests did not extend over a sufficiently long period to pemit observation of
gross sclerosis development. However, suoh pulmonary changes as the formation
of small sc1erotio foci near the bronchi, pointed to the development of gross
sclerosis.
The results of chronic tests indicated ,that the hi ply dispersed vanadiWi
pent oxide aerosol possessing a hip p~sico-chem1cal activity, produced grosser
pulmona17 changes following its inhalation in concentrations considerably
below those of a coarsely dispersed aerosol.
Ferro-vanadium dust produced grave pathological changes only at high 001'1-
centratians indicating that its toxicity was lower than that of vanadium pent-
oxide. This~. have been due partly to the low solubility of vanadium as an
alloy constituent in media, the qdrosen concentration of which approximated
the biological level, compared with the above, the solubility of vanadium pent-
oxide in biological media was several times ten as high.
Effects of acute toxicity of vanadium compounds were investigated by ex-
perimental procedures much similar to the one previously described. Ferro-
vanadium aerosol produced no aoute intoxication.of animals even with 10 malli
concentratioDs, perhaps as a consequence of slow transi tiOD of' vanadium from
the alloy into the biological medium.
Aerosol of crushed vanadium pentoxid.e produced aoute intoxication of ani-
mals exposed tor ODe hour to concentrations ot 0.08 mgfli and higher. Concen-
trations of 0.7 - 0.8 l1J8/11 were absolutely lethal to the test animals. 1-
-112-
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1.3 mg/li concentrations of ammonium vanadate were also absolutely lethal.
Animals were exposed to the vanadium pentoxide condensate for two hours.
The minimum concentration which caused aoute intoxication was 0.01 mg/li;
absolute lethal effect was produced by 0.07 flJ8/li.
The clinical picture of aoute intoxication with the vanadium compounds
was as follows: passive behavior of the animals and loss of. weight; animals
exposed to hish aerosol concentrations suffered paralysis of the hind extremi-
ties, and diarrhea, which brought about death 20 - 80 hours after exposure.
In cases of acute intoxication vasodilatation and blood stasis were 00-
served in all the internal organs; intoxication brought about cerebral flui~
stasis.
Thus, the most characteristic manifestation of vanadium toxicity was dis-
turbance of the circulatory g,ystem;vasodilatation and blood stasis in the
vessels of internal organs. These changes assume a regional character: they
were observed only in the lungs and apparently, lead to a disturbance in
vascular permeability; pulmonary lymphostasls accompanied by a lowered drain-
8B8 function which enhanced the development of the pulmonapr pathological
processes. In acute intoxication the disturbance in the circulatory g,ystem
embraced the most important regions of the organism, such as the organs in
the thoraco-abdominal cavity and the cerebrum. Nerve tissue is particularly
sensitive to lack of blood supply, and particularly 80 in stasis of the cerebral
fluid. Therefore, circulator,y disturbances lead to disturbances in the brain
funotion, which, in turn, aggravated the primary oiroulatory disturbanoe.
These phenomena were observed in vanadium aerosol intoxication caused by ex-
posure to high concentrations of vanadium pent oxide and ammonium vanadate in
the air.
For attainment of rational prophylaxis against occupational intoxication
wi th vanadium and other industrial dusts, it is necessary to reduce their con-
centrations in the air of the working premises. This can be achieved b,y di-
verting the dust into ventilating ducts installed strategically at points where
the dust was generated. The concentration of vanadium pent oxide in the air
can be substantially lowered by improving the process of vanadium PQntoxide
smelting in the direction of lowered vanadium pent oxide volatility. Vanadium
pent oxide should not be charged directly into the region of the electric arc
of the smelting furnace, wt first into the molten mass where it .ill melt
-113-
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and become reduced to the refracto17 lower oxides; such a loading procedure
will sharply lower the volatility of vanadium pent oxide.
In attempting to determine the limits of allowable concentrations of
aerosol of vanadium compounds in the air, consideration should be given not
only to the chemical composition of the aerosol particles, but to their physico-
chemical properties as we11. In this respect the degree of particulate disper-
sion is of primary oonsideration. In the case of ferro-vanad1\311 the bond be-
tween vanadium and iron renders it less toxic, than ammonium vanadate; accord-
ingly the limit of allowable concentration of the former can be set at a higher
level than of the latter; on the othe:r hand, the limit of allowable concentra-
tion of vanadium pentoxide should be set at a level lower than that of ammonium
vanadate; likewise the limit of allowable concentration of vanadium pentoxide
in the aerosol form must be set at a level lower than the concentration of
vanadium pent oxide in the form of a coarsely dispersed dust.
On the basis of the results of this investigation it is recommended that
the following limits of allowable concentrations of dust or aerosol of vanadium
compounds in the air of working industrial premises be adopted on a provisional
basi 81
For vanadium pent oxide in the form of aerosol condensate - 0.0001 mg/li;
for crushed highly dispersed vanadium pent oxide - 0.0005 mg/1i; for highly
dispersed dust of soluble vanadium salts - 0.0005 mgfli; for ferro-vanadium
dust - 0.001 mgjli.
The study of the toxicity of dust and aerosols of vanadium compounds
should be continued on a broader and more precise basis and the above recom-
mended provisional limits should be revised, amended or replaced in accordance
with the results of latest studies.
-114-
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Effect of Vitamins C, PF, and B on the Course of Acute Poisoning by
Orthonitr~ch1orobenzene.
:B;y
Yu. S. Grosman and Z. A. !fazarova.
(Department of Pharmacology, Molotov Institute of Medicine).
P'armakol. i TOksiko1., Vol. 20, No.3, 82-86, 1951.
Treatment of poisoning by methemoglobin-forming substances i8 now a pres-
sing problem due to the large-scale use by the chemical indust17 of compounds
capable of penetrating into the human organiSll and producinB methemoglobin.
Iqpoxia develops after a substantial amount of methemoglobin forms in the
blood.
Studies of A. I. Cherkes, Ye. A. Vladimirova, E. E. llart, inson V. )I.
t'otapova and A. P. Urinson have demonstrated that methemoglobinemia caused
by nitrochlorobenzene or sodium nitrite disturbed the processes of metabolism,
in particular carbo~drate metabolism, as manifested b;y the appearance of
~ergl;ycemia and. ~erlactacidemia. The abili t;y of the organism to oxidize
fatty acids is somewhat weakened, and there is a drop in the carbonic acid
content of the blood. In most instances the blood pH rises and ~erketonemia
develops. The extent of chaD88S in metabolism and the outcome of the poison-
ing depend, within certain limits, directl;y on the amount of methemoglobin
present. According to literature, concentrations exceeding 60 to 65% are to
be regarded a9 lethal. This has been confimed by Yu. S. Grosman and E. A.
Legeda in their studies on vitamin theraw in acute sodium ni tri te poisoning.
In treating comi tions ca.used b;y methemoglobin-fol'Dling poisons the conversion
of methemoglobin into hemoglobin must be enhanced to the possible maximum.
Such a process takes place as well in the absence of specific trea.tment on the
2nd or 3rd da;y, as was shown by Dittrich and Aron in their tests with dogs;
but the process was slow and gradual.
W. A. Englehardt, Warburg, Wendel, V. S. Shapot, E. A. Vladimirova, B. G.
Gordon, E. E. Jlartinson and V. M. Potapova, I. F. Seits, T. I. Ivanova and
others established that methemoglobin reduction was a complex, still incom-
plete1;y investigated, enzyme process in which the dehydrogenase s,ystems were
the cbief partioipants. In the opinion of these authors, stimulation of these
enzyme s;ystems should affect favorab1;y the rate of methemoglobin reduction
-115-
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and the general oourse of intoxication. It is generally known that sev~ra1
vitamins in the B complex group also belong to the active dehydrogenase groups;
therefore, it was decided to determine the presence of some of them in methemo-
globinemia. In this respect the most promising was a combination of nicotinio
acid and ribloflavin in the presence of ascorbic acid; according to I. F. Seits
the latter acted as an intermediar.1 in carbohydrate reduction between the in-
dividual enzyme links in the process. Such a vitamin combination was used
suocessfully in treating acute sodium nitrite poisoning in rabbits (Yu. S.
Grosman and E. A. Legeda); the effectiveness of suoh treatment was greater
than that of methylene blue. Therefore, it was deoided to experimentally ap-
ply such treatment to several cases of grave poisoning using animals which
readily fomed methemoglobin and whioh eliminated it with greater difficulty
than did rabbits.
The procedure. The experiments were performed on 35 oats in comparable
series, employing as far as possible animals of the same sex and weight.
Chemically pure orthonitroohlorobenzene in doses of 100 mg/kg in 0.5 ml of
acetone was injeoted subcutaneously in the abdominal region. Acoording to
V. F. Kel'nikova such a dose was lethal for oats. 40 ms/kg of ascorbic acid
combined with 5 mB/kg of sodium niootinate and 0.4 mg/kg of ribloflavin were
injected subcutaneously or intravenously 30 minutes after the injeotion of
the orthonitroch10robenzene.
Body temperature was taken rectally in the control and experimental ani-
mals. Blood methemoglobin was determined by Lavrovskii1s method, blood sugar
by the method of Hagedorn and Jensen, and alkali reserve by the Van Slyke
method. Blood for analysis was drawn from the femoral vein before poisoning
and 2, 4, 6 and in some experiments 24 hours after poisoning. In experiments
with rats studies were made of changes inactivity of muscle succinic dehydro-
genase following the injection of 150 mg/kg of orthonitrochlorobenzene and of
the effect of the vitamin combination on dehydrogenase activity.
A succinic dehydrogenase preparation was made from muscles of decapitated
animals according to Szent-Gyorgyts method (muscle paste washed twice with
distilled water). The paste was prepared in the cold by grinding 4 g of thigh
muscle, free from connective tissue, with the aid of 2 g of glass powder.
300 mg portions of the paste were placed into Thunberg test tubes followed by
0.8 m1 of a buffer solution made up of 0.7 ml of m/5 ~HP04 + 0.1 ml of m/5
-116-
-------
KH2P04. 0.1 ml of 11500 met~lene blue and 0.1 m/5 of sodium were introduced
according to Chep in oga . s method; the control tubes received corresponding
amounts of distilled water. Each experiment consisted of 5 Thunberg tubes
in the case of the test animals and 3 for the controls. After exhausting as
much of the air as possible, the tubes were quickly but oarefully shaken and
placed into an incubator at 380 ! 20. Observation was oontinued until the
methylene blue became completely deoolorized.
Four series of experiments were performed using 40 rats, 10 in eaoh series.
The first series was designed for the determination of normal de~drogenase
activity; the second for the dete~nation of de~drogenase activity 3 hours
after subcutaneous injeotion of a combination of vitamins C, PP and B2 in the
above-mentioned doses; the third for the determination of de~drogenase ac-
tivity 3 hours after poisoning by orthonitroohlorobenzene; the fourth for the
determination of de~drogenase activity 3 hours after poisoning by orthonitro-
chlorobenzene, followed 30 minutes later by the injection of vitamins C, PP,
and B2 combined in above mentioned doses.
Experiments with cats.
First series (oontrolt. Experiments were performed with cats weighing 2.1
to 3.7 kg. Poisoning developed oomparatively slowly after subcut.aneous in-
jeotion of nitrochlorobenzene. Three to four hours later there appeared
dyspnea, cyanosis of the muoosa of the eyes accompanied by a grayish-brown
color charaoteristic of methemoglobinemia. Six hours after poisoning the
bo~ temperature dropped by an average of 50 (from 37.80 to 32.90). Karked
hyperglycemia averaging 255 mg % developed in all the animals (Fig. 1) with
a maximum 4 hours after poisoning; the control standard amounted to 140 mg %.
After 6 hours the bn>erglycemia dropped to an average of 234 mg %, and after
24 hours the blood sugar level returned to normal in the surviving animals.
The alkali reserve after poisoning decreased (Fig. 2); after 6 hours it fell
to an average of 32% below the original. There was a definite shift toward
acidosis in the control animals. During the first 6 hours after poisoning
methemoglobin was found in the blood of 8 of the 10 oats (Table 1).
Table 1 shows wide variations in the controls with respect to time of
methemoglobin appearance and its conoentration in the blood. Within 6 hours
after poisoning the methemoglobin ranged between 47 and 74%. One cat survived
and 9 animals died during the first few dqs. The 100 mgfkg dose of ort.ho-
-117-
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!'AILB 1.
Percent ot methemoglobiB in the blood ot oontrol animals
injeo'ted .Uh orlhonitroohlorobensene.
Ihan4ar4i Jle'th8lloglobiD atter - a
a
!en I Survival
10. i 4 hours I I a
I I 2 houn I 6 hours I 24 hours i
0 0 0 0 11 o't Less 'thaD 24 hours
1 de'term1necl
2 0 0 i'race 5~ 1Io't Less than 24 hours
de'term1ned
) 0 50S + afte:, 2 hours
4 0 0 0 48.C lIot Less than 24 hours
determined
5 0 0 3~ 41% Bot Less thaD 24 hours
determined
, 0 68$ + atter 4 hours
17 0 0 0 0 Bot Less than 24 hours
determined
18 0 0 0 !raoe 11 o't Sun1 ved
determined
o 0 !raoe 69% lIot Less than 24 hours
27 de'tel'lllined
31 0 Traoe 53% 14% lo't Less than 24 hours
determ.1Ded
nUrochlorobeDSene used oame ve'Q' olo.e to beiDg lethal.
S.00Dd series (subcutaneous injeo'\i1on ot a ooabiDat1OD ot v1tudns c.
PP. aIIIl JS!>l. BEper1aenta 9i'th su'bou't8Deous iDjeo'\iiOD ot 'the vU8II1D. 30 miD-
. u'te. ~er poiaOD1Dg were pertormed .ith oat. we1gb1Dg 1.1 to 3.8 tg. The
..eral oaur.e ot p01sODiDg in t~8 group ot aD1mals was lighter 'thaD iD the
oonuols, 4spne& and C78D081s ot the _0011. membrane. were le.. pronounoed.
!'he t88perature ot 'the treated BD1mals 6 hours &tter the beg:h\"1ftg ot 1ntoxi.-
o
oat1- avera&'8c1. 0.7 abov. the control.. '!'he blood sugar level 2 hours at'ter
p01.,."--C was about the IIUI8 &. iD the oontrol experiments, but the slope ot
1t8 ourYe w.. neeper, atter 4 hours the blood sugar level ot the treated w-
aa18 &verap4 54 DIg %, aDd atter 6 hours 28% les8 thBD in the con'trols (Pig.
1). Judged b7 the relat1ve percent ri.e iD the blood sugar level, the glTcem10
-118-
-------
3-'0
300 1
.?5'il 1
2J'O
*21J
flD 250
:II 2.50 -
240
230
A 2:?O
210
"1'4200
-'90
,.. !!O
11/70
fItJ/oO
/5-0
::s fliJ
r12 /30
/20
//(1
ItJO
/\
/ ......
/ \
/ \
.I \
/ /'-
i-'
i/,
ji/
" I
.~ I
,
_.~ I
I
I
_J
o 1
,
I
24
curves ot the treated and control
animals were approxiJlate17 iden-
tical. lPig. 2 shows that 6 hours
atter poisoning the alkali reserve
in this group of aniJaals r8D&1ned
within its normal limits. !hu8,
the subcutaneous injection ot
vitamins C, PP, and B2 prevented
the appearance of acidosi8 which
normally developed in this t11>e
of poisoning.
1'0 methemoglobin was tound
in 7 of 10 experimental animals
during the first 6 hours.. 36 to
39% methemoglobin W&8 noted in 2
after 6 hours; atter 4 hours it
amounted to 40% and after 6 hours
to 60% in one test animal. It
was clear, then, that the sub-
cutaneous injection of the vita-
min combination prevented, or ef-
tectively arrested, the develop-
m8t of methemoglobin in animals
poisoned b;y orlhon1trochlorobenzene.
In the series under discussion 5
QTli I118ls surv1 ved, and 5 died.
Third. series (intravenous in-
jection of a combination of vita-
mins C. PP and ~ l. Simul taneous
intravenous injection of vitamins
C, PP and. B2 30 minutes atter
poisoning b;y orthonitrochloroben-
zene alleviated even more emphaU-
cal17 the oourse of intoxication.
Of 10 cats weighing 1.8 to 3.3 kg,
7 survived and 3 died. 1'0 mucous
Hours
rig. 1. iifect of orthonitrochlorobenzena
on the blood sugar level
I - Control, untreated animal., 2 - subcut-
aneous inject1- of combination of ascorbic
acid, Na-nicot~~, and riboflavin 30 min.
atter poiscming, 3 - intravenous injection
of same vitamin ccmb1Dation 30 min. atter
poisoning, 4 - intravenous injection of
, ms/kg of methylene blue
IJ5
fJO
:2S
';;t /20
~ 1/5
o I/O
so: 1175
~ ,'~(l
o 95
+' gO
~ 85
() -YO
t: 75
Po 7.7
65
C:7
..,r.)-
Z ,1 4 5 If
-,-----3
--
"../
/'
..~ ~ - --"................. .",.....,." 2
", .......".
"
.....................
'-
-4
,
-------
membrane coloring typical of methemoglobinemia was noted in an:r of the animals
throughout the experiments. Six hours after poisoning the temperature of the
o
experimental cats was on an average 2.2 higher than of the controls.. The
sugar curve in the treated animals rose 23% within the first 2 hours after
poisoning as compared with the controls; later it tell to a level considerably
below the controls (30 to 40 mg %) (Fig. 1). Fig. 2 shows that the alkali
reserve ot the animals in this group remained 10 to 14% higher than the original
level throughout the entire period ot observation. No methemoglobin was tound
in 8 cats during 6 hours of observation. Experiment No. 29 ot this series,
where the cat died after 2 hours (probabl;r due to the ni trochlorbenzene solu-
tion accidentally getting into a blood vessel) showed a methemoglobin concen-
tration of 52%. The methemoglobin concentration in a second oat amounted to
50% six hours after the injection of the poison. It was obvious that here,
too, the intravenous injection of the combination of vitamins 0, PP and B2
clearly arrested the development of methemoglobinemia. in most test animals
and resulted in the survival ot more animals than following subcutaneous in-
jection.
Check experiments with methYlene blue. The experiments were performed
with 5 cats weighing 2.1 to 2.8 kg. )(et~lene blue was injected intravenously
30 minutes after poisoning by orthonitroch1orobenzene, in 5 mgfkg doses. An
0.5% solution of methylene blue in an isotonic salt solution was used. Of 5
animals 3 died and 2 survived. During 6 hours of observation traces of methemo-
globin were noted in only 1 oat. This indicated that in the case ot acute
orthonitrochlorobenzene poisoning prevention of methemoglobinemia alone i8 no
index of survival. The developed hypoxia follows a complex, still inadequately
defined pathogenic course. Despite the absence of methemoglobinemia, the
sugar curves in the test animals were considerably higher than in the controls
(Fig. 1). The alkali reserve decreased, and 6 hours after poisoning was on
the average 19% below the original level (Pig. 2).
Hence, unlike the vitamin combination, met}q'lene blue did not prevent
acidosis from appearing after orthonitrochlorobenzene poisoning. The ~e
lightened the course of poisoning as compared with the control. Six hours
after poisoning the bod1' temperature of the animals dropped an average of 4.60,
the same as in the control experiments.
-120-
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kPer1ments on rate.
R.sult8 ot experiments made to dete1'll1ne changes in suooinio deh.;rdrogen-
as. aotivity after acute orthonitroohloroben..n. po18oning in rats and the et-
f'eot of treatment with the oombination of vitam1n8 0, PP and B2 81"e presented
in Table 2. The data show that 3 hours atter poisoning the animals' suocinio
de~ogenase aotivity was con8id.rably 1Dh1bited, aa was indicated by' an in-
orease in the time required for the oomplete decolorintion of meth1'lene blue
frOil an avera88 of 16 miDut.s in the oontrols to 27 ainutes in the poisoned
animab. The vitamin C, PP and B2 combination which in intaot rats bare17.
affeoted sucoin de~genase aotivity, in orthonitroohlorobenzene poisoning
considerably enhanoed its return to normal. The data support the assumption
that the higher survival rate of' orthonitrochlorobenzene poisoned animals
treated with the vita.mins C, PP and 12 combination depended not only on par-
tial or total elimination ot methemoglobinemia, but also on normalizing the
functioning ot the ondation-reduotion enZ1Jl8 system, and partioularly of'
deh1'drogenase.
TABLE
2..
I
Test :
.
.
series i
First
Second
Third
Fourth
IlwDber of
dete1'lR1nat1cm8
Test I Control
I
I
I
Average meth.;rlene blue
reduction time
Test I Control
I
50 30 11 miD 1'0 reduction
50 30 14. miD Xo reduction
50 30 27 miD No reduction
50 30 18 miD No reduction
Conolusions.
1. The injeotion ot ascorbic aoid together with sodium nicotinate (5
rlJfJ/k8) and rib10tlavin (0.4 mg/q) 30 minutes atter pOisoning cats with ortho-
nitroch10robenzene (100 rlJfJ/k8 subcutaneou8ly) tavorably affected the oourse
of pOisoning. This was indioated by' the higher survival rate of' treated ani-
mals as oompared with the untreated controls, by' the considerable iDh1bi tion
in the development of methemoglobinemia, by' the disappearanoe of acidosis
symptoma, by' the normalization of deh.;rdrogenase activity (in experiments with
rats), and b.1 a le$s pronounced h1Pothermia.
-121-
-------
2.
Intravenous injection of the vitamins was more effective than sub-
cutaneous injection.
3. MethTlene blue injected in dose ot 5 mg/kg under the same experimental
conditions prevented the development of methemoglobinemia I in all other respects
it was inferior to the' tested vitamin coabination.
4. The results justi17 recCllllDenc1.1Dg that the C, PP and B2 vitamin com-
bination be given a clinical trial in the treatment ot cases poisoned b7
methemoglobin-forming substances.
Bibl1ograpq.
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.'1eHHHrp. roc. YH-1a. N2 138, DlloxHMIlSi H $H3HOJlOrHR, B. 24, 19fi2, CTp. 148-156. -
K a r aHA. Ii. H 4 e p K e c A. 11. Bpa'!. JleJlO, 1948, N2 6, CTp. 463-468. - Me JI ..
H II K 0 B a B. <11. II K a r aHA. 11. TpYJlbl H MaTCpllaJlbl ~'Kp. roc. HH-Ta naTO.~orIlH
H rllflH'Hbi TpYJla, 1935, CTp. 45-59. - C e ii II. 11. <11. 6HOXHMHR, 1947, T. 12, B. 2,
np. 123--133. -- T P a II e 3 H H K 0 B a H. M. <1IapMaKOJl. H TOKCHKOJl., 1951, N2 4,
crp. 34--37. - 4 e n H H 0 r a. O. n. DHoxHMH'!HblH mYPHaJl, T. 14. N2 1-2, 1939,
np. fi--12.-111alloT B. C. DHoxHMHR, 1938, T. 3. B. 4, cTp.430-445.-Aron.
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The Peculiar Relationship between Air Concentrations of Some Volatile
Substances and the Development ot Pulmona17 Edema.
Dr
A. A. Golubev.
(Institute ot Labor Htgiene and Occupational Diseases, Leningrad).
Gigiena Truda 1 Professional'nye Zabolevani7a, Vol. 1, 1'0. 4, 46-50, 1957.
\
Certain unsaturated highl;y react! ve chemical compounds are used in the
\
produotion of s;ynthetical~ pOt;y1Derized materials. In this oozmectlon the
complex esters of v1n;yl al cohox , with saturated tatt7acld8, such as vin;yl
\
acetate, viJlTl prop;yonate and vi~l but;yrate are ot iDDDecl1ate intef88t. A
stuq of the toxic properties ot v~l proP7onate and of vilQ-l but1T&te 1Ja-
-122-
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clioa'teel 'tha't 'the 1DhalaU. ot 'the vapors ot 'the.e es'ters by whUe mice produced
narootic etteen. aDd develORecl pglaODa17 --. Preli.iftA"7 observations in-
clica'ted 't. 't cl1fteren't oonoen'tra'tions ot 'th. es'ter vapor e11c1 't.d pathologio
88D1te.'t.'tioD8 ot clitter8Jl\ in'tensi't7. !his w.. veritied b7 a series ot ex-
per18en't..
.1. I. ~ in 1935 aDd Poulsen in 1954 based their de'tem1nations ot
quan'ti't.'tive pgla0D8.Z7 ohanps in --s on 'the degree ot tluid accumulaUon
in '\he lap. Jafte (in 1934) de't.Zllineel 'the raUo ot weish't ot 'the edema'tous
lWIP to the weight ot the .... lunp after 4rT1DC to oonstant weight. The
s1.llplest and most o~cmq useel ae'thocl is the one known as the "pulmOD&r7 co-
ettioient. deterad.Datioa, the resulis ot whioh are expresseel .s the ratio ot
..ight ot the lUDp 'to the we1Bht ot the .~_1'. bcq. .1ccord.1ag to flU17
aDd '!sem1k (1938l '\he PUlaoDU7 coetticient of normal 11110. varied within the
11a1ts ot 6.5 u4 11.5. !his au'\hor tound tha't in 20 mioe w.ighing 17 to 21 g
the pulacmar.r ooettioia't varied .Uhin th.. I1mUs ot 7.2 aDd 9.4.
IDhala\ion expoaure tests w.re raacl8 in series ot groups ot 10 mice as tol-
1.s. con'tro1 group., and group. exponel to 'the inhalation ot 2, 4, 6, 8, 10,
16, 32 aDd 48 8&/li or 'the es't.r v~or.. The total ot II1CB useel includ1ag the
oon'tro18 ... 180. Ixpoares were llade b7the .'\&tio method. by placing the mioe
in'to gIa.. 3are. CQIaO~tra'ti0B8 ot 'the v~l es'ters in the jars were attained
'b7 the ulRlal _thod, ani8a1s were exposed 'to 'the es'ter conoen'tra'tion tor 2
hours.
ImIp W.1'8 1'8mcweel t1"Cl8 'the boq 'b7 tirs't l1ga'ting the 'trachea 'to preven't
arq leaDce tZ08 'the 1UD88' the organs were weighed on 'torsion scales with a 1
g acour&q. Bl0ck8 in fig. 1 are plots ot pulmoDU7 coettioients ot 'the con-
'trol. aDd. ot 'th. 1II10e exposed to 'thB. difterent cODCeutraUons ot ~l propyo-
nat.. Pu18cm8J7 coetfioients were plottedaloag the ordiaa te ~ the ester
vapor concentrations were plot'tecl aloag the absoissa, nuaerica1 values in-
scribecl wi thiD the blocks repre8en't pulmonary coettioient ave1'&88s tor each
group ot 10 Afti_1., 1nd.enta'tion fleps wi'\h1n each block represent the pulmo-
DU7 ooettioients ot 1D41v1chaa1 an1aals.
The blooka in fig. 1 clear17 illustrate the tacn that increase in ester
ooncentration w.. toll_eel b;T aD. increase in the palmOD&17 coetticient up to
a poin't ot _n_, which w.. 88f111i in the 0&8e under coneid.ration. AlsT in-
erease in '\he v1D;Jl euer vapor conoentration b87cmd the -.Yimal poin't, was
aoocmpud.ecl 'b7 a no'table lowe1"1Dg in 'the PUlaoDaZ7 ooetticient, pointing to
-123-
-------
28
Z6
2'
22
zg
18
1$
'~
'2
/0
;1
Cont~ol
..41
+
2
$
8
/0
/5
12 . M.
Fig. 1.
Effect of ~l propyonate vapor concentration on
the pulmOn&r7 coefficient of white mice.
the faot that vilV'l propyonate vapor oonoentraUons above the 1nd1oated IqATimull
were less tono to the mioe. It oan be aSSWIed that 10 mgJl~.of ~1
prop,ronate vapor induced in the mioe a state of narcosis not effected ~ lower
oODCentrations of' the ester. (1Iotel At this point ed1tors of the Journal
pointed out that the author formed his &ssumpUon without taking into consid-
eration sach important facts as duraUon of ede8a development, t1l1e of te8t
animal's death at different vapor concentrations, etc. B. S. L. ) .
Tests with vapor of viDTl butyrate were oonducted following the previous17
described procedure. In this oase, the narcotic state was elioited in the teet
mice at 48 mgfli vapor concentration. At this vapor concentraUon the pulIDo-
nar.r edema of the teet aniaale waa not ae pronounoed as in the animale e%poeed
to the 32 mgfli concentraUon of the vi~l butyrate vapor. The valuee of the
pulmona:q coefficiente were I 8.5 at 2 JDB/li, 11.5 at 4 mgfli, 11.9 at 6 mc/li,
12.8 at 8 malli, 20.3 at 10 malli, 20.6 at 16 mc/li, 20.0 at 32 mc/1i, and
16.9 at 48 mg,/li. Thue, the results of tests with the vapor of ~l but7ftte
followed a course similar to that of v1n1'1 propyonate, this adds some weipt
to the assumption that the narcotio effect of the viJV'l esbrs at certain COD-
centratio~ lowered their pu1mona17 edema procluciag power.
This assumption was checked as follows I 10 test mice were deep17 narcotized
by sabcutaneous injection of 0.32 ml of 0.5% 801utiOD of lia-BmTta1 and then ex-
posed to 8 mc/li oonoentration of vi~l p~ODate, a conoentration of the ester
whioh eli01 ted most proncnmced pulmon&17 edema 111 the preoecl1Aa e%periaental
e%p 0 sure , for control purposee 10 non-narcotised aniIIale. were e%posed to the
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88ID8 concentration o~ the vi~l prowonate. At the end o~ 2 hour. expo8U1'8
8 o~ the 10 control nOD-D&rcotizecl anima18 dieclf all the 10 narcotized 1I110e
survived. '!'he 8U%"Y1riDg 8I1111a18 were sacrificed aDd their pulm0D&r7 ooett1-
oients dete1'lldll8d.. '!'he values obta1Ded were plo1;1;ed. by the bloak method, &8
111ustratecl 111 Pia. 2, the legencl of which 18 .el~-u;planato17. '!'he block
plots clearq 1acl1oate that the 1nt8l181t7 o~ palaODa17 ede8ae 111 the narcotized
11108 at all cOD08ntrat1ODs of the ~l ester n.por was about 5O.C o.~ the 1A-
taait7 111 the nCD-DArootiBed 1I1100f the aver&88 pq)IIIt\nU7 coeff101ent o~ D&1"-
cot1.ed mice W&8 10.' aDd of the nOD-narcotized. 810e 19.5.
28 !he pnv1ousl3' u-
25 pres.eel aSBUllpt10n w-
.. 24 . further check8d a. ~ol-
i Zl
c: lO
e /8
. 15
g /4
f ~~
~ ~
4
Z
D
J'1.g. 2. PulmODar)' coefficients in mice poisoned' by
vi~l prop;yOD&te vaporl whUe blooks - prelim1fta"'7
1la-8II7J"'tal narcotization" followed by exposure to 1d-
entioal ~l propyonate concentrations.
lOW81 10 lllice were ez-
posed to 32 88/11 OOD-
centraUon of ~J ~1"0-
wonate ~or 5 miDute.,
as a result of which the
8I1111&1s beC&118 d8epq
narcotized.. !he the 10.
naroot1zed mice and 10
control non-Darcot1ze4
mice were exposed ~or 2
hours to 8 mg/11 CCZ08D-
tration of ~l prcP7o-
nah vapor. lIost of the vi~l prop;ycmate narcotiBed mice failed to co.. out:
of the narcoUc state. All the exposed. mice died within the 2 hour exp08U1'8.
PulmODa17 ooeffic1ent determ1naUonsmade On all II1ce are listed in the ~ol-
lowing Table. Und.r special oondit1ons of the exper1aent all the test 8d.o.
inhaled prea.rraztgeel hiper conoentrations of the~l ester vapor than the
control mice, even 111 such. oases the pulmoDaZ'7 ooetfic1ents of the te.t 8108
were of lower values than of the control.. The 80.10 plausible explanat10D ot
suoh effects lies in .the. faot that the te8t mice were 111 a state of Dal'Ooai.
at the time the pulmoD&17 edema W&8 deV8lop1Da. It should a180 be p01l1ted. on
that the test mice survived loqer than the oontro.l 1II10e. The aerie. of u-
periaents tollowed. similar it not parallel counes aDd supporl the aSllURpt10D
-125-
-------
Test mioe r Control 11108
I
1aD& I Death in I IaDg I Death iD
ooettioient lIiIlutes 008ttioi_t minutes
24.4 69 34.6 55
22.8 48 22.2 40
20.9 48 21.3 32
21.8 46 20.2 30
19.3 45 20.2 27
18.8 43 20.0 26
18.4 41 19.3 22
18.2 39 18.8 17
17.7 :)5 18.2 14
14.7 22 16.7 13
AveraRes
19.7 43.6 21.2 27.6
that the narcotio state ot the mice lowered the iDtensit~ ot thetoxio edema
of the lungs in the mioe. In 1955 V. D. Bartener working with YiQT1 acetate
obtained results identical with those presented b.J this author.
Numerous investigations, especia11~ those ot recent ~ears, emphasized the
important role plqed by the nervous s~stem in the pathogenesis ot PUlmODa17
edemas. Suisada (1928) prevented the development of adrenalin-produced pulmo-
nar.r edemas b1" the injection of morphine, ch10rethane, chloral ~drate, and
other substances, whioh had aD inhibiting etteot on the nervous s~stem. Ac-
cording to Poulsen (1954) pre1imi1'la17 narcotizaticn of mice with ether and
alcchol conaiderabq, slo.ed up the developmelIt of PUlmona17 edemas caused b1"
the inhalation of carbon dioxide. Tennecoon (1954) used a variet~ of substances
which depressed the central nervous 87stem to prevent the occurrence of pulmo-
nar,y edemas 81icited b.1 intraperitoneal injection of thiosemicarbazide. It is
possible to prevent the development of pulmonar,y edemas in mice e1io1 tad b7
ammonium chloride b.1 the intraperitoneal injection of novocain, as was shom
by Goetzegan and others in 1954. Similarly convincing evidence was presented
by I. A. Serebrovskaya (1952, 1955) who was engaged in pharmacological studies
of the effeot of exclusion of different sectioDS of the nervous system on 'the
developnent of pulmonar,y edemas in rats and in guinea pigs. S. M. Laites and.
N. P. Smirnov (1956) ~and. ~ other investigators presented experimental evi-
dence of the participation of the nervous s~stem in the pathogenesis of pulmo-
nar,y edema./G. S. Ian (1953) published a special monograph on the subject of
-126-
-------
the ettect ot the state ot the nervous system on pulmonary edema development,
he analyzed a number ot reports appearing in the literature and concluded that
the nervous system plqed a leading role in the pathogenesis ot pulmonary edema.
In view ot the above it appears reasonable to assume that the extent ot develop-
ment ot pulmonary edemas by ~l acetate, vinyl propyonate and vinyl butyrate
also depended on the. stah ot the animal's nervous system.
A peculiar characteristic ot the tonci t1' ot ~l esters and the inter-
esting theoretical aspects it presents are tound in their simultaneous etfects
as narcotics and as iDci ters ot pulmona17 edemas which produce a type ot "toxi-
cological paradox", namely, that the higher cOnCentration8 ot the vi~l esters
are less t9xic than their lower concentrations.
Conolusions.
1. Exposure ot mioe to the inhalation ot vapors ot ~1 proP1'0nate and
ot viD7l butyrate elioited toxic PUlmona17 edemas aDd a state ot narcosis.
2. The development ot pulmonar,y edemas by v~l Prop1'0nate and v~l but1'-
rate vapors is enhanoed by an increase in the concentration ot the esters oDly
up to corresponding mAThll6J conoentrations of the ester vapor above such maxima
induce in the expo8ed animal8 a state of narcosis aad produoe a les8 marked
pulmonary edema. 'l'his phenomenon has been widely observed by other investiga-
tors who studied the etteot ot the state of the nervous s1'stem on the develop-
ment ot pulmOD&17 edemas.
3. In the case of v~l esters the point ot peculiar interest is the tact
that the tonc and narootic ettects are properties of the same substanoe.
Bibliograpq.
D apT e H eBB. 11. TOKCHKOJIoro-rHrHeHH'IeCKaR xapaKTepHCTHKa BHHHJlaUeTaTa If
YCJlOBHi! ero npoH3BOD.C"':,Ba. I1Hcc., 11., 1 955.-K a H f. C. HepBHaR CHCTeMa H oCTphli! OTeK
JlerKHX. M., 1953.-11 e H T e C C. M. H C M H P HOB H. n. DIOJlJleTeHb 3KcnepHMeHTaJlbHOik
6HOJlOrHH H MeD.HUHHhI. 1956, Xv 8, CTP: 16-16. - C e p e 6 p 0 B C K a JI Ii. A. DIOJlJleTetib
9KcnepHMeHTaJlbHoA 6HOJlOrKH I! MeD.HUHHhI. 1952, Xv 3, cTp. 27-30. - C e p e 6 p 0 B-
CKaR 11. A., APXHB naTOJlOrHH. 1955, T. 17, Nv I, cTp. 67-68. CllJlIOPH H Ll.epHHK
BpeD.Hhle ra3h1. M., 1938. - 11 a p H hi Ii A. M. TOKC'H'IecKHA OTeK JlerxHx (3KcnepIlMeRTaJlb:
Rble MaTepHanbl). M., 1935.-Joffe Science. 1954, v. 120, N. 3120, p.612-o13.-
Got t s e g e n R D.p. Acta med. Acad. sci. Hung., 1"954, 6, Nl 3-4, 367-378. Ll.HT. n~
p~ «DHOJlOrHR», 1956, N2. 14, 332. N 60242. - Po u I s en. Acta pharmacal et toxlcol
(K~benhavn), 1954, v.l0, No.3, p. 253-260.-Tennekoon. Journ. pathol. a. bac-
terlOl., 1954, v. 67, No.2, p. 341-347.
-127-
-------
Acute Dich10rethane Poisoning.
:By
G. N. )(orozov.
F&CD8ko1. i Toksiko1., Vol. 2, No.1, 76-78, 1958.
In view of the comparative infrequenc;y of dich10rethane poisoning, two
such cases which were recently observed are worth describing. One patient
recovered, the other died.
On August 19, 1955, an ambulance brought to the hospital S. and. D., both
20 years old, 4 hours atter they had swallowed some unknown liquid. Their
condition was moderately serious. They stated that 30 minutes after swallowing
the substanoe they felt dizzy and nauseous, and vomited. They ~d not call for
medical help until 3 hours later, .when their condition was noticed by neighbors.
Upon admission, D. was somewhat faint, sleepy and nauseous. He continued
to vomit bile and gastric content. His face and extremities were cyanotic and
the conjunctival vessels were plethoric. An alcohol-like odor emanated from
his mouth. Heart sounds were dull, with moderate ta~oardia of 92 contrac-
tions per minute; arterial pressure was 115/75 and respiratory excursions 20
per minute; temperature was 37.50.
On the morning of Ausust 20, 1955, 17 hours after admission, hi& condi-
tion worsened despite treatment. He complained of a severe headache, pain in
the substernal region, loose stools, without mucus or blood, several times
during the night. Nausea and periodic vom! ting continued. No urine was passed
during the night; in the morning 120 ml of turbid reddish urine was obtained
by means of a oatheter (see analyses). The patient was apathetic and unwilling
to answer questions. Skin of face was hyperemic, and c,yanotic and scleral
vessels were congested. Pulse was weak, rbythmic, 120 beats per minute. Ar-
terial pressure dropped to 95/55. Heart of normal size, beats. thudding and
olear with some scattered, dry rales. Tongue coated white. Tenderness in
the subcostal region upon palpation. Liver defined along edge of costal arch,
edge soft. Spleen not palpable. Pasternatsk1 symptom weakly positive on the
right side. Pain upon movement of eyeballs. »i1ateral Karinesco-Radovichi
symptom. Decrease in tendon reflexes but no aniso reflexes. Slight stiffness
of the neck and pain in the spine upon bending head forward. Suggestion of
Kernig's symptam on both sides.
-128-
-------
The condition became serious August 21. Same complaints continued. Edema
ot the eyelids. 'Arterial pressure 105/60. Increase in scattered, dry rales.
Number of respiratory excursions 22 a minute. Rejected food as on the dqs
before. Periodic vomiting of gastric juice mixed with bile and copious loose
stools without mucus or blood. Elimination ot 250 ml of turbid reddish urine
during 24 hours.
August 22, the condition was deteriorating. Pains in the right subcostal
region became more intense, ey-elids edematous, face ~erem1c. Hemorrhage
under the conjunctiva near the outside comer of the left eye, but fundus
normal. Vomiting became less frequent, 2 to 3 loose stools a da7 with ad-
mixtures. Patient still very apathetic, answered questions reluctantly. Pulse
weak, r~bm1c, 112 beats a minute. Arterial pressure 115/60. Heart margins
normal, first sound strong at apex, systolic murmur heard there. Scattered,
dry rales. TOD8Ue coated white, dry. Abdomen distended and. tense, highly
sensitive in epigastral and right subcostal regions.
By percussion, liver edges were determined as being 2 em below the costal
arch. Spleen not enlarged. In applying a paraneural novocaine block according
the Vishnevskii in connection with oliguria and intestinal paresis, hemorrhages
were noted in the adrenal gland to the left. On the same day there was heaV7
nose bleeding and copious vom! ting of "coffee grounds". Towards the evening
hemorrhages under the conjunctiva of the left 81'e spread over the entire surface
of the sclera. Peteohial hemorrhages in the area of the thigh skin. The pinch
symptom was pronounoed. Pain on moving eyeballs. Tendon reflexes heightened,
nothing pathological. Moderate rigidity of occipital muscles and pain on bend-
ing head~ Kernig's symptom weak on both sides. Oliguria set in (Aueust 22
only 20 ml of urine obtained with catheter). Temperature throughout the ill-
ness did not rise above 380.
On the moming of August 23 the condition of the patient became grave.
He 10st consciousness. Respiration loud, gurgling. Sldn of face and extremi-
ties cyanotic. Frot~ fluid from mouth. Pulse weak, rhythmic, 122 beats per
minute. Arterial pressure 95/20. Heart sounds dull. Number of respiratory
movements 28 to 32 a minute. Vedium and coarse moist crepitantrales. Re-
action of pupil to light very weak. Despite treatment, the patient died 3
hours after losing consciousness with symptoms of heari fai lure and pulmonary
emp~sema.
-129-
-------
Clinical diaposi.: acute poisoning by aD wUm01R1 liquid. .1
Tono nephrosis .i th acute oliguria. Toxic hepati Us. B_orrhagic B7D-
drame (nasal, gastric subconjunctival, and intrademal bleeding). Tone 11170-
card1 Us .ith symptCDs of decreased vascular tonus. Symptoms of tonc menin-
gitis. Pulmonar,y emp~sema.
Pathonatom1cal diagnosis: diehlorethaDe poisoning.
There .as a necrosis of the mucous membrane of the stomach and intesUnes,
edema of the stomach .alls, intestines, gall bladder, lungs and brain, depD-
eraUve changes in heart _scle, liver, and lddnq; tiDT h_orrhaps in mcGUs
membrane of the stomach below the visceral pleura and in the. epidoardiWD and
large hemorrhages in the kidney and the adrenal tissue on the right. The
protocols mention the presence of bleod in the heart and vessels and aD odor
of "dried mushrooms" from the internal organs.
The condition of S. on August 20, the second da7 atter poisoning, also
worsened sClDe.hat. Be complained of severe headache, nausea, periodic vomiting,
the skiD of the face .as moderate17 cyanosed. Jlacroscopic examiDation of the
intemal organs revealed sensitivity upon palpitation of the abdOllen. Loose
stools t.ice a ~ .ithout mucus or blood and pronOUDced oliguria.
On Ausust 21, the patient sho.ed siens of improve~nt. The appetite .&s
restored; he experienoed dull pain in the substernal region, nausea and 00-
casional vom! ting. Scattered dr.r rales, twenty resp1rato17 excursions a min-
ute; tongue coated .hite, abc1pmen sott, ten4.er upon palpataticm in substernal
regions; liver not enlarged, spleen not palpable, diuresis 600 ml in preViou8
24 hours .ith copious fluid intake (about 41 liters).
Ausust 22, mild headache, periodic nausea and vomiting; face somewhat
~erem1c, conjunctival vessels congested, no changes in the internal organs;
diuresis amounted to 2100 sal during past 24 hours, loose mucus stools 2 or 3
times a cla7.
Ausust 23 the patient felt better. Vomiting and nausea ceased. The t--
perature, .hioh had not risen above 37.30, dropped to normal. !Pormed stool
once a d87. Internal organs unchan6ed. August 24, on17 general .eakness,
.'
1 In the diaposis the poisoning .as ascribed to the use of brake fluid .hich
often contains met~l or butyl alcohol. However, atter other symptoms appeared,
antifreeze was considered responsible. The precise ch8Dical composiUon ot
the gastrio lavage beoame known on17 atter the patient died.
-130-
-------
nobe in head, transient pain in substernal region. Heart sounds dull, first
sound unolear at apex. Patient began to improve rapidly thereafter. ADalysis
ot' the gastric juice on September 7 revealed a slight drop in acidity. Sept8D-
ber 9, X-rqs ot' the gastrointestinal tract showed no pathological changes.
Both patieDts received massive treatment ot' general oharaoter aimed at
eliminating the poison t'rom the 81'stem and at detoxication, as well as active
symptomatio therapy.
Table 1 shows how the blood analysis ot' D. and S. dit't'ered on the second
dq at'ter poisoning. The hemoglobin and erythrocyte oontent in S. was some-
what higher than in D. Moreover, leukocytosis in S. was more pronounced,
evidently indioating the superior reactivity ot' his organism. It is quite
possi ble, however, that the somewhat larger dose ot' poison taken by D., which
resulted in the suppression ot' the leukopoietic function ot' the bone marrow,
also had an et't'ect. Eosinophi1a were lacking in the initial blood analysis
ot' both patients. Within a ~ blood picture ot' S. became normal, leukocytosis
decreased, neutrophilia disappeared, eosinophils appeared. ESR inoreased, in
TABLE
1.
Blood analyses of patients D and S.
i
.
:
Blood indexes:
:
i
i
Dates and initials
: ". 23 August . : 7
20 August i 22 August I :30 August:Se t b
: : pemer
I : : : . !
D S : D S i D i S : S . S
. : :
.
70 18 58 66 15 13
4,510 4,800 3,510 4,250 4,420 4,680
13,200 18,500 11, 500 9,100 10,400 8,700
0.17 0.81 0.82 0.18 0.85 0.79
13 4 7 0 2 2
67 17 83 59 62 56
o 0 0 2 4 4
18 14 4 29 27 31
2 5 6 10 5 7
4 2 3 20 7 4
164,220
45 30
"871.5
3 min.
1 min.
-131-
Hemoglobin %
Erythrocytes
in 1000
Leucocytes
Color index
Stabnuclear
Segmented
Eosinophils
~phocytes
Monocytes
Sed'n rate mm
per hour
Thrombocytes
Res. II, JIJl!$
Chlorides, ~
Bleeding time
Coag'ln time
-------
TAILI 2.
Ur1na~.i8 ot patients ]). and S.
I :Dates and patient~. initials
Urine indexe. I 20 Aqust I 22 August I I I ,
I ,23 Augustl24 Augustl26 Augustf30 August
I ]) I S I ]) I S I S I S I S I S
I I
Speoifio grayit7 1.023. Insutt. 1.015 1.003 1.010 1.010 1.012 1.015
Reaotion Acid Acid Acid Acid Acid Aoid Aoid .1oid
AI bumin, in % 1.48 0.495 4.290 0.230 0.099 0.033 Traoe None
lqaliDe oasts One None 0 - 1 Ifone None None None None
I Granular oast. None None 1 - 2 None None None None None
I-'
\ioJ I1dne7 epithelialoells
~ 1 - 2 None 6 - 8 None ]fone None None None
per field
LeuoooTies per mioro- 5 - 6 10 - 15 30 - 50 10 - 15 1-2 1 - 2 0 - 1 0 - 1
field
ErTthrooytes per mioro- 3 - 4 2 - 3 2 - 3 0 - 1 1 - 2 1 - 2 None None
field fresh fresh chansed fresh changed changed
Alkali resistant per 1 - 2
mioro-field
Epithelial oells from Sane Some Ocoa- Ocoa- Oooa- 0008- Oooe.- Ooo&-
uriDar7 traot sional sional siona1 siona1 sional sional
-------
D., leukoa,ytosis and neutrophilia continued, eosinophils, as before, were
lacking. Both patients exhibited a marked drop in the hemoglobin and erythro-
cyte indexes, particularly so in D. Blood picture of S. gradually returned
to nomal.
Table 2 shows that kidneys of D. were seriously affected from the begin-
ning, kidneys of S. not as much. Atter a dq pathological changes in the urine
of D. continued to intensif7, whereas in the urine of S. they steadily decreased
and tinally beoame normal.
The sickness took a grave course in D., with major changes primarily in
the cardiovascular system. Furthermore, 2 to 3 d.ays after poisoning there was
a marked olisuria turning to anuria. The hemorrhagic syndrome appeared on the
3rd d.ay. Finally, on the 4th dq, pulmonar,y edema developed after a reduotion
in oardiovascu1ar activity, which was the direct cause of death.
The Toxioity of Highly Dispersed Cadmium Oxide Aerosol.
By
E. A. Melinikova.
(Sechenov Medical Institute, Moscow).
Farmako1. i Toksiko1., Vol. 21, Ho. 2, 72-77, 1958.
The increasing use of cadmium b7 industries makes imperative the studT ot
its toxic properties, since the aerosol formation of this substance ~ occur
in a number of processes.
In 1949 E. P. VishnevBka7a obtained some data on the comparative to:l:1city
of industrial cadmium dust of different dispersion and of a number of soluble
oadmium salts. The results showed that the highly dispersed aerosol of cadmium
oxide wae highly toxic. The LDlOO for rats through inhalation for one hour
W&8 0.045 mg/li. The same author and such to reign authors as J. Prodan, H. E.
Harrison, H. Bunting, N. K. Ord.wq, W. S. Albrink and Paterson performed some
chronic experiments which showed that cadmium possessed general toxic properlies.
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The cited reports emphasized the possibilit7 that the cases of industrial
poisoning described b7 Sovet, Weheller, Stephens, Th. M. Legge, L. Sohwar.,
L. Priberg and others were caused b7 cadmiUl1. 01117 two cases ot acute in-
,
dustrial poisoning with cadmium were described in the domestic literature, one
. b7 V. P. Gaivaronskil and his co-author in 1936, the other b7 K. S. Voreb'eva
in 1953, and one case of sub-acute poisoning was described b7 V. D8JV&chenko
in 1932. '1'0 . prevent the occurrence of industrial cadmium poiscning E. P. Vish-
nevskaya. recOJllDended the 11mi ts of allowable concentration for a number of
cadmium compounds in the air of industrial premises. The recommendations .ere
based on experimental results related to the threshold toxicit70f cadmium
compounds using morpholcgical" changes in the organs of the pOisoned animals
as toxicit)" indexes.
The purpose of this stu~ was to find ear17 pqsiological functional in-
dexes for the timel7 discover.y of cadmium intoxication symptoms, particular17
symptoms manifested b)" thenenous s7stem, so that prophylactic sanitar;r mea-
sures could be instituted wi thout de I 81' . This was accomplished b7 chronaxic
and conditioned reflex studies as described below.
The technique. Animals were placed inside a glass-walled chamber; cad-
mium oxide was aerosolized b7 means of an electric arc and was unifol"ll1l7 dis-
tributed throughout the chamber by a fan. The animals were free to move about
within the chamber. The attained cadmium concentration within the chamber was
determined colorimetrically'. Changes in chro~ were studied b7 means of a
condenser-chronaximeter. Flexor and extensor motor chro~ determinations
were made of the right side posterior extrem1 t7. Conditioned reflexes were
investigated according to Kot17arevskii's motor-nutritional reflex procedure.
Stereotype response was developed in white mice to red light and ringing of a
bell and to the sound of a buzzer, which acted as positive and negative stimu-
li, respective17. Control experiments were made to determine the effect of
prevailing experimental conditions upon the functions under investigation.
'1'0 accomplish this the animals were placed into the exposure chamber where
the electric arc was burning intermittent17 for one to two hours. Chronaxia
and conditioned reflexes were investigated several minutes atter quasi poisOD-
ing.The results established that the experimental conditions effected no
changes either in the cbrona:q or in the conditioned refl~x activit)" of the
test animals. ~
. <
-134-
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Efteot of a single exposure to cadmium oxide aerosol upon motor chronax:.v
and on the conditioned reflex aotivity. At the outset animals were exposed to
one-hour cadmium poisoning of lethal and threshold cadmium oxide concentrations,
since no reports were found in the literature which dealt with changes in
chro~ and in conditioned-reflex activity of animals subjeoted to the effeot
of cadmium oxide. The ooncentrations referred to were those established by
E. P. Vishnevskqa on the basis of the morphological changes manifested in
the organs of the test animals. Changes in chronu;y following exposure to a
toxic conoentration of 0.063 mg/li appeared immediately after poisoning. The
.rheobase and chro~ were enhanced, the rheobase having been affeoted firstw
The extensor chrona.q was increased more than the flexor chro~. Thus, 70
minutes after poisoning the flexor chro~ of rat No. 40 increased from 0.015
microfarad to 0.2 miorofarad, or thirteen times, while the extensor chronax;y
increased frOl4 0.02 microfarad to 0.61 microfarad or thirty times.
The threshold toxic concentration of highly dispersed cadmium oxide aerosol
acoording to Vishnev~a was 0.02 malli, with a concentration of 0.018 mg/li,
she found no changes in the organs of the rats. A concentration of cadmium in
the air ranging between 0.012 and 0.017 mg/li, i.e., a concentration below the
threshold value of acute toxic effeot produced no immediate changes in the
rheobase or chro~. However, after several hours the animals showed signs
of ~spnea and asthenia. Only one rat of five showed a slight increase in
extensor motor chro~.
Studies were also made of the effect on rats' conditioned reflex ,activity
following a one-hour exposure to cadmium oxide aerosol concentrations ranging
from 0.013 to 0.018 mg/li. Three rats, with previously developed pattern of
motor-nutritional conditioned reflexes were thus tested. During the exposure
the lU'IimaJ s showed no signs of restlessness and remained active to the end of
the experiment.
Considerable disturbanoe in the conditioned reflex activity of the rats
was noted immediately after the exposure. Prolonged latent periods, phase
reaotions in the conditioned reflex magnitudes and the inactivation of indi-
vidual reflexes in re~onse to red light and sound of bell were noted. The
\
natural reflex to the appearance and smell of food placed into the feed box
persisted. during the firet hour after exposure. One to two hours later, the
behavior of the animals began to change; ~spnea appeared and the animals be-
-135-
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came inactive. Investigation of the conditioned-reflex activity disclosed
that the natural and induced reflexes were entirely absent, and remained ab-
sent the dq following. On the third day all animals showed siens of restora-
tion of the natural reflexes and they appeared to be in normal health. How-
ever, the induced conditioned reflexes remained absent for 5 to 7 days. The
disturbance in the conditioned reflexes seemed deep-rooted and was not fully
restored for several months. After three and one-half months of rest the
higher nervous activity of the animals showed no improvement.
Effeot of repeated inhalations of cadmium oxide on conditioned reflex
activity and on motor chronaxy of rats. The animals were exposed daily to
one-hour inhalation of air containing 0.0018 to 0.002 mgfli of cadmium oxide
for three months. The animals were under observation over a period of five
months; one month preliminary to the poisoning, three months during the in-
halation exposures, and one month following the exposure period. The condi-
tioned reflex activity of the animals was checked every third day, and chro~
every week. The results of the investigation carried out during the first
month have served as the control background. No changes were observed in the
general condition and behavior of the animals to end of the observation. The
animals remained active, retained their appetite, and in some animals the
appetite increased. Same changes in the animals' conditioned-reflex activities
were noted during the first month of exposure. Continued exposure resulted in
a further deorease of conditioned reflexes of all the animals; this decrease
was in progress after the exposures were discontinued; it could be noted in
the response to all types of stimulation regardless of its position in the
stereotype pattern.
The latent period of conditioned reflex response became more delayed in
all animals during the first month of exposure. Changes in the . latent period
of conditioned reflex response to the sound of the bell and to the red light
in the case of rats 1'08. 19 and 4, are shown in the following Table.
Rat
No.
. Ii
. Type ot i
i stimulation I
Latent period in seconds (averages ot ten tests)
Before i First I Second! Third I Fourth
exPosure s month s month. ! month s month
19
Bell
Red light
Bell
Red light
1.27
4.0
1.59
4.39
1.83
4.4
1.85
4.5
1.56
4.35
1.66
5.6
1.7
7.52
3.85
5.2
1.6
7.88
4.27
5.03
4
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-~
wa~ft'-~=- Rid 20-
-1;] 'J'J: 'i .
J5 . "-J
JiJ
A~
IC
to
.'
.If,, ~tJ
17.. ?1.f.J.ltl '
4 . -=1
~~:" li.'J
ZJ loN,',} ,
Rat
at 19
- :Bell cci Red light ~ :&zzer
-Fig. 1. ~hanges in magnitude of condi tioned reflex re-
sponse in mm of water in chronic exposure
to 0;002 mg/l1 of cadmium oxide.
A - Month before exposure; 2 - First month of exposure,
C - SeOOBCl- IBBBtJi of: e%j)Osure-; D - '1'h1.rd month of expo-
sure; One month after' end of exposure."
,Rat 7
.92. 5
Rat 21
62.5
8J'
825
8fl8
&5,'6
70.0
51.5
ol,lJ
/
5lJ
27,5
J4'
/
/
:rig. 2.
. -2d...
exposure
GI E'q~alY~ationC>l Paradorlcal-0Ultraparadarl-
phase pHase cal phase
Percent of phase disturbacnce in chemical poison-
ing with 0.0018 mg/li of cadmium oxide.
A - Before exposure, B - After end of exposure'.
- Periods I
Cadmium intcxication brought about an increase in the number of disturbed
re8ponse8 to Btimuli ot ditterent intensi t7. The percentage ot more deeplT-
rooted disturbanceB in the torm ot paradoxical and ultra-paradoxical phases
inorea8ed cons1derablT in Boze animals.
-137-
-------
.
Increasing intoxication was accompanied in some cases b7 complete disrup-
tion ot conditioned reflex activ1t7 such as a complete tading out of the
responses, first to mild stimulation b1' red light and then to the sound of
the bell. Differentiation waafollowed b1' the sequence of inhibition.
As the result of intoxication the differentiation of negative stimuli
improved in the majorit7 ot the animals. Atter the poisoning was discontinued
the differentiation again deolined. A prolonged motor chro~ became detecta-
ble at the begiDn1ng of the secoDd month of poisoning. In all cases of chro~c
poisoning b7 cadmium oxide, in contrast to the cases of acute intoxication,
the flexor chro~ was more prolonged, while the extensor chro~ e1 ther
remained ..i thout change or was slisht17 shortened. Prolongation of the chrona:q
had undulant characteristics aDd was moderate. Flexor chroDUT increase fran
0.045 to 0.054 microfarad (three times that of the initial value) was observecl
on17 in two rats on separate dlqs of the investigation. In on17 a few animals
did the chronax;y return to the nomal level at the discontinuation of exposure.
Discussion of the results. Results of the observations demonstrated the
high toxicit7 of condensed cadmium oxide aerosol. The etfects of the intoxios-
t1on1n the form of disturbances in the nervous B7stem were discovered earlier
than the usual pathologic effects, such as gross morpholcgical histclogic
changes in the crgans of the cadmium poisoned animals. Changes in conditioned-
reflex aotivi V appeared first as progressive17 dellqed and diminishing re-
sponse to stimulation aDd as inhibited differentiation. However, endogenous
iDhibition W&8 lowered, as _s shown by the fact that even upon weaker stimu-
lation diff~rentiation inhibition concentrated on17 slight17 and at times
~rged into a light sleep. As the result of the intoxication a state of in-
hibition developed in the cortex simulating phase hypnosis of the paradoxical
and ultra-paradoxical t1Pe. The inhibition was of a functional character and
acted as a protective inhibition in the initial stage of intoxication.
Functional changes in the nervous 87stem were a180 determined b7 the method
of chrona:q. According to G. A. Levina a prolonged motor chronu;y and a rheo-
base increase were indications of lowered stimulability ot the motor apparatus.
The dissimilarity- in the characteristics of chronu;y changes in cases of acute
and chronic intoxication IIIEq' be due to the different intensities of cadmium
irritation. Unusually- prolonged chronut, more pronounced in the extensor
group, could be the result of irritation in the region of lung interrooeptors~
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&8 -a8 shown b;y I. M. Wool, Yu. K. Ufqand, o. W. ~tina, V. D. tik:J1q10va
aDd I. P. IlUd tina.
In the op1D1on of these authors chro~ chaDges in cases of chronio
poisoning are connected with the development of inhibition processes in the
central nervous systemJ this -as substantiated b;y the results referred to
above in relation to conditioned-reflex activ1t.1.
Conclusions.
1. Highq dispersed cadtlium oxide aerosol inhaled b;y the living organi-
can atfect the functional state of the central nervous qstem, which, in tUrD,
will cause disturbances in the conditioned-reflex activit;y of animals and
lower the stimulabl1it;y of' the motor apparatus.
2. A single inhalation of cadmium oxide in 0.013 to 0.018 mgfli, or
threshold concentration, as established by' pathomorphologic investigations,
will disturb the conditioned-reflex aotivit;y considerab1;y ahead of the appea1"-
ance of other intoxication indications. Such changes in the conditioned-reflex
activit;y are to a certain extent irreversible, and can be deteoted atter one
hour of exposure to an air concentration ranging from 0.013 to 0.018 JJJ8/li.
Such a cadmium concentration range must be regarded as one exceeding the tox-
icit;y threshold ooncentration.
3. Repeated exposure to cadmium oxide in concentrations rangiDg from
0.0018 to 0.002 JJJ8/li brought about disturbances of the conditioned-ret1a:
activiv, without arq observable ohanges in the general condition or behavior
ot the animals.
4. Disturbanoes in the conditioned-reflex activit;y of animals subjected
to acute or chronic cadmium intoxioation are of similar character and appear
as prolonged latent periods, lower ret1ex responses, and in same cases as
hypnotio phases.
5. The nature of chronu;y changes in acute and chronic oadmium intoxioa-
tion are dissimilar. In the first case the chro~ changes were more pronounced
in the extensor group, and in the second case the;y were more pronounced in the
flexor group.
6. A reverse development in the.pathologio condition of the central
nervous s;ystem, such a8 improvement in the condi tioned-ref'lex acti vi t;y and a
lowered chronu;y, should be regarded as indicative of the f'unctiona1 origin ot
some part of the pathologic changes. On the other hand, the slow course of the
-139-
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reverse prooess most like17 P01l1t8 to the pre8enoe ot irreversible, p08sib17
morphological, oh8Dg88 111 the neNOU8 87810_.
7. '!'he taet that ohaDge8 in the tunetioDal com1t ion ot the central
nerYOUS 87810- can be eUci 1084 with lower cadaium ccmoentrations in the air
than morphological chaDge8 in. the intemal orpna, and. that the threshold con-
centration, a8 e.tabUshed 'b7 chronio intoxication ot rats i. below 0.0018
8I&/u, should be taken into con8ideration in .ett1Dg allowable concentration
limits tor cadm1wa oxide in the air ot 1I1clustrial establishments.
:B1bl1ograpq.
B II III II I: Ii;:" ~ II .1::. I L <1>aIJltlaliO,l II !'UKClIKO,1., l~j51.. I. 14. ..\2..4. 11"
po6 (, ell.. . P. C. I'H~'"e"a It callHTapHlI, I 95J, N! 10, np. 4ti. ..17. - I a IIIJ a po /I,
e K Hit.\' C il ~"..a8 ,'.:i f. r e -II'" e p \&IJJ. (HrHeua TPY.la K TCXIIHKii fJe;!OIl3cHO
CTII. HI: )i~_,~Jip..J~~.J.4$. ~ ~ II ~I e H. K 0 .~':.fI~UJla!<.JII'IlIaMC.1.. 19J.&, ~ 9, crp. 40;. .
] a II( . THti ,,";0"'.11:' PCi.ifPJ.' . ~cnOIlH.I.4l" 11.'11111111111' C' ~ItIUIU. I p)',thl. JIC/lllltrpaJJ.., ,(:!'8.r. ilL. ~I"jj..
HH-T3, T. VII. 1'\.Jr.. r~I;.J"TILyt- ,:100. . II a B JIOD H. II. :leK;UIiI (I pa6?ll"OO.1bW:o\;l0
:iywapHA NO:lra. M., 1~~~'!p'.II ~ I!,.J...!O. ."'., K)' /I COli 'I B. r. 0 ~{lJ1". Illlrel;~ucIITHI',
hbiX pa3I1.pa.'U:IIII/t l' pem!pIlyrCHOHU'" .1I.8JlCIIHIIX. TpYJlbl nellllnrp. ~an.'UIi. M~~. 1II:.ra.
T. VII, M..-.rI....I~SO.-8'an'h'elcmyP. a. Moline 1{..l'ans.l!tcd., v. :iO'. IlH6,
p. 7.~' f r i be r g L. Acta media Scalldiua\ ia, St.;',JlcmentulJl. CCXZ. ACcompal!les vol
l:XXXVIlI. Stockholm, Bf.o -Pe!l'rsou J. S. J. of Hyg. a. loxlCOI.. v.. :l'J. J',. :J, Scpt.
1947. p. 2\14
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~gienic Evaluation of Atmospheric Air in the Vicinity of an Abrasive Plant.
By
)I. Xarimov.
(The Leningrad Sani tar'7-lqgien1c )ledica1 Institute).
Gig1ena i Sanitarlya, Vol. 23, 110. 11, 22-23, 1958.
The sanitar,y protection of atmospheric oity air from pollution q, emissions
of iDdustrial plants i8 an urgent problem of great importanoe to the govem-
mente Abrasive plants emit great quantities of hamful substances containing
silicates, and constitute potent sources of deleterious air pollution. Despite
that, few publications were found in the literature dealing with the hygienic
aspects of the abrasive plants as souroes ot atmospheric air pollution.
The Leningrad abrasive plant produoes abrasive instruments and inter-
mediate abrasive products on a large scale. Recently the plant was rebuilt
and its capacity was considerably increased. The raw materials used in the
production of abrasive instruments are aluminum, bauxites, cl87S, feldspars,
peematites, sodium silicate, boron glass, anthracite and other materials.
Some of these materials contain from 55 to 77% of silicates. The crushiJ:1B,
grindiTlg and distribution of the raw material are d1.7 processes which generate
and emit great quanti ties of dust. . The manual method of treat~ these mate-
rials, leakage in pipes and conduits and in other equipment and the ineffi-
oiently installed and operated dust collectors all contribute to the intense
pollution of the air with dust.
In some plants the ventl1abd exhaust air is Elldtted into the atmosphere
atter it had passed through c;yclones, which remove nearly 70% of the dust.
However, such practices are not general, since many plant departments have no
such purifying installations. The abrasive plant throws out into the atmos-
.phere daily 15 tons of tine grain dust, which is a valuable ooumercia1 product
in itself. The eleotric smeltiDg department, the boiler room and the kiln
department, which emit great quantities of gas, have no gas puri.f'yiDg in-
stallations.
During 1955 and 1956 air pollution studies of dust concentrations were
determined by the sedimentation and aspiration methods at 3 points - south,
north and east. 118 samples were collected by the sedimentation method and
136 b.1 the aspiration method. Results of the latter are presented in Table 1.
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TABLE
1.
Indexes of atmospheric air dust concentrations in g/m2/mo
in the surroundings of the plant.
Heating
lfon-heatiDg
Averages for
entire period
The data in Table 1 show that the intensity of dust polluti9n in the non-
heating season of the year was somewhat higher than in the heating season.
At 1500 m. from the plant the dust concentration sharply rose during the
non-heating season. This can be attributed to the generally dusty surface of
the streets and to their poor maintenanoe. The basic part of the atmospheric
dust consisted of inorganic substances such as ash, the content of which fluc-
tuated through the period. of observation between 66.2% and 89.2%.
Silicon dioxide was determined in all 118 samples colorimetrically by the
Polezhaev method. Depending upon the distance from the plant the average 5i02
content of the dust ranged from 233 down to 45.2%.
Dust concentrations in atmospheric air were determined in the summer and
fall of 1956 at the original five points. Rate of air aspiration ranged be-
tW8en 15 to 20 li/min, and aspiration was continued for 3 hours. Dust concen-
tration data are shown in Table 2.
Season
ot the year
.
i
.
i
I Plant i
: Rrounds :
1,867.4
1,610.5
1,732.4
250 m
:
:
:
229.7
238.7
228.4
TAB L E 2.
Dust concentration in mg/ui3
in plant surrounc1.1Dgs.
Zones
: :
I Iio. ot I
: samples I
: .
: :
Concentrations
Ave~ I VAT'hlial
Plant
. grounds
250 m
500 m
700 m
1000 m
30
33
24
14
35
13.27
5.56
5.36
2.72
0.26
30.7
27.15
19.55
7.03
0.62
Zones
500 m
:
.
i
:
700 m I
1000 m I
:
1500 m
135.9
146.0
140.3
63.5
60.8
61.4
43.4
99.1
68.6
110.5
148.5
125.5
The maximum single atmospherio
air dust concentration near the plant
exoeeded the permissible concentra-
tion limit.
Concentration ot S02 in the air
was determined nephelometrically in
148 air samples. The results are
shown in Ta.ble 3. The maximum single
concentration of S02 exceeded the
permissible concentration limit.
The subjective question and answer
-142-
-------
pheric air were regi stered
at 1000 m from the plant.
Residents 11 ving at a radial
distance of 1500 m from the
plant registered no complaints
related to dust pollution.
A 8tu~ was also made
of 'the incidence of diseases
among children up to 15 years old for the year 1955, based on their visits to
the polyclinic. Two areas were thus investigated, and records were entered on
special cards lone area clcse to the plant and the cther a control area 5 km
from the plant, the air of which was polluted b,y discharges from other types
of industrial plants. The dust concentration ranged between 0.29 and 3.94
mgjm3 and 802 between 0.13 and 1.0 mgfm3. General and home living conditions
and family incomes of the two areas were practically of same levels.
1900 cards were collected in the plant area and 2190 in the control area.
Incidence of children's diseases in the plant area was higher than in
the control area.
'1" A B L E
3.
Sulfur dioxide concentrations in mgfm3
in plant surroundi.Dss.
I .
I Concentrations
Zones I Bo. ot f
r samples I r I Average
I r Minimal I VArhllal
:
Plant 30 0.28 3.08 1.07
grounds
250 m 31 0.12 3.8 0.58
500 m 30 0.21 2.4 0.43
700 m 28 0.13 4.7 0.54
1000 m 29 0.1 0.88 .0.32
Conclusions.
method was also conducted
including 300 persons.
Considerable complaints of
dust and smoke in the aimos-
1. The abrasive plant constituted a considerable source of atmospheric
air dust pollution, it contained free silicon dioxide and sulfurous gas.
2. The plant emissions had a deleterious etfect on the sanitary and
general living conditions of the residents.
3. To prevent the hamtu1 effect of the abrasive plant discharges on the
sanitary condition of the populated areas, it is necessary: a) to adopt a wet
system of raw material clUShinB, b) to prevent dust leakage from dust generating
departments; c) to install dust and gas purifying equipment; and d) to improve
the grounds and to plant trees and shrubs around the plant and in the adjacent
vic1nit,..
4. The sanitary-protective zone must be not less than 1000 m wide.
-143-
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The nsul ts of this investigation were handed in to the R. S.' . S.R. KiD-
ist17 of Health b7 the Leningrad Sanita1'7 Organization.
Bibliograp1q'.
B 0 r y C naB C K H ii 51. M. rHr. H caH., 1947, Ng 9, CTp. 25-28.- r 0 JI b A-
6 e p r M. C. CaHHT3pHall oxp3Ha B03J1yxa. M., 19~8.- 11 0 pH W A. 11. B KH.: Bonpocbl
rHrHeHbI H MeTOllHKH rHrH(,HII~el'KHX HCC.1ellOB3HIIH. M.- 11., 1953, CTp. 129-132.-
1\ pI! C H 0 r 0 p C K 3 II H. 11., Po 6 3 ~ e B C K a II E. r. B KH.: TpYlibi J06HneiiHoA HaVQHo/\
ceCCHH HaYQH.-Hccnell. HH-Ta rHrHeilbi TPY1l3 H npo3a6oJleR3HHii. 11., 1957, CTp. 307-312.-
11 a T y W K H H a B. E. B KH.: Te3HcbI lIOKJI. 13-ro C"be311a rHrHeHhCTOB, 3nHlleMHOJlOrOB.
MHKpo6HonoroB H HHeKIlHoHHCT08'. M., 1956, R I, CTp. 193.-n a B JI 0 B 3 M. B.3a-
,ll.epJKKa npH lIblxaHHH KBapllCOllepJKalUeii nblJlH npH HeKOTopblX npOH3BOllcTBeHHblx npollee-
cax. .aHCC. 11., 1953.-P II 3 a HOB B, A. CaHHT3pH311 oxpaHa aTMoctjJepHoro B0311yxa.
M., 1954.
Detem1nation of Limit of Allowable Concentration of Iqdrochloric Acid
Aerosol (lqdrogen Chloride) in Atmospheric Air.
B7
E. V. Elfimova.
(The Erisman Scientific-Research Institute of Sanitation
and Iqgiene, )(osoo..).
Gigiena i Sanitari1'a, Vol. 24, No.1, 13-20, 1959.
HYdrogen ohloride is a oolorless gas having a strong peculiar odor; it
is usually present in the atmosphere in the fom of 1q'droohloric acid aerosol;
it is highly ~groscopic. Iqdrochloric acid is wide~ used in ~ branches
of the national economy and ranks fourth among the inorganic acids. Plants
which manufacture and use hydrochlorio acid are potent factors in the pollution
of atmospheric air with its aerosol. HYdrogen chloride is thrown into the ai-
mospherio air along w1 th other pollutants b7 plants produoing titanium, mae-
nesium, silice-organic compounds, such as resins and insulation lacquers, ex-
plosives, ~estuffs, zino chloride, etc.
Jqdrogen chloride penetrates into the workshop., heart17 polluting the
indoor air. According to A. G. Aver'yanov, B. I. Gurvioh, B. B. Bykhovskii,
V. Ikr;yannikov, A. I. Smimov, G. Ta. nebanov and I. L. IzrailOvioh, r. S.
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-------
Braneburg, T. S. Karacharov, L. Skhol'-Jimgberts and others, the concentration
of hydrochloric acid aerosol in shops varies from 5 to 365 mg/m3. Shop venti-
lation s,ystems discharge into the atmosphere air which is heavily polluted
with hydrochloric acid aerosol. The amount of hydrogen chloride emitted into
the atmosphere by industrial plants depends upon the technological process
used and on the gas purifying equipment, without which the emitted hydrogen
chloride may amount to 15 tons in 24 hours.
Despite the fact that sources of atmospheric air pollution with hydrochloric
acid aerosol are numerous, the problem has not been studied sufficiently and
the limit of its allowable concentrations have not been determined. In deter-
mining the degree of atmospheric air pollution with hydrochloric acid aerosol
use was made of the recently developed method for the differential determina-
tion of simultaneously present chlorides and sulfuric acid in the air. The
interfering effect of chlorides was eliminated by micrometric titration of
solutions of hydrochloric acid with an 0.005 N solution of sodium hydroxide;
the control and the test sample were of same volumes and contained the same
amount of methyl violet as the indicator. The sensitivity of the method was
0.002 mg. This titrimetrio method was not specific for bydroohlo:-ic acid,
because other aoids interfered with the determination. Since 502 and sulfurio
aoid were present in the atmospherio air frequently, their quantitative pres-
enoe in the air was determined nephelometrioally b,y the barium ohloride method
and subtracted from the total acid value obtained by the method of titration.
Air samples were aspirated at the rate of 1 Ii/min tbrough fresh, twice dis-
tilled water contained in V-shaped absorbers equipped ~ith glass filters No.
1.
The studies of air pollution with hydrochloric acid aerosol were made in
the immediate vicinity of four plants. In 75 peroent of the air samples col-
lected in the proximity of the three plants equipped with gas purifiers the
ooncentration of HCl aerosol in the air was below the sensitivity of the method.
The fourth, a magnesium plant, had no gas puritying equipment, and the picture
of air pollution presented by the analyses of air samples collected in its
prox1m1ty was oonsiderably different. Results of air sample analyses are
shown in Table 1.
The results show that single maximal concentrations of hydrochloric acid
aerosol were of considerable magnitude even as far as 2 to 3 km from the side.
of the plant. Residents of the area where samples were collected complained
-145-
-------
of a constant noxious odor and of the deleterious effects of the plant emissions
on the trees, shrubs and garden vegetables.
TABLE
1.
~ single concentration of HCl aerosol around the magnesium plant.
Meters from
plant
.
.
i Number of
:
: samples
i
: Number of :
i samples below i
: :
: the sensi ti vi tv :
: <# .
: of the method :
Concentration in mg/m3
Maximal
.
i
Average
300
500
800
1,000
2,000
3,000
39
44
43
49
32
34
3
1
7
5
1
4.4
10
34
34
17.3
17.3
1.77
3.7
4.7
6.1
5
5.4
Totals
241
17
The effect of low concentrations of qdrochloric acid aerosol on the
pqsiolog1cal reactions of man was studied by the method of oltactor,y thresh-
old (odor) perception. This stu~ was conducted according to the procedures
recommended by the Committee for the Determination of Limits of Allowable Air
Pollutants. The determination of the threshold value of. olfactor,r (odor) per-
ception was conducted with the aid of 13 persons 19 to 42 years of age, on
whom 336 tests were made. The results showed that in 69% of the persons the
threshold perception concentration of }qdrochloric acid aerosol was 0.2 mgfm3,
while 23% of the persons tested perceived the aerosol odor at 0.1 mgfm3. The
practice in the U.S.S.R. has been to accept the lowest experimental value as
.the standard. It is, therefore, recOllllllended that 0.1 rag/m3 be accepted as the
. olfactor,y threshold concentration of HCI aerosol.
I. P. Pavlov pointed out that the cortical elements ot the different
analyzers were intercODlllW1icat~ve and interdependent and could not be examined
independent17 of one another, since &IV' stimulus or effect which changed the
functional state of one affected all other analyzers and their elements through
reflex effects. Hydrochloric acid aerosol penetrated into an organism oh1et~
through the respirato17 organs, there'bT affecting and irritating the mucous
membranes of the respirator,y tract J therefore, it was decided to stucq the
effect of low concentrations of }qdroch1oric acid aerosol upon the central
-146-
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TABLE
2.
Determination of threshold of odor percep'tion ot
~cblor1c acid aerosol.
Subjects' 1D1tials
a
a
i
i
:
:
Concentration in 88/m3
KiDimsl perceived
:
a
:
Kax. not perceived
A. A.
B. B.
B. II.
G. O.
D. P.
E. G.
E. V.
X. I.
L. A.
II. If.
s. V.
P. G.
Ta. ,.
0.2
0.3
0.2
0.1
0.2
0.2
0.1
0.2
0.2
0.2
0.1
0.2
0.2
0.1
0.2
0.1
0.05
0.1
0.1
0.05
0.1
0.1
0.1
0.05
0.1
0.1
DerYOUS qn_, through the reflex generating zones of the respira'tor;y organs.
'ests were II&Cle tor the detemiDation of etfects on optical chr0DU7, dark
adaptation, . aDd. b7 the methods ot plet~smograpq and pne\IIDograp~.
Tests tor the determination of reflex transmission of ~drochloric acid
aerosol odor effects on optical cbronU1' were conducted on three persons with
the aid ot a GIJ' cbronax1meter, 1949 model. The threshold value of olfactor;y
percep'tioa 'b7 this retlex method was at 0.2 m8/z3 ooncentration, which i.
practical17 identical with the results previous17 discussed. The observations
were coDdnctec1 in a darkened roca. The 87es of the test persons were closed
and each observation lasted 27 II1nutes. For a period of 11 - 14 minutes prior
to the persona' exposure to the BCl aerosol odor, control t.ests. were made at
3 miDute intervals for the determination of the values of each person's normal
rb~obase aDd chroDU7. ~chloric acid aerosol in known concentrations was
. then inhaled b7 the test person. Rheobase and cbron&X1' determinations were
made and recorded immediate17 at the termination of the BCl aercsol inhalation.
The ten was repeated three times at intervals of 3 to 4 minutes. A total of
639 tests were made using five different aercsol concentrations, name17: 0.2,
0.4, 0.6, 1 and 1.5 mg/m3. '!'be results indicated that inhalation of hydrochloric
3
acid aerosol in 0.6 to 1.5 m8/m conoentrations shifted the value of optical
-147-
-------
__1'3 .
c~, whi~e 0.2 to 0.4 ~m concentrations produced no appreciable effect.
In two cases, 1.5 malm3 of the aerosol prolonged the chro~ of 0.15 to 0.2 ~,
and in one case it was shortened by 0.1 pF. As the BOI aerosol concentrations
were lowered, the shifts in the optical chrcn~ decreased. A concentration
of 0.6 mg/m3 prolonpd the chrona:q ot all tested peraons only by 0.04 to 0.08
pp.
Results of statistioal anal;ysis of the data verified the rel1abilit;y and.
significance of the shifts in optical chron~ caused b;y the inhalation ,of
~drochlor1c acid aerosol in concentrations exceecling 0.6 mgjm3. Thus, the
,threshold of reflex effect of ~ochloric acid aerosol, determined by the
method of optical ohron~ was higher than the one obtained by, oltactor.y per-
ception, and, on the basis of the experiments herein described, was equal to
0.6 mgfm3.
The effect of low ~roch1or1o
acid aerosol concentrations on the
functional condition of. the cerebral
corlex was studied nen by the meth-
od of dark adaptation. Observations
related to changes in e;ye sensitivity
to light following the inhalation of
~ochloric acid aerosol were con-
ducted on four persons of normal
vi8ion and odor sensitivity whose
olfactor,y threshold value as deter-
mined by control tests was 0.2 mgfm3.
The investigation of e;ye sensitivity
to light was preceded by preliminar,y
training to accustom the subjects
to the experimental oonditions. For control and comparison purposes the normal
curve of dark: adaptation was established by tests based on the inhalation of
pure ~irJ this was followed by tests for the detexmination of chan8es in dark
adaptation following the inhalation of air containing mown concentrations of
BOI aerosol.
0.7
/',
, '0-
I' . "-
. l "''',
---_/ /~""""" "'I.Sll
, ........ ,"" 1,0 ~
/ '.---
,
./ '
/"" ,,,,,""""",
---~_..." 9.Z-o,,,:<
'-------0,5#
~
~ Q4
~
.....43
cd
o
..... --
of" 11
C
4'
" '5 19 2J
Time in minutes
Fig. 1. Effeot ot different HOl aerosol
concentrations on cbron8X7 of female K.
3
7
27
In the first series of the exp~riment the test subjeots inhaled either
pure air or 1qdrochloric acid aerosol for 15 minutes before dark adaptation
detexminations wsre made, using the following four concentrations: 0.05, 0.2,
-148-
-------
0.56 ,and 1 mgfm3. During the second eeries pure air or ~drochlorio acid
aerosol were inhaled tor 4 1/2 minutes begiJming the 15th minute atter dark
adaptation. The HOl aeroaol concentrations ueed werea 0.2, 0.5, 1, 2, 3.2,
5 and 10 mgfm3. Results ot the f'irst series showed that inhalation ot qdro-
chlorio acid aerosol in 0.05 mgfra3 concentration caused no ohansee in the
oourse of' the dark adaptation curve, a8 oompared with the oontrol curve. '!'he
0.2 mgfm3 concentration sharply reduced the e7e sensit1vit7 to light. '!'he .
0.56 mgfm3 ooncentration reduced the qe sens1t1vit7 to light of' 3 test persons
and increased it in one person, K. The results obtained with subjeot G are
shown in F1g. 2.
. lID
200
"".
~'18
.... ..- IS 0
'"
..-s::
A :;St60
tel
....GI
.... ~14 0
or!
0..-
~ 811120
~
~ ttDO
i!'H
~ 080
",,111
~ ::! 60
GI'd
111 ~40
. III
~ SID
~
~
o 5 fO IS 20 25 30 JS 40 4S SO 55."
Jti.nutes remainiI18 in the dark
Fig. 2. Ohaz1ses in e7e sensi ti vi V to light after
15 minutes inhalation of different HOl aerosol COD-
o8J1tra.tioJ1S by' temale G before dark adaptation.
In the second series of' t8stS conoentrations ranging f'rom 0.2 to 10 mg/113
deoreased the e7e sensitiviv to 11811.10 in all test subjects. The changes in
the course of' the dam adaptation curve, at the 20th miDute, 1.e., atter 4 1/2
minutes of' inhalat10n of' aerosol of' h1drochloric acid in 0.2 - 10 mg/113 con-
centration were verified stat1stical11.
Thus, the oltactor,y threshold conc8ntration of' 0.2 mgf113, previous17
arrived at b7 the subjective method of' inqu1r;y, brought about retlex changes
in the funct10nal condition of' the cerebral cortex, as shown by changes in
the course of' ,the curve of' dark adaptation in both series of observations.
A concentration of' 0.05 TJJB!m3 not perceived b.Y the oltactor,y organ had no
-149-
-------
Z3-"
effect on the sensi ti vi t7 of
the e1'e to light. Results
ot supplemental tests showed
that five-minute inhalation
ot 10 ~m3 HCl aerosol oon-
centration, which is the
limit of allowable concentra-
tion for the air of workiDg
premises, notab11' decreased
the sensitivity of e1'es to
light.
Effect of HCl aerosol
inhalation on changes in
vascular reactions were
~ zzo
+: ZID
cd 2 DO
....
f ,I go
~ \030
. "0
~
...
~
s::
cd
at
g
..cI
...
s:: .: IZO
.... -::t:1I 0
... 9'100
~
.... ~ D
r-4
o
...
~
,:
....
...
....
at
s::
.
at
80
1D
160 I
I ~ 0 I
14C
130 .
-" J
/' -" S~t/A
/'
,/
,/
/' -Z ,.,/.,1
,/
fiB
SD
40
3D
ZD
studied in three persons
23, 25 and 26 1'ears of age,
using a triple adapter finger
plet~smograph, type 3P-2.
In this case exposure to the
~drochloric acid aerosol
was reduced to 30 seoonds.
Observations were
limited to changes in the
blood volume of the finger
blood vessels and changes in
the frequenC7 and amplitude of pulse waves. The following HCl aerosol concen-
trations were useda 0.1, 0.5, 1.0, 5.0 and 7.5 m&fm3. Results of the experi-
ment showed that inhalation of ~ochloric acid aerosol in 0.1 mgfm3 conoen-
tration produoed no changes in the plethysmogram. Beginning with 0.5 mgJm3
concentration 1nsiSD1ficant rise in tonus was observed at times, but predomi-
nantly no changes were recorded in the course of the exposure. At the end of
the exposure the plet~smogram showed a depression which reached a maximum of
10 - 12 - 18 mm atter 10 to 20 seconds. This depression is a transient one.
atter 30 to 40 seconds the plethysmogram returns to its initial level. The
effect of 1 melm3 ooncentration produced two-phase changes: a rise of the
.
:J
to
1 5 '0 15 20 25 30 3S 4D 45 SO 55 6D
Kinutes remaining in the dark
Fig. 3. Changes in eye sensitivity to light
after inhalation of different concentrations
of HCI aerosol by female G during the process
of dark adaptation.
(A~ indicate intervals of inhalation)
-150-
-------
plet~smogram during the exposure and a tall upon the termination ot the ex-
posure to ~droch1oric acid aerosol, which was more prolonged and ot greater
negative amplitude than the tall caused by exposure to 0.5 mgfm3 concentration.
The ettects ot 5 and 7.5 mslm3 ooncentrations also produced two-phase changes I
a rise up to 6 or 7 DID at the time ot exposure, toll owed by a gradual 'tall to
a considerably lower lev~l and over a considerably longer period ot time; it
,fell by 12 to 20 DUD and returned to the initial level atter 1 to 2 minutes.
The pulse rate general17 lost 4 to 12 beats per minute duriDg the ex-
posure. During the fall ot the plethysmogram, the pulse amplitude increased
by 1 - 2 mm; during the rise ot the plet~smogram, the pulse amplitude de-
creased by 1 - 2 DUD as compared with the control. The plet~smogram of subject
L was obtained at 0.5 mgfm3 HCl aerosol concentration. It is shown in Pig. 4.
. ~.
~ '.-, ',-,I,.,
~ , -'''I'l',
~ '"
~,
-..
','
~'
-b ..,;~';"."
"
Fig. 4. Changes in ths plethysmogram ()t temale L th.tring the inhalation
ot 0.5 ~/m3 of hydrochloric acid aerosol~
. Inhalation of ~och1oric acid aerosol in 0.1 to 0.2 mslm3 concentra-
tions, which is the olfacto1'7 threshold value, attected the rb.Jthm and the
depth ot respiration, a8 W&8 indicated by the decrease in the number of' re-
spirat017 waves, increased or decreased amplitudes, rapid exhalation, 8Dd
retarded inhalation. Increase in the HCl aerosol concentration enhanced the
respirato17 changes. Two pneumograms are shown in Pig. 5.
The results cf the experiments are aUlDlD&rized in Table 3.
The data in the Table show that the threshold valuee ot oltactor,' per-
ception and, changes effected in the rb.Jthll and amplitude ot respiration can be
used 1n determining the lim. ts ot allowable concentrations ot HCl aeroaol in
atmospheric air. In accordance with the adopted practice ot ..sking prov1aion
tor a coetticient ot aatet;r, it is recOllllRended that 0.05. msf.3 be adopted ae
the limit of allowable HCl aerosol concentration in atmospheric air.
OonclusiOl1S.
1. The, method described allows the difterential determ1Dation ot ~
,
-151-
-------
~
e
cd .
od ~
.. III
~ t
o .:
... ; s::
Jot ...
o
"'" s::
.g 0
0""
~~
~III
fH~
0'"
o
'S~
r~
IC\!:
. '
,OlD
o
fH s::
0...
"'"
s::
o 0
.......
... 'r-!
~,"
III
~~
o
0"'"
~ cd
... a
~~
..-t>a
Jotp
.a,
~ Jot
f:o~
~ ""',
':;$ -
ot)
s::
PI CD
"'"
~ m
...
s::P
...
"
ID
~t
ag;
~:;$
t)
.-
, "'"
. 0
IC\ID
.
fig
~
chloric acid aerosol in the presence
of chlorides and aerosol of sulfurio
acid.
2. It is recollll1ended that 0.05
mgfm3 concentration be adopted as the
limit of allowable BCl aerosol ooncen-
tration in atmospheric air.
3. In planning and building new
magnesium plants, mandatoX7 provision
should be made for the simultaneous
installation of appropriate gas puri-
fying equipment.
4. It was demonstrated that
~drooh1oric acid. aerosol was present
in the air 2 to 3 laD or farther awq
from the source of emission. It
becomes imperative, therefore, that
the sanitary clearance zone be widened
for the more effective protection of
the atmospheric air.
-152-
-------
TA:BLE
3.
Results of experimental investigations threshold reflex effects of
hTdrochloric acid aerosol.
Threshold of reflex effect and method
of its determination
aThreshold concentration
lof Bel aerosol in mR/m3
Threshold of odor perception
Threshold of eye electrical stimulation b.1 the
method of opticalohronaxy
Threshold of eye sensi ti vi ty to light
Threshold effect on vascular reaction b.1 the
plethTsmographic method
Threshold effect on respiration b.1 the
pneumographio method
0.1 - 0.2
0.6
0.2
0.5
0.1 - 0.2
:BibliographT.
ABC P b RHO B A. f., f Y P B II q 5. H. BellTlI,111UlfR nnmlblUl.1ellllbfX npe':WrllRTlf11
II 3cjJqH'KTHI,IICCTh ee I\CiiCTBIIR. ,\\.-JI., 1932, CTf). 309--316. A ,1 C K C e C n a ,'.1. R.,
A" 11. r 0 H 0 R 5. E., f Y n 1111 It C. c., )!( 1I.It K 0 I! a A. C. Onpe.1e.~elllfl' Rre.:!H"IX BeWf'CTB
B B03J1.yxe nrOMblWJlCHHblX npeJl.npIIRTHH. ,'.1., 1954. CTJJ. 49. - fj f) 3 H C 6 y r I' <1>. C.. K a-
p a q a po B T. C. fill'. n caH., 1946, N~ 7-8, CTp. 28-36. - 5 bf X 0 B C K n il 5. G. }.'aTe-
pllaJlbJ no rurnellc TpYJl.a B npOll3BO.ltCTIJe MarHIIII. Lllfcc. .ltOKT., nepMb, 1947. - G bI X 0 B-
e K II H 5. 5. B KH.: XII BcecolO3H. C'bC3,1 rHrlleH.. .3nIlJl.CMIf0,1., MIIKr061!0~. H IIHljJeKUllo-
HHCTOI!. M.: 1949, T. I, CTr. 156-158. - H K [1. R H 1111 K 0 B ~'. fllr., 6~3(JnacH. H naTO.'!. TPY-
.1a, 1931, ,~~ 2, CTf). 89-92.-KJleu.1 H::IB I. 51.. 113pall,10BIf -,II. jI. fllr., 6e30113cH.
H naTO.~. T[1YJl.a, 1931, .,,~ 8-Y, erp. 82-86. --11 a 11.10 B 11. n. n,'KIUlit 0 paGoTe 60.1bUIIIX
r:OJlYW3Pllli fOJlOBIIOro M03ra. M., I~;,:l. -. P 51 3 3 II () B B. .\. CaHIfTa[1I1JH oxpalla aTMOC-
ljJeP.Horo R03,1yxa. M., 1954, CTp. 193. - C M II pliO R A. 11. filL TpY,1a. 1927, N~ 4
CTp. 30-34. .
-153-
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The Determination of Limits of Allowable Concentration of Lead
Sulfide in Atmospheric Air.
B7
Yu. P. Shalamberldze.
(Institute of Sanitation and Hygiene, Ministry of Health, Georgian S.S.R.).
Gigiena i Sanitariya, Vol. 24, 10. 3, 9-14, 1959.
The 0.7 y/m3 limit of allowable lead concentration in atmospheric air
was arrived at by arbitrary calculation. It was adopted as a temporary ex-
pedient to be changed at some future time upon the accumulation of basic data.
The present work was umertaken for the purpose of obtaining experimental data
to serve as the basis for the determination of the limit of allowable concen-
tration of lead sulfide in atmospheric air. The work was done on the basis of
chronic experiments, following the procedures and methods recommended by the
Committee on Limits of Allowable Concentrations of Atmospheric Pollutants.
The tonci ty of lead sulfide was studied clinically and experimentally by such
authors as N. Yu. Tarasenko, S. P. Kipiani, D. Kober and V. Hansen, L. V.
Shraiber, Xh. Z. Lyubetskii and others. However, these authors were concerned
mainly with the effect of large lead sulfide concentrations.
No reports were found in the literature dealing with concentrations of
lead sulfide in the atmospheric air of lead ore mines or of lead ore process-
ing plants. The study' of this question is of particular importance from the
viewpoint of community sani tatton, since in addition to workers employed in
the mentioned enterprises, residents of the surrounding area are also chroni-
cally exposed to the effect of lead sulfide. In this connection studies were
made of concentrations of lead sulfide in atmospheric air, its contents in the
soil, in drinking water, in some food products and in the urine of man. To
determine the degree of atmospheric air pollution with lead sulfide samples
were collected at stationary points by the aspiration method at 250, 400 and
500 m from the lead ore processing plant. Quantitative lead determinations
were made by the chromate method of N. G. Polezhaev. The observations were
conducted during one spring and two sulllller seasons, and 134 samples were
analyzed. Results are shown in the following Table.
A study of meteorological conditions indicated that the dispersion of
lead dust in the air varied with weather conditions, velocity and direction
-154-
-------
Conoentrations of lead sulfide in the atmospherio air,
in terms of mg/m3 of lead
1ieter8 from : ~\!D-~ Lead in ./,) f1:
ooncentration 1. -'\~:- ~m 1.~'\Xi..I, Ave, fH.a
o
plant ~~
250 36 3,35 1.24 0,0003 0, C484 0,0188 1,51
400 36 2,82 0,84 0,0002 0,0205 0,0051 0,6
500 36 1.60 0,69 0,0002 0,0079 0,0013 0,2
A.ve. over village 0,93 I 0,9
I 0,0084
territory
---.-.
Over terrt t017 26 4,76 2,02 0,0019 0,1348 0,0509 2,5
of plant
of the wind, and degree of precipi taUon. The dust in the atmospheric air
consisted of particles 79.16% of which were up to 5 ~ in size. Lead content
in washings from the inner side of window panes indicated that lead dust
penetrated into the dwellings. At 250 m from the ore precessing plant the
lead content amounted to 1.07 mg/m2/24 brs, at 400 m it was 0.73 mg/m2/24 brs,
and at 500 m - 0.19 mg/m2/24 brs.
An increased content of lead was noted in the 80il within the community
area. Top soil scrapings contained 5.07 - 19.47 mg per 100 g of dry soil, and
subsoil contained 1.51 - 5.8 mg/lOO g of dry soil. A degree of parallelism
was noted between the concentration of lead in the atmospheric air and its
content in the soil. Results of drinking water analyses indicated that lead
in the water did not exceed 0.01 mg/1i, which is 10 times below the permissible
maximum. A somewhat higher lead content, as compared with data obtained by
other authors, was noted in some vegetable and other products of local origin.
Lead in 0 to 0.06 mg/li concentrations was found in the urine of 60 persons
of different sex and age whose occupations did not bring them in contact with
lead compounds; in 37.5% of the examined persons the lead in the urine amounted
to 0.02 mg/li; in 21.5% it was 0.04 mg/li, and in 10% it was 0.06 mg/li. In
30% of the persons examined, lead in the urine exceeded the physiological'
maximum of 0.03 mg/li.
No reports were found in the literature of the chronic effect of inhaled
small lead sulfide concentrations on the central nervous system of animals.
-155-
-------
Hence, studies were made of the effect of small lead concentrations on the
higher nervous activity of animals as manifested by changes in motor-food
conditioned reflex response. The tests were conducted on white rats by the
"dynamic exposure" method. Animals were exposed in a special chamber six
hours daily, with the exception of non-working days, for a period of six months.
Dust of the lead concentrates used contained 49.02% of lead, 10.25% of zinc,
21.8% of silver and 2.37% of 6i02.
Animals were exposed in a special experimental two-compartment dust cham-
ber of 100 lie Average lead concentration in the exposure chambers in the
first series of tests was 13.5 v/m3 ! 0.36 and 48.3 v/m3! 0.75 in the second
series of tests. The fluctuations in the dust concentrations were practically
insignificant. Check tests established that the dust of the lead concentrate
was uniformly distributed throughout the chamber. 86.6% of the dust particles
measured between 1 - 5 ~.
Conditioned reflex patterns were developed by the Kotlyarevskii method.
Ten white rats of same sex and age weighing 95 - 135 g were used in the ex-
periment. Three types of conditioned reflexes were developed in the animals:
two positive in response to sound of bell and red light, and one negative, or
differentiation, in response to sound of buzzer. These reflexes formed an
organized stereotype of definite sequence: two positive in response to sound
of bell; t"o positive in response to red light; one negative in response to
sound of buzzer; t.o positive in response to sound of bell, and two positive
in response to red light. The neuropatterns of the animals were determined by
the method of intermittent extinction of the conditioned reflexes, prolongation
of differentiation time to 3 minutes and 24 hours starvation. After the neuro-
pattern has been determined, the test rats were divided into three series:
.animals of the first series of 4 rats were exposed to lead concentration of
13.5 v/m3; animals of the second series of 4 rats were exposed to 48.3 v/m3
concentration, and animals of the third series of 2 rats were kept as controls.
After 6 months exposure rats of the second series showed the following
changes in their conditioned reflex activity: differentiation inhibition
release; same increase in the latent period of conditioned reflex response;
phase phenomena of cOOlpensating and paradoxic nature. Degree of changes varied
with the pattern of higher n~rvous activity of the animal. Thus, changes in
the conditioned reflex activity of rats of weak and strong unbalanced neuro-
pattern appeared sooner and were more olearly expressed than in rats of the
-156-
-------
strong balance'd neuropattem. Paradoxic phases were observed only in rats of
a weak nsuropattern. Normalization of conditioned reflex activity atter ex-
posure discontinuation prooeeded faster in animals of the strong balanced type
than in AnimAls of the weak type.
Results of conditioned reflex activity studies of two rats are presented
in Figs. 1 and 2. The following time data are plotted along the abscissas:
10 days before exposure; 158 days of exposure, and 27 days of recovery. The
following are plotted along the ordinate: the upper two curves represent JIIa8"'"
nitudes of conditioned motor reaction in millimeters; the two curves below
represent values of latent periods of conditioned reflex responses in seconds
(unbroken lines for the bell and dotted lines for the light), the middle line
(:a:a) marks the differentiation to the buzzer sound. The vertica.l lines mark
the differentiation inhibition release. The curves below the mid-line record
the post differentiation indexes. Reactions to all stimulation, except the
first bell sounds, are recorded in both Figs. 1 and 2. Each curve represents
the mean arithmetical sum of the data obtained in the study of two reflexes.
Thus, the first unbroken curve represents the mean value of the conditioned
motor reaction to the second and third bell and the dotted line to 1st and 2nd
light. Corresponding indicators are presented by the lower curves for the
fourth and fifth bell sound and for the third and fourth light.
It is seen from Fig. 1 that changes in conditioned reflex activity in
rat No.1 (second series) began with the appearance of differentiation inhibi-
tion release; beginning with the 30th day after exposure; the latter appeared
only occasionally and after the 13lst d~ almost daily. Isolated cases of
disturbed correlation in the force of response akin to equalization phase and
some increase in the l~tent conditioned reflex response were nated during the
last experimental period. Conditioned reflex activity in animals of the second
series was fully restored before the end of the recovery pe~iod (see Fig. 1),
indicating that ohanges in the higher nervous activity of the animals were
functional and reversible. .
In the case of animals of the first series, which were exposed to 13.5 y/m3
of lead, no changes in the higher nervous activity were noted, as can be seen
in Fig. 2. Thus, during the entire period of exposure of rat No.1 differen-
tiation inhibition release manifested itself only 3 times; however, this phe-
nomenon was seen in the animal before exposure as well. Records of rats of
the first series presented a similar picture.
On this basis it was ass\DDed
-157-
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-158-
that some cases of differentia-
tion inhibition release, which
appeared in the course of exposure,
were not the result of lead dust
inhalation. Exposure of animals
to lead dust concentrations used
in the chronic experiments had
no effect on the animals' gain
in weight.
Histopathologic examinations
were made of tissues of the heart,
liver, kidneys, lungs and brain.
Morphological changes were seen
in the brain and lung tissues.
Changes found in other organs were
insignificant and practically
identical with changes in some
organs of rats of the first, second
and control series. Symptoms of
pneumonia were found in the lungs
of rats of the first and second
series; in the lungs of rats of
the second series sections were
seen of hemorrhagic pneumonia,
panbronchitis, same vascular ne-
crosis, etc. Microscopic examina-
tion of brain tissue showed dye-
trop~ symptoms of single gangli-
onic cells, mostly of the pyramidal
type, in the third and fifth l~erB
of the cerebral cortex. Such
changes appeared more clearly in
rats of the second series.
Results of blood analyses
made after six months inhalation
exposure revealed no changes in
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-159-
the red blood cells of the first
and second series, and no baso-
philic granulo er;ythroC7tee were
noted in the blood of any of the
animals. The number of leucocytes
remained practical~ normal, with
the exception of rats of the first
and second series, the leucocytes
of which showed a slight numerical
rise; as is illustrated by the
following: leucocytes in the
blood of oontrol rats fluctuated
between 8200 - 8600 per 1 ml; in
the first series of rats the range
was between 10,100 - 12,200 and
in seoond series between 15,500 -
17,400 per 1 mI.
Resul ts of spectral ana~ses
showed that the average lead
content in the bone tissue of the
second series of animals was five
times as high as in the control
animal s, r&n8ing between 6.5 and
10 mg%. In bone tissue cf the
first series of rats the lead
content was likewise increased,
but did not exceed 3 mg%, thus
showing an average lead content
1.7 times greater than in the
control animals.
Thus, it is seen that under
a lead sulfide concentration
equivalent to 13.5 v/m3 of pure
lead, only some of it was retained
b.1 the organism; the accompanying
histopathological changes in in-
-------
ternal organs were negligible. This concentration can be considered as near-
liminal, but not entirely harmless. It must be borne in mind that daily ex-
posure lasts only six hours and that lead possessed the tendency to accumulate
in the organism, which necessitates the introduction of an accumulation co-
efficient; taking the above into consideration, it is suggested that 1.7 Y/m3
of lead sulfide b.1 adopted as the limit of its allowable atmospheric air con-
centration.
Conclusions.
1. Lead dust was found in the atmospheric air in the proximity of primary
lead ore processing plants. At 400 m from the plant the average dust concen-
trations in te~s of lead ranged b~tween 0.0051 - 0.0013 mg/m3.
2. High lead sulfide concentrations in atmospheric air brought about its
increase in the urine and should not be looked upon with indifference.
3. Daily exposure to lead sulfide dust of 48.3 Y/m3 concentration in terms
of lead for 6 hours over 6 months brought above a gradual development of tunc-
tional changes in the conditioned reflex activity, some histopathologic changes
in the brain and lungs, and a definite accumulation of lead in the bone tissue.
4. Similar chronic exposure to 13.5 Y/m3 concentration of lead resulted
in some lead retention in the organism and brought about negligible patho-
morphological changes in some organs. 13.5 y/m3 of lead can be regarded as
a near liminal concentration.
5. On the basis of this investigation it is suggested that 1.7 Y/m3 be
adopted as the limit of allowable concentration of lead sulfide in atmospheric
air, which is 2.4 as high as the existing limit set for other inorganic lead
compounds and is considerably lower than the chronic experimental concentrations
which brought about changes suoh as were described above.
6. For the improvement of sanitar.y-~gienic living'oonditions of those
who reside near plants engaged in primary lead ore processing, and for the
prevention of direct harmful effects of lead dust, sanitary clearance zones
not less than 500 m wide should be introduoed without delay.
Bibliograp~.
K H n R a H R C. n., K e T 1111 . AS e K. E. B KH.: PeclJepanl RaYQHblX pa60T ;la
19~1953 IT. (Ha)"lHO-RCCJlellOB8TeJlhCKHA RHCTIIT}'T rHrlleHbI TpYA8 H npO$eCCHOHa.lb-
HblX sa(5oneBaHHA). T(5H./IHCR, 1954, cTp. 57. - K 0 T .II II P e B C K H A n. 11. )l(YPH. BblCIfJ.
RepBH. .aeRT. HM. 11. n. nasnoBa, 1951, T. I, B. 5, CTp. 751-761. - P 113 a HOB B. A.,
5 Y W T Y e B a K. A., HOB H K 0"11 10. B. B KH.: npe.ll.e.llhHO lIon.YCTHMble ItOHueHTpauHH
aTMoc$epHblx sarpRSHelUlA. M., 1957, B. 3, cYp. 117. - PR S a ROB B. A. TaM me. M.,
1952, B. I, CTp.. 9-25. -llJ P 8 A IS e p n. 5., n JO (5 e UK H A X. 3. H lip. TesHcbI ,a,OK.l.
B KH.: KOH$epekUHH no .60pb6e C CHnRKOSOM, TaWKeHT, 1957, CTp. 22-23.
-160-
-------
Effect of Garages and Filling Stations Located in Residential Sections
on Health and Living Conditions.
By
F. F. Lampert.
(Moscow Municipal Sanitar,y-Epidemiological Station).
Gigiena i Sanitariya, Vol. 24, No.3, 74-76, 1959.
Residential pollution can be caused b.y faulty sanitary-technical equipment
such as gas appliances, heating installations, etc., and by sources of atmos-
pheric ai~ pollution located within the area of the community. Sanitar,y com-
munity surveys showed that automobile garages located within residential areas
constituted a potent source of air pollution. Sanitary investigations of se-
lected Moscow residential properties indicated that of 1042 garages located in
the residential area and housing up to 10 automobiles 66% were distributed
oontrar,y to the sanitar,y clearance regulation and 40% were in the immediate
proximity of children's and medical institutions. Such locations of automobile
garages near residences must, perforce, affect the sanitar,y living conditions
of the population. The progressive change to et~lated gasoline in city trans-
port iItparts to this problem a graver sanitar,y aspect.
To determine the true nature and extent of the anti-sanitary effects of
public garages in the residential areas, a study was made of six residential
buildings. Garages housing from 6 to 36 automobiles were parts of 2 of the
6 bUildings, in 3 of the six buildings the garages were detached b.y on~ 5 to
17 meters from the dwellings, and in one a 3O-automobile garage was located as
recommended by the sani tal')" clearance regulation. In addition to the garages,
a filling station was located at 18 m-fram the windows of an apartment house,
whioh was also investigated.
The sanitar,y investigation and questioning of 110 residents indicated that
in near~ all cases the garages occupied a considerable part of the ba~ard,
thereby limiting its use by the residents. The traffic congestion in the back-
yard. presented a constant danger to children's safety. Complaints indicated
that a filling station located 18 m from the apartment house windows caused
loud noises, and that the exhaust gases p~netrated into the apartments and
heavily coated the window panes with resinous substanoe iiiflicult to wash off.
Determinations were also made of the presence in the air of CO and of Pb. Car-
-161-
-------
bon monoxide determinations were made in the air of garages, near the filling
station, in the air of _apartments, the windows of which faced the garages and
the filling station. For the purpose of comparison studies were made of apart-
ments in the same building, the windows of which were considerably father away
and faced in the opposite direction. A total of 160 analyses were made. To
eliminate the possible effect of household gas appliances, the latter were
shut off during air sample taking. .
The results of carbon monoxide dete:rmi.nation in the air of garages, shown
in Table 1, indicate that in one third of samples the carbon monoxide concen-
tration was higher than the mR.YiIlll~m permissible concentration for workshops,
.hichis 0.03 mg/li. Under the prevailing conditions and in the absence ot a
systematically organized garage ventilation there was reason to assume that
the polluted garage air penetrated into the adjoining apartments~ Results of
investigations. confirmed this assumption. Where garages were located without
regard to the 5 - 7 m sanitary clearance from the dwellings, the carbon monox-
ide concentrations in the apartment air exceeded the 0.06 me/li single maximum
permissible concentration, and the maximum permissible concentration for work-
shops. In apartments located at the boundary of the recomnended sanitary
clearance zone the number of samples with high CO concentrations was only 12%.
TABLE
1.
Carbon monoxide concentration in the air of garages and dwellings.
Place of sample taking
:Percent of total number of samples
i with concns. in mgfli
i Up to : Up to ! above
: 0.006 i 0.030 i 0.030
Garage 40 30 30
Dwellings:
No sanitary clearance zones 38 41 21
Sanitary clearance zones 50 38 12
Control dwellings 50 42 8
In apartments of the same building with windows considerably farther from
the garage and facing in the opposite direction the carbon monoxide concentra-
tion of 0.03 mg/li and above was found only in 8% of samples (see Table 1).
The effect of a filling station on the indoor air of an apartment house located
18 m away was more pronounced. The filling station serviced up to 700 auto-
mobiles wi thin 24 hours. Analytical data in Table 2 indicate that the mean
-162-
-------
carbon monoxide concentrations near the gasoline pump and in the apartments
located 18 m from it were nearly identical (0.025 and 0.023 mg/li); the mean
carbon monoxide concentration in the air of control apartments amounted only
to 0.012 mg/li.
TABLE
2.
Carbon monoxide in mg/li in the air of dwellings and near gasoline pump.
Place of investigation
I Carbon monoxide concentration in ms/li
.
:
i
:
V~Timftl
Minimal
Average
At gasoline pump
In dwellings 18 m from pump
In control dwellings
0.036
0.042
0.021
0.018
0.004
0.008
0.025
0.023
0.012
The greatest number of samples with carbon monoxide concentration above
0.03 mg/li was found near the gasoline pump and in apartments located 18 m
from the pump which constituted correspondingly 58 and 18%. No samples with
such carbon monoxide concentrations were found in the control apartments. The
above data prove that the filling station polluted the indoor residential air,
pointing to the urgent need to develop suitable regulatory stand.ards for the
width of the sanitary clearance zone between filling stations and dwellings.
A stu~ of the lead oxide content in the air was conducted before tbe city
auto transport changed over to eth,ylated gasoline; tbe purpose was to obtain
data on tbe general picture of lead content in the air of garages and of apart-
ments located in the proximity of highways where auto traffic was heavy. For
comparison, tbe air was similarly examined for lead content in the proximity
of an arterial bighway where motor-traffic was temporarily discontinued. Lead
determinations were made by tbe sedimentation method in a total of 204 air
samples. The higbest percentage of samples with a lead fallout exceeding 0.1
mg/m2 in 24 hours was found among those collected on the busy highway and near
a filling station. At those points lead was found in nearly all samples. All
samples collected on the bighway, where the motor-traffic was temporarily dis-
continued, were negative.
In evaluating the results obtained, ~ different factors polluting the
city air with lead should be taken into consideration such, for inat~ce, as
industrial emissions, printing establishments, repair shops, etc. However, at
-163-
-------
the points where the sedimentation samples were collected such sources ot air
pollution wi'th lead compounds were absent. Based on the considerable amount
ot lead tound in the heavll;y tratticked hishwq and near the tilliIJg station,
and the absence ot lead in the air ot the "control" hishwq, it can be assumed
that the lead in the air came trom moving auto-transport which used et~lated
gasoline. The discove17 ot lead in the air ot nearb;y garages and apartments
oan be attributed to the repair work done in garages which used lead contaiDing
soldering material.
Conclusions.
1. Under the present system ot Koscow distribution ot residential build-
ings garages are trequentl;y located in close proximi t;y to dwellings, children' 8
and medical institutions, and the like.
2. Resul ts ot laboratory studies and questioning ot residents indicated
that garages located in residential areas trequent1;y polluted the air to an
intensit;y exceeding the limits ot maximum permissible concentrations, thereb;y
vi tiating the sani ta17 living conditions.
3. Heavy air pollution in apartments caused by a nearby tilling station
indicated the neoessity to enforoe the regulation that tilling stations be
looated at a prescribed distance tram living quarters.
4. Results ot the investigation emphasized the iDa~mi ssibilit;y ot the
existenoe of garages and tilling stations directly on residential grounds.
-164-
-------
THE SANITARY PRorECl'ION OF AIR. M. S. GOL'DBERG. KEDGIZ - 1948 - MOSCOW.
SUPPLEXENT OR APPENDIX NO.3. PP. 119-129.
THE SANITARY CLASSIFICATION OF nmusrRIAL PLANTS AND SANITARY
CLEARANCE ZONES.
(See remarks in foreword).
~ical Manufacturing Piants.
Class I.
Requiring a sanitary clearance zone 2000 m wide.
l.
2.
The production of bound nitrogen and of agricultural fertilizers.
The production of nitric and other acids, by processes which result in
the discharge of oxides of nitrogen into the atmospheric air.
The production of ammonia.
30
4.
The production of aniline, nitrobenzol, paranitro aniline, a-naphthol,
a, ~, and y, and N-acid, alyzarine and other intermediate products of
the aniline dye industry.
The production of bromine.
The production of paper from sulfite and cellulose sulfate.
The production of gases: illuminating, liquid, generator (more than
10 generators with a capacity of 50,000 m3/hr., and plants engaged in
the processing of natural refinery gases.
5.
6.
7.
8.
The production of sodium hydroxide by the electrolytic process.
The production of synthetic viscose fibers and of cellophane.
9.
10.
ll.
12.
The production of calcium carbide.
The production of concentrated mineral fertilizers.
The production of volatile oils (solvents) such as benzene, toluol,
xylol~
The production of medium heavy oils, such as naphthol, phenol, cresol.
The production of heavy oils, such as anthracene, phenanthrene, acri-
dine, carbazole.
13.
14.
15.
16.
The production of arsenic and its inorganic compounds.
The production of gasoline (naphtha-gas) (petroleum gas) in quantities
exceeding 5,000 m3/hr.
Plants engaged in the processing of crude oils wita a sulfur content
of over 0.5% and with a high content of volatile carbohydrates.
The production of picric acid.
The production of hydrofluoric acid and of cryolite.
Plants engaged in the processing of coal and of coke.
Plants engaged in the processing of shale oil.
The production of mercu~J.
17.
18.
19.
20.
21.
22.
-165-
-------
23.
24.
25.
26.
21.
28.
29.
30.
The production of soot.
The production of sulfuric acid, fuming sulfuric acid and 302 gas.
The production of carbon bisulfide.
The production of organic sulfur dyes such as sulfur black, etc.
The production of hydrocyanic acid.
The production of synthetic camphor, cellulose esters, etc.
The production of hydrochloric acid.
The productior1 of superphosphate by plants which have sulfurous acid
producing departments.
The production of nitrogen containing fertilizers.
31-
32.
33.
34.
The production of phosphor, red or yellow.
The production of chlorine.
The production of chlorinated and hydrochlorinated "hydrocarbons in
volumes exceeding 1 ton per day.
Class II.
Requiring a sanitary cleara~ce zone 1000 m wide.
35.
36.
Plants engaged in rubber vulcanization by the hydrogen sulfide method.
The production of generator gas from peat coal (medium sized plant,
6 - 10 generators,> general production of 25 - 50,000 m3/hr).
The production of natural tars and resins arid the processing of tar
residues (coal tar pitch, etc.).
The production of anhydrous sodium carbonate by the ammonia method in
quantities over 400,000 tons per anum.
The production of lacquers and varnishes: oil soluble, alcohol solu-
ble, typographical, for use by the rubber industry, insulation mate-
rial, etc.
The"production of chromium and lead paints.
The production of drying oils and paint vehicles.
The production of organic agents.
The production of plastic materials from cellulose esters.
The production of rare metals by the chlorination method.
The production of barium chlorides with the aid of hydrogen sulfide.
Plants engaged in the recovery of rubber and caoutchouk.
The production of rubber from ebinite.
The production of superphosphates without the aid of sulfuric acid
and with the aid of fluorides.
The production of hydrogenated fat with the aid of non-electrolyti-
cally produced hydrogen.
The production of factice (rubber substitute from linseed oil).
31.
38.
39.
40.
41.
42.
43.
44.
45.
46.
41.
48.
49.
50.
-166-
-------
51.
The production of phenol aldehydes and other synthetic resins in ex-
cess of 300 tons per anum.
The production of fluorides, hydrofluoric acid excepted.
The production of synthetic chemical drugs.
The production of chlorinated and hydrochlorinated hydrocarbons re-
quiring the use of chlorine up to one ton per day.
Plants engaged in the processing of naphtha, containins 0.5% of sulfur
and with a low content of volatile carbohydrates.
52.
53.
54.
55.
56.
57.
58.
The chemical processing of peat.
The production of chromium anhydride and of chromates.
The production of electro-insulating lacquers and varnishes and of
lacquer and varnish bases in excess of 600 tons per anum.
The production of complex ethers and esters.
The production of leather substitutes.
The synthesis of organic compounds such as alcohols, ethyl ether, etc.
from technical and natural gases.
59.
60.
61.
Class III.
Requiring a sanitar,y clearance zone 500 m wide.
62.
The production of bitumen and other products from coal tar rp.sidue,
and residue of naphtha and pine oil (coniferous products).
The production of tar and light volatile distillates from wood, methyl
alcohol, acetic acid, turpentine, turpentine oil, acetone, creosote.
The production of fats by the contact. method.
The production of anhydrous sodium carbonate by the ammonia method in
quantities less than 400,000 tons per anum.
The production of caustic soda by the lime and Levit methods.
The production of mineral paints other than chromium or lead.
The production of mineral salts with the exception of arsenates, flu-
orides and chromates.
63.
64.
65.
66.
67.
68.
69.
The production of naphtha gas in quantities of 1,000 to 5,000 m3/hr;
under this heading included generator gas in excess of 10 - 25,000
m3/hr using 3 - 5 generators.
The production of nicotine.
The production of plastic material, carbolite, celluloid, bakelite,
chlorov.
70.
71.
72.
The production of compressed and binding materials from paper and fab-
rics saturated with phenolaldebyde, tars and resins in quantities ex-
ceeding 100 tons per anum.
The chemical processing of ore of rare metals for the production of
salts of antimony, bismuth, lithium, etc.
The production of synthetic camphor by the isomerization method.
73.
74.
-167-
-------
75.
The productiop of synthetic kaoutchouk or rubber by the alcohol
method.
The production of fertilizer mixtures.
The production of coal products for the electrical industry, such as
brushes, electrical carbons, etc.
The production of phenol-aldehyde and other synthetic tars and resins
not exceeding 300 tons per anum.
The production of electroinsulating lacquers and varnishes or lacquer
bases not exceeding 500 tons per anum.
76.
77.
78.
79.
Class IV.
Requiring a sanitary clearance zone 300 m wide.
80.
81.
The manufacture of paper from prepared cellulose and rags.
The manufacture of galalith (casein plastic) and other protein plastics,
such as aminoplastics and the like.
The production of glycerine.
The production of generator gas ~rom coal and peat; 1 - 2 generators
producing 10,000 m3/hr.
The manufacture of synthetic fibers by the acetate and ammonia proc-
esses.
82.
83.
84.
85.
86.
87.
The manufacture of pencils and crayons.
The manufacture of soap on a large scale.
The production of natural mineral paints, chalk, ochre, mummy or colco-
thar (Persian red), etc.
The manufacture of inorganic reagents, manufacture of chlorine and its
compounds excepted.
The manufacture of organo preparations.
The manufacture of pressed and binding materials from paper and fabrics,
satu~ated with phenol-aldehyde tars or resins, not exceeding 100 tons
per anum.
The production of technical hydrogenated oils resulting in hydrogen lib-
eration non-electrolytically.
Plants engaged in salt manufacture by the evaporation and grinding
method.
88.
89.
90.
91.
92.
93.
The manufacture of pharmaceutical salts of potassium (KCl, K2S04'
K2C03' etc.). .
Ma~ch manufacturing.
The production of vegetable kaoutchouk or rubber.
The production of liquid fertilizers.
The production of saccharine and of vaniline.
The production of naphtha gas up to 1000 m3/hr.
94.
95.
96.
97.
98.
-168-
-------
99.
100.
101.
102.
103.
104.
105.
106.
101.
108.
109.
110.
11l.
112.
113.
114.
115.
116.
111.
118.
119.
120.
121.
Class V.
Requiring a sanitary clearance zone 100 m wide.
The production of alkaloids and of galenite preparations.
The manufacture of paper from waste paper, from prepared cellulose and
from rags without bleaching.
Plants engaged in rubber vulcanization without hydrogen sulfide.
The manufacture of liquid carbon dioxide and of dry ice.
The manufacture of synthetic pearls.
The manufacture of articles from plastic materials b.f mechanical
means.
The manufacture of perfumes.
The production of compressed hydrogen and oxygen gases.
Plants engaged in making photochemical preparations (photopla~es or
paper) .
The production of carbonate fertilizers.
The extraction of tannins.
Areas for the cleaning, washing, and steaming of cisterns or tanks.
Metallurgical. Machine Building and Metallic ProcessinR Industries.
Class I.
Requiring a sanitary clearance zone 2000 m wide.
The production of manganese by the chloride method.
. .
The secondary processing of non-ferrous metals exceeding 3,000,000 tons
per year.
Coke burning and pig iron smelting b.f the blast furnace method.
Smelting non-ferrous metals directly from ore and fram concentrates,
which includes tin, lead, copper, nickel.
The production of aluminum b.f electrolyzing melted aluminum salts.
Class II.
Requiring a sanitary clearance zone 1000 m wide.
Plants engaged in sintering ores of ferrous and non-ferrous metals and/
or pyrite cinders.
The production of non-ferrous metals in excess of 2,000 tons annually.
The production of manganese by any method, the chloride method ex-
cepted.
Secondary processing of non-ferrous metals not in excess of 1,000--
3,000 tons annually.
The reprocessing of pig iron and of steel in quantities exceeding
15,000 tons annually. .
The production of Thomas slag.
-169-
-------
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
134.
135.
136.
131.
138.
139.
140.
141.
142.
143.
The production
The production
t./anum.
The production of zinc, copper, nickel, cobalt by electrolysis of 1
aqueous solution.
of shaped pig iron exceeding 2,000 tons per anum.
of antimony by the pyrometallurgical method up to 300
The production of ferro-allqys.
Class III.
Requiring a sanitary clearance zone SOO m wide.
Stations engaged in testing aviation motors provided with sound ab-
sorbing facilities to prevent sounds from extending beyond the clear--
ance zones up to 35 decibels.
Enrichment of metals without heat processing.
The building of accumulators on a large scale.
Reprocessing of non-ferrous metals up to 1000 tons annually.
The production of pig iron and of steel from 10,000 to 15,000 tons
annually. .
The production of shaped (cast) pig iron between 5,000 and 20,000 tons
per anum.
The production of non-ferrous metals from 100 to 2000 tons annually.
The production of lead coated cables.
The production of rubber insulation.
Class IV.
Requiring a sanitary clearance zone 300 m wide.
The production of non-coated cables.
The making of boilers.
The making of machines and equipment for the electric industry, such
as ~namos, transformers, projectors, etc. by plants which are
equipped with medium sized foundries and other hot manufacturing de-
partments or sections. .
Plants of the metal-processing industry equipped with pig iron, steel
(up to 10,000 tons annually) and non-ferrous casting (up to 100 t.
annually) .
The production of articles containing mercury, such as mercury recti-
fiers, thermometers, mercury lamps, etc.
The production of
The production of
The production of
steel with the aid of electrically operated hearths.
antimony by the electrolytic method.
shaped cast pig iron up to 5,000 tons annually.
Class V.
Requiring a sanitary clearance zone 100 m wide.
Plants engaged- in metal processing oy the heat method not of the foun-
dry nature.
-110-
-------
144.
145.
146.
147.
148.
149.
150.
151.
152.
153.
154.
155.
156.
157.
158.
159.
160.
161.
162.
The building of accumulators on a small scale.
The manufacture of appliances for the electrotechnical industr,y, such
as electric lamps, etc. not requiring the use of foundries.
The production of resistant (hard) alloys and metals of high melting
point b.y methods other than chemical processing of the ores.
MininK and Other Natural Mineral Resources.
Class I.
Requiring a sanitary clearance zone 2000 m wide.
Production of crude oil with a sulfur content exceeding 0.5% or having
a high content of volatile hydrocarbons.
Class II.
Requiring a sanitary clearance zone 1000 m wide.
Production of shale fuels (oils).
Mining of coal, anthracite, brown coal, etc.
Mining iron ore b.y the open explosion method.
Production of phosphorites, apatites, colchedans b.y non-chemical
methods.
Production of lead ores, and of arsenic and manganese by the smelting,
sintering or enrichment methods.
Class III.
Requiring a sanitar,y clearance zone 500 m wide.
Production of crude oil having a sulfur content below 0.5% and also
having a low content of volatile hydrocarbons.
Production of dolOMites, magnesites, asbestos, petroleum asphalt, etc.
Rock production b.y the explosion method.
Production of metal ores and of metalloids b.y the open method, lead,
arsenic and manganese ores excepted.
The production of Drickett. from fine coal and coal dust.
The production of peat bricketts.
Class IV.
Requiring a sanitary clearance zone 300 m wide.
Production of metal ores and of metalloids by the mining method; lead
ores, arsenic and manganese exoepted.
Production of peat b.y the milling outter method.
The production of rook salt (NaCl).
Plants of the Buildin~ Industry.
Class I.
Requiring a sanitar,y clearance zone 2000 m wide.
The produotion of portland oement, s1a~portland oement and of
pusuolanic cement; over 150,000 tons per anum.
-171-
-------
163.
164.
165. .
166.
167.
168.
169.
170.
171.
172.
173.
174.
175.
176.
177.
178.
179.
180.
181.
182,.
183.
Class. II.
Requiring a sanitary clearance zone 1000 m wide.
. .
The production of portland cement, slag-portland cement a.n4- pusuolanie
cement up to 150,000 tons annually. .
The production of lime, magnesite and dolomite b.1 the burning methods
wi thin the mines or in ground-type furnaces.
Class III.
Requfring a sanitary clearance zone 500 'Dl wide.
The production of local cements up to 5,000 tons annually.
The production of alabaster.
The production of concrete asphalt.
The production of glass wool and slag wool.
The production of tar paper.
The production of "Rubberoid".
,
Class IV.
Requiring a sanitary clearance zone 300 m wide.
The production of asbestos cement and of slate.
The production of artificial stones and concrete-made objects.
Stone casting.
The manufacture of red and yellow bricks.
The manufacture of cinder blocks and ceramics and other heat resistant
items.
Glass making.
The manufacture of porcelain, glazed and
Cement~elevators and other dust creating
clay items.
construction materials.
Class V.
Requiring a sanitary clearance zone 100 m wide.
Rock production b.1 non-explosive methods and the processing of natural
rocks.
The manufacture of gypsum items.
The manufacture of reed press-boards, and other similar press-boards.
The manufacture of construction materials fram electric power station
waste products.
Plants o~ the Wood Processing Industries.
Class I.
Requiring a sanitary clearance zone 2000 m wide.
The manufacture of charcoal.
No class II requiring a sanitary clearance zone 1000 m wide is included here.
-172-
-------
184.
185.
186.
181.
188.
189.
190.
191.
192.
193.
194.
195.
1960
1910
198.
199.
200.
Class III.
Requiring a sanitary clearance .sone 500 m wide.
Plants engaged in the treatment of wood by processes of infiltration
of oil or bitumenous products (wood preservation).
Class XV.
Requiring a sanitary clearance zone 300 m wide.
The production of wood fibers.
The production of charcoal b.y the retort method.
Sawmills, the production of ply-wood and of standard house parts.
Shipbuilding wharves (for the building of large wooden ships).
The production of items for the transport industry.
Class V.
ReQuiri~ a sanitary clearance zon~ 100 m wide.
The manufacture of articles from wood fibers.
Bast fiber rug weaving.
Joiner and carpenter shops
floors, boxes, etc.
for the manufacture of furniture, .parquet
The manufacture of barrels from ready-made staves.
Plants engaged in the conservation-processing of wood b.y aqueous solu-
tions and other preservative preparations free from salts of arsenic.
Wharves for the building of small ships or similar vessels.
Textile Manufacturing.
Class I.
Requiri~ a sanitary clearance zone 2000 m wide.
Plants engaged in the chemical impregnation and other processing of
textile fabrics with hydrogen sulfide.
Class II.
Requiring a sanitary clearance zone 1000 m wide.
Plants continuously engaged in the impregnation of textile fabrics
and/or paper with oil-asphalt combination, bakelite and other lacquers
or varnishes for use by the electric industry with an annual produc-
tion volume of impregnated materials of 300,000 tons.
Plants engaged in the primary processing of vegetable fibers such as
flax, linen, cotton and indian hemp.
Class III.
Requiring a sanitary clearance zone 500 m wide.
Plants continuously engaged in the impregnation of fabrics and of paper
with oils, oil-asphalt combinat~ons, bake lite and other lacquers with
an annual production up to 300 tons of impregnated material.
The impregnation and other processing of fa~rics with chemical sub-
stances, such as dermatin, granitol, etc., but not with hydrogen
sulfide.
-173-
-------
201.
202.
203.
204.
205.
206.
207.
208.
209.
210.
211.
212.
213. .
214.
215.
216.
.217.
218.
219.
Class IV.
Requiring a sanitary clearance zone 300 m wide.
Cotton processing plants.
Cocoon boiling plants.
Synthetic wool rug weaving.
Rope and twine making.
Melange plants.
Bleaching plants, dyeing and finishing plants.
The manufacture of yarn and fabrics from cotton,
equipped with bleaching and dyeing facilities.
linen, wool by plants
Class V.
Requiring a sanitar.y clearance zone 100 m wide.
The manufacture of yarn and fabrics
dyeing installations.
Plant s engaged in making leni t goods
by plants having no bleaching and
and lace material.
Industries Engaged in the Processing of Products of Animal Origin.
Class I.
Requiring a sanitary clearance zone 2000 m wide.
Plants which make glue from remnants of hides, bones and other animal
discards.
Plants engaged in mAking bone charcoal and bone meal.
The manufacture of technical gelatin from the usual parts of animal
discards kept in the open air. .
Utilization plants for the processing of suet, dead animals, fish, and
similar material for the conversion into fat, animal feed and fertil-
izer, etc.
Class II.
ReQuirin~ a sanitary clearance zone 1000 m wide.
Plants engaged in the processing and dyeing of furs of large animals.
Class III.
Requiring a sanitary clearance zone 500 m wide.
The production of animal feed from food leftovers in the food-proc-
essing combines.
Plants engaged in the processing and dyeing of raw furs and hides of
small animals.
The processing of hides of large animals by the tannin methods, such
as the production of soft leather, shoe upper leather, sole leather,
etc.
Wool cleaning and washing.
Fat or suet melting for the
30,000 tons per anum. .
production of technical fat and suet over
-174-
-------
220.
221.
222.
223.
224.
225.
226.
227.
228.
229..
230.
231.
232.
233.
234.
235.
236.
237.
238.
239.
240.
241.
Storehouses for salted wet raw hides with a capacity of over 200
hides.
Class IV.
Requiring a sanitar,y clearance zone 300 m wide.
Fulling and felt manufacturing.
The production of gelatin of higher purity
short storage in refrigerated rooms.
The manufacture of artificial leather.
Technical fat and suet melting, up to 30,000 tons annually.
The preparation of skeletons and other educational visual material
from animal carcases.
from fresh, clean bones of
The processing of hair, fur, down, feathers, horns and hoofs.
Class V.
Requiring a sanitar,y clearance zone 100 m wide.
The manufacture of foot wear; small individually owned and coopera-
tives excepted.
The manufacture of high-polished (lacquered) hides (leather).
The manufacture of travel bags and suitcases; small cooperatives
excepted.
The manufacture of bone articles; small cooperatives excepted.
The manufacture of brushes from hair and bristle.
Felt production.
Storage houses holding 200 wet salted hides, raw, on a temporary basis.
The manufacture of musical strings and cat-gut from animal intestines.
Food Products Processing and Spice Manufacturing Industries.
Class I.
Requiring a sanitar,y clearance zone 2000 m wide.
Animal corrals holding over 3,000 heads.
Class II.
Requiring a sanitary clearance zone 1000 m wide.
Slaughter houses.
Animal corrals holding 300 - 3,000 heads.
Rendering sea animal fat.
Cleaning and processing of intestines.
The manufacture of beet sugar.
Centers for sweeping and washing of freight cars used in animal trans-
portation.
-115-
-------
242.
243.
244.
245.
246.
247.
248.
249.
250.
251.
252.
253.
254.
255.
256.
257.
258.
259.
260.
261.
262.
263.
,264.
265.
266.
267.
268.
269.
270.
271.
272.
Class III.
Requiring a sanitary clearance zone 500 m wide.
Abattoirs with a capacity for 300 heads.
Production of albumin.
Production of dextrine, glucose and sugar syrup.
Production of starch in potato-grinding plants.
Rabbit meat processing.
Fowl slaughtering.
Fish industry plants.
Class IV.
Requirin« a sanitary clearanoe zone 300 m wide.
Aloohol distilling plants.
Flour mills, hulling mills.
Meat combines.
Coffee roasting plants.
Oi1 produoing mills.
Produotion of margarine and oleomargarine.
The prooessing of vegetables suoh as preserving, drying, piokling, etoo
Cheese making.
Fish combines, fish preservation and other prooessing.
Plants of the tobacco and makhorka(Nictiana rustica) industry.
Class V.
Requiring a sanitary olearance zone 100 m wide.
Beer breweries and allied processes.
Conservation factories.
Liqueur and other alooholic beverage
Vegetable storehouses.
Sugar refineries.
Fish-smoking shops.
Macaroni manufacturing.
Dairies.
distilleries.
Bologna and sausage manufacturing.
Fancy bakeries.
Bakeries, large scale.
Prepared food manufacturing.
Production of food spices.
Refrigerators, large, commercial.
-176-
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SUPPLEXENT OR APPENDIX 4, PP. 130-131.
Limits of Allowable Concentrations of Harmful Gases, Vapors and Dust in the
Air of Industrial Production and Manufacturing Premises.
Name of the substance
Acrolein - - - - - - - - - - - - - - - - - - - - - - -
Ammonia - - - - - - - - - - - - - - - - -
Acetone - - - - - - - - - - - - - - - - - - - -
Aniline, toluidine, xylidine - - - - - - - - - - - - -
~enzidine, dianizidine, alpha- and beta-naphthilamine
~enzene, white-spirit, ligroine, kerosene, mineral
oils - - - - - - - - - - - - - - - - - - - - - - -
~enzole (benzene) - - - - - - - - - - - - - - - - - -
Divinile, pseudobutylene - - - - - - - - - - - - - - -
Di- and trinitrocompounds of benzene and its homo-
logues (dinitrobenzene, trinitrotoluol) and other
Manganese and its compounds - - - - - - - - - -
Arsenious acid - - - - - - - - - - - - - - - - - ---
Arsenic and its compounds, calculated as As - - - - -
Unsaturated fatty alcohols (allyl, etc.) - - - - - - -
Xitro- and dinitrochlorobenzene compounds (nitro-
chlorobenzenes, dinitrochlorobenzenes, etc.) - - -
Nitrobenzene compounds and its homologues (nitro-
benzene, nitrotoluol, etc.) - - - - - - - - - - -
Oxides of nitrogen as N205 - - - - - - - - - - - - - -
Ethylene oxide - - - - - - - - - - - - - - - - - - - -
Zinc oxide - - - - - - - - - - - - - - - -
Carbon dioxide - - - - - - - - - - - - - - - - - - - -
Metallic mercur,y - - - - - - - - - - - - - - - - - - -
Lead and its inorganic compounds - - - - - - - - - - -
Sulfuric acid and fuming sulfuric acid - - - - - - - -
Sulfur dioxide - - - - - - - - - - - - - - - - - - - -
Hydrogen sulfide - - - - - - - - - - - - -
Carbon bisulfide - - - - - - - - - -
Turpentine - - - - - - - - - - - - - - - - - - - - - -
~utyl alcohol - - - - - - - - - - - - - - - - - - - -
Kethy1 alcohol - - - - - - - - - - - - - - - - -
Ethyl alcohol - - - - - - - - - - - - - - - - -
Mercuric chloride - - - - - - - - - - - - - - - - - -
Tobacco and tea leaf dust - - - - - - - - - - -
Toluol, xylol and solvent naphtha I and II - - - - - -
Phenol - - - - - - - - - - - - - - - - - - - - -
Formaldehyde - - - - - - - - - - - - - - - - - -
Carbonyl chloride - - - - - - - - - - - - - - - - - -
Phosphorus yellow - - - - - - - - - - - - - - - - - -
Hydrogen phosphide - - - - - - - - - - - -
Hydrofluoric acid and fluorides - - - - - - - - - - -
Chlorobenzene - - - - - - - - - - - - - - - - - - - -
-117-
The limits of
allowable concentration
in mg/li
0.002
0.02
0.2
0.005
0.001
0.3
0.1
0.1
0.001
0.0003
0.0003
0.000 3
0.002
0.001
0.005
0.005
0.001
0.005
0.01 (1)
0.00001
0.00001
0.002
0.02 (2)
0.01
0.01
0.3
0.2,
0.05
1.0
0.0001
0.003
0.1
0.005
0.005
0.0005
0.00003
0.0003
0.001
0.05
-------
Chlorinated hydrocarbons I
dichlorethane- - - - - - - - - - - - - - - - - - -
trichlorethane - - - - - - - - - - - - - - - - - -
chloroprene - - - - - - - - - - - ~ - - - - - - - -
0.05
0.05
0.002
0.01
0.0001
0.001
0.001
0.0003
0.05
0.3
HCl gas and HCl acid - - - - - - - - - - - - - - - - -
Chromic anhydride, chramates and dichromates - - - - -
Chloronaphthalene and chlorodiphe~l - - - - - - - - -
Chlorine - - - - - - - - - - - - - - - - - - - - - - -
~drocyanic acid - - - - - - - - - - - - - - - - - - -
Carbon tetrachloride - - - - - - - - - - - - - - - - -
Ethyl ether - - - - - - - - - - - - - - - - - - - - - -
Esters of acetio acid (acetates)1
Amwl acetate - - - - - - - - - - - - - - - - - - - 0.1
Butyl acetate - - - - - - - - - - - - - - - - - - - 0.2
Kethyl acetate - - - - - ~ - - - - - - - - - - - - 0.1
Propyl acetate - - - - - - - - - - - - - - - - - - 0.2
Ethyl acetate - - - - - - - - - - - - - - - - - - - 0.2
(1) In the blast furnace and open hearth furnace departments, in foun-
dries, in gas-generating departments and in general production where carbon
dioxide appears as a raw product (ammonia synthesis) the limit of its allow-
able concentration is to be 0.03 mg/li.
Where work in gas-polluted atmosphere does not extend beyond one hour,
the limit of allowable concentration of carbon dioxide may bera1..4 to 0.05
mg/li; if not longer than 30 minutes to 0.2 mg/li. Repeat exposure shall be
permittedlprovided intermittent rest intervals of not less than 2 hours are
institutea. .
In garages servicing automobiles the limit of allowable concentration
of carbon monoxide should be based on the hourly average; where exposures do
not exceed 15 minutes the allowable lim! t of carbon monoxide conoentrd1an
can be raised to 0.12 mg/li.
(2) In the vicinity of smelting and burning substances containing sul-
. fur the 11mi t of allowable concentration shall be 0.04 mg/li.
-178-
-------
Efteotivene.. ot Sanitar,y C18&r8l10e Zone. Between IDdu8trial
Bbterprises and R8s1dent1,al Qaarlere.
D. Jr. ra:qushDTi, Ya. I. Eostovetsk1i, S. A. Davdov aDd-. B. Abel'rod.
Uk:ra1D1an'IneUtute ot C~,nit7 IV'giene.
Gigi8D& i Bani ~ Jro. 4, 1952, pp. 9-12.
Plant lite capable ot retaining dust, ..oke aDd gase. ooutUute.- 118088-
sUT and basio 8l8DI8Dt ot 88DU&17 olearanoe sones .eparaUDC iDdu.trial ente1"-
pri.e. trCII residential quarters. At the end. ot the 19th oezitU17 L Jr. VakRlcw-
8Jd.i noted t~t . "taotor;r soot atteoted not on17 pacple but a180 plant lite whiaa
noraaalq proteoted :people tram the deleterious etteot ot the soot. It i. d....
.irabla, theretore, that wide green olearanoe zones (creeD belts) eur,.-0UD4 t.-o-
torie. and iDdustrial enterprises espeoi.-lq in the presen08 ot re.idential
area.-. (L I'. Vakulovak1i. "The Iaportanoe ot Plants to Health in General
aDd tor CU7 ])well era 1D Particular". St. Petersburg, 1898.)
In reCeDt yeare Soviet 80i8nti8ts .tudied the proteotive ettect. ot greeD
olearance Bones. Duriag her studie. ot sultar and. 8USp8Dd8cl. matter in the air
Z. I'. IUliohkova noted that plant lite in parka posse. sed the oapaoi t7 to re-
tain dust and absorb pae.. She showed that when the tree. were oovered. with
leave. the air ot greeD clearanoe zones and' ot parka oontained 24.2S les. ot
sultur &DCl 21% less ot susp8Dded. matter, thaD d.id. the air ot the nearb;y street..
A. 1'. lIar.eev also demonstrated. the oapaoi t7 ot lipeous plants to retain dust
and discussed. the meohaDiem by which trees treed the air trom d.ust. V. A. Takov-
enko -as the tirst to oorrelate the width ot greeD sanit&17 olearance sone. with
their oapaoi V to remove pollution trom atmospherio air, in detem1DiDg the
width ot greeD sani t&17 zones he took into oonsideration suoh tactors as t--
perature inversions, velocit7 ot air currents, heisht .-t which waste. were di8-
charged, eto. V. A. Yakovenko aDd. D. 1'. Xa~UJvi studied the pur1t,yiDg et-
teot ot green parka in the air ot Ibar'kov, they d8nonatrated that the cit7's
green parka had a notewort~ dust-clearing etteot in the summer as well &S in
the winter. Analogous studies were made b;y A. A. Adaaova who established. that
the air puri171ag capacity ot green . ani ta17 olearance Bon8S applied. to smoke
as _ell as to dust. V. A. Ugiov tOUDd that the air ot grove. contained lower
conoentration8 ot 800t than the air ot neishboriDB oPeD' .pace. even when the
tree. were devoid ot leave.. Y. X. Pedbe1di, T.. P. 1'rugl1k0va and G. V.
-179-
-------
1),yshlto demonstrated the oapaci t7 of planted areas to retain cement dust. A. A.
.Adamova and A. G. Ionina estabUshed the sanita17 significance of trees whioh
bordered oit7 streets. M. S. Goldberg and V. ". Docuchaieva studied the dust
clearing property of green sanitar,y clearance zones. P. A. Ba~ants reported
on the considerable damage oaused to such trees as the birch, linden, larch,
ash and oak by chemioal plants 2.5 laD awq. A. P. Krasinskiy investigated the
harmful effects of gases on vegetation and the capaoit7 of the latter to purit.y
air.
The authors of this report attempted to make a more thorough study of the
protective effect of green sanitar,y clearance zones between industrial plants
and residential areas. A studJ was made of sanita17 clearance zones of two
large industrial centers of the Ukrainian U. S. S. R. In one town, the in-
vestigation was made in June of 1950 in the vicinity of large ferro-metallur-
gical plants. A green clearance zone was located south of the faotor.y grounds
between the production plants and the tempora17 settlements extending V-shaped
from 30 m to 500 m trom east to west. This sanita17 clearance zone was about
20 years old and the trees consisted chiefly of leat,y species such as acacia,
maple, etc., spaoed 0.5 - 0.7 m apart. No visible indioations were seen of
smoke and gas damage to the foliage. Studies were also made at the widest part
of the green sanitar,y clearanoe belt situated between another settlement and a
metallurgical combine with particular reference to air-polluting substances of
qgienic importance, such as sulfur dioxide, qdrogen sulfide, etc. Samples
were collected by aspiration. Sulfur dicxide was determined by the usual neph-
elometric method and hydrogen sulfide by Polezhqev's colorimetric method.
To determine the air purifying effect of the green sanit&17 clearance zones
samples were collected on either side of the clearance zone at the same time as
air control samples were collected at similar distances from the plants where
Bani ta17 clearance zones were absent. Air samples totaled 32. During the in-
vestigation the weather was 417, hot and s~; air temperature at times rose
to 300. Wind velocity varied between 1 - 4 m/sec. In the accomp~ng Figure
averages are presented showing the decrease in concentrations of sulfur dioxide,
hydrogen sulfide and of nitric oxide at distances of 1,000 - 1,500 m from the
factories, depending on the s8Oit&17 clearanoe zene type of plant life. The
data indicated that concentration of air polluting substances decreased with
the distance from the factories as a result of the air purifying effect of the
-180-
-------
sanitary clearance zones. Averages showed that the conoentration at sulfur
dioxide outside the green strip, at a distanoe at 500 m, tell tram 0.27 to
0.14 mgfm3 or, appro:rliDately 50%, and inside the green strip it tell trom 0.27
3 .
to 0.08 mgfm , or approximately 33.3%. 'lbe same was observed tor qdrogen sul-
tide. It the content ot sulfur diorlde and ot qdrogen sulfide present in the
air out side the sanitary clearanoe zones is taken as 100% then the amount ot
sulturio compounds taken at 500 m trom the initial point tell to 51.8 - 42.8%
in the sanitary clearance lIIone still tree trom plant lite, and to 15.7 - 29.6%
in the green (tully developed) sanitary olearance zones. Thus the resul't.
showed that the deorease in atmospheric air pollution by sulfur dioxide and by
qdrogen sultide was the reeult not only ot distance trom the industrial dis-
charge, but also plant lite capacity to retain air pollution. Tests were al.o
made ot air samples taken at tive tixed points tor the determination ot dust
concentration, one ot the air sampling points was looated beyond the green SaD-
itary olearance zone; another point was at equal distance trom the source ot
pollution, but had n9 intervening green belt. In interpretinB the results .ot
analyses ot the air samples collected at these two points due consideration was
given to trequency ot wind blowing trom the plants in the direotion ot eaoh ot
the air collection points.
Air collec~ed at the tixed points was analyzed daily over a period ot 5
months using the sedimentation method ot the Ukrainian Institute ot COlWllun~l
Bl'giene. For oontrol purposes air samples were collected from time to time on
the lee side ot the same tixed points. The atmospheric air dust concentration
was considerably lower at the second collection point than at the tirst even
thcup the tirst was tarther removed trom the tactory "-than the seoond. Du.st
sedimentation at the tirst point averaged 1,536.8 malm2 per 24 hour. and at
the seoond 1,004 mg. This was in agreement with the result. ot parallel asp1-
- 3 3
,ration tests which were correspondingly 1.25 mal- , and 0.58 mgj.. Results
ot all tests clearly pointed to the -taot that plants ot the green sanitary
clearanoe zones investigated absorbed dust and gase. trom polluted air.
In the tall ot 1950 a stu~ was made ot the ettecti vene.s ot green .ani-
tary clearanoe zones in another town which had a nitrogen tertilizer taotor,r.
A 500 m wide green sanitary olearanoe zone was located on one side ot thi. tac-
t017 at a distance ot 1 m. Its plant lite oonsisted ot leafy - tree. ot ditte1'-
ent speoies; the tree. were 10 - 12 m hi~ and spaced 0.7 - 0.8 m apart; there
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0,22
were no signs of visible
damage. New residential
buildings were erected
on the other side of the
0,27
0,07
I-ondes mgf.3
green strip. Air samples
were aollected by the
aspiration method. Hi trio
oxide was absorbed twice
b.1 distilled water and
determined by the Griss
reagent. A total of 51
air samples were collected
in cool and damp weather
802 mfJ/i 1128 mg/
~~itial- point
,[~:::TI-500 m tram initial point, no Banit. clear. zone
,111-500 . from 1nit1alpoint, _Banit&1'7 clearance zone
RecWction in ooncentrations ot sulfur dionde, ~
sa sulfide and oxides ot nitrogen 111 relation to
green Bani t&r)" clearance zones
at temperatures of 1 -
140 and wind velocity varying from 0.5 to 3.5 m/sec. Air samples were collected
on both sides of the green sanitar,y clearance zone; control samples were col-
lected at same distances in an area which had no intervening green beit. It
can be seen from the schematic drawing that nitric oxide was absorbed from the
air by the green sani tary cl~arance zone.
Air samples collected at 1000 m from the factory contained approximately
equal concentrations of nitric oxide (0.23 and 0.22 mg/m3); the picture mark-
edly changed at 1,500 m from the production plant; in the absence of inter-
vening green belts nitric oxide fell to 0.13 mgfm3 and in the presence of green
sanitary protection zones it fell to 0.01 mg/m3. If the concentration of ni-
tric oxide in atmospheric air in the vicinity of the fertilizer plant, i.e.,
before passing over the green sanitary clearance zone be denoted as 100%, than
the concentration of nitric oxide at 500 m from the initial point was reduced
- to approximately 50%, due to distance dispersion alone. At a similar distance
and after having passed over the green sanitary clearance zone the nitric ox-
ide concentration was reduced to 33%.
Subjective data obtained by questioning the inhabitants also pointed to
the beneficial air purifying function of green sanitary clearance zones.
Summary .
Results of atmospheric air studies in the vicinity of chemical and metal-
lurgical plants demonstrated that dust, sulfur dioxide, ~ogen sulfide ai1d
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nitrio oxide were absorbed from polluted air by suitable types of plant life to
a considerable degree. It is recommended that in creating intervening sanita17
olearanoe zones provisions should be made at the same time for planting in such
zones suitable trees and other types of plant life.
Planning and Effecting Sani ta17 Clearance Zones in the Ukraine.
B7
D. N. Kalyuzb!\1i and Ya. I. Kostovetskii.
From the Ukraine Institute of Communit7Sanitation.
Gigiena i Sanitariya, No.1, 9-12, 1952.
The creation of sanitary clearance zones between industrial establishments
and residential sections at the time when plans are made for the building of
new towns is a notable accomplishment of the Soviet bygiene and practical
sanitation. This measure for the protection of atmospheric air of residential
sections against pollution with industrial emissions has been widely used in
the reconstruction of old and building of new towns and workers' settlements.
Twent7-five 7ears have passed since regulations for the establishment of
clearanoe zones between industrial establishments and residential sections
were first incorporated int 0 the Soviet law and. the measure was put into prac-
tice. Improvements in means and methods for the abatement of deleterious by-
products and advances in the general technology of industrial production brought
about considerable purification of industrial emissions and made possible the
reduction of the width of sanitary clearanoe zones. IlSanit&r7 Norms for Proposed
Industrial Production Plants", published in 1951 (NSP-10l-51) required that
plans for new industrial plants include provisions for the installation of
dust abating and. gas purifying equipnent, elimination of gas leaks, recovery
of waste products, etc. IlSanit&r7 Standards" (NSP-IOl-5l) stipulate that when
the abatement of hamf'ul effects of industrial by-products on the population .
was teohnical~ impossible, the State Sanitar;y Inspeotor ~ demand enlargement
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of the existing sanitary clearance zone to not more than twioe the prescribed-
width. Where efficient measures for eliminating industrial b,y-products are in
effect, the sanitary clearance zones ~ be decreased in size. Such flexibili-
ty of the law is of particular value since, on the one hand, it ~powers the
State Sanitary Inspector to decrease the size of the clearance zones, depending
upon local conditions, while, on the other hand, it encourages industrial estab-
lishments to develop and install more efficient equipment to minimize industrial
air pollution by emissions. Production executives are interested in decreasing
the size of the sanitary clearance zones.
Such an approach to the problem of purifying the atmospheric air ot in-
dustrial towns iaprogressive, technically feasible and promotes good sanita-
tion. To this end, as early as 1949, Prof. T. Te. Boldyrev wroter "We are
entering a period when all the problems (size of sanitary clearanoe zone)
related to a particular industrial enterprise ~ be solved for each individual
oase by making use of most recent findings i~ the tield of hygiene". (Gigiena
i Sanitar~a, No.1, 1949).
Industrial ministries manifested a more favorable attitude toward the
problem of air purification. This change in attitude is reflected in the
greater cooperation between the State Sanitar,y Inspector and production au-
thorities. However, it does not mean that sanitary clearance, as a means of
reducing the harmful effects of industrial emissions on the sanitar,y living
conditions and on the health of the population, are losing their importance.
Together with effective sanitar,y measures applied b.1 production industries
sanitar,y clearance zones remain a factor of great importance not only in respect
to reduction of air pollution, but also in respect to noise, traffic, soil pol-
lution, etc. With respect to these effects, the twenty-five years' experience
in the planning and practice of sanitary clearance zones is of scientific and
practical importance.
The stud¥ herein reported was organized by the Ukrainian Institute of Com-
munity Hy'giene. Examination revealed that the sanitary clearance zones sur-
rounding industrial establishments, in the majority of cases, were planted with
trees, shrubs and bushes which protected the population from the deleterious
effects of industrial discharges. Such beneficial aspects were particularly in
evidence in Xhar'kov, Zaporozh'e, Dnepropetrovsk, Krivoi Rog and other cities.
The sanitary clearance zones in the vicinities mentioned were instituted and
trees and shrubs planted at the time the industrial establishments were being
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built. This separated the produotion and Processing industries from the residen-
tial seotions by wide green belts landsoaped with trees of 15 - 20 m high. The
trees were principally acacia and maple which thrive in the olimatio conditions
of the Ukraine even in strongly polluted air. Special analyses of the air and
interrogation of the population in the areas.of the industrial plants established
that the sanitar,y olearance zones constituted a fairly efficient protection from
dust and gases. It is regretable that the sani tar,- clearance zones have been
developed only on one side of the industries mentioned. Among the industries in-
vestigated were the ferrous metallurgy, the chemical industry and power plants;
here the sanitary clearance zones were not wide enough and. the trees and shrubs
were planted in an unplanned manner. The sanitary clearance zones were of par-
ticular ~nefit to miners' settlements, since such zones were the only effective
means of abating or eliminating the injurious effeots of air pollution from burn-
ing waste dumps. Sixty-nine of the 136 mines surveyed in the Stalins~ and
Voroshilovgradskqa regions had burning waste dumps of which 16 were burning in-
tensely and. 53 moderately. In 50% of the surveyed mines the burning waste dumps
produced sulfur dioxide, which polluted the air within a radius of 500 - 1,000 mJ
this onoe more pointed to the necessity for strict adherence to the provisions
of the "Sanitary Standards" related to sanitary olearance zones surrounding mines.
Up to the year 1930 miners' settlements were built in close proximity to
the mines. Soviet sanitary legislation regulating the planning of residential
centers was enacted early in 1930, and the haphazard constrUction of homes in the
immediate proximity of mines was prohibited; approved housing projects were in-
situted. Of 59 workers' settlements erected in Donbass during 1931 - 1948, 52
were built according to approved plans. But even here the space breaks were not
ot sufficient width everywhere, nor were they properly landscaped. However, the
mere fact that nearly all miners' settlements built during the last 20 years were
provided with sanitary clearanoe zones should be considered as an aooomplishment
in Soviet sanitation and Soviet building regulations.
Despite the fact that benefits of sanitary clearance zones are questioned b,y
no one, the manner 'in which they were instituted until now showed serious short-
comings. To begin with, not alw~s has suffioient consideration been given to
the creation of necessary sanitar" clearanoe zones arouad production plants which
unfavorably aff~oted the surrounding populations. This explains why some settle-
ments built between 1931 and 1948 had sanit-ary olearance zones only up to 500 m
wide, whioh is narrower than that stipulated in the last sanitar,y regulations
for the pl,\"l"Ii1"lg of industrial enterprises. The planting of trees, shrubs and
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bushes within the sanitary clearanoe zones was too sparse in IDaIV' cases. Cleal"-
&noe zones, as a rule, were not instituted at the time of construotion of the
industrial plants and of the houses of a settlement or town. Opening of the
operation of an industrial plant did not oall for an inspeotion certificate
relative to the sanitary clearance zones, as was required in cases of other in-
dustrial and residential onm~Jnity oonstructions. Tbe proper protection of the
health of the population urgently demands that building and oonstruction organiza-
tions, industrial authorities and community leaders be made more striotly respon-
sible for the effeotuation of the right type of sanitary clearanoe zones. Tempo-
rar,r settlements have sprung up inside sanitary olearance zones on frequentoc-
oaaions. Such "tSJ:lporary" eettlements, and especially those having particularly
bad sanitation conditions must be abolished.
- .
Serious derelictions were discovered in the Ukraine during the post-war pe-
riod; a stu~ was made of towns and workers' settlements prepared by two large
planning organizations in the Ukraine. This study embraced 54 plans which in-
cluded 29 plans for miners' settlements. The most striking observation was re-
.lated to the utter lack of uniformity and proper system in pl~~jng sanitary
clearance zones. Only 25 plans, the majority of which were for miners' settle-
ments, had properly developed plans for the sanitary clearance zones which
were included in the specifications and blueprints of the projects. In another
group of ten projects the sanitar,y clearance zones were mentioned only in the ex-
planatory notes, but did not appear in the blueprints. In another group of proj-
ects the sanitary clearance zones were mentioned only casually without reference
to their dimensions and locations. Finally, in several cases where the area of
the project had no sources of intense air pollution the sanitary clearance zones
were not mentioned at all. In some instances the instructions for the planting
of trees and shrubs were rather vague.
Establishing sanitary clearance zones is an important sanitary measure; they
should be appropriately developed by planning organizations, while agencies of
the State Sanitary Inspection should enforce the realization of such plans. If
sanitary clearance zones are not clearly outlined, or are omitted in the plans of
a settlement, the possibility for their being created during the construction of
the settlement will be very remote, if at all. The architects and builders
should plan for the best type of the sanitary clearance zones with regards to
planting fruit trees, berries, -shrubs, vegetable gardens, decorative plants,
water reservoirs, etc. Only thus will sanitary clearance zones between residen-
. .
tisl sections and the sources of air pollution become economically sound.
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Sanitary Clearance Zones ~etween Residential Sections and Places of Fuel
Storage in Sovkhozes of Saratovsk (Oblast) Territory.
V. A. Kononova.
Saratovsk Institute of HY6~ene and Occupational Pathology.
Gigiena i Sanitariya, 23, No.6, 1958, pp. 11-14.
The spread and development of new sovkhozes in the Saratov Volga Region
confronted us with the responsibility of making sanitary surveys and of pre-
senting plans and sanitary recommendations essential to the well-being of fU-
ture residents. In such instances the point of primary importance was the ra-
tional separation of future settlements into residential and industrial or
commercial sections. Existing sanitary regulations prescribe the width of
sanitary clearance zones which must be instituted between residential con-
structions and sections of commercial or industrial character. It must be
stated in this connection that such regulations are based on inadequate san-
itary scientific foundations.
The mechanization of agriculture is constantly growing paralleled b.1 an
extension of centers where automotive agricultural machinery is housed for
distribution. Such centers also store the fuel required for the operation
of agricultural automotive machines. For this reason the presently pre-
scribed 15 m wide sanitary clearance zone between residential sections and
places of fuel storage should be reexamined scientifically and more thor-
oughly. The presently wide-spread and continually increasing use of ethy-
lated gasoline adds to the need for such a reexamination, since this fuel can
become a cause of animal and human intoxication under certain conditions.
The reexamination extended over seven sovkhozes of the Saratovsk Volga Oblast.
Determinations were made for the presence of tetraethyl lead in the air and
soil at different distances from the storage tanks; in addition determinations
were made for the presence of hydrocarbon vapors in the air of two sovkhozes
and of tarr,y substances in 4 sovkhozes. Air and soil samples were collected
at 25, 50, 15, 100 m from the gasoline storage tanks in the direction of
winds blowing from the points of tank location. The fuel storage tanks were
located 10 - 300 m from the sovkhozes under study in areas specially desig-
nated for this purpose in the industrial sections. All auto-transportation
and agricultural machines of the sovkhozes under study were run b.1 tetraeth-
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yl gasoline. Gasoline tanks and tanks containing the different oil and
grease IDaterials were located in rows close to the ground, supported when
required by suitable reinforceIDents; some were kept in excavated pits.
In only three sovkhozes - Krasnyanskii, Komsomol'skii and Dekabrist -
was the IDethod of rubber hose gasoline delivery directly into the tanks of
motors in use. In the remaining tour sovkhozes the gasoline was poured in-
to the motor tanks by hand which resulted in much of the gasoline being
splashed near the storage tanks, and the soil was saturated in spots with
gasoline and lubrication material. The motor fuel supply center at sovkhoz
Dekabrist serviced motor vehicles of the sovkhoz and of the nearby railroad
system with a total of close to 100 automachines. The other six sovkhoz
supply centers serviced between 40 to 60 motor machines each. Concentrations
in mg/m3 of tetraethyl lead found in the atcospheric air are shown in Table
1.
Table
1 .
Tetraethyl-lead in mg/m3 in atmospheric air at different
distances from gasoline storage tanks in sovkhozeso
1- Meters from storage tank 1 Time
Wind
Sovkhoz It~ I i I \ yelo of
25 I 50 75 100 wm year
Im. Radishcheva., 0,0218 0 0 0 0 5,5 I Spring
"Zernovoi~......, 0 0 0 0 0 9,9--10,9, "
"Urozainyi" 0 0,249 0,0249 0 0 9,I-l,~! Summer
.0..' 0,0234 0 0 0 0 3,1-3,6 i Fall
IIKomsomol' skii"..
"Dekabristll.. . . .. 0,0218 0,0218 0 0 0 5,0-0,7: "
0,0234 0,0265 0,0234 0 0 2,5-5,1 II
"Dergachevskii" . 0,0218 0,0160 0 0 0 5,0 "
/
Data presented in Table 1 show that tetraethyl lead was present in the
air 25 - 50 m from the storage tanks, and that wind velocity was a determin-
ing factor of the concentration found in the air. This was clearly indicat-
ed by the fact that no tetraethyl lead was found in the air of sovkhoz
Zernovoi at any distance from the distributing tank when the wind velocity
was 9.9 - 10.9 m/sec. At the time the air sample was collected at the stor-
age tank of sovkhoz Urozhainyi the wind velocity was 9.1 m/sec. and, 8S cart
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be seen from Table 1, the sample of air was free from tetraethyl lead due to
its rapid dispersion by the wind current. The time of the year did not ap-
pear to have any effect on the tetraethyl lead concentration in the atmos-
pheric air, probably due to the high volatility of tetraethyl lead. A. B.
Reznikov pointed out that the volatility of tetraethyl lead waS high even at
temperatures below zero. In our c~se no atmospheric temperatures below zero
were encountered during the fall. of the year.
Data pertaining to soil tetraethyl lead content are presented in Table
2. Tetraethyl lead was found in all soil samples taken at the storage tanks;
at a distance df 25 m from the storage tanks some soil samples gave negative
tetraethyl lead tests; at a distance of 50 m from the storage tank the number
of negative soil samples considerably increased.
Table
2 .
Tetraethyl-lead in ~ in soil at different distances
from gasoline storage tanks in sovkhozes.
Meters from ~asoline storage tank
Sovkhoz At tank: I 25 .\ 50 I 75 1100
1m. Rodishcheva. 0,0602 0 0,0164 0 0
"Zernovoi" .... 0,0123 0 0 0
o 0
. .' " 0,014016 0 . 00246 0 0 o'
II Urozha:LnY1. ...
0,00257
"Komsomol'skiill 0,00246 0 0 0
0.0161
"Krasnyanskii" 0,0123 0,00246 0 0 0
. .
0 0,039 0 0 0
"1>ekabrist" . . . .
"Dergachevskii"' 0,0601 0 0 0 0
All soil samples were collected at locations which were free from visible
discoloration; it can be assumed, therefore, that in the case of positive sam-
ples tetraethyl lead found its way into the soil through the process of ad-
sorption. It is known that vapors of te~raethyl lead are 11.2 times as heavy
a6 air and that they are easily adsorbed b.f soil and other porous substances
(according to I. Ya. Sosnovik). It can be seen from Table 2 that the soil at
the storage tank of sovkhoz Dekabrist was negative for tetraethyl lead. In
explanation of that it should be stated that the ground at that storage tank
was sloping away and that soil samples were collected shortly after a heavy
beating rain.
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Data related to hydrocarbon content in the atmospheric air are presented
in Table 3.
Tab' 1 e
3 .
"Dekabrist" ..
Hydrocarbons in atmospheric air at different distances
from gasoline storage tanks in sovkhozes (in mg/l).
Sovkhoz f!¥tere\ from ieoline j0re&
-------
concentrations. From this point on we regarded the preence of such tarry
substances as one of the indicators of pollution of atmospheric air in the
vicinity of gasoline supply centers.
We are forced to assume that non-observance of regulations applicable
to storage and supply of ethylated gasoline, careless maintenance at the
point of gasoline distribution and the manual method of supplying it contrib-
uted to the air and soil pollution of the auto fuel storage and supply cen-
ters at the sovkhozes investigated.
Eighty inhabitants of the sovkhozes Zernovoi and Imeni Radishcheva who
resided up to 100 m from the storage centers were questioned regarding possi-
ble air pollution effects. Fifty-three complained about the unpleasant gas-
oline odor coming from the storage centers; 21 persons ascribed frequent
headaches and nausea to the presence of gasoline odor; 9 persons stated that
they suffered of eye burning and irritation when the wind blew from the gas-
oline supply center in the direction of their residences. In summary, it
can be stated that atmospheric air pollution extended as far as 100 m from
the center of gasoline supply and soil pollution up to a distance of 50 m.
Simple hose gasoline supplying did not appear to be a worthwhile improvement
over manual gasoline distribution in so far as air and soil pollution were
concerned. This was clearly indicated by the fact that in the supply centers
of sovkhozes Dekabrist, Komsomol'skii and Krasnyanskii, where gasoline was
distributed with the aid of a rubber hose, the atmospheric air and soil pol-
lution were as intense as in the other sovkhozes which used the manual method
of auto-fuel distribution. In view of the above it is felt that the present~
prescribed 15 m sanitary clearance zone between gasoline storage centers and
residences is inadequate. Our agriculture is growing and with it the use of
automotive power is also growing; as a consequence the kolkhoz and sovkhoz
autoparks and auto-fuel supply centers will cover larger areas and will in-
crease the volume of dispensed auto-fuel. It is suggested, therefore, that
the problem of sanitary clearance zones applicable to conditions unde~ dis-
cussion be reexamined with a view to widening them. In addition, protective
health measures for those employed in the various phases of gasoline handling
in connection with automotive agricultural machinery, should be prescribed b,y
laws. This recommendation applies as much to protection of soil as well as
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ot air trom pollution by factors under consideration. Responsible local
sanitar,y organizations must do all in their power to institute methods of
gasoline dispensing to automotive vehicles and agricultural machines which
would obviate ~ spilling or leakage of gasoline.
Bibliography:
Reznikov, A. B. !.i.!l - Early Diagnosis and Prevention of Tetraethyl
Lead Intoxication, Moscow, 1939. - Sosnovik, I. Ia. - Clinical Symptomatology
and First Aid in Occupational Intoxication, Moscow, 1955. Collection of Most
Significant Material Related to Sanitary and Epidemic-Preventing Problems,
Moscow, 1953.
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Ratio of Sulfur Dioxide and Sulfuric Acid Aerosol in Atmospheric Air,
in Relation to Meteorological Conditions.
By
K. A. Bushtuveva.
(From Erisman Scientific-Research Sanitation Institute).
Gigiena i Bani tariya, !lo. 11, 11-13, 1954.
The widespread poisoning which occurred among populations of foreigJ'1 cities
with developed industries attracted considerable attention in recent years.
According to records these poisonings happened under unfavorable meteorological
conditions, such as continuous fogs, stagnant air and. temperature inversions.
These poisonings were traced to atmospheric air pollution caused b.1 industrial
emissions, the effects of which were intensified by the unfavorable meteorolo~
ical conditions.
The first case on record occurred in December 1930 in the Vaas River Val-
ley, Belgium. Similar cases were recorded in October 1948 in the industrial
area of Donora, Pennsylvania, U.S.A., and in December 1952 in London. All
persons affected suffered of respirator.y tract and cardiovascular disturbances.
The toxic fogs most severely affected the aged and children. No definite proof
exists as to what particular substance mq have been the cause of such extensive
poisonings, although most investigators are of the opinion that the presence
of sulfur oxides in the air may have been the basic causative factor. Such
authors as Batta, Fircet and Lecler assumed that the cause of the poisonings
was the combined effect of sulfur dioxide and sulfuric acid aerosol.
Sulfuric acid aerosol is toxic. P. Drinker stated that exposure of guinea
pigs for 72 hours to the aotion of sulfuric acid aerosol at a concentration of
8 msfm3 resulted in grave pulmonar.y damage. Coste, Courtier, Kader, Hamming
. .
and Belling believe that the formation of sulfuric acid aerosol in city atmos-
pherio air mq take place during foggy weather. However, their assumption is
based on scattered incomplete observations; it needs to be verified. Furthel-
more, the faot of the transformation of sulfur dioxide in the air of populated
places into sulfuric acid has not been proved, and the conditions upon which
such transformation mq be oontingent have not been established.
To accomplish this the present author analyzed the atmospheric air of
Koscow for the presence of sulfuric acid aerosol in an attempt to determine
-193-
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whether or not its presence was in 8Zrf wq related to the oxidation of sulfur
dioxide. At the same time it was necessar,y to determine what correlation, if
arrr, existed between the concentrations of these two air pollutants and to
find the conditions which determined their ratios. One-hundred-ninet7-eight
24 hour samples and 50 single concentration samples were collected simultane-
ousl7. For the determination of sulfuric aoid aerosol, the air was aspirated
through an absorber equipped with a porous glass filter No.2 and containing
4 ml of twice-distilled water; a small tube containing lead peroXide was placed
before the absorber tor the removal of sulfur dioxide. Samples to be tested
for the presence of sulfur dioxide were collected into an absorber equipped
with a porous glass tilter Bo. 1 and tilled with 6 ml of a 6% solution ot
potassium ohlorate. The correlation between mean dai17 concentrations ot sul-
.. .
furio acid aerosol and sulfur dioxide is shown in Fig. 1.
"'" CIS Pig. 1 shows that an increase in the
~ . sulfUr dioxide. concentration was paralleled
If 411 ..
b;y an increase in the concentration of sul-
R
'" furic acid. On the basis of this it can be
.~
~ 11.81
~f/III.
CN IS
o
fI.I 12
~
k I
\04
.q-6
g
CN 3
~
~
assumed that the two pollutants have a cammon
origin.
Astu~ was then made of the relations,
if ~, between the ratio of H2SO4 aerosol
and S02 concentrations and meteorological
conditions, such as relative humidit7, ve-
10cit7 of wind and the type of weather.
The results are shown in Fig. 2.
The data plotted in Fig. 2 indicate
that as relative humidit7 rose the ratio
of sulfuric acid aerosol concentration
to the concentrations of sulfur dicxide
0.1 fll II 0.1 as '6 47 4141 (, 1.1 (Z 'U
. S02 in mg/m3
,tg. 1. Correlation between
~SO 4 8I1d S02 concentrations
increased. Such a condition prevailed
in the case of the 24 hour average and
single concentration air samples. Pre-
cipitations removed a considerable por-
tion of the sulfuric aoid aerosol from the atmospheric air, thereb,r lowering
the ratio of H2S04 aerosol to S02. This was due basical17 to the fact that
sulfuric acid aerosol, being highly !J1'groscopic, was removed from the air at
"'lilT. 6/-'10"1. 71-IOT. II-SOr. 91" ana. 11»
Rustift hulJlidit7
Fig. 2. Effect of air moisture
on B2S04/S02 ratio
-194-
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a higher rate than the S02. These observations accord with the opinions ot
some authors who believe that the process ot oxidation ot sult'ur dioxide takes
place not in its gaseous tom but in the liquid phase I the S02 was tirst a1>-
sorbed b,y the water, in the dissolved torm it was adsorbed b,y dust particles,
and only then beoame oxidized to H2SO4. Furthemore, concen~rations ot sul-
turic acid aerosol may become markedly inoreased in the absence ot winds.
Available data indicate that concentrations ot sulfurio aoid aerosol during
calm dqs may be 4 1/2 times greater than during w~ dqs with a velocit7
greater than 5 m/sec.
The ratio ot single concentrations ot sulfuric acid aerosol to those ot
sultur dioxide increased as- the wind velocity decreased. This phenomenon can
be explained by assuming that an air mass moving through a city at a lower rate
requires a lonser time tor the oxidation ot a greater quantity ot sulfur di-
oxide to sulfuric acid. Data related to this phase ot the stu~ are plotted
in Fig. 3.
The data plotted in Fig. 3 indicate that
the ratio ot sulfuric acid aerosol to sult'ur di-
oxide constituted 3.27% during ~s with variable
cloudiness, 6.8% during dqs with .overcast skies,
and 15.7% during tOgQ dqs. No periods ot last-
ing togs occurred during this stu~. The most
persistent tog lasted for 11 hours; during that
~ the ratio ot daily average concentrdion ot
sulturio acid to the concentration of sultur di-
oxide was 30%. During togs lasting 7 hours this
ratio decreased to 20 - 24%. During shorter pe-
riods ot tOgQ weather this ratio decreased to
10 - 18%. Single concentration air samples ob-
tained during tOgQ dqs showed that the average
ratio ot S02 to H2SO4 was 32%. It tollows that the ratio ot concentration ot
sulfuric acid aerosol to sultur dioxide and the absolute concentration values
ot sulturic acid aerosol increased during continued togs.
The results obtained in this investigation accord with the assumption ad-
vanced earlier b,y ~ authors, name 17, that sulturio acid aerosol can aocumulate
in the atmosphere ot a ci 107 during oalm tOgQ dqs. These results support the
~othesiB that the oause ot the widespread poisonings in the has River Val 187 ,
II
9
o
Iiot
IS
.
od
g
r-I
o
~
g
r-t
o
11
t:f'J
11.1
II I
2 .
~
I
g~
jj'J
'\It
:f
t)
r-t
o
Weather oondi tioii. .
Fig. 3. Effect of weather
on oorrelation between
~S04 and S02.
-195-
-------
.in Donora and in London, which occurred during calm foggr weather lasting for
several dQ's, was the highly t.oxic sulfuric acid aerosol formed by the oxida-
tion of sulfur dioxide, or the combined action of the sulfuric acid aeroBol
and of the sulfur dioxide.
Kore observations are needed for further substantiation of this hypothesis.
Bibliograp~.
Air. pollution. control. Pub!. Health, N. 84, 1951, p. 33.-.lJ. Y x8 B B~. 3.,
T0&C8Qec:!IUIA TYNaH B nOHAORe, JltypS. CrereeRa R caeHTapHP, M 12, 1953, crp. 8&.-
It. m d u r M., S c h u 1 z R., Dr 1 n c e f P., Toxicity of sulphurlc add mist te cutna
pl~, Arch. industr. hug., Occup. moo., vol.. 5. N. ~, 1952, .p:. 318: - Bat h Q:,. PI f.
c e t I. Lee 1 erE.. Les problemes. de pollution de 1 atmosphert;. Parils, 1933.-C 0 s t e G.,
C ou r tie r I.. Suliphur acid as a disperse pbase in town air, Transact. .11 .the Fanlv
Soc., vol XXXII. part 8,.N. 184, 1936, p. llOS.-Mader P.. Rammin2W:,
8eJUng A., . Determination of lIIJIall amounts 01 sulphuric acid 10 the a~.
AJl8Iyt. chem.. IVOI. 22. N. 9, 1950, 'II. 1181.
Effect of High Air Temperature on Biochemical Processes ~ !!!2,.
l\r
G. !h. Shakhbaq8D and r. II. Shleif'man.
(Institute of Labor ~g1ene and Occupational Diseases, Kiev).
Gig1ena i Sanitar1ya, Vol. 24, No.1, 30-34, 1959.
In setting standards related to industrial micro-climatic (indoor) condi-
tions it is not enough to base such standards on the usual p~iological in-
dexes prevailing under normal conditions, changes in specific metabolic proc-
esses of the organism caused by temperature, pressure, humidity and other
meteorological conditions must also be taken into oonsideration. A stu~ of
the literature indicated that immediate temperature conditions markedly af-
feoted the state of the organism's metabolic processes.
Publications com1n& from the laboratory of Professor I. P. Rozenkov during
the thirties indicated that high temperature changed the degree of o:qgen blood
saturation, affected the course of oxidation and metabolic processes in the
organism, thereby disturbing the alkali-acid balance in the blood of animals
-196-
-------
and I118D.Similar temperature effects were described. by K. :B11nova, S. E. Sev-
erin, Te. P. Georgievska.ya, G. V. Dervis, A. M. Kitte1'shtedt, and others.
A. Tu. Tilis, Ch. I. Burshte1n and other studied the effect of high temperature
and irradiation on the blood sugar, alkali reserve, etc., in animals and man
during the post-war period. In 1953 E. A. Rozin published the results of his
studies on el1Q1D8 oxidation and reduction processes in tissue(l, particularly
of deqdrogenase aDd c;rtochrome-oxidases. His results indicated that the rate
ot the oxidation-reduction processes decreased as the temperature increased.
A. L. Izbinsld.i, '1'. A. Achkasova and other studied the effect of low tempera-
ture (cooling) on the rate of metabolic processes. Results of studies by S. S.
Girgolav, '1'. Ta. Arlev, and others established that the onset of changes in
the rate of tissue oxidation processes were symptoms of the critical patho-
genic moment in the course of cooling the organism.
The above brief review indicates that the published data confi:rm the oc-
currence of chan8es in the biochemical processes of the organism, including
the oxidation and reduction processes, caused by some meteorological effects.
On the other hand, the available published information was contradictor.y, due
to the fact that the studies were made under different conditions. In the
majority of cases the investigations dealt with temperature effects of short
duratiODJ under industrial conditions such effects are usual~ of long duration.
No information was found relative to changes in biochemical processes consequent
to meteorological variations despite the fact that knowledge of these changes
is of particular interest.
The present report is a prelimin8.17 one; it describes the results of in-
vestigations of same biochemical processes of the organism under the effect of
o
high air temperature. Test animals were subjected to the effect of 40 for
three hours dai~, over a period of four weeks. Records were kept of body and
skin temperature, of respiration frequency, before and after the experiment,
and of the weight of the animals. Every five days the blood was ana~zed for
reserve plasma alkalinity and for ~ar. Results were compared with data ob-
tained from a control group of animals kept in a vivarium at 18 to 220. The
rations for the control and test animals were the same throughout the experi-
ments. The alkali reserve of the whole blood was dete:rmined by the Van Slyke
method, titrated alkalinity of plasma was determined by Panisyak's method,
blood sugar was determined by the Hagedorn-Jensen method.
After the Animals had been kept three hours in the heat chamber, the skin
-197-
-------
temperature rose by 2.5 to )0 and the body temperature by 1.5 to 20. The body
temperature rose to 40.5 - 41.30. The respiratory rate increased to 150, and
in some cases to 270 per minute. The animals were in a state of high locomotor
agi tation. Atter the exposure to high temperature was discontinued the p~sio-
logical indexes rapidly returned to nomala at the end of 30 to 45 minutes the
skin and body temperature and the frequency of respiration fell back to their
normal levels.
During the second and third weeks of experimentation the rise in the skin
and in body temperature caused by the exposure to heat in the chamber did not
o'
reach the same level as during the first week, ranging between 40 to 40.5 ;
the animals were less agitated, and their rate of gain in weight increased; it
appeared as though the animals became physiologically adapted to the new tempera-
ture environment. Results of plasma alkalinity, alkali reserve and of blood
sugar during the animals confinement in the high temperature chambers are shown
in Fig. 1.
Fig. 1 shows that titrab1e plasma alkalinity fell to 86 - 79% of the
initial level. There was also a parallel drop in the alkali reserve of blood
to 91 - 85% of the initial level. Prolonged exposure to high air temperature
brough about hypoglycemia, symptomatic of accelerated metabolism. The hypo-
glyoemia pointed to an increased tissue sugar consumption. This agrees with
the observations of E. S. Novakovslcqa and N. B. Kozlov who found that the blood
sugar level of overheated animals fell below the normal level. The same author
also found elevated levels of insulin in the blood in overheated hypoglycemio
animals., It was also noted that high temperature of the surrounding air dis-
turbed the process of sugar metabolism and resulted in the accumulation of in-
oompletely oxidized products of disturbed carbo~drate metabolism. This appears
to be substantiated by the drop in the alkali reserve and particularly in the
titrable plasma alkalinity.
The present data related to the fall in the alkali reserves of the blood
caused by high air temperature agree with the results of investigations carried
out byCh. I. Burshtein and A. Yu. Tilis who exposed dogs to solar overheating.
Burshtein and Tilis were of the opinion that the observed changes were intimately
connected with the accumulation of incompletely oxidized metabolic products in
the blood.
Data related to the state of alkali reserves during heat exposure and after
its cessation are of great interest. The accompalV'ing diagrams indicate that
-198-
-------
1%1 High te.perature at Recovery
100 -----------... ....----
...... ""'--
.95 ""'.....---- -------' ----._/
.90
35~ Z
80 ....-------
75 .
70
M J W 5 -20 li 5 W ~ M li ~
!)qs of stu~
High temperature b
%
10"
102
100
.98
.96
.9"
.92
.90
88
86
8"
82
Recovery
,,,,""',
...' ,
~...... ,*"" ,
, ...
'"",....."""
----- /
,.----- I
,
I
,
...-' /
"" ,
" ,
"
s
~
JO
10
10
15
20
15
15
%
105
20 25 5
Dqs of stu~
c
High temperature
Recovery
--
--
--
'00 ------.-----
,
,
'..
T~------'
,..-
,/
,/
" ,/
.... ,/
....
.95
10
90
f5
10
20
15
25
.M
J
10
15
20 25 5
Dqs of stu~
Fig. 1. Effect of high air temperature ons a - ti~rable
plasma alkalinity, b - alkaline blood. reserve, c - blood
sugar
1 - control group, 2 - experimental group.
-199-
-------
oessation of the thermal effeot did not oreate speoifio oonditions for the
prompt return to nomal of the indexes under invest18ation. Between the 5th
and 10th day after the oompletion of the experiment the plasma alkalini t,., the
alkali blood reserve and the sugar oontent were markedly below the initial
values. Even between the 15th and 20th dq return of the indexes to their
normal levels was still inoomplete. The plasma alkalinity remained below the
initial level 30 4&3's after the experiment had been oompleted. It is the
opinion of this author that the prolongation of the aftereffeots of exposure
to high air temperature was of significanoe, even though it had been disregarded
in the past. It was indicated by the results that while such physiological
indexes as b~ and skin temperature, and pulse frequenc,y were restored to
their normal upon cessation of high temperature exposures, the metabolic proc-
esses of .the organism retained their functional shifts for a long time.
Results of studies carried out by the author on oxygen saturation of man's
blood under conditions of thermal irradiation were of some signifioance.
Radiant heat of 1.5 to 2 cal/cm2 per minute was directed at the right side
of the chest of a full,. dressed patient for one hour. Oxygen saturation was
determined b,. means of Kreps oxygenometer and was expressed in percent. Simul-
taneous observations of skin and bocq temperature, pulse rate, and the patient' s
heat sensation were recorded. The results indicated that under the conditions
of the exposure and intensity the irradiation elicited a slight rise in the
skin temperature of the cheat under the garment, increased perspiration, and
changed the heat sensa-
tion into a feeling of
pleasant warmth. The
bocq- temperature was
not elevated, and blood
oxygen saturation mani-
fested a series of
changes as illustrated
!/S~
i g5 r--
u .
k
&.9'-
!'Z '-~
B~
I
'v'
£
18 + I 12 15 20 I" 28 J2 J5 yO "". 118 52 J5 IJO " 8 IZ
Exposure to high temp. in minutes Recovery
fig. 2. ~gen blood saturation during exposure to
1.5 cal/cm2/min of test subject S.
Plots represent averages of ten tests.
1 - control data, 2 - experimental data.
-200-
in Fig. 2.
Beginning wi th the
time ot the 2nd to the
4th minute ot irradia-
tion oxygen saturation
ot blood began t~ de-
-------
crease steadily and progressively; by the end of the irradiation, i.e., on the
60th minute, its level dropped to 89 - 8~ of the original and in same cases
lower. Cessation of irradiation was followed by an iDmediate increase in
oxygen saturation of the bloodl on the 8th to 10th minute its level rose to
93 - 94%. Irradiation of the patient by a beam with an intensity of 2 calories
elicited a slightly greater decrease in oxygenous saturation, although there
was no complete correlation between the irradiation intensity and the fall in
oxygen saturation of the blood. A decrease in oxygen saturation of the blood
during irradiation indicated an increased o~gen consumption by the tissues,
which ma;y have been oaused by changes in the metabolic processes.
Conclusions.
1. Daily three-hour exposure of animals to a surrounding temperature of
400 resulted in a sharp fall in plasma alkalinity, the alkali reserve of the
blood and its sugar level.
2. Changes in the biochemioal indexes under consideration were observed
long after the cessation of the themal effeot, pointing to the persistent
nature of the aftereffeots. ,
3. Irradiation of patients bya beam of 1.5 to 2 oal/Cli per minute in-
tensity results in a marked deorease in oxygen saturation of the blood.
4. The solution of ~gienic problems related. to surrouniliJ,g micro-climatic
conditions should be based. on a study of changes in the metabolic processes
elicited by micro-climatic (indoor) meteorological conditions.
Bibliograp~.
I> II II II 0 BaA. M., Cell e pHil C. E. 4>H3HOJI. JKypH. CCCP, 1935, Nt 6, CTp.869-
8i7. - I) Y P W Tell H 4. H., T H JI H C A. 10'. 3a COlt'. 3.l1p3BOOXp. ~136eKHcT3Ha. 1956, Nt .~
CTp. 41-45, - Be cell K H H n. H. 0 OHOJlOrHileCKOM 3Ha'leHHH JlHXOpaJlOQHOA peaKItHIf..
APXHB naTOIIorHH, 1957, Ng I, T. 19, CTp. 3-29. - OH )K e. BJlHIIHHe Bb/COKOA TeNnepsTY"
pbl lIa JKHBOTllblii opraHH3/o1 H opnlllH3/o1 'IeJJOBeKS. TpYllbl HH-Ta no H3Y'I. np04l60J1 HM.
OOyxa. M. -- JI., 1934. - H 3611 H C K II ii A. JI. B KH.: Ollb/T H3Y'leHHR perYJlRUHH 4IH3HO-
JlOrH'IeCKIIX YIIKUllii B eCTeCTBe, ,HblX YCIIOBHRX cywecTBoBaHHR opraHH3/o10B. M. - JI.,
1953, T. 2, CTP. 9--18. - HOB a K 0 B'C K a II. E. C. I>KnlJI. 3Kcnep. 6HoJl. H Me.l1., 1936, T. I'.
N~ 2. rrp. 127-129. - Po 3 H II E. A. TpYJlb/ 10-A HaY'IHOii KOHepeHItHH CJlYWSTeJle.
BMMA. JI., 1953, CTp. 123--129.
~
-201-
-------
Selection of Air Intake Points for Ventilation of Premises in
Petroleum Processing Plants.
By
B. E. Stankevich and M. I. Isaeva.
(Ufa Petroleum Scientific-Research Institute).
Gigiena i Sanitariya, No.8, 27-34, 1954.
Atmospheric air over the grounds of petroleum refineries alw~s contains
some toxic admixtures. Such air pollution is frequently considerable and the
utilization of the air for ventilation of premises becomes impossible. Spe-
cific conditions of oil processing plants, particularly of those which process
sulfur-rich oils, made the task of providing clean air for ventilation a
serious and difficult problem.
Some authors suggested purification of air for vent~lation through spe-
cial filters, such as carbon. This method can provide air of sufficient purity,
but it is expensive and massive. Other authors suggested that air filtration
be abolished and air intake points be located at higher levels. However, in
practice it can not alw~s be established at what particular height air intake
should be placed. There still is no single answer to this question, and
decisions of investigators differ sharply.
The first attsmpt to find practical~ acceptable height levels for air
intakes was made by M. I. Fonganz and E. E. Gamarnikov 1; following an in-
vestigation of atmospheric air in one oil refinery, these authors concluded
that even under most unfavorable conditions of refinery building location with
regard to hydrogen sulfide accumulation, the air intakes located 18 - 20 m
above the ground could supply air sufficiently pure for practical ventilation.
These authors concluded further that under favorable conditions of prevailing
winds, which do not pass through zones of possible hydrogen sulfide accumula-
tion, the air intake can be lowered to 12 - 15 m.
Such conclusions appeared attractive to organizations which were engaged
in planning production plants having highly efficient ventilation systems.
Indeed, a system of air intake from the height of 15 m is simple and inexpensive.
As a result, such air intake point and air conduits were included in the plans
1
M. I. Fonganz, E. E. Gamarnikov. Hygiene of Labor in Production and Proces-
iDg of Polysulfide Petroleum. M. Medgiz, 1949.
,:",202-
-------
for many oil refineries. Some planning organizations firmly believed that the
problem of air intake ventilation on the premises of oil refineries found its
final solution. Factually this was not the case. M. I. Fonganz and E. E.
Gamarnikov proceeded from erroneous premises and came to the wrong conclusions.
One of the main errors of these authors is in the evaluation of air quality
only on the basis of hydrogen sulfide concentration, assuming that the quanti-
tative content of this substance in some measure determined the quantity of
other toxic admixtures. Hydrogen sulfide is one of the most poisonous compo-
nents of atmospheric air in oil refineries, but many other substances must
also be taken into consideration, such for example, as hydrocarbons, carbon
monoxide and sulfur dioxide. The density of these gases, carbon monoxide ex-
cepted, differs considerably from the density of hydrogen sulfide and, there-
fore, conditions of their distribution in the atmosphere differ correspondingly.
This means that distribution of hydrogen sulfide in the l~ers of air at dif-
ferent heights does not follow the pattern of general distribution of other
gaseous admixtures. Accordingly the work of M. I. Fonganz and E. E. Gamarnikov
can be considered as directed toward obtaining air free of hydrogen sulfide,
but not air free from other pollutants and suitable for plant ventilation.
From this point of view the conclusions of the above authors seem to be
principally in error. In the first place air samples were not taken simultane-
ously at different levels, which could result in a collection of chance figures
having no relation to any regularity. Secondly, the stu~ was limited to one
plant in which conditions related to the type of fuel, raw materials, refining
conditions, number and size of installations may have been different from cor-
responding conditions in other plants. Results of an investigation carried
. out in an oil refinery by the authors of this report confirm the preceding
statement. Air samples taken simultaneously at 5, 10 and 15 m above the
ground were analyzed by the usual methods for the content of hydrogen sulfide,
hydrocarbons, carbon monoxide and sulfur dioxide. The results are presented
in Tables 1, 2, 3 and 4.
In installation No.1 hydrogen sulfide was found only once in identically
insignificant concentrations practically at all levels (Table 1). In this
case, the hydrogen sulfide was brought in by a westward wind from an oil col-
lector located at a distance of about 0.7 km; there were no other possible
points of B2S origin.
-203-
-------
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-204-
The distance from the test
si te and the low capacity of
the source explain the uniform-
ity of H2S distribution and its
insignificant concentration.
During all other dtqs the wind
blew from directions where no
~drQgen sulfide was liberated
and, therefore, it was not
analytically detected. As shown
in Table 2 almost all analyses
of air samples of installation
No.2 showed the presence of
~drogen sulfide; it maTinnJIJ)
~S content was 0.001 mg/li at
. heights of 5 to 15 m on the dq
the plant underwent an over-
hauling, and the equipment was
opened and drained; analyses
made during work hours gave
lower results; five air analyses
indicated uniform H2S distribu-
tion at different heights, 2 a
fall, and one analysis an in-
crease in ~drQgen sulfide COD-
centration at 15 m above the
ground.
During the investigation
directions of prevailing winds
excluded the possibility of
hydrogen sulfide inflow frail
other sources; therefore, the
~drogen sulfide must have come
from installation No.2. The
low concentrations of H2S and
its uniform distribution at
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. - COt C'I
tions for air of working premiseso
Highest hydrocarbon concentrations
were noted at 10 m, that is at the
level of ventilation air exhausts
coming from the pumping centerso
There were cases of increased hydro-
carbon concentrations at 15 m. This
was due to somewhat complicated cir-
cumsta.nces: hydrocarbons came from
unaccounted sources, or they were
liberated at the installations located
near the air sample collection pointso
Data presented in Table 4 in-
dicate that in the majority of cases
carbon monoxide was present in the air
near installation No.2 at levels up
to 15 m in a concentration equal to
the limits of allowable concentrations
for working premises, and in some in-
stances exceeding them; as was the
case with other air pollutants, the
distribution at levels up to 15 m was
uniform.
The distribution of all air pol-
lutants according to levels during the
investigation was as follows: uniform
at all levels - 5204%, decrease with
elevation - 2905%, increase with ele-
vation - 1801%0
Hydrogen sulfide and 502 in the
proximity of the installations were
present in ooncentrations below the
limits set for working premiseso If
the data obtained for 502 were regarded
ae approximate representatives of air
pollution at elevations up to 15 m,
-206-
-------
:I
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that in actuality clean air, free from the enumerated toxio admixtures, can
be taken in at a height exceedir~ 50 m.
Conclusions.
1. Under conditions existing in the oil refinery investigated by the
authors, as well as in many other refinery plants, the installation of air
intakes at 15 - 20 m fails to improve the quality of ventilation air, and in
many cases might worsen it.
2. Recoumendations made by M. I. Fonganz and E. E. Gamarnikov that fresh
air ventilation intikes for refineries be intalled 18 - 20 m above the ground
are not applicable to all oil refineries. These recommendations are based on
results of studies limited to air pollution by hydrogen sulfide only and can
not be used as a basis for generalized conclusions.
3. An appropriate solution of the problem of ventilation air intake can
not be achieved apart from the general control of air cleanliness; depending
on local conditions, it ~ involve the adoption of complex of measures,
such as the improvement of teohno10gical methods, thorough air tightening of
equipment and containers, etc. In view of the complexity and specific condi-
tions which ~ exist in some modern oil refineries,. the choice of necessary
sanitary measures can be made only on an individual basis by taking into con-
sideration actually existing conditions.
4. Where it may be impossible to assure purity of atmospheric air. at a
convenient level, a thorough purification of the incoming air should be recom-
mended, by the use of proven effective methods.
-208-
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Purification of Ventilation Air from Tetraethyl Lead.
By
A. S. Arkhipov, P. I. Bogatkov, I. V. Oreshkevich and 11. V. Serednikova.
(Gar'kii Institute of Labor Hygiene and Occupational Diseases of the
Ministry of Health, R.S.F.S.R.).
Gigiena i Sani tariya, No.3, 11-16, 1955.
In accordance with the decisions of the XIX convention of K.P.S.S. (Com-
munist Party of the Soviet Union), prevention of diseases must become the most
important task of health authorities. Action directed toward the reduction,
or the complete elimination, of atmospheric air pollution by the emission of
toxic substances and by industrial dusts, should be considered as basic pro-
phylactic measures. In the produotion of tetraethyl lead (TEL) considerable
quantities of ventilation air are ejected into. the atmospheric air. In his
1
paper "Hygienic Significance of Atmosphere Pollution in Chemical Plant Areas"
A. S. Arkhip.ov showed that TEL concentration in exhaust ventilation air emitted
into the atmosphere by TEL plants ranged between 0.79 and 36 mgfm3, and in
production of ethyl gas between 0.13 and 2.02 m8fm3. In this comection, it
should be noted that ventilation air is an important factor in atmospheric air
pollution with tetraethyl lead by the above mentioned industries.
Tetraethyl lead is a highly toxic substance deleterious to the human organ-
ism in small quantities. Acoording to the data recorded in A. S. ArkhiPOV'8
paper TEL concentrations as low as thousandths and ten thousandths of a milli-
gram per liter of air produced chronic intoxica.tion. '!'he TEL molecule is
highly stable and persists for a long time under conditions ot external environ-
ment. The purifioation of exhaust gases is widely used at present in the con-
trol of different types of industrial atmospheric air pollution resulting tram
different technological emissions by pr1.mar7 produotion equipl1ent. Until
recently few ot our industries puritied ventilation air from toxic pollutants,
chiefly because of weighty technical ditticulties. The first is the VOlU88 ot
ventilation air emitted daily which amounted to millions of cubic metera, aDd
the old small-size puritication installations could not cope with the situation.
1 .
Report thesis of the scientitic 8ession ot the Sanitation-Hygiene Institute
and Hygiene Departments of Medical InriitUt8., 1953.
-209-
-------
The second difficulty results from the relatively low concentrations of toxio
substances in the ventilation air.
Some of the investigated plants emitted the ventilation air at 50 to 75 m
above the ground without aChieving the required reduction of TEL conoentration.
The hiBb toxicity of TEL, the resistance of its molecule to the effects of ex-
temal environment and the inadequate dispersion of ventilation air even when
emitted at heights of 50 - 75 m are compelling reasons for the need of adequate
purification of ventilation air from. tetraet~l lead. Attempts were made to .
accomplish this by means of the I. V. Oreshkevich chemical fluid-filter. The
experimental filter represents a horizontal cylindrical reservoir 100 am long
.and 80 em in diameter. Two shafts run parallel to the face walls of the cylin-
der; to the shafts 12 spr~er-discs are attached rotated by 2 0.25 Xi motors
in opposite direotions at a peripheral velocity of 15 - 20 m/sec. The qylin-
der is partly filled with the filtering fluid, which contains a suitable chemi-
cal for the absorption of TEL. The fluid is poured into the apparatus to a
level of 50 - 100 mm above the discs. The level of the fluid is controlled
automatically. The filter operates on the principle of atomization of the
cylinder fluid, which creates a large surface of contact between the fil tar
. fluid and the TEL; it is economical to operate because of its low pressure
drop and rate of air aspiration which ranges between 0.3 - 0.6 m/sec. The plan
of the filter is presented in the following drawing.
The efficiency of the filter was determined by analyzing air samples taken
simultaneously before and after filtering. Samples consisted of 6.3 li of air.
Four hundred and six air samples were analyzed in this study, using 0.5% alcohol
iodine solution as the absorber. TEL was determined colorimetrically with the
aid of dithizone. All tests were made under practical industrial conditions.
Taking into oonsideration the physico-chemical properties of TEL in con-
junction with the low cost requisite of the TEL air purification process, it
was decided to perfo~ the preliminar,y tests with the use of chlorine water,
spent lubricating oils and kerosene. As the TEL absorbers additional tests
were made with 10% alkaline soap water. Exhaust ventilation air was aspirated
through. the chemical fluid fn ter containing the 10% alkaline soap water at
the rate of 0.3 m/sec and at 11.20. The resulting data are listed in Table 1.
The results show that with a TEL concentration of 1.22 to 2.3 mg/m3 the average
purification amounted to 19.6%.
-210-
-------
/1
;:/-~t-=
5
--' - . -- - ----.-
, '"
~bt~~
~;n;._l.- -
.
o
- ----- --
I -(3
Plan of wet chemical filter for the purification of
exhaust ventilation air in the manufacture of tetra-
ethyl lead
I - Electric motor, 2 - olutch, 3 - bearing, 4 -
shaft, 5 - spr~ disk, 6 - eliminator, 7 - fender
board, 8, 9 - extension supports; 10 - legs, 11.-
air intake and output extensions, 12 - peep window,
13 - emptying valve, 14 - hatoh with peep window,
15 - water level gauge, 16 - solution intake pipe,
17 - filter bodT.
abp - Air. before purifioation
aap - Air after purification
TABLE
1.
Deeree of air purification frCIR tetraet~l lead 'b7 .
1O'.C solution of alkali.
:Before
filtration
Tetraeth.T1 ~ead oonoentration in 1MIJRJ
I Atter . Before I
I filtration I filtration
Atter
filtration
1.22
1.38
1.53
1.38
1.83
0;92
1.07
,1.22
1.07
1.38
2.30
2.30
1.84
1.99
2.30
1.84
1.99
1.53
1.53
1.99
Ten tests were made using spent lubricating o11s as the absorber. The
rate of air aspiration through the filter amounted to 0.6 m/sec. Results are
presented in Table 2.
It can be seen that atomized spent lubricating oil also yielded unsatis-
facto17 results, the average purification amounting to 30.9%.
Tests were then conducted using a mirlure of water with mono- and dietq1-
pheD1'lpo17glycol ethers as the absorber. 10 ml of each ester was added to 84
-211-
-------
TABLI
2.
Degree ot air purification from tetraeth1'l lead b7
apent lubricating 011.
'1'EL concentration in w.J I 1m, ooncentration in w.J
Test I Before I After I Test I Before I After
.0. : filtration: filtration I .0. I filtration i filtration
1
2
3
4
5
1.91
1.01
1.15
1.53
2.14
1.01
0.62
0.62
0.88
1.39
6
7
8
9
10
1.76
2.45
2.29
1.91
1.91
1.65
1.76
1.76
1.65
1.15
y
1i of water, higher concentrations of mono- and diethy1phenilp01yg1ycol esters
caused exqessive foaming which clogged the filter. The rate of air aspiration
through the filter was 0.3 m/sec and the air temperature 200. Results of 20
tests are presented in Table 3.
TABLE
3.
Degree ot air purification from tetraethyl lead b7
water oontaininC mono- and diethylene ether.
T]J. concentrat~on in mJdm" I ~ concentration in mgJ~
Teet! Before i After I Teet: Before I After
WOe i filtration: filtration: .0. I filtration: filtration
1
2
3
4
5
6
7
8
9
10
3.0
2.5
3.0
2.5
4.0
4.0
4.0
5.0
4.0
5.0
2.0
2.5
2.0
1.5
1.5
2.0
2.5
3.0
4.0 .
3.0
11
12
13
14
15
16
17
18
19
20
4.0
6.0
6.0
6.0
1.38
0.61
1.07
4.44
6.27
6.27
2.0
2.0
3.0
4.0
1.07
0.46
0.37
3.06
3.98
3.52
The data show the extreme unevenness of air purification from TEL obtained
with the use of this absorber. In tests number 2 and 9 no purification was
obtained. . In other tests the air purification reached 60 - 66%. Average
purification of all 20 tests was 40%.
It is known that an addition of a small amount of household soap to water
increased its emulsifying properties. ,Therefore, its power to purify air from
TEL was tested next in 1 and 3% solutions. The 1% solution of household soap
-212-
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at air aspiration of 0.3 m/sec yielded an average purification of 33.8% and at
0.6 m/sec the purification amounted to 33.6%.
The results of tests with the 3% solution of household soap are presented
in Table 4.
TABLI
4.
Degree ot air purification from tetraeth;yl lead b7
3% soluUon of household soap.
!~ concentration in wmj I tEL concentration in mgfmJ
Test I Before I After I Test i Before I Atter
110. I filtration: filtration I No. : filtration i filtration
1
2
3
4
5
3.45
3.56
3.56
2.68
2.80
2.03
2.03
1.77
1.65
1.77
6
7
8
9
10
2.93
3.56
4.33
3.69
4.20
1.77
1.77
2.29
2.14
2.29
TEL concentrations in the above tests ranged between 2.68 and 4.33 mg/m3,
the air aspiration rate was 0.3 m/sec, the air temperature 100 and average
purification amounted to 45.9%.
According to data found in literature, TEL reacted energetical~ with
haloids. Tests were therefore made to verify the effectiveness of using chlo-
rine water as an absorber of TEL from air. Chlorine water was prepared by
saturating tap water with chlorine gas. The air was drawn through the filter
at a rate of 0.3 m/sec at air temperature of 1°. Results are presented in
Table 5.
TABLE
5.
Degree of air purification from tetraet~l lead b7
chlorine water.
TEL conoentration in mgfraJ I TEL concentration in IDRImJ
Test I Before i Atter I Test: Before : Atter
110. I filtration: filtration: 110. I filtration I filtration
1 2.30 0.71 8 2.30 1.07
2 1.34 0.56 9 3.06 1.53
3 1.53 0.76 10 1.38 0.31
4 1.53 0.92 11 3.21 0.76
5 2.60 1.38 12 3.06 0.76
6 2.60 1.15 13 3.36 0.92
7 1.68 0.76
-213-
-------
As can be seen these tests produced the highest degree of air purification
from TEL. The TEL concentrations ranged from 1.34 to 0.36 mgfm3 and average
purification amounted to 61.1%.
mowing that TEL dissolved well in kerosene, the latter was used as an ab-
sorber in additional experiments. For the first series of tests a 1:6 ratio
of kerosene and water was tested first. The air was drawn at a rate of 0.3
m/sec at air temperature of 17.40. The results are shown in Table 6.
TABLB
6.
. Degree of air purification :from tetraeth;yl lead 'b7
kerosene.
,~ concentration in mgf~ : ~concentration in mgfe'
Test I Betore I After i Test i Before i After
_0. ! filtration filtration: .0. :" filtration: filtration
1
2
3
4
5
1.53
1.68
1.15
1.38
1.15
0.15
0.15
0.12
0.12
0.09
6
7
8
9
10
1.91
1.76
1.15
1.01
1.01
0.60
0.45
0.09
0.11
0.11
It is seen from data in Table 6 that with TEL concentrations of 1.01 to
3 " "
1.91 mg/m the air purification in some tests .as 90% and above. The average
air purifioation amounted to 85.5%. The next series of 10 tests were conducted
with 2:5 ratio of' kerosene and water. The TEL concentrations in the air ranged
between 1.73 and 2.04 mgfm3, air aspiration was 0.3 m/sec. The resulting average
purification was 88.-,%, i.e., higher than in the preceding test series.
The next test series were conducted with the same 2:5 kerosene and water
ratio, but the air was drawn through the filter at a rate of 0.6 m/sec at a
temperature of 110. TEL concentration in the aspirated air ranged between 2.04
3 "
to 4.59 me/m. The average purification attained was 86.96%.
Supplemental tests with a 2:5 ratio kerosene and water, 1.91 - 4.2 mgfm3
TEL concentration, 7.60 temperature and 0.3 m/sec rate of air aspiration, pro-
duced an average purification of 90.1%. In isolated tests the purification
was as high as 96%.
Due to the particular oonstruction of the fluid filter and its mechanism
of operation, only the upper"layer of the absorber fluid was dispersed into the
air. Therefore, the kerosene was poured into the filter simultaneously with
the water, whioh was more economical. The kerosene was regained b1 blowing
-214-
-------
through it su1:f'ur dioxide or chlorine gas. Laboratory tests indicated, that
in both cases a orysta11ine residue precipitated from the kerosene.
The degree of air purification from TEL oan be raised by a 2 - 3 stage
purifioation prooess, using 2 or 3 oonsecutive filters.
The lowest TEL oonoentrations remaining in the air atter purification were
0.09 - 0.11 rD8/m3 and high~st were 0.60 - 0.76 rD8fm3. Average TEL concentra-
tions after filtering in single test series were 0.12, 0.27, 0.22, 0.21, 0.44,
0.29 rD8fm3. Thus, atter purifioation through the filter, using kerosene as
an absorber, residual TEL air concentrations were of the order of ten thousandth
of mgfli. Aooording to data presented by the Gor'kii Institute of Labor ~giene
and Oocupationa1 Diseases of the Ministry of Health of the R.S.F.S.R., prolonged
contact with TEL conoentrations on the order of ten thousandths of mg/li pro-
duoed Chronio intoxioation. li 101-54 (Official Standard 101 of 1954) presoribed
no maximum pemissib1e ooncentration for TEL. Individual papers suggest that
the limit of allowable TEL conoentration for workshops be set at 0.01 - 0.005
mgfm3.. lio maximum permissible TEL concentration has been established for at-
mospherio air. The average TEL concentrations obtained in the air.purifioation
by means of fluid filters and the use of kerosene exceeded by 12, 27, 24, 54,
42, 58 and 88 times the maximum pemissible TEL conoentrations reoamnended for
work premises.
With the given method of purifying air from TEL and subsequent emission
through gas stacks 50 - 75 m high, followed by di3persion through the air, it
was possible to decrease TEL concentrations in the atmospherio air down to the
maximum permissible ooncentration standards recommended for work premises, and
possibly even below it.
Conclusions.
1. Effectiveness of 10% alkali, 1 and 3% household soap solution, chlorine
water, mono- aiw. diet~lphe~lpolyglycol esters, spent lubricating oils and
kerosene-water mixtures in 1a6 and 2:5 ratios. in the purification of ventilation
air from low TEL conoentrations has been verified.
2. Highest effectiveness was obtained by using 2:5 ratio of kerosene and
water and air passage of 0.3 m/sec. Purification reached 90.1 - 96%.
3. Kerosene Can be regenerated by using oompressed sulfur dioxide or chlo-
rine gas.
4. The. results obtained in air purification from TEL in the above experi-
ments were not adequate; therefore, the air was emitted into the atmosphere at
great heights to obtain the desired degree of the TEL dispersion.
-215-
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Disinfection of Air b.1 Dispersion or Evaporation of Laotic Acid.
:By
V. I. Vashkov, A. K. Astraf'eva and R. M. Ginzburg.
Gigiena i Sani tariya, No.9, 40-44, 1950.
Under certain conditions disinfection of air is a sanitar,y measure of
utmost importance. The problem of disinfecting air in the presence of people
is a highly complex one, the solution of which is still lacking. The different
methods proposed, such as irradiation by ultraviolet r~s, dispersion or
evaporation of disinfectants have not produced the hoped for results. Par-
ticular attention has been given in recent years to the bactericidal properties
of trietqleneglycol which, in low concentra.tions (1 g per 100 to 200 m3 ot
air) and relative humidity no higher than 60%, destroyed m~ airborne microbes
and viruses, such as staphylococcus, streptococcus, influenza virus, and others.
Reference to the bactericidal properties of other preparations were found in
Tru~ Tsentral'nogo.Nauchno-Issledovatel'skogo Desinfektsionnogo Instituta,
No.5, p. 5, 1949.
In the search for suitable disinfectants l~ctic acid was tested first.
Lactic or alpha-qdro~ropryonic acid [CH3CH(OH)COOH] contains an asymmetrical
carbon atom and, therefore, is available in three stere~isomeric for.ms. The
boiling point at 12 mID mercury pressure is 1190 and at 0.5 to 3 mm it drops to
82 - 850, the sp. gr. is 1.2. The bactericidal properties oflactio acid were
tested in the laboratory by the methods of evaporation and dispersion.
1. Bactericidal properties of lactic acid vapor. The eftect ot lactio
acid vapor on a culture of StaphYlococcus ~ suspended in the air was studied
in two boxes, one 2 m3, the other 14 m3. The laotic acid was evaporated from
a glass container, or small aluminum cups placed over electric hot plates or
alcohol lamps at a temperature ot 1500 to 1800, to concentrations ot 5, 7.5,
10, 11.4, 13, 15 and 20 ~ per m3 ot air, or 1 B per 50 to 200 813 ot air~ Air
aamples ot 15 liters were taken trom the boxes b,y aspiration at the rate ot 5
liters per minute. Control samples were taken immediately atter the culture
dispersion and the test samples were taken 10, 20, 30, 45 aDd 60 minute. after
evaporation ot the lactic acid.
The air was aspirated throUBh two lnterconneohd absorbers, each contain-
iDB 20 811 ot sterile p~siolog1cal solution. Three Petri d1ahe. were them
-216-
-------
innoculated with 0.1 ml, 0.5 ml, and 0.5 ml of the physiological solution and
incubated for 48 hours, after which the colonies were counted. Before studying
the bactericidal properties of the lactic acid vapor, attempts were made to
determine the falling out rate of the microorganisms suspended in the air. Air
samples were taken immediately after dispersion of the culture and 10, 20, 30,
45 and 60 minutes later. The results showed that 1 minute after dispersion of
a broth culture of Staphylococcus aureus the average of counts was 10,283 micro-
organisms per liter of air in the bOx, 6,839 after 10 minutes, 5,390 after 20
minutes, 3,027 after 30 minutes, 632 after 60 minutes. (The original text
gives the number as 7,632 which is obviously an error. B.S.L.). Thus, 31% of
the microorganisms settled after 10 minutes, 50% after 20 minutes, 72% after
30 minutes, and 94% after 60 minutes. These data were taken into consideration
in evaluating the effectiveness 'of the disinfectant.
Some chemical disinfectants were effective only at relative air humidity
of less than 60%; therefore, the bactericidal properties of lactic acid vapor
were checked under conditions of different relative humidity: 53 to 68% and
84 to 89%. The counts are shown in Table 1.
The data show that lactic acid vapor possessed high bactericidal properties
for airbome staphylococci. Thus, at 5 mg of the acid per m3 of air, the num-
ber of microorganisms after 10 and 20 minutes were respectively 4 and 10 ti~es
less, than in the control. The potency of the vapor increased with its concen-
3
tration. At vaporization rate of 7.5 mg per m , the number of microorganisms
decreased to 1/14 after 10 minutes and to 1/48 of the control after 20 minutes.
At vaporization rate of 20 mg per m3 the number decreased to 1/215 after 10
minutes and to 1/700 of the control after 20 minutes.
An increase in relative humidity bad a negligible effect on the bacteri-
cidal properties of lactic acid. For example, 10 minutes after the vaporiza-
tion of 10 mg per m3 of air at 57 to 68% relative humidit; the microorganisms
consti tuted 5.5% of the original number, and after vaporization of the same
amount of lactic acid at 84 to 89% of relative humidity the number of micro-
organisms in the air was 5.9% of the original. These figures lead to the con-
clusion that for all practical purposes 10 mg of lactic acid per m3 of air was
sufficient for disinfection regardless of the relative humidity.
2. Bactericidal properties of lactic acid spray. The experiment was per-
fomed in a 14 m3 box. The method of dispersing the culture of Staphylococcus
aureus and of sample collecting was similar to the one used in studying the
-211-
-------
Tab1. 1. Efteot ot laotio aoid:vapor OD airborne Stap~looooou8 a1bus
----...--_.._~.~. --.--- --- --"---"-__0- .-..-.
.1
Test OODdit1oDSjIlOrOOrgan- Mioroorganisms per 11 % Dead mioroorgani8ID8
, ' , , isms per 11 of air atter disinteo
! of air be- ;;l;~
LaoUo aO!d "0 of I. lIlOlauva~'" 41011>- 10 20 30 45 60 45 60
in ms/m ObSe~~jTempe~a~ _~~~d1t7 "teot~:__.._-_. D. min. min miD miD min m1
\
~ 7 15-18° 55-57% 1183 286 124 99 67 46 IT 9 89,5191,6 94,4 96,2
I ~,
15-2jO 54-68% 5940 3)9 122 83 67 30 97,9 98,6 98,9 99,5,
7,5 5 193,9
I
I\) 10 7 15-200 57-68% 5046 275 187 54 47 4) 94,7 96,3 99 99,1 99,1
....
'f
10 4 15-180 84-89% 3628 216 130 80 18 94',1 96,4 97,8 99,6
11,4 2 15-18° 53-57% 1955 16 8 7 10 - 99,2 99,5 99,6 99,5
13 158 620/0 1746 21 16 16 37 98,8 99,1 99,1 97,9
15 2 23-240 660/. 6955 381 45 33 16 94,5 99,5 99,5 99,8
20 3 22-24° I 53~/. 7733 36 11 6 2 99,5 99,9 99,9 99,9
-------
bactericidal properties ot vaporized lactic acid.
Atter dispersion of the culture 5 and 10% aqueous solutions of lactic acid
were sprqed into the room at a pressure ot 2 atmospheres b;y a glass atomizer
for 6 to 10 minutes. The consumption of liquid was determined fran the dit-
fersnce in container weight betore and after spraying. Room temperature varied
between 150 and 170, and the relative air humidi 107 between 60 to 70%, the ex-
posure lasted 5, 8 and 15 minutes. The lactic acid was tested in concentrations
of 5, 6, 8, 9, 10 and 11 mg'per m3 of air. The results are presented in Table
2.
Table 2. Eftect ot lactic acid aerosol spr~ on
airborne Stapqlococcus albus. Data represent
averages ot three experiments
Test conditions Bo. ot microorganisms Dead micro-
per liter ot air. organisms
Atter disinf. in %
Lactic Tem- Relative Betore
::i~ perat. humid- disin- 5 8 15 5 8 15
it7 fection min III1n m1n ain min miD
5 15-170 688/0 3090 840 860 620 73,3 72,2 80,0
6 15-170 7()e/. 1870 520 620 600 72,3 66,9 68,0
8 15-170 60-68" 3250 370 110 35 88,6 96,7 99,0
9 15-170 62-680/. 2900 91 45 25 97,0 98,5 99,2
10-11 15-178 62-68'/. 3000 70 25 23 98,7 99,2 99,2
Results ot observations indicated that lactic acid spr~ was increasing17
effective in concentrations ot 5 to 8 mgJm3. 'lith a spr8l' dispersion of 9, 10
and 11 mg per m3 ot air, 99.2% of the microorganisms were dead after 15 minutes.
The data in Tables 1 and 2 indicate that vaporized or dispersed lactic
acid possessed high bactericidal properties for cultures ot StaphYlococcus
..!ll!:!:!!. suspended in the air. Thus, at a dispersion of 5 mg ot lactic acid per
m3, 68% ot the microorganisms died atter 15 minutes, at similar vapor concen-
trations, 76% died after 10 minutes. As the lactic acid concentration in the
air increased, its eftectiveness as a disinfectant rose. In vaporizing lactic
acid it should be borne in mind that heating to 1400 decomposed some acid into
an anh¥dride. Theretore, it should not be placed direotl7 over an open flame,
but vaporized from a vessel suspended 4 - 5 em above the flame, or it should
be placed over a l~er of asbestos.
-219-
-------
Lactic acid has several advantages over other air disinfectants. It 1s
not alien to the animal organism, since it is contained in food products. It
is a flavoring substance and a preservative used in making lemonade, extracts
and essences. Since the acid possessed bactericidal and bacteriostatic prop-
erties, as it accumulated in fermentation processes, it destroyed the micro-
organisms responsible fcr fermentation and putrefaction. Laotic acid is used
to destroy bacteria in wine mA~~ng and beer brewing. It is also used tor the
preservation of anatomical preparations and microscopic slides.
Lactic acid is used in medicine, e.g., in di.phtheria (inhalation of 5 to
6% solutions). It is recommended for achylia in combination with hydrochloric
acid. A 1% solution of it is effective as a stomach wash. All this shows that
lactic acid can be used safely as an air disinfectant in the presence of humans.
V. I. Vashkov's experiments showed that lactic acid vapor in amo\mts exceeding
bactericidal doses by 10 times, or 100 mg per m3 of air, had no effect on white
mice.
Spray or vaporization of
99% of the white staphylococci
It is harmless to white mice.
Conclusions.
lactic acid at the rate of 10 mg per m3 destroyed
suspended in the air within 15 to 20 minutes.
Effect of Atmospheric Pollution on the Bactericidal
Effectiveness of Solar Radiation.
By
A. P. Krupina, D. M. Tyukov and A. M. Ponomareva.
(The Leningrad Scientific-Research Sanitar,y-Hygienic Institute).
Gigiena i Sanitar~a, No.8, 15-18, 1954.
Studies of the bactericidal effectiveness of radiation energy were limited
to artificially produced radiation. It was established that the range of the
-220-
-------
ultra-violet spectrum was the one which manifested bactericidal properties.
The latter depended on the wave length and its radiation intensity. According
to present-d~ assumption m~Timal bactericidal action was exerted by wave
lengths ranging between 254 and 251 m~. Denoting their bactericidal effect
as a unity and the radiation effect of other wave lengths in fractions thereof,
it is possible to plot a curve of relative bactericidal action of radiation
emanation.
It is known that the short-wave range of solar radiation reaching the
earth's surface ends at wave length of about 295 m~. In the polluted atmos-
phere of industrial cities this limit shifts toward the long-wave range within
limits determined by the intensity of the atmospheric air pollution. According
to D. M. Tyukov's observations the short-wave range of solar radiation in
Leningrad at noon or at the sun's position at 53.60, terminates on the average
at a 304.6 m~ wave length, and only at optimum meteorological conditions does
~t extend to waves 300 m~ long. Under such conditions the solar spect:nun is
devoid of radiation of relatively high bactericidal effectiveness. Its highest
effectiveness of 295 m~ wave length is 6.6 times lower than the maximum ef-
fectiveness of waves 254 m~ long. Nevertheless, the intensity of solar radia-
tion is such that the bactericidal power generated by it is still considerable.
Fig. 1 presents a mean curve of
the power of bactericidal radiation
in mCb/am2 in Leningrad drawn from
direct measurements of energy distri-
bution over the solar radiation spec-
I
t:nun.
32
30
III
Q) tfB
i~6
rd,
.s144
842
~ 40
~JB
....
fH Jfj
o
834
:aJ2
~
~JO
Pt
,230.6 1.0 1,4 1.8 2,2 2,6
Bactericidal solar radiation
in mcb/m2 .
'Ia& 1 Bactericidal solar radiation
~.I.g. .
in Leningrad.
./ /'
V
/
/
V
/
/
r -
/
/
J 1
I ...~
I
I
Observations for the determina-
tion of the effect of the bactericidal
action of solar radiation were made
dur~ March and October before and
after noon-time while the sun was
1 Bact. (b) - unit of bactericidal
emanation. Bact. is the bactericidal
emanation ~ 254 - 258 IDj.I wave length,
with an energy of 1 w. Microbact.-
mcb - one thousandth of a baot.
-221-
-------
shiDing. A strain of StaphYlococcus aureus was taken as a test object after
. .
its biological properties were established. Petri dishes containing sugar
agar were innoculated and exposed to direct solar radiation. The tests were
carried out in duplicates: one dish was kept open, the other was covered with
ordinar.r window glass. Exposure time varied from 10 minutes to 2 hours.
Bactericidal irradiation fluctuated within the ranges of ~9 to 318 mCb/cm2.
The sun exposed Petri "dishes were incubated for ?4 hours at 370 C, and the
number of developed colonies was counted. Non-irradiated Petri dishes similarly
innoculated and incubated served a8 control. Fourteen series of observations
totaling 132 tests were thus conducted.
Fig. 2 presents survival rate curves. The results show that for the de-
struction of 90% of the staphylococci in the open dish a 12 - 13 mCb/cm2 ir-
radiation was required. Further increases in the bactericidal radiation brought
about only slightly increasing depressing action. At 90 mCb/cm2 radiation
surviving microorganisms amounted to 1%. Apparently the surviving microorganisms
possessed considerable resistance, as shown D.1 the fact that an increase in
radiation up to 318 mCb/cm2 failed to destroy them completely. The lowest
number of surviving staphylococci amounted
to 0.04%.
\.t
o
i
o
Jot
4:
r--
I I
J:
r
,
\.-
\: "
""
", '... -
..
1:
.
1)
.!
J
~
-i
. 3D gO ISIJ 190 J1Q
Bactericidal solar radiation
in mCb/cm2.
Fig. 2. Percent of surviving
micro-organisms.
1 - Irradiation in open Petri dishes.
2 -. Irradiation in Petri dishes cov-
ered with window pane glass.
The second curve on the same Fig. 2
shows death rate of staphylococci exposed
to solar radiation through window glass.
Bactericidal action began to appear at 15 -
16 mCb/cm2 radiation. Further increase in
radiation intensity led to a slower rate
of bacterial destruction as compared with
2
the direct exposure test. At 30 mcb/em
radiation, the number of surviving bacteria
amounted to about 30%, and at 90 mCb/cm2
intensity 9% of the staphylococci survived,
only at 185 mCb/cm2 was the number of viable
cells reduced to 1%. No complete steriliza-
tion of cultures was observed in e~ther the
open or covered dish tests. A comparison
of both curves clearly shows that bacterici-
-222-
-------
dal effect of solar radiation on hemolytic Staphylococcus aureus was weaker
in tests with the glass covered Petri dishes. In order to attain a similar
effect, for example, a 90% destruction of the microorganisms, 13 mCb/cm2 are
required for the open dish radiatj,on and about 80 mCb/cll, i.e., 6 times as
much - for the glass covered dish.
One hundred and sixteen strains were isolated for the study of the biolog-
ical properties of toxigenic Staphylococcus aureus af~er exposure to solar
radiation. The results indicated that a relatively prolonged effect of sun
radiation (2 hours) even in the swmner at the height of sunshine had practically
no effect on pigmentation, and only in a few cases was there weakening in the
color intensity. Hemolytic properties and ability to coagulate the blood plasma,
. .
tests used in determining the culture's toxigenicity remained unchanged in all
the isolated strains.
One of the characteristics of toxic Staphylococcus aureus is its smaller
size. Results of observations showed that while biogenic properties of the ex-
posed staphylococci remained unchanged, the size of the cells was notably in-
creased. In addition to the usual grape cluster type of' distribution on the micro-
scopic slide there appeared a type of rod-shaped agglutination distribution.
Conclusions.
1. Dir~ct action of solar radiation on toxigenic Staphylococcus aureus
cells in open dishes and under conditions of polluted atmosphere destroyed
considerable number of them at 12 - 13 mCb/cm2 radiation.
2. To achieve equal bactericidal effect in tests with glass-covered
dishes a 6 times higher irradiation was required.
3. Isolated strains of toxigenic Staphylococcus exposed to the action of
solar radiation retained their hemolytic ability and plasma coagulation, but
microscopically the size of the cells appeared enlarged.
-223-
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An Investigation of the Pbytoncidal Action of Live Plants.
:By
B. C. Drabkin and A. V. Dumova.
(Chkalov Institute of Vedicine).
Fitontsidy, iy~ Rol' v Prirode,_Izdat. Leningr. Univ., 22-31, 1957.
B. P. Tokin frequently stated that p~toncides were primarily an ecological
problem, ,which opened up new possibilities for the utilization of plants in the
sanitation of the environment in particular for freeing the air from pathogenic
ID1croorganisms. It is now certain that volatile and non-volatile active p~-
toncidal substances emitted by plants into the surrounding medium can affect
the microorganisms prevailing in the medium, including the airborne microflora.
This highly important aspect of phytoncides has not been fully investigated.
Vost of the recent research dealt with homogenized ground plant tissues. The
value of such procedure applied to the investigation of phytoncides can not be
denied. Nevertheless, the present authors believe that the ecological aspects
of the problem can not be developed without experimentation with intact, live
plants under natural conditions. It is known that tissue grinding disturbed
~he normal processes of enz.yme activity and markedly enhanced ~drolysis and
thereby led to the fo~ation of substances normally not present in the tissues
of intact plants, or present in minute quan'tities. Hence, in addition to ex-
periments .!!!. vitro. tests should be made with living uninjured and injured
plants. Only such a study of phytoncida1 activity can offer a basis for the
sound selection of plants for the ~gienic cleansing of air of pathogenic
microbes.
During their investigation of airborne microflora under natural conditions
surrounding different plant groupings, Xovalenok, Tokin and Yanovich discovered
in 1954 that the composition of air bacteria differed in pine forests, birch
groves, thickets of bird cherr.y, etc. The authors assumed the differences to
be due to the specific properties of the volatile phytoncidal complexes emitted
by the different plant groups. The present authors undertook to investigate
experimentally the w~ in which the volatile substances emitted b.y live intact
plants affected the microflora of the surrounding atmosphere. The first set of
experiments was conducted in a 144-liter glass box equipped with a ventilator,
one side of which had a small opening capable of being sealed he:rmetically.
-224-
-------
Two metal tubes were inserted through the bottom of the box at opposite ends.
Air entered the box through one of the tubes. To prevent bacteria from gaining
entrance into the box during the experiments a cotton plugged ourved glass tube
was connected to the extruding end of this tube. The second metal tube was
joined to the air intake tube of a Shafir apparatus used for the detemination
of the extent of bacterial air contamination. Shafir's method simplifies the
collection of samples. It also serves to maintain the airtight condition of
the box, and prevents further pollution of the air during the investigation
(Fig. 1).
a
b:
~
-
I
I
I
I
I
t
t
I
t
I
I
I
....,. ---
",r-- -
...
d
~
:;-- "
c
A known volume of air is
passed through Shafir's appara-
tus for 10 minutes; the air
suspended bacteria forced by
centrifugal action are caught
by a nutrient medium inside
special glass oylinders. Meat-
peptone agar of pH 1.6 is used
as the nutrient medium. The
cylinders are incubated at 320,
and the colonies counted after
48 hours incubation.
The effect of plants on the
Pig. 1. Setup for the stu~ of intact plazrt
effect on airborne microflora airborne microflora was judged
a - BoxJ b - Shatir apparatusJ c - inflow
tubeJ d - outflow tubingJ e - mixing faD. by the number of colonies developed
in the sample after 24 hours ex-
posure in the experimental box, as compared with the number of colonies which
developed in two controls. There were three air cultures for each experiment;
two controls and one test. Ten plant species were tested: Lolium perenne,
Festuca rubra, Pelargonium graveolens, Pelargonium zonale, Chrysanthemum
.!.ndicum, large and small flower, Cyperus alternifolius, Begonia spec., Asparagus
spec., and Tuja occidentalis. The house plants were placed in the box in vases,
the rye grass and fescue in seed boxes. Nine to eighteen experiments were
performed with each species. In addition, there were two series of special
control investigations: one an-empty box closed for 24 hours, the other box
contained a vase with-soil but no plants. The results are presented in Table 1.
-225-
-------
'l'ABLE
1.
Effect of some plants on airborne mioroflora.
Plant species
. J
I. Number i
of .
: i
: tests:
: J
Average. :
:
number of J
colonies in i
controls i
Average
number of
colonies
in tests
J Percent
I reduction
I in number
i of colonies
Fuscue rubra
~egrass, pasture
Geranium
Pelargonium
Chr,rsanthemum, large
Chrysanthemum, small
Cyperus
Begonia
AsparaeuB
Arborvitae
Box, no plants
Flower vase control
9
10
18
9
10
10
10
10
10
10
20
8
33
101
141
42
93
76
99
23
39
48
74
29
20
43
79
23
42
26
41
13
24
16
67
25
39
58
43
45
55
66
59
43
38
67
9
14
The recorded data indicate that under the influence of the plants the
number of microorganisms in the box air was considerably reduced. The highest.
decreases occurred with arbor vitae (61%), small-tlower chrysanthemum (66%),
galingale (59%), ryegrass (58%), and large-flower chrysanthemum (55%). The
effects of the other plants were less signifioant. The decrease in number of
microorganisms in the oontrols ranged between 9 and 14%.
The decrease in number of microbes in the air in the presence of the plants
may have been caused either by (1) the action of volatile substances emitted by
the plants, or (2) by the bacteria settling on the plants' surface. The method
used in this series of experiments prevented the clear determination of the
importance of each of the possibilities mentioned. Therefore, another approaoh
was adopted in the next series of experiments, whioh made possible the differ-
ential stu~ of the effects of volatile pbytoncides liberated by live leaves
and of other factors. A chamber was set up for the study of the action of
volatile pbytoncides from leaves of intaot plants (Fig. 2).
The chamber was essentially a plastic box 14 x 10 x 1 em covered b,y a
hinged lid. Fig. 2 illustrates its oonstruction and the method of its operation.
Leaves of the intact plant were fitted into the box and the lid was tightly
olosed. Three sterile glass slides with ~ops of bacterial suspension ~n
physiological saline were placed over special openings 1 em in diameter in
-226-
-------
o
a
fig. 2. APparatus for the stu~ ot whol.
leat pqtonoides
a - Kotch for the leat stemJ b - lid look,
o ... round openings for haDgiDg drop prep-
aratioDs, d - clamp fasteners
the lid 2 em apart. The drops
of the bacterial suspension were
exposed to the effects of the
volatile substances of the plant
leaves. The slides were securely
fastened with ~lamps. The microbial
suspension 0.3 to 0.5 em above the
leat surface became engulfed b.J
the vapors of volatile pbytoncides
emitted by the leat. The tecbnique
of the control tests was the same
but the leaves were excluded.
Staphylococcus aureus and
Bact. .2.2!!. (!. coli) served as
the test objects.. Eighteen hour cultures of these microorganisms were diluted
with sterile physiological saline to a concentration of 1 x 106 bacteria-per
ml. Atter 1, 3, 6 and 8 hours exposure the control and test drops were trans-
ferred onto meat-peptone agar plates and incubated at 37.00 for 48 hours. The
developed colonies were then counted. The experimental data are presented in
Table 2.
TABLE
2.
Ettect of 'Volatile pqtoncides of liv. UDdam&ged leaves of
some plants on microorgan18JDs.
I I Number of developed colonies
I Expo- i
Plant species Staph. BUreuS I E. co11
i sur. in I
! hours i
- I Test I Control I Test
Control I
1 1,389 "566
Geranium 3 1,700 179 1,303 285
(Pelargonium graveolens) 6 824 0 803 0
8 1,370 0
1 + 458
Birch 3 + 178 + +
(Betula verrucoaa) 6 517 0 + +
8 + +
Bird chen'7 1 + + + +
j + + + +
(Padua racemosa) , + + + +"
-227-
-------
The data show that non-severed geranium leaves emitted volatile substances
having antibacterial power against the gram-positive Staphylococcus aursus and
the gram-negative colon bacillus. Tbe number of microorganisns decreased in
one to three hours after the experiments began. Six hours exposure to the
volatile substances of geranium leaves completely sterilized the drops 'of
bacterial suspension. Photographs of the results of one set of experiments
are shown in Figs. 3 and 4.
:.. "" ,
-:. .~ .
-.::r;::1i'$-.
J.:..~',r,"~~:i
:~;. ~~: ~'{.t~ .~.
: 1:~~.;:-.iI'.'; ',,~r
.,'{ A~
... :1'0 ,
,
o
Ihour
O.
3 hours
C
6 hour8
fig. 3. Etteot ot volatile pq'tonc1des of live
geranium leaves on Staph. auraus.
Upper halt - experimental, lower halt - control
C.
3 hours
c '
6 hoan
c~
8 hours
Pig. 4. Eftect ot volatile pq'toncide8 ot live
geranium leaves on E. co11.
Upper half - experimental, lower halt' - control
Birch leaves had a
similar etfect on Staph.
auraue. !. sill proved
resistant to the pbytoncides
of birch leaves. Bird cherry
leaves manifested no appreci-
able antibacterial effect.
Comparison of .!a Y!!2. re-
sults with those of in vitro
--
tests brought out notewortby
differences between them.
The cODlllinuted bird cherry
tissue emitted a large quan-
tity of volatile substances
baving potent pbytonoidal
properties. The UDsevered
intaot bird oher.r,y leaves
emitted less of the substance.
The last statement applies
only to live, uninjured leaves;
specific types of injur,y
caused to the tissues of the
bird cherry brought about the formation of significant quantities of volatile
highly active substances as sh~ in special experiments. According to the
literature, ground geranium leaves possessed potent pbytoncidal properties.
The results of the experiments-here recorded showed that intact unsevered leaves
of this plant emitted large quantities. of volatile pbytoncides of marked anti-
bacterial potency and that the emanation of volatile pbytoncides seemingly ceased
during the process of the plant tissue grinding. Birch tissues manifested
-228-
-------
significant phytoncida1 activity in the intact and ground up condition.
The results of the experiments herein recorded showed convincingly that
some plants, such, for instance, as the gerani~ and the birch, emitted into
the atmosphere large quantities of active ph1toncides when intact and unin-
jured. These plants may be used to free the air of pathogenic microorganisms.
Other plant tissues possess marked phytoncida1 properties atter gr1nd~ or
atter injury and. none under normal conditions.
Thus, the experimental results indicated that the degree of phytoncidal
aotion of living uninjured plant tissues at times differed considerably from
the aotion of ground tissues in the same plant. The differences JDaY' be at-
tri buted to th~ diff~rence :1.n the chemioal structure of the ph1tonoidal sub-
stanoes and the mechanism by which they are generated in the particular plants.
The deorease in number of airborne mioroorganisms affected by piants ~ be
oaused by the volatile phytonoides they emit, and by the settling of bacteria
on the plant surfaces as well. Many mioroorganisms, including pathogens,
settle on the surfaoe of leaves, the total area of which is extensive. The
question may be asked: what happens to suoh pathogens? Do they retain their
viability or do they perish? The death of the microorganisms settled on the
leaves JDaY' be caused q, non-volatile antibaoteria1 substances emitted by the
plants. Some authors described the setting free by higher plants of non-
volatile substanoes toxic to other organisms. The possibility that bacterici-
dal substanoes ~ be present in such non-volatile substances emitted q, higher
plants can not be exoluded. Some of Z. L. Gal1keiev's 1953 data support such
an assumption.
To throw more light on this phase of the problem, a thorough stu~ was
made of the effect on the settled microorganism. Leaves of experimental plants
were spr~ed by an atomizer with a bacterial suspension in physiological saline.
Immediately atter spr~ng and also atter 1, 3 and 6 hours sections were taken
from the same leaf with a sterile cork borer 15 mm in diameter. The sections
were plaoed over the surface of meat-peptone agar in Petri dishes for 10 seconds,
and then removed. The Petri dishes were incubated for 48 hours and the developed
colonies were counted. By this method it was possible to follow the changes in
the number of microbes on the surfaces of the leaves and to determine the degree
of their antibacterial effect. Sterile slides were sprayed with the same
bacterial suspension and similarly tested for control purposes. In these tests
dilutions were used of l8-hour-old cultures. of StaphYlococcus aureus. A 1 m1
-229-
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of the dilution oontained 1. million baoteria. The experiments were performed
in the laboratory during the months of May and June, using intact house plants
and leafy shoots freshly cut from trees. The results presented in Table 3 show
.that most of the Staph7lococoal cells on the surface of poplar and birch leaves
died during the first 3 hours; in most of the experiments no viable staph7lococci
remained on the leaf surfaces atter 6 hours. Fig. 5 presents photographs of
one such experiment.
TAl\LE
3.
Erfeot of intact leaves of some plants on golden staPhTloooccu8
in direct contact w.ith their surtaoe.
Plant
specie 8
: :
: :
I Test I
: 110. I
I i
Geraniua
1
2
3
l\1rch
1
2
3
Poplar
1
2
3
Arborvitae
1
2
3
1\1rd chen'T
1
2
3
Linden tree
1
2
3
Staphyloooocus aureus impression growth in hours
o
Control: Test
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
-230-
I
:
3
I
:
: Control 8 Test
8 Control 8 Test
+
+
+
+
+
+
+
+
+
13
21
7
+
Single
col~
2
o
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
6
+
+
+
Single
oolOlV'
o
o
o
13
o
+
+
+
+
o
o
o
+
+
+
+
33
57
Single
oolony
+
+
+
+
+
+
+
+
+
+
+
+
+
-------
Leaves of geranium and ot '
white cedar have well detined,
though less potent, antibacterial
properties. The ettect ot bird
cher17 and linden on Staph. aureus
brought into direct contact with
the sUrface of the leaves could
not be determined in the laborato17.
Thus, the results indicated that
certain living intact plants emit-
ted active phytoncides capable of
destroying airborne pathogens by-a
. (1) emitting volatile phytoncides,
Pig. 5. Efteot ot live leaves ot the poplar and (2) by generating active pq-
and. ot the birch on surfaoe innooulated tonoidal substances lethal to
Staph. aur8US.
P - poplar, :B - birch, C - oontrol microorganisms which settled on
the surface of the leaves.
"
:B
:B ' P.
. . ....
~~;h):f;
~,
-------
Emission of Pbytoncidal Substances b.1 Cereal Grains.
By
N. V. Novotel'nov and I. S. Ezhov.
Leningrad Technological Institute of the Refrigeration Institute.
Fitontsi~, ikh Rol' v Prirode, Izdat. Leningr. Univ~, 40-47, 1957.
The importance of yellow flavonoid pigments in protecting plants from
, ,
various bacterial infections was discussed in a previous paper on the hip-
bearing rose. The ,antibiotic effect was thought to be connected with the
propert7 of aglucones produced b.1 the hydrolysis of flavonoid glucosides to
block the activit7 of enzyme s7stems which participated in microbial aerobic
respiration. A search .as made for ~im1lar phenomena in the plant world in
seneral. Cereal"' grains were studied first. Common experience pointed to the
fact that grains falling into the soil were not affected by microorganisms
despite the fact that the conditions were favorable: ' abundance of moisture
and predominanoeof microorganisms. Suoh anti-microbial resistance has been
oorrect~ conneoted with the life prooesses of the seed or grain. ' In this
conneotion the question arose: what was the mechanism by whioh seeds and
grains were protected against microbial attaok before germination when all
, vital fUnotions were still inactive? There must be some antibiotic substanoe
or substanoes whioh safeguarded the seeds in the moist soil.
Most inve~t'igators conoerned with the problem of seed germination regard
moisture absorption by the seeds as the primary aotive faotor in the prooess
of seed germination. In doing that th87 lose sight of the faot that moisture
is drawn from the grain after its swelling. A. B. Blagoveshohenskii conoluded
that seed sermination was held baok by carbonates. Results of experiments in
sOaking barley seeds led to the conolusion that two prooesses'took place in
soaking: absorption of moisture and emission into the surrounding medium of
some substances which colored the water pale yellow. A stu~ was made of the
nature of these substances and of their biologioal significance. On the as-
sumption that the substanoes. emitted b.1 seeds during soaking were flavonoid
glucosides, attempts were made to isolate them in pure form. Advantage was
taken of the fact thatgluoosides were not preoipitated by lead acetate in
aoid solution; exoess of lead was removed b.r Na2S04 and H2S. The solution was
then conoentrated by vaouum evaporation and repeatedly treated with aloohol,
-232-
-------
which was driven o~f b.Y distillation. The isolated flavonoid glucoside fraction
was tested for antibiotic properties by the Petri dish and by the dilution meth-
ods against different saprophytic microorganisms. The results showed that the
preparations possessed a comparatively high bactericidal potency of a broad
antibiotic spectrum. Similar preparations were obtained from wheat seeds which
were checked for antibiotic effects against phytopathogenic bacteria and, par-
ticularly, on bacteria attacking cotton seeds and sprouts. The data are'pre-
sented in Tables 1 and 2. Tests for the bactericidal effects of the prepara-
tions in 1:100 to 1:500 dilutions on the same phytopathogenic bacteria resulted'
in complete inhibition\ of bacterial growth. Further experiments showed that'
treati~ cotton seeds with the preparation not only inhibited the growth of
pathogenic bacteria, but also enhanced gemination of t,he seeds and stimulated
growth.
TABLE
1.
Effeot of the preparation on microflora attacking ootton (selection 108 f).
(Aocording to F. B. Xhetagurova).
Bature of
experiment
ill
. 1 Number of colonies I
II.
. GermiD&-' 1
i iPs. malva-i Epiphyte:
I tion in % 1 ceae in 1 bacteria ,I
. . .. I
i 1111000 diU 111000 1
Remarks
Treated .i~h 11300
dilution of prep'n
93.0
o
o
Slow gemination,
bacteria infested
, ,
orop
Aotive germination,
no bacteria
infestation
Ditto
Ditto
Control, untreated
92.0
28
81
Ditto 11500
Ditto 11700
97.0
98.0
o
o
4
5
It is believed that this phytoncidal effect on saprophytic and pathogenic
bacteria was due to the ability of the yellow grain pisments to block enzYmic
systems of, aerobic respiration of microorganisms, and that the pisments pl~ed
a similar role in the process of seed gemination. To check this assumption
and to determine the distribution of these substances in the main constituents
of barley grains, (capsules, aleuronic l~er, and endosperm), extracts were
made of such grain and infiltrated into intact and polished barley seeds in
purified and unpurified form.
-233-
-------
TABLE
2.
Baotericidal effect in minutes of vo1atlle fractions of the preparation on
ph1topathogen1c bacteria.
Bacterial species
: Dilut1cm- of preparation
.
.
:
.
. :
: 1:0 1:2 I 1:4 : 1:10
. : : :
I I . :
1 1 2 4
1 1 2 J
1 2 2 5
1 J J - 4 5
1 2 4 6
:Bac1i. &rideaa
:Bact. carotovorum
Ps.xanthochlorum
Ps. heteroceUID
Ps. herbico1a-
Remark: At the end of the time above 1nd1cated the volatlle ph1toncide
fractions stopped all bacterial growth.
'!'he method of infiltrating the above-mentioned seed parts with the con~
cent rated extracts was the same as that used to determine germination abili t1',
i.e., each sample consisted of 500 seeds of known moisture content and weight,
these were soaked in the corresponding extracts in funnels. '!'he extract con-
centrations in all samples were equivalent and were calculated on the basis
of the reducing substances amounting to 6.5 mg per 1 m1 of the solution ex-
pressed in tems of glucose. Seeds were soaked in the solution 4 hours, air
dried for 16 hours and again soaked for 4 hours in the same solution. Control
tests were made in a parallel manner. After 24 hours soaking the swollen seeds
were placed for germination in the tunnels, covered with periodicallY' moistened
fil ter paper and allowed to germinate. Five days later the rate and extent of
the seed germination were determined; the sprouts were separated from the seeds;
- 0
both were dried to constant weight at 50 to 55. B1' the usual gravimetric
method the losses in dr,y seed matter due to respiration and to the sprouts
were determined. The experimental data are presented in Table 3.
The results establiShed the fact that biologically active substances
present in seeds were concentrated in the peripheral part and were practically-
absent in the endosperm. Infiltration of these substances into seeds in con-
centrated form impeded germination and completely arrested losses in dry ~atter
due to respiration. Increase in dr,y matter noted in the experimental samples
resulted from the absorption of these substances b1' the seeds. The experi-
mental data confirmed the previous assumption that the antibiotic effect on
pbytopathogenic microflora was due to the arrest of the aerobic processes of
microbial cells.
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TABLE 3.
Effect of extracts of constituent parts of barley grain on its own gemination.
'Ge. I 1os8 in dry matter on
I :rm1na-1 fifth day ot growth
I .
Bature of experiment I tion i
I in % I By respi- : By I Total
I I ration I sprouting I 10s8
: I
Intact grain soaked in tap 96.0 5.06 7.59 12.65
water. Control
Intact grain soaked in extract 0.0 +4.78 0.0 +4.78
of grain epide1'lD, not puritied
Intact grain soaked in extract
of grain aleuronio layer, 0.0 +3.56 0.0 +3.56
ditto
Intaot grain soaked in eodo- 89.0 2.03 3.56 5.59
sperm extraot, not purified
Intact grain soaked in purified 0.0 +5.50 0.0 +5.50
epiderm extract
Intact grain soaked in purified 0.0 +1.99 0.0 +1.99
aleuronia layer extract
Intact grain soaked in purified 96.0 8.48 5.97 14.42
endosperm extract
Polished grain soaked in tap 99.0 4.58 9.16 13.14
water. Control
Polished grain soaked in
extract of epiderm, not 0.0 +2.52 0.0 +2.52
purified
v. P. Tokin, who first discovered the phytoncidal properties of plants,
believed that tissue juices and volatile fractions emitted when the tissues
were damaged possessed phytoncidal properties. Most experiments of Tokin and
of his associates on numerous plants such as garlic, onion, horse radish, and
other indicate that only freshly ground material of such plants emitted volatile
substances having potent bactericidal properties. F. I. Shevchenko, A. I.
Kazakova and M. P. Toka;eva noted that ground garlic dried at 200 retained its
antibiotic properties, but lost them completely upon drying at 800. Their
data showed that dry garlic powder was hygroscopic and absorbed moisture when
tested by the cup method for bactericidal properties. They were of the opinion
that the antibiotic action resulted from the enzymic hydrolysis of the glucoside
allin upon the absorption of moisture from the atmosphere. They expressed the
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opinion that the fo~ation of the volatile pbytoncides was facilitated b.1
crushing the plant tissues, and that intact plant tissues caretul~ dried
absorbed only a slight amount of moisture.
In the opinion of these authors the enhanced emission of phytoncides by
ground plant tissues was due to the enlarged surface of the active prj,nciples,
the role of moisture being confined to creating conditions favorable to en~e
hydrolysis. This opinion gave rise to the assumption that the seed of cereal
grasses generated volatile substances having phytoncidal properties.
The following procedure was employed in the first series of experiments.
Bacteria.l emulsions of ~. prodi/dosum, 1!!21. £2l!. communis and!!5i. pyocy-
aneum were even~ spread with a spatula over the surface of meat-peptone agar
poured in Petri dishes, to the lids of which were fastened small dishes con-
taining moistened barley seeds (winter variety, 1955 crop) in the ratio of 0.7
part of water to I part of barley. The moistened barley seeds were first kept
at room temperature ror 4 hours. An inoculated Petri dish with sli~~ ~oistened
seeds suspended from the dish lid was then incubated at 23 to 250 along with
a control dish having no seeds. Twenty-four hours later the agar plate was
examined; it showed a zone of no bacterial growth (Fig. 1). Along the edge
of the growth-inhibited area there was a zone of depressed growth showing iso-
lated colonies of inhibited development. The zone averaged 2 to 4 em in width.
Beyond this zone the growth of bacteria was normal. It was noted that in the
case of pigment-forming bacteria, particularly ~. prodi~osum, there ap-
peared characteristic color intensification at the pigmentation periphery.
The results of the test demonstrated that slightly moistened seeds emitted
volatile antiobiotic substances.
The next set of experiments was intended to determine the effect of vola-
. tile phytoncides emitted b.1 moistened seeds on mature bacterial cultures. For
this purpose a 2-day-old culture of.!!Qi. prodirlosum grown on meat-peptone
agar was exposed to moistened barley seeds as previously described. Then the
experiment~l and control dishes were incubated at 25°. A day later bacterial
lysis was noted, the bacteria-free zone being 22 mm wide. The longer the cul-
ture was incubated, the more pronounced was the lysis; after 42 hours incuba-
tion the depressed zone averaged 55 mm in width. The data of these experiments
are shown in Figs. 2 and 3.
On the basis of the experimental results it was concluded that the vola-
tile substances emitted b.J barl8.1 seeds affected not only young bacterial cul-
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Pig. 1. Fig. 2. Pig. 3.
Effect ot volatile fraction ot 24 hour soaked barley grains onl
Fig. 1 - Young culture ot !!.2!,. prodildosumJ
Figs. 2 and 3 - 24 'hour cultures ot Bact. prodildosum.
tures, but caused the lysis of adult microorganisms. A microscopic prepara-
tion of a bacterial culture taken trom the edge of the growth-free zone showed
disintegration of the bacterial cells with the fo~ation of many metachromatic
granules. In experiments with other gram-negative cultures, particular17 1!!2i.
aerORenes, 1!!Ei. fluorescens, 1!!2i. pyocyaneum, the results were substantia1l7
the same. However, no such eftect was observable in experiments with such
gram-positive microorganisms as~. subtilia. ~. ~coides, ~. candicans,
!!!£!:. carolinus, Sarc. lutea, and~. !!!.!!.
Similar tests were made with cereal grains of the 1955 crops ot V7atka
rye, ~elozernyi oats, and Tulun wheat. All the crops had the same effect on
gram-negative cultures, as can be seen in Fig. 4. It should be noted that when
the ~. prodildosum cultures were transferred from the edge of the sterile
zone to fresh meat-peptone agar spontaneous l7Sis of the culture occurred after
24 hours incubation manifested as isolated sterile zones (Ftg. 5). The im-
pression gained was that bacterial cultures exposed to volatile phytoncides
emitted by cereal grains began to undergo spontaneous lysis in the next genera-
tion.
Conclusions.
1. Swelling seeds emitted into the air yellow pigments with phytoncidal
properties, thereb7 creating a bactericidal zone around the seeds.
2. The antioxidative nature of these volatile substances makes credible
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-------
~.
/'
-.
',.
/
'.
. -.\
...,.~
rig. 4.
.
i
,
.~. .
,
, .
/
;
".
Effeot on Baot. prodigiosum of volatile fraotions ofl
1 - Bye, 2 - barley, 3 - oats, 4 - wheat.
.. .
,/
the assumption that their
emission from the seeds
augments the process of
germination.
3. Slightly moistened
cereal grains emitted vola-
tile phytoncides which lysed
mature bacterial celIe.
4.
These substances
affeoted chiefly the gram-
negative bacteria.
5. Bacteria exposed
to volatile phytoncides of
generation upon transfer to
Fig. 5.
culture
Spontaneous lysis of Bact. prodigiosum
following the effeot of volatile fract-
ion of barley grainso
grains underwent spontaneous lysis in their second
a fresh nutrient medium.
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An Experimental Investigation of Bactericidal Substances of Plant Origin
(Phytoncides) and Their Use in Disinfeoting the Air.
By
M. A. Komarova.
Tomsk Medical Institute and Institute of Experimental Medicine,
A.M.S., U.S.S.R.
Fitontsi~, ikh Rol' v Prirode, Izdat. Leningr. Univ., 84-88, 1951.
Experimental investigations of problems devoted to air disinfection are
numerous, but they do not meet the requirements of public health. Therefore,
it was thought necessary to find new and practioable means for the disinfection
of air that would accord with hygienic requirements. Experiments were conducted
with substances produced b.y several higher plants for the purification of air
with special reference to children's institutions.
Under study were 23 species of plants commonly found in the U.S.S.R. which
were investigated by Karelina and Tonn in 1944, by Tanovich in 1944, b.y Bor-
sova in 1946, by Kovalenk in 1946, b.y Pevgova in 1949, by Vitgeft in 1949, and
b.y others. A laboratory and field comparison of the bactericidal action of
the volatile products of various plants led to the conclusion that the perennial
Siberian fir and wild rosemary warranted their further experimental investiga-
tion along several lines.
In one set of experiments freshly inoculated agar oultures of staphylococ-
ci, streptocooci, diphtheria and whooping cough organisms and some representa-
tives of the intestinal bacteria were exposed to the effects of volatile sub-
stances emitted by fir needles in a concentration range from 0.1 to 5 g per
Petri dish. The growth of the diphtheria and whooping cough bacilli and of
the hemolytic streptocoooi was notably inhibited by the phytoncides. The
pyrogenio staphylococci proved more resistant than the causative agents of the
children's diseases; their growth was inhibited only slightly. The intestinal
and Grigor'yeva-Shiga rods, as well as paratyphoid and ~sentary microorganisms
were resistant to the action of the volatile bactericides emitted by pine
needles.
Cloth materials infected with pathogenio baoteria were suspended in a
lo-liter glass vessel oontaining phytonoide vapors of pine needles; maximum
suppression of baoterial growth was observed after a 6-hour exposure. Needles
oollected at different months of the year varied in their phytoncide activity.
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Most pronounced bactericidal effect on diphtheria and whooping cough rods and
on pyrogenic cocci was manifested by fir needles collected in April, May and
June, i.e., during the prime growing season.
Results of experiments with wild rosemary leaves showed that the phyton-
cides actively inhibited the growth of diphtheria and whooping cough rods, and
to a lesser degree, arrested the proliferation of the hemo~tic streptococci
and pyrogenic staphylococci; there was a marked inhibition in the growth of
the luminescent vibrio. Wild rosemary phytoncides had no worthwhile effect on
intestinal bacilli.
Exposure to wild rosemary phytoncides of cloth materials infected with
cultures of pathogenic bacteria affected a sharp reduction in the latter, in
.usomeuinstances to the point of complete sterilization. The antimicrobial
potency of wild rosemary phytoncides was greater than that of Siberian fir
phytoncides.
Tests were made to check the ability of rosemary phytoncides to disinfect
relatively large volumes of air contaminated with massive doses of pathogenic
bacteria. A finely dispersed microbial aerosol of hemolytic streptococci and
whooping cough rods was created inside a 400 liter glass box which contained
100 g of crushed leaves and stem tops of wild rosemary. Natural reduction in
the bacterial aerosol as the result of sed1mentat~on was determined by control
test and taken into consideration in the final interpretation of the results.
Parallel air samples from the phytoncide-containing box were taken at given
intervals and counts made after proper inoculation and. incubation. The results
showed that -the number of viable pathogenic bacteria rapidly and sharply de-
creased in the phytoncide-containing box as compared with the control, in a
steadily progressive .manner, until the air was completely sterilized. The
number of viable pathogenic bacteria in the control box air also decreased
steadily, but at a much lower rate. Results of special experiments showed that
the effects were bactericidal and not bacteriostatic.
In addition to volatile constituents possessing bactericidal action, the
wild rosemary also contained non-volatile water-soluble substances which ar-
rested bacterial growth. The diphtheria and whooping cough bacilli, Staph.
aureus and!!2i. m.vcoides were especially sensitive to the effects of such
water soluble substances. Aqueous extracts from rosemary leaves sterilized in
an autoclave were tested by the "trickling drop" method; the results showed
that they contained weak antimicrobial action. The effects of fir and wild
-240-
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rosemar,y phytoncides on the microflora of the air were tested in creches. The
results indicated that phytoncides had a quantitative and qualitative effect
on the air bacterial content. The number of hemolytic streptococci was reduced
to an average of 10%. On the other hand, the number of mold spores suspended
in the air rose considerably when fir needles or rosemary leaves were introduced
into the room. Control observations of changes in the air flora of d~ nurs-
eries after thorough airing showed that ventilation caused a marked decrease in
the number of bacteria, but not to the same extent as did volatile fir phyton-
cides. Ventilation had no effect on the qualitative composition of the air
flora.
The microfloral air composition changed less under the effect of phyton-
cides than by chemical disinfectants. However, the destruction of potentially
pathogenic bacteria by volatile pbytoncides, as a rule, attained hygienically
significant proportions. The (theoretical) usefulness of plant bactericides
as disinfectants appeared particularly impressive due to the absence of side
effects on the children.
On the other hand their practical application was
complicated by seasonal variations in activity and the difficulty of dose
standardization. Therefore, attempts should be made to obtain active plant
preparations of high stability during storage, capable of being measured out
in given doses and usable at any time of ~he year.
Such tests were made with several samples of a substance obtained from
balsam fir, kindly offered to us by P. A. Yakimov and his associates, and an
alcoholic extract from fir bark. Tests were made in two ways: first, their
disinfectant action was tested on materials infected with different pathogenic
bacteria placed in a glass box; secondly, tests were made for their effective-
ness as room air disinfectants. Results of a thorough and critical evaluation
of the data, indicated that only one of the 7 species of balsam fir emulsions
(No.5) manifested complete regularity in its bactericidal effect on the causa-
tive agents of children's airborne infections. Materials infected with diph-
theria and whooping cough rods and with Staph. ~ were rendered completely
sterile; in the case of hemolytic streptococcus and Staph. aureus there was
only a 3.7 to 5 fold reduction in the number of bacteria.
Results of experiments with 96% alcoholic extract of fir bark must be evalu-
ated cautiously because of complicating effect of the alcohol and other factors.
It was observed that the extract had a sterilizing effect on the diphtheria and
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whooping oough rods, that it was weak in disinfecting objects infected with
hemolytic streptococcus, and that it had no effect. on Staph. aureus or Staph.
a1bus.
A second series of experiments with stable phytoncide preparations was
conducted in different work areas to determine their effect on the usual air
microf1ora.
Resu1:ts showed that there was a marked decrease :in the number of
microbes after dispersion in the air of balsam fir. This decrease could not
be attributable to sedimentation since throughout the .experiments employees
and others continued to work and move about in the rooms as usual. Statisti-
cally the number of observations may not have been sufficient; nevertheless,
they served to confirm the regular effect of preparation No.5, previously
studied.
Tests were ~de to investigate the effectiveness of these preparations
in purifying the air of a 4QO-1iter box infected with hemolytic streptococci
and the causative agents of diphtheria and whooping cough by means of a special
atomizer. The results were gratit,yingly positive. Results of control experi-
ments unmistakably showed that the reduction in the number of viable microbes
was caused by the bacteriocidal and not by the bacteriostatic effects of the
phytoncides.
It was established that several fir phytoncide preparations which differed
considerably in degree of stability, possessed noteworthy lethal effects on
the bacteria which caused children's infections. Under certain circumstances
such preparations can also be used to disinfect the air.
Attempts will be made to secure more potent bactericidal substances of
plant orisin which could be standardized.
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The Effect of Mixed Industrial Dust on the Organism.
By
N. M. Demidenko.
(Department of Labor HYgiene at the 1st Koscow Order of Lenin
Medical Institute).
Gigiena i Sanitariya, No. 11, 26-29, 1954.
Many branches of our national economy, such as coal and ore mining,
chemical manufacture, machine-building, etc., include in their operations
processes which generate mixed dust; heterogeneous dust generated in mining
polymetallic ores is one such example. Of greatest hygienic importance are
mixed dusts which contain silicon dioxide, as their basic component or as ad-
mixtures. Quartzite mining generates dust containing silicon dioxide, aluminum,
iron oxides, magnesium and calcium; iron ore mining generates dust containing
iron compounds, silicon dioxides, aluminum oxides, manganese, phosphorus, etc.
Processes and operations in which the generated dust is of a homogenous chemi-
cal content are less numerous; examples of which are sugar, flour and sand-
blast dusts.
Soviet scientists made considerable advances in the study of the etiology
and pathogenesis of dust diseases. P. P. Dvizhkov, E. N. Gorodenskaya, M. G.
Ivanova, I. S. Ostrovskaya, M. K. Dalem, R. V. Borisenkova, N. P. Tikhomirova,
and others studied the etiology and pathogenesis of silicon dioxide, aluminum,
apatite, alloy dusts, etc. However, the pathogenic significance of admixtures
other than the basic components remains undefined. Only an occasional report
is found in the literature which deals with the biological effect of mixed in-
dustrial dust. Such reports are mostly the result of clinical observations;
only a few are based on experimental research (P. P. Dvizhkov and E. I. Vor-
ontsova) .
The experimental and clinical studies of I. M. Peisakhovich, M. M. Vilen-
skii, K. M.' Sheinin, E. S. Gottlieb, N. A. Padkaminskii indicated that the
gradual silicosis development caused by dust containing silicon dioxide and
iron could be due to the physiologically inhibitor,y effect iron had on quartz.
I. M. Peisakhovich, A. V. Walter, F. Kettle and others believed that the presence
of coal dust prevented the development of acute silicosis. On the other hand,
Nozlund in his experiments with guinea pigs and rabbits showed that admixtures
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of coal and lime failed to counteract the effect of quartz; admixtures of iron,
magnesia and aluminum lowered the effeot of quartz, while the presence of al-
kalies enhanced the pathogenic effect of silicon dioxide. MacDonald and Res-
si~ had seen cases of developing acute silicosis in workers who were exposed
to the effect of quartz dust containing an admixture of alkalies. Nikol was
of the opinion that the effect of silicon dioxide was enhanced by an admixture
of fluorospar. D. Yu. Zhbarekqa in her experiments with animals obtained
pathologic changes characteristic of silicosis, by exposing them to the in-
halation of dust containing 36% of mangapese and 62% of silioon.
Reports which deal with the possible combined action of mixed dusts are
limited, and the results are at variance. Knowledge of the combined action of
mixed dust is essential for the determination of hygienic limits of allowable
dust ooncentration in the air, and for the rational selection of means for the
protection of sanitary working conditions in mixed. dust generating industries.
Wi th the above purpose in mind plans were made to conduct supplemental studies.
Mixed dust containing quartz and hematite (ferrio oxide), quartz and fluorite,
quartz and coal, and quartz and chalk were investigated. Chalk dust was used
as bulk material in the preparation of mixed dust samples of uniform component
ratios. Each dust mixture consisted of 50% quartz and 50% admixture. The
mixtures were prepared by pulverizing natural minerals to a degree of dispersion
at which 96% of dust partioles measured up to 4 11. White rats were used in the
tests, the dust mixtures were introduoed intratracheally in 4 series. of tests.
Animals were kept under observation 6 - 8 months. Weights of animals were
recorded at regular time intervals. It was noted that test animals gain in
weight was slighly below that of the control animals; this was particularly
true of the animals which were injeoted with the quartz-fluorite dust mixture.
At the end of the experiment the rats were saorificed and their internal
organs were fixed in 10% formalin. Histologic examinations showed the follow-
ing results:
First test series. A single intratracheal introduction of 50 mg of quartz
and chalk dust produced lung changes characteristic of experimental silicosis.
Six months after the dust was introduced numerous nodules of different sizes
developed in the pulmonar,y parenchyma and around the small bronchi and vessels,
indicating a development of a chronio pathological process. Epithelial cells
were seen in the center of the nodules and along the periphery there were
-244-
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fibroblasts which separated the nodules from the surrounding tissue. The
nodules were permeated by connective tissue fibers, the distribution of which
followed no particular order. Large nodules were poor in cellular elements
and showed signs of necrobiotic changes. In lungs of rats killed 8 months
after the treatment, the silicotic nodules were larger, irregular in shape
and coalesced, manifesting symptoms of sclerosis and ~alinosis. Necrobiotio
changes in these nodules were considerably more pronounced, some showing the
presence of necrobiotic nuclei. The histologic picture also showed the presence
of non-nodular diffuse sclerosis of the pulmonary tissue and focal emphysema.
The bronchi showed signs of beginning destructive changes, the muscle layer
of their walls was gradual~ replaced by connective tissue. There were signs
of developing perivascular and peribronchial sclerosis. A light pigmentation
was seen in the peribronchial ~erplastic lymphatic follicles.
Second test series was intended for the clarification of effect of coal
dust admixture on the aotion of quartz dust. Results of this series of investi-
gations indicated that lung changes were much less pronounced than in animals
of the first test series, despite the fact that the quantity of quartz introduced
into the lungs was the same in both series.
Six months after the quartz-coal dust was introduced into the rats' lungs
a thickening of interalveolar septi was noted which was due to their having
been infiltrated by round and histiocyte cells. Sections with thickened septi
and emphysematous sections alternated in the lung parenchyma; around the small
bronchi and vessels there developed nodules of the lymphoid histiocyte cells
with fibroblasts scattered along the periphery. Sclerotic changes in the nodules
were only faintly expressed, and there was a slight hyperplasia of the peri-
bronchial ~phatic follicles. Occasionally dark pigmented clumps were seen in
the septi and in the nodules outside the cells and less frequently inside the
cells. Comparison of the histologic changes in the lungs of animals 6 and 8
months after dust injection indicated that the slight increase of connective
tissue in peribronchial tissue was the only pathological change observed. The
results lead to the conclusion that the coal dust admixture decreased the path~
genic action of silicon dioxide to some extent, judged by the fact that the
nodular and int ermediate sclerosis formed in the lungs were less pronounced.
Third test series. Introduction into the lungs of the quartz-hematite
dust mixture developed ohanges which differed in character and intensity from
those observed in the first test series. The changes were practically limited
,
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to the development of lymphoid nodules, thickening of interalveolar sept! and
vascular changes in the form of capillary stasis, perivascular edemas, swell-
ing of walls of blood vessels and lymphoid cell infiltration.
The above data indicate that the character and intensity of the lung
changes resembled the lung changes noted in the animals of the second group;
however, the changes developed were less pronounced than in the first test
series, pointing to the fact that hematite lowered the intensity of the patho-
genic effect of silicon dioxide.
Fourth test series was conducted to obtain knowledge of the effect of
fluorite on the pathogenic action of quartz dust. The simultaneous injection
of fluor! te and quartz dust e11ci ted changes in the form of grave affection of
bronchi, sclerosis of the peribronchial lymphatic apparatus, changes in the
vascular system (sclerosis of walls of small arteries and periarterial sclerosis).
A sharply pronounced growth of intermediate tissue, followed by sclerosis and
emp~sema, was noted in some animals. The histopathologic examination of one
rat of series No.4 is presented below:
Rat No. 12, weight 360 g. April 11, 1952, 50 mg of quartz and fluorite
were introduced into the trachea. The animal was sacrificed December 11, 1952.
Microscopic lung analysis. Partial and in some cases complete
destruction of the mucous membrane and of the bronchial walls.
Aoute hyperplasia of peribronchial lymphatic follicles with ooarse
collagen fibers visible after staining with picrofuchsin; also
symptoms of beginning ~alinosis. In some large peribronchial
lymphatic follicles isolated nodules with distinct outlines with
signs of fibroblast reaction along the periphery were seen in some
large peribronchial ~hatic follicles. Bronchial deformation with
destruction of the basal membrane, ooarse sclerosis of the bronchial
wall, and occasional sections with pronounced thickening of the septi
and an increase in the number of connective tissue fibers. The small
bronchi and vess~ls were surrounded b.Y small lymphoid nodules contain-
ing light refracting pi~entation granules. There were signs of
sclerosis of the small arterial walls and of periarterial sclerosis.
The lymphatic vessels were dilated and filled to overflowing with lymph.
The above histopathologic picture leads to the assumption that quartz-
fluorite dust mixture produced a graver pathogenic effect than in the quartz-
coal or quartz-hematite dust mixtures. It seems difficult to formulate a
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comparative evaluation of the action of quartz-fluorite and quartz-chalk dust
mixtures on the basis of the test series. It can only be said that fluorite
dust in no way modified the original quartz dust effect. Obviously, the
changes caused by the fluorite-quartz mixture differed in character from the
changes brought about by silica.
Conclusions.
1. Results of the experimental investigation confirm the difference in
effect produced by quartz-containing dust depellding upon the component added
to the silicon dioxide. It was shown thatl a) dust" mixtures containing 5~
of silicon dioxide and 50% of coal or hematite (ferric oxide dust) had a less
pronounced pathogenic effect than the same percentage of silicon dioxide alone;
b) fluorite admixture did not lower the effect of silicon dioxide but changed
its character; this may be regarded as due to an added inorease in pathogenic
effect of such a mixture of dusts.
2. In making hygienio evaluations of an industrial dust for the purpose
of determining the limit of its allowable concentration in the air considera-
tion should be given to the physical and chemical properties of its primary
and secondary components. It was shown that differences in the chemioal nature
of the primary and secondary dust components may necessitate a change in the
limit of allowable dust concentration arrived at on the basis of the primary
component alone.
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HbiX )KIIBOTHblX. rllrHt'n:! Tpy.na II TeXIIPlKa 6e30nal'HoCTH. 1935, N~ 4. --;- D: B II)K-
K 0 B n. n.. 113MeHeHUI! nllMljJaTH4ecKoil CHCTeMbi npH CHJJ\IK03e, Tpy.nbl AMH CCCP.
CII..111K03, M..' 1951. - 0 II )K C, BOnp()l'l,1 naTOreHCj~ nHen~\()KOIIII03[)B (CII.1IIK03a).' Te-
3Hl'bI Ao~:.'a.nOB Hav411uil CecCIlIl. nocBHlUcHHOii 30-nt'Tlllo I1HcnrryTa mrHeHbI Tpy.na H
npoljJ3a60.1eBaHIIH . AMH CCCP 23-28/XI 1953 r. - 11 B a II 0 B a M. r., 0 C T P (' B-
C K a II 11. c., D:eiicTBHe alllOMIIHHeBoil nblnll Ha opr3HII3M )KHBOTllblX, rHrlleHa II callH-
TapHH, 1950, N~ 4. - n e il C a x 0 B H 4 11. M., arOUHTapHal! .nellTeJlbHOCTb lIerKIIX npH
sanbl.leHHII TpyD.bl :\.'KpannCKoro HIICTlIT)'Ta naTO.10mH H rHrl!eHbI Tp)'.na, 193~, B. 10.-
T II X 0 M H 'p 0 Ii a H. n., CpaBHIITP:lbHoe IICC:IC!l.OllaHIIC acikTBIiR Ha ilillBOTllblH - O;>r;'fIiDM
nbinH .nHHal'a rn3MOTa H neMeHTa UpH IIHTpaTpaxeanbHOM BBeD.eHHH HX B3Becen. Tpy.[J.I~
AMH CCCP: CHnHK03, M., 1951. - ill e iI H H II M. M.. r 0 Tn 116 3. c.. no Il. K a-
M H H C K II ii H. A~ CHJ.Cp03 Y 6YPlUHKOB >Ke.1C30py.nHbI': maXT, ~~Yll~ YKp,HIHl'Koro
HHCTHT).a rurHeHbI TPYlla. 1932.- K e t tIe F. U., Exp~rImental. ~lhc?SlS,. JOU!I1. of
Indust. hyg., 1926. II. - ~ 3 e s I u n ~ c.. !'.1c prcventIQn 01. .slhc.OSlS: eXI?e~lmcntal
investigation on the action 01 certam nonsll1ceous dusts and slhc3 In the ongln and
development 01 silicosis, Journ. Indust. hyg., , 1940, v. 22, I, 1-30.
-247-
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Investigation of Air Dustiness in Agriculture.
By
S. 1. Sosnovskii and D. Kh. RhakiDlov.
("Tractor and Automobile" Department of the Tashkent Institute
for Irrigation and Agricultural Mechanization).
Gigiena i Sanitariya, No. 11, 48-49, 1954.
Extensive work is being conducted in the U.S.S.R. in the field of labor
hygiene and industrial and agricultural mechanization. Despite that, important
labor hygiene problems of an industrial and agricultural character remain un-
solved. The problem of control of dust arising during work with tractors and
other agricultural machines is still in the study stage. !nvestigation of air
dustiness in agricultural field work presents the difficulty connected with the
very motion of the agricultural machines. Only few references were found in
the literature related to methods of air dust investigation under agricultural
field conditions. In reports on the study of labor conditions in agriculture
published by Neustadt, Grodzenskii, Reznikov, Kuznetsova, Veger, Neumolotova,
Artem'eva, Berne, Kollarov, Bogushevskii, Kogan, Demidova, Pochtareva, and
I
others quantitative indexes of dustiness are either lacking or they were deter-
mined by the count method; the authors described no methods for the gravimetric
study of air dust concentration.
The present authors undertook to develop methods for collecting air samples
for dust concentration determination under agricultural field conditions. In
the devel~pment of such a method the six-volt automotive batter,y was used the
leads of which were connected with an electric motor taken from GAZ-42 automobile
which operated an air blower (fan) built by the Gor'kii Institute of Hygiene
and Occupational Diseases. The installation was assembled in a special wooden
box divided into sections by a cross-partition. The electric motor and air
blower were housed in the upper part, and the batter.y in the lower section.
The air intake pipe from the air blower was connected through a flowmeter
to the dust retaining adapter.
Tests indicated that the maximum rate of air flow with such an installation
was 50 - 70 Ii per minute. Properly charged the battery provided power for four
hours' work; a single ordinary charge of the battery supplied enough power for
the collection of 20 or more air samples of 500 - 600 Ii.
-248-
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The entire apparatus can be securely installed in the tractor's cabin
with the dust collecting adapter fastened at the level of worker's breathing.
Samples were collected when the tractor, with the plow, harrow, etc.
attached to it, was in motion. By this method it was possible to investigate
the degree of air dustiness at any desired place and with different agricul-
tural workers operating different agricultural machines.
The same method was used in studying the degree of dustiness in the air
inhaled by the operators of cotton-picking machinery (Pochtareva).
The described procedure for the determination of the degree of air dusti-
ness during agricultural work processes, could also be used in the general
dust study of atmospheric air, stationar,y or in motion, and of mine air.
Dustiness and Meteorological Conditions in Seed Houses and in
Some Sections of Cottonseed Oil Mills.
By
S. I. Sosnovski~.
From the Uzbek Scientific-Research Sanitary Institute.
Gigiena i Sanitariya, No. 11, p. 43, 1955.
Only scanty reports were found in the literature dealing with the problem
of labor hygiene in the cottonseed oil industry in general, and in particular
in the seed houses, in the gin rooms, the cleaning and hulling sections, and
in the cottonseed grinding rooms. The present study which covered 1953 - 1954
deals with the meteorological conditions in 4 factories and 5 production depart-
ments.
In the seed house of a cottonseed oil mill air dustiness ranged between
30.6 and 154 mgfm3, depending on the cottonseed variety. During transportation
and unloading of first quality seeds the dustiness was considerably lower than
when low grade seeds were processed. Air dustiness during the unloading of
seeds from railroad cars and during their transportation from .the cotion mills
-249-"
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was higher than during the seed storing. The meteorologioal oonditions were
usually similar to those of the outdoor air, sinoe the oottonseed prooessing
took plaoe in the open air. In the ootton fiber room, the seed meal room,
the cleaning and hulling sections, the average air dustiness varied between
101.4 and 290.5 mslm3 when the low grade cotton varieties were processed. The
cleaning of first quality cottonseeds produced an air dustiness which ranged
between 31.4 - 68.4 mslm3.
The dust in the seed house, fiber room and the cottonseed meal section
was of plant and mineral origin. It consisted of 82.6% organic matter and
17.4% inorganic matter, mostly wind blown silt. The degree of dust dispersion
was as follows: from 1 to 5 ~ - 25.4%, from 5 to 10 ~ - 26.6%, from 10 to 50 ~ -
30.1%, above 50 ~ - 17.9%. The inorganic dust in the above sections of the
plant contained total silicon dioxide whiCh fluctuated between 43 and 15%, and
free silicon between 15 and 18%, depending upon the composition of the soil
on which the cotton was grown. The dust in the huller-separator room was
predominantly of plant origin and consisted of 90% organic and 4% inorganic
matter. Morphologically they were Short fat-coated fibers. Analysis of the
dust showed that it consisted of 3% ash, 4% protein, 51% cellulose, 40% nitrogen
free extractives and 2% oil.
The dust in the seed house, the fiber room, grinding, cleaning and huller-
separator sections contained 0.3 - 0.5% of gossypol, which, taken in large
quantities with the food, proved toxic to animals and humans. Mature cotton-
seeds contain 0.15 - 1.9%, heat processed seeds - 0.01 - 0.9%~ oi1 cakes up
to 0.15%, crude cottonseed oil - 0.1%, purified cottonseed oil up to 0.01% of
gossypol. The maximum permissible concentration of gossypol for purified oil
is 0.01%. The dust also contained mold spores which could cause ~cotic dis-
eases in persons working in such sections of aO cottonseed oil mill.
The temperature in the seed grinding and cleaning section differed only
slightly from the outdoor temperature, and the relative humidity was somewhat
~
higher. In the fiber room the air/temperature in the summer reached 350,
while the relative humidity was comparatively normal. In the huller-separator
section the temperature and the humidity of the air was higher than in the
fiber room and depended on the effect of the adjacent oil-pressing section,
where the temperature and the relative humidity were high.
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Dust Concentration in Residential Districts of Asbest City and
Its Effect on the Children's Health.
By
A. T. Bob,y1eva, R. M. Bukhantseva, S. E. Lovtsova and M. S. Sadi1ova.
(From the Sverd10vsk Institute of Labor aygiene and Occupational Pathology
and from the Sverdlovsk State Medical Institute).
Gigiena i Sanitar~a, Vol. 23, No. 11, 9-12, 1958.
Prevention of asbestosis among the workers of asbestos plants is among
the most outstanding problems of the Sverdlovsk Region Public Health Service.
Ventilation of the asbestos work rooms is the most important of the prophylactic
sanitar.y measures; unfortunately, as practiced at present, it results in the
discharge of great quantities of asbestos dust and fibers into the atmospheric
air. This made imperative the determination of the rate of air pollution in
the residential districts of the city of Asbeet, which iethe site of many
asbestos processing plants. Theinvestigatione were conducted during the
winter and summer of 1950. Samples were collected by aspiration on the lee
side of the pollution source, at different distances from it. The results
presented in Table 1 are self-explanator.y.
TABLI:
1.
v.-n .., single dust cODc8ntratioD8 in the air in mc/.3 at
different distances frail the plant.
I Di8tance from the plant
I
I
I 0.5 k81 I 1.0 - 1.5 ka I 3la1
Plant .0. i I
.
. .Dust oODcentration
I
i AveI"- I Variation I AveI"- I Variation I AV81"- I Variaticm
I
I age I range : an I r&I1«8 age range
Plant .0. 1 23.4 34.7 - 12.4 18.9 33.4 - 7.2
Plant .0. 2 14.3 23.3 - 6.4 13.0 24.0 - 3.2
Plant .0. 3 18.0 33.0 - 10.0 11.4 17.8 - 3.2 4 6.4 - 1.6
The investigation showed that the plant-emitted asbestos dust was the
primar.y cause of a sharply delineated air pollution area surrounding the. plant
within a radius of 3 lane The lowest asbestos concentration ranged between 3.2
-251-
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and 7.2 ms{m3, .hich is in considerable excess of the permissible limits.
Highest dust concentrations were found within a radius of 1.5 km from the
plant. Sedimentation chambers were the only air purifying equipment found in
operation in the plants. Under such conditions it was not difficult to demon-
strate that the asbestos particles of highest dispersion were the ones emitted
into the atmospherio air.
Particles measuring approximately 1 ~ constituted 45.5 - 52.4% of the
emitted asbestos dust; particles of 1- 5 ~ diameter ranged between 31.4 and
39.3%; 5 - 10 ~ ranged between 9.2 and 18.2%, and particles of over 10 ~ in
diameter ranged between 1.2 and 1.7%.
It is known that asbestos dust is highly deleterious to the respiratory
system and that it causes pulmonary asbestosis. The high level of air pollu-
tion of the restdential sections of Asbest city and the data found in the
literature on the effect of asbestos dust on the health of workers in the
asbestos industries prompted these authors to undertake the study of the ef-
fect of asbestos dust on the health of the population of Asbest. The effect
of asbestos dust on the health of the children of Asbest city was studied
first, since it eliminated the complicating factors of indoor exposure under
working conditions. Under investigation were children whose residences were
located in close proximity to the asbestos plants, where the concentration of
asbestos dust air pollution was heaviest. Information was also gathered per-
taining to the family income and general home conditions of the children. It
soon became apparent that families of workers who resided closest to the asbes-
tos plants, where the air pollution was heaviest, had lower incomes and lived
under more congested conditions. (This, despite the fact that the credo and
slogan of those who claim to be communists states: From each according to his
ability, to eaoh according to his needs. B.S.L.). The people living in the
poorer areas constantly complained of dust in the air which made normal breath-
ing difficult, and living quarters ventilation impossible. The worker residents
preferred to leave the storm windows in,even in the summer as a protection
against the permeating dust.. Clinical examination of the children over the
period of 1947 - 1950 showed a high percentage of respiratory diseases; such
. diseases occurred at high frequency also among the children who resided in the
more favorable districts of Asbest city.
The data accumulated during the early stage of the investigation pointed
to the need of more thorough examinations of children living in city sections
. .
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of high air dust pollution. This was.accomplished in 1952 - 1953 by the members
of the Sverdlovsk Medical Institute. Children were examined thoroughly -
anthropometrically, spirometrically and fluoroscopically. Records were made
of duration of residence in the area, of previous diseases and of other per-
tinent facts of life. The medical examination covered 1,340 children 7 to 14
years of age; 612 of these children came from areas of intense air dust pollu-
tion and 668 from less air polluted areas. Table 2 presents the age distribu-
tion of the children.
'1' A B L E 2.
Age distribution of
examined ohildren.
A&e
i Air dust concentration
I Dusty I Less dusty
7 years
8 years
9 lears
10 years
11 years
12 years
13 years
14 years
78
76
83
132
67
77
90
69
85
63
96
54
81
92
100
97
71.5% of children from the dustier
areas resided there for more than 5 years.
The anamnesis of these children showed
that 17.3% of those children were ill with
pneumonia in the past, children with such
diseases constituted only 9.3% in the less
dusty areas. In the more dusty areas there
were twice as many complaints of cough,
dyspnea, extreme fatigue and headaches.
Results of spirometric examinations are
shown ;in Table J. Results of spirometric
tests of children younger than 11 years
were not recorded in this Table for lack
of sufficient reliability.
Results of
fluoroscopic examinations showed no deviations from the age norm. There were
no changes in t~e skin or in the tendon reflexes, and none in the skeletal or
joint systems.
TABLE
3.
Vital (lUDg) capacity in m1 of eDlD1ned children.
a Dust concentration of region
.
i
.
I Dusty a . Less dusty
.
.
a a
I i I I
i Boys Girls a Boys I Girls
1,830 1,788 2,170 1,840
2,023 1,820 2,170 2,050
2,355 2,070 2,340 2,076
2,325 2,290 2,640 2,469
-253-
Age
11 years
12 years
13 years
14 years
-------
General physical development indexes were lower in children who resided
in the dustier areas. Children who resided in areas of heaviest dust concen-
tration rarely had a normally shaped chest; asthenic and barrel-shaped chests
were twice as numerous; dry rales occurred twice as frequently; lung wheezes
were frequent; the muscular system showed inferior development; tonsils were
enlarged; adenoids and copjunctivites made their 5to'ppearance. Chest volume was
below normal. No sharply defined changes characteristic of asbestosis were
noted, but more children living in the dustier areas were affected with respira-
tory diseases as they grew older. There was some indication of the fact that
more defined symptoms of asbestosis appeared at a later age.
Conclusions.
1. The air of residential districts of Asbest city was heavily polluted
with dust discharged into the atmosphere by the asbestos plant.
2. The discharged asbestos dust affected unfavorably the health of the
children living in the proximity of the plant.
3. Results of the investigations showed the imperative need for the im-
mediate installation in the plant of efficient dust-catching equipment.
4. It is imperative that the practice of sending the children to summer
resorts and various summer camps be adopted on the broadest scale possible.
Experimental Determination of Air Dustiness in Kiev.
By
G. E. Tsapko.
(Sanitary-Epidemiological Station, Kiev).
Gigiena i Sanitariya, Vol. 24, No.2, 74-75, 1959.
The Community Department of the Kiev Municipal Sanitary-Epidemiological
Station investigated dust content of atmospheric air since 1956. The laboratory
procedures used in such investigations were those described in the 1955 temporar,y
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methodological instructions of the U.S.S.R. Ministr.y of Health. Air samples
were taken at three observation points located: a) in a densely populated
area, the site of large industrial plants and of intensive railroad and
automobile traffic (at the Railroad Station Plaza); b) in a residential
section free fram large industrial plants and abounding in trees and shrubs
(Nekrasovsk~a street, No.8); c) in a garden and park section (Pioneer park
on the slope of the Dnieper river). The air investigations were conducted by
the gravimetric method (487 samples) and by the count method (977 samples).
Records were kept of the air temperature, barometric pressure and of the rate
and direction of air currents. The air was aspirated at the rate of 25 - 30
li/min for 1 1/2 - 2 hours to a volume of 3000 liters. Dust particles were
counted microscopically at 400 magnification, using an occular and an objective
micrometer. By this method it was possible to make the counts and to determine
simultaneously the size of dust particles up to 1 ~ and larger in visual fields,
the total area of which equalled 1 mm2. The data produced by the investigation
are p~esented in Tables 1 and 2.
TABLE
1.
3
City air dustiness in mg/m .
Observation point
I
I
I
I
I
I
No. ot
samples
!
i
I
I
I
Percent of samples containing
Up to 0.5 DIg I Up to 1 mg
: or more
In tront ot railroad
station
Nekrasovs~a street,
No.8
Pioneer park
45 67
252 93
190 94
TABLE 2.
33
7
6
J'ractional dispersion of air dust.
I
Observation point I
I
Up to 1 '"
in%
I
I
I
Up to 5 '"
in%
I
i
.
Up to 10 '"
in%
I
I
Over 10 '"
in%
In front of rail- 65 6 29
road station
NekraBov~a street, 36 5 4 55
10. 8
Pioneer park 31 8 4 57
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The data presented in Table 1 show olearly that the intensity of air
pollution in the Nekrasovskaya street and in the park area was not as great
as at the Railroad Station Plaza, where the dust oontent of 33% of the air
samples exoeeded the single maximum norm of 0.5 mg/m3. The data in Table 2
show that dust partioles exoeeding 10 ~ in size prevailed in the air of the
residential and park seotions, while 65% of the dust particles in the air of
the industrial region were of 1 ~ or less in diameter.
It is worthy of note that most intensive air dust pollution occurred at
ali tested points during the fall-winter period of the year; highest air pol-
lution intensity was found at the Railroad Station Plaza. This oan be ex-
plained by the fact that during this period many of the Kiev industrial plants
operated their boilers with coal instead of gas. The effeot of industrial
emission on atmospheric pollution was manifested also by the 53% content of
oarbonaoeous substanoes in the dust oollected at the Railroad Station Plaza,
where many large plants were located. The air dust from the Pioneer Park and
Nekrasovskaya street sections came predominantly from the soil; it contained
relatively little carbonaceous substances. The high dust intensity of oity
air in industrial and adjoining residential areas should impel "sanitation
physicians" to exercise their rights more broadly and to make greater demands
on managers of the air polluting production plants. Plans for the erection of
new boiler operations should mandatorily include the installation of effioient
ash catching devices.
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The Organization and Methods of Fluoroscopic Examination of Workers
in Dust Generating Industries.
By
A. G. Shumakov.
(Krivorog Institute of Labor Hygiene and Occupational ~seases).
Sovietskoe Zdravookranenie, Vol. 17, No.7, 35-37, 1958.
The organization and procedure of mass fluorographic examination of workers
and others have been studied in the past for the purpose of disclosing cases
of pulmonary tuberculosis. Reports of studies of foreign and U.S.S.R. in-
vestigators such as S. A. Reinberg, K. V. Pomel'tsov, Ya. L. Shekhtman, Ya. S.
Beilin, S. V. Pruzhansky, T. I. MorQzova present ample proof of the above
statement. As a result of the efforts of these investigators the basic pro-
cedures of mass fluoroscopic examinations have been well established. Beginners,
who enter the field of propbylactic examinations by the fluoroscopic method,
should benefit from the experience accumulated in the past. Preventive medi-
cal mass examinations have been used widely to detect different types of oc-
cupational diseases, espeoially in the case of workers in dust-producing in-
dustries, for the detection of different types of pneumoconiosis. Unfortu-
nately the fluoroscopic method is still applied to a limited extent in preven-
tive examination of workers in dust-generating industries; the roentgenological
examinations in such cases are limited mainly to chest X-rays. As a consequence,
organizational procedures applicable specifically to the fluoroscopic mass ex-
amination of workers in dust-generating industries are still in the initial
stage of development. In the opinion of this author, the establishment of
mass fluoroscopic examinations by Public Health organizations will find wide
application in the detection of pneumoconiosis; as a contributing stimulus to
this, the author herein shares his experience and ideas in the field of preven-
tive fluoroscopic mass examinations. Forms and procedures used in mass fluoro-
scopic examinations in the detection of tuberculosis can be profitably used as
a basic procedure to be used in fluoroscopic mass examinations for the detection
of other pulmonar.y aff~ctions. In adopting such procedure of medical examina-
tion, the following factors should be taken into consideration:
The technic of fluoroscopy makes possible the examination of tens of
thousands of workers during the year; therefore, it is not practical to estab-
-257-
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lish fluorographic examination centers or clinics to serve individual mines or
factories. The greater number of workers in dust-producing occupations are
those who work in coal mines, metallic ore and gold mines, located at consider-
able distances from each other; therefore, it is sugge~ted that special fluoro-
scopic centers be established and equipped with mobile high power fluoroscopic
equipment. Such fluoroscopic stations can be operated by a comparatively small
personnel, consisting of 1 or 2 pnysicians-roentgenologists, 1 X-ray technician,
2 laboratory workers and 2 statisticians; a mobile unit of this type can take
care of periodic prophylactic examination of workers of an entire mining region,
or of an industrial district.
The organization of such mobile units is justified by many basic considera-
tions. First, the prophylactic examination of workers can and should be con-
ducted directly in the mine or in the factory. This will take care of the total
workers' examinations which can not be done b.Y asking the workers to came to
a stationary roentgenological center at some distant clinic. With the aid of
the mobile units X-ray examinations can also be made of workers suspected of
having pneumoconiosis. Second, the centralization of all pneumoconiosis detec-
tion in one center may well improve the quality of the diagnosis, provide a
dependable approach to the treatment of this pathological process; it may also
raise the level of X-ray examination of pneumoconiosis patients. Pneumoconiosis
diagnosis, based on roentgenological evidence in many cases presents great dif-
ficulties which frequently lead to individualized interpretation of some points
in the X-ray picture. In other words, different investigators arrived at dif-
ferent conclusions on the basis of the same X-ray picture. Third, the centraliza-
tion of prophylactic examination data in the hands of one group may well lead
to a more thorough scientific study without loss of time. Fourth, by the organ-
izational procedure suggested the expensive fluorographic and X-ray equipment
can be used economically to the limits of their capacities. Fifth, and final,
by taking over the routine periodic prophylactic examinations, the fluorographic
mobile units will relieve the clinical X-ray laboratories of their enormous
time and labor consuming task of routine periodic X-ray and fluoroscopic ex-
aminations and enable them to use their time for the detection of other patho-
logic conditions, especially swellings of the gastro-intestinal tract. It
should be stated here, in an incidental way, that fluoroscopic examinations
do not require the use of X-ray films, and the time consumed in developing
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-------
them should result in considerable econ~.
It is not suggested that the organization of fluoroscopic mobile units
for the prophylactic examinations of workers in dust-generating occupations
should be established as independent institutions, rather they should be made
part of municipal and regional anti-tubercular dispensaries. Such mobile fluoro-
scopic units could also be advantageously attached 'to X-ray laboratories of
hygiene and of occupational diseases, or of hospitals of which such research
institutes constitute a part. In such cases the fluorographic mobile units
may act as applied scientific centers, offering timely scientific as well as
pr~ctical solutions in the detection and study of pneumoconiosis. Such studies
under such favorable conditions should be accompanied simultaneously b.Y clinical
and usual X-ray examinations. This can be accomplished by special teams of
physicians and other medical workers.
In connection with methods and procedures used in conducting fluoroscopic
examinations this author is in agreement with T. I. Morozova, who stated that
it was not practical in prophylactic examinations to fill in the cards of all
persons for purposes of ledger registration. ~ae cards should be used for
numbering the fluorograms. Only in detected, positive cases should special
cards be filled in.
In the study of a dust-borne occupational disease the knowledge of the
years of work at the occupation is just as important as the roentgenological
data. However, in checking the fluorogram the physician may find it impossible
to establish in each case the chronology of work under dust conditions, since
the search for this information in journals or other papers would unduly delay
the checking of fluorograms, in some instances to such an extent that the primar,y
purpose of mass examination and speed would be impaired. Present experience
suggests that the patient's work chronology be entered in the fluorographic card
which registers the number of the work team and the time showing the individual's
work record. Such information should be entered alongside the number of the
worker's chest X-ray. Thus, the fluorogram record will show the worker's serial
number and the length of work at the dust-generating occupation. Some numbers
and other data can be preprinted on the cards to hasten their filling out. The
material on the preprinted record cards can be modified or amended from time
to time, as need may arise.
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The Effeot of Combustion Method and of Fuel Type on the Content of
3.4-Benzpyrene in SmoKe Gases.
By
B. P. Gurinov.
(Moscow Scientific-Researoh Institute of Sanitation and nygiene imeni
F. F. Erisman at the R.S.F.S.R. Health Ministr,y).
Gigiena i Sanitariya, Vol. 23, No. 12, 6-9, 1958.
1 . 1
In previous report~ exper1menta data were presented on the occurrenoe
of oanoerogenio substanoes in atmospheric air pollutants and in smoke gases
generated by burning different types of fuel; results of experimental check
tests conducted with animals to determine the b1astomogenic action of tars
isolated from products of fuel burning and from atmospheric dust were also
presented. The purpose of the present study was to determine the effect of
different methods of fuel burning on the content of cancerogenic hydrocarbons,
. 2
particularly of 3.4-benzpyrene in smoke gases.
Methods of burning hard fuel differ. in different plants; the pulverized
and layer bed methods are examples of fuel burning methods most commonly in
practice. Hard fuel in the shape of lumps can be fed manually or by automatic
stokers, and the grates can be stationary or of the conveyor type. In mechanized
furnaces the fuel, fed manually or by automatic stokers, moves automatically
i.nside the furnaces and the cinders are removed while the coal is burning. At
present n~chanized furnaces are comparatively rare in the U.S.S.R. In large
boiler rooms of electric power and heat plants chamber furnaces are used for
burning powdered coal, a method by which more complete combustion is attained.
Both methods of fuel burnir~ were investigated to determine their effect on the
quantity of cancerogenic substances in smoke gases, as indicated by the content
of 3.4-benzpyrene in a known weight of particulate matter discharged with the
smoke. Dust samples were collected from boiler room smoke flues by an appropriate
aspiration method. The collected dust samples were extracted with dichlo=ethane
for the isolation of tarr,y substances, which were then tested for 3.4-benzpyrene
by the spectrofluorescent method.
Twenty-one samples were collected in boiler
1 Gigiena i Sanitariya, 1953, No.2; 1954, No. 10.
2 Dete~ination of J.4-benzpyrene was carried out by staff members of the
Chemical Laboratory of the Institute - V. L. Zore ana V. I. Belczerskiy.
Physic-
-260-
-------
rooms equipped with non-mechanized furnaces, 10 i~ boiler rooms with ~echanized
furnaces, and 30 in boiler rooms using the chamber combustion and powdered
fuel method of fuel burning. Determinations of 3.4-benzpyrene content in
smoke gases were made in 4 boiler rooms of the first group, 3 of which burned
coal from the vicinity of Moscow, and tr.e 4tt burned anthracite. Table 1
shows that 3.4-benzpyrene was present in all samples and that in nearly half
the samples the content of 3.4-benzpyrene ranged from 0.005 to 0.01%.
TABLE
1.
3.4-Benzpyrene content in flue gases emitted by manually fed
fire grate type of boilers.
I : No.
. .
Boiler i i
No. : Type of fuel I of
I : tests
: :
: I
1 Lower Kosco. 3
coal
2 Ditto 10
3 Ditto 5
4 Anthracite 3
Totals 21
Number of samples containing
3.4-benzpyrene in %
I :
0.001 f 0.005 i
0.0
0.01
1
6 3
4 1
2 1
12 6
2
1
3
In 3 boiler rooms 3.4-benzpyrene determinations were made at fuel feeding,
stirring, cinder removing, etc. The results indicated no regularity of dif-
ferences in the benzpyrene content; in only one set of samples collected d~ring
the poking and cinder removing stages were the concentrati0ns 5 - 10 times as
high as at other stages of fuel burning. Investigations in boiler rooms equipped
with different types of mechanized furnaces were conducted also in 4 industrial
plants. Two of the boilers burned coal from the vicinity of Moscow, one burned
anthracite, and one burned peat.
Results lieted in Table 2 show that the ma-
jority of samples from mechanized furnaces contained no 3.4-benzpyrene in the
smoke gases; in the remaining samples its content was at a minimum. Investiga-
tions for cancerogenic substances in smoke gases coming from burning of powdered
fuel were made in boiler rooms of electric heat and power plants during the
firing stage and when the fuel burning reached the steady burning stage. Fuel
oil was burned in the chamber in the first hours of the firing stage, after
-261'"
-------
which coal dust was blown into the furnace. The brief firing stage was char-
acterized by an uneven burning and was followed by steady and even process of
fuel burning. A follow-up study was made of the 3.4-benzpyrene content in
smoke gases of one boiler of an electric heat plant st~rting with the firing
through 14 days of boiler's functioning. In addition to benzpyrene content
in the samples of discharged smoke gases, the percentage of tarry substances
was also determined. The results are presented in Table 3.
TA:BLE
2.
3.4-Benzpyrene oontent in flue gases emitted by mechanical17 fed
fire grate type of boilers.
: : 1'0. : Number of samples containing
:Boiler : . :
I 'lype . 3.4-benzpyrene in ~
of fuel I of .
.0. :
I : tests .l 0.0 ! 0.001 : 0.005 : 0.01
I . .
. . i
: :
5 Lower 1Iosoo. 3 2 1
coal
6 Ditto 2 1 1
7 Anthraoite 4 3 1
8 Peat 1 1
Totals 10 6 3 1
TJ.BLE
3.
If'fee1i of chamber type of fuel burning on the content of tarr,y substances
and 3.4-benzpyrene in flue gases.
: Course of : Tarr,y : 3.4-benzpyrene
: : :
Sample taking time I ccabaS'tion : substances : in~
. :
. ' in % :
.
24 - 48 hours (~eriod Unstable 0.02 - 1.1 0.001 - 0.005
of coal tusing 0
7th'dtq Stabilized 0.02 Trace
9th dtq Stabilized 0.02 Traoe
o 11th dtq ~tabilized 0.00 Trace
12th dq Stabilized 0.01 Trace
13th dq Stabilized 0.00 0.00
14th dB.7 Stabilized 0.00 0.00
-262-
-------
The results show that the smoke gases contained tarry substances and
3.4-benzpyrene only during the firir~ stage; after even burnir~ became estab-
lished 3.4-benzpyrcne was no more detected. Similar results were obtained in
boiler rooms of several other electric power stations. The above can be re-
stated as follows: 1) with regard to atmospheric air pollution with cancero-
genic substances burning of powdered fuel appeared least harmful; 2) it was
possible to judge the degree of fuel combustion by the content of tarry sub-
stances in the smoke emission. Both points appear clear in Table 4.
TABLE
4.
Effect of combusticn regime and cf ccmbustion chamber construction on the
content of tarr,y substances in flue gases.
Type of fuel
I Type of I Tarr.y
I I substances
I fire chamber , 1n%
Manual 5.0 - 5.3
)(anual 3.6
Mechanized 1.4 - 3.4
Kechanbed 0.8 - 1.2
Chamber type 0.0 - 0.2
Chamber type 0.0 - 0.2
i
I
Combustion
regime
Lower Moscow coal
Anthracite
Lower Koscow coal
Anthraoite
Lower Moscow coal
Anthraoite
Oil
~er (ruel bed)
~er (tuel bed)
~er (tuel bed)
~er (tuel bed)
Powdered coal
Powdered coal
Peat
Analogous investigations in
boiler rooms using oil as fuel
showed that all soot samples had
a high content of 3.4-benzpyrene
(0.01%) and a large amount of
tarry substances. The results
are summarized in the fo:rm of a
block diagram which indicates
that the process of oil burning
liberated into the atmospheric
air the greatest amount of cancel-
ogenic substances. The method
of layer or bed burning in non-
mechanized furnaces produced considerably greater quantities of 3.4-benzpyrene
u
0:1.1 bur.nc,J'ire..grate _feedings Chamber
]land 1(eoh8ft1oa1 powd.ered
IIIi!II 0.01$ 3,4-benswrene. Leaa thaD 0.001%
m:a 0.005% II " E3 lione found
ESj 0.001$ II II
Content of 3,4-benzpyrene in flue gasea uaing
different types of fuel and different methods
of firing and combustion
-263-
-------
than in mechanized furnaces; chamber burning of powdered fuel did not produce
a~ cancerogenic substances in smoke discharges. On the basis of the above
it is recommended that boiler rooms using the bed or l~er coal burning method
should be equipped with mechanized furnaces; boiler rooms with non-mechanized
furnaces should be replaced b,y central regional boiler rooms and heating centers.
Bibliography.
r Y P H HOB 5. n., 30 P 3 B. n., 11 JI b H H a A. A. H ilp. fHr. H caH., 1953, Nt 2,
CTp. 10--16. - r Y p H HOB 6. n., M a ill Ci H ~ cII. Lt, III a Ci a il n. M. TaM >ICe, 1954, Ng 10.
CTp. 12-16. - K e H A H C b n. H., 6 a p ill Tell H 11. K. TonKH AJlI! C>lCHraHHI! MecTHOro
ronJlHBa. n.-M., 1949.-KHoppe r. cII. TOnO'lHble npo~eccbI. M.-J1., 1951.-ll.{ero.
JI e B M. M. TonJlHBo, TonKH H KOTeJlbHble YCTaHOBKH. M.-n., 1940. .
Purification of Cupola Furnace Gases Discharged into the Atmosphere.
Discussed at the Moscow City Council of National Economy.
By
L. S. Rozanov.
(Moscow Municipal Sanitary-Epidemiological Station).
Gigiena i Sanitariya, Vol. 23, No. 11, 86-87, 1958.
The problem of rendering harmless cupola furnace gases discharged into the
atmosphere was discussed at a meetine held M~ 26, 1958, b,y the Metallurgical
Section of the Technical Economic Council of the Moscow City Council for Eoono~.
Among the partioipants were staff members of teohnioal and planning institutes,
representatives of industrial enterprises, of the Sanitary-Epidemiologioal Sta-
tion of the City of Moscow, and of many other organizations, including represen-
tatives of various oities in the Soviet Union.
In his report Engineer A. M. Katsnelson pointed out that modem require-
ments for oity air purity make it mandatory that foundry operators develop
measures for dust elimination and for improved gas oombustion before they are
emitted into the atmosphere. The question of utilizing the heat produced by
the oombustion process for blast furnace heating was considered at the same time.
The speaker mentioned the faot that a method was found abroad for the operation
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of cupola furnaces with closed charge hole and complete suction removal of
waste gases which were subsequently burned in special chambers. A. K. Kats-
nelson stated that in January 1957, a cupola furnace was installed in the
foundr.y shop of a machine plant which was equipped with a separate air pre-
heater. The cupola furnace had provision for possible blast heating by burn-
ing waste gases and by utilizing the hsat produced b,y burning fuel in the fire
box. This furnace had an inside diameter of 400 mm and an operating height of
1700 cm which made possible the utilization of waste gas heat. The cupola
furnace had two rows of tuyeres, brick lined air box, and partition zones,
through which the cupola furnace gases entered the separation column, and
therefrom the supplemental combustion chamber. Then b,y means of a flue gas
pump the gases were drawn through a recuperator (recovery unit) and discharged
into the atmosphere. The air was forced into the recuperator b,y a high pres-
sure blower; from there is passed through a fett1ed air conduit into the tuyere
box of the cupola furnace. The recuperator consisted of a combination of a
radiation and tubular sections in one tower which permitted complete utiliza-
o
tion of furnace gases with a temperature of 1200 .
Observations of the operation of this cupola furnace indicated that the
utilization of waste gas heat made possible the attainment of high temperature
blast and cast and pig iron temperatures acquired by modern foundries. At the
same time it helped to solve to a considerable extent the problem of supple-
mental burning and purification of the gases before they were emitted into the
atmosphere. Due to the above features, the content of carbon monoxide and of
dust in the exhaust gases of this cupola furnace was 10 to 11 times lower than
in a furnace with a cold blast. A hot blast cupola furnace is economical in
the use of coke and cuts down on the amount of second grade products. Metal
turnover per m2 of furnace cross-section increased, indicating that a furnace
of such construction was highly efficient in addition to having sanit~ry-hygienic
advantages, as compared with cold blast furnaces. The gases given off during
24 hours b,y an ordinary cupola furnace of 15 - 16 tons p/hr production rate
carry with them into the atmosphere 730 - 760 kg of dust containing 40% of coke
and 1500 - 1700 kg of carbon monoxide. The above indicated ten- to e1evenfold
reduction in these air polluting substances constituted a considerable improve-
ment in the conditions of the atmospheric air.
I. O. Tsypin reported on a closed cupola furnace designed and constructed
-265-
-------
by the Central Scientific-Research Institute of Heavy Machine Building (TsNIIT
MASh). This furnace is equipped with a suction system which forces the cupola
gases through a two-step recuperator constituting a combination of a radiation
and a convection recuperator; it includes a combined cyclone and scrubber dust
removing system. Before the cupola furnace gases enter the convection recuper-
stor they pass through two vertical pipe dust retainers and a supplemental
combustion chamber. A cupola furnace with a 600 mm inside shaft diameter has
double-level tuyere arrangement and is equipped with two outlets for removal
of gases from below the grate and at same level above the furnace smelting
zone. With this furnace it is possible to superheat cast or pig iron to 15000,
increase the casting productivity by 50%, lower the coke consumption and purify
the furnace gases from dust and carbon monoxide. Dust removal by the cyclone
amounted to 65% and by the scrubber to 95%.
The management of the Voikov Cast and Pig Iron Plant decided to install
in foundr,y section 1 a closed type cupola furnace with a 15 - 16 ton per/hour
production capacity. of the Leningrad Institute "GIPROSTEKLO" design; the main
characteristics of this design were the complete removal of all blast furnace
gases through the side outlets located under the charging platform; this per-
mitted maximum utilization of heat produced by coke burning inside the furnace
and completely eliminated the emission of dust by blast furnace gases. Waste
gases taken from the cupola furnace entered the supplemental combustion chamber
where, in addition to combustion, the gases were subjected to preliminary dust
purification in a cyclone. Therefrom the blast furnace gases, heated to 8000,
entered the convection recuperator where they preheated the blast air to 5000.
After yielding most of their heat in preheating the blast air, the waste gases
passed through a second convection recuperato~ where they preheated the intake
air needed for shop ventilation; from there, now having a temperature below
.2500, they passed through an electrostatic precipitator for fine purification
from dust, and were then discharged into the atmosphere.
The operating characteristics of this type of cupola furnace, with blast
air preheated to 5000; are an increase in the furnace productivity, a reduction
in coke consumption, an increase in cast or pig iron temperature to 1430 -
14800, which results in better quality metal, in addition to improved sanitar,y-
~gienic conditions of the vicinity adjacent to the plant.
In connection with the fact that removal of waste gases in the cupola
-266-
-------
furnace is accomplished through side outlets beside the grate, the designers
introduced the following features I a special charging device which permitted
air-tight closing of the cupola furnace; the bringing up of charge material
into the charge compartment by a skip hoist; central blast furnace charging
and automatization of all lifting and charging operations, etc.
At present the plant is testing the. efficiency of Nlnu recuperators,
which are based. on the principle of regeneration. Plans are made to utilize
a recuperator of this ~pe instead of a convection recuperator of preliminary
preheatinB.
V. S. J9'sovak1i reported on "The Principles of a Cupola Furnace Design
Provided with Automatization of Controls and Regulation of the Smelting Process";
V. P. Jlizikin reported on "Intensified Cupola Furnaces with Tubul~ Water-
cooled Tenaion Screen, Rammed Lining and Distributed Blasti~t. Utilizatiqn
of suggestions contained in the reports offered possibilities for higher produc-
tiOl1 efficiency, improvement in the working conditions of cupola furnace opera-
tors.
It is of interest that the meeting of the Metallurgical Section of the
Technical-Economic Council ot the K08COW City Council of National Economy
demonstrated that, while the prilD8r7 purposes of the changes suggested and
applied to the operation ot cupola turnaces was to improve the quality and
increase the rate of produotion of metallurgical products, they also brought
about improvements in working conditions and in the 8an1tary~hygienic conditions
ot the atmospheric air and. in the general living conditions in the nearby
populated areas.
Industries having foundr,y shope should, on demand of sanitation authorities,
undertake a more erlensi ve reconstruction of cupola furnaces of medium and
larse production capacity. Plante with turnaces of small production capacity
mq not be able to rebuild their furnaces as per above suggestions, for sound
reasons ot econOlDl'. AccordiD6 to the plans of Councils of National EconoII\V
they must gradually discontinue operating and their assignments should be trans-
ferred to plants where reconstruction of furnaces has resulted in significant
capacity increase, or additional new foundry plants should be built.
-267-
-------
Street'Noise Abatement by Proper Allocation of Tree and
. Shrub Plantings in City Blocks.
By
P. I. Leushin and M. Ya. Nildtin.
(From the Leningrad Soientific-Research Institute of Sanitation and Hygiene).
Gigiena i Sanitariya, No.9, 8-15, 1954.
The importance of tree and shrub planting to city planning is great and
ma~ sided; trees deoorate the streets, parks and squares, absorb the air dust
and gases, reduce the number of air suspended baoteria, and lower the intensity
and spread of noise between city dwelli~s. Tree and shrub planti~g can also
serve as a positive psyoho-hygienic factor.
The sanitary hygienic importance of trees, shrubs and other green plants
has been well studied and described by U.S.S.R. hygienists Adamova, Anastas'yev,
Bragin, Beryushev, Fedynskii, Kharakhinov and others. However, only few reports
dealt with the effect of green belts on the intensity of city noise and its
reverberation from one place to another. Observations conducted in Moscow and
Leningrad by Fedynskii, Alekseev, Shapshev and Leushin were mere orientations;
the authors frequently oame to contradictor,y conclusions, stating that in some
instances the noise was intensified by the presence of trees, and in other cases
the noise intensity was reduoed. However, most reports noted the beneficial
effect of green belts in decreasing oity noise. None of the reports proposed
~ methods or green belt systems to be used in combatting city noise. Profes-
sor IC. N. ,Shapshev in his work "Problems of City Noises and Struggle Against
Them", published in Leningrad in 1939, attempted to approach the problem of
planning green zones in cities with a view to oombatting the street noises.
He measured the intensity level of the noise in the gardens and parks of Lenin-
grad in the summer, when the trees were in full foliage, and in the fall, after
leaf shedding.
The present authors studied the noise abating effects of green plantings
in the blocks of a residential area built and landscaped during the Soviet
regime. The purpose of the study was to determine the best way of planting
trees and shrubs in ~ city block to attain maximum noise abatement in the
streets and yards and arresting noise penetration into apartments through the
windows faoing the street. The study extended over three blooks along Lesnoi
-268-
-------
Avenue in Leningrad, which had been investigated by Professor K. N. Shapshev
in 1936 with regard to noise. At that time the trees and shrubs had just
been planted and they were free of foliage. At the present study the trees
have grown so that their tops reached the 4th floor level, and offered the
opportunity to study their effect on street noise blocking and abatement when
in full foliage.
The patterns of tree and shrub planting in the three blocks are shown in
Figures 1, 2 and 3. Dwellings in blocks 1 and 2 were built perimetrically;
the trees were tall and the shrubs were 2 - 3 meters high; they were planted
inside the block's perimeter 10 - 15 meters aw~ from the buiidings. Residences
in block 3 were arranged differently as shown in Fig. 3. The tall trees were
planted in the sanitary clearance zones between the dwelling rows; the main
entrance to the block, at the right comer, was surrounded by a. thick belt of
shrubs 2.5 m high.
The intensity level of the street noise coming from Lesnoi Ave~s
determined at different points of the block area. Lesnoi Avenue is an arterial
transport highw~ along which passed street cars, buses, trucks, etc. Sound
measurements were taken at 16 points for each of blocks No.1 and 2 and at 12
points for block 3. Addi tional sound determinations were made at three points
19
Q - rhe.s. -. Bushes
miD'lioise ~ncreasing
IZZJ .Iois~ ~abat1n&
Pig. 1. Block .0. 1.
1Jroe:- u::~~~
~ loise abating. .
JI1g. 2. Block 1io. 2.
-269-
-------
at the second floor level in
block 1. The noise intensity
determinations consisted of 15 -
19 readings taken on the sound
scale over a period of 20 minutes.
The 20 minute .readiDgs were re-
peated when necessary to obtain
a numerical value of the average
noise level for a given point,
with an error not exceeding ~ 0.3
of a phon (unit of sound). ' Such
a high degree preoision of sound
intensity determination was dic-
tated by the fact that changes brought aDout by the green clearance rare~
reached 6 - 7 phons. Unlike K. N. Shapshev, the present writers excluded the
sound of automobile horns. The noise from horns (determined in front of the
entrance of the block) was heard on~ on rare oocasions in this bloc~; in ad-
dition, automobile horn noise intensity inside the block differed somewhat
from the usual n~ise of 50 - 60 phons caused by the wheels and exhaust of the
traffic. The curves of noise intensity are inversely proportional to the die-
, tance from the point of origin, as shown by the straight line presented in Fig.
4. The points' numbers where noise measurements were taken are indicated in
Fig. 1.
Curves in Fig. 4 show that the horn noise decreased considerably more than
the general traffio noise, but at point 7 it inoreased by 3 phons as compared
with point 6, owing to the reflection from the wall of the rear building. The
average traffic noise dcreased more evenly and had the same intensity at point
7 as at point 6. In addition, the intensity level of the noise from traffio
was considerably below that from the horn. It soon became apparent that measuring
of natural street noises, representing the true picture of the noise field in
the block, required greater precision than measuring the noise from an artificial
loud source. The results of the street noise determinations inside the three
blocks are listed in the following Table.
1-
~. .M OJ> 0 Q
O~~. :
oQ ! 00 ~4 !
Jo8~ I
00 ,~O 0 0 QP 6
~: J,QO ~ ~ ::~i~]
O-tree. ,,<) .ahe.
Iig. 3. Block 10. 3.
o
3
. Areas of'increased and decreased noise
and 2 as per legends, thus illustrating the
ings. Investigations of noise intensity at
-270-
intensity are indicated in Figs. 1
noise-abating effect of green plant-
the level of man's height in block
-------
increased noise intensity was recorded
at points 2, 6, 7 and 15. All other areas
in block 2, including those close to the
inside walls, showed a considerable de-
crease in noise intensity. Thus, at
points 3, 4, 5, 13 and 14, lying close
to the inner walls of the buildings, noise
intensity decreased by I - 5 phons in the
summer, when foliage was fully unfolded.
In comparing the conditions under
which the noise penetrated from the street
into blocks 1 and 2, it can be seen that
the street noises penetrated into block No.1 through the clearance spaces ba-
tween the buildings and entered into the space between the green belt and the
walls. In block No.2 the street noises penetra~ed into the space surrounded b.y
the green strip. It has been known that green tree crowns not only'absorbed
sound energy, but also reflected it. According to P. I. Leushin (P. I. Leushin,
The Effect of Tree Planting on the Distribution of Street Noises, Gigiena i
Sanitariya, 1949, No.6) 14% of sound energy which encountered leaves was re-
flected by the green tree crowns. This explains why the noise near the building
walls of block 1 increased when the trees were in foliage. The space between
the green belt and the walls is a corrider along which noise spread without ob-
struction; the brick walls reflected about 91% of the noise'falling upon them;
the ground surface, paved with cobblestones and forming the floor of the oor-
ridor, reflected less of the noise; the third side of the corridor was a solid
row of trees with wide crowns. Hence, the large concentration of sound energy
60
78
2
"
.~ rJ
""
,
,
'\4
"
~\"
~
2
'6 "
:,...'
.?..: ~
0 ,4
8 -i""-- ~
6 ........ 6 7
4
2
0
76
71
72
CD 70
!68
o
.J:t 66
PI
s:: 6#
...t
62
~
~.60
~ "6
CD
,.a 56
s::
...t 54
: 52
...t
05
.
4
4
4
4
4
.10 20 JO 40 50 60 70 80 9Jl 100 1//0 /20
..ters from source or no se
---Whistle - -1frimsporl
rig. 4. Abating intensity ot noise
in & block bu11 t Q pe1"1metrical:q
as' tiie' s-tii,ight-line distanoe trom
the source ot noise inoreases.
1 indicated that in the summer, when
the foliage is fully unfolded, the noise
decreased only at 3 points located within
the green belt at the center of the block.
At the points inside the block, close to
the building walls, the noise was louder
in the presence of full foliage. This
seemingly paradoxical phenomenon can be
explained on the basis of the results of
observations in block 2 where slighly
-211-
-------
Average level of street noise in phon.. which penetrated into
the blocka in the 8UIIII1er d~~ fUll foliage and in the fall
atter foliage shecl-'i-c
Block '0. 1 Block No.2 Block 110. 3
A'"" NO A'"" A~ . A" ~N':
~... .
. .... pi P .. . .
: . Ar-I : .. Art 0 .0 . . '""
80 .. .0 .. Pt 'SIIII "" ~ A
'S'" ~~ ....... 'SI: 0
... .: l1li.. .. ... E4
2 52,5 52,8 -0,3 1 56,4 55,9 +0,5 1 56,1 52,4 +3,7
3 51,5. 51,5 0 2 48,6 49,1 -o~5 2 48,6 45,8 ,+2,8
4 48,2 49,'2 -1 3 43 41,8 +1,2 7 45 43,4 +1,6
5 46,6 47 -0,4 4 46,5 41,6 +4,9 8 41,6 40,6 +1
6 44,6 45,6 -1 5 44 41,9 1+2,1 9 42 39,6 +2,4
7 44,4 45,9 -1,5 6 42,4 43,3 -0,9 12 44,1 37,8 +&,3
8 41.2 43 -1.8 7 38.3 38,8 -0,5 13 42 41.1 +0,9
9 43.1 43 +0.1 8 44,4 42,S +!,9 14 42 40,2 +1.8
10 46 44,6 +1.4 9 44.1 41,6 +2.5 1 46,3 44,7 +1.6
II 45.1 44.5 +0.6 10 43 40,8 +2,2 18 45,6 43,6 +2
12 44.8 46.6 -1.8 II 43.9 41,7 +2,2 19 44,3 38.5 +5,8
13 45,1 47 -1.9 12 - - - 20 43,1 36.4 +6,7
14 43.5 45 -1,5 13 45,3 44,2 + 1.1
IS 44.7 47,4 -2,7 14 43. 42.3 +0.1
16 45,7 47.1 -1.4 15 41,8 42,3 -0,5
17 46.5 47,2 -0,7 16 42,9 41,9 +1
18 46,8 46.2 +0.6 17 42,7 38,9 +3.8
19 '42.9 47,5 -4,6
20 35.8 42,4 -6.6
in this corridor finds its explanation. In block 2, the flowing noise directed
into the space surrounded b;y green vegetation was absorbed to a considerable
degree b;y multiple reflections from the green tree crowns. A small amount of
noise energy' penetrated into "the corridorstl between the dwelling walls and
the clumps of trees. The pattem of noise diffusion observed and its explana-
tion are the chief governing'aspects to be considered in planning the location
of green strips between urban buildings. By taking into account the reflected
and absorbed energy', it is possible to determine all other deflections from
the noise diffusion caused by green tree crowns. It is to be noted that at
points 19 and 20 sound measurements taken at the 2nd floor level in the summer
-272-
-------
were louder by 5 - 7 phons, due to sound energy reflected from the tree crowns.
An examination of the pattern of noise diffusion in block No.2, after
the leaves have unfolded, showed that intensity of the street noises at point
1 remained practically unchanged, since the 0.5 phon decrease observed barely
exceeded the limits of experimental error. At point 2 the noise slightly in-
creased due to the reflection of sound waves from the tree crowns in the first
row. Although the increase at this point was also 0.5 phon, its value was ac-
cepted as significant because the initial noise was slightly lower at point 1
in the summer. At points 6 and 7, where the noise entered through the clear-
ance space between the buildings on the right, the slight increase in noise
intensity in the summer can be explained by the same fact of the sound re-
flection from green tree crowns. The increase in noise intensity in the summer
at point 15 in comparison with points 14 and 13 can be explained by the clear-
ance space implanted with shrubs near point 15, through which sound waves
penetrated from the green belt.
The results of observations on noise penetrating from Lesnoi Avenue to
block 3 (see Fig. 3) show that at all points of this block there was a slight
decrease in the intensity of noise caused by the trees in full folia~. The
greatest decrease of about 6 phons was observed at points 12, 19 and 20. All
these points were surrounded by green strips, protecting them from the direct
penetration of sound waves. At points 1 and 2, outside the green belt, con-
sisting of lilac shrubs, noise intensity decreased by 3 - 4 phons in the summer.
At points 17, 18, 19 and 20, noise from Lesnoi Avenue came chief~ in the form
of sound wave reflection. In the absence of foliage on the trees, the brick
walls of dwellings served as the sound wave reflectors when the trees were in
foliage, the leafy crowns of the trees and shrubs reflected the sound waves.
The noise intensity decreased as a result of the absorption of sound waves b,y
the foliage of the green belts. The cause of decrease in noise intensity was
as follows: the effect of foliage was significantly more noticeable at points
19 and 20, which were further removed and which the sound waves reached after
multiple 'reflections.
Some authors are of the opinion that covering the outside walls of build-
ings with sound-absorbing plaster or some other sound-absorbing material, such
as climbing vines was a useless adaptation for the combat of street noises
(S. P. Alekseyev. Investigation of Noises in Moscow, M. 1950, page 85). This
opinion was based on a maximum difference between noise intensity determined
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at similar distances from the source (30 m), but under different conditions,
such as in an open space where the sound travel was unobstructed, and in a
street with intervening 6 stor,y buildings. The difference amounted to 10
phone. The author erroneously assumed that to decrease noise intensity by
10 phons it was necessary to cover the walls with a plaster which provided
sound absorption equivalent to that of open space, that is, a sound-absorbing
. coefficient equal to 100%. This assumption might be correct only if the in-
tensity of the noise in the streets was produced by direct sound.waves re-
flected only once. Actually, however, noise created in a narrow street re-
sults from repeated reflections of sound waves superimposed on. the primar,y
ones. For this reason the effectiveness of sound absorbing plaster or of
climbing vines is considerably greater than that which might follow from the
above reasoning. The results
62
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Meters fram source of noi,.e
- Grass covered grouild
- - - - Bare ground
Fig. 5. Brfect of grass on noise intensit7
at different distances from source ot Doise.
-274-
of our observations conducted
at Mars Field in Leningrad
convinced us that the position
taken by the present authors
was correct. The curves in Fig.
5 record the intensity of noise
caused by traffic at different
distances from the street-car
line; determinations were made
under different conditions of
grass-seeded or bare soil. The
results show that covering the
ground with growing grass and
obviating the sound-reflecting
properties of only one surface
decreased the noise intensity at
all points by 6.3 to 7.5 phons
on the average. It is also
generally known that street
noises decreased in intensity
when there was light snow on
the ground. Therefore, it seems
safe to asgume that climbing
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vines on the walls of buildings or
sound-absorbing plaster covering the
external surface should be effective
means for street noise abating.
Figure 6 indicates that the loud
traffic noise decreased in the summer
and fall farther away from the main
highway (Sadovaya Street) in Mikhail-
ovs1di Park where, in addition to grass,
there were century old trees.
This is a report of studies of
methods for planning locations of tree
and shrub plantings in city blocks to
absorb noise originating in the out-
side streets.
However, a source of
noise originating inside the block is
of equally significant and practical interest. To protect residential dwellings
from such noise, it is recommended that trees be planted along the perimeter of
the area from which the noise originated. An effective impenetrable green
barrier should consist of a combination of shrubs and tall trees with heavy
foliage. .
Summary .
1. By proper distribution of green belts inside a city block, it is pos-
sible to maintain the noise within the limits of ! 6 phons.
2. To decrease the noise penetrating from the outer streets and to reduce
their reflection from the building walls facing inside the block, it is neces-
sary to plant the trees in such a way that sound waves which penetrate into the
block would be directed towards the surrounded space.
3. A shrub barrier located between the source of noise and the enclosed
area of the block is beneficially effective.
4. Wall climbing plants and ground grass
penetrated into the block.
covering decreased noises which
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A Compendium ot Ofticial Materials Related to Problems ot Sanitation
and Prophylaxis.
Supplement to Books 1 - 3 ot the U.S.S.R. Ministry of Health,
State Ptlblishers, Medical Literature, Moscow - 1955 - J(edgiz.
P8B88 89, 90 and -21; items 28, 29 and 30.
Item 28. - Limitations in the Use ot Jalousie Ash Abaters "V'l'I" (All-
Union Technioal Institute) tor the Purification ot Smoke Gases trom Ash.
A circular (letter) issued b.1 the Main State Sanitary Inspeotion ot the
U.S.S.R. tinistry ot Health, March 27, 1953, and coded 128-53.
Jalousie ash abaters ot theVTI design have been adopted recently by
boiler-operated plants and electric heat and power stations tor the purifi-
cation ot smoke gases trom ash. Authorities ot the State Planning organiza-
tions included this type ot jalousie ash abaters in their plans ot industrial
building construction on the basis ot questionable recommendations; their
choioe ot this typeot puritier in preterenoe to battery cyclones, cyclones
and electrostatic precipitators appears to have been motivated primari~ by
the fact that the VTI jalousie ash abater was ot smaller dimensions and its
construction and installation were more economical. By now evidence has ac-
cumulated which I'ilows convincingly that most of the WI jalousie ash abaters
operated at low efficiency and,henoe, the ~egree otsmoke puritioation from f~
ash left much to be desired. The information now in possession ot the various
organizations ot the All-Union State Sanitary Inspection and the results ot
investigations carried out b.1 the Institute Giprogazo-otchistka and b,y the
Institute WIIOGAZ and by Trust Gazo-otchistka accumulated during their 1949 -
1952 studies ot the operation ot jalousie type ot ash abaters can be summarized
in the following conclusions.
1. In the case ot burning powdered coal the residual ash content ot smoke
gases atter having passed through jalousie ash abaters amounted to 5 - 7 g or
more per nm3 (at 00 and 760 mm mercury), this is approximately 2 - 3 times as
high a residual ash content as -as found in smoke gases ot similar type purified
b;r battery cyclones. Such a high pollution ot atmospheric air with ashes must
not be allowed. The serviceability ot jalousie ash abaters in the case ot
smoke gases coming trom powdered coal burning ranged beheen 6 - 10 monthe.-
due to the fact that jalousie grates wore out under the impact ot the ash par-
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ticles; as compared'with this battery cyclones, for instance, have approximately
five times as long a period of serviceability.
2. In layer bed combustion of coal the residual content of ash in smoke
gases after purification with jalousie ash abaters amounted to 1 - 2 slnm3,
when lower Moscow coal was burned, which is 3 - 5 times as high a residual
ash content as was found after smoke gas purification with a batter,y cyclone
or cyolone of NIIOGAZ design (NIIOGAZ-Nauchno-Issldovatel'skii Institute
Otchistki Gaza, or Soientific-Research Institute of Gas Purification).
3. In burning lump or milled (cut) peat. the residual content of ash in
jalousie ash abaters amounted to 1 - 2.5 g/nm3 of the smoke gas.
Attention should be called to the fact that the efficiency of jalousie
type of gas pur,ifiers is greatly affected by changes in the volume of gas
passed through per unit time. Deviations above or below the rate of gas pas-
sage for which the jalousie purifier was designed greatly reduce its efficiency,
and under normal praotioal conditions such deviations occur frequent~. The
jalousie apparatus manifested the tendency to frequent clogging by ash, which
constitutes another faotor leading to considerable drop in performanoe effi-
cienc,yJ the need to frequently clean the jalousie gas purifiers hinders its
convenient utilization in practice.
In view of the above the All-Union State Sanitar,y Inspection offers the
following suggestions to industrial administrators and to industrial planning
organizations:
a} In boiler operated plants and in electric hut and power stationsl
whioh burn powdered coal, the installation of jalousie apparatus for the purifi-
cation of smoke gases is not recommended. Built in jalousie ash abaters are
mere technical adaptations for the sole purpose of protecting the tail surfaces
of the heat unit, of the economizers, the air preheaters, etc. It is, therefore,
recommended that in making plans for the purification of smoke gases no provision
should ba made for the installation of jalousie ash abaters.
b) In boiler units which burn coal in layers over fire grates jalousie
ash abaters may be installed where the coal consumption is not in excess of 5
tons per hour and only in such plants which are located favorably in so far as
sanitar,y-h,ygienic conditions are concerned, i.e., plants which are surrounded
by adequate sanitary clearanoe zones, or plants which are located in regions
where the sanitary-hygienic requirements are not too high. In a11 other in-
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stances it is imperative that ash abating installations be of high efficiency,
such, for instance, as cyolones of the NIIOGAZ design or batter,y cyclones.
c) Boiler-operated plants and heat and power electric centers which burn
lunlp or cut (milled) peat may resort to the use of jalousie ash abaters pending
special instructions and regardless of the rate of fuel consumption.
Item 29. - The Use of Ash-Removing Apparatuses "Cyclone LIar with Water
Film" for the Purification of Ventilation Air.
Circular (letter) issued by the All-Union S;ate Inspection, Karch 27, 1953
as code No. 127-53.
The All-Union Scientific-Research Institute of Labor Protection VTsSPS
in Leningrad (LIar-Leningradski Insti tut Okhrany Truda) designed a dust sepa-
rating apparatus trade-named "Tsiklon Liot with a Water Film". In its design
this apparatus is a vertical qyltnder made of steel sheeting. A continuous
film of water runs down its inner surface; the water comes from a series of
water outlets arranged at the uppermost part of the cylinder. The dust-laden
air enters the cylinder at right angles to the axis of the cylinder from an
inflow pipe attached tangentially to the cylinder; after having been purifiedJ
the air en ts at the upper part of the cylinder from an outflow pipe similarly
attached to the cylinder. Upon entering the cylinder the air is given a ro-
tating motion. The separated dust drops down into a conical bin attached to
the lower part of the main cylinder, wherefrom it is removed through a speoial-
ly provided opening attachment.
It can be readily seen that the basic principle of this dust remover is
that of a cyclone type of separator the efficiency of which is considerably
enhanced by the continuous water film. In the usual dry cyclones the final
removal of the separated dust is accomplished in the lower end of the cone ~
a special opening which forces the dust into a special bin or bunker. Thus,
in the dry cyclone the dust particles thrown against the inner wall of the
cylinder by the centrifugal force upon the entrance of the dust-laden air into
the cylinder continue to stay wi thin the cyclone as components of the total
whirling mass. In the water film cyclone (wet cyclone) the dust particles
thrown against the inner surface of the cylinder wall by the centrifugal force
are immediately taken out of the whirling air by the downflowing water film.
This, then, is the essential difference between the dry and wet (water film)
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c,yolone types of dust separators. The separated duet partioles in the water
film oyclone oan not be torn aw~ from the surfaoe of the oyclone and, hence,
can not re-enter the general whirling mass of air or gas; onoe separated from
the dust-laden air the dust particles can not be carried out into the atmos-
pheric air, hence the greater purifying effioiency of the "Cyolone LI01' with
Water Film".
The Institute designed six sizes of this type of cyclone with capaoities
ranging between 1200 and 10,000 m3/hour of air. Where greater air purifying
oapaoi ty is required, several such _oyclones can be installed in parallel series.
Another advantage of the "Water-Film LI01' Cyoloni" is its ease and simplicity
of oonstruotion; aQy well supplied equipment building plant or shop can oon-
struot it.
Cyolones LIOT with Water Film can be recommen~ed for the purification of
aspi~ation and ventilation air from dust wherever wet type of air purifiers
can be installed. It is not recommended for the removal of adhesive or cementing
type of dust. It is recommended that air with a dust content exceeding 2 g/m3
undergo preliminary dust purification in a dry cyolone or inertia dust abater
before passing it through the Cyolone LI01' Water Film type.
The Leningrad Institute of Labor Protection (LIOT) obtained the following
infomation (data) regarding the performance efficiency of the water film
oyclonea
1. Tests were made with a two-step air purification, the first consisting
of two parallel operating dry LIOT cyolones and the seoond of two wet film LIOT
oyclones. The dust-laden air was ooming from a ooal grinding section and from
the coal dust conveyer department of an electric heat and power station; the
original dust content ranged between 1.5 - 2.0 g/m3; after the above system of
purification the residual air dust ranged between 13 - 16 mg/m3.
2. Tests with foundry air dust removal by the water film LIOT cyclone
gave the following results a
a) With a gravimetric 16% content of dust particles of up to 1 cm/seo
motility the degree of dust purifioation reached 98.7%;
b) With a gravimetric 26% content of dust particles of similar motility
the degree of dust purifioation was 93.4%.
3. Results of tests with sand blast dust particles were as follows:
a) With the use of a two-step dust purifioation, oonsisting of a
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dr.y LIOl' cyclone and a water film LIOl' cyclcne and with a gravimetric 25% ot
dust particles ct up to 1 em/sec motility the degree of purification reached
99.1%,
b) With the use of a 'two-step dus!_{l~fication, consisting of
inertia dust abater and LIOl' water film cyclone and with dust load a8 above,}
the degree of dust purification amounted to 99.4%.
It required 45 -.65 kg of metal to build a water film cyclone of 1000
m3/hour capacity, exclusive of the metal required for installation and a
water consumption of 0.13 - 0.3 1/m3 of air. The cyolone oreated a pressure
drop of 40 - 80 mm of water.
More detailed information conceming the LIOl' oyolones can be obtained
from the Soientific-Research Institute of Labor Protection, Leningrad, Gagarin-
~a 3 (U.S.S.R.).
The All-Union State Sanitar.y Inspectorate suggests that in making provision
for ventilation and aspiration installations authorities responsible for in-
dustrial production plants request of the basic planning organizations a more
general resort to the use of Cy-clones LIOl' with Water Film for the purifica-
tion from dust of air discharged into the atmosphere by industrial production
and processing plants.
. Item 30. - Supplement to Circular (Letter) Issued by the State Sani ta1'1
Inspectorate of the U.S.S.R., Karch 27, 1953 under Code No. 128-53, Regarding
Limitations in the Use of Jalousie Ash Abaters VTI for the Purifioation of
Smoke Gases fram Ash. (September 7, 1954, No. l12~2/5-l002).
Wi th reference to inquiries coming in regarding the possible application
of jalousie type ash abaters to the purification of smoke gases the )lain State
Sanitary Inspectorate of the Ministr.y of Health of the U.S.S.R. offers the
following clarifying oomment I
In boiler operated plants which bum ooal by the
grates the use of jalousie ash abaters is permissible
sumption is not in excess of 5 tons per hour.
.
In exceptional cases where the boiler operated plant is located in a
region where the sani t8l'1-qgienic surroundings and other conditions are highly
favorable, jalousie ash abaters may be installed for the purification of
smoke gases, provided, however, that the coal oonsumption is not in excess of
8 - 10 tons per hour. The same applies to boile~operated plants, the technical
l~er method over fire
only where the coal oon-
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\
taolli tie. ot which make 'the installation of other types ot ash abaters not
teasible, provided, in 'this ca.e, that other stric'tly local supplemental cor-
rection measure. oan be resorted to.
In the preparation ot new plans tor the oonstruction ot boile~perated
indnstrial production and processing plants the responsible industrial opera-
tors must dcand that provisions be made for the installation of ash removers
ot hipe.t operating ettioienC7, suoh, for instanoe as oyolones NIIOGAZ, if
the volume ot puritied p.e. 1s not expected to exoeed 50,000 m3/hour, or
batte1'J' 0101one.,1t the volume ot pIB8 to be purified is '%peoted to be in
0:0e8S ot 50,000 113/hour.
\\
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