TT-64-11574
$3.50
U.S.S.R. LITERATURE ON AIR POLLUTION
AND RELATED OCCUPATIONAL
DISEASES
Volume 9
IN TWO PARTS
A SURVEY
*>Y
B. S. Levine, Ph. D.
Introduction by Luther L. Terry,, M. D. , Surgeon General
United States Public Health Service, Department of Health,
Education, and Welfare. Washington 25, D. r.
Distributed by
U.S. DEPARTMENT OF COMMERCE
OFFICE OF TECHNICAL SERVICES
WASHINGTON, D.C. 20230
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,
-
U.S.S.R. LITERATURE ON. AIR POLLUTION
. .
. AND RELATED OCCUPATIONAL
.DISEASES
. Volume 9
,. ~
, . ~~2~V\O'V .
INTWO PARTS L'1?=ks Vi 'b'VU-
A SURVEY
by
8. S. levine, Ph. D.
. ,
. Introduction by Luther L. Terry,. M. D., Surgeon General
United States Public Health Service, Department of Health,
Education, and Welfare. Washington 25, D. ('. '
Di,tributed by
U.S. DEPARTMENT OF COMMERCE
OFFICE OF TECHNICAL SERVICES
WA~t1'NGTON n, O,C
i
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- ~ -- . ---- ,?~.
The two original Russian Books of which this Vol. 9 consists
are entitled as follows in transliteration
PREDEL'NO OOPUSTIMYE KONTSENTRATSn ATMOSFERNYKH
. : ZAGRYAZNENII' /.
--..-- --- -- -----
Vypusk VI --.. _. -- -. .
. Pod Redaktsiei Prof :V.. A. Rya.zanova : (1962)
'-------------------
Ditto as above word for word
Vypusk VII
1963
ii
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OTHER TRANSLATIONS, lOOKS ANI SURVEYS BY DR. B. S. LEVINE DEALING'WITH USSR AIR AND WATER ~OLLUTION
CONTROL AND RELATED OCCU~ATIONAL DISEASES AVAILAILE FROM U.S. DEPARTMENT OF COMMERCE, OFFICE OF TECHNICAL
SERVI CEG, WAGHI NGTON 25, D.C. '
SANITARY PROTECTION OF ATMOSPHERIC AIR"
PURIFICATION OF INDUSTRIAL DISCHARGE
GAGEG FROM SUSPENDE8 SUISTANCES.
LIMITS OF ALLOWABLE CONCENTRATIONS 0'
ATMOSPHERIC POLLUTANTS, BOOK 1
LIMITS 0' ALLOWABLE CONCENTRATIONS 0'
ATMOSPHERIC POLLUTANTS, BOOK 2
LIMITS OF ALLOWA8LE CONCENTRATIONS OF
ATMOSPHERIC POLLUTANTS, BOOK 3
LIMITS OF ALLOWAILE CONCENTRATIONS 0'
ATMOSPHERIC POLLUTANTS, BOOK ~
LIMITS OF ALLOWA8LE COICNETRATION6 0'
ATMOSPHERIC POLLUTANTS, BOOK 5
U.S.S.R. LITERATURE ON AIR POLLUTION ANI
RELATEI OCCUPATIONAL DISEA6E$o
j SURVEY. VOLUME 1
U.S.S.R. LITERATURE ON ~IR POLLUTION ANI
RELATEI OCCUPATIONAL DISEA6E&.
A SURVEY. ,VOLUME 2 '
U.S.S.R. LITERATURE ON AIR POLLUTION ANI
RELATED OCCUPATIONAL DISEASEG.
A SURVEY. VOLUME 3
U.S.S.R. LITERATURE ON AIR POLLUTION ANI
RELATED OCCUPATIONAL DISEASES.
A SURVEY. VOLUME ~
U.S.S.R. LITERATURE ON AIR POLLUTION ANI
RELATEI OCCUPATIONAL DISEASES.
A SURYEY. VOLUME 5
U.S.S.R. LITERATURE OR AIR POLLUTION ANI
RELATEI OCCUPATIONAL DISEASE&. '
A SURVEY. VOLUME 6
U.S.S.R. LITERATURE OR AIR POLLUTION ANI
RELATED OCCUPATIONAL DISEA&ES.
A SURVEY. VOLUME 7
. U.S.S.R. LITERATURE ON AIR POLLUTION ANI
RELATEI OCCUPATIONAL 0ISEA6ES.
A SURVEY. VOLUME 8
59-21092 153 pp 3.00
~21173 135 pp 2.75
~21174 163 PP 3000
~21175 I~ PP 3.00
61-111<48 123 PP 2.75
6~116C6 I~pp 2.75
OG-21 O~
210 PP
3.&>
60-21188
04.00
260 pp
60-210475
352 PP
4.00
60-21913
281 pp
4.00
61-11149
3.&>
219 pp
c.;~
61-21928
299 PP
. 04.00
6a.lll03
336 pp
5.00
63-11570
04.00 '
275 pp
ill
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U.S.S.R. LITERATURE OU WATER SUPPLY ARD
POLLUTiOn COUTROL.
A SURV(Yo VO~~E 1
61~31MI
233 pp.
UoS.S.Ro L'T(RAfUQ~ OU WATER SUPPLY AUD
POLLUTIOU COUTROLo
A SURVEY. VOLO"E 2
61-311'.01':'2
249 pp
U.S.SoRo LITERATURE 06 ~TER SUPPLY ADD
POLLUT,eu COUTftOLo
A SURVEYo VOLUfiE 3
t;1-31501-3
248 PI'
UoSoSoRo LIYERATUR~ Og.WATEQ SUPPLY 4De
POU..,T I ElD COUTR O&,. .
A SHRVEYo VOLDflU 4
61-31001-4
204 PI'
3050
4000
4000
3025
FOR 80"PARIBOU OF "[TRIC AUD CUGT~ARY uniTS FR~ 1 TO 10 SEE HAUDBOOR 0' CaEfllGTRY ADO.PNVSICQ
POOLI80ED BY Tua CnEfllCAL RUDBER PODLI6NIU6 COo, 2310 SUPERIOR AVENUE, NoEoo CLEVELABO, 0"100
II3CtlEG AnD "ILLlftETU60 IUlltES ADD CEUTlfiEHAS, FEET AU flETUliI, UoSo VADOGI. &138 "nUll,
U.So "ILES ADD KILCAET!BG-
SQUAua I!CUEG ADD aQUARE MILLIMETERS, SQUABE laCNES ARB SQUARE CEUTlfiETER3, BQUARE FEET
ADD 6QOARE "ETaDS, 3QUARE YARDO AaD SQUARE I'IETEA8, GQUARE MILES AUB SQUARE RIL~ETIRg -
CUBIC IBcnES AUB CUBIC fllLLlfiETERSo CUBIC IACNE8 Aao CUOIC CEDTI"ETERSo cuole FEET ADD
CU81C "ETERS, COBIC YARDS ADD CUOIC flETERS, ACRES Aao HECTARES-
MILLILITERS A~D Uo50 OYUCE&D MILLILITERS ABD.UoS. APOTMECARIES' GRAI'IS, AILLILIT2AQ ABD
U.So APOTnECAQIES' SCRUPLES, LITERS Aao U.So LIQUID QUARTS, LITERS AAD U.S. LIQUID
GALLOU60 (C~PUT2B OR T~E OA&16 1 LITER m 1.000027 60018 DECIAETERS)o
LiHR6 AIiID U.So DR.Y QUARTS, LITERS AlII} U.So PECKS, IHCALITERG UP U.S. PECItS,
~ECTOLITERS AAD UoSo BUaQELS9 UECTOLITERS PER HECTARE ANB U.So BUSHELS PEa AeaE.
(C~PUTE9 OR ABOVE 04515)
OYQ~B P2RTIDEQT CODVEROIOO TABLES AD2 POE6EBTED O~ succaEOIAO PAOE50
iv
hiE 2947
PAGE 2948
PAGE 2949
PUE 2950
PAGE 2951
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Russian Alphabet
STANDARD ITALICS NAME TRANSLITERATION
A a a ah a
E 6 6 beh b
B B 8 veh v
r . r t geh g
J1 ;( iJ deh d
F. e e yeh e
iK H< :Nt: zheh zh
3 3 a .zeh z
11 H U ee
n ". jj ee kratkoye
}\ K " ka k
.TI .' .II el 1
M roc .M em m
H H H en n
o 0 0 aw 0
n n n peh p
p p p ehr r
C c c e88 s
T T M teh t
y Y 11 00 u
cII $ rfi ef f
X X. z hha kh
~ 11 If t8eh ts
q 'I .. tcheh eh
1lI ill au sha sh
~. 1.U 1If sheha sheh
o D " mute hard sign
bl y w yeri y
b b b mute 80ft Sign
a 3 a eh oborotnoye e
JO JO KJ yoo yu
II II II ya y.
----
. .
v
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INTRODUCTION
This, the ninth volume of a series of English translations,
by Dro Benjamin So Levine, of U.S.S.R. scientific papers on air
pollution, consists of Books 6 and 7 from a series edited in .
the original by Va A. Ryazanovo Professor Ryazanov is chairman
of the Committee on the Determination of Limits of Allowable
Concentrations of Atmospheric Pollutants, and a member of
Moscow.s Institute of Postgraduate Medicine and of the Fe Fe
Erisman Central Scientific Sanitary Institute.
Like its predecessors, this volume contains mainly papers
related directly to allowable concentrations of various air
pollutants, or indirectly, as is the case with a number of
papers devoted to the detection and measurement of certain
pollutants 0 Descriptive tables of contents appear at the
beginning of this volume and on page 1370 The first three
paragraphs of the opening paper further indicate the scope
and approach of the entire volum~o
Especially in view of the new interest in the development
of Federal criteria for ambient air quality and emission
limitations--as exemplified recently in a specific provision
of the Clean Air Act, which President Johnson signed on
December 17, 1963--these papers should be timely and usefulo
To a large extent, they reflect a basic difference between
Russia and the United States in the scientific approach to,
and study of, the complex problem of developing air quality
criteria and standards of allowable concentrations of air
pollutants.
In the Soviet. Union, the limits of allowable concentrations
are developed from data obtained from animal and human subjects,
by checking their responses--such as conditioned reflexes,
sensory physiology, neurophysiology, and electroencephalographic
I
[
i
I
vi
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.. - -... --- - -- --------
- .
-- --- --~
-------
changes--to various concentrations of various pollutants at
different time exposures. In the United states, the basic
research on the adverse effects of air pollutants has been
in the fields of pulmonary physiology and pathology; the
etiology of bronchitis, asthma, emphysema, and other obstruc-
tive ventilatory diseases; enzyme and immunological studies;
and the carcinogenesis of certain air pollutants.
A highly complex research problem is involved here and,
before the final solution is found, all avenues must be
explored and thoroughly evaluated. Certainly, scientists
should be informed of the philosophy of approach and the
procedures and techniques of study being used by their
colleagues in other nations. Dr. Levine has earned the
commendation of all of us who are concerned with this serious
problem of environmental health for continuing to make the'
Russian findings available.
Educa~ion,
vii ,"
------.-----------.-.- -----
-------
.--..
CONTENTS
-.....---...- -.
Introduction by Luther L.. Terry, Surgeon General \U.S.'P.H~S~ I
Li~;ts ~. ~'~~I(ow~b(e G~c~1~i,\~: -~l'.~~~'i>~~
\>c\\u1-~j-S ~ I
New Data on Limits of Allowable Atmospheria Air Pollutants.
-~ V.A. Ryazanov. Chairman of the Committee on Sanitary
Protection of Atmospheric Air of the Chief State Sanitary
Inspectorate of the USSR
vi
Hygienic Evaluation of Formaldehyde as an Atmospheric Air
Pollutant. V. P. Melekhina.
!",
1
9
18
29
40
47
Data for the Hygienic Evaluation of Hydrochloric Acid Ae rosol
(Hydrochloride Gas) as an Atmosphe ric Pollutant. E. V. Elfi mova.
A Restudy of the Maximal Allowable Single Concentration of
Carbon Disulfide in Atmospheric Air. R.S. Gil'denskjol'd.
Atmospheric Air Pollution with Manganese Compounds and their
Effect on the Organism. V.F. Dokuchaev and N. N. Skvortsova.
Supplemental Data on the Accumulation and Distribution of Mercury
in the Organism of Experimental Anim.:".ls. V. M. Kurnosov.
HygieniC Dete rmination of Limits of Allowable Concentrations of
Chlorine and Hydrochloride Gases Simultaneously Present in
Atmospheric Air. V. M. Styazhkin.
Acetone as an Atmospheric Air Pollutant.
Yu. G. Fel'dman.
55
62
~ New Data for the Hygienic Evaluation of Carbon Monoxide in
Atmospheric Ai~. T. M. Shul 'ga. .
Hy'gienic Evaluation of Dinyl as an Atmospheric Air Pollutant.
G.1. Solomin.
73
82
Methods for the Control of Atmospheric Air Pollutant with Radio
Active Aerosols. Yu. V. Sivintsev and N.N. IS:hvostov.
93
viii
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conTENTS (Can.)
Methods for the DeterminatiQn of Atmospheric Pollutants.
M. V. Alekseeva.-
107
107
109
111
114
115
117
119
121
123
125
127
129
131
Determination of Acetates
Determination of Dinyl
Determination of Isopropylbenzene
Determination of Styrol
Determination of Acetone
Determination of Acetophenone Vapor
Determination of a -Methylstyrol
Determination of Isopropylbenzene Hydroperoxide (IPBHPO)
Determination of Furfurol -
Determination of Ethylene Oxide
Determination of Total Monobasic Carbon-containing Acids
Determination of Methylmetac rylate
Determination of Dimethylformamide
Appendix. Yu. D. Lebedev. Approved by the Deputy Chief
Government Sanitary Inspector of the USSR. 14th February,
1961, No.221-61.
134
-.
ix
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CONTENTS (Con.)
l;~lt~ ~~ Al(ow~b(e ~c~ih.'fc'~.r d~ Ai~d'rl~~c-
\>aUU\"&4.r ~l?o.::Jk 7
A Summary of 1961 Studies in the Field of Limits of Allowable
Concentrations of Atmospheric Air Pollutants. ,V.A. Ryazanov.
Atmospheric Air Pollution with Furfurol and its Hygienic
Evaluation. R. Ubaidullaev.
Experimental Data for the Hygienic Evaluation of Atmospheric Air
Pollution with Styrol. Lee Shen.
Hygienic Evaluation of Atmosphe ric Air Pollution with
Dimethylformamide. D. G., Odoshashvili.
Experimental Basis for the Limit of Allowable Nitrogen Dioxide
Concentration in Atmospheric Air. P. P. Yakimchuk.
The Effect of Low Phenol Concentrations on the Organism of Man
or Animals and their Hygienic Evaluation. B. Mukhitov.
An Automatically Regulated Apparatus for Chronic Toxicity
Expe ri me nts with Ani mals. B. K. Baikov and V.!. Shull gin.
Methods for the Determination of Some Organic Atmospheric Air
Pollutants. M. V. A1ekseeva and' P. G. Tkachev.
Determination of Aniline
Determination of Xylol
, Determination of n-butylvinylester
Determination of Dimethylterephthlate
Determination of Phenol with 4-Aminoantipyrine
Determination of Some Air Pollutants by the Spectrophotometric
Method in the Ultraviolet Region of the Spectrum. M. D. Manita
Spectrophotometric determination of Naphthalene in Indoor Air
, Spectrophotometric determination of Acetophenone in the Air
Spectrophotometric determination of Isopropyl Benzene in the Air
Spectrophotometric determination of Styrol in the Presence of
Dinyl in the Air
x
138
142.
; 155.
169 ..
177
185
200
203
203
205
207,
209
210
213
215
.. 216
218
- 219'..--
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PART
I
LIMITS OF ALLOWABLE CONCENTRATIONS OF
ATMOSPHERIC POLLUTANTS
BOOK 6
Professor V. A. Ryazanov, Editor
B. S. Levine, Ph. D. .
Translator and English Editor.
Washington, D. C., U. S. A.
1963-1964
This survey was'supported by
PHS Research Grant AP-00176
Awarded by the
Division of Air Pollution, U. S. P. H. S.
xi.
- -----
-------
New Data on Limits of Allowable Atmospheric Air Pollutants
V. A. Ryazanov
C.hairman of the Committee on Sanitary Protection of Atmospheric
Air of the Chief State Sanitary Inspectorate of the USSR
This volume contains material discussed by the Committee on Sanitary
Air Protection partly during its 1959, but basically during its 1960 session.
The material contained in this volume is of heterogenous character in its
methodological presentations and completeness and finality of the reports.
Thus, the reports of Yu. G. Fel'dman, G.I. Solomin, and T. M. Shul'ga
are carry overs from the previous period of the Committee's work, when
the search for basic principles underlying the determination of limits of
allowable concentrations included 24 hour animal exposure and electro-
encephalography, investigational procedures which were being progressively
improved. Reports of E. V. Elfimova, R.S. Hildeskjold, and V. P. Melekhina
had been completed at an earlier period of the Committee's activity when the
investigational methodology was in a sense limited. Some of the included
material represents portions of incomplete investigations; such, for instance,
is the report of Dokuchaev and Skvortsova; or the material may be supple-
mentary to previous communications, such, as the report of V. N. Kurnosov.
It is not possible to evaluate all the material included in this volume on
the basis ofa single standard; but on the whole, the material shows a gradual
yet progressive tendency in the direction of more basic investigations, finer
scientific judgement, and less speculative approach.
The Committee took the position that the level of methodology reached
during the last period of investigation and the degree of reliability of results
obtained did not represent the ac me of perfection, and therefore, the proposed
limits of allowable concentrations should be regarded as me re points of ori'en -..
tation for future studies, leading to more basic, more scientific and hence, more
reliable limits of atmospheric air pollutants. In this connection it is the aim
and purpose of this Committee to act as the stimulator, guide and directing
agent leading into investigational channels based on the above outlined prin~
ciples. .
Formaldehycie-: Melekhina was the first in the USSR who studied formaldehyde
as an atmospheric air pollutant. No information could be found in the USSR
literature prior to Melekhina' s work on formaldehyde concentration in the
atmospheric air of populated areas. Melekhina was the first who showed that
formaldehyde could be detected at long distances from the source of discharge,
such as formaldehyde producing plants, and that it was a widespread atmos-
pheric pollutant, since it was one of the components of the automobile gas
-1-
-------
discharge, especially of the Diesel engines. Melekhina I s laboratory studies
determined that the concentration of threshold formaldehyde odor perception
in highly odor sensitive persons was 9.07 mg/m . afd that odor nonpercept-
ible concentration for formaldehyde was 0.05 mg/m. The concentration of
threshJ>ld reflex effect, as indicated by optical chronaxy tests, was 0.084
mg/m . Inhalation of formaldehyde vapor elicited considerable changes in .
the character of the curve of d~rk adaptation; the3threshold formaldehyde
concentration was 0.098 mg/m , and 0.07 mg/m was the inactive concen-
tration. However, she recommended that the limit of allowable formaldehyde
concentration in at~ospheric air be set at 50% of the determined threshold,
i. e. at 0.035 mg/m , to allow for the coefficient of safety. At such concen-
tr~tiori the odor of formaldehyde was non-perceptible and elicited no reflex
changes in optical chronaxy and optical analyzer sensitivity to light.
At the time Melekhina conducted her experiments the electroencephalo-
graphic method had not been adopted as a practical means for the study of
limits of air pollutant concentrations; this method was characterized by a
considerably higher sensitivity than any of the methods used by M.dekhina.
However, this was fully compensated by the safety factor fortunately re-
commended by ¥elekhina. The Committee approved Melekhina's recommend-
ed 0.035 mg/m as the maximal single formaldehyde concentration in atmo-
spheric air as well as the 0.012 mg/m3 limit of average 24-hour concen-
tration, which is 1/3 of the above limit of single concentration of formaldehyde
in the air. Investigation of formaldehyde as an air pollutant must continue;
Melekhova I s work must be checked by the methods of reflex effects, includ-
ing the electrocortical conditioned reflex method and chronic animal toxicity
experiments. Such studies have been included in the Committee's plans for
future investigations.
Hydrochloric acid aerosol: E. V. Elfimova investigated basic conditions for
the determination of limits of allowable HC 1 aerosol concentrations in atmo-
spheric air. Plants producing magnesium and titanium constitute potent
sources of HCl discharge. E. V. Elfimova was first in the USSR to become
interested in atmospheric air pollution by HC 1 aerosol. Most of the previous.
investigators were interested in total chlorine in the air, pollution _which included
hydrogen chloride gas and chlorides, despite the fact that the toxic properties
of these components were different. E. V. Elfimova recognized this and began
her investigation with a search for methods for the determination of HC 1 in
the presence of C 1 and chlorides. She used the titrimetric method for the
determination of acids, taking care to eliminate effects of H2S04 normally
present in the air.
Elfimova found high HC 1 aerosol concentrations in the atmospheric air
on the lee side of a magnesium plant. Her laboratory studies established the
concentration of threshold HC 1 odor perception, thresholds of HC 1 effect on
reflex optical chronaxy manifestations. on eye sensitivity to light, on the fre-
quency and rhythm of respiration, on finger plethysmograph. (vascular toni-
city), etc. The concentration of HGl threshold odor perception, as deter-
,"
r.,
-2-
-------
mined by Elfim<3va, was O. 1 mg/m3, and the non-perceptible concentratlon
was 0.05 mg/m . No reflex reaction changes were recorded by any of the
above mentioned indicators during the inhalation of air contajning O. 05 mg/m 3
of HCI gas. Therefore, Elfimova recommended 0.05 mg/m as the maximal
single concentration of HCl aerosol in atmospheric air. Elfimova conducted
no chronic toxic animal experimentj. Despite this omission, the Committee
provisionally accepted 0.015 mg/m as the average Z4-hour HCl aerosol
concentration in atmospheric air.
Carbon bisulfide: The report of R. S. Hildenskjold deals with the problem of
carbon bisulfide air pollution. . This pollutant is discharged by the growing
viscose industry in progressively increasiny quantities into city atmospheric
air. The previously established 0.5 mg/m limit of CSZ concentration
in atmospheric air was criticized by practical sanitarians. The odor of CSZ
was felt at distances from the source of its discharge at which its concen-
tration in the air was below the limit of allowable concentration. It was im-
perative that the old standard be carefully checked and revised, if necessary,
at the earliest possible opportunity, since the old limit was used as the sani-
tary basis by the Planning Committee and by managers of viscose plants who
used the old CSZ limit standard as reason for not installing equipment in their
production departments. R. S. Gil'denskjold was assigned the task of checking,
and if necessary of revising the old standard.
Results of Gil'denskjold's inve stigations indicated that the odor of CS Z
vapor was clearly perceived Z km on the lee side from the viscfse plant
where the atmospheric air contained not more than 0.18 mg/m of the vapor,
or approximately 1/3 of the officially allowable CSZ vapor concentration i~
atmospheric air. Results of a laboratory restudy showed that 0.05 mg/m
was the absolute odor perception threshold of CSZ vapor concentration as
indicated by tests made wit~ persons highly sensitive to the odor of CSZ gas,
and that only at 0.04 mg/m air concentration did the CSZ vapor odor ~ecome
non-pe rceptible to all the test subjects. EmployiJlg the optical chronaxy pro-
cedure Gil'denskjold demonstrated that O. 5 mg/m3, the then existing official
limit of CSZ vapor concentration in atmospheric air, elicited a sharp rise in 3
optical chronaxy. In fact, even concentrations as low as 0.05 C3fd 0.04 mg /m
elicited some changes in optical chronaxy, and only 0.03 mg/m of the gas
elicited no change in optical chronaxy. In the case of eye adaptation to dark-
nes s the statistically reliable concentration was 0.04 or slightly higher. In-
crease in eye sensitivity to light during CSZ vapor inhalation was directly
proportional to the concentratio~ of the gas in the inhaled air. In one case
inhalation of 0.04 - 0.05 mg/m of CSZ vapor raised the eye sensitivity to
light, while higher concentrations lowered it. In brief, the results indicated
that the previously adopted limit of CSZ vapor allowable concentration in
atmos~heric air was too high. Therefore, the Committee accepted 0.03
mg/m ; recommended by Gil'denskjold, as the limit of allowable single CSZ
vapor in atmospheric air, since it was the subthreshold concentration accord-
ing to the results of all the tests made.
-3-
-------
However, R.S. Gil'denskjold conducted no chronic experiments and
failed to present new evidence related to the limit of allowable average 24-
hour concentration. On the basij of the above experiments the Committee
temporarily adapted 0.01 mg/m as the limit of allowable average 24 hour
CSz concentration in atmospheric air, with the understanding that the norm
was subject to future experimental verification or revision.
Manganese: The limit of3allowabl~ Mn concentration in atmospheric air was
previously at 0.03 mg/m on the basis of approximation and called for ex-
perimental checking. It should be added at this point that no basic data had
been found in the USSR-literature relative Mn. concentrations present in the
air surrounding sources of Mn discharge. V. F. Dokuchaev and N. N.
Skvortsova were the first to present factual evidence regarding the presence
of Mn in the atmospheric air surrounding a metallurgical plant smelting
ferromanganese. They found that the air was considerably polluted even at
1 km from the plant, and that the pollution with Mn was high in the air
surrounding the plant. In fact, the Mn penetrated into dwellings polluting
the inside air, indicating that the problem of manganese air pollution was
factual wherever the ferrometallurgical industry existed. A medical study
among the children of the region had shown a high morbidity rate in diseases
of respiratory organs, ears, throat and nose. However, Dokuchaeva and
. Skvortsova were not able to establish any direct causal relationship between
the morbidities and Mn as an air pollutant, and further. studies in that direc-
tion are still indicated.
Dokuchaeva and Skvortsova tried to supplement and to reinforce their
studies by subjecting animals to experimental intratracheal MnO'Z dust. s~s - .
pension administration which produced changes in the histological picture o~
the lungs. Howeve r, the evidence thus obtained was not adequate as a basis
for the dete rmination of limits of allowable Mn concentrations in atmosphe ric
air. Chronic inhalation experiments must be performed in series of graded
Mn concentrations in the air, which the authors of the report. are planning to
cOriduct in the near future. In this connection it should be noted that intra-
; .traCheal introduction of dust suspensions can not be regarded as a basis for
. the hygienic standardization of particulate atmospheric air pollutants, since
the data presented by such a method are remote and indirect; it is recommend-
ed that it be replaced by a more basic procedure having a more direct bearing
on the problem.
Me rcury: A report by V. N. Kurnosov appeared in Book 5 dealing with the
effect of mercury on the higher nervous system of experimental rats sub-
jected to chronic mercury vapor inhalation. The experiments demonstra.te.~
that inhalation by rats of mercury vapor concentrations as low as 2 I-L.
affected the functional state of the cerebral cortex. In the present volume
-'V.N. Kurnosov reports on the results of his contInued studiesrelated'to mercury
. accumulation within the organism and its effect on the morphology of internal
organs of the rats which he previously used in his conditioned reflex studies.
The results indicated that rate of Hg accumulation in the internal organs was
- --_.. -- .
... -_.- ".-. -------.
-"--- ---
-4-
-------
directly proportional to the mercury vapor concentration in the inhaled air.
Accumulation of Hg in the organs was' notable even at such a low concent1:.ation
as Z u. . ' Tissues of rats which inhaled air containing 0.03 I-L of
mercury could not be distinguished from tissues of the control rats. The
pathomorphologic pictures of the internal organs of the experimental rats also
ran in direct proportion to the 'Hg vapor concentration in the inhaled air. An
analysis of the accumulated data led V. N. Kurnosov to the conclusion that the
existing USSR official limit of 0.3 mg, Im3,of mercury in atmospheric air was
well founded.
The combined effect of chlorine and hydrochloride gas: Chlorine and hydro-
chloride gas are present in combination in the air of many production indus-
tries, especially of plants producing manganese and titanium. This Committee
felt the urgency of the problem related to the determination of the limit of
allowable concentration of simultaneously present chlorine and hydrochloride
gas in the atmospheric air. V. M. Styazhin's report included in this volume
deals with this subject. V. M. Styazhin accomplished the following - (I) he
verified the threshold odor concentration previously established by E. V.
Elfimova for hydrochloride gas and by M. T. Takhirov for chlorine, (Z) he
showed that the odor of the two components acted in a direct additive manner
in above threshold concentrations, and {3} he demonstrated that the odor of
the two substances combined was not pe.rc-eptible at levels of their correspond-
ing limits of allowable concentrations, nor did the combination of the two gases
have any effect on reflex reactions of eye sensitivity to light or of optical chron-
axy. Accordingly, V. M. Styazhkin concluded that in the simultaneous HC 1 and C'l
presence in atmospheric air, the limit of their simultaneous concentrations can
be evaluated on the basis of each component individually. The Committee felt
that V. N. Styazhkin's conclusion had to be varified by the methods of electro-
cortical conditioned reflex procedure and by chronic experiments with labora-
tory animals.
Acetone: The production of acetone has been gradually increasing in connection
with its expanding use by diffe rent industries in the USSR, and especially by
plants producing acetone silk. New plants are now being built in the USSR for
the production of synthetic acetone, and simultaneous production of synthetic
phenol, the demand for which is also constantly increasing in the USSR. This
created the need for the determination of the limit of allowable acetone con-
centration in atmospheric air. The study of this problem was assigned to Yu.
G. Fel'dman.
The concentration of threshold acetone odor perception by highly odor
sensitive persons was established at 1. 1 mg/m3, and the concentration of non-
perceptible odor was 0.8 mg/m3. The acetone concentration representing th~
threshold of eye sensitivity to light in most sensi!ive persons was 0.55 mg/m ,
and the non-active concentration was 0.44 mg/m . However, this concentra-
tion of acetone in air elicited conditioned electrocortical reflexes when it was in-
haled in association with light as an unconditioned stimulator, and resulted in
the desynchronization of the alpha-rhythm. No electrocortical reflexes could
-5-
-------
be developed with O. 35 mg/m 3 concentration of acetone. Therefore, Fe11dman
recommended that this concentration be adopted as the maximal single allow-
able concentration. .
Fe11dman then conducted_chronic experiments with rats for the purpose
of establishing the limit of allowable average 24-hour acetone concentration.
His experiments indicated that no deviati0rlj from the normal were noted in
rats exposed to the inhalation of 0.5 mg/m of acetone vapor 24 hours daily.
uninte rrupted for 45 days. Records kept of gain in weight, growth, blood
picture, and histology of internal organs and brain tissue appeared normal.
Motor chronaxies of muscle antagonists were also normal, evidencing com-
plete absence of function<'31 changes in the central nervous system. Fel'dman
concluded that 0.5 mg/m of acetone was not harmful even- under conditions of
contin~ous 24 hours of animal exposure ~ Fe11dman recommended that O. 35
mg/m of acetone in the air be officially adopted as limit of maximal single
as well as average 24-hour concentration in atmospheric air. The Committee
felt that Yu. G. Fel'dman IS presentation of expe rimental data and his reason-
ing and recommendation were logical and convincing and adopted his recom-
mendations.
Carbon Monoxide: The limit of allowable CO concentration in atmospheric air
adopted in the USSR was arrived at by the method of calculation. L.S. Gor-
sheleva found that chronic 3xposure of experimental animals to inhalation of
air containing 20-30 mg/m of GO for six hours daily disturbed the animals'
conditioned reflex activity. In accordance with the calculation I;>revailing jt
that time the Committee adopted 1/10 of that concentration, or! 2 mg/m of
CO, as the limit of3allowab1e average 24 hour CO concentration in atmospheric
air, and 6 mg/m , or three times the average of 24 -hour concentration, as
the maximal allowable single concentration of CO in atmospheric air. These
standard values had not been based on experimental data and were in fact
strictly conditional, and, accordingly, were subject to future verification ~r
revision. The paper by T. M. Shull ga is a report of results of such a study.
It has been generally agreed that the limit of allowable maximal single -
concentration of any air pollutant must be of magnitude at which a short period
exposure must produce no effect on the conditioned reflex reactions of the
organism. Therefore, Mme. Shullga undert<.?s>k, as thE) first step of her study,
to determine whether the previously adopted 6 mg/m concentration limit for
CO accorded with the above definition of a maximal single concentration. For
this purpose she had chosen the electroencephalographic ~ethod as the most
sensitive. Results of her tests showed that even 20 mg/m of CO had no effect
on the reflex reaction of brain biocurrents either directly or through the forma-
tion of conditioned electrocortical reflexes. This indicated that CO w<'3s not
taken up by the receptors of the respiratory organs and that the mg/m concen-
tration of CO accepted by the Committee as the maximal allowable single CO
concentration in atmospheric air had no effect on the human organism when
inhaled for a, brief period of time.
-6-
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The validity of the average 24-hour 2 mg/m3 CO concentration in atmo-
spheric air was checked by T. M. Shul 'ga by chronic animal exposfre experi-
ments. Results showed that inhalation of air confaining 2.0 mg/m of CO
continuously for 24 hours slightly depres sed the experimental animals' por-
phyrin metabolism, produced slight histopathological changes in the tissues
of the central nervous system, especially of the brain cortex. Changes in the
motor chronaxy of muscle antagonists could not be disregarded even though
they we1je not of substantial values. . Mme. T. M. Shul'ga recommended that
1 mg/m of CO in atmospheric air should be officially adopted as the limit of
its allowable average 24-hour concentration in the air. In considering Mme.
Shul'ga's recommendation the Committee felt that full justification for the re-
commended concentration was lacking, but unde r the existing circumstances,
the Committee agreed with Mme. Shul' ga' s rec~mmendation and lowered the
average 24-hour3concentration limit to 1 mg/m and retained the previously
adopted 6 mg/m value as the limit of allowable single concentration of CO in
atmospheric air.
Dinyl: Development of the synthetic industry, especially of the synthetic fibers
industry, brought about the need for high degree heat carriers. Dinyl is among
the best heat carriers which attained wide distribution in the world industry.
The use of vinyl in many industries resulted in the pollution of air with its
vapor which raised the problem of the hygienic evaluation of atmospheric air
poUution with vinyl vapor. The study of this problem was assigned to G.!..
Solomin. Dinyl is a mixture of diphenyl and of diphenyl oxide. At first ~on--
sideration it might appear that under the circumstances the study ofdinyl as
an air pollutant should begin with a study' of each component's limit of
allowable concentration. This assumption proved to be wrong. Dinyl is .
a eutectic mixture of the two substances and upon vaporization retained its
original composition. Therefore, dinyl although a complex of two compounds,
behaved as an entity even upon evaporation, and should be evaluated as an
entity from the sanitary-hygienic view-point.
Dinyl possesses a highly unpleasant specific odor. Results of G. 1.
Solomin's investigations had shown that the concentration of dinyl ~dor per-
ception, as registered by odor sensitive persons, was 0.08 mg/m. However,
lower odor non-perceptible dinyl concentrations were physiologically actire,
and elicited in man different reflex reactions. Thus, even at 0.04 mg/m con-3
centration dinyl affected the optical analyzer sensitivity to light; at 0.03 mg/m
concentration dinyl had no recordable effect on eye sensitivity to light. Yet,
even such a dinyl concentration could not be accepted as the official limit of
its allowable concentration in the air, since Solomin demonstrated that at this
concentration in association with some unconditioned stimulator, such ~s light,
it was possible to develop conditioned reflexes, and only at 0.01 mg/m dinyl
concentration was he unab~e to elicit conditioned. reflexes; in othe: wo~ds, o~ly .
beginning with 0.01 mg/m concentration does vmyl become physlologlc~lly- m-
acti've for man. Accordingly, G.1. Solomin recommended that 0.01 mg/m3
dinyf concentration be officially adopted as the limit of its allowable single
concentration in atmospheric air.' The Committee on the Protection of Atmo-
-7--
-------
concentration in atmospheric air be set at the
he recommended for the single concentration.
recomrnendation.
This volume also contains two methodological reports. One was pre-
sented by Yu. V. Sivintsev and N.N. Khvostov, dealt with some problems re-
lated to the determination of radioactive pollution of atmospheric air; the other"
report by M. V. Alekseeva contained new data on methods for the determi~a-
tion of different chemical air pollutants in atmospheric air. M. V. Alekseeva
described methods officially adopted by the Committee for the determination
of acetone, dinyl, isopropyl-benzene, styrole, acetates, acetophenone, alpha-
methylstyrole, hydroxide of isopropylbenzene, furfurol, ethylene oxide,
carbonic acids, methylmetacrylate and dimethylformamide. Selection of
the methods was not purely accidental. Some of the methods have been under
investigation in the past and some material had been included in Book 5 of
this Committee (acetates), or in the present volume (dinyl and acetone),
other material is still under investigation and will be- included in a forth-
coming book. The analytical procedures as such are characterized by
simplicity of procedure and use of material and equipment accessible to
most provincial laboratories and are designed to possess high degre~ specific-
ity and sensitivity. "
The volume ends with a Table of limits of allowable concentrations of
atmospheric air pollutants adopted by "the USSR, 1st of January, 1961.
spheric Air accepted Solomin I s recommendation.
Solomin then reported on the results of his chronic experiments with
animals, exposed 24 fours daily for 70 days .to the inhalation of air contain-
ing 10 and 0.1 mg/m of dinyl. Results indicated that at 10 and 0.1 mg/m3
concentrations, dinyl elicited in the experimental anim3.1s progressively in-
creasing functional shifts which disappeared shortly after the discontinuation
of the experiments. The shifts were in the nature of disturbed muscle ant-
agonists I chronaxy ratios, reduced rate of _porphyrin elimination with the
urine, changes in cholinesterase activity and considerfble increase in the
numbers of leucocytes and lymphocytes. At 10 mg/m dinyl concentration
these shifts were more pronounced. Data obtained with either of the dinyl
concentrations we re analyzed statistically and found reliable. The gene ral
condition of the3experimental animals which chronically inhaled air contain-
ing 0.01 mg/m differed in no particular aspect from the general condition
of the control animals. Therefore, Solomin concluded that the limit of allow-
able single concentration of dinyl in atmospheric air previously recommended
by him should be considered harmless even under chronic conditions of ex-
posure. Following the example of Fel'dman and many other investigators,
G.1. So!omin recommended that the limit of allowable averaQ'e .24 -hour diny!
3 .
same 0.01 mg/m level which
The Committee accepted his
-8-
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Hygienic Evaluation of Formaldehyde as an Atmospheric Air Pollutant
v. P. Melekhina
Department of Community/Hygiene of the Central Institute of
Pos t -G raduate Medicine
Formaldehyde (HCHO) . is an organic aldehyde which possesses a specif-
ic sharp odor, turns into a c0lorless immobile thick fluid having a b. p. of -210, .
and hardens into a snowy mas s at -920. Its density as compared with air is
1. 04. It is easily water soluble and takes on a molecule of H20 which converts
it to a monohydrate (CH20H- H20) or to methyleneglycol - CH2(OH}z; 35 - 40%
aqueous solution of formaldehyd.e..is known as formalin. At normal room
temperature, and especially at warm temperature, formalin gives off formal-
dehyde gas. Upon boiling formaldehyde forms a polymer which precipitates
in the form of a white amorphous substance, known as paraform. Formal-
dehyde easily reacts with a number of organic and inorganic substances, and
in the presence of acids and alkalies forms condensation products, as describ-
ed by G.S. Petrov and others in 1946. By such a procedure ~echnical forma_l-=_-
dehyde resins are formed; the bases of such resins can be phenol, cresol,
_l'!~P.t~()~, casein, urea, etc. Formaldehyde synthetic resins have found wide
application in the production of plastics, glue s, lacquers, etc. Examples of
these are rongalite, ethylene glycol, pentaerythrin, and others. Formaldehyde
is also used in the manufacture of dyes, such as indigo, rosamine, aurine,
acrylic dyes, and other; formaldehyde has been used in the hi de tanning in-
t~~stry, in tanning furs, in the paper industry, to render paper fat and water
impermeable, and in metallurgy, to lower oxidizability; in the texile industry
formaldehyde was used to inc rease fastness of dyes, pigments, powders.
Formaldehyde is used in many other industries in the form of rongalite,
geraldite, decrolyn, and in combination with bisulfite and hydrosulfite.
Formaldehyde has been used in photography in perserving plant and
animal anatomical specimens, etc. It has also been used in the preparation
of urotropin, explosives and in the rubber indstury. In his book "Formalde-
hyde", published in 1953, Walker des.cribed 3.0 types of industrial production
in which formaldehyde was used as such or in the form of one of its conden-
sation products. It is easily seen why formaldehyde has become one of the
most important products in the chemical industry. According to Walker's
incomplete figures the world consumption of formaldehyde amounted to 600,000-
800,000 tons annually, of which more than .400, 000 - 500,000 tons were con-
sumed in the production of synthetic resins, constituting 60-65% of the total
amount of formaldehyde.
-9-
-------
17- ",.
--~--.
. .
.. ,,'_.~.O~'- -"~.-'.r'J,~' '-1"::'-~';,;", ; . .-
No reports were found in the literature which dealt with formaldehyde.
as an air pollutant; some scanty reports were found which dealt with studies
of the air in working premises of plants using formaldehyde. Therefore, the
present author undertook to make a study of this subject and to secure mater-
ial for the hygienic evaluation of formaldehyde as an atmospheric air pollutant,
using the colorimetric method described by Deniges in 1910 and the Schiff re-
agent.At the end of this investigation the present author used the method of
Eegrirve, published in 1937, in which chromotropic acid was used as the main
reagent. Formaldehyde entered into reaction with chromotropic acid forming
a soluble substance of a violet color. Data of this investigation and results of
Yu. N. Gladchikova and N.' I. Shumarina presented in 1958 coincided ve ry
closely'. In both instances the chromotropic acid and the Schiff reagent methods
were used. The sensitivity of the Schiff reagent method was 0.0007 mg/ml.
A modification of the Schiff reagent method was developed under the direction
of M. V. Alekseeva using the FEK-M electrophotocolorimeter; the modifica-
tion established optimal conditions for the development of the determining color.
Fresh double distilled water was used as the formaldehyde absorber. Air
samples were aspirated through U -shaped absorbers equipped with porous glass
plates #2. Results of preliminary tests indicated that complete absorption of
the formaldehyde occurred at air aspiration rate of I li/min. For the deter-
mination of high formaldehyde concentrations 6 -8 li of air were aspirated through
the absorbers; determination of low air formaldehyde concentrations required
the aspiration of 60-70 Ii of air. Limits of the o~timal test sensitivity were
. established between 0.014 mg/m3and 0.2 mg/m . The threshold of formalde:-
hyde odor sensitivity in man was used as the index for the determination o( the
limit of allowable formaldehyde concentration in atmospheric air. A review of
. .
the literature showed that no unanimity of opinion existed regarding the thres-
hold concentration of formaldehyde odor perception. Thus, V. B. Isachenko
, (1940) shored that the threshold of formaldehyde odor perception ~ man was
0.3 mg/m , while Van Ven-Jan (1956) believed it to be 1. 4 mg/mJ. In view
of such opinion differences the present author found it neces sary to reinvesti-
gat~ the problem of formaldehyde concentration of threshold odor perception.
Desired formaldehyde vapor concentrations in air were attained by the method
recommended by the Committee on Limits of Allowable Concentrations of Atmos-
pheric Pollutants. (1) Air was aspirated through a special glass apparatus
which contained 5 ml 'of formalin. The volume was kept constant by replacing
amounts evaporated by the air current. Twelve persons, 19 to 64 years of age,
were used as test subjects in determining the threshold concentration of formal-
dehyde vapor odor p'e rception. Only one concentration of the formaldehyde was'
tested on anyone day, and tests were repeated on three successive days. Thres-
hold concentrations were established for each of the test persons. The final
threshold concentration of the vapor odor perception was the one which the test
subject positively identified in two of three tests.
(I) OTS 59-21175, Book 3, 1957, p 96
-10-'
-------
Persons who identified correctly one threshold concentrations in three. .
successive tests were subjected to a new series of tests. The total number of
tests was 269. Data in Table 1 show that the concentration30f formaldeh~de
vapor odor perception ranged between 0.07 and 0.11 mg/m ; 0.07 mg/m of
the vapor was jhe threshold concentration for most odor sensitive persons,
and 0.05 m/m was the subthreshold concentration.
The concentration of formal-
dehyde vapor threshold percep-
tion established by the tests re-
flected the interaction between
the exte rnal medium and the
organism. Appearance of per-
ception, that is, consciousness
0,05
0,07 of effect on the sense organs'
0,08 involves the participation of the
---- .---- brain cortex. However, absence
of odor perception is no indication of the fact that formaldehyde concentration
below the level of odor perception had no effect on the central nervous system.
The correctness of this postulate was checked experimentally with low formal-
dehyde concentrations and their effect on some physiological functions. ..
The method of optical chronaxy has been recently used in hygienic in-
vestigations on a wide scale by M. T. Takhirov, MoM. Plotnikova, E. ,V.
Elfimova, and K. A. Bushtueva, and others. It was also used by the present
author in the hygienic evaluation of formaldehyde in atmospheric air. The
chronaximeter used in the present study was the one used in the State Institute
of Physiotherapy. Optical chronaxy was measured by the appearance of a
phosphene. Rheobase and chronaxy were determined every three min. for 15
min. Preliminiary control determinations were made of the rheobase and
chronaxy by the inhalation of pure air. When the test persons learned to clearly
recognize appearance of the phosphene, tests were made for the determination
of chronaxy changes produced by the inhalation of formaldehyde vapor between
the, sixth and ninth minutes of the experiment. Optical chronaxy determinations
were made before and after formaldehyde inhalation. Tests made with formal- 3
dehyde vapor concentrations of 0.07, 0.084, O. 104, O. 136, 0.207 and 1. 59 mg/m
amou~ed to a total of 468 chronaxy determ:.nations. Results indicated that 0.084
mg/m of formaldehyde vapor shortened the chronaxy in two test persons and
delayed or lengthened it in one person. This formaldehyde vapor concentration
lowered the electrical chronaxy from 0.06 to O. 23 ~F. Most pronounced changes
were noted at concentrations of 0.2 and 1. 59 mg.{m . The rheobase increased
by I V in one person beginning with O. 105 mg/m concentration.
. . Inhalation of 0.068 - 0.075 mg/m3 of formaldehyde vapor had no effect on
optical chronaxy or on the rheobase, as was the case with pure air. Threshold
formaldehyde va~or concentration eliciting reflex activity in optical chronaxy
was 0.084 mg/m . This formaldehyde vapor concentration elicited odor per-
ception in two test persons and no odor perception in one, indicating that non-
odor perceptible formaldehyde concentrations could elicit reflex effects in
/--- . .- -- , TABLE I !
:.- CONGENTRA TJ ONS OF.l-'i~IS~QULL<2~M~ LDEHYDE ODOR. PERCEPT,' QN.! .
, . -- . CO~~~NlRA-":JOIl_~"
. .
I NUHIER OF TEST;E";SO'NS i. . MINIMAL ii' --NOT---:
'~,':;~' ."E~C.~!_~E8'''ERCE~~~ J
. 7,
4
1
0,07
0,08
. 0,11
-11-
-------
optical chronaxy ip. some persons through cerebral cortex stimulation.
Table 2 presents qata on chr\)naxy changes in microfarads elicited by formal-.
dehyde vapor inhalation by the three test subjects. '
Results of s'tudies obtained with one of the test persons are graphically,
presented in Fig. 1. (see page 13)
. ._.- . -.--
TABLE 2
'~.9~AX!..~_HANG_E~ ~,F ~.~~OR~_AND AFTER FORMALDEHYDE INHALATION:
M6/,..3 OF CHRONAXY DEFORE FORI1AL-, I 'CHROnAXY AFTER FOR"'AL~-
DEHYDE INHALATION' 9EHYDE INHALATION
FORI1AL- -. - .-.ow -
DEHnE TII1E OF TEST IN MINUTES
. . .----
0 3 6 9 12 15
TEST PERSOII D . j
PURE ' -------.- .-
AIR 0,63 0,63 0,63 0,63 0,64 0,63
- 0,068
0,63 0,62 0,63 0,63 0,64 0,63' ';
0,073 0,63 0,64 0,63 0,63 0,63 0,64 j
0,084 0,63 0,62 0,63 0,52 0,62 0,63
0,10 0,63 0,63 0,63 0,51 0,62 0,62
0,136 0,62 0,62 0,63 0,51 0,63 0,63
0,206 0,61 0,62 0,63 0,51 0,51 0,63
1,59 0,61 0,61 0,62 0,57 0,53 0,62
TEST PERSOII J(
,PURE '--'-----
, "IR 0,94 0,93 0,93 0,93 0,94 0,93
- 0,668 0,95 0,94 0,93 0,94 0,94 0,94'
0,073 0,95 0,94 0,94 0,94 0,94 0,94
0,084 0,95 0,96 0,95 0,72 0,96 0,95
0,10 0,95 0,94 0,95 0,75 0,96 0,93
0,136 0,93 " 0,93 0,95 0,75 0,96 0,95
0,206 0,94 0,93 0,94 '0,72 0,96 0,93
],59 0,93 0,93 0,93 0,70 0,93 0,93'
- PURE TEST PERSON S
AIR 0,54 0,54 0,53 0,53 0,53 0,53
"0,068 0,55 0,54 0,54 0,54 0,53 0,54
0,073 0,55 0,55 0,54 0,54 0,53 0,54
0,084 0,55 0,54 0,54 0,62 0,54 0,54,
0.10 0,55 0,53 0,53 0,62 0,53 0,53
0,136 0,54 0,55 0,54 0,63 0,53 0,53
0,206 0,53 ,0,52 0,52 0,62 0,53 0,54
1 ,59 0,54 0,52 0,52 0,93 0,53 0,53
The threshold effect of formaldehyde vapor on the central nervous system
through the receptors of the upper respiratory passages was studied by the
method of dark adaptation. Tests were conducted with the aid of adaptometer
ADM in a: dark room free from odor and noise; tests were conducted daily
during the same hours using test persons having normal vision and odor per-
ception. All. test persons had undergone a preliminary five day training period.
This was followed by a determination of their initial curves of dark adaptation
during inhalation of fresh air and using the same inhalation apparatus which
was employed for the delivery of the formaldehyde vapor and fresh air mixture.
Determinations were made every five minutes for one hour. Following this
15 min. tests were made with formaldehyde vapor concentrations of 0.06, 0.07,
-12 -
-------
I -
0.098, 0.2, 0.3 and 1. 7 mg/m3 formal-
dehyde vapor-air mixture was inhaled by
the test persons for 4.5 minutes. The
purpos e of the study was to determine the
limit of allowable maximal single concen-
tration of formaldehyde vapor, as indicated
by the immediate reflex effect on the organ-
ism. For this reason, the duration of the
vapor-air mixture inhalation wa:flimited
to 4-5 minutes. The 0.2 mg/m formal-
dehyde vapor-air mixture was inhaled by
the test persons once on the 15th and again
5 g 12 15 on the 31st minfte. The test began with
T'ME III MIIIUTE& the 0.06 mg/m , which is the odor non-
~--FIG. -I ~ FORMALDEHYDE ON OPTICAL CHRONAXY OF perceptible concentration, followed by
TEST PERSON D. ARR~ INDICATES BE-
GINNING OF FORMALDEHYDE INHALATION higher concentrations. The tests conduct-
I - O.O~ ~;/H3 OF FORMAlDEHYDE; 2 - ed during 56 days produced 112 dark adap~-
0.084 H;/M OF FORMAlDEHYDE; 3 - ation curves, established that 0.07 mg/m
0.205 M,/M3 OF FORMALIEHYIE
----- - --..- - - b_-.__- ---.- ----- b_- was the concentration of threshold formal-
dehyde vapor odor perception ~r all the test persons. The results also show-
ed that inhalation of 1. 7 mg/m - of formaldehyde sharply lowered eye sensitivity.
to light in all the test persons, which sli~tly rose at the end of the tests.
Formaldehyde vapor in O. 38 mg/m concentration likewise lowered eye
sensitivity to light in two te st persons immediately upon the vapor inhalation.
A sharp rise in eye sensitivity to light was noted in one test person on the 20th
min. of adaptation and only on the 25th min. did it djop below the normal,
followed by a gradual rise. Inhalation of 0.2 mg/m of formaldehyde vapor
enhanced the sensitivity to light in all test persons. Repeated inhalation on
the 35th min. of adaptation elicited a sharp rise in sensitivity to light in two
of the test persons. This occurred at the threshold concentratio~ in one of
the test persons. Formaldehyde vapor concentration 0.98 mg/m elicited a
rise in sensitivity to light in two of the test pe rsons. Lower formaldehyde
vapor concentrations effected changes in the curves of dark adaptation the
magnitudes of which were statistically insignificant. Results obtained with
one person are presented graphically in Fig. 2 (see page 14). Fig. 3 (page 14)
is a graphic summary presentation of the results obtained with the three test
persons. The results established that the concentration of threshold reflex
formaldehyd~ vapor effect on the functional state of the cerebral cortex was
0.098 mg/m , as determined by the adaptometric method, and that it was
slightly below the concentration of threshold formaldehyde vapor odor per-
ception.
Attempt was then made to determine the effect of low formaldehyde con-
centration on the respiratory function using pneumographic method. Frequency
and amplitude of respiration were determined in three test persons with the aid
of the usual pneumograph. No substantial changes were noted in the frequency
and r~thm of respiration at formaldehyde vapor concentrations below 2.5
mg/m. Based on the results of the above described experiments it can be
470
461
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-13-
-------
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S 10 /5 20 25 JO ,ji 4(J ;v 60 . CLEAU . 400; .4070 0.0;0 0.200. tJ,380 .P~
{'ME III 111 NUTES . -. ~'!. I CONCENTRAT.l.0N. tN 116/,;3
1-'" . .IFIGo 3"" CHANGES IN EYE SENSITIVITY TO LlGHT'ON
i FIG. 2- EYE SENSITIVITY TO LIGHT OF PERSON S DURING I THE 20TH MIN. OF EXPERIMENTAL FORMAL-
INHALATION OF DIFFERENT FORMALDEHYDE CONCEN- I DEHYDE INHALATION
TRATIONS. ARROW INDICATES BEGINNING OF I - TEST PERSON L; 2"" TEST PERSOU S;
FORMALDEHYDE I NHA LATI ON ! 3 "" TEST PERson E
1 - PURE AIR; 2 - 0.07 11&/M3 OF FORI1ALDEHY9E~ 3 - .. - _....... _...,h. - -.
, 3 - 0.093 I1Q1113 OF FORHALOEHY9f; 4 - 0.20 116/"
! OF FORMALDEHYDE; 5 - 1.71 116/113 OF FORI1ALDEHYDE, .
recom~~~~de;that O. 035 mg/~3-of-formaldehyde vapor be adopted as the limit
of allowable maximal single formaldehyde concentration in the atmospheric air
of inhabited areas, with a provision for an appropriate safety coefficient. Such
a formaldehyde vapor concentration was not odor perceptible and elicited no
reflex activity changes upon inhalation. The concentration recommended was
approved by the Chief State Sanitary Inspectorate of the USSR. Having estab-
lished the limit of allowable formaldehyde vapor concentration for atmospheric
air in inhabited areas, samples were then collected of air surrounding two in-
dustrial plants for checking, or control purposes. One of the plants produced
formalin and discharged its vapors without previous purification into the atmo-
sphere 18 m above the surface of the ground. Determinations were rrtade for
the. maximal single formaldehyde vapor concentrations directly below the flume
at distances ranging from 50 to 100 meters from the discharge point. Results
are presented in Table 3.
Analysis of the data shows that at 250 - 500
~ - . - --
.
~~ .~.....o........_..
0..............0 .
o
~-- --_._---- ---
TABLE 3
MAXIMAL SI NGLE FORMALDEHYDE COPICENTRATION I N THE PLA~ ~RO~I..MJ.!!_'
I'INO:~F -A~i ~~~T A:~:~I-I' MAX., Ii Ii A V. IN 'j'~~ST~F .
SA"'PLES'I ,116/,;3: 11(;/113 AGOvE
, .., TlvlTY /' . _L.A.Co
M FRO'"
,IISCHARSE
SOURCE
50 2 2 1,5 1,4
250 33 33 0,578 0,211
500 25 17 0,155 0,063
1000 ?:T. 4 0,042 0,0055
2
33
17
. 3
- --- - --- --_.-- -~--- ------ ---- ~
L.A.C. = LI"IT 0' AlLOWAilLE COHCEUTRl.TIOtl
. -.--- ._-------
---- ------ -
-14-
m from the plant all single
concentration air samples
were above the allowable
limit, and that only at 1,000 m
from the plant did 3 of the 27
air samples contain formal-
dehyd~ vapor in 0.038 - 0.042
mg/m concentrations, i. e.
slightly in excess of the limit
of allowable concentration, but
below the threshold of odor
perceptibility. The odor was
-------
perceptible up to the 500 m zone when winds carried the air pollutant
away from the plant which discharged odor ema.nating gas pollutants other
than formaldehyde. Accordingly, the odor perceived by inhabitants of that
zone was due to the presence of vapors or gases other than formaldehyde.
Questions were asked of 122 residents. Nine of 52 persons residing in the
250 m zone complained of irritation of upper respiratory passages, of the
eyes, and of the throat. Persons who collected air samples - 50, 250 and
500 m from the plant clearly perceived the odor of formaldehyde. The odor
was detected with some difficulty 1000 m from the plant. The second plant
in the vicinity of which air samples were collected produced galalith; this
plant used forma.ldehyde as the protein plasticizer. Gases and vapors were
discharged without previous purification at 10m from the ground and 0.5 m
below the top of the second floor. The atmospheric air was also polluted by
unorganized discharges through open ventilators, doors and other leakage
points. Samples were collected on the lee side of the plant at 100, 200 and
400 m. It should be noted that rapid changes in the wind direction during air
sample collection frequently turned the flume away from the sample collection
point. This was particularly true at 100 m from the plant during 15 - 20 min.
collection periods and also at 200 - 400 meters from the plant during 75 - 100
min. collection periods. Results of this study are presented in Table 4. Data
in Table 4 show that the maximal single formaldehyde vapor concentration
fABLE"" dropped to lower levels
with the distance from the
plant. At 100 m from the
plant concentrations of all
samples we re above the
allowable limit; at 200 m
from the plant 15 of 36 air
samples had formaldehyde
vapor concentrations below
the allowable limit. All
samples collected at 400 m had formaldehyde vapor concentrations below the
allowable limit. Answers to questions asked of 154 residents of a 400 m zone
indicated that formaldehyde vapor odor was felt at all times in that vicinity.
It should be added that some of the persons residing within the 100 m zone
complained of irritation of the upper respiratory passages, especially during
the warm seasons of the year when the residents spent much of their leisure
time in the open air. Thus, the results indicated that the investigated plants
constituted potent sources of air pollution with formaldehyde and that installa-
tion of efficient gas purifying equipment and widening of the sanitary clearance
zones were matters of urgency.
S. E. Levedev in 1938, Pattle, Collumbine in 1956, V.G. Kedrova in
1931 and Z. G. Vol'fson in 1950 called attention to the presence of aldehydes,
and in particular of formaldehyde, in Diesel engine exhaust gases. Apparently
formaldehyde was formed from the methane contained in automobile fluids.
Optimal temperature for the formation of the formaldehyde was 7.00. During
MAXIMAL SINGLE FORMALDEHYDE CONCENTRATION IN "G/M3
-- c,, 1 I CONCENTRATIONS IN HGi/M3 ,
M FROM. -- - . - -
"6CHARGE- NO.OF A' Mu. CON; I I I 'NUMHR
. _SOURC_~_- 6A~I'~E$ I N ",I 0,21-0,15 0,15-0,07 0.07-0,035 IElOW
-- - - - - L."..C.-
100
200
400
28
36
25
0,167
0,145
0,014
21
19
lIeT
4
lIeT
lIeT
3
11
Her
NONE
15
25
-15-
-------
the engine ope ration lubricating oil and benzene dropped on the engine surface
heated to 2,0000 and became oxidized to aldehydes. No evidence was found in
literature regarding the kind of aldehydes present in automobile exhaust gases.
Most authors assumed them to be acrolein. The purpose of the present in-
vestigation was to establish with certainty the presence and concentration of
formaldehyde in auto engine exhaust gases. Samples were collected at the
mouth of the exhaust pipes into vacuum gas pipettes filled with an appropriate
absorption solution. Determinations were made by two methods: the Shiff re-
agent and by the chromotropic acid method. Both'methods yielded practically
identical results. Twenty-five exhaust gas samples were collected from Diesel
engines operating on solar oil and gas oil. All samples contained formaldehyde.
Determ~nations were also made of total aldehydes of which formaldehyde con-
stituted 23%. Formaldehydes concfntrations fluctuated in the exhafst gas
samples between 49 and 378 mg/m , with an average of 115 mg/m .
Irritating effect. of engine exhaust gases was basically due to the pre-
sence of unsaturated aldehydes. The lowest threshold of harmful effect' was
that of formaldehyde; it was, therefore, assum.;::d that the irritating effect of
engine exhaust gases was due to the presence of formaldehyde.
Similar studies were conducted with exhaust gases of gasoline engines.
Results of analyses showed that 4 of 25 exhaust gas samples were positive for
formaldehyde which constituted ,7. 1 % of the total aldehydes3in the exhaust gas.
Formaldehyde concentrations fluctuated from 6 to 9 mg/m. The avera~
formaldehyde concentration of all 25 exhaust gas samples was 1. 2 mg/m .
Tests were then made to determine the presence of formaldehyde in exhaust
gases of automobile street traffic by taking samples of the air on the sidewalks
and in a neutral zone of Moscow parks 1-2 m from the automobile traffic. Sam-
ples were collected during maximal automobile traffic just before twilight.
Collected samples amountfd to 26, 13 of which contained formaldehyde in con-
centrations of 2 -10 mg/m . The average formaldehyde concentration in jhe air
samples collected on the sidewalks and neutral park strip was 2.6 mg/m , or
74 times in excess of the maximal single allowable concentration. Twenty-four
hour samples were also collected on sidewalks of streets with intensive auto-
mobile traffic and at 7-8 m from the traffic proper. Thirty-four of the 42
collected samples contained ifrmaldehyde, mostly in concentrations ranging
from 0.0068 to 0.0010 mg/m . Maximal average 24 hour concentration of
formaldehyde was 0.017 mg/m 3. The high fluctuation in the formaldehyde
vapor concentrations in the average 24 hour samples was probably due to the
fluctuating intensity of gas automobile and especially of diesel traffic during
the night.
Conclusions
1. Formaldehyde was discharged into the atmosphere by many industrial
enterprises; therefore, it is important that a study of formaldehyde vapor effect
on the human organis m be reliably dete rmined. .
2. Concentration of threshold forf1aldehyde vap,or odor perception for
most sensitive persons was 0.07 mg/m . Concentratlo~ of threshold formal-
dehyde reflex effect, as determined by the method of optical chronaxy, was
-16-
-------
0.08 mg/m 3, and O. 1 mg/m 3 as determine~ by the method of dark adaptation.
3. It was suggested that 0.035 mg/m of formaldehyde vapor in atmo-
spheric air of inhabited areas be accepted as its maxima1 single concentration,
with provision for a safety coefficient.
4. The atmospheric air in the vicinity of the plants under investigation
contained formaldehyde vapor concentrations in excess of the allowable con-
centration limits at a distance of 1,000 m from the point of its discharge.
In addition to the allowable formaldehyde concentration limit in atmo-
spheric air proposed by the present author, it is recommended that sanitary
clearance zones be established around such industrial plants which have no gas
purifying equipment as follows: of not les s than l, 000 m for plants producing
up to 50 tons of formalin in 24 hours, and not less than 400 m around plants
producing galalith.
No formaldehyde trapping installations have been in use up to the present,
which raises the problem of developing formaldehyde trapping equipment. The
physiochemical properties of formaldehyde suggest that the advisability of
using scrubbers for formaldehyde trapping be rechecked.
5. The presence of formaldehyde in Diesel engine exhaust gases must be
taken into consideration in developing means for the protection of atmospheric
air against automobile exhausts and industrial plant discharges. .
The study of formaldehyde concentration in automobile exhaust gases also
ralses the problem of developing te~hnological means for the elimi.nation of
aldehyde formation by internal combustion engines and for the purification of
engine exhaust before it is thrown into the atmospheric air.
BIBLIOGRAPHY
I
t
I
I
.
t
1-
An e K C e e:B a M. B. On~eJleHHe aTMoccpepHblx 3arp!!3HetIJleKTOpHOro .I1eHcrBH!! cepHHcTOro ra3a
:H 33po30JlH CepH'J"KHCJlOTbI npH C08MeCTHOM npHCYTCT.BHH. <:6.
dlpe.l1eJJl,HO JlOnYCTltMble KOJluelli1paU'HH aTMoccpepHblx 3arp!!3He-
H~A:o. B. 4, 1960, C11p. 92-101.
5 Y W T Y e B a ~. A. MaTepHaJlbl K YCTaHOBJIeHHIO npeAeJlhHO .I10ny-
CTHMOH KOHueHTpaUHH 'UP030JI!! cepHoA ,K-Hcnorbl B aTMoc4lepHO!\l
oB03.l1yxe. <:6. Cn~eJJbHO JlorryCTHMble IIroHlI,eHT.paUHH ai'Moccpep-
HbIX 3arp!!3HeHHlb. B. 3, 1957, C11p. 23.
Bon b 41 C 0 H 3. r. BJrHImHe BblXJJOltHbiX ra30B Ha 3.110pOBbe HaCMe-
HH!! H np<$HJJaKTH'IetlOle MeponpHHTHI1. .lI.HCC. M., 1950. .
B a II - B 9 PMaJlbA~a B .B03J1yxe. fHMleHa H caHHTa.pHR,
1958, 4, 83-84. .'. .
Ii c a II e H t( 0 B. 5. KOJnI'IecTBeHHoe' 1h.C;/le.l1osamte opa3.l1paJKalOwero
AeAc1mHII napo:a lIeKoropblx HapKOTHKOB"-!fa. 8epXIJI.He AbiXaTeJIbHble
nyrs. Hccne.noBaHHII oS 06nacTH .n~~bllifolk:.l'~_A TOKCKKWlOnt'H.
n.. 1940, c'fII. 207-<214. .
-17-
'".":...~...
-------
BIBLIOGRAPHY contld.
K e Jl po B a B. r. AnbllerHJlbl n BblxnonHblX .a3ax npH HcnblTaHIIII
a,BTOM06HnbHblX llBllraTeJleil. fHrHeHa' 6e30naCHOC11l1 II naTonor.HH
TPYlla, 1931. ~. 75-78.
11 e 6 e II e B C. E. npHMeHeHlfe ra30Boro aHaJTll3a npll IfcnblTaHHH llBH'
ra.reJIe» BHyTPeHHero cropaHHR. M., 1938.
neT p 0 8 r. C.. P Y T 0 B C K H it 6. H., 11 0 c e B 11. n. TeXHOnOrHII
CHHTeTII'lecKHx Macc. M.. 1946. .
n nOT H H K 0 B a M. M. K 06ocHOBaHllIO npelleJIbHO llonycTHMo» KOH-
ueHTpalUIH aKponeHHa B aTMoc!jJepHOM B03Ayxe, C6. «npellenbHO
J10nycTHMble KOHueHTpauml aTMoc!jJepHblX 3arpR3HeHHib. B. 4.
M., 1960. CTp. 75-91.
T a x H p O'B M. T. MaTepHa.1Ibl K 060cHoBaHHIO ,npelleJIbHO 1l0nYCTHMot!
KOHueHtpauIIH xnopa B aTMoc!jJepHoM B03J1.yxe. CO. «npeliMbHo
llonycTHMble KOHueHTpaUHl1 &TMoc!jJepl!blX 3arpH3HeHllit:l>. / B. 4.
M., 1960, CTp. 39-60.
Den i g e s D. Recherche de trages de methanal en presence d'etha.
na1 par la fuchsine hisulfitee. Compt. rend., '1910, ISO, 259.
P a 1 tie R. E., Cullum bin e H. Toxity of some atmospheric po-'
lu13nts. Brit. Med. J., 1956, 4998, 913-916. .
W -a I k e r J. F. Formaldehyde. Amer. Chern. Society Monograph, 1953,
ser. 98, 48-49. '. .
Data for the Hygienic Evaluation of Hydrochloric Acid Aerosol
(Hydrochloride Gas) as an Atmospheric Pollutant
E. V. Elfimova
The F. F. Erisman Moscow Scientific Research Institute of Hygiene
Hydrochloride is a colorless gas having an unpleasant odor; it is heavier
than air, 1 Ii of it weighing 1. 52 g; it easily dissolves in water forming hydro-
chloric acid. Hydrochloride gas is thrown into the atmosphere with industrial
discharges by plants producing titanium, magnesium, silica, organic com-
pounds, such as resins, insulation lacquers, explosive substances, dyes, zinc
chloride; it is also discharged into the atmospheric air in large quantities by
the chemical industry. During the above mentioned production processes'
hydrochloride gas permeates into workin~ premises accumulating in concen-
trations ranging between 5 and 365 mg/m as described by A. G. Aver'yanov,
B. I. Gurvich, B. D. Bykhovskii, V. Ikryannikov, A.1. Smirnov, G. Ya
KlebanovandI.L. Izrailovich, F.S. Bransburg, T.S. Karacharov, and others.
Polluted air of production departments is discharged into the atmosphe re by
ventilation installations systematically polluting the air with hydrochloride gas.
The amount of organized hydrochloride gas discharged into the air varies with
the production .technology, the presence of gas purifying installations, and in
the absence of the latte r, frequently amounted to 1'5 tons in 24 hours. The
amount of unorganized hydrochloride gas discharged into the atmosphere varies
with the degree of processes hermetization.. Hydrochloride gas is highly hygro-
scopic and is' present in the air as hydrochloric acid aerosol. Hydrochloric acid
-18-
-------
is widely used in many branches of the national economy. Production and use
of hydrochloric acid is generally accompanied by atmospheric air pollution.
with its aerosol. The presence of hydrochloric acid aerosol in the atmospheric
air unfavorably affected the organism of man, animal and of vegetation; there~
fore, hygrenists have been concerned with the problem of atmospheric air' .
pollution with hydrochloric acid aerosol for many years.
In its anhydrous form hydrochloride gas is a strong irritant affecting
the upper respiratory passages, mucous membranes and the conjunctivas of
the eyes. Depending upon the concentration and inhalation duration hydro-
chloric acid ae rosol produced acute and chronic intoxication. The harmful
effect of hydrochloride gas was confirmed by F. Flyuri and F. Tsernik who
studied its effect on s mall animals. V. Ikryannikov, A.!. S mirnov, Lehmann,
Gess, Henderson, A.G. Aver'yanov, B.!. Gurvich studied the effect of hydro-
chloric acid aerosol on the efficiency and general well-being of workers in
production premises. According to F. Flyuri and F. Tsernik hydrochloric
acid aerosol disturbed the proces s of carbon as similation by plants. Needles
of coniferous trees and leaves exposed to the effect of hydrochloric acid
ae rosol became cove red with brown spots and then fell off. Plants easily
perish in hydrochloric acid ae rosol c'oncentrations of 73 -147 mg/m 3. The
destructive effect of hydrochloride gas on green vegetation has been known
for many years. Laws have been issued by the Government of Belgium in
1856 and England in 1863 which forbade the discharge of high concentrations
of hydrochloride gas by soda producing plants the discharges of which kill-
ed all vegetation and seriously reduced the crops within a radius of 200 m
from plants. This gas discharge 'was also accompanied by an inc reased mor-
bidity among residents of surrounding regions. Similar observations were
described by Eulember in 1865 and by Ronzani in 1908. However, no detailed
investigation was made of the effect of hydrochloride gas on the human organ-
ism and especially on its higher nervous activity. The effect of hydrochloride
gas on the organis m' s reflex activity vIa the receptors of the respiratory
organs have not been investigated, and the concentration of threshold hydro-
chloride gas effecting irritation in animals and in man had not been establish-
ed. Different authors presented contradictory results regarding the concen-
tration of hydrochloride gas which affected man, animals and plants. Some-
authors mentioned development of tolerance in -man to the effect of tjte gas to
a degree at which they could withstand the effects of 100-200 mg/m of HC 1
gas. All this points to the fact that the problem must be basically and ration-
ally re -investigated, since no limits of allowable concentrations of hydro-
chlori,de gas in the atmospheric air could be established on the basis of exist-
ing information.
Industrial plants which produced magnesium and titanium constitute the
most potent present day sources of atmospheric air pollution with hydrochloric
acid aerosol. Carnallite ore is the raw material from which magnesium is
obtained electrolytically. During the dehydration of the ore in rotating furn-
aces and during the processes of smelting and hydrolysis of magnesium
chloride tail gases and hydrochloride gas are eliminated into the air in 0.27-
1. 280/0 of volume. Titanium tetrachloride is the raw material from which
-19-
-------
I~ .,.-~'-~.. ..,~.,.,,~, ~~"-~'i;;'-.... -,.....
,., ,. "" r,--'----'----'-'--;;-"-
,...~ .....',- ~.---,--;-"..~..- - - .,....,
----. ----~
'--" ~. -,' -- '., ,-~.. - ..
-- --- - - -
,-' -""-'-',_.u~-~~~ ----,--.----""~- ,,.-. -
;.
metallic titanium is prepared; titanium tetrachloride is prepared by the
chlorination of rutile or ilmenite concentrates in electric furnaces. The
gases liberated in the process of chlorination enter the atmospheric air in
the form of titanium tetrachloride vapor which becomes. conve rted into hydro-
chloric acid aerosol in the presence of air moisture. No detailed study has
been made of atmospheric air pollution with hydrochloric acid aerosol, due
primarily to the lack of specific and precise methods for the determination
of hydrochloric acid aerosol in the air. For instance, B. B. Bykhovskii in-
vestigated the pollution of atmospheric air with hydrochloride gas using the
method employed in the determination of total free chlorine, hydrochloride
gas and chlorides. This method did not enable him to determine. the concen-
tration of hydrochloric acid as an individual component in the air. Therefore,
it was not possible to establish the limit of allowable hydrochloric acid aerosol
concentration in th~ atmospheric 'air. Professor V. A. Ryazanov proposed in
1954 that one mg/m of hydrochloric aci1 ae rosol be adopted as the maximal
single concentration limit and 0.3 mg/m of the aerosol as the average 24-
hour concentration. This suggestion was not based on any experimental evi-
dence. . For the reasons above discus sed the present author unde rtook to
conduct series of experiments along the following channels: 1) to determine
the intensity of atmospheric air pollution with hydrochloric acid aerosol in
the vicinity of plants discharging it; 2) to determine the effect of low hydro-
chloric acid ae rosol concentrations on the physiological functions of man; 3)
to use the data thus accumulated for the hygienic evaluation of hydrochloric,
acid aerosol in atmospheric air, and to establish its maximal single concen-
tration Ii mit.
As the initial step in this investigation an attempt was made to develop
a method for the quantitative dete rmination of hydrochloric acid aerosol in the
air in the presence of chloride and sulfuric acid. The method used for the
elimin:ation of the effect of chloride on the determination was attained by
using the micrometric method in which O. 005 N solution of hydrochloric acid
was titrated against a solution of sodium hydroxide with methyl red as the
indicator. Sensitivity of the method was 0.002 mg. None of the titration
methods used in the determination of hydrochloric acid aerosol were specific,
since other acids inte rfe rred with the dete rmination. In this respect sulfuric
acid and sulphur anhydryide (S02) were the most frequently occurring air
pollution components which interferred with the above determination. The
presence of these two pollutants in the atmospheric air was accounted for by
determining the S02 and H2S04 in the sample by a nephelometric method using
a solution of barium chloride and by subtracting the calculated amount of the S-
containing acid from the total acids determined titrimetically.
Samples were collected by aspirating the air at the rate of 1 Ii/min.
through U -shaped absorbers made of molybdemum glass equipped with glass
filters # 1 and containing freshly double distilled water. Air samples were
collected in the vicinity of industrial plants, the emission gases of which con-
tained hydrochlorfde gas. Air samples were collected in the vicinity of the
following four industrial plants: (a) ache mical-metallurgical-plant, (b) and
-20-
-------
(c) two chemical plants and (d) a magnesium plant. The emission gases of
the first three plants were preliminarily passed through gas purifying equip-
ment to free them from the hydrochloride gas. Emission gases and vapors
of the magnesium plants were discharged into the atmospheric air without
previous purification. Seventy -five pe rcent of the air samples collected 100-
500 m from the three plants which were equipped with HC 1 gas removing in-
stallations contained hydrochloride gas concentrations below the sensitivity'
of the analytical method. Air samples collected in the vicinity of the magne-
sium plant which was not equipped with gas purifying installations were collect-
ed under somewhat unfavorable conditions of flume dispe rsions, atmosphe ric
pressure, stagnant air and high humidity. Analysis indicated that the atmo-
spheric air was highly polluted with hydrochloric acid aerosol, as shown fn
Table 1. Data in that table show that hydrochloric acid aerosol concentration
-.. .-.. . in the atmospheric air surround-
TABLE I i ing the magnesi~m plant exceed-
, ed the 10 mg/m limit of allow-
able concentration in working
premises. At 2000-3000 m
from the plant the atmospheric
air pollution with hydrochloric
acid aerosol was less intense
than in other zones. However,
even in these distant zones the
maximal single hydrochloric
acid ae rosol concentration ex-
ceeded the concentration Ii mit
allowable for working premises
by about 50%. Residents of zones in which air samples were collected com-
plained of the constant presence of unpleasant odors and of the harmful effects
of the plants discharges on green plants and ve getable cultures.
Lehmann, Ronzani, V.A. Litkens and W. Machle and others studied the
effect of hydrochloric acid aerosol, that is, of hydrochloride gas on the organ-
ism of animals; they found that the general toxicity of hydrochloric acid aerosol
was weak and that its effects appeared in concentrations exceeding the thre shold
of irritation effect. Taking the above into conside ration the present author
studied the effect of hydrochloric acid aerosol on the organism's reflex activity
and general physiological reactions. Since hydrochloric acid aerosol possessed
a specific irritating odor, the present author found it desirable to determine
first the concentration of threshold hydrochloride gas odor perception, using
the method recommended by the Committee on Determination of Limits of
Allowable Concentrations of Atmospheric Air Pollutants (1957). . Tests made
with h3drochloric acid aerosol concentrations within the range. of 0.05-7.0
mg/m amounted to a total of 336. Results of the determinations are shown in
Table 2 (see page 22). Tests we re ~ade with 13 persons, 19 to 42 years of
age; results indicated that 0.1 mg/m hydrochloric acid aerosol was the mini-
malodor perceptible concentration, and that no odor was detected by any of
HYDROCHLORIC ACID AEROSOL CONCENTRATION IN THE ATMOSPHERIC
AIR IN THE PLANT VICINITY IN 1957
~ --.-
-- -. r- I COtICNS. IN MG/M3
.-- - NU/'I8ER
M fROM I IELOW'
.,SCHAUE NO.Of AIR METI/OD I MAXIMUM I
AvERAGE
SOURCE SAMI'LES SENSITIYITY SINHE
"-- - .- -- . .- -~-- -- . SINGLE
300 39 3 4,4 ] ,77
500 44 ] 10,0 3,7
800 43 7 34.0 4,7
-1000 \ 49 0 34,0 6.]
2000 32 5 17.3 5,0
3000 34 ] ]7,3 5,4
-21-
-------
the test persons at 0.05 mg/m3 of hydro-
chloric acid aerosol. 1. P. Pavlov believed
that cortical elements of different analyzers
did not function independently as though they
were completely isolated from one another,
but that "each of the elements was inter-
connec ted with all the others" and that any
reflex effect on one of the elements auto-
matically affected the functional state of
the others. On the basis of such a postu-
late the present writer attempted to deter-
mIne whether low concentrations of hydrochloric acid aerosol coming into con-
tact with receptors of the mucous membrane of the respiratory passages had
affected the state of the central nervous system through the reflex zones of the
respiratory organs. This, the present author attempted to establish by the
methods of optical chronaxy, dark adaptation, by plethysmography andpneumo-
graphy. Experiwents were conducted with the aid of three test persons for
whom 0.3 mg/m was the threshold concentration of hydrochloric acid aerosol
odor perception.
Experiments were conducted in a darkened room with the test persons'
eyes closed. During 5-7 days prior to the actual experiments the test persons
were trained to unmistakably recognize the appearance of the phosphene. In-
dividual observations lasted 27 minutes. A basic background for the compara-
tive evaluation of the results was established prior to the hydrochloric acid
aerosol inhalation and 3 minutes after its inhalation by determining the rheo-
base and chronaxy magnitudes at 3-4 minute intervals. Known hydrochloric
acid aerosol concentrations were inhaled by the test persons between the 11th
and 14th minute of obser3ation using the following five concentrations: 0.2, 0.4,
0.6, 1.0, and 1.5 mg/m of ~he aerosol. Results of such tests showed that the
inhalation of 0.3 - 0.4 mg/m of hydrochloric acid aerosol produced no notable
effect on optical chronaxy. Changes in optical chronaxy were noted after the in-
halation of 0.6 mg/mj of the aerosol accompanied by increased chronaxy values
of 0.04 - 0.08 jlF. Chronaxy values increased progressively with the increase
of hydrochloric acid ae ro~ol concentration in the inhaled air. Hydrochloric
acid aerosol in 1. 5 mg/m concentration elicited sharp changes in the optical
chronaxy; thus, an 0.15 - 0.2 1J.F increase occurred in two test persons and
. O. 1 P-F in one test pe rson, without having any effect on the rheobase values,
as illustrated in Fig. 1 (see page 23).
Statistical analysis of the' data,confirmed the significance 30f the changes
in optical chronaxy values following the inhalation of 0.6 mg/m of hydrochloric
acid aerosol and higher. Thus, the concentration of threshold hydrochloric
acid a~rosol reflex effect" as determined by optical chronaxy method was 0.6
mg/m , or above the concentration of threshold Hel aerosol odor perception.
Effect of low hydrochloric acid aerosol concentrations on the functional state
of the cerebral cortex was studied by the method of dark adaptation. Tests
for the effect of hydrochloric acid aerosol inhalation on eye sensitivity to light
TABLE 2
'CONCENTRATIONS OF THRESHOLD HYDROCHLORIC
'- A,CIO AEROSOL ODOR PERCEPTION IN MG/M3
CONCENTRATIONS OF
HC I AEROSOL
'NUMBER OF TESTS MAX. PER- I NO~PER-
CEPT;OLE CEPTISLE
3
9
1
0,1
0,2
0,3
0,05
0,1
0.2,
-22-
-------
were conducted with 4 persons
, for whom 0.2 mg/m3 was the
concentration of threshold
hydrochloric acid aerosol odor
perception. All persons had
, undergone preliminary medical
examinations and were declar-
; ed normal with regard to odor
and vision acuity. Two series
of tests we re conducted for the
dete rmination of eye sensitivity
to light: 1) in this series test
persons inhaled hydrochloric
acid aerosol prior to dark
adaptation; 2) in this se ries
test persons inhaled hydro-
chloric acid ae ros 01 while in
l the process of dark adaptation.
15 IJ 23 21 Tests for eye sensitivity
- T"~E' IN~I~UTES ' to light were initiated during
;FIG. 1'- OPTICAL CHR'mIAXY CHANGES IN TEST PERSONS A, I, AND M ,the preliminary training period
j EFFECTED BY THE INHALATION OF HYDROCHLORIC ACID AEROSOL' of the test persons and during
I
I I - PERSON A; 2 - PERSON J; 3 - fER$ON M (Hel AEROSOL the determination of character-
, CONCIS.) A - 1.5,,;/,,3; . - 0.6 ";/113; ARROW INDICATES istic or control curves of dark
'EGINNING OF AEROSOL INHALArlON '"
-------- . ,---- - -- adaptatlon resulting from in-
halation of fresh air. With such data on hand tests were made to determine
changes in eye sensitivity to light during the inhalation of different hydrochloric
acid aerosol concentrations. Control curves of dark adaptation were plotted
on the basis of measurements made every 15 minutes for one hour. Formation
of conditioned reflexes in relation to the time of experiments made with the
vapor was prevented by making control observations associated with the in-
halation of pure ai r.
During the first series of experiments, test persons were inhaling known
concentrations of hydrochloric acid ae ros 01 or pure air for 15 minutes prior to
dark adaptation, usi~g the following four aerosol concentrations: O. OS, 0.2,
0.56, j'nd 1.0 mg/m of the aerosol. Results showed that inhalation of 0.05
mg/m of hydrochloric acid aerosol had no effect on eye sensitivity to light,
and that the path of the curve coincided with the path of the curve of dark
adaptation manifested during the inhalation of pure air, which was taken as
the basic or control curve. Cfanges in eye sensitivity to light in all test
persons began with 0.2 mg/m of aerosol and appeared as a drop in the curv3
of dark adaptation by 23 -37% of the initial or control curve. The O. 56 mg/m
concentration iowered eye sensitiv~ty' to light in three test persons, and
raised it by 30% in test pe'rson K. Higher hydrochloric acid aerosol concen-
trations affected eye sensitivity to light of the tested persons to different
degrees and in different ways. See Fig. 2 (page 24). Results of tests con-
0,6
/', 2
, \
! ' ,
,/ \
"
,
,
----------"
a
0,5
, 0..
,
\
,
.~--
. ;I' --~- '
, . ~~ ----
" J / ~::;.-.-
',......'
--.-.-.-.-.
'~,
::L ; o,J
;' ~,
,. >
= 42
. ..
.0
""
~ '44
o
~
....
u'
E ! oZJ
o
./', J
'" .
",' ---~ 2 '
~.--,..;.......... ':..._~c-_:..:::.~-=
....--~----- '.-.-- .
0,=
4'
o
. J
1
II
-23-
-------
ducted with person P are also illustrated
in Fig. 2. Changes in eye sensitivity to
ligh.t following 15 minutes of hydrochloric
acid aerosol inhalation before dark adapta-
tion, expressed as averages of eye sensi-
tivity to light for a period of 60 minutes
are listed in Table 3.
In the second series of tests known
hydrochloric acid ae rosol concentrations
were inhaled by the test persons on the
15th min. of dark adaptation for 4. 5 min.
Results indicated that inhalation of dif-
ferent hydrochloric acid aerosol concen-
trations changed eye sensitivity to light as'
J 10 '.5 1025 JO 35 40 M .50 55 50
TI/1E IN I1INUTES compared with the original level mani- --
.----.-., - fested by pure air inhalation. In this case,
FIG. 2 - CHANGES I N EYE SENSITI VITY TO LIGHT as in the previously de sc ribed cas e, iden-
I N PERSON P., AFTER 15 MI N. AEROSOL
INHALATION BEFORE DARK ADAPTATION. tical aerosol concentrations produced
I - CLEAN AIR; 2 - o.o~ I1G/Pl3 OF. different effects in different individuals.
AERosoL; 3 - 0.56 HGlt1. OF AEROSOL; As for instance, inhalation of O. 2 mg/m3
4 - 0.2 I1Q//13 OF HCI AEROSOL.
---- --- '-' - ._----- - of hydrochloric acid aerosol by test per-
son G caused a drop in his eye sensitivity to light reaching the lowest level on
the 20th min.., after ~h~ch eye sensitivity ,to light began t~ rise gradually, but
never reachIng the onginallevel. Inhalatlon of 10 mg/m of hydrochloric acid
aerosol elicited lowest fall in eye sensitivity to light. The sensitivity to light
dropped by 63% as compared with its level on the 20th minute and retained that
low level to the end of the ~_xpe~~men!.
2800tJtJ
uotJL'O
240tJOO
J:7otJOtJ
z :tJtJ tJtJo
. )0 '" I!OOOU
. !: !:,ltftJotJo
, .. ..
~ ::::0 /too:;o
- ...'
'~ ~ >2tJOOO
... 1-,
-------
TABLE 4 halation on eye sensitivity to
. light during the 20th min. of
MEASUREMENTS OF HCI AEROSOL EFFECT ON EYE SENSITIVITY TO liGHT
DURING D.~RK ADAPTATION, Itj RELATIVE UNITS adaptation are listed in Table
. . EYE SENSITIVITY T~ LlGKT ON 23D Hili. 0' 4. Statistical analysis veri-
DAftK ADAPTATION, IN RELATIVE UNITS. fied the significance of the re-
corded value s .
Changes in the course of
dark adaptation on the 20th min.
of observation, i. e. after 4.5
min. of hydrochloric acid aero-
sol in~alation in 0.2 - 10.0
mg/m concentration were also
found statisticall3 significant.
Thus, 0.2 mg/m of hydro-
chloric acid aerosol, which is
the threshold concentration of
its odor perception, elicited conditioned reflex changes in the functional state
of the cerebral cortex, expressed as changes in !he' course of dark adaptation
in both series of experiments, while 0.05 mg/m of hydrochloric acid aerosol,
which was not perceptible by odor, notably affected f)ye sensitivity to light.
Hydrochloric acid aerosol concentration of 10 mg/m , which constituted the
limit of allowable aerosol concentration in the air of working premises, elicit-
ed sharp changes in eye sensitivity to light. Inhalation of such a concentration
of hydrochloric acid aerosol sharply lowered -the test persons' sensitivity to
light, indicating that the presently adopted limit of allowable concentration
must be lowered, indicating that inhalation of fydrochloric acid aerosol affect-
ed eye sensitivity to light, and that 0.2 mg/m constituted the concentration
of HC 1 ae rosol threshold reflex effect on eye sensitivity to light.
Tests were then made to determine the effect of hydrochloric acid aerosol
inhalation on vascular reactions in man using the three -lead plethys mograph
3P-2. Plethysmography enables the investigator to conduct observations on
changes in digit vascular blood volume and on fluctuations in the frequency and
amplitude changes in the pulse -waves. See Fig. 3 (page 26).
Each test pe rson had to go through a pe.riod of training and se ries of
tests for the determination of the so-called zero or control plethysmogram
wh.ile inhaling pure air.. Studies were conducted with the followifg hy~rochloric
aCId aerosol concentrations: 0.1, 0.5, 1. 0, 5.0, and 7.5 mg/m , whIch the
test persons inhaled for 30 seconds. Experiments were conducted w~th 3 per-
sons 23, 25, and 26 years of age. Results indicated that 0.01 mg/m concen-
tration of the ae rosol elicited no shifts in the vascular reactions. Changes
appeared in the plethysmograms upon the inhalation of 0.5 mg/m3 of the ---
ae roso!. A total of 22 tests were conducted Wl th the test pe rsons, 7 show-
ed a slight rise in the person's vascular tonicity. In one test-, the .vascular
tonicity fell below the normal level, and in 14 the plethysmogram showed no
changes. The plethysmograms fell to lower levels upon the discontinuation
of hydrochloric acid aerosol inhalation reaching lowest tevels of 10, 12, and
MQ/,,3 0' HCI
AEROSOL
INITIALS OF TEST PERSON
G
N
p
K
~LfAN AlR- 99 300 100 500 96 6:)() 165 800
0,2 58 900 .62800 53100 67 800
0.56 80 900 54 900 72000 83 500
1,0 109300 77200 45 700 111000
2,0 58 700 63100 65 900 I NOT -
TESTED
3,2 71500 81 400 54 300 66 000
5,0 77 200 66 300 72 300 86 500
10,0 60 600 37 900 44 600 NOT .
TESTED
- - .-. - .' - --. ..-- .
-25-
-------
15 mm between the 10th and
20th sec. This drop in tonicity
~ was only a temporary one, and
after 30-40 sec. the plethysmo-
gram returned to its original
level, as shown in Fig. S'
Inhalation of 1 mg/m of
hydrochloric acid aerosol re-
suIted in a plethysmogram
which sugge sted that changes
FIG. 3 - EFFECT OF 0.5 MG/M3 OF HYDROCHLORIC ACID AEROSOL occurred in two phases: during
, ON THE PLETHYSMOGRAM 'the inhalation period the finger
A - PERSON S; D - PERSON L; (SOLID LUtE DHOW THE vessels became dilated, and
PLETHYSHO'RAI1 INDICATES DURATION OF AEROSOL INHALA- 'towards the end of the inhala-
Ti ONo)
, , ' - , ---.., , tion the finge r ve s sels became
constricted. Upon discontinuation of the aerosol inhalation the digito -vascu-
lar constriction became more prono~nced pe rsisting for a longe r time than
following the inhala,tio~ of 0.5 mg/m of hydrochloric acid aerosol. Inhala-
tion of 5.0, 7.5 mg/m of the aerosol, produced a plethysmogram indicative
of two-phase changes: it rose by 6-7 mm above the control level at the beginn-
ing of the ae rosol inhalation, then began to descend- gradually and ve ry slowly,
dropping 12-20 mm below the control level returning to the original plethysmo-
gram level after 1-2 min. As a rule the pulse became' slower by 4-12 beats
per minute during the period of the aerosol inhalation. The drop in the plethysmo-
gram level was accompanied by a rise in the pulse wave amplitude by 1-2 mm,
and the rise in the, plethys mogram level was accompanied by a 1-2 mm drop in
the pulse wave amplitude. Thus, the obse rvations indicated that inhalation of
hydrochloric acid aerosol elicited vascular reaction changes of a reflex charac-
ter. This was indicated by the brief period of dilation followed by constriction'
of the blood vessels.
Stimulation of the olphactory organs by different hydrochloric acid aero-
sol concentrations affected the blood vessel tonicity in direct proportion to the
aerosol concentration. These tests indicated that 0.5 mg/m3 of the aerosol
was the concentration of,threshold plethysmographic reflex effect on the blood
ves sels.
Effect of hydrochloric acid on the nature of respiration was studied by
the method of pneumography using pneumograph 3P-2. Experiments were
conducted with 3 test persons; knorn concentrations of HCl aerosol were in-
haled for one minute. 0.05 mg/m concentration of the- ae rosol, which was
non-perceptible by odor, elicited no changes in the respiratory ~pth and
rhythm of any of the test pe rsons. Inhalation of O. 1 - 0.2 mg/m of hydro-
chloric acid aerosol (threshold odor. concentrations) elicited characteristic
changes in the respiratory rhythm and depth of all test persons. ,Changes
appeared on the pneumogram as a reduced number of respiration waves of
higher amplitudes and as shorte r inspiration and longer expiration periods.
With the increase in the hydrochloric acid aerosol concentration the changes
c.
d
~f~~
-- ".1~-
-26-
-------
imal single concentration in atmospheric air;
elicited no changes in the physiological states
cedures employed in this investigation.
Conclusions
became more pronounced, as
can be seen in the pneumogram
of Fig. 4 produced by te s t pe r-
son S duri~g the inhalation of
FIG.<4 - EFFECT OF 005 MIi/1'I3 OF HYDROCHLORIC ACID INHALATION 0.5 mg/m of the aerosol. . Thus.
ON PNEUMOGRAM OF TEST PERSON S results of tests conducted for the
(HORIZONTAL SOLID LINE INDICATES TIME OF AEROSOL 1If- determination of low hydrochlor-
------- --- - H~LA_TI_~N)~____---- ------ ic acid aerosol concentration'
effects on the receptors of upper respiratory passages were paralled by the
results of tests performed for the determination of threshold reflex effects of
the same aerosol concentrations using optical chronaxy, eye sensitivity to
light. vascular and respiratory reactions as the indexes. Results are summar-
ized in Table 5. Analysis of the data showed that inhalation of hydrochloric
acid aeroso:! beginning with
TABLE 5 . 0.01 mg/m concentration
HYDROCHLORIC ACID AEROSOL CONCENTRATIONS OF THRESHOLD REFLEX, elicited symptoms indicative
EFFECTS, IN MG/M3 - - of respiratory organ receptor
1._- - stimulation. Threshold odor
REflEX EFFECT \.JAS DETERMINED BY , perception and respiratory
I - -- picture effects we re the most
0,1-0,2 sensitive indicators of hydro-
chloric acid aerosol inhalation
. ~:~ effect. Based on the results
obtained in this investigation,
it is r3commended that 0.05
mg/m of hydrochloric acid
aerosol be adopted as the max-
this is the c once ntration which
of the organis m by the pro-
ODOR PERCEPTION
ELECTRICAL EYE STIMULAIILITY IY THE OPTICAL
CHRONAXY MET HOD
.EFFECT ON EYE SENSITIVITY TO LIIiHT
EFFECT ON DIIiITa-VASCULAR REACTIVITY, DY THE
METHOt OF rLETHYSMOIiRAPHY I
EFFECT ON RESPIRATION, DETERMINEI IY THE METHOI
OF PNEUMOIiRAPHY
0,5
0,1-0,2
1. It was shown that 0.1 mg/m3 was the concentratiof of threshold
hydrochloric acid aerosal odor perception, thc~l 0.05 mg/m was the odor
non-pe rceptible concentration, that 0.6 mg/m was the co~centration of
threshold reflex effect on optical chronaxy, and 0.2 mg/m the concentration
of threshold reflex effect on eye sensitivity to light. The ~oncentration of
threshold effect on digito-vascular tonicity was 0.5 mg/m , and the threshold
concentratio~ of change in the rhythm and depth of respiratory movement was
at O. 1 mg/m of the aerosol.
2. On the basis of the above results it was recommended that 0.05 mg/m3.
be accepted as the limit of allowable single concentration of hydrochloric acid
aerosol in atmospheric air. 3
3. Results of this investigation indicated that 10mg/m of the aeros~l,
representing the limit of allowable concentrati'on for working premises. elicit-
ed sharp shifts in the physiological reactions. Therefore. the present writer
-27-
-------
suggested that the existing limit of hydrochloric acid aerosol concentration
for working pre mises be rechecked with a view to bringing it down to a lower
level.
4. The method used for the determination of hydrochloric acid aerosol
in atmospheric air can be applied to the determination of the aerosol in the
presence of HZ 504 ae rosol and in the presence of free chlorine and chlorides.
5. The present investigation indicated that atmospheric air in the vicin-
ity of a magnesium plant was highly polluted with hydrochloric acid aerosol,
that such air pollution extended over considerable distances from the magnesium
plant, and that the sanitary protection zones around magnesium plant discharg-
ing hydrochloric acid aerosol. in the absence of gas purifying equipment, should
be in excess of 3,000 m. Plants for future magnesium plants should mandator-
ily include provisions for the installation of hydrochloric acid absorbing equip-
ment.
BIBLIOGRAPHY
A B e p b H HOB A. r:., "r y p B Ii'l 6. 11. BeHTHnHlI.lIH npoMbllll.1eHHblx
npe.llnp1UlTHH ,H 9ll H II H K 0 'B B. BeHTHnllll.'HSt 9 ri~~"'<\pblX lI.exax XHMH'IecKOA
npOMbllllnellHOCTH. r'HrHeHa, 6e30naCHOCTb H naTOIIorHH TPY.lla,
1931,2,89.
K n e 6 a HOB r. SI., 113 P a II n 0 B II 'I 11. JI. npo
-------
"
A Restudy of the Maximal Allowable Single Concentration of
Carbon Disulfide in Atmospheric Ai~
R. S. Gil'denskjol'd
F. F. Erisman, Moscow Scientific Research Institute of Hygiene
In 1949 K. G. Beryushev recommerided and ~he Committee on Limit~
for Atmospheric Air Pollution accepted 0.5 mg/m of carbon disulfide as the
maximal single, and 0.15 mg/m3 'as the average 24-hour concentrations in
atmospheric air. These norms were base~ on results obtained by F. D.
Shikhvarter in his studies of carbon disulfide odor perception and on data
of othe r authors who investigated the toxicity of CS 2 to man, and on informa-
tion obtained regar,ding atmospheric air pollution with CSZ in the vicinity of
some industrial pl~nts. Investigations conducted in the vicinity of viscous
plants showed that CS 2 concentrations exceeding the allowable limits we re
found only in the 500 m zone, while the odor of CS was perceived at con-
siderably greater distances. This indicated that tfie adopted allowable con-
centration limits for CS2 were too high, and that they created a sense of
false security, which arrested attempts to develop appropriate equipment
for the purification of gases discharged by viscous combines.
This prompted the present author to undertake a restudy of the problem
of carbon disulfide air pollution in relation to limits of its allowable concen-
tratio~ in atmospheric air. The work was conducted along two investigational
channels: (1) a study was made of carbon disulfide's zonal distribut~'~min
atmospheric air surrounding viscous plants; and (2) a parallel study was made
of the effects of short time inhalation of low CSZ concentrations on the respira-
tory organ receptors. .
Carbon disulfide was not present in the air in its pure form under nat-
ural conditions. No unanimity of opinion was found in the literature regarding
the character of carbon disulfide odor; thus, N. D. Rozenbaum stated that the
odor of carbon disulfide was reminscent of chlor-oform, while F. Flyuri and
F. Tsernik described the odor as peculiar and aromatic. N. V. Lazarev
thought that carbon disulfide had a pleasant odor, while M. N. Grodzovskii
thought the odor was obnoxious. The present author found that double dis-
tilled CSZ possessed a peculiarly unpleasant odor even in low concentrations.
The yellow color of technical carbon disulfide is due to the presence of
sulfur-containing admixtures; it posses se s a repulsive odor re minscent of
rotten radishes. The b. p. of chemically pure CSz is 46. 30, and the refrac-
tion index is 1. 623Z at Z5°. Carbon disulfide vapor is 2. 63 times 'as heavy
as air and its solubility coefficient in wate r at 200 is 1. 7. It is miscible with
alcohol and ether in all proportions. Carbon disulfide vapor is highly in-
flamable; mixed with air it becomes explosive breaking up into SOZ and COZ'
-29-
-------
The toxic properties of carbon disulfide vapor have been known since
1843, when it was first used in cold vulcanization of rubber. Since then many
studies have been devoted to the investigation of the toxic properties of carbon
disulfide throughout the world. However, such studies have been limited to
high carbon disulfide concentrations. It has been established that carbon di-
sulfide was a potent neurotropic poison which acted as a narcotic in high con-
centrations and, therefore, has been classed with chloroform and chloral-
hydrate. The chronic toxic effect of low carbon disulfide concentrations pro-
duced grave organic disturbance of the central, peripheral and vegetative
nervous systems. Vapors of carbon disulfide penetrated into the organism
basically through the upper respiratory passages; liquid carbon disulfide can
penetrate intact skin upon direct contact. Having penetrated through the
respiratory passages, carbon disulfide rapidly entered the blood system where
it accumulated in high concentrations. According to Fabre, as cited by N. V.
Lazarev, ~xposure to inhalation of carbon disulfide concentrations of 80 to
450 mg/m may result in the accumulation of 23 mg of CS per 1i of blood.
Demus found the highest rate of carbon disulfide accumula1ion in the blood
occur~ed within the first 30 min. of exposure to its inhalation, that 90% of
the inhaled carbon disulfide was deposited in the organis m within 5 hours,
and that 1-2% of it was absorbed by the blood system. Businf3 and Sonnenschein
exposed mice to the inhalation of air containing 50 -300 mg/m of radioactive
carbon disulfide. Radioactive sulfur was then found in conside rable amounts
in the liver and kidneys of animals sacrificed during the inhalation; however,
at the end of the inhalation the rate of radioactive sulfur deposition in the
organs was considerably reduced. Radioactive sulfur was slowly absorbed
by brain tissue, then by liver and kidney tissues; its rate of elimination from
the brain tissue was also considerably prolonged.
V. A. Kisilenko and G. G. Lysina found that the accumulation of radio-
active sulfur in the liver and lungs reflected the high metabolic activity of
these organs. The high carbon disulfide accumulation in the kidneys reflect-
ed their specific functions as organs of elimination, although opinions differed
regarding the mechanism of carbon disulfide elimination by the organism.
Thus, MacKee believed that 85-90% of carbon disulfide entering the organism
became converted into other products and were eliminated as organic sulfates
and other sulfur-containing compounds, and that only 8-13% of CS2 was elimi-
nated thr.ough the lungs in its original form. Weist examined worKers of a
viscous plant and found that rate of carbon disulfide elimination with the urine
during the workday at first increased and then gradually fell to lower levels,
amounting to 25% of the initial at the end of the day. V. A. Kisilenko afd
G. G. Lysin exposed experimental animals to the inhalation of 10 mg/m of
.carbon disulfide for an extended time; this c.on:centration was. equivalent to
the carbon disulfide concentration limit allowable for indoor working premises;
they also found that up to 86% of the absorbed carbon disulfide was rapidly
eliminated by the organism in its original state via the respiratory organs.
-30-
-------
Carbon disulfide was formed by the interaction between melted sulfur
and wood charcoal at 800 -9000. giving off hydrogen sulfide. sulfur dioxide
and carbon dioxide as byproducts. The mixture of gases is then condensed
for the conversion of the carbon disulfide vapor into a liquid which accumu-
lates at the bottom of the condensor, from which it is run off by gravity.
It was found that the air surrounding plants producing carbon disulfide was
heavily polluted with its vapor even around plants equipped with recuperating
equipment installations. Chemical plants used small amounts of carbon di-
sulfide as resin, phosphorus, sulfur, fat, and wax solvent, but the basic
amount of CS2. is used by viscous producing plants which are also the basic
offenders of an pollution with carbon disulfide. It was estimated that several
million cubic mete rs of air was blown out into the atmosphe re by ventilation
systems or plants usin~ or producing carbon disulfide. Such ventilation air
contained 20-250 mg/m of carbon disulfide. The immensity of such a volume
of ventilation air viciates the problem of gas purification prior to discharge by
such plants. In May of 1958 the Plenum of The Central Committee of the
Communist Party of The Soviet Union realized that furthe r extension of the
artificial and synthetic fiber industry and the need for purifying the gases
discharged by the plants will become increasingly urgent.
. K. G. Beryushev, N.M. Tomsom, L. F. Glevova, M.A. P.inigi and
others have shown that the volume of carbon disulfide discharged daily into
the atmospheric air by viscous producing combines fluctuated between 1.5 -
6.5 and 25 - 40 tons depending upon the size of the plant. Air samples col-
lected by different investigators within the range of discharge flumes of differ-
ent plants at different distances from the source of discharge contained differ-
ent concentrations of the air pollutant, which may be due to one or several of
the following factors:
a) the ventilation systems used in the plants may vary from centralized
to decentralized and from organized to unorganized;
b) the production capacity of the plants may have varied greatly;
c) air samples may have been collected at different seasons of the
year;
d) the sensitivity of the methods used for the chemical determination
of carbon disulfide in the air may haye been different;
e) there may have been other factors.
The present author studied atmospheric air pollution with carbon di-
sulfide in the vicinity of a viscous plant in 1956. Studies we re conducted at
different seasons of the year, and samples were collected at 10, 150, 500,
1000, 1500, 2000, 2500 and 3000 m from the point of CS discharge. The
plant investigated discharged up to 4000 tons of carbon d1sulfide into the air
in 24 hours through many decentralized exhaust ventilators. Air samples
were collected and analyzed by a method developed by A. L. Khritinina, and
recommended by the Committee for the D_etermination of Allowable Atmo"'-
spheric Air Pollutant. The sensitivity of the method was 0.0005 mg/ 2 ml.
A photometric modification of the method was developed for the present in-
vestigation using photoelectrocolorimeter N -1. Three hundred forty-two air
-31-
-------
-
'1 . 1
. D 15- i NUMDE,R '~MAX. CONCN'
TANCE' OF I I 3
. - I N M ~"~~ES IN 111:/11 .
. samples were collected by the aspiration method on the lee side of the in-
dustrial combine ,. of which 331, or 96. 79% contained carbon disulfide in con-'
centrations above the method sensitivity. .- Results are shown in Table 1.
TABU I Data in this table. show that
. MAXIMAl SINGLE CARBON DISULFIDE CONCENTRATIONS IN ATMOSPHERIC single carbon disulfide con-
AIR AND THEIR AVERAGES centrations fell to lower levels
~.__.- .-" ~- -...- -----
as the distance from the point
ODOR AT THE TIME OF iof pollutant discharge increas-
6AM~LE COLLECTION ---- ed. Results showed that car-
.bon disulfide concentrations
in the order of the previously
adopted limit of allowable max-
imal concentration were found
.in the samples collected at
distances up to 500 m from
--. . _.--.- - - _.-- -. .-- - - ---the plant, and that among the
samples collected at 150 m zone, five contained carbon disulfide concentra-
tions in excess of the allowable l~mit, while among the samples cojlected in
the 500 m zone one sample contamed 0.64 and another 0.55 mg/m . There-
fore, it can be reasonably concluded that highest atmospheric air pollution
with carb.on disulfide was fou:rd in th~ zone c1os~st to the viscous plant, and
that conslde rable (0.4 mg/m ) pollutlOn of the au was found up to 1000 m
from the combine. CS2 concentrations below the sensitivity of the method
were found in 11 of 28 air samples only in the 3000 m zone. Air sample
collectors of different zones stated that a persistent strong odor of CS2 was
clearly perceived in the 500 m zone, and a less intense odor was perceived
at the 1000 and 1500 m zones. During intermittent winds the CS2 odor could
be perceived at 2000 m, 3where the maximal sinc1e CSZ concentration was of
the order of 0.18 mg/m . No CS odor was perceivea in the 3000 m zone.
Residents in the vicinity of t~e viscous plant we re then inte rrogated;
this had to be done with considerable understanding and caution to avoid
possi ble confusion caused by the lack of familiarity on the part of the inte r-
rogated with the characteristic CS2. odor as distinct from H2S, Questions
were asked of 318 persons who reslded within a 2000 m radlus of the com-
bine; most of the questioned were housewives. Analysis of the answers in-
dicated that a persistent CS2 odor was sensed within the 500 m zone surround-
ing the plant and that the intensity of the odor became stronger during windy
days. In t~e 500 to 1500 m zones the odor intensity becam'~ considerably
weaker. and in the 1000 to 1500 m zones only a slight odor was sensed when
the wind was from the plant towards the residential areas. Practically no
CS2 odor was sensed beyond the 2000 m zone. Thus, the experience of the
sample collectors coincided with that of the residents, indicating that odor
perceptible CS concentrations were not found beyond the 2000 m zone. It
was further esFablished that even during the windy periods CS2 vapor odor
could be perceived not only on the lee side of the plant, but 011 the opposite
side as well; naturally, the pollution intensity on the opposite side was con-
AVERAGES
IN MG/113
:10IS(
501
I DOC
1500
2000
2500
3 000
80 1.20 0,21 STRONG & PERSISTANT
73 O,6
-------
siderably below that on the lee side. Thus, the m::tximal CS2 concentra~ion
at !OO m on the le~ sid~ of the plant ranged between 0.522 - 1>.73 Wg/m ,
whlle on the Opposlte slde the range was only 0.115 - 0.118 mgLm . Highest
air .pollution with CS,2 at 500 m was found directly below the plume, and the
maxi~al concentration on the side opposite to the plume did not exceed 0.025
mg/m . In addition, 50% of air samples collected at 500 m on the opposite
side of the plume contained carbon disulfide concentrations below the sensi - ",
tivity of the method. V. A. Ryazanov called attention ts> the fact that p~e-
sence of air pollutants on the side opposite to the p1ume may be the result of '
one or both following factors:
a) intermittent .nature of the wind with an occasional brief reverse
flow, and
b) gas absorption by ve getation, soil, walls of buildings at the time
when winds blew in one direction, and gas desorption when the
wind direction was reversed.
There may be other causes.
For the hygienic evaluation of the determined CS2 concentrations in the
air tests were made by the method of threshold CS2 odor perception and, by
the method of ,threshold reflex effect on the functional state of optical analyzer
using changes in optical chronaxy and dark adaptation as the indicators.
I ,.P _.' TABLE 2 Air containing known concentrations of
carbon disulfide was attained by means
of a special glass apparatus. The air
was first saturated with carbon di-
sulfide by passing it through a measur-
ing apparatus consisting of a bottle
filled with 2 Ii of double distilled water
containing a small amount of carbon
8:8g g:8~ disulfide in solution. Constancy of
0.10 0,06 delivered CS2 concentrations was es-
0,20 0,10 tablished by preliminary 5-6 days
, -., 3 . standardization. F. D. Shikhvarger
found that one mg/m was the concentration oj threshold CSz odor perception,
while K. G. Beryusheva found that 0.5 mg/m had a perceptible odor. The
present author conducted experiments for the determination of odor perception
properties of carbon disulfide with the aid of 15 test persons, 17 to 29 years
old. ResuIts~9f 256 dete rminations indicated that the conc~ntration of thres-
hold CS2.~ctof 'perception ranged between 0.05 - 0.2 mg/m . Results of the
investigation are listed in Table 2. Thus, the present studies indicated that
0.05 mg/m3 was the concentration of threshold CS2 odor perception, and
0.04 mg/m 3 was not odor perceptible. In other words, the pre'3iously adopt-
ed limits of allowable carbon disulfide concentration (0.5 mg/m ) was 10 3
times the concentration established by the present investigation (0.05 mg/m ).
The metflOd used by the present author was carefully checked and rechecked -
without .finding any technical errors; therefore, it was resolved that the re-
suIts should be checked by the F. D. Shikhvarge r method. Twelve tests we re
ICONCENTRATION OF CARBON DISULFIDE THRESHOLD
! ---'-- . ODOR PERCEPT I ON .
CARDON D'ISUL;F ID.E' CONC.
IN 1'111 1'13
MAX. I'ER- I CONCH. OF NO 1
CEI'TlIlLE
CONCN. OIlOR I'ERCEI'TION
NUMIIER 01' TEST
PERSONS
4
2
3
6
-33-
-------
thus made with the same test persons~ the results coincided with those of
Shikhvarger'3indicating that 42 mg/m of CS possessed a sharp odor, that
at 4.6 mg/m the odor was considerably wea~er, but was still sensed by all
the test persons, and that in 1.0 - 1.6 mg/m concentrations most of the
test persons perceived no CS odor. Coincidence with Shikhvarger's previous
results was evidence of the f;ct that the method used by Shikhvarger in 1950
was unreliable. Basic feature s of the procedure used we re as follows:
air was supplied by a water aspirator at the rate of 20 li per hour;
the aspirated air passed through a kerosene flow meter which
enabled the test person to perceive the CS2 and kerosene odors;
the carbon disulfide liberated from activated charcoal was not
preliminarily mixed with clean air, but was run directly into
the inhalation cylinders;
the apparatus had no cylinder for pure air supply required for
comparative and control purposes;
e) the low rate of air flow and the small size of the inhalation
cylinders created conditions favoring in-flow of outside air
during experimental inhalation of air at a rate exceeding the
supply of the experimental air and CS2 mixtures;
tests for the determination of the concentration of threshold
CSZ odor perception were conducted in a chemical laboratory
in the presence of extraneous odors; .
tests for the determination of odor perception of different CS2
concentrations were conducted with the same test pe rsons the
same day.
These defects in the experimental procedure employed by F. D. Shikh-
varger were responsible for the incorrect results. It has been indicated on
previous occasions that the absence of odor pe rception of a specific substance
in a given concentration was no indication of the fact that it had no physio-
logical or neurological effect on the organism; therefore, tests were made
to determine what effect brief inhalations of different CS2 concentrations
might have on optical chronaxy. For this purpose, tests were made em-
ploying chronaxymete r GIF of 1949 and using three test subjects whose
thresholds of CS2 odor perception were O. I, 0.006 and 0.005 mg/m3. Deter-
minations were made in a slightly darkened room; the test persons were given
a period of eight days training to acquaint them with the appearance and char-
acter of the phosphene phenomenon, and t~ obtain initial or control values of
optical chronaxies and rheobases during pure air inhalatJ.on. Tests with
fresh air "and diffe rent CS 2 concentrations we re conducted afte r three dete r-
minations made at 3-minute intervals established the control rheobases an.d
chronaxies of the test persons' optical analyzers. Four or more determina-
tions were made following the administration of a given CS2 concentration for.
12 minutes at three mi.nute intervals. Tests with different CS2 concentra-
tions were alternated at times with tests of fresh air; the purpose of such a
procedure was to avoid possible formation of conditioned reflexes associated
a)
b)
c)
.d)
f)
g)
-34-
-------
1l.65 .
o.B~
0.8J
0.82
. u. : 0.8/
?i . 0.80
-'
>- Q,l9
..
::= 0.78 .
o
~ . 0,77
Co>
; I 0.75
~ I 0.75
~,
, ~ 10.7-
! 0.73
---1
0.72
0.71
o
/'
0,82
0,8/
O,SO
0, 7.9
0.78
,0.77
.'
0.7/
: 0.70
'. u.' 0.69
::1.' 0.08
:z
: - 0.67
'::c 0.65
'::= 0,55
, ~; 0.5"
:r:
Co> 0.5.1
; 0,52
, Co>
I;: 0.5/
'~j D,60
I ~ O,5!
'- o,,fB
0.57
0.55
0.55
0,5"
0.53
.- ..-..
...,
...'2 \
...'" \
I '
, ,
, ,
, .,'
, /J"
, .,,' ," \ \
,..... . \
..... \ ,
. ,
.----..- \ .
. . 4. "----
3
, G ,- .9. _'-2~ /s
ITIME IN MINUTES I.,
18
~,
. ~ --:--
FIG. 1 - EFFECT OF DIFFERENT CARBON DISULFIDE
CONCENTRATIONS ON ELECTRICAL EYE STIMUL,;.:
ABllI TY OR TEST PERSON A. .
I - 0.5 Mo/M3 OF CS2J 2 - 0.1 M,/M3 OF CS2; 3 -
0.04 MG/M30F CS2e .
II
~\
I \
I \
I \
I \
I \
I \
I \
I \
I \
I \
I \
I \
, \
, \
: ' 2
, \
, \
, ,
, \
, /'. J ,
, . ,', '.
" // 4. ",,,:-.
I .(.'" :~
I.,,!,'" .-.- ',,-"
f:":...........- S "..
f
o
J 5 .9 12 15
T"ME "N 'M,'NUTES'-
18
j. .. --~\/ #' ~--- --- --.---- "--
I FIG. 2 - EFFECT OF DIFFERENT CARBON DI-
! SULFIDE CONCNS. ON ELECTRICAL'
EYE STI MU LAB III TY OF TES PER-
SON I.
j I - 0.5 MG/M3 OF C~2; 2 - 00 I MG/M3 OF
! CS4;33 - 0.05 MG/M' OF CS4; 4 - 0.04
MG/M OF CS2; 5 - 0.03 MG/M3 OF CS2
,:,,35-
-- - - -- - . --
with surrounding conditions. Tests were made with CS2 concentrations of.
0.5,0.1,0.05,0.04 andO.03 mg/m3. Chronaxymetric results are graphi-
cally presented in Figs. 1, 2 and 3. (see Fig. 3 page 36).
, S:urves in the graphs indicate that a .short duration-inhalation of 0.5 '
mg/m of carbon disulfide, which is the established limj t of allowable maxi-
mal single concentration, elicited in all the test persons considerable delay
in the optical chronaxies; thus in person A, the average was O. 14/lF, in
pe rson I it was O. 29 /IF, and pe rson Al the aver~ge was 0.3 /l F. P:rolonga-
tion in the optical chronaxy caused by 0.5 mg/m of CS was of a persistent
character, as shown by the fact that 12 minutes after th~ cessation of carbon
disulfide inhalation values of the optical chronaxy in all test persons were
still greater than thos1 of the controls. Short duration inhalation of carbon
disulfide in O. 1 mg/m concentration likewise elicited optical chronaxy pro-
longation of lower values; thus, the maximal increase in optical chronaxy of
person A average 0.07 JlF; in person I the average was 0.186 jlF, and in
person Al the average was 0.267 IlF.. A considerably shorter, .yet statisti-
cally reliable, chronaxy projongation was observed in all test persons during
the inhalation of 0.05 mg/m of carbon disulfide as determined by the thres-
-------
OJ~ hold odor perception test. Optical chronaxy
['.55, was prolonged in person A by an aye rage of
o.:,~~ .
0.6J 0.04 f.lF, in person I by an av'erage of 0.036
0.52 JJ.F, and in person Al by an ave rage of
- .~~; .0. -075 /IF. Following the discontinuation
, 10.'51. of carbon di-sulfide inhalation in this con-
o . i~~.ntration chronaxy returned to norma.l
~o.~ ,
':::ti . I within 12 minutes.
J z: 0.52 I 3
: -,0.51 I Inhalation of 0.04 mg/m of carbon di-
o ~' 0.50. I I
.. . I sulfide elicited statistically re liable in-
.'6:0..49 /' I
,::; o,u I crease in optical chronaxy only in persons
; u, 0.47 I I I and Al to an aveJ;.age of 0.03 jJ.JF. lnhala-
, ~i o..~t I' f 0 0 /.5 f
; ~I' 0.1.5 . I I hon 0 . 3 mg m 0 carbon disulfide
t~ 0.1,1. / J' elicited no statistically reliable changes
I' / I
:::;- o,f,J /'. I in optical chronaxy 0 Thus, it was e stab-
I \ ~:~ / \. \ lished that 0.04 mg/m 3 was the lowest
.- o.HJ I I \ I carbon disulfide concentration which eli-
. I 0 I '
0,3J I . i 4 '., cited statistically reliable increase in the
o..J8 I ; /"" \. I chronaxy of two test Pe rsons; this concen-
0.)7 , './ ""
o,J6 1
-------
tivity to light during brief inhalation
of different CS concentrations by all
test persons. 4rhus, in the case of
person Ch all CSZ concentrations
elicited drops in sensitivity to light
the magnitudes of which we re directly
proportional to the CS Z concentrations.
In the case of person S higher carbon
disulfi:re concentrations, such as '0.5
mg/m , lowered, and low concentra-
'tions enhanced the eye sensitivity "to
light. In the case of person St high
CS concentrations elicited persistent
dr~ps in eye sensitivity to light, and
concentrations such as 0.05 - 0.04
3
mg/m of CSZ brought about short
duration drops which returned to nor-
mal on the 40th adaptation minute.
Results of changes in eye sensitivity to light produced by different carbon di-
sulfide concentrations are presented in Table 3. Results are expres sed in re-
lative units on the ZOth minute of dark adaptation by all test persons who inhaled
pure air or different carbon disulfide conce~trations. Values of changes in light
sensitivity of all test persons at 0.04 mg/m carbon disulfide concentrations.
were statistically significant. Lower concentrations had no effect on the curves
of dark adaptation. Thus, experimental results indicated that receptors of
olphactory analyze rs we re functionally affected by carbon disulfide concentra-
tions considerably below the previously adopted maximal single concentration
in atmosphe ric air; this was indicated by the appearance of brief functional
shifts in the activity of the central nervous system. It can be stated in the way
of su~mary, that the concentration of CSz. threshold odor perception was 0.05
mg/m and that the concentration of thresnol~ CSZ reflex effect on optical
chronaxy and dark adaptation was 0.04 mg/m ; based on the results of the pre-
s ent investigation it is suggested that the limit of allowable single, ca:r:.bfn di-
sulfide concentration in atmospheric air should not exceed 0.03 mg/m . The
Committee for the Determination of. Limits of Allowable Concentrations of
Atmospheric Pollutants resolved to examine the validity of the previously
adopted norms for carbon disulfide concentrations in atmospheric air of resi-
dential areas. On Z7th of July 1957, thephief State Sanitary Inspector of the
USSR provisionally approved 0.03 mg/m as the maximal sinyle limit of allow-
able carbon disulfide concentration in the air and 0.01 mg/m as the average
Z4 -hour concentration. A complete' and basic reexamination of the subject is
now in progress.
TAB LE 3
RESULTS OF ADAPTCt1ETP.IC STUDI ES
I NITIALS OF
TEST PERSONS
MiO/,,3 OF CA'RDOII
IISULFIDE
EVE SENSITIVITV TO
LIIOHT ON 20TH MIN.
OF ADAPTATION IN .
RELATIVE utllTS
CH .
'CLEAN AIR" - I -
0,03
0,04
0.05
0.1
- .0.5
'CLEAN AIR,
- O,OJ --
0.04
0,05
0,1
- 0.5
'CLEAN AIR "~-L
0:03 "
0,04
0.05
0.1
0.5
'5
ST
117 OOG
109 000
65 500
53 700
20 100
9000
88 280
88 680
138600
177 200
69 300
50 200
36 580
36420
32 780
24 080
13300
8340
Conclusions
'1.' Examinations of air samples indicated t~at even at 3000 meters from
the investigated plant the air contained 0.03 mg/m of carbon disulfide.
, -37-
-------
Z. Results of tests conducted with th~ aid of most odor perception
sensitive persons indicated that 0.05 mg/m was the concentration of thres-
hold odor perception for CSZ and that 0.04 mg/m3 was the odor nonpercept-
ible concentration of CS2.'
3. The concentratlon of threshold carbon disulfide reflex effect, as
determined by the method of optical chr~naxy was 0.04 mg/m3, and the sub-
threshold concentration was 0.03 mg/m . .
4. . The concentration of threshol1 CSZ reflex effect on optical analyzer
sensitivity to light was also 0.04 mg/m . .
~. The limit of allowable CSZ concentration should not exceed 0.03
mg/m.
6. Results of the present investigation suggest that the present ZOOO m
width of sanitary clearance zones surrounding viscous plants should be widen-
ed to 3000 m.
Sanitary bodies must insist on the immediate installation of effective
equipment for the purification of viscous combine gas discharges containing
CSZ' Gases discharged by viscous plants contain vapors othe'r than CSZ' It
is, therefore, suggested that a comprehensive and complex study of the.
atmospheric air in vicinities of viscous plants be initiated without undue delay.
BIBLIOGRAPHY
..
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pOHbI 4Ia6pHKH HCKYCCTBeHlloro BOJlOKHa H caHHTapHoA oxpami
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IIHToKcHKaU'HH. 06'beJJ.HHeHHaR HaY'IHaH. CecCHH, nOCBHU!eHHaH
4O-neTHIO BeJJJiKO!! OKTH6pbCKOii cOUHanHCTII'IecKoH peBOnlOltHH:
Te3HcbI JJ.OKJIaJJ.OB. I(HeB, 1957, C1'p. 14-2-144.
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. We i s t H. Biochemische un
-------
Atmospheric Air Pollution with Manganese Compounds and their
Effect on the Organism
V. F. Dokuchaev and N. N. Skvortsova
The A. N. Sysin Institute of Gene ral and Community Hygiene of
the USSR Academy of Medical Sciences
Mining and processing of manganese ore, alloy smelting, and the prep-
aration of special types of steel are accompanied by the formation of highly
dispersed particulates which contain a high- percent of ma.nganese dioxide. A
considerable amount of highly dispersed manganese oxides is thrown into the
atmospheric air by blast furnace gases due to the fact that most manganese met':'
allurigical plants have no gas purifying installations. The -g-r[nding . . -
of manganese ore and of ferromanganese creates dust, 50% 0f which ~onsists
of particles less than 2/J. in diameter. Metallic dust of such high dispersion
discharg~d into the atmospheric air spreads- Dve r vas t distances. Not much
information was found on this subject in the pertinent literature. Hence, th~
present investigation which was conducted along the following three lines:
1)
A study of atm0spheric air pollution with industrial manganes~
discharges.
Effects of manganese plants discharges on the health and living
conditions of nearby residents.
Effect of low manganese concentrations on the organism.
2)
3)
Atmospheric air studies were conducted in the vicinity of a metallurigi-
cal plant smelting pig iron and ferromanganese. The blast furnace gases
were discharged at a height of 50 m. Up to 1955 the blast furnace gases were
purified by the method of "dust retention bags" which removed only the larger
particles suspended in the- discharge gases. Four electric filters of the B. M. -
30-1 type were installed in 1955 for the purification of blast furnace gases in-
tended for use by the plant. Only 25% of the total blast furnace gases wer-e
thus purified to a reasonable degree. The re maining volume of gases dis-
c~rged by the ferromanganese blast furnaces, amounting to 50000-70000
m / hour, was passed through so-called "candles", bypassing the "dust-
bags ". Continuous clouds of heavy 'dust, .at times. completely engulfing the
plant and spreading over considerable distances, presented a common sight
around the plant.
The study of the atmospheric air in the vicinity of the plant consisted
in the determ:nations of the dust concentrations in the air, the manganese
concentrations in the dust, in the atmospheric air, and in the air of living
quarte rs, paralled by recording of basic metallurigical conditions prevailing
during observation time. Samples were collected for the determination of
-40-
-------
i-
manganese by aspirating the air for 29 ~inutes ,using the automobile aspira-
tor devised by L. F. Kachor equipped with an hygroscopic cotton filter. ~l)
No absorption media were used in this. case because of the higher rate of .
aspiration required for the. collection of manganese dust. Snow samples were
also collected for the determination of the environment pollution with manganese
dust. ,Window and house plant wash water samples were also collected and anal-
yzed. Manganese determination was: made by the usual method, dissolving the
manganese compounds in a mixture of oxalic and sulfuric acids, followed by
oxidation with ammonium persulfate in the presence of silve r nitrate, which
converted the manganese pollutants into permanganic acid. The standard solu-
tion was prepared to suit the mangane.se concentrations suspected to be pre-
sent in the atmospheric air. Air samples ~ere collected at 38 points equally
distributed over an area of 4 km radius. Three hundred and ten air samples
were thus collected during the winte r of 1954 - 1955 and during the summe r of
1955. The summer samples were collected at 500 - 3000 m from the source
of discharge. Analytical results" are' presented in Table l.
- . . TABLE I I Results of the investiga-
, ' tion indicated that consider-
MG/M3 OF MANGANESE IN ATMOSPHERI C AI R JURI NG THE SUI"MER SEASON bl t h" 11 t'
a e a mosp erlC air po u Ion
by industrial manganese dis-
charges prevailed in the air
nearest to the plant grounds.
Results also indicated that
even at 3 km from the plant
the average 24-hour concen-
tratio'ns we 3e 50% above the
0.01 mg/m allowable aver-
I . age daily concentration. It
should be mentioned at this
point that the above data were obtained with samples collected during warm
sunny weather mostly unde rneath a high flume, i. e. at conditions favoring
wide dispersion of the industrial discharges. Thus, results of the observa-
tions indicated that atm.')spheric air pollution with manganese extended over
considerable distances from the ferromanganese plant. Manganese intoxica-
tion under industrial production conditions manifested itself as changes in the
central ne~vous system which resulted in grave and basically irreversible
symptom-complexes of Parkinson's Disease of manganese etiology. Cases
of such poisoning were noted mostly iJ? places of heavy air pollution, such as
hundreds of mg per 1 m3 of dust containing 50% of manganese. Such cases.
occurred infrequently but were noted in all metallurigical industries, as was
shown by N. M. Shishkiria in 1934, by ¥. S. Surap, A. P. Sapozhnikov in
1934, 1. D. Makulova and K. M. Manil'ova in 1951, etc.
(1) See USSR Literature on Air Pollution and Related Occupational
Diseases, .¥ol. 3, OTS 60-21475, p 165. .
I N THE I'RESE NC~. OF Sf'1.0K~.
, MAXI~~ I ~I_~.I~"-~I ~~~K~F .
I N .TH~."BSEIICE .0.F_S_~9K_E .
M"~~M"L I MI:NIMA'L:I Av. OF
. SMOKE
Ktt FR OM
SOURCE
OF D IS-
CHARGE
-
0,5 0,262 0,082 0,203 O,I1~ I 0,004 0,020
0,8 0,228 0,014 0,081 0,057 0,013 0,032
1 . 0,136 0,002 0,036 0,043 0,002 0,012
1,7 0,029 O,U04 0,013 0,014 0,002 0,005
2,5 0,041 0,005 0,013 0,011 0,004 0,005
3,0 0,027 0,004 0,015 0,002 - -
CORRESI'OND TO MAXIMAL SINGLE CONCENTRATION, EDITOR.
-41-
-------
-~ ~-------- ~
The following can se rve as an example:
Examination of miners working at the Chiatursk mines disclosed no
employees with symptoms of neurointoxication, but many of the workers had
disease of the respiratory organs, as disclosed by V. G. Gogibedashvili and
S. P. Kipiani in 1948, and N. E. Machabeli in 1958. Occurrence of respira-
tory organ diseases among workers employed by the metallurigical industry
caused by manganese intoxication, had been noted by many authors since
1953. The most frequent manifestations of manganese poisoning were pneu-,
monia and pneumoconiosis. It was estimated that 17-52.5% of workers in
the metallurigical industry had pneumonia and in many instances repeatedly.
Generally, manganese pneumonia was characterized by a grave course of the
disease which resulted in high mortality. On the other hand, manganese
pneumonia occasionally found among isolated groups of workers, and mis-
taken1y diagnosed by some physicians as silicosis, ran an even and slower
course than silicosis; patients affected with this type of manganese pneumonia
manifested no specific subjective pathologic symptoms, maintained normal
work capacity for a long time and presented no particular complaints.
Pneumonia and manganoconiosis symptoms in such patients were frequently
complicated by chronic bronchitis, laryngitis, tracheitis, rhinitis, pu1"monary
tuberculosis and silicotube rculosis. High mt1rbidity of respiratory organs
noted by many investigators under industrial conditions was regarded as a
specific manifestation of manganese intoxication. Reports, appearing in the
,literature also p'oint to increased morbidity and mortality caused by pneu-
monia among those who resided in close proximity to plants producing man-
ganese alloys.
At the 1938 VIII International Congress on Occupational Diseases and
Technical Safety, D.Elstad reported on conditions noted by him i.n the small
town of Saude located on the Western shore of Norway. Up to 1923 the town
was frequented by tourists. The same year a plant was built in that town for
the manufacture of manganese alloys which viciated the sanitary hygienic
living conditions by discharging into the atmosphere clouds of dark brown
smoke. This ended the inflow of tourists into that town, and gave the town
of Saude the reputation of a high morbidity center due to the frequent occurr-
ence of croupous pneumonia which resulted in a high mortality. Data pre-
sented by Elstad indicated that gene ral total Norway mortality was the same
as in Saude, amounting correspondingly to 10.7 and 10.1 per 1000, but
mortality due to croupous pneumonia was 8 times as high in Saude as in
Norway, amounting to 3.27 as compared with 0.4 per thousand. In 1924-
.1935 mortality due to croupous pneumonia was 3.65% of Norway1s total mor-
tality, while in Saude it was 32.3% or nearly 10 times as high. Post-mortem'
exami.nations indicated that manganese concentration in lung tissues of persons
dead of croupous pneumonia was considerably higher than in the lungs of post-
morte m controls. This was equally true of the plants employees and of those
who resided in the vicinity of the manganese plant.
Such high morbldity and mortality caused by croupous pneumonia in
Saude was regarded by Elstad as the result of system3.tic manganese discharge
into the atmospheric air by the manganese plant. Examination showed that the
-42-
-------
, '
, ,
ventilation system of the electric sr'n~1til1g furnace department was adequate
insofar as the working premises we~re concerned, but the smoke containing
manganese compounds was discharge'd into the atmospheric air of the vicinity
close to the metallurigical plant. :fiowever, at 3 km from the discharge point
Mn concentrations in the air were h~gh and the particle diameters were 511
or greater. During the seasons of pr,evailing wind the smoke was dispersed
in a short time, but during calm andJoggy days the valley in which the town of
Saude was located was covered with;, a continuous cloud of smoke. Elstad noted,
that the rise in morbidity caused by 'croupous pneumonia and its consequent
mortality ran parallel with increase;in the amount of ferromanganese dis-
charge s by the plant. This se rV,ed .ats ,additional evidence of the ~ausality between__-
the plants discharges and the frequency of morbidity and mortality among the
population caused by croupous pneuI11.0nia. 'To further verify the above postulate
regarding the cause of croupous pneumonia morbidity and mortality among resi-
dents living in the vicinity of the ma~ganese plant the present author resorted to
the following: I i
1) residents living in the 2 km: ion~' surrounding the plant were asked
certain pertinent questions;:' ,
2) tests were conducted for the ~etedion of manganese in smears made
from nasal mucosa and children's hand wash water;
3) a sanitary statistical study whs 'made of morbidity am,::mg the
children living in the 2 km zone; -
4) groups of children we re subjected to medical examination.
Questions were asked of 1200 r~sidents; the answers indicated that
95.6% of the interrogated within the ;500 m zone complained of unfavorable
effects of the plant discharges; the complaints are summarized in Table 2.
Residents of the 500 m zone
TABLE 2
, complained of high dust den-
EFFECT OF I NDUSTRIAL DISCHARGES ON THE GENERAL HEALTH AND lIVI NG sity; when the wind blew from
.-- -_..,_CONDITIONS OF1HE POPULATION --.', -", .:-:--the plant in the direction of'a
'"Z.O"NE. "I I KM FR'OM I' NU,I'1BER' I %OF COM- residential area house windows
,- . -.' '.- "LANT . ~~E_RRO~D.. -.~LAI~~!- - had to be closed; it was not
FIRST 110 0,5 341 95,6 possible to hang the wash out
: SECOND 0.5-1,0 571 69,7 in the open air; snow became
1.0---2,0 282 '47,5
THIRD covered with a layer of black
dust in the winter; dust rap~
idly accumulated in the house, making frequent house cleaning impe rative, etc.
Analysis of nasal mucosa s mear..s made of 700 children, mostly of pre-
school age, showed the presence of manganese in 62% of the cases, frequently'
amounting to 0.095 mg. Analysis of-childrens' hand wash water contained
38.8 mg of manganese per m'2 of s'kin area.' For the determination of a mor-
, bidity, a study was made on the, basi~ of clinical histories of 1200 children,
-'/'~up to 16 years of age; the histories' c:optained sanitary hygienic and other health -
information accumulated in the past 6 years~ No evidence of neurointoxica-
tion was found in workers. The histories of employees in the blast furnace
department, who were exposed period!caJ-ly to 'the effects of high manganese
-,43-
-------
concentration, In view of the above, it would appear unlikely, that changes
should occur in the nervous system of children living in the vicinity of the
plant as a result of inhalation of the mangane se polluted air, Studies of
morbidity established that frequency of ne rvous syste m effects among resi-
dents of the nearby village occupied the 10th place; in other words, the data
were analogous to those obtained in examining the adult population of the in-
dustrial town. Morbidity studies were also made among children pertaining
to diseases of the ear, nose, throat, etc.; results are summarized in Tables'
3 and 4. Neuropathologic studies were made of Z04 children; findings were
positive in 16 children only, and were represented by light asthenia, vertigo,
neurosis and ve getati ve synd rome" Roentgenological examinations disclos.ed
pulmonary changes in 75% of the children, many of them' of tuberculous etiology.
Other changes were perio-
bronchitis of diffe rent degree,
pe riovascularitis, thought by
the roentgenologis t to be
residuals of past diseases,
especially in repeat cases.
Thus, results obtained in the
study of morbidity among
children of the plant village
pointed to the presence of
shifts unfavorably affecting
the children's health. The role
TABLE ~ ,played by manganese, and in
particular by fe rromanganic
,RHINITIS, TONS\LlTIS, AND ADENOID MORBIDITY AMONG CHILDREN OF dust, in the etiology of such
_DIFFERENT INDUSTRIAL REGIO~S, IN % O~ ALL CHILDREN EXAMINED.,
, - tissue diseases as inflamma-
-" \' ".. ---- CHEMICAl"coMaINE ANO ElECTRI"; ,
N THE ,CAL HEAT AND POWER STATIOII tory processes of the resplra-
PLAHT'-----'", .... ,
I VILLAGE! 'PR~MnING -I COIITROL tory passages and Sc1er?tlc
lung changes was establIshed
: RHINITIS t.' " '. 20,8 19,2 5,0 with certainty by animal ex-
j TONSILITIS t 11,3 } 34 9 17,5 8 6
,!ADENOIDS 23,6' ,periments. However, such
..'-- -- manganese concentrations were
tens and hundreds times as great as the limit of manganese concentration
allowable in working premises. Experimental animals were exposed to the
inhalation of manganese in the following concentrations:
('
-.
'filS LE 3
---- - -
EAR, NOSE AND THROAT'MORBIDITY
, -
.-------
ZONE
I',M FROM TilE': I MORBIDITY % AMONG'
PLANT ,_EXAM~NED ,:.,:!_~_o~~~
-~
FIRST
SECOND
THIRD
500
500-] 000
1000-2000
43,8
48,1
34,3
. "Ty'';£-o'i--I,
, I
, ~_~~~,~I.~~j
a) equivalent to the limit of allowable
working premises; .
b) twice in excess o~ the above;
The manganese dust was administered intratracheally. The basic
monthly dose was the equivalent of Z. 5 mg of chemically pure MnOZ' A
chemically pure MnO of ferromanganese dust was used for the intra-
tracheal administrati~n. The dust contained 80% of particles 5Jl in diameter
highly dispersed in physiological saline. Experiments were conducted with
180 rats divided into 8 groups; rats of 4 group's were administered MnOZ;
concentration in the air of
-44-
-------
, ;.
t
rats of 2 groups were administere~ p?-ysiological solution; rats of 1 group
received a suspension of ferromang~n~se',du~t containing 40% of manganese
calculated as Mn02' and rats of the !~st g~oup served as controls. In situ
examination of the lungs of autopsieQ tats indicated that 62-89.5% of the
rats injected with MnO or with ferromanganese dust showed changes in the
exte rnal appearance o/the lungs whi'l~ i~ the: control animals, injected with
physiological solution, only 35-39. l~ol:,o£the rats manifested such changes. '
Most extensive microscopic change:s were noted in rats injected with ferro-
1 ' ,',
manganese dust which appeared as cha.~ges In the normal lung color and as
lung wrinkling. Microscopic examirtC
-------
BIB LIOG RAPHY
1) aK'P a.a 3 e 3. H. MaHranoKoHHo3. fHrHeHa TPYJI3, 1'923, 10-11.
60 p II C e H K 0 B a P. B. 0 TOKCIIIIHOCTH npoH3BoIlcTBeHuoH nblJlH
Mapr311lteBbiX cn,13BOB. rUnteHa H caulITapHII, 1954, 1.
6 Y 6 ape B A. C. 0 BpeJIUOCTIIX, CBII33UUbI'5c C norpY3Koii MapraHua
H3 CYIl3. flfrlfeH3, 6e30n3ClfOCTb If naTOJlOrlili rpYIl3. 1931. 6.
Bop 0 H U 0 n a E. H. K Ronpocy 0 JIeiiCTBllH Ha opr3UH3M a3po3o,,1l1,.
06pa3YIOUterocli npll 3MKTpocnapKe MaprallueBblMH 3J\eKTpo.aaMH.
~HI'HeHa H caHHraplIII, 1949,4. . .
for1f6en.awBH.111 B, r.. KH,nIl3,HH C, n. CIIJllfK03 CpeJ1!H pa6u'j
IIHX 4HaTypcKHX MapraHueBbix pyn.HHKOB. Tpyn.bI HaYIIHo-HCCJle.ilo'j
BareJlbCKOrO HHCTIIT)'r3 I1lIl'HeHbI Tpy.:ta H "'npoq>J.a6oJleBa~Hii. T. II :
T6HJlHCH, 1948. '
r 0 n b n. 6 e p r M. C. 0 BJlIIIIHIIH Bb/6poCOB Te11JJOBbiX 3J\eKTpOCTaHuHtP
Ha 3IlopOBbe IleTeii. fllrHena II c3uuTapHII, 1957, 4. '
K 0 3 JI 0 B n. M. C:JUHTa'pHali craTHCTI!:Ka. M., 1955.
JI e oS 'H H a 3. H., Po <> a II e 'B C K a II H. r. H3MeHe'HHII B JlerollHoft
TKaUH npll BUYTpHTpaXe3J1bHOM BBen.eHHH OKHCJlOB' MapcaHua. rH"
rHeHa H caHill alpHIi. 1955, 1. .
M a I/( Y JI 0 'B a H. 11,., M a 'H H JJ 0 B a K. M. npOH3BO.ltCTBeHHble O'I'paB-
JleWHII MapraHueM npH 3BTOMaTlllleoJ{oii cBa.pKe non. q>JlIOCOM.
fHrneHa H ca,HHTapHII, 1951, 3.
M a II a (\ e JI H M. 3, K Bonpocy 0 MaHraHOKOHH03e. rHrHeHa H caHH-
TOpHII, 1957, 4.
M H J\ JI e ,p C. B. 0 npeIleJlbHO IlonycTHMoM COJlep>KaH'HH MapraHua
B B03Jlyxe I1'p'H cB3'j)Ke, TOJIcToo6Ma3aKHb/MH 3J1eKTpOJIaM'H. fHrHeHa
H caHHT3pHII, 1939, 12.
H a B p 0 UiK H ii B. K. Me.!1llKO-C3HIITa,pHoe 06C.rry>KHB3HHe npOMblWJJeH-
HbiX npeJIltpHIiTHH. KHeB, 1951. "
C yp a T B. C., Can 0 >K ,H 'H K 0 'B A. n., ill H JI 0 III a A. H. K paH.HeA
JlHarHOCTHKe, KJlHHUKC. H npcq>HJlaKTHKe HHTOKCHKaUHII MapraHlleM..
Ka3aJlCKHH MM'IIUHHCKHi'J >KypHa.1, 1936, 2.
ill H W'K H JI a H. H. CaHHTapHblc YC.10BHII B uexe pa3MOJIa MapraHue-
II'OH PYAbi 3a'BOJla ra.1bB2HHIICCKIIX ",,1eMeHTOB. npOMblwneHH311
, TOKOKKOJiOrHII. COoplfHK I1HCTUTyTa HMenH 06yxa. M., 1934.
-46-
-------
Supplem~~tal Data on the Accum°cllation and Distribution of
Me rcury in the Organis m of Expe rimental Animals
V. M. Kurnosov
The A. N. Sysin Institute of General and Community Hygiene
of the Academy of Medical Sciences of the USSR
The present author presented a paper before the Committee
of Allowable Atmospheric Air Pollutant Concentrations which was
in the Committee's Book 5, OTS No. 62-11605, 1962, page 39.
It was shown in that paper that 0.002-0.008 mg/m5 of mercury vapor in
atmospheric air under chronic experimental conditions elicited clear cut
functional changes in the higher sections of the central nervous system
manifested as disturbed higher nervous activity. In the present communica-
tion results are presented of investigations conducted for the determ~_nation
of the accumulation and distribution of mercury in the organism of experi-
mental animals and of consequent morphologic changes in the organism
elicited by minimal me rcury vapor concentrations in the air.
It has been known for some time that the living organism, including man,
contained mercury. It has also been known that mercury as a trace element
was present in all biological sped mens. On the othe r hand, A. Stock, W.
Zimmermann and many others established that mercury as a poison rapidly
accumulated in living organs even unde r normal conditions, forming points
of m'~rcury deposition, located chiefly in the parenchymatous organs, such
as kidneys and liver, and to a lesser degree in other organs. Studies of
grave m~rcury intoxication indicated that pathologic manifestations appeared
first in organs in which mercury deposition was most pronounced; thus, K. Z.
Lyubetskii in 1953 alone and in cooperation with D. V. Shraiber in 1957 ~on-
ducted experiments with dogs exposed to the inhalation of 0.5-8.0 mg/m of
mercury vapor and found clearcut changes in the kidneys and in the liver.
Similar results were obtained by many other investigators, as was indicated
by reports which have appeared in the literature in 1872, 1931, 1937, 1957,
1959, etc. Some of the reports indicated the presence of morphologic brain
changes. The reports also indicated that chronic inhalation of O. 1-7.0 mg/m 3
of mercury vapor resulted in the anima.1s I death. No reports we re found in
the literature on experiments performed with low mercury vapor concentra-
tions under chronic conditions. The present author studied the effect of low
mercury vapor concentration in the air to check on the validity of the exist-
ing limit of allowable mercury vapor concentration in atmospheric air. The
work was conducted along the following channels:
on Limits
published
-47-
-------
A study
-------
sensitivity of the original procedure. Quantitative determination of mercury
was made by the method described by N. G. Polezhaev in 1936, which was
as follows: The biological specimen was comminuted and placed into a
Kjeldhal flask which contained a mixture of concentrated sulfuric and nitric
acids in 1:1 ratio. Other steps in this procedure were described by N. G.
Po1ezhaev in Gigiena i Sanitariya, 1946 No.' 5 and 1956 No.6. Determina-
tions were made in triplicate. Results obtained by this procedure are tabu-
lated in the table below. It can be seen from this table that the highest mer-
cury deposition was found
in the, li ve rand kidne ys
followed by the brain and
other organs; this was in
agreement with results
- obtained by previous authors.
EN
Data in this table als 0 in-
dicated that intensity of mer-
cury deposition in the organ
was in direct proportion to
the mercury vapor concen-
tration present in the air in-
haled by the experimental
animals. Highest me rcury
vapor deposition was found
in the organs of rats belong-
ing to groups 1 and 2 which
were exposed to alr containing highest concentrations of mercury vapor; this
was followed by mercury deposition in the organs of rats belonging to group 3.
The amount of me rcury deposited in the organs of rats belonging to group 4
was ve ry slight and was nearly identical with that found in the organs of rats
belonging to the control group and which inhaled pure air. Accordingly, the
amount of mercury deposition found in the organs of rats which inhaled air
containing mercury vapor concentration below the allowable limit for atmo-
spheric air could be regarded as normal.
No clearcut regularity was noted in the rate of mercury deposition in
the stomach, lungs, and heart comparable to that observed in the liver,
kidneys and brain of the experimental animals. No pre'sence of mercury was
disclosed in the spleen by the method used, probably due to the small amount
of mc.terial this organ contained, and to the inadequate sensitivity of the method
used. Data obtained on the rate of mercury accumulation in the brain were of
considerable significance. Mercury was found in the brain of one rat of each
of groups 4 and 5 (control) in the amount of 0.01 u of fresh material. There-'
fore, it can be safely stated that no mercury was present in the brain
tissue under normal conditions. Analytical results obtained with rats of
groups 1, 2, an~ 3 which inhaled me rcury v.apor~ in the gene ral range of O. 02
and 0.002 mg/m indicated that highest mercury deposition was found in the
brain of rats belonging to groups 1 and 2, and that, generally speaking, degree
of mercury deposition in the brain tissue depended upon the mercury vapor
MERCURY ACCUMULATION I N THE ORGANS OF EXPERIMENTAL ANIMALS'
EXPOSED TO CHRONIC INHALATION OF DIFFERENT MERCURY VAPOR
CONCENTRATIONS
.. .. -. ..
- . MKG OF HG I'ER I G OF FRESH ORGAN
MIi/M3 OF He; RAT
GRoUPS VAI'OR IN No. KI~I I J \ST01' I
.:!!I.~..~"''! - HEYS La YER BRA' IHEARTi~CH LUN~S '5'I'L~
0,02-0,03 1 I I I I ' I
FIRST, 1. 0 0, 81 0,2 I 0,461 0, 1 0, 1 . 0
2 0,8 1°,011 0,111 0,6 0 0,06 0
SECOND 0,008-0,01 14 0,8 0,8 0,2 I O,U1! O,C6 0 0
'. 6 1,0 I 0.12 0.1 ! 0.04; (J.08 0 0
8 2.0 0,2 O,08i 0 I 0 0 0
THIRD 0,002-0,005 15 0,4 O,R 0.C6j 0,01' 0,02' 0 ()
... . 7 0,6 0,1 0,08 0 i 0 0 0
18 0.8 0,081 0,08 0,02: 0 ° 0
FOURTH 0-0,0003' 4 0,081 0.081 0 0 j 0.02 0 0
- -- 20 0.09: 0,091 0 0 U 0 0
16 0.061 0,(6' 0 0 0 0 0
A 0.03 o,ORI 0.01 0 I 0.021 0,02 0
ONTROL D o,o~ 0,C6 () 0 0 0 0
B 0,02 0,08 0 I 0 i 0 0 0
c
-49-
-------
concentration in the inhaled air. The process of mercury deposition in the
organs of rats belonging to group 3 was less clearly defined. Nevertheless,
the totality of results indicated that the degree of mercury vapor accumula-
tion in the brain tissue of the experimental rats ran closely parallel with the
functional disturbances of the rats' higher nervous activity.
A study of the morphologic changes in the rats' livers, kidneys, brain
and other organs indicated that considerable morphologic changef" ccurred
foremost in the parenchymatous organs in which mercury deposition was most
pronounced. Rats of groups 1, 2 and 3 mani.fested morphologic organ change s
which were not very clearly defined, but which were in correspondence with
the mercury vapor concentrations present in the air inhaled by the corres-
ponding rat groups. Thus, the morphologic changes we re more clearly de-
fined in the organs of rats belonging to group 1 than in the organs of rats be-
longing to group 3 which inhaled the lowest concentration of mercury vapor in
the air.
Changes in the organ morphology of rats belonging to groups Nos. 1 and
2 were as follows: There appeared fairly but not very clearly defined symp-
, toms of irritation of the upper respiratory passages in the form of a slight
catarrhal bronchitis. There were also symptom3 of a slight proliferative
process in the interalveolar septi; there was also a slight degree of fatty in-
filtration in the liver cells and a poorly defined protein dystrophy. The kid-
neys showed a slight protein dystrophy of the convoluted, tubules and a
slight microdrop fatty infiltration. The above morphologic organ changes
were less pronounced in rats of group' 3. The spleen showed a diminution of
the amount of lymphoid tissue pulp and a slight deposition of cells containing
a brown pigment. Changes occurring in the brain matter were of interest.
Rats of groups 1 and 2, and to a degree of group 3 manifested slight peri-
vascular and pericellular
edema and vacuolization of
individual cortical cells.
Histologic sections stained
by the Nissl method showed
edema and protoplasmic
vacuolization in the pyra-
midal and in the round cort-
ical cells. Similar changes
were noted in the subcorti-
cal nodes in the thalamo-
hypothalamic region and in
the trunk. The described
manifestations, including
those found in groups land
2, were of slightly defined
charac te r and showed no .
cellular destructive changes,
which leads to the assump-
tion that the pathologic pro-
FIG. I - RAT NO.9 a: GROUP 2. HI VAPOR CONCN. 0.008-0.01
~/"3. INHALATION EXPOSURE 9.5 MONTHS. KIDNEY
CHANGES. MAGNIFICATION 10 x 20.
MICRODROP ADI POOlS a: THE CONVOLUTED, TlI9ULAIII EPITHELI UM.
-50-
-------
FIG. 2 - RAT NO. 12 OF GROUP 2. HG VAPOR CONCN. 0.008-001
MG/M3. INHALATION EXPOSURE 9.5 MONTHS. LIVER
CHANGES. MAGNIFICATION 10 X 20.
MICRODROP ADIPOSIS OF LiVER CELLS. FATTY INFILTRATION IN
THE LD5lJLI CENTERS.
FIG. 3 - RAT NO.3 OF GROUP 3. H& VAPOR CONCN. 0.002-0.005
MQ/M3. INHALATION EXPOSURE 9.5 MO~IHS. LIVER CHANGES.
LIvER CELL ADIPOSIS LESS INTEN;;;: THAN IN RAT 110.,12.
S(tiE FAT I NFl LTRATED CELLS f£A TERED (1\IE"I THE PREP-
ARATION SURFACE. t-'AGNIFI ',ITInN 10 X 20.
, \
-51-
i
I,
.. : ~
ce s s in the b rain was only
slight and was fully com-
pensated by the high corti-
cal plasticity of the brain.
The described changes are
illustrated in Figs. 1,2,3,
4 and 5 correspondingly.
(See Fig. 1 on page 50.)
(See Fig. 4 and 5 on page
52). Figs. 4 and 5 clearly
illustrate the degree of cell-
ular integrity pointing to the
absence of gross destructive
cortical changes and to the
reversible nature of the ob-
served phenomenon.
A comparative study was
made of the results obtained
in the study of chronic low
dose mercury intoxication on
the hi ghe r ne rvous ac ti vi ty
with the results of accumula-
tion and distribution of mer-
cury in the organism and of
the morphological changes;
the study indicated that all
observed functional and
morphological changes we re
closely associated with one
another and depended upon
the me rcury vapor concen-
tration in the inhaled air.
Most clearly defined changes
in the higher nervous activity
were noted in animals of
groups 1 and 2 which inhaled
air containing the highest
mercury concentrations.
This was paralled by greater
mercury deposition in the in-
te rnal organs and in the brain
tissues, paralleled by more
clearly defined morphologi-
cal organ changes. The de-
scribed changes were less
manifest in animals oCgroup
3, which inhaled air contain-
-------
FIG. ~ - RAT NO. 13 OF GROUP I. H' VAPOR CONCN. 0.01-0.03
M,/"3. INHALATION EXPOSURE 9.5 MO~.'THS. BRAIN Goqrex
CHANGES. SOME CELLULAR PROT~PLASMIC VACUOLIZATION,
EDEMA AND CLEIo.RING ItlOlCATIVE OF IRRITATION. M.A.GNI-
FIGATION 10 X 40.
. . ,
~.. ,. .
&"'..' "- - .
FIG. 5 - RAT NO.3 OF GROUP 3. H' VAPOR CONCN. O.OO~.OO5
M&/M3. INHALATION EXPOSURE 9.5 MONTHS. BRAIN CORTEX
CHANGES. IRRITATION INDICATIONS ARE NOT AS CLEARCUT
AS I N RATE NO. 13. ISOLATED CELLS Ir.4 TH UNEVENLY STAI N.
EO PROTOPLASM MID I SOLA TED VIo.CUOLES.
ing lower mercury vapor concentrations. It should be noted that animals of
group 4, which inhaled air containing m~rcury vapor if concentration below
the limit allowable for atmospheric air (0.0003 mg/m ) manifested no changes
in their conditioned reflex activity. no mercury accu:Tlulation in the organs and
no pathomorphologic changes. Thus, it can be safely stated that a direct and
regular relationship existed between the accumulation of mercury in the organ-
-52-
-------
is m on one side and the morphologic changes occurring at chronic exposure
to diffe rent me rcury vapor concentrations.
In the opinion of the present writer the results of this investigation in-
dicated that chronic inhalation to air containing 1 mg/m3 of mercury vapor
was harmful to normal health and that appropriate means should be instituted
without delay to lower the degree of atmospheric air pollution with mercury
vapor.
Conclusions
1. Chronic ex~e ri ments conducted for the dete rmination of the effect
of 0.002-0.005 mg/m mercury vapor on the organism showed the following:
Chronic exposure to the e.ffect of mercury vapor'in concentrations at-
times found in atmospheric air adversely affected the organism by disturb-
ing the functional activity of higher nervous centers, by excessive deposition
of mercury in the organs and esp'ecially in the brain, and by producing patho-
morphological changes. .
2. The extent and gravity of the neurological and pathomorphologlcal
changes were directly proportional to the mercury vapqr concentration in the
inhaled air.
3. Experimental exposure of animals to the inhalation of mer.cury
vapor in concentrations below the limit of allowable concentration in atmo-
spheric air elicited none of the above desc ribed pathological symptoms. This
confirms the conclusion previously arrived at, namely, that 0.0003 mg/m3 of
mercury vapor should be regarded as the limit of its allowable concentration
in atmospheric air.
4. Results of the present investigation have shown that c~ronic ex-
posure to mercury vapor in concentrations of 0.008-0.01 mg/m , resulted
in the deposition of mercury in organs and brain tissues, which disturbed
the higher central nervous activity centers and other organs, accompanied
by pathomorphological changes. Therefore, it is suggested that the existing
limit of allowable mercury vapor concentration for air of working premises
was ill founded and should be revised after appropriate investigation.
-53-
-------
BIBLIOGRAPHY
,
I
) .
I
,
,
I
I
I
I
I
I
I
!
I
I
I
I
I
A w,6 e n b C. H., T peT b R K 0 B a B. A. 0 UIlp.KynRUIIH H .QeiJOH'Mpo-
BaHlI1(. coen.lllleHH!! PTYTH B opraHlI3Me. <1>apMaKo.~orHR H NKCHKO-.
JK)rHII. 1968, 21. 2.
r e JI b
-------
Hygienic Dete rmination of Limits of Allowable Concentrations
of Chlorine and Hydrochloride Gases Simultaneously Present
in Atmospheric Air
V. M. Stayzhkin
The F. F. Erisman Moscow Scientific Research Institute of Hygiene
Existing official limits of allowable concentrations of harmful substances
in the air are based on studies of individual air pollutants. ' It is known how-
ever, that in many instances two or more pollutant components are simulta-
neously present in the investigated air. It has been known for sometime that
results arrived at on the basis of individual air pollutants may not represent
the true physiological effect of two or m:ne simultaneously present pollutant
components. The present study was unde rtaken for the dete rmination of physio-
logical effects of low concentrations of chlorine and hydrochloride gases simul-
taneously present in the air, especially their effect on the central nervous sys-
tem and on the respiratory organ receptors,. It was hoped that the resl,llts
might either confirm or establish the need fora revision of the existing offi-
cial norms for chlorine and hydrochloride gases present in the air individually
or simultaneously. Chlorine and hydrochloride gases penetrate into the organ-
ism primarily through the organs of the respiratory passages. Contact with
such gases irritated the mucosa of the respiratory passages, the lungs, the
stomach, the conjunctiva and of the skin. Numerous efforts have been'devot-
ed in the past to the study of chlorine and hydrochloride effects individually,
but no reports have been found dealing with the combined effect of the two gas-
es. T. A. Shtessel investigated the combined effect of chlorine and sulfur
anhydride and of chlorine and nitrogen oxides. He first established lethal con-
centrations for each of the gases individually and then for some combinations
of these gases. His results indicated that inhalation of chlorine and oxides of
nitrogen in lethal doses by cats and mice produced summary effects, and that
inhalation of chlorine and sulfur anhydride simultaneously in lethal concentra-
tions produced somewhat weaker results, ,indicative of slight antagonistic
action.
The present study was confined to the use of low concentrations of
chlorine and hydrochloride gases and their effect on the physiological re-
activity of man. The methods of investigation were: determination of thres-
hold odor perception, optical chronaxy and adaptometry. Constant concen-
trations of the two gases in the experimental air were obtained by methods
described elsewhere. Constancy of gas concentrations in the air, alone or
mixed,were checked appropriately in the course of the experiment. The method
used in this connection is the same as was recommended by the Committee on
'Sanitary Protection of Atmospheric Air, described elsewhere. The investiga-
-55-
-------
tion was conducted with 12 test persons, 17 to 28 years of age. Appropriate
medical examination indicated that all persons were normal with regard to
their olpha,ctory sensitivity. M. T. Takhirov previously found !hat the con.- .
centration threshold of chlorine odor perception was 0.8 mg/m , while E. V.
Elfimova found that the threshold concentrations '3f hydrachloride gas odor.
perception was within the range of 0.1-0.2 mg/m . Such data were used as
orientation' values in the present investigation, results of which are shown
in Table 1. Results indicated that 0.75 mg/m3 of chlorine in the air con-
. stituted the threshold of
TABLE I ,
. its odor perception, and
CONCENTRATI ONS OF THRESHOLD CHLORI NE AND HYDROCH LOR I DE GAS PER-: that at O. 7 mg/ m 3 chlorine
CEPT' ON.
_.._-~- ----- --~ in the ai r was not odor pe r-
MG/113 OF HYDROCHLORIDE ceptible. . The minimal odor
. . "AS _..--
I. . pe rceptible concentration of
~~~~,:~~ ~-~~T~~~i- hydr0<3hloride gas was g. 2
mg/m and 0.15 mg/m was
not odor perceptible. Simi-
lar results were obtained by
M. T. Takhirov and E. V.
Elfimova.
The next step in the investigation was to determine the combined con-
centrations of thre shold chlorine and hydrochloride gases odor perception in_.
the air. The technique of the test was practically the same as for the dete r-
mination of concentrations of threshold odor perception of the gases individ-
ually. This investigation engaged the services of 22 test persons, 17-28 years
of age. According to information found in the literature, this represented the
age range of most sensitive odor analyzer perception. The study consisted
of 404 determinations made with 7 different chlorine and hydrochloride gas
concentration ratios. Results are shown in Table 2. Results indicated that
-' '--- -~ -- ._- ... - -------- - a combination of chlorine
TABLE 2 .
and hydrochloride yas ln
0.3 and 0.1 mg/m corre-
spondingly' constituted the
threshold odor pe rceptio~
of the combined gases and
that corresponding concen-
. tratio~s of 0.2 and 0.13
mg/m constituted a com-
bination of the two gases
which was not odor per-
ceptible. It has been known
that chlorine and hydro-
chloride gases irritated the
mucosa of uppe r respiratory
passages. Therefore, it was assumed that in the present investigation two
additive factors were under study, and that the effect of the two gases in com-
bination was that of the sum of their individual effects, and, accordingly, any
'c
-,
MS/M3 OF CHLORINE
No. OF :
TEST
PERSONSi MAX. I'ER-. I I
CEPTISLE
5
5.
:2
0,80
0,75
<0,80
NON I'ER-
CEPTIBLE
0,75
0,70
0,80
No. OF
TEST
I'ER~OtlS
8
2
2
0,15
0,:20
0,25
0,2
0,25
<0,25
DOOR PERCEPTIBLE COMBINATION CONCENTRATIONS OF SIMULTA- ,
. NEOUSLY PRESENTCHLORI NE AND HYOROCHLORI DE GASES ---.-
!"NUM-SER ;OF"TEsr-I'E'RSO-I/S--
M";~
_.cQtlCN~
- - - -- ~_-:.' NUMBER qF i
CI +'HCI ..AS TEST~_I
---- -
- --
ODOR I'ER- I' NOT PER- -I
CEPT~SLE_.I _g.~T~BLE i
':"--'O,i 1 +0,05
0,2+0,10
.0,2+0,13
. O,2+U,15
0,3+0,10
U,4+U, JO
O,4+0,U7
0,5+0,07
66
41
55
!j3
63
66
16
14
12
82
3
65
fiG
41
43
1
50
I
16
J
13
-56-
-------
concentrations of the two gases which added up to unity or less, as shown
below, would not exceed the limits of their allowed concentrations. Thres-
hold o~or concentration for .chlorine gas was pre3viously established at 0.75
mg/m , and for hydrochlonde gas at 0.2 mg/m . Accordingly, concentra-
tions shown in co.lumn 1 of Table 2 should be interpreted as follows: Results
0,1 + n,05 0, .
-- _.. -- = 0 .1R -' DDR NOT PERCEPTIOLE;
0,7:) 0.2' .---------
O.~ + n,] ,
----- -- = 0 76 -- ODOR tlOT PERCEPTIBLE;
0.75 O.~ .
n.:! + 1J.13
-0.7":'- -n7 =n,\JI~DDOR PERCEIVEa BY 12 OF 55 I'ERSOIIS;
----------
n.2 , 0,]5
- -;- ---- = 1.01'-
0.75 0,2 ODOR PERCEIVED BY 82 OR 83 PERSONS;
-- ~. .._-"---- ------- - -- .-,---
~+-~ =0,0 -' - -- ---- - ----------
0.75 0,:2 ODOR PERCE I VEil IN 3 OF 63 TEST5;
- -- - ---
--~- +~ -103-
U,75 O,:! -. : ODOR PERCEIVED BY 65 OR 66 PERSONS:
- -------- -. --.- ----
-- ---.-
0.4 . 0.07 . -
~ " --;-' = 0,1-;8 - ODOR
0,10 0.-
0.5 + O,n!
--. -=1,01-
0,75 0,2' , ODOR
NOT PERCEPTI8LE;
- - -- -
PERCEIVED IN 13 OR 14 TESTS
-----~-_.
..-~-_._-- ----- --.--
of the above calculations clearly indicate that in the case of chlorine and hydro-
chloride gas the physiological effect of their s,imultaneous presence in the air
was one of simple summation.
M. T. Takhirov showed that short time inhalat~on of different chlorine
concentrations affected optical chronaxy: 1. 5 mg/m of chlorine sha3Ply pro-
longed the chronaxy, while inhalation of air containing 1. 0 -1. 6 mg/m of
chlorine gas had no effect on it. In a sim~lar manner E. V. Elfimova showed
that inhalation of air containing 1.5 :rg/m of hydrochloride gas prolonged
optical chronaxy and that 0.6 mg/m hydrochloride gas constituted the con-
centration of its threshold reflex effect on optical chronaxy. Similar results
we re obtained by othe r investigators. The optical chronaxy method was used
in determining the effect of different chlorine and hydrochloride gas concen-
trations simultaneously present in the air on the functional state of the cere-
bral ~ortex, using the impulse electron stimulator -recorde rISE -01-58. A
1 cm electrode was used as the active one and was attached by an elastic
belt to the head; by turning a screw on the electrode direct contact was estab-
lished between the electrodes and tlze outer orbit of the eye. The indifferent
electrode was a plastic plate 50 cm ; it was attached to the shoulder. The
active and indifferent electrodes were covered by a piece of flannel moistened
in physiological solution.,
- Experiments were conducted as recommended by the Committee for
Sanitary Protection of Atmospheric Air using 4 persons 18-24 years of age
who were previously examined medically and found fit as test subjects for the
present investigation. The remaining of the 'procedure was conducted as else-
where described for the determination of concentrations of threshold odor per-
ception. Fresh air and air with a mixture of gases were run into the inhalation
-57-
-------
tubes on the 6th and 9th minutes of observation. Tests were also conducted
in a similar manner with fresh air in orde r to obviate the pos sibility of con-
ditioned reflex formation in relation to the experimental environment. Re-
suIts of tests performed with person TL are illustrated in Fig. 1. Curves
in Fig. 1 indicate that at com-
binations of chlorine 0.75 mg/m3
.' \ 3
I ~ and hydrochloride gas O. 3 rrJfS/m
, \ and als 0 chlo rine O. 3 mg/ m and
I \ hydrochloride gas 0.1 mg/m3 the
/ \ gas odor was clearly felt and that
i . \ optical chronaxy values corres-
I \. pondingly we re 0.034 j.l F and
, ~\ O. 0019 ).l F. Howeve r, the effects
'.
! \ of electrical eye. stimulation were
. i brief and eyes returned to near
I "'. normal at the end of the observa-
,: .-¥~. "'" S
, ,.' '. "...... tion. Exception to this case was
" .. 1- ,
, /... 7 , ~. ., t d b h b' t' f
i /. .. v "II presen e ,y t e com lna ion 0
.. ...#~~~-~o "". 0 75 / j
, .v .-~~ ,,'/ . ~g m of chlorine and O. 3
2: mg/m of hydrochloride gas. At
r;' ff IZlf Ie the end of the obse rvation optical
TIME IN MINUTES chronaxy increase amounted to
FIG. I - EFFECT OF SIMULTANEOUSLY PRESENT CHLORINE I 0.013 j.lF. Rheobase ch'3nges were
AND HYDROCHLORIDE GASES ON OPTICAL CHRON- . noted o~ly at 0.75 Tg/m of chlo-
AXY OF T. L. I rine and 0.3 mg/m of hydro-
I - CLEAN AIR chloride gas combination. No
2 - CI+ HCI 0.1 MC/113+ 0.05 MG/M3 rheobase changes were noted in
3 - It + " 0.2" + 0.1 "
4 - It + It 0.75 If + 0.3 If 2 other concentration combina-
5 - .. + If 0.3" + 0.2 II tions. Significance of the data
6 - It + II 0.3" + ".1 II 'f' d "11 S.
7 - " + .. 002" + 0.2 .. were veri le stahstlca y. 19-
B - " + II 0.2" + 0.3 " nificant results were obtained with
.. .. '3 . , . ..' ---'" - -'---'" concentration combination1 of 0.2
mg/m of chlorine and f. 3 mg/m3 of hydrochloride gas and 0.3 mg/m of
chlorine arid O. 2 mg/m of hydrochloride gas. Active and inactive chlorine
and hydrochloride gas concentrations obtained by the optical chronaxy method
for the 4 test persons are listed in Table 3. (see page 59) Data in that table
show that threshold concentrations established.by optical chronaxy tests 'for
simultaneo~sly present Cl and HCl gases were higher than their active or odor
pe rceptible concentrations.
. The effect 'of low chlorine and hydrochloride gas combinations in different
concentrations on the functional state of the cerebral cortex was then investi-
gated by the method of dark adaptation using adaptometer ADM. Here, as in
the other tests, three persons 20, 22 and 23 years old who had been selected
afte r medical examinations, we re used as te st subjects. Fresh air and air
containing mi xtures of the two gases were run into the inhalation tube on the
15th and 20th minutes of inhalation. Tests were made with the following chlo-
rine and hydrochloride gas concentration mixture s:
OJ?
{J,IZ.
0. fG!
J. ~:..:}
1."5.
I<. .
::1. :o,flJ
z.
: .o,M
. >< '
. ~ {l,ft7J'
'0.
: = JWJ5
0.
'_i'(J.IJ2
o"co
U,U,- 7"
f!tJII
0. Oi'
o
-8
-58-
-------
O. I + 0.05 mg/m, 0.2+ O. I mg/m3, 0.4 + 0.2 mg/m3
Changes in eye sensitivity to light in 1. V.
following brief inhalation of low chlorine
and hydrochloride gas concentrations are
graphically presented in Fig. 2. The
curves in that figure indicate that a brief
inhalation of the chlorine and hydrochloride
gas mixture lowered eye sensitivity to light
in proportion to the concentration of the
gases. The drop in eye sensitivity!o light
effected by the combined O. 2 mg/m chlo-
rine and O. I mg/m3 hydrochloride gas con-
centrations was substantial and pe rsistent.
Even at the end of tests m'ade with 0.2 +
O. I mg/m3 concentrations of CI and HC I gases eye sensitivity to light failed
to return to its original level at the end of the experiment. Eye sensitivity to
light dropped to still lower levels with a double increase in t~e concentrations
of the two gases. A chlorine gas concentration of O. 4mg/m was only 50%
of the threshold concentration as d~termined adaptometrically by M. T. Takhirov,
1/20000' and hYfrochloride gas concentration of 0.2
;fIJOOO mg/m was the equivalent of the threshold
:116000 concentration dete rmined by E. V. Elfimova
1"701J0 using the same method. See Table 4 (page
lIiMO 60) Th d" ""
'115000 . e note rIse In eye jensltlvlty to
Imoeo light effected by O. 1 mg/m ff chlorine in
~ '119000 combination with 0.05 mg/m of hydro-
~ ;i/woo ./~:" ,chloride gas on the 30th minute of obse rva-
~ fff1J6/J ./ tion was statistically insignificant. Aver-
t- ffOOOl7 / 1 f h' , , ,
j , /. age va ues 0 c anges In eye sensltlvlty to
... '/00000
a: S17000 // light elicited by different concentrations of
:: I,BOuOO ./ q. chlorine and hydrochloride gases in all test
~ II"OOOO :,,.,,/ ..-..-..- persons on the 25th minute are listed in
; 150000 '~.." .."'" Table 4 (see Page 60).
- 150000 '........""" Th d 'd' h' h I' f
~! " e ata In lcate t at In a atlon 0
... : /j(JOOO hl' d h d hI ' d ' ,
: ; J17000 c Orlne an y roc Orl e gas mIxture In
;; : 20000 concentrations equivalent to their adopted
.::i! /0000 limits of allowable concentrations elicited
o .f /11 15 Z/J 25 .,](j j5 ~J .~Il 50, 1 1, ht' ,
--- ----. - : In two persons on y s Ig Increase In eye
: T'ME IN MINUTES: h I f' h
-- - '-. .--- - ---~-:- - ---' sensitivity to light, t e va ues 0 WhlC were
FIG. 2 - CHANGES IN EYE SENSITIVITY rc; u'GHTiNi statistically insignificant. Double increase
, JEST PERSON J.v. UPON INHALATION OF CI in the chlori~e and hydr~chl~ride 'gas con-
HC I , ff d ' , , ,
centratlons e ecte a drop In eye sensItIvIty
,to light in all three test persons, with the
lowest drop in person 1. V. , This is shown
by the fact that on t~e 25th minute and under
----~------- ---
normal conditions this person's eye sensi-
-59-
TABLE 3
RESULTS OF OPT! CAL CHRONAXY STUD I ES WI TH ,
T ..9., !. v~, leD. AND K.G.!
, CONC!IS. IN:
_...MGI.~3
RESULTS
-- .--------
CI + HCI
0,10+0,0,5
0,20+0,10
0,30+0,10
0,30+0,20
0.20+0,20
0,20+0,30
0,75+0,30
INACTIVE
. . ~-_.- - --
:t
:t
ACTIVE
1 NACTIVE
ACTIVE
---»-
- - - .. -- ,-
I - CLEAN AIR
2 - CI + HCI GASES
3 -" +" "
4-"+" ..
0.1 MG/113 + O. Os I1G/M3
0.2" + 0.1 tI
0.-4" + 0.2 "
-------
tivity to light was 108640
relative units and after in-
halation of a gas mixturf
consisting of 0.2 mg/m of
chlorine and O. 1 mg/ m 3 of
hydrochloride gas eye sensi-
ti vity to light dropped to
53640 relative units; in the
case of test person K. Z. eye
sensitivity to light dropped
correspondingly from 175400
to 134600 relative units. In-
halation of a mixture of 0.4
mg/ m~ of chlorine and O. 2
mg/m of hydrochloride gas
was followed by a drop to
52200 relative units in person
1. V. and to 120200 in person
K. Z. The results indicate that a mixture '30nsisting of chl~rine and hydro-
chloride gases in corresponding 0.2 mg/m and O. 1 mg/m concentrations
elicited statistically significant drops in eye sensitivity to light, despite the
fact that the above concentrations were odor nonpe rceptible. Accordingly,
the data clearly indicated that the method of eye sensitivity to light was more
sensitive than any of the other physiological methods used for the determina-
tion of chlorine and hydrochloride gas effect on the central nervous system.
--- -- ---
TABLE 4
RESULTS OF ADAPTOMETRIC STUDIES
---...- ---. . . - . ,- - . -
~CONCHS. IN MIO/M3
~ - RELATIVE UNITS OF LIGHT
SENSITIVITY ON THE 25TH
-~ ~APTATI~fI M1NUTE -
TEST PERSON'S
I NIT fALS
CI + HCI GASES
. -
---~.
. I. v.:
, CLEAN AIR,
~o:1+tr;05--
0.2+0,1
0,4+'0,2
CLEAN AIR
0,1+0,05'-
0.2+0.1
0.4+0.2 ,
CLEAN AIR -
--0,1+0,05-- --'
0,2+0,1
0,4+0.2
108 640
108040
53 640
52 200
175400
177 000
134 600
120 200
102 800
103 720
71 680
64 500
--.---.-
K.Z.
I
P.V. ,
Conclusions
1. Results of the present investigation indicated that O. 75 mg/m 3 was
the concentration of threshold chlorine odor perception, and 0.02 mg/m3 the
concentration of threshold hydrochloride gas odor perception.
2. Results also indicated that the simultaneous presence in the air of
ch'lorine and hydrochloride gases was not odor percepti~le when the gases co-
existe~ in the following ratio concentrations: 0.3 mg/m of chlorine and 05 1
mg/m of hydrochloride gas, also 0.2 mg/m3 of chlorine and 0.13 mg/m
hydrochloride gas.
3. The additive physiological and neurological effects of simultaneously
present chlorine and hydrochloric gases in the air were in the nature of
arithmetical summation. .
4. Optical chronaxy tests indicated that threshold reflex ~ffects' we re
~roduced by .chlori~e and h~dr~chloride g~s simultaneous1Y present in the. air
m the followmg3raho combmatlOns: chlonne, 0.3 mg/m and hydrochlorlde
gas, 033 mg/m and also chlorine, 0.3 mg/m3 and hydrochloride gas, 0.3
mg/m.
-60-
-------
5. Jests of eye sensitivity to. light indicated that the combination of
0.2 mg/m of chlorine and 0.1 mg/m3 of hydrochloride gas constituted a
threshold combinaition mixture of the 2 gases which elicited changes in eye
sensitivity to light.
6. Results of the present investigation indicated that the previously
adopted limits of allowable single chlorine concentration of O. 1 mg/m 3 and
of hydrochloride gas of 0.005 mg/rh3 simultaneously present in atmospheric
air were below the threshold of odor perception and of effect on reflex activity
and, the refore, required no revision.
BIBLIOGRAPHY
6 Y ill T Y e' B a K. A. TIopor pe.p.~eKTopHoro neHcTB1l1i cepHllcToro J:"a3a
H a3po3o.~11 cepHoH KIIC.10TLI npll CORMeCTHOM npHcYTCTBIlIl.
B KH.: TIpe.'leJlbHo nonycTjf~lhle KOHueHTpau1l1l aTMo,cKalOlUerO
neHcTB1f1i napOR HeKOTopblX 1Ia pKOTIlKOB Ha BepXHlle .'lbiXaTe1lbHble
nYTIl. B KH.: COOplflfK Ifcc.le,loRalllfil .B OOJlanll npOMblW1IeHHOH
TOKCIIKOMrHll. M.. 1940. CTfJ. 207.
KpaBKoB H. n. OCIfOBbi .papMaKOJlorim. 4. 2. M.-n.. 11931,
CTp. 313.
nil T K e H C B. A. OnblTbl 3KcnepllMeHTanblioro 113Y'lell'HIi B1I1IIIHHII Ha
opraHII3M pa60TbI P anlOc.pepe Bpe!lllblX .napOB 'H ra30B: fllrlleHa
Tpyna, 1926, 12, 3-24.
~\--;:~ ~ x II If a B. n. K Bonpoey 0 npC.1cJlbHO' .ilOnycTII~IOH KOlfueHTpa-:--
1.1:1111 .p0pMaJibner'lIna B anlOe.peplfoM B03.1yxe. ,ilIlCC. M., 1958.
TI Jl 0 T II II K 0 B a M. M. 3arpll311cHile anloc.peplloro B03'lYxa aKpo-
JlCIlIiOM II ero rlfrllellllKalOlUIIX ra-
3011. <1>apMaKo.l0rllll II TOKr,IIKOJ10flIH, 1!141. 4.3,55.
<1> JlIO P II <1>.. U e pHil K <1>. Bpe.'lHble ra3b1. M. - n.. 1938. CTp. '164.
B i 11 Z C. Narkotische \\'irkllngo \'011 Jod, Brom lInd Chlor. Arch. f. expo
Patho1. ul1d Pharmakol... 1880. 13.8. 139.
Lei t e s R. 3KencpHMeHTaJlbHoc 113Y'lcHlle OJIIiORpeMeliHoro neHCTBII!I
TCnJ10TbI II Bpellllbix ra30B Ha opralf1l3M. Arch. f. Hyg., 1928, 102.
91-102.
L e h m
-------
Acetone as an Atmospheric Air Pollutant
Yu. G. Fel'dman
From the Department of Community Hygiene, Central Institute
of Post Graduate Medicine
Acetone is one of the simplest members of the ketone group. It is a'
colorless fluid possessing a characteristic ester odor and narcotic proper-
ties. It is one of the be st organic solvents, and is widely used in the varnish,
dye, cellulose products industries, etc. Acetone is also used as raw mater-
ial in the synthesis of chloroform, s ulfonal and ac richir1. Its effect on the
animal organism was studied by E.M. Kagan in 1924, N. V. Lazarev and A.I.
Brusilovskkya in 1934, :and by many others. However, most of these investi-
gators worked with high concentrations of acetone. It has been shown that the
higher nervous activity was the first to be affected by the inhalation of acetone
vapor. E. 1. Lyublina showed in 1957 that inhalation of air containing 0.5
mg/li of acetone produced pathological manifestations in the higher nervous
system. N. A. Zhilova demonstrated that exposure of rabbits to the inhalation
of air containing 0.2 mg/li of acetone 4 hours daily for 3 months considerably
increased neuro-muscular chronaxy. E.M. Kagan (1924), I. D.Mishenin (1935)
and 1. S. Tsitovich in 1935 de monstrated that inhalation of air containing low
concentrations of acetone for a long time' affected the organism more pro-
foundly than high concentrations inhaled for a short time. They believed that
this was 'due to greater acetone accumulation during prolonged inhalation of
lower acetone vapor concentrations.
Not much information was found in the literature on the effect of acetone
vapor on the organism of man. S. L. Danishevskii in 1948 found that inhala-
tion of air containing 3 mg/li of acetone vapor had no irritating effect on the
test subject. N. V. Lazarev in 1954 found that inhalation of air containing
1.2 mg/li for 3 to 5 minutes produced eye, nose and throat irritation. In
1957 M. D. Shpatserman described an acute case of psychosis developed in a
painter who inhaled vapor of acetone which was the paint solvent. In 1930
N. F. Okunev reported on a case of chronic acetone poisoning which re suIted
from the inhalation of ai r containing 0.45 - 2.0 mg/li of acetone vapor. This
occur'red in one of 60 workers exposed to inhalation of the acetone vapor. All
worke rs complained of acute headaches, ve rtigo, and some complained of
general intoxication similar to that produced by alcohol. Workers presented
a variety of other complaints. In 1958 O. G. Masenkova investigated the
gastric functional activity of 43 .employees in a shoe factory. Acetone concen-
tration in the air of the working premises varied between 0.1 - 0.3 mg/li.
Medical examination showed that the stomachs of nearly 50% of the workers
were only half empty before breakfast, and that the concentration of free
-62-
-------
hydrochloric acid was above the u~per normal levels. Highmoritis, pharyng-
itis and rhinitis were found in 17 of :43 examined persons. Masenkova assum-
ed that developed foci of pathologic ~1a)se and throat receptivity may have pro-
duced reflex changes in the gastro-~~cretory function. Acetone production
and its utilization in many processes 'are generally accompanied by the dis-
charge of its vapor into the atmospneric, aii-. This is particularly true of
the wood pulp chemical industry al1d the chemical plants which produced
varnishes, paints, acetate silk, of furniture manufacturing plants, etc. No
extensive study of the degree of air ;pollution with acetone has been made thus
far and no data we re found in the lit~ raturedealing with acetone concentrations
found in atmospheric air surroundin:g plants connected with the use of acetone
in their manufacturing processes, aind no' limit of allowable acetone concen-
tration in atmospheric air has been (determined or provisionally adopted. Hence,
I '
the present investigation. r. 3.
In 1948 Skramlik found that 4 rng/mwas the concentration of the thres-
. I
hold acetone odor perception. The present author reinvestigated this phase of
the problem by the method described by'V. A. Ryazanov, K. A. Bushtueva,
~ . ,
" and Yu. V. Novikov in 1957, using ~ 3 test pe rsons, 20 -57 years of age. Re-
sults are listed in Table 1. The data indicate that the concentration of thres-
TABLE J hold (~cetone odor perception of the tesj persons
was Within the range of 1.1-5.0 mg/m . In
most! odor sensitive pers03ns the threshold con-
cent~ation was 1. 1 mg/m , and the maxima~
nonp~rceptible concentration was 0.8 mg/m .
Effect of low acetone concentrations on the re-
flex ~Gtivity of test persons was then investi-
gated by the method of eye sensitivity to light.
This ;method was found technologically the'
easi~st and most convenient as well as the
CONCENTRATION OF THRESHOLD ACETONE ODOR
- .--.. ~ERCEPT I ON I N MG/M3
~-- -- ,- '/ C011CENT'RAT'IONS
, No. OF TEST I
MIN. PER. MAX. NON-
-_,-.2E_RSONS - . -' CHTI BLE I PERCE PT IBLE.
4
3
2
4
1 ,I
1,6
3,2
5,0
0,8
1,1
2,2 '
4,3
most sensitive.
It was mentioned on seve ral previous occasions that the sensitivity of
the, optical analyze r may be affected by gas concentrations below the level of
threshold odor perception. Present investigations on eye sensitivity to light
were conducted with 3 persons 20-57 years of age, using adaptometer ADM.
Preliminary tests were conducted to determine the basi.c concentration of
threshold acetone vapor odor perception of the 3 persons. Tests were first
made with inhalation of pure air to establish a dark adaptation control curve
for each of the test persons. Such surves were used as bases of comparison
in future tests. Individual observations lasted 40 minutes. Air containing
different acetone vapor concentratio~s and free air were run into the inhala-
tion tubes on the 15th minute of dark adaptation for 5 minutes. Results in"3
dicated that the inhalation of acetone ~on.centrations of 1. 5 and O. 55 mg~m
lowered the level of the adaptation curve in person L, while 0.44 mg/m of
acetone vapor had no effect on eye s~nsitivity to light. SeeFig. 1 (page 64).
Previous investigations esta~l~shed the concentration' of threshold ace-
tone odor perception as 1. 1 mg/m .' Above results indicated that inhalation
of odor nonperceptible acetone conc~ntration affected the functional activity
>-63-
-------
of the cerebral cortex, as shown by reflex c~anges.
In the case of test pe rson C 1. 6 mg/m of acetone was the odor non-
perceptible con<3entration and changes in eye sensitivity to light began with
0.81-1. 5 r:ng/m acetone concentrations. This was shown by the fact that
inhalation of air containing such acetone vapor concentrations raised the
level of the adaptation curve. The O. 55 mg/m 3 acetone concentration was
inactive, as shown by results of dark adaptation tests. Thus, the re sults in-
dicated that the method of eye sensiti.vity to light was more sensitive than the
method of threshold odor percepLon in test person S. The curve of dark
adaptation or eye sensitivity to light in person D was lower than in persons L
and S, which may have ben due to the fact that she was 57 years of age. In-
halation of air containing 1.5 mg/m 3 of acetone vapor raised the curv~ of
dark adaptation in this person. Concentrations of 1.2 and 0.55 mg/m of
acetone vapor were of subthreshold character. The concentrrtion of threshold
acetone vapor odor perception for this person was 3.2 mg/m . Consequently,
in the case of person D, as in the previous two cases, changes'in eye sensi-
tivity to light (optical analyzer) were elicited by an acetone vapor concentra-
tion below the concentration of its threshold odor perception. Data of all
previous tests were found statistically
significant. Results of the studies con-
ducted by the method of eye sensi- '
tivity to light clearly indicated that
inhalation of air containing diffe rent
acetone vapor concentrations had
diffe rent effects on the functional
state of the cerebral cortex in differ-
ent persons. This was illustrated by
the fact that i~halation of air contain-
ing 1.5 mg/m of acetone vapor en-
hanced eye sensitivity to light in persons
S. and D. and lowered it in person L.,
See Fig. 1.
,'Of equal interest is the fact that ~nhala-
tion of air containing 0.55 mg/m of
acetone vapor had no effect on the curve
of dark adaptation in 2 of the test per-
, sons and lowe red it in the 3 rd one.
10 15 2Q ~"i JQ #{J Such results point to the idiosyncratic
TIME IN MINUTES reactivity of the nervous systems in
'!-FiG-.-I-:-CHANGES IN-EYE SENSIT-iVITY TO LIGHT IN L.' different individuals. A comparative
DURING INHALATION OF DIFFEREtfl' ACETONE' evaluation of the results obtained by
VAPOR CONCNS. ARROI,/S INDICATE BEGINNING the determination of the concentration
AND END OF ACETONE VAPOR DELIVERY.
. of threshold acetone vapor odor pe r-
: I - CLEAN AIR; 2 - ACETONE VAPOR 0.44 ,.,;/,.,3; 3 - k
: ACETONE 0.55 1'1;/1'13; ~ - ACETONE VAI'OR 1.5 MS/H3. ception and of reflex effect on dar
---------------- - ---------- adaptation indicated that threshold con-
centrations established by the -adaptometric m'ethod were 50% below the con""
centration thresholds established by the odor perception method. Data obtained
. ,
I BOCtJO'
I
[75000
[70000
~I 050fJO
::>
...1 00000
>1
;:: ,550tJO
~!
~ 50030
c: ,
;
::: 45000
~: 40000
'"
-:,1 J5000
o
... 30000
>'
=iZ5000
~I '
~'ZOOOO
':.1'5000
(f)1
~I'OOOO
...1
15000
-, 0
o
t 1
5
-64-
-------
: ,
j
1 :
1 '
I
in the present investigation were i~ ~greem'ent with the results of observa-
tions made by F. 1. Dubrovskaya'i~ 1955, by M. K. Borisova in 1957 and
other authors who found that eye seinsitivity to light was in fact affected by
odor emanating substances in conc~ntrations below the threshold of their odor
perception. This means that odor honperceptibility of a given vapor in a
I
given concentration was no indicatipll of the, absence of effect on the central
nervous system in the same conce~tration. Results of the present investiga-
tion established that the concentratton of threshold reflex acetone effect on
the functional state of th~ ~erebral icor~ex, ~s. determined by the adaptometric 3
method, was 0.55 mg/m ln most ~d.0rsensltlve persons, and that 0.44 mg/m
was the nonactive concentration of fLcetbne vapor.
Tests were also made to dete{rmine acetone vapor effect on the reflex
and electrical activity of the brain \..Ising th~ technique described by K. A.
Bushtueva, E. F. Polezhaev and At D. Se menenko in 1960. These authors
used electroencephalography in est~lpli$hing concentrations of threshold sulfur
dioxide and of sulfuric acid aeroso~ ~eflex effects. The first affected the
olfactory organs, the second affe~tfd the trige minal ne rve ends. The index
of effect in this investigation was d~synchronization of the alpha-rhythm.
In their series of experimentjs ,these authors had shown that i~dividually .
applied, these substances chanqd the encephalogram at 0.9 mg/m of sulfur
dioxide and at 0.75 - 0.6 mg/m of ~ulfuric acid aerosol. Adaptometric te.sts-
showed that these were threshold c;oncentrations. In the second seri~s of ex-
pe riments the above authors estab~i~hed c oncentra~i~ns of. threshold ~ SO 2 and -
H2S04 aerosol effect on electrocor;tlcal reflex actlvlty uSll:g 502 and
H2S04 aerosol as the conditioned shmulators and continuous light a~ the un-
conditioned stimulator. They found that sulfur dioxide in 0.6 mg/m ,which
was the subthreshold concentration established by the adaptometric method,
was also the threshold 502 concen~ration which elicited conditioned reflex
desynochronization of the alpha-rhythm after 6-15 association!? with.~ight. -The'
corresponding concentration for HZS'Oj, ae rosol was 0.4 mg/m:; of acetone
vapor which was conside rably below that of the sulfur dioxide concentration.
Thus. the authors were able to dem~nstrate the high sensitivity of the electro-
cortical conditioned reflex method; and its practical application to the deter-
mination of threshold concentrations of irritating and odor emanating sub-
stances on the reflexogenic zones ~f the olfactory organs.
V. A. Gofmekle r in 1960 us~d. the electrocortical conditioned reflex
method in determining the allowable' acetone concentration in atmospheric
air; he found that the concentration of threshold methyl acetate ~ffect on con-
ditioned. reflex alPha-rhyt~IT)..de.SYrio_c~ronizati?n was O. O!? ~g/m3, for butyl
acetate lt was 0.13 mg/m , and fo;rvlnyl acetate 0.32 mg/m3. These thres-
hold concentrations were below thqse ~btained by adaptometric tests. The
present author worked in cooperadon with 3 test persons 20-32 years of age
I -
using an 8-lead electroencephalog~a:ph'of the "Al'var" system. This appara-
tus has been in use in the Department of Clinical and-Experimental Physiology
in the Central Institute of Post Graduate Medicine. Test persons were seated
In a specially equipped sound-prodf chamber in comfortable chairs completely
. -65-
-------
relaxed physica)ly and mentally. The test person' was asked to keep his
eyes ope~;cthe test chambers were completely darkened. The experimental
procedure and other surrounding conditions were the same as were used by
other investigators in similar studies as described elsewhere.
Unexpect~d stimulation of the optical receptor provoked sharp desyn-'
chronization of the alpha-rhythm. However, individual effects of low gas con:"
centrations in themselves had no such effect on the alp}la-rhythm. On the
other hand, the inhalation of odor emanating gas in as sociation with light
developed conditioned electrocortical reflexes in the form of alpha-rhythm
,'desynchronization, which appeared before the light was switched off; by
grad'ually reducing the tested gas concentration, a threshold concentration
was found below which no conditioned reflex alpha-rhythm de synchronization
was effected even in the presence of light. This briefly describes the mech-
anism of action of the cerebro-cortical electroencephalographic method.
Experience indiCated that not less than 10-15 gas and light associations
were required to bring about conditioned reflex alpha-rhythm desynchron-
ization. In isolated cases 20-25 associations may be required.' 'There-fore--;--
'., any concentration of acetone vapor which failed to elicit alpha desynchroniz.::-/
:~,tlon in 20-25 associations with light could be considered as non-active.
Brain biocurrent records were made by the universal method using a
four-lead recorder. Evaluation of results was based orily on biograms in
which alpha~hythm desynchronization: was clearly recorded by all four bio-
current leads. Test persons inhaled the gas for 15 seconds; continuous light
was used as the unconditioned stimulator during the last 5 minutes of con-
ditioned stimulation. Tests
with each acetone vapor con-
I I ! I I I ! I I I ; I I !, I I rt ~ centration were made in dup-
. II~' I \I'I"~I".:"I.' ''''!~r'''''''r--r-'i'''''.rl.VN'''.!-----r---'''''I' , """'.
1,.\ ! ! I, I I !' I '.licates once daily during the
:L,I".~tt.i\'r'I~'\\'II""'~~' """~""\"1il\~ I i II~\~ I " ::~: :fo~::t:f~::ed:~h ::;-
-... son G. had shown that inhala-
, : don of3air containing 0.44
, i! I I'''' I mg/m of acetone vapor
\' $ I I_I elicited conditioned electro-
: 6, ' : ' cortical reflexes on the 5th
: i I! I I ii, association of the vapor' with
F-iG:"i - CHANGES-IN ELECTROC'EREBRQCORTICAL ACTI VI TV OF G~ DUR I NG
I NHALATION OF 0.44 MG/~ OF ACETONE VAPOR ON THE 7TH : light, as was indicated by the
ASSOCI ATiON OF ACETONE VAPOR AND LIGHT. ; appearance of alpha-rhythm
I - OCCII'ITAL EEG ON 6111E OF RIGHT CEREilRAl HEMISI'HERE; 2 - Oc- etesynch'ronization for one
CIPITAL EEG ON 6111E OF LEFT CERE8RAL HEMISPHERE; 3 - TEMPORAL, second prior to switching in
EEG ON SI9E OF RIGHT HEMISPHERE; 4 - TEMPORAL EEG ON SIDE OF, '
LEFT CERE8RAL' HEMISPHERE; 5 - RECORD OF ACETONE VAPOR INHALATION; the l1ght. On the 7th aSSOCla-
6 - ARROWS INDICATE SWITCHING IN AND OUT OF LIGHT. tion the conditioned reflex
-----.- ..
. ---, became fixed, as can be seen
in Fig. 2. Curves in Fig. 2 indicate that alpha-rhythm desynchronization dis-_,
appea'red on the 6th second of acetone vapor inhalation and 'persisted for 3
seconds. The alpha-rhythm returned to normal on the 10th second. Switch-
ing the light in on the 11th second depressed the alpha-rhythm. This was
-66-
---- ---- -...
-------
:: I ~
i "
! ;
, i.5
expected. Soon after the conditioned~nd:~n,conditioned stimulations were dis-
. ~ [ ;.'. ~ .. ! . .
continued the electroencephalogram iacquired a normal. course. The condition-
. ed reflex began to show signs of ext~n~tion on the 9th association of gas in-,
halation with light and thereafter co~,pletely disappeared. Similar effects
were noted in experiments conducte~ ~it,h person T. i~ ~hom inhalatio~ of 9-ir
.! ,', . contalmng 0.44 mg/m of.
acetone vapor developed a
: conditioned reflex on the 10th
association of vapor in inhala-
. tion with light, but the re-
action was not as intense.
, The same was noted on the
lith association; on the 15th
association the alpha-rhythm
, de synchronization became'
. j, .! clearcut. The reflex began
FIG. 3 - CHANGES IN ELECTR'OCEREB~OCORTICAL ACr'~IT;Y OF 1. DURING to fade out between the 16th
INHALATION OF 0.-44 MG/M OF ACETONE VAIfO~ ON THE 1,5TH and 18th associations. This
ASSOCIATION OF ACETONE WITH LIGHT'
1 ! :, ' . ',," ,was illustrated by the results
I 2 3 4 SAME AS III FIG. 2' 5 - TIME LINE OF 'ACETONE INHAL#.- .
T~O"': ~I'I'~R LEvEl OF LINE I'E~IOD OF ACETONE VA~OR INH~LATlON; ,obtalned on the 15th vapor
ARROWS INDICATE BEGINNING AND END OF LIGHT 6TIM'LUION. and light association graphi-
; " ,-'---- cally presented in Fig. 3.
1 .
Curves in Fig. 3 show that alpha de:synchronization appeared on the 5th second
of acetone inhalation and continued ~o,r 5 se~onds before the light was switched
in. Inhalation of air containing 0; 44mg/m of acetone vapor failed to develop
conditioned reflexes in person B ev~n on the 35th association of the vapor in-
halation with light, indicating that t~is concentration was of subthreshold in-
tensity for person~. Thus, it was~demonstrated that inhalation of air con-
taining 0.44 mg/m of acetone vapC)!r had no effect on the electrical condition-
ed reflex activity of the brain of 2 t~5t persons but that conditioned electro-
cortical reflexes could be develope4 with such a concentration of acetone 3
vapor. Tests with lower acetone v~i?or,concentration, such as 0.35 mg/m ,
failed to develop electrocortifal co*d~tioned reflexes in any of the test per-
sons, therefore, 0.35 mg/m of ac~tone vapor can be recommended as the
limit of allowable single acetone. (frcentrat~on in atmospheric air. It is
considerably below the 1. 1 mg/m Foncentration of threshold odor perception
and. alsob~low the concentratifri offt~reshold reflex effect on ~ye sensitivity
to hght whlch was 0.55 mg/m , an~ ::als:o below the concentratlOn of threshold
refle~ effec! on electrical brain ac~i;ity in more sensitive persons, which was
0.44 mg/m . . 1 . .' .-
Determination of limit, of allojwable 24 -hour acetone vapor concentration
in atmospheric air was conducted'vri~h whit~ male rats under chronic-inhala-
tion conditions. Rats weighing 60:-80 g~wer:e divided into 3 groups of 10 rats
. i .,
each. Rats of the first groupwe're1~posed to the inhalation of air containing
200 mg/m3.of acetone vapor, W?iC~ fs:~~<~quivalent of the allowable concen-.
tration for working premises. Inh~.1'ation exposure was 8 hours daily for 45
days; rats of the second group were \exposed continually for 45 days to the
-67-
i
4
I. . f '
'.
I
t ~
i "
"'....
,"" ~, " I
l "
', .. ,
" ~} '
T ",.;
:
i
i , '
- ~ -, -
i
'. I :
.,
...
3
-------
inhalation 6f O. 5 mg/m 3 of acetone vapqr, a concentration clo~e to the one
recommended as the maximal single concentration. Rats of the third group"
served as controls. The gas -air mixtures were run into the exposure cha~-
ber at an average rate of 15 li/min. Control analysis showed that the ace-
tone vapor 'concentration in the first chamber ranged between 162-230 mg/m3
during the ~ntire 45 days, ave raging 199 :*: 1; the ~oncentration of acetone vapor
in chaTber 2 fluctuated between 0.42-0.87 mg/m , with an average of 0.53
mg/m * O~ 005.
RecQrds were kept of the animals' gene raJ condition, their weight,
changes in motor chronaxy and in the morphological blood picture. Experi-
mental animals manifested no particular deviations in their behavior in th,e
course of the experiments, and no symptoms were detected indicative of it'Fj.-
tative effects of acetone vapor. In fact, all 'animals were normally active, ate
with normal appetite, and gained, weight throughout the experiments. Animals
were weighed once every 10 days and no notable differences were found in the
weight records of the experimental rats as compared with those of controls.
In other words, the results indicated that
inhala~ion of air containing 100 and 0.53
mg/m of acetone had no unfavorable
effect on the rats kept unde r chronic ex-
perimental conditions.
The functional state of the central
nervous system of the rats was tested
by the method of motor chronaxy. Motor
chro'naxy was determined in 7 rats of each
experimental group once a week, by means
'of the condenser chronaximeter used in the
State Institute of Physiotherapy. Chronaxy
determination averages for each group are
shown in Fig. 4. Extensor chronaxy cur-
ves of the, control rats were of a higher
level than the flexor chronaxy curves in-
dicating that the muscle antagonist ratios
in these animals we re of normal values.
Curves of some antagonist muscles in the
rats of group 7 present a different picture.
The curves crossed on the 4th week of the
vapor inhalation indicating that the chron-
axy ratios of the flexor and extensor mus-
l, 2 3 . .5 6 7 8 9 /0 1/ 12 fJ
-T-'HE'iN-WEEKS "- . cles were of a reverse character. During
i .
-"-- ---'-- the 5th week both curves were of equal
--- .----.--.- ----- -.--
, FIG.'" - ACETONE VAPOR EFFECT AVERAGE MOTOR levels. A similar coincidence of curve
CHRONAXY IN RATS. , levels occurred during the 2nd week of the
i A - CONTROL GROUP; B - GROUP I; c - GROUP 3. .. d Th hi
' I - EXTENSOR CHRONAXY; 2 - FLEXOR CHRONAXY; . recuperatlon pe rlO. e c ange magn -
, A - AT TH'E BEGIHNING OF ACETONE VAPOR INHALA-, tudes were statistically significant; The
, TlON; 8 - AT END OF ACETONE VAPOR INHALATION i flexor and extensor muscle chronaxy cur-
. ves of rats of Group 2 showed a slight
-68-
0.020
0.015
, 0,010
0.00:'
\ ! 0.015
\ u..:
1::1.:
\ ~;O.OIO
; >- I
; )C !
;,O,oOf
,Of.
a:; .
.""",
.1°,
:---.;
0.0/5
, ' 0,010
;,-, o,OOf
. .J
o
\. A
. \
,
,;
1 2 J q J 5 1 8 9 10 11 12 13
,~j:l'!Eo'-LI{~tK.S -~;
A 5
"
I '
I 2. J- 4 J 6 7 8 9 10 If 12 1.1
-- -T"'ME-'-IIWEEKS.
---',- ----'--
,4 6
-.-
2
-------
I "
j
i
I
tendency toward approach during thei;p'e'riq,d of ' acetone vapor inhalation, but
the shifts were not statistically sign~flcant. :Therefore, it was concluded that
the flexor chronaxies were significa~tl.Y prolonged in all test animals and in
~o~e rats resulted ~n ~evers~ musC\e~'antago~ists ratios. The results, thus,
~nd1cated that chr~mc lllhalatlon of ~ ~9 mg/m of aceto~e .vapor e.lic~t~d changes
ln muscle antagonlst motor chronaxl~s WhlCh were statistically slgmflcant.
These changes in motor chronaxy weire the result of disturbed central mani-
festations indicative of functional ch4nges in the cerebral cortex, and clearly
indicated that the adopted 200 mg/m r allowable acetone vapor concentrations
in the air of working premises was tp
-------
The solvenf vapor formed in the air of the drying room was drawn off by
suction into the recovery department. The presence of acetone vapor in the
air of the p\antl~ vY0rking premises was due'to the leakage in the gas remov-
ing conduits and to its Ii be ration in the course of many acetone silk making
processes.. Despit'~ the fact that the acetone solution vapors formed in the
spinning room were removed by suction into the recovery room, they still
remained the primary source of atmosphe ric air pollution with acetone. It
was estimated that acetone loss into the atmospheric air during five months
in 1958 amounted to 606 tonS,or an average of 4.5 tons per day. Data obtained
during the investigation of the air in the vicinity of the acetone silk plant are
listed in Table 2. '
TABLE 2
SINGLE ACETONE VAPOR CONCNS. IN ATMOSPHERIC AIR ON THE LEE
SIDE OF THE PLANT.
- ,
I. -.
, M FROM DIS-
CHARGE
SOURCE
25
50
100
150
200
300
4:>0
SOO
600
750
1000
TOT AL
NUMBER OF SAMPLES 'I . MG/M OF
. . '.. ACETONE
_0- -. -- ...
ISAMPLES ABOVE 'I I .
TOTALMET~~~I?~NSI-. ~~X_I.~Al MINIMIIL
. I .
26
22
29
26
2R
2.5
26
27
8
I 2~ J
I I
"I 251 i
SAMPLES ABOVE'
0.35 MS/M3
-- - I
26
22
29
26
28
25
22
21
7
19
14,83
10.54
6,48
4,45
2,70
1,08
1,37
1.29
0,41
0,20
7,64
5,22
3,79
2,68
1.43
0,81
0.44
0,43
0,29
0,15
26
.22
29
26
28
2-5
21
20
3
.-
215
The investigation indicated that the atmospheric air in the vicinity of
the acetone cellulose silk plant was syste matically polluted by acetone vapor.
Analysis had shown that the acetone vapor concentration in the atmospheric
air exceeded the allowable concentration limit even at 600 m from the plant,
and that the 100 m wide sanitary clearance zone was inadequate. for the pro-
tection of the population's health; and that it should be widened to 750 m for
plants which discharged an average of 4.5 tons of acetone daily. The limits
'of allowable maximal single and ave rage 24 -hour concentrations of acetone'
in atmospheric air recommended in this report has been approved by the
State Sanitary Inspector of the USSR.
Conclusions
1. It was found that 1. 1 mg/m3 was the concentration of threshold 3
acetone vapor odor perception in most sensitive persons, and that 0.8 mg/m
was the odor nonperceptible concentration.
-70 -
-------
i l
3 I ,'.
2. 0.55 mg/m was the conc~n'tra.tion: of threshold acetone
effect on the functional state30f cereqral cortex, as determined by
metric method. 0.44 mg/m was th~ ~ubthreshold concentration.
3. The concentration of threspold. acetone reflex eff~ct on the forma-
tion of electrocortical conditioned ref1~xes was 0.44 mg/m , and the maximal
inactive concentration was 0..35 mg/m .
t '
j. Chronic inhalation of an a'1erage acetone vapor concentration of 199
mg/m , 8 hours daily for 45 days prpduced motor chronaxy changes in the ex-
perimental animals. ;
r
Continu'3us 45 day inhalati., CeMeHeHKo A..lI.. 113'
Y'leHue noporOB pe$'leKTopHOfO .ilciicTBHR aTMoc$epHblx JarpR3He-
Huii MeTOD.OM 3,leKTpo:mue$a~ofpa$HH. fHrHelia H caHHTapHR,
1960, I, 57-61. ' .
r 0 $ ~( eK ,1 e p B. A. MaTepHa.1b( K 06OCHOBaHHIO npe.J.e,lbHO ;xonYCTH-
MblX KOHueHTpauuli au'eraTOB; B aT:llOc$epHOM BOJ,wxe. rHfHeH:!
H caHHTapuR, 1960, 3, 9-15.'
.lI. a H.U weB C K II Ii C. JI. a pa3,;ip3lKalOlUeM ;1ciiCTBlIH BblCWHX KeTO-
HOB. C6. "HCc.1e.10B3HuSJ B o6nacTII npm!blWJleliliOH TOKCUKOJlO-
fHH:!>. TpY.J.bI JIcHHllrpa.ilCKOrc> HaY'IHO-HCCJlC;lOBaTe.1bCKOfO HHCTlI-
Tyra fHrUCllbJ TpY.ila H npo$J360.1eBalwH. T. XII, B. 5, JI., 1948,
cTp.207-219. j ,.
.lI. y 6 P 0 B C K a R <1>. H. rUrHellll'iecKaR. OUCHKa 3arpR3HeHHocTH aT:lIO-
c$epbl 60.1bworo ropo.ila cepKHcTbl~1 ra30~1. .D.ucc. M., 1955.
)I(.H .1 0 B a H. A. K Bonpocy 0 GOBMecTHOM ;xeHCTBIllI Ha OpraltH3M
napOB 6eH3o,la H aueTOHa. fHhlcHa II caHHTapHR, 1959, 12, 18-23.
K a r a H 3. M. 3KcnepHMeHTa,lbHoe H3}"IeHHe .ileHCTDHR aueTOH3 Ha
IKHBOTHblH opraHH3M. fHmelial TPV.ila, 1924, 9, 1 1~30.
:. 71-
-------
Bibli~graphy C ant 'd.
1(.'1 e HOB a E. B. K BOnpaey 0 npepbHJHeTOM (HHTepM1IITTIIPYlOweM)
.D.eiicTBIIII npOMblw.'IellllbiX H.l0n lIiI opraHII3~\. r,lIrHeHa H caHHTa-
pllH, 1949, 2, 27-31.
n a 3 ape B H. B. (pe.D..). BpetUlble BeweCTBa B npOMblWJleHHocTH.
T. I. JI., 1954, CTp. 406-409.
n a 3 :I P e B H. B. II 5.p)' C H JI 0 B C 1< a R A. H. 0 33SHCHMOCTH .'leHcT'
BIIR JleTY'IHX HapKOTHKOB OT 3!\cn03HUUH H KOHueHTp3uHH. . l'bMeHellllH HepBlIoil 0'11,1 dllJ npH HHTOKCii'
Kal.l,HH Mapr3Hue~l. KlleB. 1956. eTp. 105-1 :?2.
Mae e H K 0 B a O. r. B.1JIRlllle :lJpOR aueTOHa 11<1 41YIIKI.I,HOH3J1bHOe
COCTORfllte )f(I'W.1Ka p"r'("IIlX . ouynlloro npOH3BOD.eTB3. C6opH.I\K
HaY'IlIblX I'a(,": \\"",. ., 0 \lI'.1I111.HHCKoro HlicTHTYTa. T. 21. MHHCK,
1958, crl'. ~I~. I'~;
Me.'I ex H II a 13. 11. K Bonpocy 0 npe.1CJlbHO .'lOn)'CTlIMoi'l KOHI.I,eHTpa-
1.1,1111 41opMa.lb.1erH.!la B aTMoc41epHoM B03.'lyxe. rllrHeHa H caHHTa.
?IIR, 1958. 8, 10-14.
}\\ IllU e H II H 11. L!.. K 6110XIIMIIH a11.eTOHOBbiX OTp3B.'ICHHH. B KH.:
TpY.1b! POCToBcKoro-Ha.L!.oHY HaY'IHo'lIeCJleioBaTCJlbc.Koro IIHeTHTY'
Ta oxpaHbI TpY.1a. C60pHII.K pa60T no TOKCHKQJlOI'HIl. 4. II. PQc,
TOB-Ha..l1oHY, 1935, erp. 47-55.
OK Y H C B a H. <1>. 0 TOKeH'ICCKO~1 .'lei'lcTBHII al.l,eTOH3. Bpa'le6HaR ra-
3eTa, 1930, 8, 621---Q27.
n JI 0 T H H K 0 B a M. M. MaTepHa.'Ibi K rHrHeHII1leCKOH O11.eHKe 3KpO-
JlCIlHa KaK aTMoe41epHoro 3arpH3HHTeJlH. .l1Hec. M., .1957. ,
PR3aHoB B. A., 5YllJTyesa 1(. A.. HOIBHKOB 10. B. K MeTO'
,!J.IIKe 3KcnepHMeHTa.'IbHOrO 060cHoBaHHH npeD.eJlbHO .D.0nYCTHMblX
KOHI.I,eHTpaI.l,IIH aTMoc41epHblx 33rpH3HeHHH. B KH.: npe..1eJlbHO ,!J.O-
nYCl'HMble KOHlleHTpau.II'H aTMoc41epllbix 3arpH3HelfHH. B. 3. M.,
1957, erp. 117-137.
T a x H p 0 B M. T. MaTepHaJlbl. K 060cHoBaHHIO npe.D.eJlbHO .D.OnycTHMoii
KOHueHTpa11.HII xnopa B aTMoc41epHo.\! B03.llyxe. fnrHeHa II caIlII'.
TapHR, 1957. 1. 13-18. ,
Y 41 JI H H..1 10. M. TeqpHR II np3KTIIK3 XpOHaKc.IIMeTpIlH. n., 1941.
Ll H T 0 B II 'I 11. C. B.1I1RH'IIe aueTOHa Ha l.I,eH'rpaJlbHYIO HepBHYIO CH-
cTeMY II\IIBOTHblX. B KH.: TpY.'lbi POCToBcKoro-Ha-.l1oHY H3YliHO-
IICC.le.llOB3Te.'Ibe'KOro HBcTIITYTa ox'paHbI TpYD.a. C60pHHK pa60T no
TOKCHKOJlOrim. 4. 2. PocToB-lIa-.l1oHY, 1935, CTp. 35-47.
ill n a 11. e p M a H M. L!.. nCIIX03 B CBH311 e 01'paBJleHIICM aueTOHOM.
)KYPHaJl HeBpOnaTOJlOrll1l II nCIIXHaTp-H'H IIMeHH C. C. KopcaKoB3,
1957, 64-65.
.l1 y a H b
-------
New Data for the Hygienic Evaluation of Carbon Monoxide
in Atmospheric Air
T. M. Shul'ga
Department of Hygiene of the Smolensk Medical Institute and Department
of Community Hygiene Central Institute of Post Graduate Medicine
Carbon monoxide is the most widely distributed atmospheric air pollu-
tant. It is formed by burning carbon containing substances in an atmosphere
of insufficient oxygen; it is found in fuel gases and is a constant component of.
gases discharged by different industrial plants, by blast furnaces, byauto-
mobiles, etc. It is used as raw material in the synthesis of different chem-
ical substances. The toxicity of carbon monoxide to man and animals has been
known for some time. Despite the fact that the toxicodynamic prope rtie s of
carbon monoxide have been studied by numero~s' investigators, there exists no
uninimity of opinion regarding its mechanism c, ': toxicity. In 1871 Claude
Bernard concluded that the toxicity of carbon monoxide to man was due to its
combining with he moglobin and the formation of. carboxyhe moglobin which
blocked the capacity of hemoglobin to transport oxygen to organ tis'sues, giving
rise to acute anoxe mia or oxygen deficiency. This theory regarding'the carbon
monoxide toxicity mechanism still prevails among investigators. However,
the existance of chronic low grade hypoxia without causing fatalities throws.
some doubt on the adequacies of the 'carboxyhe-moglobin.theory of carbon mon-
. oxide poisoning.
Many authors adhere to the so-called tissue theory. According to this
theory, it is assumed that carbon monoxide reacted not only with hemoglobin
but with related complex respiration enzymes, which had a ferroporphyrin
base, such as cytochrome, oxidase, catalaze., etc. Carbon monoxide blocked
the oxidative capacity of the ferroporphyrin base of tissues inhibiting it and,
bringing about anoxia which adversely affected the central nervous system.
h This theo!y adequately accounts for and explains the results obtained by L. S..-
Gorsheleva. in 1944 who exposed expe rimental animals to the inhalation of
:1' _.
20-30 mg/m of CO 6 hours daily for 70-75 days; the experimental animals
did not die but developed disturbances of higher nervous system. Simi-
'lar conditions had arisen upon chronic'. inhalation of low CO concentrations.
Based on the results obtained by L. S. Gorsheleva, Z.' G. Vol'fson recom-
mended that 2 mg/m3 of carbon monofide be accepted a~ the limit of its
allowable concentration, and 6 mg/m as its, maximal single concentration.
The Committee for the protection of air accepted these limits which were
also approved by the Chief State Sanitary Inspector of the USSR. However,
experience indicated that the recommended and approved norms did not serve.
the expected sanitary hygienic purpose. Facts pointed to the need o~ revising
-73-
/'
-------
the allowabie limits adopted for carbon monoxide in atmospheric air. This
problem was as~igned to:,the present author. Preceding studies pointed to
the unfavor~ble affect of :carbon monoxide on central nervous activity. the re-
fore, ,the pr'esent investi'gation began with a study of the effect of 6 mg/m3 of
carbon mon~xide on the electrocortical reflex activity; the method was de-
sc ribed elsewhe~e. Two persons 19 and 30 years of age and an 8 -lead electro-
encephalogram of trademark IIA11var" rere selected for this study. Test per-
son V~ inhaled air containing 20 mg/m of carbon monoxide during five 15 -
minute inte:vals,and one ~O-minut~ interv~l.. This had n~ effect on the alph~-
rhythm. Test person O. lnhaled all" contalnlng 21 mg/m of carbon monoxide
during three IS-minute intervals and one 45-second interval without disturb-
ing the alpha-rhythm. Tests were then made to determine the possibility Qf
eliciting conditioned electrocortical reflex reactions by the inhalation of car,-
bon monoxide in the above indicated concentrations. This was done by the
procedure desc ribed by K. A. Bushtueva, E. F. Polezhaev and by A. D.
Semenenko. Results of the investigation indicated that no alpha-rhythm de-
synchronization appeared even on the 21st as sociation of carbon monoxide
(conditioned stimulator) with light (unconditioned stimulator), indicating that
no conditioned reflex was formed and that carbon monoxide in the indicated
concentration had no stimulating effect o,n the recep:£ors of the respiratory
organs. The results clearly indicated that 6 mg/m of carbon monoxide, which
represented the maximal single concentration and which was adopted by the
Committee on Sanitary Protection on Atmospheric Air, did not have to be re-
vised. , Tests were then made with white rats to determine the resorbtion
effect of low carbon monoxide concentration in the chronic experiment. Under
experimentation were 30 young male rats weighting 90 to 100 g. Rats were
divided into 3 groups of 10 rats each. Rats of gr~up 1 inhaled air containing
, 30 mg/m of carbon monoxide, or the
equivalent of the limit of allowable con-
centration for working premises 8
hours daily for 10 weeks. Rats of the
2nd grfup inhaled air containing 2 '
,mg/m of carbon monoxide uninter-
ruptedly for 10 weeks. Rats of group
3 served as controls. Twenty- .
four hour urine specimens were collect-
ed once weekly when rats inhaled only
clean air.
Constancy. of carbon monoxide con-
centraHon in the exposure chamber..:>-
was tested titrimetrically with the aid
of a gas analyzer. Curves in Fig. 1
snow the fluctuations in the carbon
monoxide concentrations in the air of
the exposure chambers. The air of
the control chamber which received
presumably clean street air occasion- '
4~ 'I
\"k '..A A "" M ""' A... /'-1"\.
V. V~p -o~ -W \.jY v "\
;--Yl'
~ ~ /20
I-
i ~ 1'0
j ~i.
I I:!
, '
i ~ :.:
",'
. a::
, ~ ,4,0
, I
; ~ :3,0
, i
- ,(\') '20
'~1'
, ~I ',0
; i
-- 0
jO_JD-.__.JO- ,J! .f0
I DAYS OF I NHALATI ON EXPOSURE
60
-------- --
fO 2tl SO 40 50
~ -DAYS OF INHALATION EXPOSURE
50
.---
---:---~-------- --~- . _.. -
------ - u - . - -
! FIG., I - CARBON MONOX I DE CONCENTRA T IONS I N EX- '
i POSURE CHAMBERS.
, J - CURVE OF CO CONCNS. FIRST EXPOSURE. CHAMBER
I 2 - CURVE OF CO CONCNS. SECOND EXPOSURE CHAMGER
, 3 - CURVE OF CO CONCNS. THIRD EXPOSURE CHAMGER
'----- _._--
-74-
-------
ally contained carbon monoxide up to 1.2 mg/m 3, which indicated that the
local atmospheric air was pe riodically polluted--by carbon mon0xide.
Carbon monoxide concentration average~ in the exposure chamber dur-
ing the inha~ation period were 29 :-1:0.37 mg/m in the firs,t chamber, 2.4-:1::
0.32 mg/m in the second chamber, and O. 1 :I: 0.004 mg/m'3 in the control
chamber. Air te mpe rature in the chambe rs fluctuated within the range of
17 -230. Tests we re als 0 made for the effect of CO inhalation on chronaxy,
on coproporphyrin metabolism, using its rate of elimination with the urine
as the index, and records were kept of the animal's general behavior and
weight. Previous investigators had established that motor chronaxy values
were affected by secondary cerebro-cortical nlanifestations, that changes in
motor chronaxy could be taken as fine and objective indexes of the functional
state of the central nervous system, and that constancy of flexor and extensor
muscle chronaxy ratio under normal
physiological conditions was an expres-
sion of the secondary cerebro-cortical
manife stations. Numerically such
ratios were 1:2 or 1:1. 5.
In 1956 A. S. Lykova examined
traffic directors who we re exposed to
the inhalation of low carbon monoxide
concentrations and noted prolonged and
disturbed physiological chronaxy ratios
of the flexors and extensors in such per-
sons. Many investigators who ?tudied
the effect of low concentrations of dif-
ferent chemical substances on the cen-
tral nervous system of white rats noted
change s in motor chronaxy. The pre-
sent author deter~ined the knee flexor
and extensor muscle chronaxies, using
the condense r chronaximeter GIF. All
rats were tested once weekly. .Nerve
trunks of corresponding muscles were
stimulated by the unipolar method.
Chronaxy and rheobase averages are
presented in Fig. 2. The chronaxy and
rheobase ratios of the flexors and ex-
tensors were within the normal range in
rats of the control group. Beginning
with the 7th day of carbon monoxide in-
: halation chronaxy ratios of muscle ant-
,agonists acquired reverse values in rats
of group 1; their curves came close to-
gether and even crossed on the 2~d and
. 4th weeks of the recuperation period.
CI
: ::I.. 0.015
. -
, >- 0,010
Ix
.<
~ iO.005
c'
=1
0'
;
0.0/5
0,010
0.005
A
I
a
B
0,011
"", ",__,2
-- .... ,~, I' ""....' ,
..- '.......--....-...'''' I '
0.010
0,005
/2J~S'78Im"U~U~M"
'--!.!!!L!- N W_E E K5.
J
b,
B
/2J4S6789m"~~u~~n
T IME .:!.:j-W~EK5 .
.0
12J4S1789mnQQUMMn
TIME IIJ HEEY.S
--
- - ---- -_._-- - -- -_._~-
- - -- - - .
FIG. 2 - EFFECT OF CARBON MONOXIDE ON AVERAGE
MOTOR CHRONAXY OF RATS.
. A - CONTROL GROUP; e - GROUP I; C - GROUP 2;
I - FLEXOR CHRONAXY; 2- EXTENSOR CHRONAXY
I A - START OF VAPOR INHAlATIOIJ; e - ~NC OF
, VAPOR IIJHAlATION
,
=~ ---- ---
-75 -
-------
The expe:timental data were statistically significant; the
probably the result ot" weakened secondary effects of the
tem. -,
No ~tatistically significant changes were detected in the rheobases.,
Muscle antrgonist chronaxies of animals of group 2 exposed to the inhalation
of 2 mg/~ of carbon monoxide tended to come together on the 8th and 9th
weeks. However, the shifts were too slight and were not statistically signifi-
cant. Th_e same was true of rheobase change s in the rats of this group.
Chronaxy ratio averages of muscle antagonists' for each group during the
first pe ri,od of inhalation exposure are pre sented in Table 1.
, -, -Data in that table show
TABLE I '
, . that the average ratio of
, AVERAGES OF FLEXOR MJD EXTEtlS0R CHRm!AXY RATIGS li1 RATS DURING I muscle antagonist chronaxies
co I NHAlATI ON
-- -------"---'-"-- '--- .--., . --__-.n.--- --- in the control group was 1.4.
. RAT-NO~--I 1- ~!ROL~, , GROUPS . Such a ratio reflected the
--- .-- FIRST I - SEcall!': physiologically normal second-
1 1,45 1,2 I 1,2 ary central nervous system
2 1,45 1,1 I 1,2 manife stations . None of the
. 3 1,3 1.5 :2,0.
4 1,3 0,9 1,1 control rats had a chronaxy
56 1',2 1,0 1,3 ratio less than 1.2 while 2
1.4 1,3 J ,5
7 1,5 1.0 ,I 1,3 rats of g~oup 1 which inhaled
~ L~ L~ J :~,) . 30 mg/m of carbon monoxide
10 1,3 1,4 1,2 had chronaxy ratios of 1.0 -
: MAXIMAL:' '-, 1,6 1,5 2,0
; MINIMAL 1,2 0,9 1,1 and 0.9. The average chron-
: AVERAGE '1,39:1:0,0374 1,18:1:0,0558 1,3;t0.129 axy ratio of rats of this group
----.-
was 1.2. Changes in muscle
antagonists' chronaxy ratios of rats of group 1, as compared with those of
rats of group 2, were statistically significant,since their values were 3 times
as great as the average error. This indicated that lowered muscle antagonists'
chronaxy ratio. in rats of group 1 was the result of lowered secondary cerebro-
cortical effect on peripheral muscle chronaxy.
" Th~ avera~e ,muscle ant~gonists I chronaxy rat~o of rats ~f group 2 which
lnhaled an contci.1mng 2 mg/m of the carbon monoXlde was shghtly lower than
in the control group, but the diffe r~nce was not statistically significant, since
its value was only 70% of the value of the ave rage 'error. Ave rage values of
muscle antagonists' chronaxy ratios were as follows: 1. 318 * 0.046 for the
control group, 1. 248 :I: O. 042 for the first group, and 1. 147 ::I: O. 093 for the
second group. Such values indicated that the muscle antagonists' chronaxy
ratios returned to normal in all groups. The fact that muscle antagonists r
chronaxy curves crossed in some cases also indicated that the central nervous
system 'suffe red some functional changes. This is shown by the data presented
in Table 2. (see page 77)
During the period of experimental carbon monoxide-air inhalation nine
rats of group 1 produced 24 intercrossing chronaxy curves and 9 rats of group
2 produced 14 intercrossing chronaxy curves while only 3 rats of the control
group produced 1 inte rc rossing chronaxy curve e~ch. This indicated that rats
of group 1, which inhaled air containing 30 mg/m of carbon monoxide, all
changes were most
central nervous sys-
-76-
-------
suffered changes in motor chronaxy as a
TABLE 2, result of cerebral cortical functional
disturbance, and that only slight shifts
in the functional cerebro-cortical activity
occurred amo~g rats of group 2 which in-
haled 2 mg/m of carbon monoxide 24-
hours daiJY' The results indicated that
30 mg/m of carbon monoxide, in effect
as the limit of allowable carb'on monoxide
concentration for working pre mises, was
too high; at the same tim~ the re suIts also
indicated. that 2 mg/m 3 of carbon monoxide
can be regarded as the indifferent 24-hour
average CO conce,ntration.
Results of previous investigators in-
dicated that coproporphyrin concentration
inc reased in the urine of pe rsons suffe ring
of certain types of poisoning. This was shown by Pecora, Fatty and others in
19,58. It was also shown by Yu. K. Smirnov in 1953 and others that pathologic
changes in porphyrin metabolism was frequently accompanied by grave dis-
turbances in the central nervous system; therefore, tests were conducted ,to
determine the effect of carbon monoxide inhalation onporphyrine metabolism
using its rate of elimination through the urine as the index. Expe riments we re
performed with rats in groups of 5. Each group was placed in a glass chamber
specially equipped for the collection of 24-hour urine. Drinking bottles were'
so arranged as to prevent the possibility of any water finding its way into the
urine collection bottles. Rats received the same daily diet as during the in-
halation exposure. About 20 -25 ml was collected in 24 hours. After the re-
moval of urine from the collecting bottles the latter were rinsed with a known
volume of distilled water, and the rinse water added to the collected urine.
The amount of water added was taken into account in making analysis and final
calculations. Ave rage 24-hour coproporphyrin elimination with the urine, was
as 'follows: 5.4 :1:0.3 mkg for the control group; 3.9 :I: 0.24' I-L for group 2,
and 3.65 :I: 0.2 11- for, rats o( group 1. Results indicated that inhala~ion by
rats of carbon monoxide in the investigated concentrations depressed porphy-
rin metabolis m, and more so in rats of group 1 than in rats of group 2. The
da.ta were statistically significant. Rate of coproporphyrin! . "elimination with
the urine rose in rats of groups 1 and 2 during the period of recuperation and
approximated that of the control group; the differences between averages of
'the two values ,became statistically insignificant, indicating that rate of copro-
porphyrin elimination with the urine during the recuperation period was close
to normal. It is evident then, that the study of porphyrin- metabolisT con-
firmed the .conclusions previously arrived at, namely, that 30 mg/m of carbon
monoxide w.as too high for working premises. Porphyrin metabolism was 3
also depressed by 24 hours inhalation of carbon monoxide in average 2 mg/m
concentrations. Experimental rats were weighed every 10 days; results dis-
closed no differences between the weights of the experimental and control' .
NUMBER OF MUSCLE ANTAGONISTS CHRONAXY CURVE
INTERSECTIONS DURING RATS' INHALA.TlON OF CO~:
I GRoUPS I
CONTROL I FIRST I SECO/iO
, RAT NO.
1 - 2 1
2 -, 3 1
3 - 1 1
4 - 4 2
5 1 7 2
6 - 2 -
7 - 2 2
[\ 1 1 2
9 - - 2
10 1 2 1
-I-~"'.I
I. 24 ,
3
14
-77-
-------
1-
animals. At the conclusion of the experiments all rats were active and free
from any visible disturbances.
Results of pathohistologic investiga-
tions conducted under conditions of
chronic and acute CO intoxication
conditions produced similar changes
in the central nervous system but of
; diffe rent intensities. In chronic CO
~ intoxication the pathologic changes
were fewer - more localized, the
nerve cell structure was less pro-
; foundly affected, and the histologic
picture showed the presence of differ-
ent types of degenerative nerve cell
changes in the cerebral cortex and in
other brain sections. Immediately
after the discontinuation of inhalation
exposure 3 rats of each group were
sacrificed and pathohistologic studies
made of the brain and the spinal cord.
Mic roscopic examination showed
localized disappearance and destruc-
tion of nerve cells in the region of
Betz pyramids in the cerebral cortex
I of rats of group 1; this was accom-
panied by frequent destruction of the
Betz pyramid nuclei and 1 ysi s of the
Nissl substance. There were also
signs of cellular constriction and in-
duration, as shown in Fig. 3. Similar
changes were also noted in other sec-
tions of the cerebral cortex, indicating
that the histopathologic changes we re
not of a local characte r.
Some cerebellar Purkije cells were
deformed, wrinkled, shaded and their
nuclei shrank and became hype rchrom-
ic; some cells we re completely lysed
and some became edematous. The
simultaneous occurence of cell shrink,;.
age and edema was probably the result
of ' prolonged chronic intoxication in the
course of which new cells constantly,
came into play. Similar changes
occurred in the cerated cerebellar nuclei, as shown in Fig. 4; this was accom-
panied by the appearance of swollen cells, frequently of constricted character
and ppssessing hyperchromic properties. Wrinkled and ghost cells were also
. ~ "'-"".---'."
- :..
-.r;..' ....., .~~-.;~. , '
~ . ~...;.~ ~ .?i-::'"
" .:" ' ,
~ . . '". .
..
\..
~
.
,
~;
..... .
"
,.
1.1..
, , ..:., ...
.., ", ~<~~'..,-~- H~__' ..;:....:.::~~~~.~~~
~:j...i:.-.~; 0;".",'
FIG. 3 - RAT NO.5 OF GROIIP I. DEFORMATION. LYSIS
OF BETZ PYRAMIDS. NISSL STAIN. MAGNIFICA-
T I ON ,-400
..
.
....
.~
, '
,..'" .;::..
. ~.,. ~
, ' -, .~;'(""- '.;I~
,~~~ ,':,!?~Zltt:':::y. -
j:;;~>:~~~~_:~..~
FIG. 4 - RAT NO.2 OF GROUP I. SERRATED CEREBELLAR
NUCLEUS. PRONOUNCED CELLULAR CHANGES.SOME
PYKNOTIC CELLS. NISSL STAIN. MAGNIFICATION
900
-'
-78-
-------
seen in the histologic sections.
Examination of the spinal cord showed the presence of deformed or
completely desintegrated nerve cells; the synaptic ends were also affected,
showing frequent granulation and losing their original rounded shape, un-
evenly distributed impregnation, i'ncrease in size due to swelling, and a
close clinging together of the cells; the number of synapses was reduced in
carbon monoxide intoxication as the result of granular disintegration and dis-
appearance; intact synapses were frequently deformed, and the re we re othe r
signs of structural changes, as shown in Fig. 5. Synapses lost their chemi.-
cal properties, failed to take the silver stain and developed :rericellular edema.
The histologic pictures indicated that inhalation of 30 mg/m of carbon mon-
oxide by rats of group 1 brought
about structural changes in the
ganglionic ne rve ce lls of the brain.
Degenerative changes were also
found in isolated ne rve cells of
rats belonging t~ group 2, which
inhaled 2 mg/m of carbon mon-
oxide, but these changes were less
clearly expressed and could be re-
garded as indications of compensa-
tory reactions and gradual reve rs-
al of the morphologic disturbances.
No morphologic change s we re dis-
closed in the brain tissue of rats
belonging to the control group.
The res~lts thus indicated that
2 mg/m carbon monoxide adopted
as the average 24-hour concentra-
tion limit for atmosphe ric air was
slightly highe r than it should be.
This was supported by results of
:porphyrin metaboli3 m te sts which
showed that 2 mg/m of carbon
monoxide depres sed p'Jrphyrin
metabolis m, brought about faintly visible chronaxy changes, and some change s
in the morphology of the central nervous system.
As stated above the enumerated changes were comparatively slight;
therefore, it can be assumed t~at concentrations lowe r than 2 mg/m 3 of CO,
such, for instance, as 1 mg/m could be safely re garded as indiffe rent or
inactive.
, .
\ '.'
~. ..
,.
- \.
..1 _. -~...
FIG. 5- RAT NO.2 OF GROUP I. SPINAL CORD. ANTERIOR
HORN. MOTOR CE lL. REDUCTI ON I N SYNAPSE TER-
MINI AND SYNAPSE DEFORMATION. MODIFIED CAJAl
STAIN. MAG~IFICAT'ON 1400
Conclusions
1. Inhalation of ai: containing 20 mg/m3 of carbon monoxide had no
detectable effect on the rt:1 ~ptors of the respiratory organs.
. \
: \
11 .
-79-
-------
2. Iz:thala~ion of air containing 29 mg/m3 of CO 8 hours daily for 10.
days (chronic) brought about in the experimental animals significant changes
in motor chronaxy, depres sed ]PO~phyrin metabolis m, and elicited gross
changes in brain tissue.
. 3. Inhalation of 2.4 mg/rri3 of CO uninterruptedly for 10 weeks (chronic)
brought about no visible changes in motor chronaxy, depressed the porphyrin'
metabolis m and produced reve rsible morphologic changes in individual nerve'
cells of the brain.
4. The limit of allowable average 24-hour farbon monoxide concentra-
tion in atmospheric air should not exceed 1 mg/m .
5. The present limit of allowable carbon monoxide concentration in tl're'
. . . '2 3 . . .
_.an of worklng premises, namely, 0.03 .mg/li, or 30.0 mg/m , is too high,and:
. s hould b~ lowe red. . . --_.~--,- -~- .. - -- .
BIBLIOGRAPHY
5 e p Hap K. .JIeKUH11 no 3KcnepH~leIlTa.~bHOH naT~Mornll 3a 1871 r.
5110~1E:'.1rn3, 1937, err>. 73, 95. .
5 Y UJ T )' e B a K'. A., fI o.~ e >K a e B E. <1>.; C e ~I e H e H K 0 A. lI.. 1.13-
YQCHlie noporOB pc~neKToplloro BCHCTBHH aTMoc~epllwx 3arpH3He-
111111 MeTO!1.0M 3.1eKTp03HLte~aJIOrpa~IIH. fHnreHa H caIIIITapHH,"
. 1960, 1,57. .
B 0.1 b ~ C 0 H 3. r. fIpe.1e.1bllo .'lOnYCTIlMble KOIIuellTpaUHII OKHCII yr-
.1epO.'la II aTMoc~epHo~1 B03.lyxe. B KH,: fIpe.J.e.1bllo ,!lOnycTHMbIe
KOllueIlTf'aUHII anloc~epllblx 3at:PH3HeIlHii. B. 1. M., 1952,
CTp. 68--79. .
fop UJ e.1 e B a JI. C. B.1HHHlle OCTporo H XpOH1!QecKoro OTpa'BJIeHHii
OKHCblO yr.~epoJ.a lIa BbIClli)'IO lIepBHYIO -'1eHTeJIbHOCTb iKHBOTHbIX.
ap~laK:J.10rIlH II TOKCHKo.10rIlH, 1944,5,47-51.
f 0 ~ ~I e K.1 e p B. A. MaTepna.lbl K 06OCliOBaHHIO npe-'1eJIbHO .'lony'
CTIIMblX KOIIUCHTpaUHi: aueTaTOB B aTMoc~epHO~1 B03!tyxe. M.,'
1960,4. .
r y C e B M. B., 'C M II pH 0 B 10. K. Onpe.'le.1eIlHe cneKTpO~OTOMeTpH' '
'lecK:r~1 MeTO.lO~1 Konponopqmplilla, Bbl.'le.1SJe~lOro C MOQOH. B KH.:
fIpe.le.1bHo .'lUnYCTlI~lble KOIIueliTj)aUHII aTMoc~epllblx 3arpH311eHllii.
B. 4. Me.'lr!u, 19~O, erp. 139.
lI. y a II b b! H - >K Y ii. MaTeplla.lbl K 06ocHoBaHHIO npe.'le.lbHO ,!lony-
CTlI~IOii KOIIUCIITpaUHH CepOBO.lOpOJ.a B anlOc~epllo~1 B03.J.yxe.
fHrHet:a H caliliTapllH, 1959, 10. 12-17.
lI. 0.10 UJ II U K H Ii Jl. M. B KII.: XpoHHlIecKHe oKclI)'rJlepO!lllbie HHTOK-
CIiKauml. JlbBOB, 1957. CTp. 143.
K e BOp K b II H A. A. fIpocpeccHolla.%Hble HeiipoTOKCHK03bI. MIIlICK,
19;.5, 5. .
JI a 3 ape'B H. B. Bpe.'lHble BelllecTBa B npoMblill.1eHHocTH. 4. 2. Jl..
19.>4, erp. 207.
.rI hi K 0 B a A. C. B KH.: BonpocbI 0511leii H KOM~IYHaJlbHoii rnrljeHbI.
lo\.-Jl.; 1956, CTp. 45. .
JI 10 6 Y ill I<' 1111 A. A. a .J.o1IlTe.lbIlO.\I !leiiCTBHII MaJlblX .1103 OKHca yrJle.
po.:la. fHrHeHa TpY.J.a, 1931, 1,32. .
--_.- . -
-80-
-------
Bibliography cont'd.
Mar H H U K H ii A. H. (pCLl). Cy60PAHHauHSI B ncpBHoA CHcreMe H ee
3Ha'leHHC B apM3Ko.1onISi II TOKCIIKOJlOrHR, 194::s, 6, 5, 14.
n ,p e Ll T C 'I e II C K II Ii B. E. PYKOBOLlCTBO no Jla60paropHblM MCTOLlaM
.IICCJJeLlOBaHHR. M., 1950, np. 337.
T a X 'II po 'B M. T. MaTCpllaJlbl K 06ocHoBaHHIO npe;teJJbHo ;tonycrll~loii
KOIIUCH'i'p3UHH x.10pan anlOc e JI b Ll M a H 10. r. MaTcpu3.1b1 K 06OCIIOBaHHIO npeAe.1bHO LlonYCTII-
Moil KOHueHrpaUHH aUeTOHa B aTMocupHHOB. B K!i.:
Y'IeHlle 11. n. naBJlOBa B TeopeTH'IOCKoli If np3Kl'H'IecKoil MeAHUIf'
He. M.. 1951, Cl'p. 259.
l{ )K a 0 l{ )K 3 H - U If. MaTeplfaJl K rlfrlleHH'IecKOMY IfOp~I'lIpOB311111O
npe;te.1bHO LlonYCTHMOH KOHUCHrpaUIfH MeTaHOJla B aTMoclIlI. M., 1956,
- CTp. 28.
-81-
-------
Hygienic Evaluation of Dinyl as an Atmospheric 'Air Pollutant
G. 1. Sqlomin
Department of Community Hygiene of the Central Institute for
Post Graduate Medicine
Dinyl possesses many properties which make it one of the best heat
transfer media available. It has found wide application in the chemical in-
dustry in the production of intermediate organic products, synthetic fibers,
synthetic rubber, plastic materials, and .in the varnish and dye industry.
Because of its che mical and physical versatility, dinyl may be used in the
future in many branches of the industry such as crude oil, wood fiber, metal-
lic processing and even in the confectionary and baking industries. Diny). is
a eutectic mixture of two aromatic hydrocarbons diphenyl and diphenyloxide
in 26.5:75.3 ratio. It is a colorless fluid having a sharp characteristic odor.
Technical dinyl is of. a light brown color; its b. p. is 2580 and it solidfies at
12.30. The' mixture of the two hydrocarbons, known as dinyl, evaporates
azeotropically retaining the constancy of component ratio, and also its initial
properties. Dinyl is highly heat resistant and possesses a sp. gr. close to
unity and is practically not water miscible. . Dinyl vapor is discharged into
the atmospheric air by plants producing chemical wood fibers, and by plants
of metal processing industries. The wide use of dinyl in the national economy
and its discharge into the atmospheric air by the above mentioned industrial
plants requi.re that a sanitary hygienic evaluation be made of dinyl as an at-
mo:,pheric air pollutant for the purpose in establishing limits of its allowable
concentration in atmospheric air and in the air of industrial working premises.
Information found in the USSR and foreign literature regarding the tox-
icity of dinyl vapor was scanty and inadequate. Parmeggiani and Sas si showed
in 1955 that dinyl concentratio~ in the area of plants producing nylon ranged
between 0.679 and 12.6 mg/m ; they also found that workers exposed to the
vapor inhalation complained of irritation of the conjunctiva and of the pharynx,
of respiratory system irritation, of lowered appetite, headache, loss of sense
of odor and impairment of hearing. Medical examination of such worke rs dis-
closed c'onsiderable hypere~ia of the conjunctiva and the nasal pharynx. En-
largement of the liver was found in one case. The skin and blood picture show-
ed no changes. The above authors found no indications of dinyl accumulation.
Deichmann and Kitzmiller made a similar investigation and came to the con-
clusion that dinyl vapor was only midly toxic. S. Z. Kogan and A. V. Chechet-
kina regarded the toxicity of dinyl as only slight. In 1957 A. P. Martynova
investigated the acute and chronic effects of dinyl on white mice and rats
which were exposed to the inhalation of 1000 mg/m,j of dinyl vapor for 2 hours.
-82-
-------
All animals survived. Microscopic examination of the mice organs showed
acute organic disturbance which was reflected in the morphologic changes of
the liver, . kidneys, lungs and heart. The chronic effect of dinyl was i:rvesti-
gated experi mentally using white rats which inhaled 10 and 100 mg/m of
dinyl 4 hours daily for 6 months. Examination of the animals at the end of
the vapor inhalation showed disturbed trophis Ln, lowe red vascular tonicity
and blood pressure, increased number of lymphocytes, lowered cholines-
terase activity, and changes in the functional condition of the central nervous
system in rats of both groups. A. M. Vodovskaya examined workers employ-
ed in a capron plant in 1960, and found notable change s in the physiological
reactivity of the organism. At the end of the work day the time of optical
motor reaction was delayed 10-60 5 " respiration rate increased by 5-6 per
minute; pulse changes were slight, body temperature showed a slight tend-
ency to fall,and oxygen blood saturation dropped by 2-3%.
The presently a10ptedlimit of allowable dinyl concentration in working
premises is 10 mg/m. The brief ~iterature review indicated that dinyl toxic
properties have not been adequately investigated. No data were found on the
dinyl pollution distribution in atmosphe ric air surrounding plants producing
or using dinyl. As a first step of this investigation the present author in co-
operation with M. V. Alekseeva modified the Martynova method for the quan-
titative determination of dinyl vapor. in air. By this modification aromatic
compounds are first nitrated by a m:ixture of nitric and sulfuric acids to nitro
compounds which are then dete rmined in an ethe r, acetone and alkali solution.
This resulted in a product which colored the solution a raspberry-red color;
intensity of the solution was then dete rmined colorime trically. The method
is not specific, since other aromatic hydrocarbons inte rfe rred with the re-
action. However, dinyl becomes nitrated in 60 minutes or less, whereas, .
benzene requires 24 hours for its nitration. Therefore, dinyl can be nitrated
and determined in the presence of benzene. The sensitivity of the method is
0.5/.L or O. boos mg in 2 ml. Tests were first made for the determination
of the dinyl concentration of threshold odor perception, and of the concentra-
tion of threshold dinyl reflex effect on eye sensitivity to light arid on electro-
cortical activity. The procedures used in this test were the same as d~s-
cribed elsewhere. Tests were conducted with 15 persons, 18 to 60 years old.
All were first examined medically and found normal in relation to the purposes
TABLE I of the present tests. Odor sensitivity tests
were. made once or twice daily at 4 hour inter-
vals. The number of tests amounted to 545.
Results indicated that the minimum dinyl odor
pe rceptible concentrations ra~ed within the
limits of 0.29 and 0.06 mg/m with the lower
limit being characteristic of persons of high
odor snesitivity. Re~ults are presented in
Table 1. 0.04 mg/m was the odor nonper-
ceptible dinyl concentration.
CONCENTRATION OF THRESHOLD OINYL ODOR
PERCEPT ION IN MG/M3
NU-;;BE-;:
OBSERVEI/.
LOWEST ODOR
PERCEPTI BLE .
CONCHS.
MAX 111.I.L 00 OR
NOIJPERCEPT-
'BLE conCHS.
---,-- --
3
1
4
4
1
2
{~
0,20
0,15
0,11
0,08
0,06
0,04
0,29
0,20
0,15
0,11
0,08
0,06
-83--
-------
".
Test~~ werr then made for the determination of the effect of low dinyl
concentrati:ons on reflex effect of eye sensitivity to light, using the method
of dark adaptation and adaptometer ADM. Eye sensitivity to light was deter-
mined eve'ry 5 minutes for the first 30 minutes and then once on the 40th
minute. Clean air and air mixed with dinyl vapor were supplied to the nostrils
through a special apparatus for 5 min. on the 15th minute of dark adaptation.
The followi~g dinyl vapor air concentrations were tested: 0.07, 0.04, and
0.03 mg/m. Triplicate tests were made for each concen3ration. Results
presented in Table 2 indicate that inhalation of 0.07 mg/m of dinyl vapor
TABLE 2
EYE SENSITIVITY TO LIGHT DURING OINYL VAPOR INHALATION IN PER
" CENT OF SENSI T I VI TY MANI FESHD ON THE 15TH MI NUTE
"I
" I
." . .CLEAN AIR . MG/~ OF D INYL
glULS -"
HI NUTES ! I 0,04 I 0;03
RVED Av. OF 7
- TESTS 0,07
--- + ". ~.~ERAGE.~F- 3 .TESTS. ".
o 0,3 0,3 0,4 0,3
5 7 8 8 7
,--; 10 57 61 70 77
' A.P.'
'----1 15 100 100 100 100
20 140 102 116 146
25 174 112 156 179
30 204 158 192 217
40 266 206 224 261
0 0,4. 0,3 0,3 0,3
5 9 7 7 8
,..----- 10 60 60 60 68
. L.SH. I '15 100 100 100 100
~. 20 135 151 146 129
25 171 182 150 170
30 199 190 171 198
40 243 212 194 234
0 0,2 0,2 0,3 0,3
--- 5 5 5 6 6
' 10 60 73 69 63
N.'. I .,
]5 100 100 100 100
-. 20 ] 16 98 115 119
25 140 129 151 147
30 ]75 150 178 177
40 220 174 209 214
TN
08
shifted the dark adptation curves in all test persons, and that of ~. 04 mg/m3
acted similarly only in 2 person's. Eye sensitivity to light dropped in .persons"
A. P. and N. 1. as a re3ult of dinyl vapor inhalation and rose in L. Sh. In-
halation of 0.03 mg/m had no effect on eye sensitivity to light, as shown by
data listed in Table 2.
A study was also made of the effect of dinyl vapor inhalation on electro-
cortical conditioned reflexes. The method used possessed high sensitivity
and recorded effects on eye sensitivity to light by vapor concentrations below
those of odor perception. Such effects were detected and recorded by the
electroencephalogram. In the pr~sent investigation the 8 -lead "Al'var~' "
encephalograph was used. The procedure was as desc ribed elsewhe re. Light
was used as the unconditioned stimulator which elicited desynchronization of
the alpha-rhythm recorded on the encephalogram. The conditioned reflex
stimulator was dinyl vapor inhaled in diffe rent concentrations. Inhalation of
low dinyl concentration alone, conditioning stimulator not associated with any
-84-
-------
other unconditioned stimulating factor produced no alpha-rhythm desynchron-
ization, but in association with light .as an unconditioned stimulator the in-
halation of dinyl vapor in known concentrations elicited alpha-rhythm de syn-
chronization which was recorded on the electroencephalogram. In the latter
case conditioned reflexes were developed, as indicated by the alpha-rhythm
desynchronization, following inhalation of low dinyl vapor concentration in
association with unconditioned light stimulation. Dinyl vapor was supplied
for 15 seconds; during the last 5 seconds it was reinforced with light. By
gradually lowering the dinyl vapor concentration it was possible to arrive at
a concentration below the one which even in association with light stimulation
was the last to elicit conditioned reflexes, i. e. no conditioned reflexes could
be elicited upon the inhalation of such dinyl vapor concentration even iri a
association with unconditioned light stimulators, and no alpha-rhythm desyn-'
chronization was recorded on the electroencephalogram. Tests were con-
ducted with two persons. whose natural alpha-rhythm was c1earcut, Test
persons were seated in specially equipped chambers in a semi-reclined posi-
tion. Dinyl vapor was supplied into the inhalation cylinders at the desired
time, while clean air was continuously supplied into the control inhalation
cylinder.
Test results indicate1 that
0.04 and 0.03 mg/m dinyl
vapor concentration elicited
electrocortical conditioned
reflexes in both persons as
shown by the encephalogram
presented in Fig. 1. En- .
cephalogram of test pe rson
L. Sh. shows that electro-
corti'cal conditioned reflex
was developed in this person
FIG. J - EFFECT OF DINYL INHALATION ON ELECTRICAL BRAIN
ACTIVITY OF L. SHe by the3inhalation of 0.04
I AriD 2 - OCC'I'/TAl BRAIN ElECTROCURRENTS; 3 A/HI 4 - mg/m of dinyl vapor on the
'TEMPORAl BRAIN ElECTROCURRENTS; 5 - 2 UPSTROKES IIIDI- 18th association "3ith light,
CATE TIME OF SWITCHED-'N LIGHT; (; - ELEVATED LIIIE 'NDI- while 0.01 mg/m had no -
. CATES TI_H~_~~ DINYl IIIHAlATION.
""--'~---- ~~ effect on the elec trocortical
activity of the brain, as shown in Table 3. By these tests 3 threshold concen-
trations we re obtained as follows: concentration of threshold dinyl vapor pe r-
ception, concentration of threshold dinyl reflex activity in eye sensitivity to
------------._--- ". - . - . - TABLE 3. light, and concentration of
threshold effect on electro-
cerebral cortical activity.
Examination of the three
corresponding values showed
that the electrocortial con-
ditioned reflexes method was
the most sensitive, as shown
by data in Table 4. (see page 86)
6
ELECTROCORTICAL CONDITIONED REFLEX APPEARANCE DURING
INHALATION OF DINYL VAPOR
. - - --- --- - -
DINYl CONCN.I~ MG/M3
I
I
'\ NITI-ALS I
OF .
OBSERVED
L. \. . I
L. SII. \
0,04
0.03
0,01
+
+
+
+
-----.
--
-85-
-------
T AS LE 4
_H.__U J:_H~E.SHOLDGONGENTRAT_IONS OF DINYL
Based on the results obtained
-_____.d__' _d in this investigation it ~s sug-
gested that 0.01 mg/m of
dinyl be regarded as the maxi-
p,06 mal allowable single concen-
0,04 tration of dinyl vapor in atmo-
0,03 h. .
0,01 sp enc aIr.
I DIN/Yl3IN
NG 11
INDEXES
ODOR PERCEPTION
EYE SENSITIVITY TO LIGHT
ELECTROCORTICAL BRAIN REACTION
No REACTION
. ------- .--------
-- - --,.
. EXPOSURE
I 2 J 4 ! 0 - '-- 8 .;' III If 1/ IJ 14 (S
--. '--'-'u. - . '--- TIME IN WEEKS!' .
FIG. 2 - EFFECT OF DiNYL INHALATION ON MOTOR GHRONAXY-----:
OF RATS OF GROUP I. AVERAGES OF FIVE RATS.
----'-_: .EXTENSOR CHRONAXY; 2 - FLEXOR CHRONAXY.
~ -. -- -. - -- .---....- -.--'-'----- - -~
It was then necessary to establish a norm for average 24-hour dinyl
vapor concentration in atmospheric air. This was accomplished by the foHow-
ing experiments: sixty white rats, weighing 60-80 g, were divided into gro.u,ps
of 15 rats each and exposed to the inhalation of dinyl vapor continuofsly for
70 days as follows: rats of group 1 inhalJd air containing 10 mg/m ; rats of
group 2 inhaled3air containing 0.5 mg/m ; rats of group 3 inhaled air contain-
ing 0.01 mg/m of dinyl vapor, while rats of Group 4 ~e rved as controls.
These dinyl vapor <30ncentrations were not chosen fortuitously. The concen:-
tration of 10 mg/m is the equivalent of the allowabl~ concentration limit
for industrial working premises, and the 0.01 mg/m dinyl vapor concentra-
tion is the equivalent of the proposed limit for t~e allowable single dinyl vapor
concentration in atmospheric air; the 0.3 mg/m concentration was the inter-
mediate between the two above mentioned concentrations. Animals were placed
into inhalation chambers of 100 li capacity. Air and dinyl \Tapor mixtures in
different concentrations were run into the chamber at the rate of 25 to 30 li/
min. Constancy of the diny1 vapor concentration in the air was checked twice
daily before the mixture was run into the chambers. Fluctuations in the con-
centrations wJre slight. In the first chamber the fluctuation ranged3between 8
and 12 mg/m , in the second chamber between O. ~3 and 0.09 mg/m , and in
the third chamber between 0.022 and 0.008 mg/m. No dinyl vapor was de.,.
tected in the air of the control chamber. The air temperature in the chambers
was also recorded. The clean air supplied into the chambers was previously
purified by passing it through filter FP. Records were kept of the animals I
general behavior, of their changes in weight, motor chronaxy of muscle anta- ----
gonists, changes in porphyrin.
metabolis m, in cholineste rase.
. activity, and in the morphologic
comDosition of the blood. Dinyl
. .
vapor inhalation produced no
noteworthy changes iri the gene ral
condition, behavior, and weight of
the expe rimental animals. At the
end of the inhalation pe riod all
rats appeared healthy, well-
nourished and gained in body.
weight. Motor chronaxy of the
flexor and extensor hind leg tibia
was tested. Results showed that
o,o/! .
.... '0.015
::1.: .
~ :0.0/2
/
>-;
~ : 0.00,9
z
~ 0.005
:C'
o . 1.00J
f
,---',
,'.... " ,
" ..---,
"
"""--l Z..'"
.. "
~,-,'
-86-
-------
'inhala~ion of air containing lO
mg/m of dinyl brought about
motor chronaxy changes which
appeared in rats of group 1 on
the 3rd week of dinyl vapor in-
halation as change s in the flexor
and extensor muscle chronaxy
ratios. This is shown in Fig. 2
(see page 86). Cases were noted
in which the motor chronaxy ratio
was reversed, which indicated
, that changes have occurred in the
central nervous system as the
I - EXTENSOR CHRONAXY; 2 - FLEXOR CHROUAXY; :,
'---'- result of reduced or lowered
sublater,al or secondary act-
i vi ty .
Chronaxy ratio returned to
normal after two weeks of re-
cuperation. Similar motor chron-
axy changes were noted in rats of
group 2, but they were of lower
magnitudes and appeared after 4
weeks. Return to normal chron-
axy was noted at the end of the
first recuperation week, as shown
in Fig. 3. Chronaxy ratios re-
mained normal in rats of groups
3 and 4 throughout the experimen-
tal period, as shown in Figures
4 and 5. The rheobase values of
muscle antagonists remained un-
changed in rats of all groups
throughout the expe riment. Re-
sults of the present inves tigation
agreed with results recorded in
I 2.J ~ 5 4 l 8 J 10 II : 12 13 (II 15, the lite rature, indicating that
, :rJ ME.,~N\o1EEKS
changes in muscle antagonists
motor chronaxy constituted high
sensiti vity indexes of the effect
of exte rnal factors on the central
nervous system.
Reports appeared in the liter<}ture indicating that mercury, lead, bismuth,
selenium, nitrotoluol, oxides of nitrogen, carbon tetrachloride intoxications
which affect the nervous system, aiso disturbed porphyrin metabolism.
Accordingly,' tests were made for th~ determination of ~ffect of dinyl vapor
inhalation onp~'rphyr{~ . metabolisI!l' M. 1. Gusev was the first to apply
studies of :porphyrin -ml~tabolism to the problem of hygienic standardization
-87-
0.0/8
0.01 j
1>...'
:::"'0.012
> .
~ o,O{}g
z
o
, ~O,o05
o. '
.OIlOJ
I
"
,
...-
""
/'
"
"
----, ""~
'...'"
2
E XPOSU"RE
I
2 J
5 6 7 8 9 m H n ~ ~ "
TIME III WEEKS
"
FIG. 3 - EFFECT OF D' NYl I NHA LA TI ON ON MOTOR ;CHRONAXY
OF RATS OF GROUP 2. AVERAGES OF FI~VE RATS.
.. .- - - -
o.{)'!
-,- -. .- ._0____" --..-.---------------
/ 2 J ~ .5 5 1 ,f .9 10 II /2' IJ /~ /5
, TIME IN WEEKS'
FIG. 4- EFFECT OF O"NYL INHALATION IN MOTOR CHRONAXY"
OF RATS OF GROUP 3. AVERAGES OF FlyE RATS.
I - EXTENSOR': CHRONAXY; 2 - FLEXOR CHRONAXY' ~:
~:: - II'
:::..'
; >0.012
..
~ MOg
a:
c3 o.CJ!
t&. 0.015
:::..!
4012
>'
~ o,fJfJ;
z
o
~fJ.OO!
0'
- o,OfJJ
O.DUJ
, .
~I
"
2 ,---,~
-----------"" . ',,,,'" ,""
........A....~.
EXI'OSURE
---,'
..... 2 ,... tt'
~---.........~,,,,--------, ";'"
E'XI'OSU"RE
'iIG~'5::'--EFFECT OF OINYl'INHALATION ON MOTOR CHRONAXY----'
OF CONTROL RATS. AVERAGES OF FIVE;RATS.
1- EXTENSORY CHRONAXY; 2- FLEXOR CHRONAXY;
--~ ---- --- -- ------
j
"
,
~
~
"
j
!
1
,~
-------
of allowable lead concentrations in the air. The effect of chronic inhalation
of low' dinyl vapor concentrations on porphyrIn metabolism of white rats was
studied next. Determinations were first made- of coproporphyrin concentra-
tions in the urine of normal rats. The amount of this substance eiiminated
with the urine under normal conditions ranged between 1 and 21-£. Rats in
groups of 5 were housed in special chambers, and 2~-hour urine specimens
were collected once every 10 days from which coproporphyrin. was extracted
by the Fisher method. Quantitativec?y_rop~:ph'yri!l determinations were made
spectrophotometrically using electrospectrophotomete r labeled SF -1. Quali-
tative determinations were made by the method of spectral absorbtion by a
Icoproporphyrin solution in 10% hydrochloric acid at 400 -410 ml-£. From
readings thus obtained the quantity of coproporphyrin was computed on the\'
basis of optical density at maximum 410 m~al:)5"""--;rb£i-on. Results .of the in-
vestigation indicated that 10 and 0.2 mg/m of dinyl vapor had a notable effect
on porphyrin. metabolis m of the experimental rats, as shown in Fig. 6.
Rate of copro.por.I~hyri_n elimina-
. tion witli the urine sharply dropp-
ed in rats of groups 1 and 2 afte r
. 20 days of vapor inhalation, and'
on the 40th day it was 0.5 IJ. or
16. 7% of the amount eliminated
by rats of the control group
(3.2 I-£). The low levels of copro-
:porphyr-in elimination pe rsisted
in rats of both groups to the end
/ . 2. . 3 4. 5 Q 7 8 .; /U II 12 of the inhalation exposure. It 3
--- - . - - .. _.-_~_..l-'M~!EN-:'..o~~_!.'!..TE_RVi~~__- was als 0 shown that O. 01 mg/ m
FIG. 6 - EFFECT OF DINYL INHALATION ON COPROrORPHYRINE of dinyl vapor in the air was
ELiMI NATION WITH THE URI NE I N RATS OF THE DIF- ' physiologically inactive.
FERENT GROUPS. Further studies indicated
COPROI'ORPHYRINE ELIMINATION IN RATS OF I - GROUP I; 2 - h' h l' f d' 1 '
. GROUP 2; 3 -GRouP 3: 4 - CONTROL GROUP. t at In a atlon 0 3-1ny vapor In
----. - --. ---- --... --- ---- 100 and 10 mg/m concentra-
. tions depressed blood cholin-
esterase activity. Previous investigations demonstrated that blood cholin-
esterase activity differed in different individuals, but that it stayed within'
well defined ranges in each individual. It was also found that cholinesterase
activity was. affected by different diseases and by different chemical sub-
stances. Many of the substances,. such as ether, chloroform, morphine,
carbon tet:-achloride, etc. completely inactiviated the enzyme in high concen-
trations. Most potent among the inactivators were phospho-organic compounds
of the insecticide group, such as thiophos, me rcaptophos, carbophos, phos-
phacol, and others, also war poisons and aromatic compounds of phosphoric
acid. Inactivation of cholinesterase may be complete or partial, reversible
or nonreversible. A rise in the intensity of cholinesterase activity was noted
in some pathologic processes which were accompanied by effects on the sym-
pathetic nervous system. It was previously demonstrated by D. E. Al'pern
(1958) and by othe rs that the brain cortex played an important role in the
i6
. '
..l
:LIS
. 21
; -I
. ",It,.
. z::
.' ;.
~lJ
. ....!
0:1
*12
c::.
8):
-88-.
-------
re gulation of cholines terase activity.
Many methods have been proposed for the determination of cholinesterase
activity which can be divided into three groups; biological, chemical, and histo-
chemiCal. The biological methods are based directly or indirectly on the chemo- r
physiological activity of the basic component of the enzyme, name ly, acetyl
choline. Because of their complexity, such Hlethods are now rarely used. The
histochemical methods offe r the advantage of defining enzyme localization in
organ tissue cell structures. The chemical methods are based on the principle
of quantitat~ve determil}-ation of free acetic acid liberated in the process of acetyl-
choline hydrolysis. The acetic acid liberated by hydrolysis is then determined
by alkaline titrimetry. It can also be determined gasometrically on the basis
of C02 volume liberated.in the course of hydrolysis. The .chemical method is
the most rapidly and most easily accomplished. The chemical method used in
the present investigation for the determination of cholinesterase activity in
whole blood was developed by A. A. Pokroyskii in 1953 and modified by A. P.
Martynova. It is a colorimetric method based on the time required for the
indicator color to change as the result of change in the pH produced by the acetyl
hydrolytic system.
Cholinesterase activity was studied in five rats of each group. Blood was
taken from the tail vein. Results showed that at the end of the first month of
vapor inhalation cholineste rase activity in rats of group 1 amounted to 124% of
the normal. Beginning with the second month intensity of cholinesterase activ-
i ty gradually abated, and at the end of the inhalation pe riod dropped to 76% of
the control, as shown in Fig. 7. Curves in that figure show that in rats of 3
group 2, which inhaled 0.2 mg/m
of dinyl vapor, cholinesterase activ-
ity gradually and evenly rose, reach-
ing 134% at the end of the vapor in-
halation pe riod. Intensity of blood
cholinesterase activity in all rats
returned to normal levels after vapor
inhalation was discontinued'3 Dinyl
concentration of 0.01 mg/m had no
effect on cholinesterase activity.
Thus, the results indicated that high
dinyl vapor concentrations lowe red
, blood cholinesterase activity and low
concentrations enhanced it.
~'
= IJO
-I
1
I
,
,," \
2 /' \
~----'" "
, \
, \
, \
I \
\
\
\
, ::: fZO
'>
;: "0
u
..
u: fOO
. ..
::; gO
tij.
...
:: 80
..
o
~ 70
EXPOS'URE"
20/V tjYl 15/111 30/Yl, 15/YlI 30/YIl flJ/Yllf 25/M
DATES OF ENZYME ANALYSIS
FIG: '7 ~ EFFECT OF 01 rNL VAPOR I NHALATI ON ON BLOOD
CHOLINESTERASE ACTIVITY IN RATS OF DIFFER-
ERE~JT GROUPS.
'--
.. . . - . . . - ,
Morphologic blood studies showed notable leucocytosis in rats of groups
1 and 2. Counts showed 38000 leucocytes pe r mm3 of blood in rats belonging
to group 1, 22000 per mm 3 of blood in rats of group 2, and 9000 -11000 in the
blood of rats belonging to groups 3 and 4, as illustrated in Fig. 8. (see page
.90). The letJ,cocytosis was accomP<3nied by an inc rease in the numbe r of lymph-
ocytes v:fich rose to 28?00 per mm in rats belonging to gro~p 1 an~ to 17~00
per mm in rats belonglng to group 2 at the end of the vapor lnhalatlOn pe nod.
-89-
-------
This is shown in Fig. 9. Hemo-
globin concentration and erythro-
cyte numbers remained within
normal ranges. All data were
statistically significant. Based
on the results obtained, it is
suggested thatO. 01 mg/m3 be
accepted as the limit of allowable
average 24-hour dinyl vapor con-
centration in atmospheric air,
which is the limit of allowable
maxi mal single concentration.
Results previously presented in~
dicated that the inhalation of such
a dinyl vapor concentration had no
effect on the functional characte r-
istic s of man or laboratory animals.
I The sanitary hygienic environ-
I mental conqitions of a capronic
2 ---_.' plant were investigated next. Dinyl
.-,-,- -------'(' . was manufactured in this plant, and
" '
/" ", was also used as a heat transmitt-
J .-.-. ing medium. Dinyl vapor, as an
. =~_C '~':;~'=~='E:;~~-~~'~~~'l":u :: ::stt~e :~~ ;:i::t l:;~~;n; ~':::d
zOjv tjVl 15/VI JO/J7l 1.5/Yl1 JO/Yll to/JfilJ 251Yll1 dinyl synthesizing departments and
DATES OF LEUCOCYTE COUNTS from the dinyl boiler room. Dis-
FIG. 9 - EFFECT OF DINYL VAPOR INHALATION ON NUMBER charge of the dinyl vapor was well
OF BLOOD LYMPHOCYTES. organized and reached the atmo-
IN RATS OF: I GROUP I; 2- GROUP 2: 3- GROUP 3; 4- spheric air through a stack 10-15 m
.'-- . COr/TROL GROUP", . h- - -. -- high. However, the discharge was
not unified and each department had its own ventilation and discharge systems.
The plants' vapor discharge also contained caprolactam. Single concentration
air samples were collected in the vicinity of the plant in 1959 at 100, 200, 400,
600, and 800 m from the discharge sources on the lee side of the plant. Anaf
lytical results are shown in Table 5. Data in the table show that 0.01 mg/m
of dinyl ,vapor was found even at 600 m from the plant. Sp~.cific dinyl odor was
ITABLE 5'
I
. -- ". ..........1
RATS OF: 1 - GROUP I; 2 - GROUP 2; 3 - GROUP 3; 4-
_.~.~!~O,=-_~R_O~~ .--- - - -.----
. ~SO
z
~.
cg 40
o
=
"'JO
:: ..
I
i
. f ~
. '2 r
-------------
,...,- ....,
~ ,
---~ J ',',
---.....---'----------........-.. ~._.-. ...~------
---. ------...-----..... ---...........-.......--
4 -
EXPOSURE
II> 20
....
...
>-
g,o
,..
'=>
,:;: 0
'- 2D/V tjVl -t5/V[ 3D/VI I5jJJJ JO/I/ll
. DATES OF LEUCOCYTE COUNTS
IO/V1l/ 25/Y1!I
- ., "'. - ~
FIG. 8 - EFFECT OF DINYL VAPOR INHALATION ON NuMBER
OF LEUCOCYTES
~, 25
z
~I .
g20
=
..'
'15
2,
-,
I
:2 ! 10
, ~I'
. g .5
. u
=>,
,j' 0
I - RATS OF GROUP 1; 2 - GROUp- 2; 3 - Gr.OUP 3; 4-
CONTROL GROUP
------...--
_._-_.....-. .------ ----"-- -..
SINGLE DINYL VAPOR CONCENTRATIONS IN ATMOSPHERIC AIR AROUND THE
CAPRONIC' PLANT
: M FROM No. OF SAMPLES MG/H3CONCN.OISTR/BUT/O~'~
DISCHARGE IBELOW METH- MAXIMUM 0.6-0.,/ I~' O.O(~'
SOURCE TOTAL 00 5EIISI- CONCNSo 0,1-0,01
. 11 V ITJ .
100 20 I 20 0,55 20
200 20 20 0,38 19 1
400 25 25 0,18 15 10
600 30 30 0,09 30.
800 40 31 0,008 31'
-90-
-------
also sensed at the same distance. The refore, it is suggested that sanitary
clearance zones surrounding capronic plants, which discharged dinyl vapor'
up to 6 ton per month should not be less than 800m wide. '
Conc lusions
1. Results indicated that3the concentration of threshold dinyl vapor'
odor perception was 0.06 mg/m and that the concentr~tion of threshold dinyl
reflex effect on eye sensitivity to light was 0.04 mg/m .
- 2. The concentration of t~reshold dinyl electrocortical conditioned --
reflex formrtion was 0.03 mg/m , and the subthreshold concentration was
0.01 mg/m .
3. The maximal single allowable ~inyl vapor concentration for atmo-
spheric air should not exceed 0.01 mg/m . 3
4. Dinyl concentrations of 10 and 0.2 mg/m under conditions of
chronic vapor inhalation elicited changes in the muscle antagonist's chronaxy
in white rats. '
5. Rate of coproporphyrin elimination '1th the urine was lowered in
rats which chronically inhaled 10 and 0.2 mg/m of dinyl3'apor. '
6. Prolonged inhalation of air containing 10 m3/m of dinyl lowered
cholinesterase activity, while inhalation of 0.2 mg/m under similar condi-
tions enhanced cholinesterase activity. , - 3'
7. Inhalation of air containing 10 and 0.2 mg/m 'by rats increased the
number of leucocytes and decreased the number of lymphocytes. 3
8. Chronic 24-hour inhalation by rats of air containing 0.01 mg/m of
diny1 vapor for a period of 70 days had no effect on the rats' functional activ-
ities noted in rats inhaling air having higher dinyl vapor concentrations.
9. The limit of average 24-hour dinyl. vapor concentration in atmo-
, spheric air coul~ be the same as the limit of maximal single concentration,
i.e. 0.01 mg/m . - '
10. Sanitary clearance zones surrounding capro~ic pla,nts which dis-
c~rged up to 6 ton of dinyl per month should ~o; be.le,ss thaI?- 800.m wide._-
-91-
-------
BIBLIOGRAPHY
An.. 0 e p H .It. E. BmrRHRe RepBRoit CHCTeMbi
. 3CTepam R xOJIHHeprHqeOKYIO peaKUHIO
B KII..: CospeMeHHble BOnpOCY HepBR3Na
, nOrHH. MeJ1rR3, M., ,1958, ap. 41--40.
ApT ell e fI x 0 B M. A. TeXH1I.xa 6eJonacHoCTH npH n,poH300ll.CTBe
18HCK03HOro BOJIOKHa, ueJl.'Io4Iaiia. H KanpoHosoro WeJlKa. fH3ner-
apou. M.. 1957. , '
6ywTyeaa 1(. A., nOne:IKaeB E.
-------
Methods for the Control of Atmospheric Air Pollution with Radio
Active Aerosols
Yu. V. Sivintsevand N. N. Khvostov
From the Atomic Ene rgy Institute of the USSR Acade my of
Sciences and the All- Union Research Institute of Railroad
Hygiene of the Ministry of Communications
Limits of allowable leve Is of ionized radiation applicable to the human
organis m have been steadily reduced .as the result of information accumulated
regarding the nature of radioactive substances and of ionized rays and thei r
effect on biological specimens including man and animal. Scientists all over
the world have concentrated their attention on the effect of radiation on the
living organism from the viewpo,int of genetic con~equences. Th~ importance
, of continued accumulation of infor'mation in this sphere of knowledge is em-
phasized by the increase of atmospheric air pollution by radioactive fallout
connected with atomic nuclear bomb explosions. Extensive investigations in
the field of genetic radiation showed that a linear d~pendence existed .between
the damaging action of ionizing radiation ~n the one hand and the large doses.
absorbed by the tissue (in the order of 10 r or more) on the other; there was
also the possibility that the concept of threshold magnitudes or intensities was
not applicable to the field of ionizing radiation. The Inte rnational Committee,
on Protection Against Radiation recogniz~d the. possibility of a potential radia.-
tion danger, and in 1958 recommended that the total accumulated dose of pro-
fessional or occupational radiation be' reduced from 600 to 200 rem. The
Committee also recognized the necessity for the reduction of the radiation
dose and the danger contingency to the personnel on an international basis,
th~reby, bringing to an end the uncontrolled exposure of pertinent personnel
to the effect of ionizing radiation. Accordingly, the Committee recommended
that the limit of allowable radiation dose to which whole groups of people may
be exposed should not exceed twice the naturally existing radiation dose, the
average value of which ranged for different localities between 0.1 and 0.18
mrem/week according to findings of Yu. V. Sivintsev. Such limits of allowed
radiation intensities in atmospheric 'air are indeed small.
Based on the above recommendation of the Inte rnationa1 Committee for
the Protection Against R'idiation the USSR "Sanitary Regulations Pertaining
to Work with Radioactive Substances and Sources of Ionizing Radiation" speci-
fied in 1960 - the following radiation limits are: 1 x 10-13 cu/li for C 137,
2 x 10 -14 cu/li for 1129, and 3 x 10 -15 cu/li for S r.90 ~I90. Alpha-a~tive
aerosols are characterized by a relatively high biological effectiveness
(OBE (Y. = 10). In this case 1 x 10-16 cu/li was the limit of allowable concen-
tration for p~210, 3 x 10-16 cu/Il was the limit for Ra226, and 2 x 10-17 cu/li
for Pu239. These sanitary regulations implied inspection based on the deter-
-93-
-------
mination ~f long-lived radioactive aerosol concentrations of the order of
10-14 - 10-17 cu/li. Specific radioactivity coming from an active substance
in such low magnitudes represented th.ousands and at most tens of thousands
of active atoms per liter of air. Such a radioactive concentration range is
below the sensitivity limits of presently available radiometric methods.
Accordingly. an analyzable concentration of active atoms can be obtained
only by aspirating large volumes of examined air through appropriate parti-
culate matte r retaining filte ring mate rials. See Table 1.
TABLE I
LIMITS OF ALLOWABLE CONCENTRATIONS AND ASSOCIATED PHYSICAL PARAMETERS OF SOME BETA-ACTIVE ISOTOPES
.-.--.-...-.. (ISOTOPES ARE ARRANGEp_I.N. T,HE INCREASING ORDER ?~..!_~~~-~ ~ADIO~9.T_I--V~_E.~~G_~~L___---- .-.
-- -.-
HALF-HCA Y
__~_ER I 011 -
1
2
3
4
LI OF NIH.AIR SAMPLE VO!.-:
;UME NECESSARY TO INSURE I
STATISTICAllY SIGNIFICANT:
. COUNTS WITH END WINDOW:
I
I "BACK- .-
GROUNDLESS
\..
B-2
. - ..
160TOPES
.'-"'-'---
~-._- ---
: C HL()R I KE~38! 37_) MIN.! 1 ,11 (31 %) 2 . 10-11 44,4 7,4
.-- 2,77 (16%)
4.81 (53 %)
SOD I UM-24 15.1 HOURS 1.39 1. 1O-1~ 2,2 6.2 1,45 . 102 0,35. 102
_~.~.R_I_U ~ '-40 . _J ; ~ 2.8 ..o.~ 0,4'1 (30%) 4. 10- 13 B,9. 10-1 4,7 4,8. 102 1,2. 103
1,02 (6)%)
. STR ONT I uM-89 53 DAYS 1.46 3 . 10-13 6,7. 10-1 6,3 4,7. 102 1,2. 102
. CESI UM-137 33 YEARS 0,51 (92 %) 1. 10-'3 2,2. 10-1 4,0 2,3. 10~ 0,6. 1()3
--..--- --.-- ~.. - -~-- -" ----- 0,17 (8 % )
, lOD .!.~~1 ~J._; 8.1 DAYS 0,2> (2,8%) 9. 10-" 2,0. 10-1 3,7 2,8 . 1(;3 0,7. 103
0,335 (9,3%)
0,608 (87.2%)
. ----. ...-. 0,815 (0,7%) 6,5.
YTTR I UM-91 61 DAYS 1,54 7 . 10-1' 1,5, 10-1 2,1 . 103 . 0,5. 103
CERIUM-I-44 282 DAYS! 0,30 (70%) 6. 10-" 1,3. 10-1 3,9 4,0 . 103 1,0 . 103
----..--.- ..- -- "-- '-:~._'- '. .~: 1,70 (30%)
ToDi-NE':129 - - I. 7x 1070 A YS ""0,] 2 f). 10-" 4,4. 10-2 1,0 4,5. 10' 1 . 1 . 10'
~.
STROIITI UM-90 : 19.9 YEARS 0,61 3. 10-'6 6,7. 10-3 4,1 7,3. 10' 1,8 . 10'
--~, -" -. L
-_._- --------- --_. ----.---. n.. .-._, _...-
I. MAX. ENERGY OF BETA-~ARTIClESt MEV.
2. MAC III ATMOSPHERIC AIR III cull I. .
3. SP. ACT. CORRESPONDIlIG TO MAC III DECAYS/MIN/li
~- -~PECTRUM % OF AN ISOTOPE RECORDEB BY COUNTER MST-17
Unfortunately, the universal existence of natural atomi"c radiation in
atmosphe ric air in. diffe rent concentrations inte rferes with the direct method
of solving the dete rmination problems. Among the naturally existing radio-
active isotopes are uranium. radium, thorium and other substances. as well
as artifically produced radioactive isotopes of split and activated nature re-
sulted from radioatomic bomb explosion tests. .Present day atmospheric air
pollution with radioactive substances consists mainly of the following th.ree
components:
-94-
-------
.
. h
, J
1. Pollution coming from natural radioactive substances which is a
part of the external environment in~luding air, water, soil, etc. This
natu~al radioactive background:con~ists basically of::adbn and thoron iso-
topes and their split products whiC(l'radi'ated alpha-and beta-rays with hal£-
life periods averaging 30-40 minutes. The concent-t"ation of such isotopes in
the atmospheric air ranges betwee~,10~~3 and 10-14 cu/H.
2. Pollution with radioactiv'e substances formed as the result of atomic
..
bomb explosions, gene rally refe r,r~d to as the atomic bomb background; such'
radiation comes from fragments. 0i<~ uranium and ,plutomhim (isg9opes 99.:/ ele 90
ments found in the center of the Mendeleev Table; they are Sr ,Sr + Y ,
'136 144 144 ", ,
Cs ,Ce + Pr and others).. ThlS class of components lncludes un-
spent or unreacted nuclear fuel, mo:stly ur'~nium and plutomium isotopes. The
atmospheric air. concentratio~of'ra~io~yti~e fr~~ments. which existed in the air
for some years ln concentratlons.~£ ,1,0, 5 '~- 10 6 cu/h has recently come to
lower levels due to the discontinuation of citomic bomb explosions.
, .
3. Pollution coming from 'r~qiodctive aerosols and radioactive gaseous
end products discharged into the a~ri1os-phe bc air by industrial plants which
produced or proce ssed to a large &e:gre,e, if not. exclusively, radioactive sub-
stances and sources of ionizing r~(F:ation. This group of radioactive atmo-
spheric air pollutants is generally~rfeferred to as the "industrial pollutants".
Depending upon the volume and pa~ticular program of.work of any institution
such radioactivity may be the result of a variety of isotopes. In the mining
industry, the metallurigical and ore concentration industries uranium, thorium,
radium, radon, thorom and their daughter split products are the predominant
atmosphe ric air pollutants, while in the radiochemical industry polonium and
plutomium isotopes predominated;iin the field of nuclear reactors uranium
split products predominated; in qlE~rapeutic institutions the predominant radio-
active air pollutants are isotopes 6f phosphorus, iodine, etc. The concen-
tration of "industrial" atm':)spheric air pollutant radioactive isotopes amounted
to 10-16 - 10-17 cU/Ii. :
Simple methods of radiomet1;y, such as measurements of total sample
activity and of its half -life cannot be applied to the study of radioactive atmo-
spheric air pollution, because such methods do not diffe rentiate between the
previously described three types'<# atmospheric air pollution; simple radio-
metry in such instances merely gi;ves rise, to a fourth conception, namely the
total or summary effect. In this 1fespect, short-lived isotopes composed the
first, IInatural" background, the 19n9-liv'ed isotopes constitute the second or
bomb-explosion background,. and the third or industrial type of radioactive
atmospheric air pollution can 'not be determined by simple or elementary:
methods of radiometry except' whe,n,' the radio pollution is of conside rable
magnitude. The last statement is: based on the assumption that only long-
lived isotopes were of hygienic si~nificance in atmospheric air pollution with
radioactive substances, and that.rnethq.ds of radioactive air pollution investi-
gation must primarily be directe'd; towards solving the problem of long-lived
isotopes. Determination of concentrations of short-lived natural radioactive
-95-
-------
products or radon and thorom decomposition in atmospheric air at present
presents no particular urgency from a hygienic viewpoint; the firs t component
group of radioactive atmospheric air pollution includes only radon and thorom
decomposition products activity ~hich emanated from the soil, buildings ," con-
struction materials, etc., but not those which come from ores or from dif- "
ferent uranium, radium and thorom compounds found in the radiochemical in-
dustry or In radiological institutes." Data presented in Table 2 show that the
concentrations of "total"
T AS lE 2
radioactivity in atmospheric
I 1 .
MAGNIT,UDE OF "TOTAL" ATMOSPHERIC AIR SPECIFIC ACTIVITY _lair are genera ly of conslder-
I SPECIFIC ACTIVITY IN cull! able magnitudes and exceeded
ISOTOPES ALPHA-RADIATION I BETA-RADIATION, "the established limits of all'6w-
I ! able concentrations of long-
SHORT-LIVED 10-13-10-14 10-1~-10-13
lONG-LIVED 10-15-10-16 10-14-10-15 lived isotopes in the atmospher-
----,-- , - ,..--' , ic air by two to four times.
Quantitative data presented above are of" decisive significance, since they
conditioned the basic parameter ramifications of the analytical methods, such
for instance, as air sample volume, time of the sample analysis, etc.; this
indicates that the control of atmospheric air pollution with radioactive sub-
s tances presents two basic difficulties:
1. In determining the concentration of long-lived isotopes approximat-
ing the level of limits of allowable concentration, the effect (pollution) which
is to be determined is usually only 50-25% of the atmospheric background
pollution.
2. ,Present day limits of allowable atmospheric air pollution with radio-
active substances are so narrow that even when the active isotopes have be'en "
concentrated from large air volumes they still require special radiometric
methods for a reasonably precise determination of their activity.
Several methods have been proposed fo'r the solution of the first diffi-
culty; these solutions vary: The final determination can be ddayed untilthe
short-lived isotopes have become inactive, or the nuclear radiation of the
collected sample can be measured spectrophotometrically. Efficient methods
for such determinations of atm~sphe ric air pollution with radioactive sub-
stances have been previously described by Yu.' V. Sivintsev, P. P. Kornilenko,
et aI, P. P. Kornilenko and V. Bybin, L. M. Luzanov and A. A. Chubakov, and
wilGot be discussed here. Suffice it to say that the proble'm under. considera-
tion can be considerably simplified by instituting measures for the control of
atmospheric air pollution with radioactive substances at the source of their
discharge, thereby limiting the problem of measuring radioactivity to the dis-
charge 6f gaseous radioactive end products; such a procedure could facili-
tate the analysis of the composition of radioactive air pollution, the identifica-
tion of discharge sources and the development of means for the reduction of
the total activity of the discharges and of "their radioactive danger. Solution of
the second difficulty related to the low allowable limits of radioactivity con-
centrations constitutes the subject of discussion in the present report. The
-96,"
-------
1___.._--.-...... .
. ~. j . .~ ," "! ," .,. ~ J: . ~.- .~."- ..~. ".
1 ~!. ii ~ ~
',' ' . I~
\. 1 ,~~ ~. ..
~ 'L'. .." . ~
purpose of the report was -to pr'ese~f~?- ~h~o'retiGal'analy~is of experimental in-.
vestigations arid results o~ pr~~ti~~r 'exp'eri.t';n,ce in thE!' control of radio ema-
nating ae.rosols of low specific 'activity. Regulations defining the control of
atmospheric air pollution ~ith radi~~ctive, substances must be based on activ-
\ . r. .
ity measurements by radiometric 'e('111ipment which '~rielded statistically signif--
icant results. Therefore, the pres~rt 'authors pre:;;ent a general dis~uss.ion
of factors upon which determinatio~ of radioactive aeros'ol activity must be' '
based expressed in cu/li ,taking ~n~q c~risideration the count rate (N) in terms
of imp/min during the time of measiuring the radioactivitY of the collected air
samples. The statistical ~hara,cte ~of nuclear radioactive decomposition is
, ;j . , .
such which makes count rates of ~n.y"nu~lear radiation detector inconstant and
fluctuating around som,~ average va~u,es.; 'rherefore, results of activity measure-
ments made by a radiometric d'evic~: c;an be expressed only in the form .':)f the
following generalization N :tV~ ~~~h defines the probable limits of the sought
for quantity; in this generalization N~represents th,e nuciber of impulses count-
ed in time t. The relative precisioP,'~f such measU:reme:nts is defined by the
relative average of the quadratic ~jl';or;- see formula 1 below:
. ~r-- ',' r 'j
y N "j ~,
a=:!:~~ '"
N ',' ';,,-
Factors or causes enume'ratel<'rbeiow point to the fact that each ionizing
ray detector has its specific backg~ound, s~ that tlie total count Nimp register-
ed in time t actually is the sUm of ~wo values, namely, the number of impulses
recorded by the activity measuremb~t, denoted as Nef' and the number of
, I
impulses representing the bac~gr9~nd (count 2), denoted as Nf. The true effect
is determined as follows: the detec~or background (Nr) is determined for time tf
in minutes and is subtracted fr'orri ~he total count rate. N t imp/min. According
to theory of probability the relativ~ quadratic error of such results can be com-
puted on the basis of the following gene ralization - see formula 2 below:
. a = :I: ~Vna1> + nt/J ;; + -!!.'IL , (2)
narp t., ,.'.. trp
in which n = Nef .", Nf which is the r;ate of the detector count (imp/min. ) .
which depended upon the activity rn~asurement Nef and upon the .background
count Nf. Generalization (2) indic~t,es that increase in the precision of activ-
ity dete r.minations by any nud~ar' ~adiation: detector can be attained only when -
, ,
...or' .'" "...' ",'
~J
(1 )
.,
nat/J > nt/1 or' n3rjJ :;> i.
nr{J ;
. t~ '. .
Conditions defined by gene ralization (3) can!;>e fulfilled either by in-
creasing the value of Nef while' keeping Nf constant or reducing it; or vice
versa, by reducing Nf while ke'epiIlg Net constant or increasing it. The
. " ,.
following is an examination of ~ith~.r of the two pqssibilities in relation to the
problem of active aerosol radicim~~r-y u?de! present <70nsideration.
(3)
-;"
? '-97-
1" ::'
,
, '
-------
are not acceptable in most cases since they do not offer the opportunity to
accum".llate the number of radioactive aerosol on the filter required for ob-
taining statistically significant results. Significant radioactive aerosol
measurements can be obtained only when the artificially introduced activity
concentration was at least twice as great as the naturally existing (background)
radioactive substance s.
It must be remembered that radiometric equipment efficiency was of the
order of 5-10%, as is the case, for instance, when counter MST-17 type B is
used in determining radiation intensity of beta-rays; in such cases consider-
ably greater volumes of air must be passed through the filter in order to ob-
tain statistically significant values. Where radio activity determinations are
made with a counter yielding 20 imp/mi.n. it becomes necessary to collect a
sample the count rate of which would yield 30 imp/min. which means an activ-
ity of 300 to 400 charges pe r minute. Activity of such magnitudes can be
accumulated on the filte r by pa-11ing through at 1east 10 Ii of the air containing
an aerosol concent:r:.C).tjon of 10 eu/li, ~r 2 m of air contair:if¥ an aerosol
concentration of 10 cu/li, or 20000 m of air containing 10 cu/li, with-
out accounting for the slip-through coefficient. More detailed data are pre-
sented in the preceding Table 1 - see page 94. 3
The previous discussion indicates that an air sample of 1 m would
suffice only for the determination of intensity of radio~3ive pollution in air,
the radioactive aerosol concentration of which was 10 cu/li. From a practi-
cal viewpoint this means that the method used could be applied only for the
determination of the specific activity of radon and thorom decomposition pro-
ducts as previously indicated, the determination of such radioactivity is of no
sanitary hygienic value under pre sent conditions. The efficiency of alpha-
radiation activity determination with detector P-349-2 amounts to 25-40%;
therefore, the volume of aspirated air in such cases can be 1/3 or 1/4 of the
volume above indicated. "
The preceding discussion in connection with data presented in Table 1
show that the volume of air collected for the determingtion of air polluted by
rad,ioacti ve concent3ations in the range of 10-4 - 10-1 cu/li should be in the
order of 20-2000 m .
It was officially recommended that air pumps delivering 7-10 li/min. /
1 cm2 of filter area shouIzl be used in collecting large volumes of "air. Where
the filter area was 12 cm the pump must be able to deliver 80-120 li/min.
This shows that the recommendation must be reviewed and revised. In ex-
treme cases the aspiration rate can be reduced to 50 Ii/min. but not below,
in which case the slip-through would amount to only a few percent which can
be disregarded. Air collection for radioactive aerosol activity determination
should be done using special assemblies consisting of a filter-holder, gaso-
meter, and air pump. In the USSR satisfactory performance was obtained by
using dust suction pumps of the "Dnepe rll and "U ralets II labels which can as-
pirate 150 li per/min. According to generalization (6)"it is possible to use
filters of larger areas which would permit to increase-the total activity of a
- sample collected in time t, not only because of its linear relationship to the
activity accumulated on filter surface S, but also because of the possibility to
-99-
-------
enhance the efficiency af the emplayed equipment. Experience af the present
writers indicated that dust suctian apparatus "Uralets" cauld aspirate air at
the rate af 300-400 H/min with a filter af 4 em diameter and with the filter
halder cannected with aut intermediate rubber hase directly to. the dust pump,
and gasameter. Increase in the filter diameter to. 20 cm raised the filtratian
rate to. 1-1.5 m 3 / min. The valume of aspirated air can be dete rmined by an
anemameter ar by a special flaw meter af law resistance. The apparatus is
schematically illustrated in Fig. 1. In this cannectian experience has indicat-
ed that dust suctian pumps recammended far use in the study af air radia-
activity did nat overheat even at the rapid rate at which they were ape rated in
4
.7
to
'';:'./r. r, .;',' /
, ?"
o I 2 j ~ 5 "-If
WIlli
'3 BOL TS M 2. 5 I. 7
12 BACK WAU
II t1IoI SCALE WtTII A
10 PftE&&UftE IAIE
9 GASKET A&SEMel'
8 PftESSURE TuelNe
7 TU8E CONNECTION
6 GAilln
5 PRESSUftE CAIE COVER
4 PRESSUftE eAIE CONNECTION
3 BOLT H4 I = 16
2 FlOWMETE- 101'
I CO.,CAl 8ECTIO.
No. NAME OF 'UT
8:
...
.f t-
~ ;
6
: ~
E
J E
2::;
..
.
2 j . J 6189 ' :.
HUNIREI& 1I/"..
CAll8RATIO. IRA'H
4 BRASS
I PLEX"lA&S
CAll8RATION IRA'" ON THE lACK
I PlEXI'LAS&
BRASS
I HAfti Run u
, BR AS6
I HARI ftU88ER
I PlEXISlAiS
I B-AU
, Buss
I EeOHlTE
I DUftALUM I NUM
No. MATERIAL
FIG. I - STROCTURE AND CALIBRATION GRAPH OF A SIMPLE FLOW'1ETER
3
the USSR Institute af Atamic Energy. See Fig. 2 (Page 101). In fact 30-40 m
af air cauld be aspirated by these pumps thraugh the filter in 30-45 min. using
large diameter filter halders. Such valume af air is regarded as adequate for
the cantral af air radioactive up to. a concentration of 10 -14 cu/H. Howeve r"
in most investigations af atomic bamb explasian and industrial pallutian, the
tata1 accumulatian of radiaactive particles on the filter callected as abave
described, was inadequate far praper pallutian determinatian and, therefore,
greater air valumes shauld be aspirated.
-100-
-------
I
V'!:.:~..I,v~',l{ I1p:ff.5'{J"If,HIIz,O I.. Experience of the pre se'nt
;"';J.4/Af~',.,. iJ;J'6JiJ;I(,.y1lz02. authors in the field of air pollu-
::f::!S~7.;;I,Ht:1I .oO:580""A(!,IzO~~., tion under study indicated that
; :-':.:.+.#~'..,. ,jp:557.M"'I1'z{J .: the work above desc ribed could
.:.:...;;C,Y,1f/:j! 5. I -~ be accomplished by employing
i I j o.rdinar~ exhaust fan installa-
: I ' tlons WhICh enabled the collec-
I tion of adequate air samples in
! a short pe riod of tim'~ or, if
necessary, in prolonged time
]( ~t 5517 50 1<7 periods such as one day or even
FILTRATION TI~IE IN MINUTE ,
longer. The latter apply to in-
FIG 2 - HEAT CHARACTERISTIC CURVES OF VACUUM PUMP tlDNIEPER" .. "
. vestlgatlons dealIng wIth aver-
\. V=12 LI/MIN V=35 LI/MIII V=69 LI/MIII,~p'690 ~1M H2O; 2. V= .
IL45 LI/I1INb.p=660 I'll H20; 3. V=250 LI/MINt.,..=590 W1 H2O; 4. age 24-hour concentratIons of
. \1=380 LI/I1IN:JP::557 HI1 H2O; 50 \1=620 LI!MItI',),r=330 rn H20. radioactive aerosols. For ex-
. '. . .
ample, exhaurt fan EVR-2 enables the collection of air samples at the rate
of 200-500 m / hour. Exhaust fan FVA-49 can be particularly advantaQ'eouslv
. used in such work. This fan can exhaust an average of 50-100 m3/ hour. This
ventilator is portable and can be used for the collection of radioactive air
samples at any desired point. The Institute of Atomic Energy of the USSR
Academy of Sciences has been making determinations of average 24-hour and
average 7 -day radioactive aerosol concentrations in the atmospheric air using
continuously operating air pumps specially developed in the laboratory of D. L.
Simonenko, ope rated by electric Totors AD-4l-2 of 2880 rpm. The examined
air is moved at the rate oj 4-5 m / hour uninterrupedly. The air is forced
through an area of 0.5 m of FPP-15 type fabric filter. The filter is connected
at one end and along the generating line of a hollow metallic cylindical grid. ,
The filter adapter is changed daily and determinations ,are made for the total
beta radioactivity. Other parts of the filter are changed once a week and are
sent to the laboratory for radiochemical analysis.
Motor AD-41-2 operates with a high degree of constancy obviating the
neEfd for the installation of a flow-ocontrol device. The high volume flow-rate
of the examined air afforded by this method of air filtration enhances the de-
tection sensitivity to 10-17 cu/li; this makes possible the detection of atmo-
spheric air activity resulting from the presence of decomposition products in
concentrations generally produced by atomic bomb explosions. Gene ralization
(5) indicates that it is possible to increase the count rate of effect, Nef' Gen-
eralization (5) covers a wide range of parameters; however, the correction
factor which accounts for radio-self -absorption (1- e-i~ "'; X;) is introduced only
in gases of low penetration radiation, namely, alpha-radiation and beta-radia-
tion of H3 , C 14, S 35 , and 1131 , the maxim3..1 beta spectrum limit of which
did not .exceed 0.7 MEV. In the majority of other practical instances the
value of the correction factor is practically insignificant even whe re the beta
radiation layer is considerable. See Table 3 (page 102).
Need for counter efficiency!:, correction results from the fact that beta-
particles of different isotopes are characterized by different patterns of energy
distribution and, therefore, are differently recorded by end counters. The
-101-
50
!V::':'/r~.i')
50
.
o
Q'~Q
z
UI' '0
a: ~
::>
~;
<
a:'
~ j20
5,
1-110
. '
J..----L-..!-
! : I
I '
{1
"
,"
-------
TABLE 3 soft part of the spectrum is
partially abs orbed by the laye r
of air and by the end windowor.
. walls of the counte r. In addi-
SAI1P!.EjlA,(ER THICKNESS
It! MG ~I1Z REQUIRING tion, there simultaneously oc-
CO;JRECTlorl
curs a dispersion of beta-part-
icles, the value of which approx-
p~~ 1,69 O,OC63 3,1 ]6.1 imates the value of the investi-
~~I~' b:~~ g:~~ i:~ 1~:3 gated volume, and an increase.
. . . in the counter volume sensi!iv-.
ity to high ene rgy beta-particles, etc. The effect of air, window and counte r
walls absorption of beta-particles can be reduced by covering the walls of the
ins truments lead -shield with a substance of low atomic value, such, for in-
stance as plexi-glass, aluminum, etc. The theoretical analysis of such effects
is a highly complicated one; therefore, an experimental curve is first con-
structed on the basis of records of different beta-radiation intensities. Fig. 3
illustrates a typical curve for the end window counter MS T -17 having a'lead-
shield 5 cm thick (+ 1 mm aluminum), and.
for beta-radiation .in a base layer made of
stainless steel having a diameter of 18 mm .
and 0.5 mm thick at a' distance of 18 mm
from the end window. The efficiency co-
efficient of the instrument 2: and the factor
of correction for self absorption of the re-
corded radiation depend only on the nature
of the investigated air pollutant; therefore,
the only possibility for the increase in the
count rate of the effect Nef as shown in
. 1 2 J 4 f) /Tltll generalization (5), lies in the enhancement
.t-'MAXIMAL'LIMi-T -oFJ3~ ". .of the geometri~ para~eter '.0. This can be
_..!W..!~uM '.'!~- accomplished by changing over to nuclear
FlG-;"3-:-R'ECORDING EFFICIENCY" OF'~::'PARTICLES radiation detectors of high volume sensitivity
. OF DIFFERENT SPECTRA tilTH MAXIMAL and by increasing the size of the filte.r upon
LIMIT Ej3'1AX~:J~D WINDO\" COUNTER which the active aerosol is being collected.
------- -----. - "-'-'-'-'" --.- In the USSR this can be accomplished by
changing over from MST-17 to T-60DFL, from STS-5 to STS6, from.detecting
elements "IRIS", to counter SAT and. to. scintillators ZnS (Ag) with the aid of
light guides. . Where counters STS-5 or'STS-6 are used considerable advantage
can be gained by placing the filte r outside of the cylindrical cathod along its
generating line; as a result of such re-arrangement it is possible to attain a:
practically,a 2 TT geometry state and to elimin'ate absorption by the air layer
between the sample and the counter-wall. In working with end window counters
and filters the dimensions 'of which are considerably greater than the diameter
of the end window, the radiation surface must be reduced in order to obtain an
applicable value of the geometric factor ill. This can be accomplished as
follows:
THICKNESS OF BETA-RADIATION LAYERS WHICH REDUCE SELF ~BSORPTION
ERRORS TO 1% AND ~
,
i LIP=AR RAD-
" MAX .SPECTR.,'BrioN AIJ-
LIMITS IN I SORPTION 'I
f}EV COEF. I II CI12 G
," 'I-SOTOPE .
-- .------
Hi
5"0
8
8
17
~15
=!5
>,
g! ~
~;J
u,
;;:12
... '
...i
II
_.io
lJXz
/(~2
-102-
-------
(a) By folding the filter to the desired size; in the case of fabric FP
the bottom gauze layer can be removed; the material can be pre-molded and
a supplementary coefficient introduced into the computation to account for
self -absorption. -
(b) By dissolving the filter and remodeling it to the proper size; this
can be done easily with filters of fabric FPP which easily dissolves in acetone;
upon evaporation of the solvent a film is formed of the desired size and shape.
(c) By incinerating the filter and forming a target of the desi red size
from the ashes. A radio counter of special construction applicable to such
cases has been used in the Institute of Atomic Energy of the USSR Academy
of Science. It is schematically presented in Fig. 4 and a curve depicting the
functional relationship between efficiency and beta-particle energies is pre-
sented in Fig. 5. -
'220
£
f 14.
2 IJ
12
J If
4 10
5 ~;
5 ~ 6
7 t 7
.
III
;:; 5
::: 5
...
4
J
"
<.
1
0 ljJ I17.7X
1 2 J 4
~
~
MAXIMAl LIMIT Of p-
SPECTRUM" Mn
FIG. 5 - RECORD I NG EFFICIENCY ~;: -PARTICLES
OF DIFF,ERENT SPECTRA I.J1TH MAXIMAL
LIMIT I15MU OF CYLINDRICAl COUIoITER
AS.2
FIG'. 4 - DATA UNIT OF RAOIMTRIG APPARATUS FOR
t1EASUlU NG FRI ABLE SAMPLE'; OF LOW SPECI FI C
ACT! VITY.
I - lEAl ."ILElI 2 - STOPPER,.3., ALUM"1m cnlluR,
, 4 - SPECI"", 5 - ALUM'IUM fOIL ",'LIiIER 0.05"", 6 -
ALU"IIUM AlaoRIERI, 7- (OUITER A5-2.
-103-
: j
-------
Background Count Rate and Methods for its Lowering
Back,ground count rate Nf imp/min of a nuclear radiation detector is
a complex function of the following:
1) Cosmic radiation activity; at sea level and at average latitudes;, it
is charac~e rized by a rate of ionic formation in the air' amounting to 2 iono-
pai r s / c m / s e c .
. 2) Pollution of soil, construction materials, atmospheric air and
other objects in the vicinity of the radio-counter by natural radioactive sub-
stances such as uranium, radium, thorium, calcium-40, etc.
3)
stance s.
Pollution of the -counte r -components with natural radioactive sub;-
4)
Spontaneous counte r discharges.
Cosmic radiation at sea level consists basically of low-energy electrons,
commonly referred to as soft components, and of high-energy meson, or the
so-called hard components. The low-energy electrons are completely ab-
sorbed by a lead-sheet 6-8 cm thick; the high-energy mesons have a high
penetration capacity. The latter produce ionization similar to that of high-
energy beta-particles; they can be recorded by self-quenching counters at
close to 100% efficiency. Cos mic radiation contributed to the background of
the counter -rate Nf by high-energy mesons can be easily excluded by applying
atomic electron counter-complements surrounding the main detector of beta-
particles(which can be either MST-17, SI-2 B, SI-3 B or the cylindrical count-
er STS -5 or STS-6 ).
The USSR Academr of Science Institute of Atomic .Energy has been using
two types of such devices, mistakenly designated as "non-background" counters.
One of them has been developed by V.A. Bryz'gunov, and was intended for the
measurement of hard flat preparations such as filters with radioactive aerosol
samples, radio-chemically isolated isotopes, sample water, evaporation etc.
This device use s end window counte r MS T -1 7 which is surrounded by 35 AS -1 .
counters fastened to organic glass plates. Counter AS-l ~akes possible_- --- .
the attainment of higher radioactive densities in the environment s.ur-.
rounding counter MST-17. However, it must be borne in mind that these c.oun-
ters are inferior to other counter types. The specimen is placed on a special
base in front of the counter end window. Absorbers of 10 mm thickness can be
placed between the specimen and the MST-17 counter end window with the aid
of an up and down movable support. The AS -1 counters are shielded by an
. organic glas s screen seve ral mm thick against the effects of beta -particles.
The entire device is shielded by a' 6 cm lead plate which absorbs the low-
energy electrons and the naturally emanating gamma radiation; this is further
shielded by the 20 mm red-copper plate as.a protection against possible pollu-
tion of the lead plate with radioactive substance s.
-104-
-------
The basic scheme of the entire set-up is illustrated in Fig. 6. Im-
pulses, coming from counter MST-l7 are transmitted through a cathode
follower 6ZhlP to amplifier 6NIP and are formed into impulses by a uni-
vibrator on lamp 6N15P. The negative impulse formed by the univibrator
passes through a cascade on lamp 6Zh2P and activates the out-going uni-
vibrator AN 15 and of the mechanical summator. The 35 AS 1 counte rs have
a gene ral charge which gives rise to positive polarity impulses. The latte r
are transmitted to amplifier 6NIP through the cathode follower and activate
univibrator 6N15!. The negative impulses of the univibrator have approxi-
mately double the life of impulses coming from the univibrator of the pre-
ceding detector channel. Arriving at the suppressor grid of lamp 6Zh2P.
BHIP
BHI5P
BZ H 2P
BMI5P
BNI5P
"r
BZHI P
.... ...
'" '"
". ..,
-.
" '
48.7:1 "1..: "to
35
...
::;
... '
... ..,
~ ~
'"
~
...
..,
"
....
~
MST-17
20.0,: :
240 ( )
Z.' r
,.
...
0.;
~
...
..,
't
:;t
...
,::. O,Oj
16m
!JoJ!
5fl;
(
srs4S
~
.m.. E4PsJsUPPLY'
, S\:SIEM
.~ 40.1' 220V
i' z
:L~d-~ .
.
35 AS-I COUNTERS ~
.r
. J."
....
~.
...
'" ...
I;. ~
~
100 ..,
" ".
\ )
...
""
... ...
'" .. ..
.... ".. f"'o
, , .,
BSE-2Md
..
a31
...
~
""
FIG. 6 - ELECTRICAL SYSTEM OF ANTICOINCIDENCES FOR REDUCING BACKGROUND OF COUNTER MST-17
These impulses prevent the end cascade from becoming activated by the
simultaneous pulse appearance in both channels. All 35 AS -1 counters have
the same high voltage, therefore, it is imperative that the selected AS-l
counter be operated on the same voltage level. It should be noted however,
that even if this condition is scrupulously fulfille.d, impulses coming from
different counters may still differ considerably in their amplitudes. The
proposed system eliminates the difficulties and complications connected with
the impulse amplitude level diffe rences.
According to data recorded on the background rating plate' of counter
MST -1 7 in a radioactivity free room did not exceed 25 imp/min. By the use
of a lead shield it is possible to reduce this background to 14-17 imp/min, and
-105-
-------
ln some instances even to 10 imp/min. Shielding of counter MST-17 by a
screen of self-quenching counters included into the plan of anti-coincidences
with counte'r MST -1 7 makes possible the reduction of the background to 5
imp/min.. The lowest level of radioactive background attained for counter
MST-17 was 4-5 imp/min. This background level is probably a reflection of
the calciurri-40 content in the mica of the counter end window, and in the glass
as the resu:lt of spontaneous counter discharges. It has been determiI1fd that
approximately 3 decays occurred every minute in a mica window 1 c m of which
weighed 5 mg. Another type of the mistakenly called "backgroundless" counter
was developed in the laboratory of S. A. Baranov, designed for measurement of
radioactivity of sand-like and powde r -like speci mens and of large volume water
specimens of low activity, and for other similar purposes. The calibration of
both devices is done with the aid of beta-radiating substances within ene rgy
range of 0.3 and 3.5 Mev. The efficiency of such counter standardization fluc-
tuated between 2-6%, indicating that the background count rate of so-called
IIbackgroundless" counters used for a long time can be reduced to at least 1/5
an~ It~at the range of activity measurements <':12 be broadened to' approximately
10 cu with an accuracy of 5%, or up to 10 cu with an accuracy of 30%.
The brief analytical pre sentation of theoretical conside rations, expe ri-
mental invest~gations, and practical tests related to the control of radioactive
aerosols of low specific activity, was accompanied by concrete recommenda-
tions on the basis of which it should be possible to make statistically signi-
ficant measure ments of atmos phe ric ai r pollution with radioactive substances
within the range of the recommended allowable radioactive concentration limits.
. BIBLIOGRAPHY .
HHCTPYKTIIBHO-MeTO,'lllqf1l0BaHHe 3cj>cj>eKTHBHOCTII
QJH.1bTpaUlHl ;\3p030.1eH TKaHII~fH DD.15 II DA.15 npH 60.~b-
UIIIX CKOpOCTS1X npOKaqllBaHIIII B03llyxa. C60pHIIK pa60T no HeKO'
TOpblM BonpocaM l1031L\1 eTp II II II pa.1HOMeTpHIl HOHH311PYlOUlIIX
113.1yqeHlfil. DOll peJ.. KilHlllI.1aTa TeXHH4eCKllX HaYK 10. B. Cli-BHH'
ueBa. ATO~flf3.1aT. Moo 1960. CTp. 182-186.
K 0 p H H .1 e H x 0 D. D., E r 0 p 0 B b. H.. 50 q K 0 D A. A. YqeT npo.
.ilYKTOB pacna.1a pa.10Ha npll HenpepblBHoil pa.1110MeTpllH HCKYCCT'
BeHHblX pa.1110aKTIlBHbIX a3p030.1eil. C60PHHK pa60T no HeKOTOpl>!~
.BonpocaM .J03IBleTpIlH H pa.JHo~leTpHH IIOHlf3HPYIOUlHX H3.~yqeH!lII.
Do.1 pe.1. Kall.'lH.1aTa TeXHllqecKHX HaYK 10. B. CHBHHIleBa. ATOM'
'H3.1aT. l..t, 1960. CTp. 163-1~1.
Jl Y 3 a HOB a J1. M., 4 Y 6 a K O'B A. A. HCCJIellOBaHHe 3arp!l3HeHHOCTI!
B03.1yxa H pacTeHHii pallll0aKTHBHbI~m OCKO.~OqHbIMIf npollYKTaMH.
C60pHHK p360T no HeKOTopbl~1 BonpocaM .'103HMeTpIfH Ii pa.'llio'
MerpHH HOHH3liPYIOUlHX H3.~yqeHHii. Do!! pell. KaHlIH!!aTa TeXHHqe.
CKIIX Ha)1< 10. B. CHBHHueBa. AroMlI3llaT. M., 1960, CTp. 187-188.
CaHHrapHble npaBH.1a pa60Tbl C palIHoaKTHBHblMIi BeUlecTBaMH H HC'
TOqHHKaMIi IiOHH3HPYIOUlIIX H3:IyqeHHii Ng 333.60 OT 25 HIOH\!
]960 r.
C H B H Hue B 10. B. Pa.aHO~leTpHS1 pa.JHOaKTHBHblX a3p030J!eil. C(jop.
.HHK pa60T no HeKoTopbl~l. BonpocaM 1l03HMerpliH H pa.aHoMeTpHH
HOHH3HPYICUlHX H3J1yqeHHH. DOlI pe.a. KaH.1lH.'laTa TeXHHqecKHX
HaYK 10. B. CHBHHIleBa. ATOMH3.'laT. M., 1960. CTp. 139-151.
C H B H Hue B 10. B. OHOBoe 06J1yqeHHe qe.~OBeqecKoro opraHH3Ma.
ATOMH3.1aT. ,..t, 1960.
R e com men d a t ion s of the Jl1ternational Commission .on radio.
logical protection (adopted 09.09.1958), Per~amon press., LOD'
don, 1959.
Rap 0 r t 0 f Com m i t tee II on permissible dose of internal
radiation (!()59). Health Phys.. 1960, 3, 1-380:
-106-
-------
Methods for the Determination of Atmospheric Pollutants
N. V. Alekseeva
From the F. F. Erisman Moscow Research Institute of Hygiene
Development in the synthesis of high molecular compounds resulted in
the production and utilization of many new organic substances by the USSR
national industries. Plants producing these substances and their intermediate
products discharge into the air gases, vapors and by products as surrounding
atmospheric air pollutants the detection and quantitative determination of which
require special and highly sensitive analytical methods. In the following page.s
methods are described for the detection of acetic acid esters, acetates, dinyl,
isopropylbenzene, furfurol, ethylene oxide, monobasic carbonaceous acids,
methylmetac rylate, dimethylformamide, and isopropylbenzene hydrope roxide.
DETERMINATION OF ACETATES
.
Principle of the method:
Acetates react with hydroxylamine to form hydroxamic acid, which in
turn reacts with iron chloride producing a yellowish-green to yellowish-rose
color the intensity of which is directly proportional to the concentration of
acetate in the sample. The method is not specific; esters of acrylic acids" .
. formaldehyde and antioxides of organic acids interfere with the reaction. The
sensitivity of the method is 1 J.l in 2.5 ml.
Apparatus:
U -shaped absorber with porous glass filter plate #1; aspirator and air
blower aspirating air at the rate of 2 li/min, equipped with a flowmeter; colori-
metric test tubes, 110 mm high and 10-11 m;-n in diameter; volumetric flasks of
50-100 ml capacity pipettes of 1-2 ml capacity, calibrated into 0.01 m1; a 2 ml
Shilov microburette.
Reagents:
(1)
Ethyl alcohol as the absorbe r solution which is prepared as follows:
take 500 ml of the alcohol, add to it 20 g of potas sium hydroxide,
leave stand for 3-4 hours with occasional shaking and then redistill
at 780.
Standard acetate solution prepared as follows:
(2)
-107-
-------
(3)
nlace lO -15 ml of the redistilled alcohol into a 50 ml volumetric
flas k; weigh the flask; introduce 3 -4 drops of acetate and weigh
again; add alcohol to the 50 ml mark; the' diffe rence between the
two weights represents the amount of acetate added; the latter
divided by 50 will represent the amount of acetate per 1 ml. This
is the acetate stock solution. Prepare the standard solution so that
each ml contained 10/1 or 0.01 mg of the acetate.
Hydroxylamine hydrochloride; use a 100 ml volumetric flask and
place into it 20 g of the hydroxlyamine hydrochloride; add distilled
wate r to the 100 ml mark; shake until solution is clear and store
in a cool place.
hydrochloric acid, 5 N solution;
hydrochloric acid, O. 1 N solution;
sodium hydroxide, 5 N solution standardized by titration with
standard 5 N hydrochloric acid by the usual chemical standardiza-
tion procedure;
iron chloride, 3% solution in O. 1 N solution of hydrochloric acid.
(4)
(5)
(6)
Collection of the sample:
(7)
For the dete rmination of maximal single acetate. concentra~ion, aspirate"
the air for 30 minute s on the lee side of the source of dis charge using a U-
shaped absorber equipped with a porous glass filter No.1; place 4 ml of ethyl
alcohol into the glass absorber, and aspirate the air at the rate of 0.5 li/min;
avoid excessive absorber solution evaporation by submerging the absorber into
ice water; replace evaporated amounts by new absorber solution.
. For the determination of average 24-hour concentration aspirate the al,r
as above described twelve times for 20 minutes at 2-hour intervals. Keep the
absorber submerged into ice -water through the 24-hour collection period, and
replace amounts of evaporated absorbe r.
Analytical Procedure:
Prior to making analysis make sure that the volume of the absorber
solution was exactly 4 ml; if it is less than 4 ml add new absorber solution to
replace evaporation; shake well and place 1 ml into a colorimetric tube;
simultaneously set-up 7 similar colorimetric tubes and add solutions as in-
dicated in Table 1; make sure that all tubes contained the same volume of
final solution; add 0.25 ml of 20% hydroxylamine to all the standard scale tubes
TABLE I and shake. then add 0.25 ml
of 5N solution of sodium hydro-
xide; shake again and leave
stand for 5 min., then add to
each tube 0.25 ml of 5N hydro-
1,0 chloric acid, shake again and
add O. 7 ml of 3% solution of
10 ' iron chloride; shake well and
leave stand for 15 -20 min.
ST ANOARO COLOR SCALE FOR THE OETERMI NATI ON OF ACETONE
I T EST TUB E NO..
a It\213i4\S\6
MI OF STANIARI SOLUTION
MI OF ALCOHOl.
ACETONE IN 1.1
I ° 0,1 0,2' 0,4 0,6 0,8
, 1,0 0,9 0,8 0,6 0,4 0,2
o 2 4 6 8
"
- 108-
"""::" ,...>;:,~:,.,
.>:_~:,;..........
-------
until color fully develops, then make colorimetric comparison.
Calculation of results:
l5H of air was aspirated at 170 and 7'63 mm of mercury; adjustment to
standard temperature and pressure reduced the volum~, to 14.2 Ii. Only 1 m1
or 1/4 of the sample was used; colorimetric determination indicated that the
1 ml contained 211",of the acetate, or 2 x 4 = 8 IJ. in the enti,re sample; accord-
ingly, the acetate concentration in the air was:
8XlOOO / 3
= 557.611, orO.56mg m
14,2 ,..
DETERMINA TION OF DINYL
Principle of the method:
Dinyl components react with the nitration mixture forming nitro com-
pounds which react with alkalies producing a raspberry red color the intensity
of which is directly proportional to the dinyl concentration in the air. The
method is not specific, since' other aromatic compounds interfere with the
reaction. The sensitivity of the method is O. 5 /J. in 2 ml.
Apparatus:
An aspirator equipped with a porous glass filter No.1 and a flowmeter
registering 1 up to 2 Ii/min.; colorimetric tubes 110 mm high and 10-11 mm
in diameter, marked at 3 ml, with ground-to-fit glass stoppers; 25 ml burette;
1 ml pipett,e divided into 0.01 ml; 5 and 10 ml pipettes divided into 0.1 ml;
ice -cold water bath; porcelain dishes 5 -6 mm in diameter. .
Reagents:
(1)
(2)
Dinyl.
Nitration mixture 1 prepared as follows: .
dissolve 10 g of sodium nitrate desiccated at 800 in 100 ml
sulfuric acid of 1.80-1.82 sp.gr.
Nitration mixture 2, prepared by diluting nitration mixture 1 with
distilled wate r in 1:2 ratio;
Standard dinyl solution; prepare stock solution as follows:
place 10 ml of nitration mixture 1 into a 50 ml volumetric flask
and weigh on an analytical balance, then put in 2 -3 drops of dinyl,
mix and weigh again; add nitration 1 solution to the 50 ml mark.
The difference between the two weights represents the amount of
dinyl added; divide same by 50 thus obtaining the amount of dil!yl
contained in 1 ml of the final standard solution; now, add 10-15 ml
of nitration solution 2 to anothe r 50 ml volumetric flask and add a
volume of the stock dinyl solution which by computation contained
5 mg of the substance; mix and add nitration solution 2 to the 50 ml
mark; the final solution represents a standard which contained 100 IJ.
of dinyl in 1 ml of the solution;
-109-
(3)
(4)
-------
(5)
(6)
(7)
(8)
(9)
NaOH, 50% solution;
H2 S04 of 1. 80-.1.82 sp. gr.,
Freshly redistilled acetone colorless of 560 b. p.
Ether (C2H50C2 H5) of 350 b.p.
Ether saturated water prepared as follows:
place 5 ml of etner into a separatory funnel containing 20 mlof
water; shake for 5 mi.nutes and all9w to rest~ separa,te the water
which is now ethe r saturated; pre pare this solution on the day of
the air analysis.
Sample collection:
For the determination of maximal single dinyl concentration aspirate the
air for 15 minutes on the lee side of the discharge source using 1 aspirator
equipped with porous glass filter No.1 and containing 2 ml of nitration mixture
1; aspirate the air at the rate of 0.5 Ii/min.
For the determination of av'era;~e 24-hour concentration use the same air,
aspir2.tion procedure as above described repeated 12 times at 2-hour intervals"
thus representing 24 hours.
Analytical procedure:
Place 6 ml of water into a flask submerged into ice water; carefully
pour the absorbe r solution containing the air sample into the flask containing
6 ml of cooled water; rinse the absorber with 1 ml of water twice and add the
rinse water to the 6 ml of water; prevent the collected solution from becoming,
warm; pour the content of the collection flask into a separatory funnel and add
5 ml of ether; close the funnel with a ground-to-fit glass stopper and shake for
10 minutes; allovJ the funnel to rest; remove the lower layer of water and add to
the remain~ng ether layer 5 ml of ether-saturated water and shake for 5 min-
'-.ttes; acain allow the layers to separate and remove the separated ether into a
';mrcct..~n Ci.:::.h; C:<";>
-------
TABLE 2
7
pare the standard set as shown
in Table 2, then add 0.5 ml of
40% NaOH to all tubes; shake
and leave stand for 15-20 min.
until a raspberry-rose color
developes and make the colori-
metric determination. -
STANDARD SCALE FOR THE DETERMINATION OF DINYL
I TEST TUBE NO. -
011121314151 ~I
I
MI OF STANDARD IINYL 0,05 0,1 0,2 0,4 0,6 0,8 1,0
ESTER SOLUTI ON 0
MI OF ETHER 1,0 0,95 0,9 0,8 0,6 0,4 0,2 U
MI OF ACETONE 1,0 \,0 1.0 1,0 1,0 1,0 1.0 1,0
DINYL CONTENT IN ~ 0 0,5 1 2 4 6 8 10
Calculations of results:
Assume tbat the volume of aspirated air adjusted to standard tempera-
ture and pressure was 6.3 1i; the entire sample was taken for the final analysis;
colorimetric comparison indicated that the sample contained I ~ of dinyl; accord.
ingly, the dinyl concentration in the air was as follows:
1 X 1000 3 3
6,3 :ro;: 160.1 /Jim, or 0.16 mg/m
DET ERMINA TION OF ISOPROPYLBENZENE
Principle of the m-ethod:
Isopropylbenzene is first nitrated and the nitration compounds extracted
with ether or with butanone. The extract solvent is evaporated and the residue
dissolved in ethyl alcohol. The solution is then alkalinized for the production
of a primary yellowish-orange color, the intensity of which will be proportion-
al to the concentration of isopropyl benzene in the sample. Tp.e method is n~t-
specific since othe-r aromatic compounds inte rfe re with the reaction. The
method sensitivity is 1 J.L in 2 ml. It should be noted here that the addition
of alkali during the nitration of isopropylbenzene with butanone may develop
a secondary rose color.
Apparatus:
A 5-6 1i aspirator; absorbers equipped with porous glass filter No. l.
10 mm in diameter; colorimetric tubes 110 mm high, 10 mm in diameter, -
marked at 2 m1, with ground-to-fit glass stoppers; pipettes of 1-2 ml divided
into 1. 01 m1; pipettes 5-10 m1 divided into 0.1 ml; separatory funnels of 50-75
m1; assorted reagent bottles.
Reagents:
(1)
(2)
Isopropyl benzene , C 6 H 5CH(CH ) 2;
Standard solution of isopropylbJnzene prepared as follows:
place 8 -15 ml of nitration mixture into a 25 -50 ml volumetric
flask and weigh on an analytical balance; add 2-3 drops of isopropyl-
benzene and weigh again; then add nitration mixture to the 25 or 50
m1 mark, as the case may be. The diffe rence between the 2
weighings represents the weight of the added isopropylbenzen~;
this divided by either 25 or 50, as the- case may be, will represent
-111-
-------
th,= amount of isopropylbenzene per ml of the standard solution. Use another
50 ml of volumetric flas k and add 10 ml of nitration mixture and a volume of
isopropylbenzene solution which contained 5 mg of the reagent; mix and place
over a boiling waterbath for 1 hour; cool and add nitration mixture to the 50 ml
mark; 1 ml of this final solution will contain 0.1 mg of isopropylbenzene;
(3) Nitration mixture prepared as follows:
dissolve 10 g of ammonium nitrate desiccated at 800 in 100 ml
of sulfuric acid having a sp. gr. of 1. 82-1. 84;
Ethylol; .
Ethyl ether orbutanone (methylethylketone) freshly prepared;
Sodium hydroxide, 40% solution.
(4)
(5)
(6)
Collection of samples:
For the dete rmination of maximal single concentration aspirate the air
for 20 minutes on the lee side of the pollution source, using a' U -shaped ab-
sorber, 10 mm in diameter equipped with a porous glass filter No.1 and con-
taining 1 ml of the nitration mixture. Aspirate the air at the rate of 0.5 Ii/min.
For the determination of the average 24-hour concentration aspirate the
air as above described, 12 times at 2-hour intervals at a rate of 0.2 li/min.
Analytical procedure:
Extraction of the nitro compound with ether.
Submerge the sample into a boiling water bath for 1 hour and cool;
pour the entire sample into an Erlenmeyer flask; submerge the flask into a
cold water bath; rinse the U -shaped absorber several times with water not to
exceed 6-8 ml; pour the rinse water into the Erlenmeyer flask; remove the
flask from the cold waterbath and pour its contents into a separatory funnel
equipped with a ground-to-fit glass stopper; shake the mixture for 10 min. and
allow the laye rs of liquid to thoroughly separate; remove the lowe r laye r through
the long stem of the separatory funnel and add to the funnel 5 ml of water and
. shake again; allow the layers to separate again; remove the lower layer as de-
scribed above and pour the upper layer through the funnel neck into a procelain
dish; evaporate the ether at room temperature and dissolve the residue in 2 ml
of alcohol; pour this into a colorimetric tube marked at 2 ml. Simultaneously
prepare the color scale as follows: add 1 ml of the standard solution and 1 ml
of the nitration mixture to either a 50 or 100 ml Erlenmeyer flask; mix and
cool, then carefully add 8 -10 ml of water. Now, pour this mixture into a sepa-
ratory funnel, add 5 ml of ether and shake for 10 minutes; allow the mixture to
rest until liquid layc 1:"S completely separate; remove the lower layer carefully
through the long sLc:n of the funnel; add 5 ml of water; shake and again allow
the laye rs to completely separate. Re move the lowe r layer as previously de-
scribed and the upper layer through the funnel neck into a porcelain dish and
allow to evaporate at room temperature. Dissolve the dry residue in alGohol
and pour into a test tube marked at 10 ml; rinse the porcelain dish several
times with s mall amounts of alcohol, adding the rinse to the 10 ml tube; add
alcohol to the 10 ml mark. This is the standard alcoholic solution 1 ml of which
contains 0.01 mg or 10jl of isopropylbenzene. Prepare the standard scale using
-112-
-------
HI OF STANDARD ALCOHOL
SOLUTION
MI OF ALCOHOL
ISO'RO'YL8ENZENE CONTENT
u/l
- 0,1 0.2
2 1.9 1.8
o 1,0 2,0
0,4
1.6
0.6
1,4
6,0
this solution as indicated in
TAB LE 3
Table 3. Add to each of the
tubes O. 1 ml of 40% NaOH
solution; shake the tubes . well,
and leave rest for 15-20 min.
for the development of a yellow-
0.8 1.0 ish-orange color, the intensity
1.2 1,0 of which is directly proportion-
8,0 10,0 al to the isopropylbenzene con-
centration.
5 I
6
STANDARD SCALE'FOR THE DETERMINATION OF ISOPROPYLBENZENE
I 0 I 1 I 2 TIE 513 TUtE :°81
4,0
, STANDARD SCALE FOR THE DETERMINATION OF ISOP~OPYLBENZENE.
I TEST TU8E tlO.
0/1/2/3/4/5161
Extraction of the nitrated compounds with 'butanone:
Submerge the samples for 1 hour into a boiling waterbath; remove; cool
and transfe r from the absorbe r into an Erlenmeye r flask submerged into an ice-
cold waterbath; rinse the absorber several times with a total of 4-6 ml of water
and carefully add to the Erlenmeyer flask; remove the cooled solution and neu-
tralize with 25% of ammonia using litmus paper as the indicator; neutralize with
the the aid of a special burette preventing over heating of the solution. Pour the
neutralized sample into a separatory funnel; add 2.2 ml of butanone and shake
for 5 minutes; leave the solution rest until layers are well separated; remove
the lower layer through the long stem of the separatory funnel and the separated
upper layer through the funnel neck into a colorimetric tube, marked at 2 ml;
add butanone to the 2 ml mark.
At the same time prepare the standard scale as follows: place ,I ml of the
standard solution and 1 ml of the nitration mixture into an Erlenmeyer flask sub-
merged into ice-cold water, followed by the addition of 8-10 ml of distilled water;
after the solution has cooled neutralize it with 25% ammonia using litmus paper
as the indicator; pour the cooled and neutralized solution into a separatory funnel,
add 10 ml of butanone and shake for 10 minutes; leave rest until layers are well
separated; remove the lowe r laye r through the long -ste m of the funnel; add to
the funnel 5 ml of water and shake again; allow to separate into layers; again
re,move the lower layer through the long stem of the funnel and the upper layer
through the funnel ne ck into a colori metric tube equipped with a ground -to -fit
glass stoppe r marked at 10 ml. Add butanone to the 10 ml mark and mix. This
is the standard butanone solution, 1 ml of which contains 0.01 mg or 10 /l of
TABLE 4 isopropylbenzene. Using this
, standard prepare the standard
series as indicated in Table 4,
then add 0.5 ml of 40% of NaOH
1 to each of the tube s; shake and
leave rest for 15-20 minutes
until a rose -color develops. This
color is then compared with the
colors of the standard scale.
HI OF STAtiDARt SOLUTIOti 0 0,05 0,1 0,2 0,4 0,6 0,8 1,0
MI OF 8UTANOL 2 1,95 1,9 1,8 1,6 1,4 1,2 1,0
ISO,RO'YLBENZENE COIITEHT 0 0,5 1 2 4 6 8 10
IN IJ.
.-
-113-
-------
Calculation' o~ results:
Assume that the volume of air aspirated through the, absorber adjusted
to standard temperature and pressure was 7.2 Ii. The entire sample was used
In the determination; colorimetric comparison showed that it contained 2/1;
accordingly, the isopropylbenzene concentration in the atmospheric air was:
2 X 1000 -
7,2 -
3 3
/m or 0.278 mg/m
277.7
DETERMINATION OF STYROL
Principle of the method:
The styrol is nitrated and the nitrated product neutralized with ammonia.
imparting to the solution a yellowish color. The reaction is as follows:
CaH6CH = CH2 + HNO, - CaH~CH = CHN02 + H2()'
The method is not specific, since other aromatic compounds interfere with the
reaction. The method sensitivity is 1/.1. in 4 ml.
Apparatus:
U -S4aped absorber equipped with porous glass filter No.1 10 mm i.n dia-
meter. Colorimetric tubes 110 mm high, 13 mm in diameter, marked at 5 ml.
Pipettes 1-2 ml divided into 0.01 ml. Pipettes 5-10 ml divided into 0.01 ml.
Erlenmeye r flasks of 50 -10 ml capacity. Thermomete r. Burette s, 25 ml.
Reagents
(1)
(2)
Styrol;
Nitration mixture prepared as follows:
dissolve 10 g of ammonium nitrate desiccated at 800 in 100 ml
H2 SO 4 of 1. 82-1. 84 sp. gr.
Acetic acid, 80-100% solution;
Standard styrol solution prepared as follows:
place 10-15 ml of acetic acid into a volumetric flask 25 or 50 ml
and weigh on an analytical balance. then place into the same flask
2-3 drops of styrol and weigh again; the difference between the 2
weights represents the weight of the added styrol, on the basis of
which it can be dete rmined how much of the styrol was contained
in 1 ml of the final solution. Use this solution for the preparation
of the standard as follows:
pour into another 50 ml volumetric flask 15-20 m1 of acetic acid;
add an amount of the previously prepared solution containing 5 mg
of the styrol, and add acetic acid to the mark; 1 ml of this solution
should contain O. 1 mg of styrol.
Ammonia, 25% solution.
Litmus paper.
(3)
(4)
(5)
(6)
-114-
-------
Sample collection:
For the determination of maximal single concentration aspirate the air
for 20 .mi.nutes on the lee side of the discharge s~)Urce through a U -shaped
absorber equipped with porous glass filter No.1 of 10 mm diameter and con-
taining 1 ml of the nitration mixture; aspirate the air at the rate of 0.5 Ii/min.
For the determination of average 24-hour concentration aspirate the air
for 10 min. as above described, 12 times at 2-hour intervals, which will
represent 24 hours.
Analytical procedure:
Place 0.5 ml of the absorbed sample into an Erlenmeyer flask contain-
ing 2 ml of water. To prevent the solution from becoming overheated sub-
merge the Erlenmeyer flask into ice cold water. Prepare the standard scale
as shown in Table 5 using a simi.lar Erlenmeyer flask. Carefully neutralize
the contents of all tubes by ammonia, using a drop burette until the solutions
acquire a slightly alkaline reaction, as indicated by litmus paper and com-
pare colorimetrically as usual.
Calculation of results:
Assume that the aspirated aIr
-~-- -.- ---..
I 0 I 1 I 2 I : Klt" 4 I 5 I. 6
-. )0.0!!0.02J 0.04) O.o~ I 0.081 0.10.
- 0..)1 0.5 0.5 0.0" 0.5 0.5
SHAKE WELL AUD LEAVE REST fOR ~IO MIN-
UTES, THEN CAUTIOUSLY ADD TO ALL TUDES
2 ML Of WATER
- ° r" "Il 2 I 4"/. 6 r - 8 T 10"
4 X 1000 =- 445. 5-11 /m 3,
.8,98
volume adjusted to standard temperature
TABLE 5 and pressure was 8.98 Ii.
Only 1/2 of the sample was
taken for colorimetric com-
parison which contained 21..l
of styrol, accordingly the
entire sample contained 41..l
of styrol, and the concen-
tration of styrol in the air
was as follows:
STANDARD SCALE FOR THE DETERMINATION OF STYROL' -
..- . --'--...-.-
-,- ---~~_. --- ------- --- ----- ---
----
- -<-" -.--.-.-... --
HI OF STANDARD iOLUTION,
HI OF niTRATION MIXTURE
. - "
STYROL conTENT I" I..l
3
or 0.46 mg/m
DETERMINATION OF ACETONE
Principle of the method:
Acetone reacts with iodine in alkaline solution forming iodoform, the
concentration of which can be determined nephelometrically. The reaction
is as follows:
CH.COCH. + 3J2 + 4NaOH ~ CHJ. + CH.COONa + ~NaJ + 3H20.
The method is specific; however, large volumes of alcohol and aldehyde inter-
fer with the reaction. The sensitivity of the method is III in 4.5 ml.
-115-
-------
Apparatus:
U -shaped absorber equipped with porous glass filter No.1; 5 liter
aspirator; volumetric flasks of 50 and 200 ml; 100 m1 cylinder graduate;
25 ml burette; one ml pipette divided into 0.01 ml; colorimetric tubes 110 ml
high and 10 mm in diameter; ice-cold waterbath,.
Reagents: .
Distilled water for use as absorber;
,KOH, 50% solution;
Iodine, O. 1 N solution;
.dissolve 15 g of Kl in 12-15 ml of water, when the potassium
iodide is completely dissolved add the 12.7 g of resublimed
iodine, and when the latter is completely dissolved pour into a
1000 ml volumetric flask and add distilled water to the 1000 ml
mark;
Standard acetone solution prepared as follows:
use chemically pure redistilled acetone; add 2-3 drops of the
acetone to a previously weighed volumetric flask containing
some water; weigh again and add water to the 1000 ml mark;
use this iodine solution for the preparation.of standard solution
A containing 0.1 mg of acetone per 1 ml; prepare standard solu-
tion B, containing 0.01 mg of acetone per 1ml from standard
solution A by 1:10 dilution; standard solution A will keep for 1
.' month, while standard solution B should be' r.enewed every 3 days.
Collection of air samples:
(1)
(2)
(3)
(4)
For the determination of maximal single concentration aspirate the air
for 20 minutes at the rate of 0.5 li/min through a U -shaped absorber equipped
with a porous glass filter No.1; the U -shaped absorber should contain 4 ml of
dis tilled wate r.
For the dete rmination of ave rage 24 -hour concentration aspirate the
aiJi" 40 mi~. through the absorber containing 4 ml of distilled water at the
rate of 0.25 li/min 12 times at intervals of 2 hours.
Analytical procedure:
Place 2 ml of the sample containing absorber solution into a colorimetric
tube. Prepare a 7 tube standard scale as indicated in Table 6. Add to the
. TABLE 6 . sample tube and to the standard
scale tubes 1.5 ml of 50% KOH
and 1 ml of O. 1 N iodine solu-
tion; mix; in the presence of
acetone a turbidity will develop
in the sample -containing test
tube within 5 minute s; compare
the developed intensity with
that of the standard scale using
a dark background. Make nephelometric c'omparison within i hours.
-116-
STANDARD SCALE FOR TiiE DETERMINATION OF ACETONE
. I ° 11 I 2 T,EST3 TU,DE :°-1
5 I
6
HI OF STANDARD SOLUTION
B
MI OF WATER
ACETONE CONTENT IN IJ.
- 0,1 0,2 0,4
2 1,9 1,8 1.6
012 4
0,6
1,4
6
0,8
1,2
8
1,0
1.0
10
-------
Calculation of results:
Assume that the volume of aspirated air after adjustment to standard
temperature and pressure W!iS 9.5 Ii. Only half of the sample was taken for
analysis, and it contained 2 p, of acetone, which means that the entire sample
contained 4 p,. Accordingly, the acetone concentration in the air was:
.4XlOOO 429 p" or 0.43 mg/m3
9,5
DETERM[NATION OF ACETOPHENONE VAPOR
Principle of the method:
The method is based on the formation of a rose -colored substance as
the result of acetophenone reaction with metadinitro benzene in alkaline med-
lum. The color intensity is compared with that of a standard color scale.
Benzene, isopropylbenzene, isopropylbenezene hydrope roxide, Q'-methylstyrol,
dimethylphenylcarbonol and phenol do not interfere with the reaction. Acetone
in amounts exceeding 100 J.L interferes with the reaction. The reaction sensi-
tivity is 0.5 P, in 2-3 ml.
Apparatus:
U-shaped absorber equipped with a porous glass plate No.1 or a modi- .
fied Zaitsev absorber. Colorimetric test tubes of 2-3 ml. Colorimetric test
tubes of 5-10 ml. Pipettes of 1-2 ml divided into 0.01 ml. Pipettes of 5-10 ml
divided into 0.1 ml. Volumetric flasks of 25-100 ml capacity. A Kachora
apparatus for sample collection. A Petri absorber with a shortened inside tube.
Reagents:
(1)
(2)
Ethyl alcohol used as the absorber;
Acetophenone, standard solution in ethyl alcohol containing 1 mg
per 1 ml; also a standard solution containing 100 and also 10 p, per
1 ml, prepared immediately before the determination by dissolving
the stock standard solution with alcohol in proper ratios;
M-dinitrobenzene, 1% solution in alcohol containing 0.1 g in 10 ml;
KOH, 30% aqueous solution;
ASM silicagel, 0.25 -0.5 mm granules; wash the silicagel in a
mixture of concentrated hydrochloric and nitric acids, followed
by distilled water until the Cl and N03 are completely removed from
the solution, as indicated by tests with silver nitrate and with
diphenylamine; wash the silicagel, and activate it in a muffle
furnace for 20-30 minutes at 4000; store in a glass bottle with
a ground-to-fit glass stopper.
(3)
(4)
(5)
-117-
-------
Collection of samples:
The tested air can be aspirated through liquid or solid absorbing media.
(1) Aspirating the air sample through ethyl alcohol.
For the determination of maximal single concentration
aspirate the air for 30 minutes on the lee side of the
pollution source through 2 U -shaped absorbe rs 10 mm
in diameter equipped with porous glass filter No.1 and
containing 3 ml of alcohol; aspirate the air at the rate
of 1 Ii/min with the absorbers covered with crushed ice.
For the determination of average 24-hour concentra-
tion aspirate the air through I absorber for 20 minutes
12 times at intervals of 2 hours at the rate of 0.2 Ii/min.
(2) Aspirating the air through silicagel. For the deter-
mination of maximal single concentration aspirate the
air through a modified Zaitsev absorber, such as is
illustrated in Fig. 1; fill the Zaitsev absorber with 2 g
of ASM silicagel; aspirate the air for 10 minutes at the
rate of 10 Ii/min.
Analytical procedure:
For final determination place 2 ml of the sample -containing alcohol into
a colorimetric tube; then prepare the standard color scale as shown in Table 7;
TABLE 7 bring the volumes of all test
tubes to the same level, and
add to each O. 1 ml of the
metadinitrobenzene followed
by O. I ml of the KOH solutlOn
and then by O. 1 ml of distilled
water; compare the developed
red color after shaking with the
~ colors of a standard scale; in
the case of siIicagel collected air samples proceed as follows: remove the
silicagel from the absorber tube into a test tube equipped with a ground-to-fit
stopper and add 4 ml of alcohol; shake vigorously several times in the course
of 30 minutes, then take 2 ml of the clarified eluate and proceed with the dete r-
mination the same as was described for the alcohol absorber.
" i
:. ~
I j: ~
, ,
FIe. I - MOIIFIEI ZAITSEV
ABSOR8ER
.'
STANDARD SCALE FOR THE DETERMINATION OF ACETOPHENONE
, OF STANIARI SOLUTIO. I
(I 111 = IO~) 0 0,05 0,10,2 0,4 ''ToR 1,0 1.2 1,6 2,0
I OF ETHYl ETHER 2 1,95 1,9 \,/j 1,6 1,4 1,2 1,0 0,8 0,4 0
ACETOPHENONE CONTENT
III . 0 0,5 1 2 4 6 8 10 12 16 20
I 0 I
M
M
TEST TUSE No.
J I 2 I 3 I ~ I 5 I 6 I 7 I 8 I 9 110
f=:alculation of results:
Assume that the volume of aspirated air after adjustment to standard
temperature and pressure was 9 li; 2 ml, or 2/3, of the sample was taken for
the final determination, and it contained 2 ~of the acetophenone, which means
that the entire sample contained 3 ~ of acetophenone; the second absorber'
-118-
-------
.' .
developed no color, indicating that it was free from acetophenone; accordingly,
the acetophenone concentration in the air was:
3 X 1000
9
3
333.3/J or 0.333 mg/m
DETERMINA TION OF 0' -METHYLSTYROL
Principle of the method:
(Y-methylstyrol is nitrated by, a mixture of nitric and acetic acids at
1000, after which the solution is neutralized with ammonia as a result of
which a yellow color develops. The reaction can be represented as follows:
CeH~C(CH.) = CH~ + HNO. .:,CeH;,C(CH.) = CH - NO~., + H20
The intensity of the developed color is compared with that of the standard
scale. The method is not specific, since phenol interferes with the reaction.
The sensitivity of the method is 1 /J in 4. 5 ml.
Apparatus:
U -shaped absorber equipped with porous glass filter No.1 of 10 mm
diameter; modified Zaitsev absorber; colorimetric tubes 110 mm high and
13-14 mm in diameter; pipettes of 1-2 ml divided into 0.01 ml; pipettes of.
5-10 ml divided into 0.1 ml; pipettes of O. 1 - 0.2 ml divided into 0.001 ml;'
Erlenmeyer flasks 50 ml capa~ity; distillation flasks; burettes of 25-50 mt;
Kachora apparatus for sample collection of 5-6 Ii capacity; Petri absorber
with a shortened inside tube.
Reagents:
(1) (y -m'~thylstyrol, freshly distilled, of 162-1640 b. p.;
(2) Nitration mixture' consisting of nitric acid 1. 4 sp. gr. and glacial
acetic acid, in 1:1 ratio, or in equal volumes;
(3) Standard solution of (y -methylstyrol. Prepare the' stock solution
as follows:
place 10 -15 ml of glacial acetic acid into a 25 or '50 ml volumetric
flask and weigh on an analytical balance; add'3-4 drops of (Y.-methyl-
styrol and weigh again; the difference in the weights represents the
amount by weight of the 0'. -methylstyrol; now, add acetic acid to the
volumetric mark; compute the amount of a -methylstyrol in 1 ml;
from this stock solution; prepare the final standard solution as
follows: place 10-15 ml of the nitric and acetic acids mixture
into another 50 ml volumetric flask and add a volume of the stock
solution which contained 5 mg of the methylstyrol; place over a
boiling waterbath. for 15 minutes; cool and fill to the mark with
the mixture of the 2 acids; this is the final standard solution, 1 ml
of which contains O. 1 mg of CI. -methylstyrol;
-119-
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(4)
(5)
(6)
(7)
Ammonia, 250/0 solution;
Acetic acid, 98% solution;
Litmus paper as indicator;
Silicagel of trademark ASM granulated, 0.25-0.55 mm size; wash
the silicagel in a hot solution of hydrochloric acid, followed by wash-
ing in a solution of nitric and glacial acetic acid in 1:1 ratio; wash
with tap water, followed by distilled water until all chlorine and NO
ions completely disappear as shown by tests with silver nitrate and 3
diphenylamine; dry the silicagel at 100-1050 and activate in a muffle
furnace for 20 -30 minutes at 3000; store the activated silicagel in a
glass bottle with a ground-to-fit glass stopper.
Sample collection:
(1) The air can be aspirated through liquid or solid media for 30 minutes
on the lee side of the discharge source. Use a U -shaped absorbe r 10 mm in
diamete r equipped with a porous glass filter No.1 and containing 1 ml of acetic
acid; aspirate the air for 30 min. at the rate of 0.5 Ii/min. For the determina-
tion of average 24-hour concentration aspirate the air for 10 min. as abov.e
described 12 times at 2-hour intervals at the rate of 0.5 li/min.
(2) ° Collection of air sample with silicagel. .For the determination
-------
Calculations of results:
ST ANp~~__~C~- LE- FOR__~~E--E~TiRMI NA II ~N__OF - (Y. .:-.M_~T_HY~~Y~O_L - .
I ° I 1 f 2 ITE63T JUBE. NOj 5 I
Assume that the volume of aspirated air adjusted to standard temperature
TABLE 9 and pressure was 9 Ii; only half
of this was used in the colori-
metric deteTmination which con-
tained2 p. of the ,y-methylstyrol;
accordingly,. the entire san:-ple
o 0,01 0,02 0,04 0,06 0,08 0,10 contained 4#J. of the substance;
1 0,990,98 0,96 0,94 0,92 0,9 compute the concentration of
ry-methylsty.rol in the an as
follows:
4X1000 3
9 = 444,4 Ij, or 0.444 mg/m
6
MI OF .TANDARI .OLUTIOH
HI OF NITRATION MIXTURE
(y -METHYL.TYROL CONTENT
up.
o
2
4
6
8
10
~--~-- -
DETERMINATION OF ISOPROPYLBENZENE HYDR6-
PEROXIDE (IPBHPO)
Principle of the method:
Isopropylbenzene hydroperoxide is decomposed with sulfuric acid form-
ing phenol, which is dete rmined colorimetric ally with the aid of diazotized
paranitroaniline. The method is not specific, sit:lce phenol interferes with
the reaction; the sensitivity is 0.5 P. in 5 ml.
Apparatus:
Aspirator of 5-6 Ii capacity and a Kachora aspirator; U -shaped absorbers
equipped with porous glass filter No.1; colorimetric tubes marked at 5-10 ml
equipped with ground -to -fit glass .stoppers ;waterbath; volumetric flasks of
25, 50, 100 ml capacity; pipettes of 5, 10 ml divided into 0.1 ml; pipettes 1,
2 m1 divided into 0.01 ml; thermometer. 1000.
Reagents:
(1)
Standard solution of IPBHPO prepa red as follows:
place 10 or 15 ml of ethyl alcohol into a 25 ml volumetric flask
and weigh; add 2 or 3 drops of the IPBHPO and weigh again; add
alcohol to the 25 ml mark; compute the amount of IPBHPO in 1 ml
of the prepared solution; this is the stock solution; prepare the
working standard solution as follows: add to a 100 ml volumetriC
flask as much of the stock solution previous ly prepared which will
make a final standard solution containing 0.01 mg of the IPBHPO
per 1 ml; add 0.5 ml of alcohol, 1 ml of distilled water, 2 ml of
H SO of 1. 84 sp. gr. and heat over a waterbath for 1 hour keep-
in~ tJe flas k in an inclined position, and cove red with the glass'
stopper in the reverse position; remove and slowly add water to
the 100 ml mark;
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(2) Ethyl alcohol (C2HSOH);
(3) Sodium carbonate, saturated soltuion and 0.8% solution;
(4) Hydrochloric acid of 1. 19-1. 16 sp. gr.;
(5) Sulfuric acid of 1.84 sp. gr. ;
(6) . Nitric acid, 25% solution;
(7) Diazotized paranitroaniline, prepared as follows:
place .50 ml of wate r into a flask and add 2. 5 ml of hydrochloric
acid, 2.5 ml of nitric acid and 0.01 g of paranitroaniline and. mix
thoroughly;
(8) Absorber solution, prepared by diluting 1 part of alcohol with 2
parts of wate t;
(9) Silicagel of trademark AS.M, granular 0.25-0.5 mm; wash the
silicagel with 50% solution of hydrochloric acid heated to 800 for
3-4 hours or until the yellow color disappears; place the silicagel
into suction funnel and wash with tap water fqllowed by distilled
water until all chlorine ion disappears, as indicated by the silver
nitrate test; dry the silicacfel at 1050 and activate for 20-30 min.
in a muffle furnace at 400 ; cool the activated silicagel and store
into a glass bottle closed with a ground-to-fit glass stopper.
Collection of samples:
For the determination of maximal single concentration aspirate the air
for 20 minutes on the lee side of the air pollution source through a U -shaped
absorbe r 10 mm in diamete r equipped with a: porous glass filte r No.1; the
absorbe r should contain 3 ml of. the ab.sorbe r solution; aspirate the. air at the
rate of O. 5 Ii/min.
For the dete rmination of 24 -hour ave rage concentration aspirate the air
for 20 minutes at the rate of 0.5 li/min 12 times at 2-hour intervals. Keep
. .
the absorber solution volume constant by replacing any that may have evap-
orated. The air sample can also be aspirated through the silicagel described
under No.9 above:; place 2 g of the silicagel into a modified Zaitsev absorber
anp aspirate the air for 10 minutes at the rate of 10 Ii/min.
Analytical procedure:
I TE~~ TUDE No.
. 0/11213/415/61718
MI..OF-6TANUARII SOUlT-IONi\O /0.0510.1 .10.210.410.610.8 .ll. 12
SATURATED 60LUT I ON 0' . ..- - - - -, -
60tlUM CAR'ONATE . :BEFORE NEUTRALIZATIO~ ,
O.~ 608. CAR80NATE sou. . . U~ .TO. 5 I}I. -- .
. :'PBHPO COIITEIIT III f..L I 010,5 )1,0 )2.0 }4.0 16.0 /8,0 110,0120,0
Place 2 ml of the absorber solution into a colorimetric tube and add
0.1 ml of sulfuric aCid of 1. 82-1. 84 sp. gr.; submerge into a water bath heated
------- - --_--h - - -... T~:B.LE 10 to 70-800 for 1 hour; place the
tube in an inclined position and
STANDARD SCALE FOR THE DETERMI NATION OF ISOPROPYLBENZENE HYDRo..
PEROXI DE cove r with the glass stoppe r in
- the reverse position; re move
the tube, cool and neutralize
with sodium carbonate, using
litmus paper as the indicator;
neutralize the solution very
slowly adding the sodium car-
bonate 1 drop at a time; add
0.8% of the soda solution to the
-~..~. ._- - -...-
... .- - -. ~
-122-
-------
5 ml mark; at the same time prepare the standard color scale, as shown in
Table 10. (see page 122).
In the case of the silicagel aspirated air sample, proceed as follows:
remove the silicagel from the Zaitsev absorber into a test tube equippeci with
a ground-to-fit glass stopper and add 4 ml of alcohol; carefully shake several
times in the course of 30 minutes; place 2 ml into a colorimetric tube and add
0: 1 ml of sulfuric acid; submerge into a 'waterbath heated to 70-800 for 1 hour;
from this point proceed as described above; the volume in the tube containing
the sample solution should be the same as the volumes in the standard scale
test tubes; now add O. 1 ml of the diazotized ,paranitroaniline solution; shake and
'let stand for 15-20 minutes; then make colorimetric comp'arison.
Note: In the presence of phenol in the air divide the test sample into 2
equal parts; determine the phenol in 'I part of the sample by adding 0.8% solu-
tion of soda and O. 1 ml of the diazotized paranitroaniline; analyze the second
half of the sample as previously described. Determine the amount of IPBHPO
in each half of the sample; subtract the smaller amount from the larger; the
difference represents the amount of IPBHPO in the air.
Calculation of results:
Assume that the volume of air aspirated adjusted to normal temperature
and pressure was 18.4 H; 2/3 of the sample was used in the analysis which con-
tained III of phenol; hence, the entire sample contained 1. 511 ; convert the
phenol to hydroperoxide as follows: 1. 5 x 1. 627 = 1. 441l ; accordingly, the
concentratlon of IPBHPO in the air was as follows:
144)(}Ooo . / 3 / 3
. , =78.25 mkg m or 0.0783 mg m
18,4
DETERMINA TION OF FURFUROL
Pr,inciple of the method:
Furfurol reacts with aniline to form furfuraniHne.
as follows:
The reaction proceeds
C5H402 + 2C6 H5NHz -+C 17H 1802N2
In the presence of acetic acid the solution acquires a rose-color. The intensity
of the color is compared with color intensities of a standard scale. The method
is not specific in the presence of formaldehyde, isopropylalcohol and other high-
er alcohols; these substances do not react with aniline but they do react with
furfurol and may color the solution. Sensitivity of the method is 0.25 Il in 2 ml.
Apparatus:
Aspirator of 5 or 6 Ii capacity, or Kachora aspirator; U -shaped absorbers
equipped with porous glass filter No.1; pipettes of 5 and 10 ml divided into 0.1 ml;
pipettes of 1 and 2 m1 divided into 0.01 ml; pipettes of O. 1 and 0.2 ml divided
into 0.001 m1; volumetric flasks of 50 ml capacity; tubes volumetric 50 ml;
-123-
-------
tubes colorimetric marked at 2 and 3 ml, 50 mm high and 11 mm in diameter;
burettes, 5 and 10 ml; reagent bottles, assorted.
Reagents:
Absorber solution, prepared by diluting 1 volume of ethyl alcohol
with an equal volume of distilled water;
Standard solution of furfurol prepared as follows:
place 10 or 15 ml of th~ absorber solution into a 25 or 50 ml
volumetric flask; weigh on an analytical balance, then introduce'
2 or 3 drops of furfurol, and we.igh again; the difference represents
the weight of added furfurol; add absorber solution to the mark;
mix; divide the amount of ~urfurol by the ml capacity of the volu-
metric flask; the result represents the amount of furfurol per 1 ml
of the final solution. Prepare standard solutions A and B as follows:
use two 50 ml volumetric flasks; mark one flask A and the othe r
flask B; add to flask marked A just enough of the previously pre-
pared furfurol stock solution so that upon the additiQn of alcohol
to the 50 ml mark each ml will contain O. 1 mg of the furfu:t"ol;
similarly, add to flask marked B an amount of the previously
prepared furfurol stock solution so that upon dilution to 50 ml
each 1 ml will contain 0.01 mg of furfurol. Solution B can also
be prepared by diluting solution A with distilled wate r to 1: 10;
Ethyl alcohol;
Acetic acid, 80% solution;
Solution of aniline in acetic acid prepared by placing 1 ml of aniline
into a test tube equipped with a ground-to-fit glass stopper marked
at 10 ml and adding 80% of acetic acid to the mark.
Collection of samples:
(1)
(2)
.(3 )
(4)
(5)
For the. dete rmination of maxi mal single concentration aspirate the air on
the lee side of the discharge source for 20 minutes through a U -shaped absorber
coptaining 4 ml of the absorber solution; aspirate the air at the rate of 0.5 li/
min; ke'ep the absorber solution volume constant by replacing amounts evapor-
ated; keep the absorber submerged in ice cold water during the air aspiration.
For the dete rmination of ave rage 24 -hour concentration, aspirate the air
through 6 ml of the absorber solution for 20 minutes at the rate of 0.2 li/min,
12 times at 2 ~hour intervals.
Analytical procedure:
Place 2 ml of the absorber into a colorimetric tube; prepare the standard
color scale at the same time as shown in Table 11 (see page 125); equalize
volumes in all tubes and add to the sample -containing tube 0.5 ml solution of
aniline in acetic acid; shake all tube s thoroughly but carefully and leave stand
for 5-10 minutes, then make a colorimetric comparison.
-124-
-------
Calculation of results:
" -
MI OF STAND ARI -
SOLUTION B - 0,025 0,050 0,075 0,1 0,2 0,4 0,6 0,8 1,
:MI OF ..SORIER I
SOLUTION ; 2 1,975 1,95 1,925 1,9 1,8 1,6 1,4 1,2 1,
FURFUROL CONTENT : 0 0,25 0,50 0,75 1 2 4 6 8 1
n1J. I
Assume that the volume of
aspirated air adjusted to st'L:.'
STANDARD SCAlE FOR THE DETERM!NATION OF FURFUR9l.. - "- .. dard temperature and pressure
"I TEST TUBE No. was 9.4 Ii. The sample absorb-
o I I I 2 I s I 4 I 51 61 71 81 9 er solution volume was 4 ml;
only 2 ml was taken for the
o analysis; colorimetric deter-
I mination has established 0.5 J.L '
o meaning that "I ~"w~~ "in -the
o total sample; hence, the furfurol
concentration in the air was as
follows:
1 X 1000 / 3
l06.4/1,or 0.106 mg m
9,4 ,..
TABLE II
DETERMINATION OF ETHYLENE OXIDE
Principle of the method:
Ethylene oxide is absorbed by sulfuric acid producing ethyleneglycol;
the latter is oxidized with hydriobic acid to form;~.1dehydet which is then deter-
mined colorimetrically afte r treatment with chromotropic acid. The method
is not specific, since formaldehyde and ethylglycol inte rfere with the reaction.
The sensitivity of the method is 0.5 J.L in 5 ml.
Apparatus:
A 5 or 6 li aspirator, or a Kachora aspirator; U -shaped absorbers equipp-
ed with porous glass filters No.1; pipettes of 1 and 2 ml capacity divided into
0.01; pipettes of 5 and 10 ml capacity divided into 0.1 ml; colorimetric tubes
marked at 5 and 10 rol; reagent bottles, assorted; volumetric flasks of 50 and
. 0
100 rol capacity; theromometer, 100.
Reagents:
(1) Absorber solution, which is a 40% sulfuric acid solution;
(2) Standard solution of ethylene oxide; prepare stock solution as
follows:
place 10 or 15 ml of 40% sulfuric acid into a 50 ml volumetric
flask and weigh; add 2 or 3 drops of ethylene oxide and weigh
again; add 40% sulfuric acid solution to the 50 ml mark and
thoroughly mix; compute the amount of ethylene oxide per 1 ml
of the solution; prepare standard solutions A and B so that 1 ml
of solution A would contain 100 1J. ' and one ml of standard solu":
tion B would contain 10 J.L of the ethylene oxide; the standard solu- "
tions can also be prepared from ethyleneglycol, in which case
-125-
-------
standard solution A should contain 140 f..L per 1 ml and standard solution B
should contain 14 f..L of ethylene glycol per 1 ml; these values correspond to 100
and IOu of ethylene oxide; .
(3) Potas sium oxyiodide (KI04) 2% solution in 40% H2S04 ;
(4) Sodium sulfite (Na2S03 7H20) 20% solution;
(5) Chromotropic acid prepared as follows:
dissolve 0.1 g of the acid in 2 ml of water in a 50 ml volumetric
flask; fill to mark with a 15 M. solution of sulfuric acid, (100 ml
of water + 900 ml of sulfuric acid of 1.82-1.84 sp.gr.)
Collection of samples:
For the determination of maximal single concentration aspirate the air
for 20 minutes on the lee side of pollution source through a U -shaped absorbe r
provided with a porous glass filter No.1; the absorber should contain 6 mlof
the absorption solution and aspiration rate should be 0.5 Ii/min.
For the determination of average 24-hour concentration aspirate the air
as above described for 10 minutes 12 times at 2-hour intervals and at the rate
of 0.5 Ii/min.
STANDARD SCAlE FOR THE DETERMI NATION OF ETHYLENE OXIDE
- .. -- -- - ..
~ --- - - ~---
I TEST TUllE No. ' '
0/112131415/61;]819
MI OF STANDARD 1 I I I I I I I
MfO~~T~ ~ULFURIC "CIII, 0 j'?'05 0,1 0,2 0'41 0.6, 0.81 ,Oj1.5:2,O
'ETHYLENE OXlaE CONTENT: 3 2,9512.9 2,8 2,6 2,4,2.22.°11,511,0
IN IJ. 0 0,5 1,0 2 4 6 8 10 15 20
Analytical procedure:
Place 3 ml of the sample absorber solution into a colorimetric tube. Use
exactly the same type of colorimetric tubes; prepare the standard color scale
as shown in Table 12; equalize
, volumes in all tubes, and add
0.1 ml of 2% potassium oxyiodide;
mix well and leave rest for 30 min.;
add to all tubes 2 ml of the chro-
motropic acid; then add sulfite to
redissolve the precipated iodine;
place all tube s into a boiling
water bath for 5 minutes until
a violet color develops; make
colorimetric comparison.
TABLE 12
Calculation of results:
Assume that the volume of aspirated air after adjustment to standard
temperature and pressure was 4.5 Ii. Only 1/2 of the sample was taken for
the determination, and it contained 1 IJ. of the ethylene oxide. Hence, the
entire sample contained 2 p. of the ethylene oxide. Accordingly, the 'ethylene
oxide in the air was as follows:
2XlOOO / 3
4,5 = 444.. 4 IJ., or 0.4444 mg m
-126-
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DETERMINATION OF TOTAL MONOBASIC CARBON-CONTAINING ACIDS
Principle of the method:
Monobasic fatty acids of the gene ral formula CnHtn + 1 COOH are con-
verted into their methyl esters, and the total of the complex esters thus formed
is determined with the aid of hydroxylamine and iron chloride. The re!?ulting
yellowish-brown color is then compared colorimetrically with a standard color
scale. The reaction is not specific in the presence of original complex esters.
The sensitivity of the method is 5 I-L in 3 ml.
c;--
---/
Apparatus:
An aspirator of 5-6 li capacity, or a Kachora electroaspirator equipped
with a flowmeter; absorbers equipped with porous glass filter No.1, 160 mm
high and 10 mm in diameter; colorimetric tubes equipped with ground-to-fit
. glass stoppers, marked at 5 and 10 ml; pipettes, 5 m1 divided into 0.1 ml;
pipettes, 1 ml divided into 0.01 ml; distilling g1asks of 250 ml capacity; flat
bottom or Erlenmeyer flasks; volumetric flasks of 25 or 50 ml capacity; assort-
ed reagent bottles.
Reagents:
, ,
(1) Absorber solution, in this case methyl alcohol; the alcohol is first
treated with sodium or potassium hydroxide as follows:
add 20 g of the hydroxide to 500ml of the alcohol and leave stand
for 3 hours with occasional stirring, then distill the alcohol at 650;
(2) Standard solution of monobasic fatty acids in methyl alcohol; prepare
the stock solution as follows:
place 10 or 15 ml of methanol into a 50 ml volumetric flask and
weigh on an analytical balance; add 0.2-0.3 ml of fatty acid and'
weigh again; the difference between the 2 weights represents the
weight of the added fatty acid; now, add methanol to the 50 ml
mark; shake well; compute the amount of fatty ~cids per ml of
this stock solution; from this stock solution prepare two standard
solutions of the fatty acids, one containing 1 mg/ml and the othe r
containing 0.1 mg/ml of the fatty acid; follow the same general
procedures as was previously described; ,
(3) Hydroxylamine hydrochloride, 200/0 solution prepared as follows:'
dissolve 20 g of the hydroxylamine hydrochloride in ~ small,
volume of water in a 100 ml volumetric flask; shake and add water
to the 100 ml mark; store in a cold room;
(4) Hydrochloric acid, O. 1 N. solution;
(5) Iron chloride, 60/0 solution prepared as follows:
add 6 g of iron chloride to a small volume of O. 1 N hYdrochloric
acid using a 100 ml volumetric flask; shake until dissolved and
add the hydrochloric acid solution to the 100 ml mark;
-127-
-------
(6)
(7)
(8)
Sodium hydroxide, 5N solution;
Hydrochloric acid, 5 N solution;
Phenolphthalein, O. 5% solution; (Note) Titrate the prepared 5N
solution of NaOH with 5N solution of hydrochloric acid with phenol-
phthalein as the indicator; if necessary, further adjust the NaOH
solution to the required degree of precision using the commonly
employed analytical titration procedure.
Sulfuric acid of 1. 82-1. 84 sp. gr.
Silicagel of ASM trademark of 1-2 mm granule size; wash the sili-
cagel in hydrochloric acid diluted with an equal volume of wate r
heated to 800 for 3-4 hours until the silicagel acquires a yellowish
tint; place the silicagel on a suction funnel and completely draw off
the adhering hydrochloric acid wash solution, then wash with tap
water, followed by distilled water until the chlorine ion has' com-
pletely disappeared, as shown by the silver nitrate test, then dry
the silicagel at 105-1100 and activate for 20-30 minutes in a muffle
furnace at 4000.. Store the silicagel in glass bottles equipp~q
with ground-to-fit glass stoppers.
Collection of samples:
(9)
(10)
For the dete rmination of maxi mal single concentration aspirate the air
for 20 minutes on the lee side of the pollution source through two U -shaped
absorbers of 10 mm diameter equipped with porous glass 'filter No.1 con-
taining 2 ml of the absorber solution. Aspirate the air at the rate of 0.5 Ii/
min. Keep the original solution volume constant by replacing amount evaporated
during the aspiration. Keep the a'bsorbers submerged in ice water during the
pe riod of aspiration. The air sample can also be aspi'rated through the pre - '
viously prepared silicagel using a modified Zaitsev absorber as previously
described. In this case the aspiration period should be 10 minutes and the
rate of lO Ii/min. .
An9-lytical procedure:
In this case the content of each of the aspirators is analyzed individually;
take 1 ml from each of the aspirators and place into each of two 10 ml colori-
metric tubes; at the same time prepare the standard color scale as shown in
Table 13; using the standard solution 1 ml of which contained 0.1 mg of the
acid; add 1 drop of sulfuric acid
: as specified under (9); mix all
tubes and leave stand for 30 min.
until the methylcarbonates (esters)
are formed; then add to all tubes
0.4 ml of the hydroxylamine,
followed by the addition of 0.4 ml
of NaOH solution. A white pre-
cipitate of sodium sulfate will
form which is insoluble in methyl
TABLE '13'
STANDARD SCALE FOR THE DETERMINATION OF SMAll QUANTITIES OF
,. . , , , CARBONACEOUS ACIDS
I TEST TUBE No.
I I 2 I 3 I 4 I 5 I
6 I
7
,
,MI OF STANDARD SOLIf.
; MI OF I1ETHANOL
ACI0S' CONTENT IN ~
o 0,05 0,1 0,2
1 0,95 0,9 0,8
o 5 10 20
0,3
0.7
30
0,4
0,6
40
0,5
0.,5
50
-128-
-------
alcohol, but which does not interfere with the formation of hydroxamic acids;
. l\::ave star.d fo:!." iO -15 minutes and add 0.4 ml of 5N solution of hydrochloric
acid; shake all tubes until the precipitate dissolves; now, add to all tubes O. '3
ml of 6% iron chloride solution; leave stand for 5 minutes until a brownish-
yellow color develops and make colorimetric comparison.
In the case of silicagel place the latter into a.tube equipped with a ground-
to -fit glass stoppe r and add 3 ml of methyl alcohol; shake well and leave stand
for 1 hour with occasional shaking; take 1 ml of this solution and follow the same
procedure as was outlined for the colorimetric measuremt~nt used in the case of
the methyl alcohol absorbe r.
Calculation of results:
Assume that the volume of aspirated air adjusted,to standard temperature
and pressure was 13.6 Ii. Only' 1 ml.was taken from each tube for the deter-
mination amounting to 1/2 of the sample. The colorimetric dete rmination in-
dicated that 2 ml taken from the first absorber contained 10 ,." of the acid, and
that the second absorber contained none of the acid, therefore, the acid concen-
tration in the air was: 20 X 1000 . 3
13,6 1472,.", or L 472 mg/m
. In the case of silicagel use only 1/3 of the sample for the determination.
DETERMINATION OF METHYLMETACRYLATE
Principle of the method:
Methylmetac rylate is hydrolyzed by alkali forming methylol; the latte r
is oxidized to formaldehyde which is then determined by the chromotropic
method. The reaction proceeds as follows:
CH2 = C - COOCH, + H20 ~ CH2 = C - COOH + CH,OH.
I I
CH, CH,
The method is not specific, since methyl alcohol and formaldehyde inte r-
. fe re with the reaction. Sensitivity of the method is 1 fJ. in 4 ml.
Apparatus:
An aspirator of 4-6 Ii capacity, or a Kachora electroaspirator equipped
with.a flowmeter. U -shaped absorbers equipped with porous glass filter No. .1.
Colorimetric tubes marked at 5 and 10 ml. Volumetric flasks of 25 and 50 ml
'capacity.. Pipettes of 5 and 10 mJ capacity divided into 0.1 ml. Pipettes
-------
Reagents:
(1)
(.2)
Absorber solution which is 2.5% solution of sodium hydroxide;
Standard solution. Prepare first the stock solution as follows:
place 10 or 15 ml of 2.5% sodium hydroxide solution into a 50 ml
volumetric flask and weigh on an analytical balance; add 1 or 2
drops of methylmetacrylate and weigh again; add 2.5% sodium
hydroxide to the mark; the diffe rence between the 2 weights divided
by ml of the volum~tric flask represents the amount of methyl-
. metac rylate contained in each ml of the solution; use another 50 mI.
volumetric flask for the preparation of the working standard solu-
tion; proceed as follows: place into the 50 ml volumetric flask a
volume of the previously prepared stock solution which would
contain O. 5 r:ng of methylmetac rylate; add the 2. 5% sodium hydroxide
solution to the 50 ml mark; each ml of the working standard solution
should contain 0.1 mg of the metacrylate;
Sodium hydroxide, 2.5% solution;
Sulfuric acid and distilled water in 1:1 ratio;
Potassium pe, rmanganate 2% solution;
Sodium sulfite, 30% solution; .
Chromotropic acid or its disodium salt; dissolve 0.1 g of the acid
in 2 mI of wate r in a 50 ml voluml~tric flask and add 15 N sulfuric
acid to the 50 ml mark; .
15 N sulfuric acid; place 10 ml of water into a glass flask; gradually
. .
and cautiously add to it 90 ml of sulfuric acid of 1. 82-1.84 sp. gr.
(3)
(4)
(5)
(6)
(7)
(8)
Collection of air samples:
For the determination of maximal single concentration aspirate the air
for 30 minutes on the lee side of the pollution source through two U -shaped
absorbe rs equipped with porous glass filte rs No.1; each absorbe r should con-
tain 4 ml of 2.5% NaOH; aspirate the air at the rate of 0.5 li/min.
For the determination of the average 24-hour concentration aspirate the
air through one absorber containing 6 ml of the alkaline absorber solution for
20 minutes at the rate of 0.2 Ii/min. 12 times at 2-hour intervals.
Analytical procedure:
- ... -
Analyze the content of each
: absorber separately; place 2
: ml of the solution from each
absorber into properly marked
colorimetric tubes; prepare the
standard color scale at the same
0,6 0,8 1.0 1,5 2.0 time, as shown in Table 14;
1.4.1.2 1,0 0,5 0 equalize the volumes in all the
6 81101520 tubes, and add to each tube 0.5
n ml of the 1: 1 sulfuric acid,
followed by the addition of 1 drop
T,1.BLE 14
STANDARD SCALE, FOR THE DETERMINATION OF METHYlJ'iEUCRYLATE ..
I T EST TUDE No.
01112131~15161718
MI OF STANDARD SOLUTIO" 0 0,1
MI OF ABSORDER SOLUT I ON I
METNYLHETACRYUTE COrO- : 2 1.9
TENT III J.l 0 1
0.2 0,4
1.8 1.6
2 4
-130-
-------
of permanganate; shake all tubes and leave rest for 5 - 10 minutes; then add
. to each tube 1 drop of the sulfite solution which should decolorize the solutions;
now, add to each tube 2 ml of chromotropic acid. submerge all tubes into a
boiling waterbath; remnve, cool and make colorimetric comparison.
Calculation of results:
Assume that the volume of aspirated air adjusted to standard temperature
and pressure was 13.4 Ii. Only 1/2 of the absorber solution was used in the
analysis which indicated that the 2 ml ai the solution in the first absorber: con-
tained 2 J..L ; accordingly, the methylmetacrylate concentration in the atmo-
spheric air was:
6 X.1Qoo = 448 or 0.448 mg/m 3
]3,4 J..L.
DETERMINATION OF DIMETHYLFORMAMIDE
ture
Principle of the method:
Dimethylformamide is hydrolized by alkaline solution at higher
according to the following equation forming dimethylamine.
(CH.)2N - C=O + NaOH - (CH.hNH + HCOONa.
I
H
tempera-
Dimethylamine reacts with 2,4- dinitrochlorobenzene resulting in a compound
which imparted to the solution a yellow color the intensity of which is directly
proportional to the concentration of the dimethylamine. The method is not
specific, since all amines inte rfere with the reaction, but polyacrylonitryl in
amounts not exceeding 10 mg does not interfere with the determination. Sen-
sitivity of the method is O. 5 J..L in 2 ml.
Apparatus:
One aspirator of 5 or 6 li capacity, or a Kachora electroaspirator equipped
with a flowmeter. A modified Zaitsev absorber. Colorimetric tubes marked at
5 ml. Pipettes of 5 and 10 ml capacity divided into 0.1 mJ. Pipettes of 1 and 2
ml capacity divided at 0.01 ml. Waterbath. Water pressure pump. Volumetric
flasks marked at 25 and 50 ml. Volumetric cylinders 25 and 50 ml.
Reagents:
(1) Absorber solution, which is 0.05 N hydrochloric acid;
(2) Dimethylformamide;
(3) . Standard solution of dimethylformamide: prepare stock solution
as follows:
place into 25
hydrochloric
or 50 ml volumetric flask 10 or 15 ml of 0.05 N
acid solution; weigh the flask and add 2 or 3 drops
-131-
-------
(4)
(5)
(6)
(7)
. 'of dimethylformamide and weigh again; the difference between the
2 weights represents the amount of weight of added dimethylform-
amide. Add O. 05 N of hydrochloric acid to the volumetric mark
and mix thoroq.ghly. The weight of the added dimethylformamide
'divided by the capacity of the volumetric flask in ml repr~sents
the amount of dimethylformamide contained in each ml of the stock
solution; now, take a volume of this stock solution which ~ontained
5 mg of the dimethylformamide and place into a 50 ml volumetric
. flask; add 0.05 N of hydrochloric acid to the 50 ml mark; mix well;
each ml of the last solution should contain 0.1 mg ,of the dimethyl-
formamide; mark the bottle containing this solution' A; prepare
standard solution B from standard solution A by taking 10 ml of
the solution and adding to it 90 ml of hydrochloric acid; 1 ml of
this solution should contain 0.01 mg of the dimethylformamide;
Hydrochloric acid, 0.01 N 3.nd 0.05 N solutions;
Sodium hydroxide ~r potassium hydroxide, 20% solution;
Crystalline sodium carbonate, 8% solution;
2,4 -dinitrochlorobenzene, 1 % alcoholic solution p~'epared by
warming the alcohol over a waterbath;
Hydrochloric acid, 0.25%;
Chloroform.
(8)
(9)
Collection of air samples:
For the determination of maximal single concentration aspirate the air for
20 minute s on the lee side of the pollution source through a modified Zeitsev
abs orbe r which contained 5 ml of the 0.05 N hydrochloric acid; aspirate the air
at the rat~ of 1 U/min. .
,O-'-r1E-THYLiORt1At1','BE ..coiiiENT./
.~. . III. IJ._, - -,. --.- - --- -.
Analytical procedure:
Add .to the absorbe r containing the aspirated sample 1 ml of 20% sodium
hydroxide; connect this absorbe r to anothe r Zeitsev absorbe r which contained
4 ml of 0.01 solution of hydrochloric acid; now, place the absorber containing
the absorbed sample ove r a boiling ring-type waterbath for exactly 5 minutes;
aspirate air through the absorbers at the rate of O. 1 li./min by means of a water
pressure pump. The dimethylformamide formed during the reacti~n will become
absorbed by the O. 1 N hydrochloric acid solution.
Proceed with the analysis as follows: remove 2 ml from the absorbe r
which contains the 0.01 hydrochloric acid solution and place into a test tube.
Prepare the standard scale as shown in Table 15, and proceed as follows with
-.----.---- the test tube containing the
T AS lE 15
: sample and with a standard
scale test tubes; with the aid
of a long pipette or tube place
standard solution B into a series
of Zeitsev absorbers in the follow-
ing quantities: 0.1, 0.2, 0.4, 0.6,
0.8, 1. 2, 1. 6 and 2.0 ml;
STAtIOARO SCALE .F.0~_J~.QgJg~~'1I N.A~.19~ OF DIMETHYlFORMAMIDE
I TEST TUBE No.
0/1/213141516/1
o I 0.5/1 12 i' ~ I 6 I 8 110
-132-
-------
similarly with the aid of a long pipette place into each of the absorbe rs 4 ml of
the 0.05 N hydrochloric acid for the purpose of washing down any adhering
dimethylformamide; place 1 ml of 20% solution of the alkali into each of the
absorbers and treat it the same as the sample tube; after the air has been
aspirated, as previously described, take 2 ml from each absorber and place
, into test tubes; this will introduce into the tubes quantities of dimethylform-
amide indicated in Table 15 (see page 132).
The control test is treated similarly but should contain no dimethylform-
amide. Now, add to all tubes 0.2 ml of 8% sodium carbonate, shake and add
,0.2 ml of 1% dinitrochlorobenzene; submerge all tubes into a boiling waterbath;
remove and cool; add 0.2 ml of 25% hydrochloric acid; shake and add 0.5 ml of
chloroform; again shake and leave stand for 15-,20 minutes until yellow color
develops; compare co10rimetrically.
Calculation of results:
Assume that the volume of air aspirated and adjusted to standard tem-
,perature and pressure was 18 Ii. Only 1/2 of the sample was used in the
analysis. It contained 1 p. of dimethylformamide or 2 p. in the entire sample.
Accordingly, the dimethylformamide concentration in the air was:
2 X 1000
.-
18
3
III P. , or O. III mg/ m
-13: -
, I
,
'-1
: 1
,
,,,;'
-------
APPENDIX
; . .
Approved by the peputy Chief Government Sanitary Inspector of the USSR
Yu. D. Lebedev
.\ NQ£X
1100
14th of February'1961.No. 221-61
ALLOWABLE CONCENTRATION LIMITS FOR HARMFUL SUBSTANCES IN
- _.--.-- PMOSPHJ.~J9_~I.!I QF. I_NHAB-'TE~_A~~AS
I LIMIT OF - .-
AlLgWADLE
CONCo
MAX. I; A YER.
101 NGL~ 24 HR.
NAME Of AIR POLLUTANT,
FORMULA
1
2
3
4
5
Acrolein
Arr>j I acetate
30
31
32
33
Chlorine
Hydrogen chl9ride gas
Chloroprene \2-cnloro-
buh.di M-I,3)
Chro~ium hexavelGnt
computed &$
Etl\y I acehte.
34
SEE NOTES PAGE 135
CH~CH CHO
CH,COOCH2
CH~CH(CH,h
CH,CO CH,
C6H6
~6~
H25
CS2
Acetone
Benzene
Benzene petrolic of
lOR S in terms of
carbon
6 Buty I acetate CH,COOC.He
7 Vit\y I &cehte CH,COOCH = CH2
8 Dichlorethane . CH2CICHaC\
9 Diny I ,
10 Methanol . CH,OH
11 Methy lacetate CH,COOCH,
12 ,Mang&ne:>e {, j h corapounds Mn
.13 Ar61;f1ic (inorganic compound
except hyfjrc.gen ar$enide As
14 Carbon monoxide CO
15 0" j des of ni trogen , N~Os
16 Inert dust
17 Mehllic mercury
18 Sulfur dioxide
19 HYdrogen sulfide
20 Carbon bi$ulfide
. ~..._.. -- ..-.--.----
21 Soot
22 Sulfuric acid
23 Lead {, it6.compound
4-ethylle.d excluded
24 Lead sulfide
25 . Forma I dehy de
26 Pho6phorue pentoxide
27 Fluorides
28 Pheno I
29 Furfurol
, H2SO,
Pb
PbS
. HCHO
P20s
0,30
0,10
0,1 0,1
0,35 0,35
2,40 0,80
5,0 1,5
0,1 0,1
0,2 0,2
3,0 1,0
0,01 0,01
1,5 0,5
0,07 0,07
0,03 0,01
0,003
6,0 1,0
0,3 0,]
0,5 0,15
- 0,0003
0,5 'I (1,15
0,008 O,\IO/j
0,03 L:!.!UI_-
0,15 0,05
0,3 0,1
0,0007
- 0,0017
0,035 0,012
0,15 0,05
0,03 0,01
0,0\ 0,01 '
0,05
C6HbOH
HC-CH
H~ tHO
"0/
C\ 0,10 0,03
HCI 0,05 0,015'
i.
: CI2=CCICH = CH2 0,25 0,08
I
; Cr20..l 0,00\5
I CH.~OOC2H6 0,\ 0,1.
- 134 -
-------
NOTE: I. I.WU SUlFUII "OXIIE UI 5UlFURIC ACII AEROIiOl AIlE
'I"UlTANEOUSlY PREliEHT II THE AIR THE I TIE au" OF THEIl 11£-
SPECT I VE ll'" TIi OF AllOWUlE" COICUTU T lOllS. Ali COHPUTEI IY
TIE FORMULA aHOWN IElOW. HUST lOT EXCEEI UIITY
" A E
X=-+-,
m n
WHEIIE X I' TilE UIKIOWI} A I~ XHE ll"IT OF AlLOWAllE SULFUR
IIOXIIE COICEITIIATIOII II HIV~ } B I' THE LI"IT OF ALLOW-
AILE SULFU.le AC.I AEROSOL COIC£ITIlITIOI .1 "~~.
2. LlH"ns OF ALLOWULE IPPROVEI IY IIElUUTt ola Noli. All
IATES .II'CATEI IELOW HAVE IEEII REYOKEI Alii IIIE lOT AIIV
lO.'EII .11 FORCE: No. 221-56 .&aun 16 JUIE '956} No. 253-
57 "iUEI 26 JULY 1957} No. 30'-59 'S'UEI 9 DECEHIE. 1959;
No. 32>60 ISSUEI 31 MUCH t 960.
Genetic prognosis of radioactive fallout effect
-135-
-------
PART
II
LIMITS OF ALLOWABLE CONCENTRATIONS OF
ATMOSPHERIC POLLUTANTS
BOOK 7
Professor V. A. Ryazanov, Editor
B. S. Levine, Ph. D.
Translator and English Editor
Washington, D. C., U. S. A.
1963-1964
; 137.~ .
-------
A SUMMARY OF 1961 STUDIES IN THE FIELD OF LIMITS
OF ALLOWABLE CONCENTRATIONS OF ATMOSPHERIC
AIR POLLUTANTS
Prof. V. A. Ryazanov
The .Committee for the Sanitary Protection of Atmospheric Air approved
limits of allowable concentrations in the air for the following new substances:
furfurol, dimethylformamide and styrol.
Furfurol - is a heterocyclic aldehyde which is a good solvent for many
organic substances used in the preparation of some plastics and a selective
solvent for the purification of crude oil lubricants. Furfurol is produced
from agricultural wastes especially those of corn and cotton. It has a sharp
odor reminiscent of benzaldehyde. Furfurol was investigated by R. Ubaidullaev.
The threshold of ~ldehyde odor perception in most sensitive persons was estab-
lished at 1 mg/m . However, R. Ubaidullaev had found that even in odor non-
perceptive concentrations furfurol elicited a series of reflex reactions on the
part of the respiratory organs. Thus, at 0.31 mg/m of furfurol eye sensi-
tivity to light changed :perceptibly, and the conditioned electrocortica1 reflex
could be developed with furffrol concentration as low as 0.084 mg/m . It was
determined that 0.05 mg/m of furfurol constituted the subthreshold concen-
tration in a~l the tests employed. Therefore, R. Ubaidullaev proposed that
0.05 mg/m of furfurol be accepted as the maximal single allowable concen-
tration. .
R. Ubaidullaev exposed white rats to low furfurol concentration for 60
days and found symptoms of developing changes, which gradually disappeared
after the rats were returned to formal conditions. Such changes were partic-
ularly in evidence at 10 mg/m concentration which :was the same as the limit
of its allowable concentration in the air of industrial premises in the USSR.
The animals manifested disturbed flexor and extensOT chronaxies, a drop. in
the cholinesterase activity, a shift in the blood serum protein fractions, -
namely ,a drop in the albumin concentration and a rise in the concentration.
of globulins. There was also a change in the albumin a-globulin coefficient. 3
Similar shifts, but at lower levels, were noted in rats exposed to 0.33 mg/m
furfural concentration. It should be noted that this concentration was equiva-
lent to 1/30 of the lim~t of the allowable furfurol concentration in working
premises; 0.05 mg/m of furfurol in the air had no harmful effects. The
average 24 hour furfurol concentration must not be in excess o~ the maximal
single concentration; theref0:fe, it must not exceed O. 05 m~/m . N;eit~er.
shall it be below 0.05 mg/m . At the3present state of our lnformatlon it is
reasonable to assume that 0.05 mg/m furfurol concentration in the air can
138
-------
be accepted as the maximal allowable single and average 24 hour concentra-
tion. This was proposed by R. Ubaidullaev and was accepted by the committee
and approved by the State Sanitary Inspector of the USSR. .
Styrol - is a benzene homologue with one double bond at its side chain.
Styrol is a colorless liquid having a characteristic odor; it is easily polymeriz-
ed into a polystyrol. Styrol is frequently used in the preparation of copolymers
with other synthetic resins and rubbers for the improvement of their qualities.
Lee Shen was the first to study styrol as an atmospher~c pollutant; it was he
who first indicated that this monomere was actually encountered in the air
surrounding industrial plants in determinable concentrations. For.example,
300 m from a polystyro~ producing plant Lee Shen was able to detect hundredths
of mg of styrol per 1 m of air. The concentration of this pollutant was greater
in the air surrounding larger plants.
Lee Shen also found thtt the threshold of styrol odor perception was in the
range of 0.020-0.036 mg/m , depending upon the olphactory sensitivity of the
individual. Threshold of eye sensitivity to light in most sensitive persons was
0.02 mg/m3 styrol concentration. The condit~oned electrocortical reflex was
devel0:fed with a concentration of 0.005 mg/m. The concentration of 0.003
mg/m produced no effects. On the basis of such data the maximal single
allowable co~centration of styrol in the atmospheric air. was suggested as
0.003 mg/m . Chroic exposure ~f experimental afimals for 70 days con-
tinuously to 50 mg/m , 0.5 mg/m and 0.03 mg/m indicated that the first
two concentrations elicited noteworthy physiological shifts in the animal organ3
isms. These shifts were more .pronounced in the animals exposed to 50 mg/m
of the styrol. The muscle -: antagonist chronaxy ratio of the experimental
animals was disturbed, rate of coproporphyrin elimination with the urine was
lowered, and the intensity of blood cholinesterase activity was enhanced, the
number of blood leucocytes and of monocytes increased, while the number of
erythrocytes was reduced. Statistical analysis indicated that differences
between the index data of the experimental and control animals were statis-
tically significant and reliable. It should be noted that the intensity of the
physiological shifts was in direct proportion to the exposure duration, and
that after the animals had been returned to their normal habitat the indexes
returnrd to their normal levels . As stated above, the concentration of 0.003
mg/m had no effect on any of the indexes; therefore, Lee Shen concluded that
the limit of allowable 24 hour styrol concentration should be the same as the
level for the maximal single concentration.
Dimethylformamide - is a colorless liquid having a nauseating herring
odor; it is used as a polyac rylnitryl solvent in the synthetic fiber industry
known as orlon and nitron. Plants producing this fiber are the chief sources
of dimethylformamide air pollution. D. G. Odoshashvili was the first who
investigated the possibility of atmospheric air :f0llution with dimethylform -
amide. He found a concentrat~on of 2.2 mg/m of the pollutant 100 meters
from the plant and 0.08 mg/m 200 meters from the plant. The plant,under
investigation was of comparatively low production capacity, and it was reason-
able to assume that the air pollution with dimethylformamide would be more
intense in the surroundings of newly constructed large plants. D. G. Odoshashvili
139
-------
established'that the concentration of dimethylffrmamide threshold odor per-
ception was in the range of O. 14 - 0.88 mg/m for different persons. He then
investigated concentrations of the pollutant relative to the development of
conditioned electr<3cortical reflexes afd found them to be in the range of
0.055-0.08 mg/m , with 0.03 mg/m being the subthreshold. The author
proposed the latter concentration as the maximal single allowable concentra-
tion. Similar to the effects in the preceding two instances the 0.03 mg/li .
dimethylformamide concentration had no noteworthy effect on the organic
~unctions of white rats even under conditio~s of continuous 24 hoUf exposure
In closed c:fambers. However, conc3ntratlons above 0.03 mg/m , such as
0.5 mg/m , and especially 10 mg/m (now regarded as the allowable con-
centration for working premises), elicited significant physicological shifts,
such as a fall in the blood cholinesterase activity and in the porphyrine meta-
bolis~. On the' basis 6f his results Odoshashvili recommended that 0.0'3
mg/m be adopted as the limit of allowable single and 24 hour concentration
of dimethy~formamide vapor in the air, since it proved to be the subthreshold
concentration in relation to all the test indexes. This recpmmendation was
accepted., '
Oxides of Nitrogen - P. P. Yakimchuk was the first to experimentally
investigate the effec'tof low nitrogen dioxide concentrations found in ,atmos-
pheric air. Yakimchuk' exposed white rats to the effect of nitrogen dioxide
after stereotype conditioned reflexes have been developed in these animals
by the procedure of 1. P. Pavlov. Rats were exposed to the inhalation of
nitrogen dioxide 6 hours daily fo{ 164 days;' rats of one group we re kept in
a chamber containing ~. 7 mg/m and rats of the other group in a chamber
containing 0.84 mg/m of nitrogen dioxide. The conditioned reflexes of rats
in chamber 1 were definitely affected; phase manifestations appeared, there
was evidence of differentiation disinhibition, falling out of individual reflexes
in response to 1ight stimulation. The animals of the second chamber contain-
ing 0.84 mg/m of the pollutant manifested conditioned reflex shifts of a lower
intensity, indicating that the effect of such a low concentration of the nitrogen
dioxide was not an indifferent one. It was felt that investigations conducted
by P. p. Yakimchuk on the effect of nitrogen dioxide were not sufficiently'
exhaustive. The Committee recommended that the study be continued.
Phenol - The limit of allowable phenol concentration in atmospheric
air was ap:froved by the Chief Sanitary Inspector of the USSR in 1955 a~
0.3 mg/m , which is the maximal single concentration, and O. 1 mg/m as the
24 hour average concentration. However, it was felt that this standard con-
centration had to be rechecked, a task which was assigned to B. Mukhitov.
His report is published in this volume. Mukhitov's studies indicated that the
threshfld of phenol odor perception was in the range of 0.022 and O. 184
mg/m according to tests made with different pe3sons; lowest concentration 3
affecting eye sensitivity to light was 0.015 mg/m , and 0.0156 - 0.024 mg/m
was the concentration range at which electrocortical conditioned reflexes could
be developed; no conditioned reflexes could be developed with phenol con- 3'
centration below that range. Thus, the maximal single allowable 0.3 mg/m
phenol concentration in the air adopted in the USSR was considerably above the
140
-------
one indicated by Mukhitov's3investigation, and Mukhitov proposed that it be
replaced by the 0.01 mg/m concentration. .
Mukhitov also reinvestigated the effect of phenol in chronic experiments.
His data indicated that continuous 24 hour exposuJe of white rats for 2 months
to phenol vapor concentration of 5 and O. 1 mg/m elicited changes in the
muscle antagonist chronaxy ratio and in the coproporphyrine metabolism as
well as the blood cholineste rase activ1ty. These shifts were more sharply'
expressed3in rats exposed to 5 mg/m concentration than in rats exposfd to
O. 1 mg/m concentrations. Phenol vapor concentration of 0.01 mg/m had
no effect on any of the rats' physiological indexes. These results indicated
that the maximal allowable phenol concentration proposed by Mukhitov 3'as
safe even at conditions of chronic exposure; therefore, the 0.01 mg/m phenol
concentration proposed by B. Mukhitov was accepted by the Committee.
The section of this book dealing with methods of investigation contains
three study reports. The first one is by B. K. Baikov and V. 1. Shu1'gin, in
which the authors describe an automatization system developed by them for
the control of conditions in experimental animal exposure chambers. The
system proposed by these authors facilitates the investigator's work and
. enables automatic recording results of 24 hour exposure, which is essential
in experiments reproducing atmospheric smoke conditions prevailing in cities.
This is the first rational attempt to introduce automatization into atmospheric
air pollution investigations and it is hoped that more of this kind of innovations
will be forthcoming in the future.
The second report is by M. V. Alekseeva, a specialist in the field of
atmospheric air analysis. Alekseeva describes methods for the determina-
tion in the atmospheric air of aniline, xylol, n-butylvinyl ester, dimethyl-
terephthalate and phenol.
In .the third report M. D. Manita, describes spectrophotometric methods
for the determination of some organic compounds in the atmospheric air. The
report includes control data checked by M. D. Manita, which are now used in
our laboratory for the determination of napthalene, acetophenone, isopropyl-
benzene, styrol and dinyl. A method is desc ribed for the determination of the
last two mentioned components simultaneously present in the air.
141
-------
, Atmospheric Air Pollution with Furfurol and its Hygienic Evaluation
R. Ubaidullaev
From the Uzbek Research Institute of Hygiene, Sanitation and
Occupational Diseases and from the Department of Community
Hygiene of the Central Institute of Post-Graduate Medicine.
Furfurol is a heterocyclic aldehyde of the furan group which was first
discovered by Deberainer in 1832. In its pure state furfurol is a clear highly
refractive colorless liquid having a characteristic odor reminiscent of bitter
almonds. -Upon exposure to the air, especially in the presence of acids and
some other admixtures, furfurol turns yellow, then darkens, acquiring a
final black color. Furfurol is heavier than wate r having asp. gr. of 1. 59;
boiling point of 1620, and freezing point of -36.50. Furfurol and water are
mutually soluble, the degree of solubility increasing with the~rise in temper-
ature. It is easily soluble in methyl and ethyl alcohols, in acetone and in
ether. It mixes with such organic substances as benzene, butyl alcohol,
chloroform and with ethyl acetic ester and other similar compounds. At the
same time furfurol itself is a solvent of many organic compounds. Furfurol
is obtained from plants containing pentosane. According to L. V. Kotovskii,
N.M. Chetverikova and A.I. Lazareva, P.A. Moshkina, D.M. Basina,
A. S. Sadykov furfurol is obtained on a commercial scale basically from sun-
flower husks, wood shavings, pine cones, corn cobs,' cottonseed hulls, and
the like, which,contain 20-40% of pentosane. Furfurol is used largely in the
crude oil industry as a selective solvent in the purification of lubricating
crude oil products, and also in the production of synthetic resins and plastic
. mflterials. The primary sources of furfurol air pollution are industries which
use this material in their production and processing.
1. M. Korenman and Ya. B. Reznik investigated the sanitary conditions
prevailing in hydrolyzing plants and fou~ that even in the presence of ventila-
tion the indoor air contained 7 -53 mg/m of furfurol. Similar concentrations
of furfurol in the air we re found by Ya. 1. Palii. According to his data the
air in the plan! which he had investigated con~ained not only furfurol, but
18-100 mg/m of acetone and 10.1-19 mg/m of methanol. G. N. Nazyrov 3
investigated air in 3 hydrolyzing plants and found that it contained 10 mg/m
of furfurol, which is six times in excess of the allowable concentration.
. Grezgorzyk and Mozurowa investigated the air of a crude oil processing plant
and found that it contained furfurol in concentrations exceeding the allowable
limit. The extensive use of furfurol in the USSR national economy and the
consequent pollution of air with this vapor make it imperative that a restudy
be made of its sanitary significance and that an exact determination be made
of its limit of allowable concentration in the air.
142.
-------
Furfurol is a neurotropic poison and affects the central nervous syste'm;
according to N. V. Lazarev it also has a local effect as well as an irritating
effect on the mucpsae. Acute experiments wit~high furfurol vapor concentra-
tions ranging between 1000 and 10,000 mg/m , were conducted by E. N.
Levina in 1950, using cats, rabbits and white mice as the experimental animals.
1. M. Korenman, Ya. B. Reznik and B. 1. Kardasevich in 1936 investigated the -.
sanitary conditions in one of the hydrolytic plant~ where the furfurol vapor con-
centration in the air amounted to tenths of mg/m and found that the workers
complained of irritation of the mucous membrane of the upper respiratory
passages, salivation, conjunctivitis and persistent headaches, which appeared
only three months after the industrial plant l:>egan to use furfurol. -G. N.
Nazyrova and Kh. Ya. Vengerskaya examined the blood of workers employed
in the hydrolytic plant and found that the blood contained furfurol ranging from
traces to 20 mg/li and in the urine from traces to a mg/li. These investigators
emphasized the fact that employees of the plant who had been exposed to_the
effect of furfuro1 in the air in concentrations less than tens of mg/m3 con-
tained a considerable quantity of furfurol in their blood.
No reports were found in the literature which contained infor~ation re-
garding the concentration of furfuro1 in the atmospheric air and no limits of
allowable concentration was established for atmospheric air in populated areas.
The present author had undertaken to fill in this gap and in making this in-
vestigation used a highly sensitive colorimetric method for the determination
of furfuro1 in the air, which represented a modification of the Korenman and
Reznik method improved by M. V. Alekseeva of the F. F. Erisman Research
Institute for Hygiene; by this modification determinations could be made of
furfurol concentrations as low as 0.25 mg in 2 ml. However, the method was
not specific, and the presence of formaldehyde and of high molecular alcohols
interferred with the reaction. In this particular instance, these two sub-
stances were absent from the air and, therefore, the results were regarded
as specific and reliable. The absorbent solution used in this case consisted
of 96% alcohol and distilled water in 1: 1 ratio. The air was aspirated first
through a porous plate and then through the absorber solution for 20-80 min.
at the rate of 0.5 Ii/min. The absorbers were then submerged into melting
crushed ice. The procedure used for the determination of the limit of allow-
able concentration was the same as recommended by the committee for the
sanitary protection of atmosphe ric air. Known concentrations of furfuro1
vapor were obtained by bubbling pure air through liquid furfurol in a special
type of glass container at a regulated air volume. Table 1 (see page 7} shows
the constancy of furfurol air concentration during this experiment. .
The concentration of threshold furfurol vapor odor perception was deter-
mined as the average of tests conducted with 17 persons. The test persons
were subjected to appropriate medical examination and declared normal
insofar as their olphactory organs were concerned; they were all nonsmokers.
Only one known concentration of furfurol in the air was tested on one day.
Tests were usually made either in triplicate or in quintuplicates. In each
case the individual threshold was established first. The final 'Value adopted
for the threshold concentration was the one which occurred successively in
143
-------
T AS LE I
,
CONSTANCY OF 'FURFURO( CONCENTRATION IN THE
COURSE OF A DAY
.
I MG/M3 OF FURFUROL AT 2 HR, INTERVALS'
DATES '-10 'I 12 I 14 1,- 16--
O'CLOCK O'CLOCK' O'CLOCK O'CLOCK
TABLE 2':
THRESHOLD OF FURFUROL VAPOR ODOR PERCEPTION
21/X II 4,41 4,40 4,39 4,39
22/X11 3,0 2,99 2,98 2,98
23/X J I 2,15 2,14 2,14 2,14
22/X I I 1,70 1,70 1,69 1,69
25/X1I 1,72 1,71 1,71 -
26/XI I 1,69 1,68 1,69 1,68
27/XI I 1,29 1,28 1,29 1,29
28/XII 1,28 1,26 1,26 -
29/XII 1,26 1,25 1,25 -
No. OF HI N. PER- MAX. PER-
TEST CEPTABLE CEPTABlE TOTAL '100
CONCH. III CONCH. trl
SUBJECTS I1G/M3 I1G/113 OF TESTS
6 1,0 0,86 161
3 1,18 1,0 80
6 1,32 1,18 133
2 1,51 1,32 37
I
three determinations J or in three separate determinations of four or five
tests; 411 d~terminations were thus made, and concentrations of furfurol
in the air were checked at the beginning and conclusion of the tests. Data
presented in Tabe 2 (see above) show that the minimal perceptive furfurol.
vapor concentra!ion in the air by the odor test was witfin the range of
1.0 -1. 51 mg/m , for most sensitive persons 1 mg/m was t~e lowest
perceptible furfurol concentration in the air, and 0.86 mg/m the highest
nonperceptible concentration.
Tests were then made for the determination of lowest concentration of
furfurol on reflex reactions relative to eye sensitivity to light. Adaptometer
A. D. M. was used, and experiments were conducted with three previously
examined persons of 20 - 27 years of age. Pure air and air containing
different furfurol vapor concentrations was run into the inhalation tubes on
the 15th min. of adaptation to darkness for a period of 5 min. The follfwing
furfurol air concentrations were tested: O. 8, 0.6, 0.31 and 0.22 mg/m .
. 7000' " . ". Results are presented in the
U) 6300 form of curves in Figure 1 ~
I-
;; Results ~ndicated that 0.8 and
~ 5500 0.6 mg/m furfurol vapor con-
S 4$170 centration elicited changes in
;;: the dark adaptation curve of all
: 4200 three tested persons, :and in
~ 3500 only two persons were c.fanges
<10 noted at the 0.31 mg/m con-
-' 2800
:: conceIJtration, while at 0.22
~ 1100 mg/m no changes were observ-
,. - PURE AIR ed. The data were subjected to
: 1100 ..... Il,S Afz/Af.1 statistical analysis for their
~ l" -... 0.6 Af2/Af.1 reliability as shown in Table 3
(/) u. -.- 0.31 AfejM3
--- o,ZZ.MtjMJ (see page 8). Thus, data in
Table 3 shows that in test person
Yu. A. furfurol vapo3' concen-
tration of 0.8 mg/m .manifested
a change in dark adaptation on
o
,~.
of
10
15 20 Z5
T 1 PIE IN 111 NUTES
JO
Jof
~o
FIG. I - SENSITIVITY TO LIGHT OF TEST PERSON Yu. A.
I N TERMS OF lIE x 10-2
. r '
144
-------
the 20th min. which was statistically unreliable. On the other hand, on the
25th, 30th and 40th min. sensitivity of the eye to light dropped to lower levels
and the results were statistically reliable; accordingly the threshold of furfurol
vapor foncentration effe3t on eye sensitivity to light was at the level of 0.31
mg/m , and 0.22 mg/m concentration was non-effective.
, TABLE 3: ,Tests made for the deter..,
EFFECT OF FURFURaL VAPOR INHALATION ON EYE SENSITIVITY mination of furfurol vapor
TO LIGHT ON THE 20TH ADAPTATION MIN. IN % OF SENSITIVITY threshold concentration effect
AT 15 MINUTES on the development of the con-
I NITIALS OF I'PURE AIR \ CONCENTRATION I II I1G/~ ditioned electrocortical reflex
TEST PERSON 0.8 I 0.6 I' 0.31 I 0.22 were conducted next. The high
Yu. A. 200,2 155,0(0) 296,9(c) 261,2(c) 197,7(0' degree of sensitivity and re-
L. SH. 126,9 145,9(3) 159,4(b) 150,2(c) 125,9(0) liability possessed by this
V. YA. 144,9 175,7(c) liB,4(c) 153,2(0) 142,5(0) method were established on
~IOTE: LETTERS IN PARENTHESES I HDICATE DEGREE OF RELIABILITY: previous occasions by K. A.
A - ~; 8 - 99%; C - 99.9%; 0 - UIIRELU8LI!_____----- Bushtueva, E. F. Polezhaev,
A. D. Semenenko, and later by V.A. Gofmekler, Yu. G. Fel'dman, G. I.
Solomin and by Lee Shen. The test persons were kept isolated in dark chamber
in a semi-reclined position with the eyes opened and in a completely relaxed -
state. Communication with the test persons was through a microphone. A
glass cylinder was installed in front of each person through which tested air
was run in for inhalation in the concentrations required for the determination
of threshold of eye sensitivity to light. All apparatuses and other equipment
used in the determination were housed in a room concealed from the sight of
the test persons. Whenever required the proper mixture of air and furfurol
vapor was run into the inhalation tubes by opening the appropriate stop-cocks
gauged for the supply of definite concentrations. Electrodes were placed over
the heads of the test persons as follows: two - occipitally, two - temporally
with the indifferent electrodes attached to the ear-lobes. Records were made
by means of the "Alvar" encephalograph. Intermittent light was used as the
unconditioned stimulator produced by the desynchronization of the alpha-rhythm
in, the test I3ersons; inhalation of furfurol concentrations of O. 12, 0.084 and
0.05 mg/m se rved as the conditioned stimulator. In eliciting the conditioned
electrocortical reflex the conditioned stimulator was applied up to 20 times in
association with the unconditioned stimulator. The furfurol concentration used
was regarded as inactive if at 20 association stimulations no conditioned reflex
was effected. On the other hand, if the de synchronization had occurred prior
to turning on the light, then the conditioned reflex was regarded as having been
established, and the furfurol vapor concentration was accordingly regarded as
an active one. By gradually lowering the furfurol vapor concentration, i. e. by
reducing the stimulator, the thre.shold concentration was determined, below
which no conditioned reflex could be elicited. See Fig. 2 (page 9). The furfurol
vapor concentration in the air of the inhalation cylinder was checked at the
beginning and conclusion of the experiment. Two persons were thus tested.
Tests were limited to a single concentration per day with definite rest inter-
vals; this was done for the purpose of obviating the possibility of developing
time conditioned reflexes. See Fig. 3 (page 9).
145
-------
I
~J
"""'-'~-----.~~~"
J
~
6
FIG. 2 - ELECTROENCEPHALOGRAM OF TEST PERSON lol. NO CmJOITIONEO
REFLEX DESYNCHRONIZATJON OCCURRED UPON THE 1ST ASSOCIA-
TION OF FURfUROL VAPOR INHALATION IN 0.12 "'/1'13 CONCN.
I - LEFT OCCIPITAL ENCEPHALOGRA"; 2 - RIGHT OCCIPITAL ENCEPHALo-
GRA"I 3 - LEFT TE"PORAL ENCEPHALOGRAMI 4 - RIGHT TEMPORAL ENCEPH-
ALOGRA"; 5- TI"I! OF VAPOR SUPPLY; 6 - TI"E OF LIGHT SWITCHING IN.
The conditioned electro-
cortical reflex was estab-
lished in both test per~ons at
0.12 and 0.084 mg/m of
r--~./'o~~ furfurol in the air, as shown
in Figures 2 - 5. (See Fig. 5
page l~). In this case 0.05
mg/m of furfurol in the air
was inactive; as can be seen
in Fig. 6 (page 10). A sum-
mary of the data obtained in
the study of furfurol vapor
effect on the reflex activity
of the respiratory organs
receptors are presented in
Table 4, (see page 10). Based
on the data presented in Table
4 it is 3sugge sted that 0.05
mg/m furfurol concentration
in the atmosphe ric air be
adopted as the maximal limit
r of allowable single .concentra-
tion of furfurol vapor in the
FIG. 4 -. ELECTROENCEPHAlOGRAM OF TEST PERSON L. I. CONDI TI OHED
REFLEX DESYNCHRONIZATION ON 1HE 17TH ASSOCIATION \.JITH air. This concentration was
. THE INHALATION Of 0.084 "6/" FURFUROl VAPOR. \, 2, 3, accepted by the CommHtee on
4, 5, 6, SA"E AS IN FIG. 2 the Sanitary Protection of
Atmospheric air and approved by the State Sanitary Inspector of the USSR.
, ~~rW..-~..,r'v,/w(t':Jftt,~
i~~JV~~''''.W~
3 -- ----':'" ~"'""--~----
4
5
5
-
r
FIG. 3 - ELECTROENCEPHALOGRAM OF TEST PERSON L. M. CONDITIONED
REFLEX DESYNCHRONIZATION ON THE 15TH ASSOCIATION WITH
THE INHALATION OF 0.12 "G/"'" FURFUROL VAPOR. I, 2, 3,
4, 5, 5, 8A"E AS IN FIG. 2
r
~
'. ~.
146
J
,
J
-------
I
J
~~
.'--,
of
L 4
FIG. 5 - ELECTROENCEPHALOGRAM OF TEST PERSON L. M. NO CONDITIONED
,REFLEX DESYNCHRONIZATION ON THE IITI ASSOCIATION WITH IN-
HALATI ON OF 0.084 "8/"3 OF FURFUROL VAPOR. I, 2, 3, ~ 5,
. /'i, SA"I A8 II FIe. 2
~ - "- '.'.,
. I
2
4 -
..~-
~~.L-4>
...-...... ~ J.'-
5
6.
FIG. e - ELECTROENCEPHAlO6RAM OF'TEST PERSON L. I. CONDITIONED
REFlEX .DESYNCHRONIZATION ON THE 1211 ASSOCIATION WITH
THE I NHALATI ON OF 0.05 HG/,.3 FURFURaL VAPOR. I, 2, 3,
.' .., 5, e, SA"~~_8_.~.1 FIG. 2 .
. HBLE" The next step of this in- .
EFFECT OF THRESHOLD FURFURaL ODOR PERCEPTION CONCENTRATIONS vestigation was the determina-
ON THE RECEPTORS OF RESPIRATORY ORGANS. tion of average 24 hr. allowable
concentration limit of furfurol
in the air. Experiments were
performed with 60 white male
rats of 90-100 g; they were ex-.
posed to the effect of furfuro1
vapor in the air uninte rrupted1y
. for 60 days. The rats were
divided into four ~oups (If 15 animals each; rats of the first group wefe ex-
posed to 10 mg/m of furfurol; ~ts of the second group to 0.30 mg/m ; rats
of the third group to 0.05 mg/m , which was the concentration proposed above
as the maximal allowablE concentration of furfurol in atmospheric air. Animals
of group 4 served as contc-ols.'. .
. In each set of expe:~imentsair containing the corresponding furfurol con-
centration was run into be exposure chamber at the rate of 15-17 Ii/min. Daily
checks .were made for th,~ determination of the furfurol concentration in E)ach
exposure chamber. In tl:~ yrst group the values were 10. 14~. 36 ~g/m , in
the 2nd - 0.33 :1:0.33 mgi In , and in the 3rd- 0.052 :i: 0.0033 mg/m. The
following indexes were taLen into consideration in evaluating the effect of
furfurol on the. animals: cnimals general condition, their weight. muscular
FUNCTION OR INOEX
I THRESHOLD
COIICN. IN
. 110/M3
1.0
0,31
0,084
0,05
ODOR PERCEPTION .
EVE SENSITIVITY TO LI6HT .
FORMATioN OF ELECTRICORTICAL CONDITIONED
NOI-ACTIVE CONCENTRATION
REFLEXES'
147
-------
CD
;: 0,25
o
""
~ ,0.20
=>c
o.
;: ~ 0,15
...
:0:(1)
'- ~ 0,10
>-
Ko..
;: c 0.05
o
= f7/){ 2¥X .J!jX 8jXlIOjXl Z5pI:7 2/XII.9jXlI I7/XlI 24/X1l2/1 9/1
o " OATES ,OF STUDY
- EXTENSOR, --- FLEXOR
FIG. 8 - AFFECT OF FURFUROl VAPOR ON MUSCLE MOTOR
CHRONAXY OF RATS OF GROUP NO. I
, (AVERAGE OF 5 RATS)
motor chronaxy, activity of cholinesterase and effect on blood protein serum
fractions. Pathoanatomic and histopathologic studies were made of organs.
Data were subjected to statistical analysis. Weight of the animals was affect-
ed only slightly, and only towards the end of the experiment did the rats of
groups 1 and 2 lose s orne weight as compared with the controls as shown in
Fig. 7. Chronaxy and rheobase were determined daily in 5 rats of each group
at the same time and under similar conditions of electrical stimula.tion. Muscle-
antagonists chronaX'y ratio ~o~titutes a sensitive test reflecting the functional
state of the central nervous system following the inhalation of low concentra-
tions of toxic substances, as was described by P. O. Makarov, R. V. Borisen-
kova, V.A. Gofmekler, Yu. G. Fel'dman, and others.
JBO EXPOSURE PERIOD RECUPERA- : Changes in muscle motor chronaxy
.JoO I I TlON .: appeared on the 4th week of exposure
I I PERIO~,. in rats of group 1 in the form of dis-
J40 I f I .~
J20 .'7'/,' turbed chronaxy ratio of the flexor
I ''-'1 ...-:"
~ JOO I 4 .....'~ ,.{..'2 and extensor muscles. The ratio.
... I /' ."",:...""", returned to normal at the end of the
~ 2"0 .., . ..
0' I .' ,.' ".." I f
z .~" ,... 3 I 4th week 0 recuperation as shown
: 260 I /o.f",..."" I in Fig. 8. Disturbed muscle antag-
;; 240 I ,,",/ . I
.,(.' " I onists chronaxy ratio appeared in
:3.! 220 /:~. ,/ j rats of group 2 only on the 5th week
200 /~;,,/( - GROUP I , of exposure in a less pronounced in-
,,1 uu. ,GROUP 2
"1 ---- GROUP 3 tensity. These chronaxy changes
:. -.- CONTROL, GROUP disappeared at the end of the 1st
, I recuperation week. No clearcut
fJ/.x 26/% njXl 2J~ 1jXl 2JjXI/ 1// and reliable changes in the motor
DAToS OF ANIMAL WEIGHING
chronaxy ratio were observed in
rats of group 3 as can be seen in
the curves of Fig. 9 (see page 12).
Under normal conditions the ex-
t RECOVERY tensor chronaxy is longe r than the
" PER I aD .
flexor chronaxy; changes in their
ratio indicates changes in the central
ne rvous control of motor func tions.
No changes were noted in the rheo-
base of any animals in any group.
Evidence has been presented in
the literature concerning changes
in' cholinestrase activity following
into;xication of the nervous system;
this fact was utilized in this type of
work and served as one of the in-
dexes. Ch6linestrase determinations were made in whole blood colori-
metrically by the method of A.A. Pokrovskii as modified by A. P. Martynova.
The method is based on the time required for the indicator to change color .as
a result of pH changes following acetylcholine hydrolysis. G.1. Solomin and
Lee Shen adopted this method for ~he practical hygienic standardization
180
160
11,0
FIG. 7- CHANGE IN AVERAGE WEIGHT OF RATS OF
DIFFERENT GROUPS
EXPOSURE
I
I
I
I
..., I --..-
--- '~------~--~-
I
I
I
I
..
148
-------
2
J
.-...-... ~
.. ---..J
J
. ~ 6
FIG. 5 - ELECTROENCEPHALOGRAM OF TEST PERSON L. 1'1.. NO CONDITIONED
REFLEX DESYNCHRONIZATION ON THE 1118 ASSrx:IATlON WITH I~
HALATION OF 0.084 "8/"3 OF FURFUROL VAPOR. " 2, 3, 4, S.
. fI, 8A"1 A8 II FIe. ~
~ - -.- -.'--
. I
2
4..-
."~-
-----~
~ y..~ v--" .L -q --
5
6
FIG. e - ELECTROENCEPHALOGRAM OF- TEST PERSON L. I. CONDITIONED
REFLEX .DESYNCHRONIZATION ON THE 121. ASSOCIATION WITH
THE INHALATION OF 0.05 t'1O/~ FURFUROl VAPOR. I, 2, 3,
.. .., ~ e, SA"!~8_~1 FIG. 2 .
. HBLE" The next step of this in- .
EFFECT OF THRESHOLD FURFUROL ODOR PERCEPTION CONCENTRATIONS vestigation was the determina-
ON THE RECEPTORS OF RESPIRATORY ORGANS. tion of average 24 hr. allowable
concentration limit of furfurol
in the air. Experiments were
performed with 60 white male
rats of 90-100 g; they were ex-
posed to the effect of furfurol
vapor in the air uninte rruptedly
. for 60 days. The rats were
divided into four ~oups (If 15 animals each; rats of the £irst group wefe ex-
posed to 10 mg/m of furfurol; :rts of the second group to 0.30 mg/m ; rats
of the third group to 0.05 mg/m , which was the concentration proposed above.
as the maxitnal allowablE concentration of furfurol in atmospheric air. Animals
of group 4 served as conl-.("ols.. . .
. In each set of expe:~iments .air containing the corresponding furfurol con-
centration was run into be exposure chamber at the rate of 15-17 li/min. Daily
checks.were made for th,~ determination of the furfurol concentration in E)ach
exposure chamber. In tl:~ ~rst group the values were 10. 14:rQ. 36 ~g/m , in
the 2nd - 0.33 :1:0.33 mgl In , and in the 3rd- 0.052 :i: 0.0033 mg/m. The
following indexes were tal:en into consideration in evaluating the effect of
furfurol on the. animals: ,nimals general condition, their weight, muscular
FUNCTION OR INDEX
I THRESHOLD
COIICN. III
. I1G/M3
1.0
0,31
0,084
0,05
ODOR ~ERCE~TION .
EYE SENSITIVITY TO liGHT.
FORMATiON OF ElECTRICORTICAl CONDITIONED
NON-ACTIVE CONCENTRATION
REFLEXES.
147
-------
(0
;: 0.25
'"
""
~ ,0.20
"'IC>
0...
;: Z 0,15
IU
01:(0
- ~ 0,10
>
MOo.
;: 0 0.05
o
: f1/X 2.yX Jf/X BjXI fOjXl Z5;ID 2/Xll!ljXll 17/Xll2"/X1l2/1 .9/1
(.;) . DATES.oF STUDY
-' EXTENSOR --- FLEXOR
FIG. 8 - AFFECT OF FURFUROL VAPOR ON MUSCLE MOTOR
CHRONAXY OF RATS OF GROUP NO. I
(AVERAGE OF 5 RATS)
motor chronaxy, activity of cholinesterase and effect on blood protein serum
fractions. Pathoanatomic and histopathologic studies were made of organs.
Data were subjected to statistical analysis. Weight of the animals was affect-
ed only slightly, and only towards the end of the experiment did the rats of
groups land 2 lose some weight as compared with the controls as ~hown in
Fig. 7. Chronaxy and rheobase were determined daily in 5 rats of each group
at the same time and under. similar conditions of electrical stimulation. Muscle-
antagonists chronaxy ratio contitutes a sensitive test reflecting the functional
state of the central nervous syste m following the inhalation of low concentra-
tions of toxic substances, as was described by P.O. Makarov, R. V. Borisen-
kova, V. A. Gofmekler, Yu. G. Fel'dman, and others.
.180 EXPOSURE PERIOD RECUPERA-! Changes in muscle motor chronaxy
JoO I I TIOII .' appeared on the 4th week of exposure
I I PERIOD in rats of group 1 in the form of dis-
.1"0 I (. I .~
JZO I ."'," turbed chronaxy ratio of the flexor
........-, ,~_."
~ 300 '., I 4 "'"'~ ..~"2 and extensor muscles, The ratio.
"" I /' ",'.:~.~"I returned to normal at the end of the
~ 280 I ./ .";>.. I f.
z ".-(." ", 3 I 4th week 0 recuperation as shown
- 260 I ,,' ..
~ /.~" ..'" I in Fig. 8. Disturbed muscle an tag-
; 2"0 I ",' ..'" I . . d .
"f.',," I onlsts chronaxy ratio appeare In
~ 220 /:~.,' I rats of group 2 only on the 5th week
200 /~;",..( - GROUP I of exposure in a Ie ss pronounced in-
.' I un. ,GROUP 2
" ---- GROUP 3 tensity, These chronaxy changes
-.- CONTROL GROUP disappeared at the end of the 1st
I
I recuperation week. No clearcut
(J/.x 2¥y 5/Xl 2:JjX1 1/XI 2:JjXll 1// and reliable changes in the motor
OAT~S OF Ain'MAL WEIGHING . b .
chronaxy ratio were 0 served In
rats of group 3 as can be seen in
the curves of Fig. 9 (see page 12).
Under normal conditions the ex-
I RECOVERY tensor chronaxy is longe r than the
II PER I 00 . . .
flexor chronaxy; changes In thelr
ratio indicates changes in the central
nervous control of ' motor functions.
No changes were noted in the rheo-
base of any animals in any group.
Evidence has been presented in
the literature concerning changes
in'cholinestrase activity following
intoxication of the nervous system;
this fact was utilized in this type of
work and served as one of the in-
dexes. Cholinestrase determinations were made in whole blood colori-
metrically by the method of A. A. Pokrovskii as modified by A. P. Martynova.
The method is based on the time required for the indicator to change color .as
a result of pH changes following acetylcholine hydrolysis. G.1. Solomin and
Lee Shen adopted this method for the practical hygienic standardization
180
150
11,O
FIG. 7- CHANGE IN AVERAGE WEIGHT OF RATS OF
DIFFERENT GROUPS
EXPOSURE
I
1
I
,I
148
-------
(/) 0.25
=
...
~ 0.20
<
I/J
~ ~ 0.15
%0
......
== ;g D,l0
..
>-
~ ~ 0.05
~ Il/X ZsjXJtjX 8jXlfO/XlZS/XlZ/AlI.9/XlII7/X1l2f,/XI12/1 .9/1
c3 DUES OF STUDY
- EXTENSOR --- FLEXOR
FIG. 9 - EFFECT OF FURFUROl VAPOR IN MUSCLE MOTOR
CHRONAXY OF RATS OF GROUP NO.3
, (AVERMOE OF ,5 RATS) ,'TABLE 5
CHANGES IN MOTOR CHRONAXY OF EXTENSOR MUSCLES IN RATS
DURING FURFUROl VAPOR INHALATION
EXPOSURE PERIOD
: RECOVER Y,
I' PE R I 00
"- ...' '
~---....
I ----------------- -
-~--- I
I
I
I
I
I
I
RAT GROUP
EXPOSURE FIRST I SECO~O I THIRD I 'C.ONTROL
I DUES
PER I OD THOUSANDTHS OF A SECOND
BEFORE EXPOSURE 17/X 0,20 (0) 0,17 (0) 0,182(0) 0,182
DITTO 25/X 0,188(0) 0,188(0) 0,18' (0) 0,174
EXPOSURE pER 100 ,31/X 0,176(0) 0, 178(0) 0,18 (0) 0,176
]I 8/XI 0,18 (0) 0,178(0) 0,18 (0) 0,18
]I 16/XI 0,166(0) 0.172(0) 0,178(0) 0,174
]I 25/XI 0,182(0) 0,178(0) 0,176(0) 0,178
]I 2/X11 0,156(0) 0,172(0) 0,178(0) 0,178
]I 9/XII 0,166(0) 0.172(0) 0,176(0) ,0,182
]I 17/XII 0, i74(0) O,166(b) 0,19(0) 0,18
]I 24/XII O,172(a) O,I68(a) 0.194(0) 0,184
I
RECOVERY PERIOD 2/1 0,177(0) 10,175(0) 0,195(0) 0,187
- 9/1 0 I 185(0) 0.18 (0) 0,19 (0) 0,187
NOTE: DEGREE OF RElI ADI LITY: 2 - 95}1:; 8 - 99}!:; I'
0- NOT RELIABLE I
--- _."HO .-.-------.-- --.
of atmospheric air pollutions. Tests were performed with rats in groups of
five; blood was taken from the tail vein under sterile conditions every 15 days.
Results indicated that 30 days after the beginning of exposure some depression
appeared in the cholinesterase activity of animals of group l,and the time of
acetylcholine hydrolsis was extended to 47-48 min. as compared with 37-41
min. of the controls; at the end of 60 days the hydrolysis time extended to
54-55 min. as sho~n in Fig. 10 (see page 13). Depression in cholinesterase
activity of rats of group 2 'was less pronounced, and hydrolysis time at the
end of the exposure amounted to 44 min. No recordable changes of the above
described character were noted in animals of group 3 as compared with the
animals in the control group. Statistical analyses established the reliability
of the results obtained with animals of the first two groups, as shown in
Table 8 (see page 14).
Many reports have appeared in the literature recently indicating that
total blood serum protein and its fractional composition changed in different
diseases. This was clearly indicated in the reports of N. D. Morozova,
A.I. Burlui and others. It should be noted in this connection, that L.N.
149
-------
TABLE 6
CHANGES I N MOTOR CHRONAXY OF FLEXOR MUSCLES I N RATS
DURING FURFUROl VAPOR INHALATION
RAT GROUPS
I NHALATI ON FIRST I SECOND I TH 1 RD I COIITRO~
OATES -
PER 1_00 ABSOLUTE TIME IN THOUSANDTHS
-.--. OF A SECOND
EfORE INHALATION 17/X 0,18 (0) 0.14 (0) 0,154(0) 0.168
'TTO 25/X O,16~(0) 0,156(0) 0,156(0) 0,148
31/X 0,162(0) 0.16(0) 0,162(0) 0,158
XPOSURE PE R I 00
8/XI 0,162(0) 0,158(0) 0.162(0) 0,165
~ 16/XI 0,18 (a) 0,16 (0) 0.162(0) 0.156
~ 25/XI 0,222(0) 0,178(0) 0.162(0) 0.164
~ 2/XII O,176(a) O,196(c) 0.164(0) 0,16
II 9/XII 0.218(c) 0.198(c) 0,162(0) 0,164
II 17/XII 0, 184(b) O,178(a) 0.166(0) 0,162
II 24/XII O,206(c) 0,172(0) 0,168(0) 0,16
ECOVERY PERIOD 2/1 0,172(a) 0.168:0) 0,168(0) 0,162
9/1 0,160(0) 0,155(0) 0,162(0) - 0 162
B
o
E
R
NOTE: DEGREE Of RELI.~5Il1TY: A - ~; 8 - ~; C - 99.9%;
0- UNREliABLE
Surodeikin, Granati, Scavo, Motervino
dealing with the effect of chemical
substances on protein metabolism re-
ported a fall in the blood se rum albumin
concentration and a rise in the concentra-
tion of globulins in animals subjected to
poisoning with carbon tetrachloride and
carbon bisulfide. See Fig. 10. The pre-
sent author studied the effect of low
furfurol concentrations on blood serum
protein fractions in chronically exposed
rats by the method of paper electro-
phoresis. Total blood serum protein
was determined refractometrically using
refractometer PLR-2. The phoregrams
were analyzed using a german densito-
meter followed by integrating the curves by the gravimetric method. Blood
serum protein fractions were thus studied in 5 rats of each group; blood was
taken from the tail vein on an empty stomach every 15 days. At the end of
two weeks I exposure total albumin was reduced to 33 -46% in rats of the first
group as compared with 41-50% in the control group. The concentration of
globulins rose to higher levels as can be seen in Fig. 11 (see page 15). At
the end of the exposure period similar changes in rats of group 2 were less
pronounced and in rats of group 3 were entirely absent. Most manifest were
changes in the albumin: a-globulin coefficient, as shown in Table 9. (see
page 15.) At the end of the exposures and at the end of the recupe ration
w 50
U)
~ 58
o
~ w-J6
- :r '"
D ~ JO
z ...
-:~ '-5
g", 62
u -
...
)-
...
'"
u
<
1 EXPOSURE I -
I PERIOD IRECOVERY
I I PER I 00
I ......-;.
I 0... "
I #- I .
I ... t "
I ...- I .'.
I ",- -..--.-1.....
I ...:....--.....-- : .'..
.." ----- -"-:,,
-.,.
I
I
38
31(
30 .
.9/X f6/X 6/Xl20/XJ6/XllfS/Xll25jXJ1 8/1
QAYS OF _STUDY
....... FIRST GROUP -.- SECOND GROUP
--- THIRD GROUI' - CONTROL GROUP
FIG. 10 - EFFECT OF FURFUROl VAPOR ON BLOOD
CHOLINESTERASE ACTIVITY OF RATS
OF DIFFERENT GROUPS
150
-------
TAB LE 7
CHANGES IN MUSCLE ANTAGONISTS CHRONAXY RATIO IN RATS DURING
FURFUROL VAPOR INHALATION
Rn GROUI'S
EXI'OSURE OATES FIRST I SECOND I THIRD I CONTROL
I'ER I 09 MUSCLE ANTAGONISTS CHRONAXY
R AT I OS
. --
BEFORE EXI'OSURE I 17/X - 1.11(0) 1,20(0) 1,18(0) 1.08
25/X 1,16(0) 1,21(0) ] ,]7(0) 1,17
EXI'OSURE I'ERIOD 31/X 1.08(0) .1.11(0) 1.11(0) I,ll
:t 8/XI 1,05(0} 1.15(0) 1,12(0} 1,09
Jt 16/XI 0,92(0) 1,07(0) 1,1 (0) 1.11
Jt 25/XI 0.81(e) 1.01(0) 1,09(0) 1.07
Jt 2/XII 0.89(0) 0.9 (a) 1,09(o} I,ll
Jt 9/XII O,76(b) O,87(b) 1,08(0) I,ll"
Jt ]7/XII 0,93(0) O,93(e} 1,14(0} 1.111
Jt 24/XII 0.83(b) O,98(0} 1.15(0) 1,15
ECOVERY I'ER109 2/1 1.03(a} 1.11(0) 1,16(0) 1,15
- 9/1 1,15(0) 1,14(0) 1,16(0) 1,13
.
R
NOTE: DEGREE OF RELIABILITY: A - ~; . - 99%; C - 99.9%;
0- UNRELIABLE
----------- --
TABLE 8
CHANGES'IN CHOLINESTERASE ACTIVITY IN RATS EXPOSED TO THE INHALATION OF FURFUROl VAPOR
-----.------
BEFORE INHALATION INHALATION EXI'OSURE RECOVERY
GROUI' IUHBER EXI'OSURE I'ERIOD I'ERIOD
9/X I 26/X I cpeAHee 6/XI I 20/XI I 4/X II I 18/XII I 25/XII 8/1
FIRST . . .. 40,4(0) 38.8(0) 39.4(0) 43,6(e) 46. 2(e) 51 .8(e) -53.2(e) 54.0(e) 42.2(0)
SECOND . . .. 39,4(0) 37.8(0) 38.6(0) 40,4(0) 4I,O(a) 42.0(b) 42.6(b) 43.0(e) 38,7(0)
THIRD . . .. 39.0(0} 37.4(0) 38.2(0) 38.4(0) 38.4(0) 38.2(0) 38,2(0) 38.3(0) 38.3(0)
CONTROL . . .. 37.8(0) 38.2 38,0 "37.8 36,8 37,8 38,2 37,0 38.0
NOTE: DEGREE OF RELIABILITY: A - ~; B - 99}6; c - 99.9}6; 0 - UNRelIABLE
period some of the rats were sacrificed for histopathologic and patho-
anatomic studies of the internal organs and the central nervous system. No
substantial changes were observed in the animals of groups 1, 2 and 3 as
compared with the control group. Thus, exposure of white3rats continuously
for 60 days to furfurol vapor concentration of 10, 14 mg/m produced mOfe
pronounced effects than in the animals which were exposed to 0.33 mg/f1
furfurol concentration and no effect on animals exposed to 0.052 mg/m of
furfurol. On the basis of such data it was concluded that the averj-ge 24 hour
maximal concentration of furfurol in the air should be 0.05 mg/m .
A sanitary hygienic study was then made of the intensity of furfurol
pollution which existed in the air surrounding a hydrolytic plant which pro-
duced 2,000 tons of furfurol annually accompanied by the production of
methyl alcohol and generation of carbon dioxide. In this study 157 air
samples were tested for the content of furfurol and 70 samples for the
151
-------
TAB LE 9
CHANGES IN THE ALBUMIN/Cl-GLOBULIN COEFFICIENT IN RATS EXPOSED
. TO FURFUROL VAPOR 1 NHA LAT ION
GROUPS
OATES .FIRST I.SE.COND I TH I RD I CO~T~OL
21-23/X 2,0 (oj 1. 9 (0) 1. 8 (0) 1,9
1O-13/Xr 1,8 (0) 1,8 (0) 1.8 (0) 1,9
28/XI-I/XII 1..1 (b) 1,6 (0) 1,8 (0) 1,8
12-15/XII 1,2 (c) 1,7 (0) 1,9 (0) 1,8
23-26/Xr I 1,2 (c) 1. 6 (a) 1,95(0) 1,9
9-10/ I 2,1 (0) 2,0 (0) 2,0 (0) 2,0
NOTE: DEGREE OF RElIA8IL'ITY:, A";' 95}1:; I - ~; c..;. 99.~;
0- UNRELIA8LE .
. -........-----------.----------- _.-
TABLE 10
FURFURAL VAPOR POLLUTION OF ATMOSPHERIC AIR SURROUNDING THE
ANDIZHANSK HYDROLYSIS PLANT
"" FURFUROL I CONCN. DliTRI8UTION
VAI'O, i
...0 ...U) IN I1G 113 IN 11,./,.,3
:r-'"
......... 0...
~"" .. I I A80VE\+oO: I
:I:-'~ . ... 0.51 0.1 I LESS
0....0 0:1: MAX. MI H.
",OU) ;zc 621 .O~05' o:~~
LLL CQ I .0 ' O. 5
SO 33 2,02 0,45 7 23 3 -
.250 -
. 33 '1,57 0,09 2 9 21 1 -
500 31 0,91 .0,03 - 1 26 2 2
700 31 0,47 0.02 - - 11 10 10
1000 29 0,09 - - - - 1 28
II
0 d
I II
~
II
t1 d
2
, FI G. II - EFFECT OF FURFUROL VAPOR ON BLOOD SERUM
PROTEIN FRACTIONS OF RAT NO.1 GROUP I
(I), AND RAT NO. 12 GROUP 3 (2),BEFORE
(A) AND AFTER (B) I NHALATION EXPOSURE
A - ALlUt11 ris. a~ ALI'H~GLOB UL INS; po.
IETA-GLOIULINS; Y -GAt1t1A-QLOIULINS
content of methanol at distances of
50, 250, 500, 700 and 1,000' m leeward
from the furfurol plant. Samples were
collected by aspiration through two
absorbe rs equipped with porous plate s.
For each sample 10 -40 li of air had
been passed at the rate of 30 li/hr,
In collecting the air samples r.ecords
were kept of the velocity and direction
of the wind ',temperature, baro-
metric pressure and relative humidity.
The temperature ranged between
17 -360, relative humidity between
20 -72%, barometric pres sure between
711-719 mm of mercury and wind
velocity between 1-7 m/sec. Through-
out the period of sample collection
weather conditions were those of, dry
spring season of the year. Results of
the tests are listed in Table 10. Data
in Table 10 show that only at 1,000 m
152
-------
from .the source of discharge wfre the concentrations of furfurol in the air
below the proposed 0.05 mg/m maximal concentration, with the exception
of one test.
Supplemental information was obtained by the question and answer method
from inhabitants residing at 200-1,000 m from the hydrolysis plant; 91 persons
lived in the 200-400 m belt; 99 persons in the 400-600 m belt; 81 persons in the
600 -800 m belt and 106 persons lived in the 800 -1,000 m belt. 87% of the
questioned persons complained of specific furfuro1 odor during the summer
months when the wind was in the direction of specific populated area. However,
it was difficult to ascertain whether the odor complained of was specifically
that of furfuro1, since the plant discharged vapors of such other substances as
methanol, acetic acid, etc. Persons who collected the air samples stated that
they had perceived a nonspecific odor, suspected to be of furfurol at 1,000
meters from the discharge point, especially when the wind was in their direc-
tion. Undoubtedly, this nonspecific odor was due to a mixture of vapors from
the substances discharged by the plant.
Conclusions
1. The atmospheric air surrounding plants, producing or using furfurol
was polluted by furfuro1 vapor.
2. The concentration of threshold furfujo1 odor perceptiop. in most odor
sensitive p~rsons was determined as 1 mg/m , of eye sensitivity to light as
0.31 mg/m an~ for the deve1.fpment of electrocortical conditioned reflexes
as 0.084 mg/m , 0.05 mg/m of furfuro1 constituted a nonactive concentration.
3. The proposed maxima13sing1e allowable furfuro1 concentration in
atmospheric air was' 0.05 mg/m . .
4. Chro~c 24 hour exposure to furfuro1 vapor at concentrations of 10
and 0.33 mg/m for 60 days elicited in experimental rats shifts in the flexor
and extensor chronaxy ratios, in the cholinestejase activity and in the blood
serum protein fraction picture. In 0.05 mg/m concentration furfurol had no
ef~ect on the organism of the experimental rats.
5. The recommended average 24 hour allowable concentration limit of
furfuro1 in atmospheri3 air according to results obtained with chronic experi-
ments was 0.05 mg/m .
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154
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Experimental Data for the Hygienic Evaluation of Atmospheric
Air Pollution with Styrol
Le e Shen
From the Central Institute of Post-Graduate Medicine
Styrol (C6H5CH = CH2) is a homologue of benzene; it is a colorless
liquid having a specific odor~ it slowly polymerizes at ordinary temperature;
it is used extensively in present day industries, especially in the manu-
facture of synthetic rubber and plastics. Stryol is found in the atmospheric
air and in working premises in the form of vapor and in this way enters the
human organism through inhalation. Styrol is absorbed by lipids and can
permeate the intact skin. Styrol belongs to the class of narcotics; it possess-
es an irritating hepatotropic and narcotic action. Inhalation of styrol can
produce disturbance of the central nervous system and shifts in the hemo-
poietic syste m. Styrol affected the upper respiratory passages, the gene ra1
metabolic processes and female sex functions. Styrol poisoning produced
parenchymatous changes in the veins, lungs, liver and kidneys, as described
by E.I. Nuse1'man in 1936, by L.F. Larionov in 1936, by T.A. Blinova and
M. L. Rylova in 1937, by Ya. Taradin in,l954, by V.A. Pokrovskii in 1955,
and by othe rs. Spencer and his collaborators reported on the results of their
studies in 1902, conducted with rabbits and rats; the animals were exposed
to the inhalation of styrol vapor, or were administered the same inte.rnally;
this resulted in increased elimination of total benzoic acid, neutral phos-
phorus compounds and in the elimination of hippuric acid via the urine. Sub-
cutaneous administration of 20% styrol solution to rats in the form of labeled
carbon was followed by an increased concentration of C 14 in the liver and
kidneys, as described by Danishefskii and Willhite in 1954. A review of the
literature failed to disclose any reports regarding atmospheric air pollution
with styrol and the effect of low styrol concentration on the organis ms of ma.n
or animals. .
Styrol determinations were conducte'd under experimental conditions by
the M. 1. Poletaev (1953) method which was improved under the guidance of
M. V. Alekseeva. The method is based on nitration of styrol which formed
nitro compounds;, upon reaction with ammonia the solution acquired a yellow
color. the intensity of which was then compared with a standard color scale.
The method is nonspecific. since other aromatic hydrocarbons interferred
with this determination; however. no other aromatic hydrocarbons were
present under the conditions of the present study, sO.that for the present
investigation the method was regarded as specific. ;S~nsitivity of the method
155
..:'"
-------
was 0.001 mg/4 ml, as established by M. V. Alekseeva in 1959. The maxi-
mal allowable single concentration limit of styrol was determined as re-
commended by the Committee for the Sanitary Protection of Atmospheric
Air affiliated with the State Sanitary Inspection of the USSR. .
Concentrations of threshold styrol odor perception were determined
which effected reflex changes in eye sensitivity to light and elicited condition-
ed electrocortical reflex formation. Threshold styrol odor perception was
determined with the aid of 15 previously medically examined normal persons.
Tests were made with 11 different concentrations within the range of 0.8 -
0.01 mg/m3. All test persons were familiarized with the odor of styrol
before being subjected to the experiments. Equipment used in the experi-
ments was the same as recommended by V. A. Ryazanov, K. A. Bushteuva,
Yu. V. Novikov in 1957. Styrol co.ncentrations used in the tests were checked
at the beginning and conclusion of the experiments; results showed that the
fluctuations were insignificant. Results. of test for threshold odor perception
concentrations are prese.nted in Table 1. Data in the table show that concen-
tration of thres~old styrol vapor odor percept~on for most se.nsitivepersons
was 0.02 mg/m and that the odor no~perceptlble concentratlon was 0.0 1
. TABLE I mg/m. Threshold reflex effect of styrol
vapor on the functional state of the central
nervous system was determined by using eye
adaptation to darkness as the index. ,. Test
persons were previously examined medically
and their odor perception and eye adaptation
were of normal range. The concentration of
threshold styrol odor pe~ception in three
persons was 0.02 mg/m. Determinations
were made each day with only one concentra-
tion, and always at the same hour of the day.
Before tests were initiated test persons were subjected to deadaptation in
the dark. ..Changes in eye sensitivity to light were tested every 5 min. for
30 min., and then every lO min. for an additional 30 min. Test persons in-
haled fresh air and air containing styrol between the 15 an1 20th min. of
adaptation to darknes s. Results indicated that 0.01 mg/m styrol concentra-
tionhad no effect on eye sensitivity to light, but that at 0.02 and 0.03 mg/m3
concentration~ eye sensitivity to light became enhanced, more at 0..03 than
at 0.02 mg/m concentration, as ~own in Fig. 1. (See page 20). Data
obtained with 0.02 and 0.03 mg/m concentrations were check statistically.
It was, thus, found that the threshold of styrol reflex effect on the curve of
adaptation to darkness, as determined by adaptometer ADM.coincided
with the threshold of styrol odor perception, which was 0.02 mg/m5. Electro-
encephalographic tests were conducted to check the correctness of the results
previously obtained and to establish the limit of allowable single styrol con-
centration.in the air. This method has been recommended for the purpose
under conside ration by K. A. Bushtueva, E. F. Polezhev and A. D. Semenenko
in 1960. The method is based on the determination of pollutant threshold
DETERMINATION OF STYROL ODOR
PERCEPTION THRESHOLD
STYROL IN M'/M3
NUMREI! OF U.-
OBSERVATIONS MINIMUM IMAXIMUM NON-
PERCEPTIDLE PERCEPTI8lE
6
3
3
.3
0.020
0,026
0,032
0,036
0,010
0,020
0,026
0,032
156
-------
. ".;::?~.;r1;":~'~ '; ( , , .
/.."~.;<~-~ia".: .:/c~o~centrations at which
ct'!:.; ......_.:""7,:::( >;electrocortical conditioned
<; :~': . r.eflexes could be developed
'. . ::at ,which de synchronization
:'. "'. of the alpha-rhythm appeared
. ' ;:' '-f?;h.'!response to gas ~nhalation
.. ",jo
" ..: '"prior to exposure to light.,
. :) ;;': Tests were ,made with ~. 01,
.' .'.~ ,0.005 and 0.003 mg/m con-
. :centrations. Only one con-
, .'centration was used during
one day, and checks were
. made to determine the con-
stancy of the styrol air upon
.' concentration. Time between
. .': associations was varied to
prevent the possibility of
. formation of conditioned re-
'flexes to time and general
experimental conditions.
. Results obtained showed that
styro13vapor inhalation in 0.01
mg/m concentration, which
is not perceived by odor,
FIG. I - SENSITIVITY TO LIGHT OF TEST PERSON YU. A. IN TERMS elicited alpha-rhythm de-
OF I/x10-2. ARRO\-l I NOI CATES MOMENT OF VAPOR
INHALATlO~1 pression in test person L. N.
, , -, --- beginning with the 8th associa-
tion prior light switching in. On the 9th association the conditioned reflex
became more pronounced, as can be seen in Fig. 2. (See page 21). Beginning
with the 22nd association signs of conditioned reflex e.xtinction appea)ed.
Similar phenomena occurred in test persons G. O. Thus, O.?; mg/m con-
centration was active in both test persons. The 0.005 mg/m styrol concentra-
tion similarly elicited formation of conditioned reflexes in test person L. H. ,
which became especially clearly manifest on the 18th, 20~, and 22nd associa-
tion, as shown in Fig. 3 (See page 21). The 0.005 mg/m concentration flicit-
ed no conditioned reflex formation in test person G. O. The 0.003 mg/m con-
centration elicited no conditioned reflex formation in test persons G. O. or L. M.
Results are listed in Table 2. (See page 21). . Thus, the threshold concentration
causing conditioned 3eflex shifts in electrocortica1 brain activity was at the
level of 0.005 mg/m and no activity at the level of 0.003 mg/m3 styrol con-
centration in, the air. Summa ry of the data obtained in the study of reflex
action of styrol vapor on the receptors of the respiratory organs is presented
in Table 3 (See page 22). Of the basis of the data llsted in Table 3 it was
suggested that 0.003 mg/m of styrol vapor in the atmospheric air be accepted
as the limit of maximal single allowable concentrat~o~. ' <
"
). "
1500
"00
f200
.~ ~'.. ..~
1';00
CQ fI 00
I-
~ 1000
bJ
:> 900
I-
-<
;;; BOO
a::
~ 700
I-
:c
: 600
-'
~ 500
>-
~ 600
:>
-.- PURE AIR
--- 0.03 .Nt/AlJ -- - - .:
-..- 0.02 AI!! AlJ
- 0.01 AfZ/AlJ
~ 300
co
...
c'j; 200
. 100
o
6
10
15
20 25 30
T I HE I N MINUTES
60
50
60.
..
157
"""
, ~ ~
, .
!' '.
, .
, -.-.----., -'."-
-------
I~
j~
l~
. J.
1t~;l~
4
s.
'----
b A ~
FIG. 2 - ElECTROENCEPHALOGRAM OF TEST PERSON l. N. SH0\11 NG
CONDITIONED REFLEX OESYNCHRONIZATION AT THE 9TH ;
ASSOCI ATI ON \1ITH I NHALATION OF 0001 MG/M3 OF STYROL.. :
I - ELECTROENCEPHALOGRAM OF LEFT OCCIPITAL REGION;
2 - ELECTROENCEPnALOGRAM OF RIGKT OCCIPITAL REGIOU;
3 - ELECTROENCEPHALOCRAM OF LEFT TEMPORAL REGIOn;
4 - ELECTROENCEPHALOGRAM OF RIGHT TEMPORAL REGION;
5 - STYROL VAPOR SUPPLIED; 6 - SWITCHING IN AND OUT i
OF LIGHT
----
I
.;
J
a.
'I
L--J
. '" V-- 5
FIG. 3 - ELECTROENCEPHALOGRAM OF TEST PERSON l.N. SHOWI NG
CONDITIONED REFLEX DESYNGHRONrZATION AT THE 20TH
ASSOCIATION WITH INHALATION OF 0.005 MG/H3 OF STYROL.
..:.
" 2, 31> 4, 5, 61> SAME AS IN F I Go 2
TABLE 2
EFFECT OF STYROL VAPOR INHALATION ON THE CONDITIONED REFLEX
THRESHOLD OF ;lEGTROCORTICAl ACTIVITY
1111
TES
MG/H3 OF STYROL
. 0,01 0,005 0,003
T JALo OF I
T PERSOIl COND'D ASSOCI A- COHD'D, AssoCl1r- COIIDtD
. AssOCI
REflEX TION : REflEX TlON REFLEX 11 014
n. H. + 8 + 11 - -
r. O. + 7 - - - -
A-
158
-------
TABLE 3
STYROL THRESHOLD CONCENTRATIONS AS INDICATED BY EFFECT ON
ORGAN RECEPTIONS
..
FUNCTIONAL INDEXES
THR ESHOLD COIlCN.
III MG:/ H3
ODOR PERCEPn ON
EYE SENSITIVITY TO LIGHT
FORMATION OF ELECTROCORTICAL REFLEX
: ,
0,02
0,02
0,005
-----.-,h___- -
White rats were chronically exposed to different concentrations of styrol
vapor in the air for the determination of the average 24-hour limit of allowable
styrol concentration. Experiments were performed with four groups of fifteen
white male rats each, weighing approximately 50-60g. Rats were exposed to
the inhalation of styrol vapor in the air continuously for 70 days. Concentra-
tions of st~rol vapor in the air were as fo110"3s: 50 mg/m3 for rats of group 1,
0.5 mg/m for rats of group 2, 0.003 mg/m for group 3, and no styrol vapor
for rats of group 4, or the control animals. See figure 4 and figure 5 (Fig. 5
page 23).
0.020
0,0'5
A
INHALATION
EXPOSURE
2 J 466 7 89m N ~ 8
co
..
c
'"
c
...
o
: 0.015
~ 0,010
B
a::
...
...
'"
o
-
>- 0,005
><
c
...
o
'"
'"'
o
l-
e
'"
...
...
=>
OJ
...
a:
I 2 J 4 .f 5 7 8 9 '0' 'f 1.2
.0.015
c
------
O,O~O -""'...,.-------"-------....------
. I
I
,
I
I
InHALATION
EXPOSURE
0,005
f 2 J
4 5 6 7 8 $ 10 II 12
.. . T-'"E III WEEKS
- .EXTENSOR ! ---- FLEXOR
. ---------..----... .-
FIG. 4- AVERAGE MUSCLE CHRONAXY IN RATS (A) OF GROUP I.
(8) GROUP 2 AND (C) OF GROUP 3.
-----..- _. - -.+-,
. - ... - .- - .'
. .--- --..--- . .-.... - -. ._-"-
159
-------
Styrol concentration in the air
to which rats of group 1 were
exposed was the same as the
limit of allowable styrol vapor
concentration in working pre-
mises, and the concentration
to which rats of gro:up 3 were
exposed was the same as the
,proposed maximal single allow-
able concentration of styrol in
atmospheric air. Records were
kept of the general condition of
the rats, changes in their weight,
changes in muscle antagonists
motor chronaxy ratio, rate of
coproporphyrin eli,mination
with the urine, changes in
cholinesterase activity of whole
blood, in the blood picture, and
also of the appearance of patho-
logic symptoms in the internal
organs of the experimental ani-
mals. Observations indicated
that the animals were in good
health, active and gained weight
throughout the course of the
chronic exposure to styrol
vapor inhalation. Concentrations of s.tyro1 vapor in the air of the exposure
chambers, fluctuated only slightly. Thus, for rats of group 1 the styrol con-
centration,was350. 88 1: 0.037 mg/m3, and for rats of group 3 it wCl.~ 0.0031 1:
0.00014 mg/m. The styrol vapor concentrations in the exposure chamber
were checked once or twice daily in the course of the experiment. , See Fig.
6 (page 24) .
The effect of styrol vapor on the functional state of the cent:r:a1 ne rvous
system wa's determined by the method of chronaxy ratio of the right hind leg
muscle antagonists. Chronaxy determinations were made in five rats of each
group under similar conditions and at the same hour of the day. At the end
of the 3rd week of inhalation exposure disturbed extensor and flexor chrofaxy
ratios appeared in rats o£: group 1 which inhaled air containing 50 rng/m of
styrol vapor. This was clearly indicated by dips in the curves illustrated in
Fig. 4 (see page 23). Prior to the vapor inhalation the extensor and flexor
chronaxy ,ratio was 1.28, wi.th the flexor chronaxy taken as unity. On the 3rd
week of experimental exposure the chronaxy ratio was reduced to 0.41. This
condition persisted to the end of the experimental inhalation and at the end of
the experiment the chronaxy ratio did not exceed O. 77, i. e. it was less than
unity; howeve r, at the end of the recuperation pe riod it returned to its normal
1-
0.025
Q020
v. 0'5
0. Of:J
,~ ':f
[ RAT No. I
I
RECUf'ERA-
IrION
: f'ERIOII
r"''''--
8 9 '0 f/ 'Z
-
. : /,025
, ~ q,020
II: u,Of5
~ 0. Of 0
fJ.oOJ
0.025
0,020
~Of5
,Of 0
0.005
" ,
I '...'
I
I I I r
9 '0 fI (2
I
( 2 oJ. ~ 5 5 7 89 '0 If '2
TIME IN WEEKS
- EXTENSOR --- FLEXOR
FIG. 5 - MUSCLE CHRONAXY) N I ND) VI OUA L RATS OF GROUP I
, OURI NG CHRONI C I NHALA T/ ON EXPOSURE
160
.,~. \; ~ 1
.,
-------
value. It should be mentioned
at this point that the above
values represented averages,
and that the intensity of styrol
vapor effect on the muscle anta-
gonists chronaxy ratio differed
with individual rats, although the.
general picture was of the same
character. The effects were also
generally the same in rats of
group 2, although the intensity
was less pronounced. This is
illustrated by curves in Fig. 6.
The muscle antagonist chronaxy
ratios in rats 01 group 3 exposed
to 0.003 mg/m of styrol re-
mained normal, ranging between
1. 09 and 1. 35, with an average
of 1. 2. Absolute values of
chronaxy ratio changes in the
muscle antagonists of rats of all
groups are presented in Table 4.
(See page 25). Data in Table 4
show that 34 instances of reverse
muscle" antagonist chronaxy ratio
occurred among the rats of group
1 during the periods of exposure
and recuperation; only 17 such
instances, or 50%, were noted among the rats of group 2; no such phenomena
were noted among the rats of group 3. However, analysis indicated that the
magnitudes of changes in the - rheobase of the muscle antagonists in animals of
a~l groups were slight and statistically insignificant. See Table 5, (page 25).
The effect of chronic inhalation of sytrol vapor on the rats I general
metabolism .was studies using changes in the rate of porphyrin meta-
bolism as the index. M.l. Gusev first studied the rate oj p~rphyri~ elimina-
tion following the inhalation of lead oxide in 10-11 mg/m concentration for 6
hours daily for 6.5 months (1960). M.1. Gusev regarded the appearance of
porphyrin in the urine of rabbits .subje.cted to lead intoxication as the result of
depressed enzyme systems and changes in cellular metabolism of the nervous
system, the liver, and the bone marrow. Porphyrin determinations were made
spectrophotometrically as described by M.l. Gusev and by Yu. K. Smirnov in
1960. Quantitative estimations were made -on the basis of optic density of
maximal absorption at 402 m f.L' measured with the aid of spectrophotomete r
SF -4. The amount of coproporphyrin eliminated with the urine by the rats of
each group was determined once every 10 days, and the total of such deter-
minations amount to 36. Results are presented in the form of curves in Fig. 7.
(see page 26).
0,025
0.020
O,Of.5 - I
0.010 i-----
0,00.5 I
RECUPERA-
TlOIl
: PERIOD
--...........-..-----.-.:.
0,02.5
0.020
0. Of .5
0.010
. 0. 005
In
£>
~
'"
~. 0.025
~ 0.020
cr'
.. o,Of 5
~ 0.010
., 0, 005
1 2 J 4
! RAT No.2
I
I
7 8 $ 10 fI 12
I
I
I
5 5
.5 5 7 8
$ 10 If 12
I
I
1,
~
..
~
~ 0.025
1:1 0.020
(.) 0.015
.0.010
.0.005
1
2
~ -,' I -.-...
fNHALATION :
EXPOSURE ' , I I ,
J 4 .5 5 7 8 9 10 II f2
: RAT No. ~
I
1 2 J
RAT No.5
4
9 fO If 12
557 8
'0,025
tJ,OZO
0.0f5
0.010 - "
0.005 ""!--'
1
2
,--'" I
,'--...~' '",..,--......1
,'" . ~-,
, I
~ KHALATION I
EXPOSURE ,.
. I 1 I .J I ~
J 4 5 5 7 8 $ 10 Ii 1£
T I ME IN WEEKS
--- FLEXOR
- EXTENSOR
~~ -"
FIG. 6 - MUSCLE CHRONAXY IN INDIVIDUAL RATS OF GROUP 2.
161
,
-------
. - ~
T AS LE 4
MUSCLE-ANTAGONISTS CHRONAXY RATIOS IN RATS OF ALL GROUPS DURING
CHRONIC INHALATION EXPOSURE
BEFORE EXPOSURE PERIOO RECOVERY
EXPO$-,
' URE pERIOD
GROUPS 2\31415\6171819110111 113
I 12
ORE 1,3 l,s11,210,41,olo,710,810,~ O,7!O,8!0 6 t ,2 1,4
Two 1,3 1,311,1 1,4 1,3jO,91,2 1,1 0,80,90,9 1,3 1,3
THREE 1,3 1,211,2 1 ,3 1 ,211 ,211 ,1 1.2 1 ,211 ,211 , 1 1,2 1,1
CONTROL 1,6 2,°11,712,812,81,71,71,71,71,71,7 1,7 1,8
TABLE 5 \
,
NUMSER OF 01 STURBEO EXTENSOR AND FLEXOR MUSCLE CHRONAXY
- RATIOS IN RATS OCCURING DURING THE EXPOSURE AND
RECOVERY PERIODS
--
GROUPS OF, RATS '
DATES OIlE \ Two \ THREE I CONTROL
-, 0 '
27/V 0 0 0
BEFORE EXPOSURE ° 0 °
8/VI i ' °
IS/VI 0 0 0 0
21/VI 5 ° 0 0
28/VI 2 0 0 0
S/VII 5 2 0 0
12/VII 4 2 0 0
19/VII 4 2 0 0
26/V II 5 5 0 0
2/VII 3 3 0 0
9/VII S 3 0 0
EXPOSURE' 0 0 0
16lVIII I
23/V I II I 0 0 0
RECOVERY
I' ER I OD
-
----!
The curves in Fig. 7 (page 26)
show that the quantity of copro-
,.porphyrin eliminated with the
urine by the control group grad-
- ually rose, probably as the re-
suit of the rats I gain in weight
with age. The correlation co-
efficient between the amount of
'coproporphyrin 'and th,e animal
.. . ---
weight was rather high amount-
ing to + O. 90.. The nature of
curves' depicting the rate of
COpt'opo:..",?hyrin elimination
-- ...- - -- . -
wlth- the urine of rats' belonging
to group 3 were identical with
those of rats belonging to the
Gontrol group. The curves of
coproporphyrin elimination with
the urine of rats belonging to
I groups 1 and 2 exposed to 50
ToULS ' ,,34 17 0 0 and 0.5 mg/m3 concentrations
, ,
of styrol vapor showed at first a rapid ascent followed by a drop which per-
sisted to the end of the experimental inhalation exposure. Following the te rm-
! ination of the exposure, rate of coproporphyrin elimination began to rise,
/ without returning to the original level. Thus, results of t~e experiments in- ,
/ dicated that inhalation of styrol vapor in 50 and O~ 5 mg/m concentration de-
.1 pressed coprop':>rphyrin metabolis m. A correlation of the rats' weight
with the data obtained on the rate of coproporphyrin elimination with the
urine showed that the depression in the elimination of coproporphyrin was
in no way connected with the ,animals I loss of weight. Statistical analysis
showed that coproporphyrine values obtained in connection with rats of
groups land 2 were 99.99% reliable. This can be seen from data recorded
in Table 6. (See page 26). The rate of copr::>porphyrin elimination with the
urine of rats belonging to groups land 2 returned to their near normal levels
during the period of recuperation. As was pointed out above; rates of copro-
162
-------
.,..
/----,.."'"
/
/
1", ---_/
/ ,~",. ..,..:;
I. ,'/
~,' V ---.', .....-";,, .
,..' z..",."".~ ,....-:......".,.,-
',.. ,,,...
" ~. '\ .~;
~---'..~. ~ ,,,,,..., ,,-""',,':
........",8 ":.....~'" ';:W':.: " :
. '....... --.. "'.....,' :
: RECOVERY
:. PERIOD
I
to/VI cO/VI JOin fOIVll . 20/YII JO/VlJ IO/JIllJ 2tJ/V1ll JO/Ylll
DATES OF 08SERVATION .
. .
........ GROU' ONE -.- GROUP' TWO
--- GROU' THREE ~ CONTROL SROUP
FIG. 7 - MICROGRAMS OF COPROPORPHYRINE ELIMINATED WITH THE URINE
------. <. IN RAT~- OF DIFFERENT GROUPS
TABLE 6 por.phyrin elimination with /
RATE OF COPROPORPHYRINE ELIMINATION \-IITH THE URINE OF RATS the urine of ~ats exposed to
DURI NG AND AFTER EXPOSURE TO STYROL I NHALAT I ON . O. 003 mg/ m of styrol in-
halation on a chronic basis
were .nearly identical with
those of rats of the contrql
3 . group. This was further
verified by results of statis - .
tical analysis of fluctuations.
Similar results were obtained
by T.M. Shu1'ga in 1961, by
G. 1. Solomin in 1961 and
othe r inves tigators in similar
experiments with low concen-
NOTE: DUREE '0' RELIAlILlTY: A - 95}1:; 8 - ~; C - 99.9%; trations of carbon monoxide
0- HOT RElUDLE and dinyl vapors.
Inte resting and significan~ results were obtained in the study of cholin-
esterase activity in whole blood. In the present experiments cholinesterase
activity was determined by the che.mical method of A. A. Pokrovskii in 1953.
The average time required for the indicator color change under normal con-
ditions was 43 :1:0.4 min. for animals of all groups. Results listed in Table 7
(see page 27) show that the time required for the hydrolysis of acetylocholine
was reduced .at the end of the intoxication period to 32.2 min. in t~e rats which
were subjected to the prolonged effect of styrol vapor in 50 mg/m concentra-
tion. All results were verified statistically with exception of the data obtained
on 28- V. 1. Similar low values were obtained in the experiments with rats of
Group No.2. Fluctuations from the normal in the time of acetylcholine hydro-
lysis of rats belonging to the control group were statistically insignificant.
5,(1
4,C'
~
"'CO
z'"
;;; ~ J,i1
>- :J:.
3:
~((j
~ ~. 2,0
a:ac
LJ:
o .
o 1.0
o
EXP'OSURE PER I OD .
DATES
CO'ROP'O\P'HYRINE ELIMINATED IN
"KG/IOO 6 OF 80DY WEIGHT
CONTROL I GROU' 1 I GROU' 2 I GROUP
I - 30/vi
, I/vlI-
9/v III
1,90 .
1.63
1.47 (0)
0.58 (c)
1,13 (0)
0,61 (c)
1.39 (0)
1,18 (0)
RE80VERY !'ER 10'
10 - ~VIII
1,74 .
1,05 (0)
1,04 (0)
1,48 (0)
163
-------
TABLE 7
CHOLINESTERASE ACTIVITY IN MIN. IN RATS OF ALL GROUPS DURING CHRONIC INHALATION TESTS
. --
BEFORE EXPOSURE PER I OD RECOVERY
RAT GROUP EXPOSURE PERIOD
30/V. 14/VI I 28/VI j 13/VII I 25/V II I 9/VIII 23/VIII
..
GROUP I 44,6 (0) 38,8 (a) 39,4 (0) 35,8 (e) 32,6 (e) 32,2 (e) 40,6 (0)
GROUP 2 - " 43,0 (0) 41,2 (b) 40,4 (0) 41,6 (0) 40,6 (0) 39,8 (b) 42,0 (0)
GROUI" 3 44,0 (0) 43,2 (0) 41,4 (0) 41,2 (0) 42,4 (0) 43,8 (0) 43,6 (0)
ONTROL GROUP 44,0 43,4 41.2 42,8 42,4 42,8 43,2
..
C
NOTE: DEGREE OF RELIUILITY: A - 95l'; D - 99%; c: - 99.9%; 0 - UNRELIULB
'TABLE 8
RAT GROUI"
B EF ORE
UI"OSURE
,EFFECT OF SYT.ROl. VAPOR I NHA LAT! ON ON NUMBER OF LEUCOCYTES
EXPOSURE PER I OD
DETERHINATIOHS
I. 3RD
2ND
4TII
I . 5TII
RECOVERY
PER I OD
1ST
GROUI" I 10 600 (0) 15000 (0) 19650 (b) 17200 (b) 16400 (b) 12700 (0) 9840 (0)
G:!OUP 2 9 280 (0) ]0500 (0) 12700 (a) 11300 (a) 12600 (a) 10 400 (0) 9170 (0)
GROUI" 3 8830 (0) 9990 (0) 9330 (0) 9600 (0' 10 300 (0) 9800 (0) 9060 (0)
CONTROL GROUP " 8940 9360 9660 9020 9300 10 000 8920
NOTE: ,DEGREE OF RELIABilITY; A - 95}6; 8 - 99J'; C - 99.9%; 0 - UNREllUlI
Thus, the exposure of rats to the inhalation of air containing 50 and 0.5 mg/m 3
of styrol. vapor continuously for 70 days produced statistically reliable increase
in the activity of blood cholinesterase. Parellel studies were made of the
morphologic blood picture s of the rats. T. A. Blinov showed in 1955 that the
chronic effect of mg/li of styrol vapor produced by subjecting rabbits to the
inhalation of the styrol 78 hours daily for 62 days elicited monocytosis and
reticulocytosis. At the end of the inhalation period the rabbits showed a
marked increase in the number of pathologic granular pseudoeosinophiles.
V. A. Pokrovskii showed in 1955 that 0.6 mg/li of styrol vapor frequently
elicited l,eucocytosis and monocytosis accompanied by the appearance of
anemia and thrombopenia. See tables 7 and 8.
Effect of styrol vapor on the, morphologic composition of the blood was
studied by making two observations in the course of one month. Results in-
dicated that the numbers of leucocytes and monocytes increased and of the
erythrfcytes decreased in rats of group 1 which inhaled air containing 50
mg/m of styrol vapor. Actual numbers were as follows: prior to the vapor
inhalatiori the leucocytes of rats belonging to group l' amounted to 10, 700, .
and at the end of 30 days exposure the number rose to 19,650, after which
there was a gradual drop in the number of leucocytes and at the en<;l of the
recupe ration pe riod was 9. 840. Similar results, but of lower levels. were
noted in the rats belonging to group 2; no statistically significant changes
were. noted in the blood morphology of rats of group 3, as can be seen from
the data listed in Table 8. .
The information obtained thus far can be summarized as follows: in-
i64 - ~
----- -.---
-------
halation of air containing 0.5 mg/m3 of styrol lowered the number of erythro-
cytes to a considerably lesser degree, but the values were still statistically
significant. Changes in the numbe3 of erythrocytes in rats of group 3, which
inhaled air containing 0.003 mg/m of styrol, were insignificant statistically.
The number of blood monocytes increased considerably. Monocytosis appear-
ed in all rats of group 1, as shown in Fig. 8. At the end of the first month of
exposure to styrol vapor the number of monocytes of rats in group 1 rose to
4% as compared with 1. 2% in rats of the control group. At the end of the 2nd
month of exposure the monocytes rose to 8.4% and in one rat rose to 15%.
Increase in the number of monocytes
in rats of group 2~ inhaling air con-
9 /\ taining 0.5 mg/m of styrol, was
I;; 8 ... ... . . 11
.... " .., statlstlca y insignificant. No changes
~ 7 ,/ \ were noted in the number of monocyte
.. "
",' 5 ,/ "'" in any rats of group 3. It should be
- .;; .....
W 5 ..,' '. noted at this point that chronic intoxi-
w ...-
E..6 .:',.,.. .-:-; cation of rats with styrol vapor brought
~, J 0 about variable changes in the blood
~ 2 EXPOSURE :RECOVERY morphology, which were in greatest
10D . : PERIOD
( PER' evidence during the first two months
I/Yl IJjVI JO/VI IJ/VU .J(}/VII 9/VUI 2J/VIU of exposure. Similar observations in
DATE OF 086ERYATI?~
..... GRO-UI' OIlE -'- GROUP TWO connec tion with styrol intoxication we re
--- GROUP TYREE - CONTROL GROUP made by V.A.- Pokrovskii in 1961.
FIG. 8 - NUMBER OF MONOCYTES IN RATS OF DIFFERENT Pathohistologic studies of the ex-
- GROUPS 3 pe rimental rats indicated that chronic
inhalation of air containing 50 mg/m of styrol brought about in rats of group 1 .
small foci of interstitial pneumonia, pulmonary emphysema, bronchitis and
focal dystrophy of the kidney convoluted tllbules. No changes were noted
in the heart, liver and spleen. The histologic picture was of the same general
character in rats of group 2, which inhaled air containing 0.5 mg/m3 of styrol,
but to a considerably lower degree. No notable changes were observed in the
hi::;top~thologic pictures of rats of group 3 which inhaled air containing 0.03
mg/m of styrol. Thus, the experimental data showed that in 0.003 mg/m3
concentration of styrol vapor elicited no changes in the organism of rats;
therefore, it was recommended that 0.003 mg/m3 of styrol be regarded as.
the limit of allowable 24 -hour conceni rat.ion in a~mospheric air.
This limit of allowable styrol concentration in atmospheric air was then
used as the basis for the hygienic evaluation of atmospheric air pollution in
populated areas surrounding a chemical plant which had two departments
producing polystyrol, using styrol as the raw material. The atmospheric air
surrounding the plant was polluted by styrol vapor discharged into the air by
the plants ventilation syste m and by vapor leakage due to the absence of a
hermetically closed system of production. Styrol concentrations were de-
termined spectrophotometrically by a method developed in cooperation.with
M. D. Manit in 1961, which was also applicable to the determination of dinyl
vapor discharged into the air by the plant together with the styrol vapor.
10
165
-------
T AS LE 9
MAXIMAL SINGLE STYROL VAPOR CONCENTRATION IN THE ATMOSPHERING AIR
IN THE VICINITY OF THE'CHEMICAL PLANT
~ TABLE 9 - NO.OF &LES WIT" MG/M3 CONCHS.
:z:m
.. ~
7-'
S ~ OVER
~ :z 0.\
<-
~
....",
:1:0<11
o ..
"'1-<
...:Z:Z:
-U
J0(/)
~A.-
..
~
cCllI
...
.......
gA.
:E:
. ..
OlD
Z,
50
100
300
500
34 0,3316 9
26 0,0402
34 0,0213 -
40 0,0023 -
0.1 - 0.049 - 0.099 - BELOW
0.05 0.001 0.003 0.003
\0' ,I 10 5
8 6 12
2 2 30
40
TABLE 10
:MAXIMAL SINGLE AND 24 HOUR AVERAGE DINYL VAPOR AIR CONCENTRATION
1 N THE VI C\ NI TY OF THE CHEMI CA L PLANT
, Me FROM THE - MG/113 OF D I NYL CONCS.
'DiSCIUR6E MU. 61 HilLE j' AVER. 241ft
POlrT CONCN. conCN.
50
100
300
500 ..
0,7423
0,3046
0,3949
0,0934
0,2788
0,0901
0,1204
0,0536
The spectrophotometric determination of styrol and dinyl simultaneously
present in the air was made by subjecting an alcoholic solution of the vapors to
ultra violet absorption in the region of 211.5 and 245 mp. wave lengths in a
colorimetric tube containing a 10 mm column of the alcoholic solution. The
concentrations of styrol and dinyl are computed with the aid of formulas de-,
rived by the method of Firordt as described by A. Gilem and E. Shtern in
1957. The sensitivity of this method was 0.24 /.L Iml for styrol and 0.3
/.l Iml for dinyl..', Results of the determination are listed in Tables 9 and 10.
Data in Table 9 show that the maximal single concentration of styrol exceeded
the proposed limit of allowable concentration even at 300 m from the 'point of
discharge, and that at 500 m from the ~lant, the maximal single styrol con-
centration in the air was 0.0023 mglm , which is considerably below the pro-
posed limit of allowable concentration; Data in Table 10 show that dinyl vapor
discharged by the plant extended over a considerable distance from the plant,
as shown by the fact that maximal single concentrations of this vapor exceeded
the limit of allowable concentration even at 500 m from the point of discharge.
Thus, the study conducted in the vicinity of the chemical plant had shown that
the atmospheric airwas heavily polluted with vapors of styrol and dinyl. ,Con-
centrations of styrol in the atmospheric air at 300 m from the plant and of
dinyl vapors at 500 m from the point of discharge exceeded the limits of tl),eir
allowable concentrations.
166
-------
Conclusions
1. The concentration of thr3shold styrol vapor odor perception in most
sensitive persons was 0.01 mg/m . and the subthreshold non-perceptible con-
centration was 0.01 mg/m .
2. The threshold effect on reflex changes in eye sensitivity to light in
response to styrol ~halation was the same as the threshold of odor perception.
namely 0.02 mg/m . . . .
3. The threshold st3'rol concentration capable of forming electrocortical
. reflexes was 0.005 mg/m .
4. The recommended limit of allowable single styrol concentration in
atmosphe ric air was 0.003 mg/m 3.
5. Rats yposed to continuous 70 days inhalat: on of air containing 50.
and 0.05 mg/m of styrol vapor manifested disturbed muscle antagonists
chronaxy ratios. a lowered coproporphyrin elimination with the urine. en-
hanced blood cholinesterase activity. increased numbers of leucocytes and
monocytes and reduced number of erythrocytes, also some histopatholo~c
changes of the inte rnal organs. Inhalation of air containing 0.003 mg/m of
styrol under similar experimental conditions had no effect on any of the above
mentioned indexes.
6. Results of the present investigation suggest that 0.003 mg/m3 of
styrol in the air can be recommended as the limit of allowable styrol con-
centration in the atmospheric air.
7. Sanitary examination of the atmospheric air in the vicinity of a
chemical plant producing polystyrol clearly indicated that styrol vapor air
pollution extended over considerable distances from the plant and that only
at 500 m from the source of pollution was the styrol concentration in the
atmospheric air below the proposed limit of its allowable concentration.
167
-------
BIBLIOGRAPHY
5 JI H HOB aT. A. BJlHRHHe MaJlblX KOHueHTpallHii 6eH30Jla.
CTHpOJla H a-MeTHJlCTHpOJla Ha Kp08b 8 YCJl08HIIX XpOHH'IeCKOrO onbiTa.
n.. 1955.
5 JI H HOB a T. A., P bI JI 0 B a M. JI. TOKCII'IeCKOe .l1eiicTBlle
CTHpOJla H a'MeTIIJlCTHpOJla. B KH.: MaTepHaJlbl no TOKCH'IeCKIlM BelUe-
CTBaM: npHMeHlleMbiM 8 npOH3B0.l1CTRe nJlaCTH'IeCKHX Macc H CHHTeTH-
'IeCKIiX KaY'IYKOB. JI., 1957, CTp. 5-25.
5 Y ill T Y e B a K. A.. no JI e >K a e B E. 4>., C eM e H e H -.
K 0 A..ll. 113MeHeHlle nopor08 peJJeKTOpHOrO .l1eiiCTBHR aTMoc. naTOJloroaHaTOMH'IeCKHe H3MeHeHHR npH
OTpaBJleHlI1I CTllpO.10M. B KH.: 3KcnepHMeHTaJlbHble HCCJlC,'J,OBaHHR no
npl>\lhlUI.1CUllbiM R.l1aM. n.. 1936, CTp. 104-111.
H y c e JI b M a II 3.,11. TOKCH'IeCKOe.l1eiicTBHecTllpo.la Ha opra-
HII3M >KIIOOTHbIX. B KH.: 3KcnepllMeHTaJlbHble HCCJleAOBaHIiR no npo-
MblillJle'HHblM R.l1aM. JI., 1936. CTp. 95. .
no K po B C K H ii B. A. TOKCIIKOJlOrHR H rHrHeHa npoH3Bo)J.cTBa
CHHTeTH'IeCKOro KaY'IYKa. M.. 1955.
, n 0 ,1 eTa e B M.. 11. KOJlopHMeTpH'IeCKHii MeTOA on pe,'J,eJlell II II
MiI.lb1X KOJlll4eCTO CTllpOJla B 003)J.yxe. fHrueHa H caHHTapllR, 1952,
Ng 3. CTp. 46-47.
P R 3 a HOB B. A., 5 Y ill T Y e B.a - K. A., H 0 8 H K 08 10. B.
K MeTO)J.lIKe 3KcnepliMellTaJlbHOrO 060CHooaHHII npeAeJJbHO AonYCTH-
MbiX KOHueHTpallHii anlOcK, 1954.
ill y JI bra T. M. HeKOTopble ,'J,aHHble K 060CH08aHHIO npe.l1eJlbHO
,'J,onYCTHMoii KOHlleHTpaUIiH OKHCH yrJlepo)J.a 8 aTMoc
-------
Hygienic Evaluation of Atmospheric Air Pollution
with Dimethylformamide
D. G. Odoshashvili
Department of Community Hygiene of the Central
Institute of Post-Graduate Medicine
Dimethylformamide is a colorless mobile liquid having a specific heavy
odor reminiscent of spoiled herring. The sp. gr. is 0.96, boiling temperature
1550 and evaporation temperature 11. 90. It mixes in all proportion with water,
alcohol and simple and complex esters, ketones, aromatic hydrocarbons,
amines, alkaloids, etc. It is easily evaporated by steam. Dimethylformamide
is an excellent organic solvent. It is used as a polyacrylonitryl solvent in the
preparation of the synthetic fiber known as "nitron", which is expected to be
produced in the USSR on a large scale. Dimethylformamide is used in the ex-
plosive industry for the preparation of gelatinized nitroglycerin imparting to
the latter a high degree of stability. Because of its high solving properties in
relation to aromatic compounds dimethylformamide is used in the purification
and anlysis of diesel fuel and other combustible materials in the determination
of aromatic compounds. Dimethylformamide is a solvent for some resins used
as lacquers directly or as supplements and for the production of glue and color":
ing materials used by the printing industry. Dimethylformamide is widely used
in the production of polyacrylonitryl fibers which occupy second place in the
international production of fibers, being next only to the production of poly-
amide fibers. It is easily understood that in the vicinity of some plants, which
use dimethylformamide, atmospheric air pollution with this substance can easily
oc cur.
In this connection a dete rmination of the effect of low dimethylformamide
concentrations on the organism, and a consequent determination of the limit of
its allowable concentration in the atmospheric air, present a matter of sanitary
hygienic importance. Information contained in the literature regarding dimethyl-
formamide toxicity is ve ry limited. Workers of the Ivanovsk Institute of Labor
Protection studied the hygienic conditions in an industrial"nitron" production
installation in 1957. Results of the investigation showed that the air of working
premises contained high concentrations of dimethylformamide producing in-
toxication and illness. The investigators noted several instances of subacute
intoxication accompanied by general weakness, vertigo, bitter taste in the mouth,
nausea, vomiting and shortness of breath. They also noted one case of acute.
poisoning accompanied by loss of consciousness, vomiting and cardio-vascular
weakness. Morbidity among the workers engaged in the production of "nitron"
was 3. 1 times as high as among workers in the viscose silk spinning depart-
ment. The symptoms were predominantly those of damage to the bile ducts
and to the kidneys.
169
-------
~ ;.,.~):,.
K. P. Stankova described experiments with inhalation by whit~ :mice .of
dimethyl£ormamide in concentrations ff 20,000 - ~3, 000 mg/m 3 for .'twoh'O''o1FS.
Results show~d that the 23,000 mg/m concentratlOn was absolutely lethal and
20,000 mg/r:n was the maximal tolerance concentration. In another series of
experiments white mice were administered different doses of dimethyl£ormamide
per os; in .this case 5 g/kg was the absolute lethal dose, 1. 25 g/kg \i.;as thej'~
minimum l~thal dose, and O. 5 g/kg was the maximum tolerance dose. K'. p,
Lobanova conducted chronic intox1cation experiments with rats in concentra-
tions of 300-500 and 30-50 mg/m for 4 hours daily for 6 months. 'Effects of
exposure tq,the above dimethylformamide concentrations on the ani~a1s I~'cbri-
ditioned reflex activity, on blood morphology, on the weight and on ,morphologic
changes in the ce~tra1 nervous syste m we re used as the indexes. Mice exposed
to 300-500 mg/m of dimethyl£ormamide manifested changes in their conditioned
,.
reflexes, a drop in the hemoglobin concentration and a slight reduCtion in th'e
numbe r of)euc~cytes. Results showed that a dimethylformamide c9ncentration
of 30-50 mg/m was inactive as shown by the above indexes. On t~e, basis of
such re.s1.llts the limit of allowable dimet~ylformamide concentratiop in the 'air
of workinR.premises was set at 10 mg/m '. '. !
Massmak investigated the capacity of dimethylformamide to p~netrate the
intact skin. He subme rged rats' tails into a concentrated solution 6f dimethyl-
formamide for 8 hours; the experimental rats died of dimethy1formamid~ poison-
ing. Thus,. it was demonstrated that dimethylformami.de could pene.trate into
the animal organism through the respiratory passages, through the gastro-in-
testinal tr:acts and through the intact skin. It was also shown that chronic poison-
ing with di,methylformamide damaged the central nervous system, ~he paren- .
chymatous :qrgaIls, such as the liver and kidneys, the cardio-vascular system
and affect.ed, the blood picture. No information was found in the litE7rature of
USSR and foreign literature on the atmospheric air pollution with dimethyl-
formamide vapor in the vicinity of plants using this substance in the production
or procesl3ing of materials. Low concentrations of dimethylforma~ide vapor
in the atmospheric air were determined by the method of M.D. Babin and G.S.
. P~vlovskay~, as modified by the present writer in cooperation with M. V.
Alekseeva, which resulted in a ten-fold increase in the sensitivity?f the method. '
By this method the dimethylformamide was saponified into a dimethylamine;
the latter was determined colorimetrically following its reaction with 2, 4-
dinitrochlC?robenzene. Sensitivity of the method was 0.001 mg of dimethyl-
formamide; in 2 ml of solution. The method is specific for dimethylformamide.
Determination of the limit of single allowable dimethylformafnide con-
centration'in the atmospheric air was conducted by the method of d~~ethyl-
formamide.threshold odor perception. Tests were made during the morning
hours, once daily. The total number of tests was 344. The minim~al dimethy13
formamid~.odor perception concentration ranged between O. 14 and,~. 88 mg/m .
Accordingly, con<3entration of threshold odor perception of t~is su~.stance was
set at O. 15 mg/m .. Further tests indicated that O. 11 mg/m constituted the
maximal nonperceptible subthreshold concentration of dimethylfor~amide.
Actual da~a are reported in Table 1 (see page 34). f'
.; I
170
"
'.,
-------
K. A. Bushtueva in 1960,
V.-A. Gofmek1er in 1960, Lee
Shen in 1961 and G. 1. S o1omin
in 1961, and others success-
- fully employed the method of
conditioned electrocortical
reflex development in their
studies of the hygienic stan-
dardization of atmospheric
air pollution. They showed
that low concentrations of
chemical substances usually
not perceived by the olphactory
analyzer elicited definite
changes in brain electrocor-
tical activity. The present
F writer followed the method
described by K. A. Bushtueva,
E. F. Polezhaev and A. D.
Sememenko in 1960 in his
study of threshold reflex effect
of dimethylformamide on brain
ele~trocortical activity result-:
ingfrorn the inhalation of dif-
+ REFLEX E~I~ITE'; -REFLEX NOT EU.CITEI ferent dimethylformamide
vapor concent~ations. In the
present studies use was made of the Kaizer 8 lead electroencephalograph. '
Of the 22 persons observed 6 were selected for the final test; none of them
were over 30 years of age and all had a clearly expressed alpha-rhythm. The
test persons were kept in specially equipped test chambers in a semi-reclined
position in a state of absolute rest. Light was used as the unconditioned stimu-
lator which elicited desynchronization of the alpha-rhythm, and inhalation of the
dimethylformamide vapor was used as the conditioned reflex stimulator; the
vapor was run into the inhalation tube for 15 sec. in a definite concentration.
During the last 5 sec. of the vapor inhalation the eyes were subjected to stimu-
lation by light. Conditioned reflex was regarded as elicited and the dimethyl-
formamide concentration as active when desynchronization of the alpha-rhythm
became manifest before the light was switched in. The dimethylformamide con-
centration was gradually reduced until the threshold was found below which con-
ditioned reflex could no more be elicited.
Forty-six investigations were thus conducted wi~ the following dimethyl-
formamide concentrations: 0.12, 0.08, 0.05, andO. 032 mg/m~ One of these
concentrations was expect~d to represent the threshold effect on the electro
brain activity; 0.08 .mg/m of dimethylformamide proved t03be such a threshold
concentratio~ for three of the test persons and 0.055 mg/m for the other three;
0.032 mg/m proved> to be the nonactive concentration for all six test persons,
TABLE I
CONCENTRATIONS OF DIMETHYLFORMAMIOE VAPOR ODOR
PERCEPTION
TEST No.
NUHBER OF
TEiTS
01 HETMYLFORI1AIU DE CONCIIS. .
IN MG/H3
:M 1/1. PER-; I Mu. NON- .
cErTIBLE PERCEPTI8LE'
1
2
3
4
5
2
2
1
6
1
0,14
0,37
0.55
0,74
0,88
0.11
0.15
0.37
0,55
0,74
TABLE 2
ElECTROCQRTI CAl COND I TI ONED REFLEX FORMAT! ON
ELI CI TED BY DI MET HYLFORMAMI DE VAPOR I NHALAT I ON
- . .
COICII. IN H'/H3 I
I NITlAL6 OF 0,12 I I I . rNRESKOLD NUHDEII 0
TEST PUSOI 0,08 0,055 0,032 CONCN. TUT'
: l.. E. . 0.055 6
+ + + -
: V. s. + + + - 0.055 .8
L. P. + + + - 0.055 8
G. G. + + - - I 0,08 8
v. P. + + - - 0,08 8
E. M. . + + - - 0.08 8
171
-------
as can be seen in Table Z. (see page 34). Curves in Figures land Z illustrate
the fo 1jmati on of electro cortical conditio.ned reflexes by the inhalation of 0.05
mg/m of dimethyl£ormamide in test persons, L. E. and L. P. .
. . The Figures sho'wthat de-.
sychronization of the alpha-
YI~.' ~ rhythm appeared prior to the
switching in of the light. The
~ absence of re£lexrespon~e to
the effect of 0.03Zmg/m of
dimethyl£ormamide -in the case
. .. of test person L. E. is shown
in Fig. 3. In this case de-
sychronization appeared only
after switching the light stimu-
lator. In two test .subjects the
encephalograms were accom-
panied by electrocardiograms
made from the standard II lead
electrocardiograph and myo-
grams of the left-a:rm, of the
thumb and of the respiration.
It was necessary to keep the
test subjects in a dark room
but in an active mental state.
This was accomplished by
placing in front of .the test
persons a screen with geometric
figures, - a circle, an eHips,
a square, a rhombic figure.
A,.:;I""'. _.......-- 't.,4It_I.~. '. ....:..... During the test light was.
; ~~~/""",,~j". thrown interchangeably on
~"~"'i'P"".I"."'--IIf_"" ".,. ~..... one of these figures: the test
.' . person was asked to press the
5 - 7 .... button of a switch the moment
. I . . . .
FIG. 3 - ElECTROENCEPHALOGRAM OF TEST PERSON L. E. NO COIIIDITION- one of the figures was illuminat-
. ED REFLEX DESYNCHRONIZATION DURiNG INHALATION OF 0.032 ed. The button of the electric
, .. . "t/"3OF DIMETHYLFORMAMIDE VAPOR
switch had to be pressed by the
~.. 2. 3. .., 5, All 68A"E 101 iii! FII. I. test person one, two, three or
, four times, depending upon the
partic~lar figure illuminated .at the mome~t. During the period of gas !nhalation
the test person 's electrocardiogram remamed unchanged (0.032 mg/m). During
the inh~lation of air containing 0.05 mg/m 3 of dimethyl£ormamide v~por sharp
changes were recorded in the respiration of test persons L. E.and L. p. From
the beginning of inhalation of this vapor concentration the -respiration of test
. person .L. P. became shallow and extended. In the case of test person L. E.
,such Pfenonoma appeared upon the inhalation.of dimethyl£ormamide in 0.08.
mg/m concentration. See Fig. .4 (page 36). Respiratory changes appeared
f
z.~..~~
3
f.
5
'. . . .. .
6
7
~
FIG. I - CONDITIONED REFLEX DESYNCHRONIZATION ON THE 16TH
ASSOCIATION WITH INHALATION OF 0.05"0/"3
DIMETHYLFORMAMI DE VAPOR BY'TEST PERSQN L. E.
1-5- ELI8TROE.CEPIALOSRAMS OF t8FFERIIT 8R6'1 180CIRR!'T
, LUIIII, 6 ... COllltT. OIl. IT '"BLATGR (""ETlYLFO"'i" 8 II! ); 7 -
. .1.ONI'T80IEI ST'"ILATOR (L8"T)
. f ~~od>Y\..-.......,-..- . ---..~ -.""-"""",.....-..
z~~~.,....~.......,........."'-~
3 -,t~.~.~ ,""~ ....".,... ~ \..,,.......,................. ..............'.....
. P~.- ,. - .. -...- - ."...,...~.. - ... ~ .of-'4J
5~" ""o/'M"""~ . ,,,,,,-... --("'oJ ."''''' ,._~~~
. ..... 6 .J 7.
.....--.. .
FIG. 2 - ELECTROENCEHPAlOGRAM OF TEST PERSON L. P. CONDITIONED
. REFLEX DESYNCHRONIZATION ON THE 14TH ,ASSOCIATION WITH
THE I NHALAT I ON OF 0.05 ",,"3 OF DIMETHYLFORMAMI DE VAPOR.
I, 2. 3, 4. 5,. A.' 6 8A"1 AI 'I F81. I.
172
-------
simultaneously with the
I" - '" ......... ~ v ~ ",-
2..,..- J. -1IIiI "".. _ilia . t.~ ... -II. electrocortical reflexes, and
.JW---..t .'. .... ... If~ r.. disappeared with the extinction
4 ~...,.. !,. T ~.... J. ~ ./1 _.r.. of suc~ reflexes. The 0.032
I..... .. -. 1 -" 't .... ~ ' - ..~ mg/m dimethyl£ormamide
'.concentration had no effect on
F16. .. -ELECTROENCEPHALOGRAM OF TEST PERSON L. E. CONDITIONED the respiration of the test
. REFlEX OESYCHRONIZATION ON THE 15TH ASSOCIATION WITH Persons. Thus, results in-
INHALATION OF 0.08'"8/'"3 OF DIHETHYLFORMAMIDE VAPOR. 3
dicated that 0.03 mg/m of
I. 2. 3. 4, 5, UI e SA"! &8 II,F... I. dimethylformamide in atmo-
, spheric air could be re-
commended as the limit of its allowable single concentration. '
The following chronic experimental studies were made for the determina-
tion of the average 24-hour limit of,allowable dimethylformamide concentration
. in atmospheric air: white rats were subjected to continuous 603day exposure to
dimethylformamide concentrations of 10, 0.5, and 0.05 mg/m . Another group
of white rats were kept as controls. The standard limits of dimethylformamide
. vapor in the air presently adop~ed are as follows: 10 mg/m3 for the air of
working premises, 0.05 mg/m , which is close t~the proposed maximal single
. concentration,for atmospheric air, and 0.5 mg/m as the intermediate between
the two. .
.. .
Experiments were performed with 60 young white rats divided into 4 groups
of 15 rats each; the animals were placed into four 100 liter capacity chambers.
Air containing the previously mentioned dimethylformamide concentrations was
run into the chambers at the rate of 17 -18 li/min. 'Check tests indicated that
fluctuations in the dimethylformamide concentration did not exceed 10%. The'
following indexes were under observation: general condition, weight, porphyrine
metabollism, cholinesterase activity, and muscle-antagonists motor chronaxy.
Rats of all groups were healthy, active, gained weight at the normal rate, and
in every other respect, including the muscle -antagonists motor chronaxy ratio,
appeared the same as the control rats. Investigators such as A. p. Martynov
in 1957, G.!. Solomin in 1961, and Lee Shen in 1961 successfully applied the
method of cholinesterase activity det::rmination in their studies of limits of
allowable concentration of a number 11£ toxic substances in the air. It has been
established that normal humans had characteristic or specific blood cholin-
esterase activity intensities, which,v:ried widely with the tested individuals.
Cholinesterase activLy in the same p, rson varied with the pathologic conditions,
of the person; thus, in liver disease: holinesterase activity dropped to lower
levels, as was shown by Faber in 19,t3. In persons having hyperthyroidism,
blood cholinesterase activity, as 'a r lie, rose to higher levels, as was shown
by Antopol in 1938, and by others. :~i.khter and Lee noted in 1942 that high
emotional tension in patients with ps) chiatric reactions was accompanied by
increased blood cholinesterase activ, :y. Some pharmacological agents, such
as ether, chloroform, morphine, cal'eine, cocaine, phenol, eserine, proserine,
etc. inactivated blood 'cholinesterasl Blood cholinesterase activity of the ex-
perimental anima]) was determined! y the A. A. Pokrovskii method based on the
fact that hydrolys:.s of acetylcholine c hanged the medium pH, which in turn
, 173
-------
'. ,
, -changed the color of the indicator.
I EXPOSURE ' I RECOVERY'
! " PERIOD ~,t f'ERIOD ! Cholinesterase activity was deter-
: / 1\ ,- mined in 5 rats of each group once
. I " I \
: ~,~< ./1",\ every 15 days. Results showed
: .~~~., .,,/ .: ',~\ that acetylcholine hydrolysis time
I ..'.' I '"
I .~.~ ,..."'" 1 \ in the rats of the control group
J~ -;~-----' -."". I . - .,j.
ranged between 34-40 min.
Results of tests made at the
be ginning of the second exposure
. ?O/XIl uP' month showed that cholineste rase
activit! of the rats exposed to ,10
mg/m of dimethylformamide was
con~iderably lowered and that
FIGo 5.;. EFFECT OF 01 MET HYLFORMAMIO'E 'VAPOR I NHALATI ON 'ON
. . BLOOD CHOLI NEST ERASE ACT! VITY I N RATS. I acetylcholine hydrolysis time was.
. '---_P-=-.'~--~""'--':'~ extend~d to 50 min.) and at the end
~f the i~halation exposure ~o 62 min.~,.as sh?wn in Fig. 5. Cholinfster~se activ-
ity was regularly lowered ln rats of group 2 exposed to 0.5 mg/m of dlmethyl-
formamide; however, statistically :reliable results were obtained only one month
after the initiation exposure, as shown incTable 3. No changes in the cho~n-
esterase activity were noted. in rats, oLgroup 3 which received 0.05 mg/m of
the vapor. Cholinesterase activity of rats of groups 1 and 2 returned to normal
at the end of the second week of recuperatioI1;at that time acetylcholine hydro-
lysis time ranged between 30 -40. r:l)in.;'rfius., dimethylformamide concentrations
of 10 and ,0',5 mg/m3 dep~esse(dth~ a~tlvityof blood cholinesterase and had no
effect -~_~2.~n_~?~~_gl~.~~~_en~r.a..t~o~r:-'_.._. '-- ._-- -, ' --'---" .-----
i--l " " ' T~BLE 3 '
, BLOOO CHOLINESTERASE ACTIVITY IN (./HITE RATSOllRl'NG THEINHALATION'OF OIMETHYLFORMAMIOE VAPOR
05
(j) ,
(;j '00
>-
~ 55
c: i
; ~ ~'50
,: -
, ... %:. 6S
1/)'"
I: - 110
.... ....'
. I- %:
(;) -.15
, ~ ...~
... ;30
o
=
(,)
(1jX
(I/O 25/Xl (tjXIl
OATES OF. QBS~RVATION.
UU-- GROUP ONE -'- GROUP TWO
--- GROUP TIIREE - ConTROL GROUP,
20/%
,
I
I
I
I
L-
I
i__~~~~TE~... O~~~~~ O!.,~I~,~~~~~.:'~; s ~.~; C - 99o~; 0 - .U.N.RE~I.Ati.LE--. "
Porphyrin ,metabolism studies were conducted with 5 rats of each group.
This method was first used by M. 1. Gusev in his studies of the determination
of limit of allowable lead concentr.ation in atmospheric air. Gusev found that
rabbits intoxicated with)o.~.concentrations of lead developed porphyrinuria.
The normal content of coprop.:>rphyrin in the urine of rats of each of the 4 ~
groups prior to inhalation exposure averaged 1. 5 - 2. ° Y per .day per 100 g of
body weight. The' 24-hour urine spe~imens were collected in special chambers.
.. ~ -+- :. " . ....-+'. . ..
, '; Pllo.l,njE~TER"~E.AC.,!,1 vlTY -.---[
, " I" Mill"
I - I
! ----+ - I
, P1G/M3 ----; /' B'E"li'o'ii E ...
i -+- 0'.' ... .' I
I _RATE .~~~ I) I METHYL- J EXPOSURE EXPOSURE PERIOD RECOVERYI
I 'FORMAMIDE 'I ----- -
. - - ._+ . PER 1.09 - i
i - --... - ---- J
25/IX I 10/X 25/X I ' IO/XI I 25/XI I IO/XU I 25/XII 10/1 I
I
GROUP,ONE - :
;. 10 38,8 (0) 39,6 (0) 39,8 (0) 46,0 (b) 52,9(b) 60,2 (c) 60,2 (c) 40,0 (0)
G R ou pTw.o ; 0,5
i: 39,8(0) 39,3 (0) 39,6(0) 40,4(0) 44,4(0) 50,2 (c) 55,0 (c) 40,4(0)
GROUP TIIREE 0,05 38,8 (0) 38,6(0) 39,4(6) 39,4 (0) 38,6(0) 39,8 (0) 39;8 (0) 39,7 (0)
CONTROL GROUP ~ 38.0 38,1 ' 37,8 36,8 ,=39,8 38,6 '
36.7 38,3
.-- . ,
.,.
,_.--C--~
. 174 . I
~~ .~.;;P ...~..,.,. -.- .~-",."""-
-------
...
o
TABLE 4
COPROPORPHYRINE ELIMINATION WITH THE URINE IN MKG PER 100 G OF
BODY w~IGHT IN 24 HOURS
FIRST 3 SECOND I "OHM!)' CONTROL
10 I1G/1'1 0.5 "G/M,' M~lM3 I
EXPOSURE
RECOVERV
. . . . . .
0,21 (c)
1,16(0)
0,34 (c)
1,17 (0)
I
I
1.06 (0) " 1,0
1.27(0) 1,24
. . . . ."
-.--.----
NOTE: DE;REE 0' RELIA81LITY: A - 9SJ'; D ~ 99%; C - 9909}6;
0- UNRElIADLE
J
I
, --
: : ... --,..&..
---.-:1'l-.... ',....,,;" ,~JI"
~..., ,\ ... I /1
-....... \ : I
I '......::,. I ~;
I -"'. I ."
I \'. I / l
: \,\ """'-"--....... ,,.A',l
" '. .'" I,
: \'_-'."'..-"":::-~~~::::".'1
I' I
.EXPOSURE.
. PERIOD
-.-. .-- .
Coproporphyrin was extracted
by the Fisher method and deter-
mined with the aid of spectro-
photometer SF-4. Urine was
tested for coproporphyrin
elimination eve ry 15 days-. At
the end of the 14th day of ex-
posure to dimethylformamide
inhalation in 10 and 0.5 mg/m3
Z5/XIl 10/1 WI
concentratio'ns the rate of copro-
!porphyrin elimination was con-
siderably reduced, especially in
rats of group No.1, as can be
seen from the data presented in
Table 4. The lowered rate of
coproporphyrin' elimination with the urine persisted to the end of the inhalatlon" ,
expe riment in all the rats, as can be seen in Fig. 6. The rate of coproporphyrin,
elimination with the urine in rats of groups 1 and 2 amounted to 0.4 - 0.6 'Y which"
was approximately 12.5% of the amount of coproporphyrin eliminated in 24 hours
by the control rats. During the recupe ration pe riod the rate of coproporphyrin
elimination with the urine of rats belonging to groups 1 and 2 became gradually
normalized, reaching the control lev1l on the 14th day of recuperation. In-
halation of air containing 0.05 mg/m of dimethylformamide had no effect on
the rate of .p~rphyrin elimination with ~he urine. Thus ,the results indicated
that concentrations .of 10 and 0.5 mg/m vapors of dimethylformami:re lowered
the rate of .por_phynn "elimination with the urine, and in 0.05 mg/m concentra-
tion had no effect on the rate of its elimination wit~" the urine.
-------
.:r.':.:T"..t.'-t"~-"-
'.'- ,......,.... '. ...~ '.-
.M.,
Following the above cited expe rimental investigation a sanitary hygienic
evaluation of the atmospheric air pollution of dimethylformamide was conduct-
ed in the vicinity of a plant producing the synthetic fiber "nitron"; dimethyl-
formamide was used as the polyacrylonitryl solvent in this plant. "Nitron"
fibers were produced in this plant by the so-called wet process in the course
of which 300 g of dimethylformamide was discharged into the atmospheric air
for each 1 kg of produced fiber. During September and October of 1.960, and
again, during August of 1961, air samples were collected at 25, 50, 100, 150,
200 and 300 meters from th~ plant and analyzed for the concentration of
dimethylfo~mamide. Results are listed in Table 5. Data in the Table show
that only at. 300 m from the plant was the concentration of dimethylformamide
vapor in the air below the proposed limit of allowable concentration'3 i. e.
TABLE 5 below 0.03 mg/m . It should
51 NGLE DIMETHYLFORMAMIDE VAPOR CONCENTRATI ONS I N ATMOSPHERIC. be noted at this point .that the
AIR IN THE VICINITY OF THE INVESTIGATED SYNETHIC "NITRON" plant under consideration was
FIBER PLANT. a prototype of plants, to be
erected in the future which
would also use dimethyl-
03 formamide as a resin solvent.
The capacity of the projected
plants would be 10 times as
great as the production
capacity 0.£ the plant under
study,and it was, therefore,
expected that the air pollution
with dimethylformamide in
the vicinity of the new plants would be more senous.
o
NUMDER OF DISTRI8UTION OF DIMETHYv.
SAMOLES . FORMAMIBE VA~O~ CONCNS.IN
== MI: M
FROM THE U(T) - .
J. :t... '" :E:
POINT OF In 0",", 15-1 10-/5- j /1-10 I -I <
UCII
I SCIURGII ... wu...... :E: -10 -5 -3 3-1 -0,1 ":'0,3 o.
... SU20 c:;, - 0
... u-... .c ~ ":E
0 .. ... - ... -
I- ILl ... ... J: NUMBER OF .r.E6T8
25 6 6 13,3 6
50 11 11 7,7 4 7
100 12 12 2,2 10 2
150 36 36 0,38 26 10
200 50 23 0,08 14 9
300 25 3 25
Conclusions
1. The concentration of jhreshold dimethylformamide odor perception'
was determined as O. 14 mg/m '.
2. The threshold concentration which permitted the development of
electrocortical refle~es was 0.05 mg/m3.
3. 0.03 mg/m was recommended as the maximal allowable single con-
centration of dimethylformamide vapor in atmospheric air.
- 4. Exposure of white rats continuously for 2 months (chronic intoxica-
tion) t~ inhalation of dimethylformamide vapor concentratio~ of 10 and 0.5
mg/m brought about statistically reliable reduction in the cholinesterase
activity and a drop in the rate of coproporphyrine elimination with the urine.
- 5. 0.03 mg/m3 of dimethylformamide vapor should be adopted as the
limit of its allowable concentration in atmospheric air.
176
-------
BIBLIOGRAPHY
A H 0 X II H n. K. 9JJeKTp03Hue4>aJJOrpa4>H'Ie~KIIH aHanH3 ycnOB'
Horo pe4>JleKca. Me~rH3. M., 1958.
A caT II a H II B. C. MCTo~bI 6110XIIMH'IeCKHX IIccne.o.oBfjHHH.
T611JJHCH, 1957, CTp. 383-384. :
5 Y W T Y e D a K. A., no n:e)K a e B E. «1>., C eM e Hell'
K 0 A..Il. IhY'lellHC noporOB pe!f>JiC:KTopHoro ,ltClicTBIHI aTMoc4>epllblx
3arp!l3HCIIIIH MeTo~oM 9JJCKTp0311I.lc4>aJlOrpa4>"II. rllrllClia II call1lTa.
PHil, 1960, N2 I, nv. 57-61. :
r y C C B 11. M..II eM II pliO B 10. K. Onpc.n.CJlCHIiC cnCKTpo'
4>OTOMCTpH'ICCKHM MeTO~OM Konponop4>Hplllla, BbI~eJJlleMorO C MO'IOH.
B KH.: npC~CJlbIlO ~onycTHMbie KOllp,eHTpaUHII aTMoccpepHblX 3arpll3'
IICHHH. Mc~rIl3. M., 1960, 13, 4. .'
3 Y 6 K 0 B A. A. MaTepllaJlbl K 4>1I3110JlorHH H naTOJlOrliH XOJlIIH.
3CTepa3b1. BoeHIIO-Me~IIUHHcKHH >K}'p II aJl , 1958, N2 9, CTp. 61. .
P II 3 a II 0 B B. A.. B Y ill T Y e B a K. A., HOB II K 0 B 10. B.
B KH.: npeAeJlbHo ~onycTHMb!e KOII;uellTpauIIII aTMoc4>epllblx aarpll3-
IICIIHH. M., 1957, B. 3. .
Co JI 0 1.1 n II r. H. rHrHella II caHHTapHH, 1961, N2 5, 3.
eTa c C II K 0 B a K. n. TOKI:IIKOJlorll1l )J.HMCTIIJJ4>oPMaMH~a II
BonpOCbI rHrHCHb! TpYAa B npOH3~o.o.CTBC CHIITCTII'IeCKOrO BO~OKlla
IIIITpOIl. .IlIICC. Kall~.. 1960. ,
, .
Experimental Basis for the Lirhit of Allowable Nitrogen Dioxide
Concentration in'Atmospheric Air
P. P. Yakimchuk
Department of Hygiene of the J:. P. Pavlov Ryazansk Medical
Institute and from the Departrhent of Community,Hygiene of
the Central Institute of Phst-Graduate Medicine
Nitrogen gases are a mixture of p.igher and lower nitrogen oxides, such
as nitrogen dioxide, anhydrides of nitrogen, nitrogen tetroxide, etc. However,
the basic component of the mixture is nitrogen dioxide. Oxides of nitrogen are,
discharged into the atmospheric air as' tail gases by many production and pro-
cessing plants. The limit of allowable' concentration of oxides of nitrogen in the
air had been determined by indirect calculation. The purpose of the present
investigation was to secure direct expe~rimental data for the determination of the
limit of allowable nitrogen dioxide concentration in atmospheric air. White rats
were used as the experimental animals. They were exposed to chronic inhala-
tion of air containing low concentratio~s of nitrogen clioxides, and the effect of
. such inhalation on the conditioned reflex activity of the rats was obse rved. A
\
review of the literature failed to find r~ports dealing'with the effect of nitrogen
oxides on the conditioned reflex activity of animals. .The experiments were con-
ducted with 3 groups of 12 rats each w~ighing 75-110 g~ The motor nutritional
conditioned reflexes were developed using theL.I. Kotlyarevskii chamber. The
, ,
'~ 177
-------
technique was the same as described by V.A. Ryavanov, K.A. Bushtueva and
Yu. V. Novikov in Book 3. Three conditioned reflexes were developed in all
the animals of which 2 were positive in response to the sound of a bell and red
light and 1 negative in response to the sound of a buzzer; all reflexes formed
a stereotype group; after the stereotype became fixed, tests were made for
the determination of the pattern of the animals I higher ne rvous activity through
24-hour starvation and prolonged differentiation. The 12 rats were divided into
3 groups; each group was placed into a chamber of 100 li capacity.; the rats in--
haled different nitrogen oxide concentrations six hours daily for 6 months,
holidays and other days of personnel absence excepted. The air was supplied
into the chamber by the Gubkin air supply system as described in Book 3
OTS-59-21175, page 103.
The air was first purified by passing it through a filter made up of cotton,
silicagel, and activated charcoal; the air was run into the chamber at the rate
of 12. 5 -13 li/min. The nitrogen dioxide used in the expe riments was obtained
by the Mozer method by heating dry chemically pure lead. nitrate mixed with
quartz sand to 2230. Constancy of nitrogen dioxides supply into the chamber
was attained by aI¥'ropriate means. Rats of the fi.rst grou~ inhale~ ~ir con-
taininl3 5. 7 mg/m NO and rats of the 2nd group mhaled an contalnlng 0.84
mg/m of NO compute~ as nitric anrhydride; rats of the 3rd group inhaled
clean air ancfconstituted the control group. The N02 concentration in the
chambers was checked by the method of metaphenylenediamine as proposed
by M. V. Alekseeva. Air samples were collected with the aid of gas pipettes.
(/) ,. EXPOSURE CHAMBER No. I Fig. 1 illustrates results of check
~ i 1 slt':"-:-~ ,--;- ,-;~";" ,--:--:-~ .--:-, ~-:..~-~...> :-:-:-:, tes ts for NO concentration in the
1/ J I S " 18 '1!IfftIJ''''1I'171''8tlJl'IUJ3'-I~Z4l?lI2IJ'' chambers. Results indicated that
4f7'JfK(IK~'M/If8} fluctuations from the basic con-
centration were statistically not
EXPOSURE CHAMBER No. 2 signi£icant~ After 6 hours inhala-
~$.f OI+~~, ,:-:---:-:-:---;-, , ::-,--:--.~, ,-; ,-:~-:-:-:-', tion of air containing the particu-
L , 2 J . , I 1 8 9 l"lf 121J ,. IS fll7 II f8 ZUZUZ !.'l; :SZIlJ21l1.'Q lar ni trogen dioxide concentration
TaH-E IN WEEKS checks were made for the deter- .
FIG. 1- wHKLY NITROGEN DIOXIDE CONCENTRATIONS IN mination of effect on the conditioned
THE EXPOSURE CHAMBERS reflex activity of the rats. Such
check tests were made daily for a limited period of time and every other day
thereafter. The chronic intoxication experiments were conducted for 164 days,
after which 3 rats of each of groups 1 and 2 were taken for pathohistologic and
pathoanatomic studies. In addition, observations were continued for- 31= days
in connection with 2 rats - of each group for the determination of the rate of the
animals higher nervous activity normalization. Changes in t~ higher nervous
activity of rats belonging to group 2, which inhaled 5.7 mg/m of nitrogen di-
oxide 6 hours daily for 6 months are presented in Table. 1. (see page 42)
Changes in the conditioned reflex activity of the rats appeared on the 8lst day
of exposure to N02 and indicated that the magnitude of the conditioned motor
reflex reaction was reduced and was less than the reaction in response to light,
i. e. a change has occurred in the reflex force ratio indicating the appearance
:II:
~.
o <'I,
zz
......
00
178
-------
TABLE 1
CONDITIONED REFLEX ACTIVITY OF RAT NO.2 DURING PERIODS OF
EXPOSURE AND RECOVERY AT 5.7 MG/M3 OF NITROGEN DIOXIDE
TEST No.181 OF TEST No.218 OF TeST No. 231 OF
9/XII/I958 17/111/19'"".)9 2/1 V/I ~
81 EXPOSURE BAY 164 EXP'. D!-_Y- 114 RECOVERY DAY
-
,--
STIMULATING II) a: to a: (J) a:
z oza: z 0 za: z . O:Ea::
AGENT 0 " 1--'" ~ .. 1--'" 0 .. It--&&J
- ~"'Q 0 I- 0 1- ;: 0 l-
I- J:Z-< I- ...... %: z.c ",>C.. J: z-<
-< 2WO O~ -< :zwO o~ -< z...o ' o~
... 0"'- ><- ... 0...- ><- ... 0"'- ><-
::0 uu.", wI-'" ::0 uu.", "'...... => uu.", .........
J: .w... -,uo = .w w -'<>0 J: . w... ...uo
o-a:L ...-< ... '" L "'-< ;: o-",L ......
;: -< wwJ: I- -< .... w2: -< W"'2:
en ..... - c: a: J: en ~-- . c: a: 2: VI ...J c: "'2:
BELL 850 0,2 115 1036 0,5 130 1101 0,5 150
If 851 0,3 140 1037 0,5 135 1102 0,8 165
lI;IIT 672 1,9 160 822 0,4 160 904 3 140
If 673 2,5 160 823 1 145 905 3 130
BELL 852 0,2 140 1038 1 130 1103 0,6 175
BUZZER 163 - 0 201 4 60 214 - 0
BELL 853 0,4 160 1039 1 130 1104 0,4 165
If
854 0,2 150 1040 1,5 160 1105 0,5 160
LIGHT 674 2,7 160 824 1,5 140 906 2 165
"
675 2,,4 160 825 0,6 175 907 3,5 130
of a paradoxyca1 phase.' After 164 days of chronic intoxication differentiation
disinhibition appeared in addition to the paradoxyca1 phases. The rats were
not as active as at the outset of the experiment.
At the end of 5 months exposure the rats began to lose some of the fur
over the spinal area. At the end of 164 days the NOZ inhalation intoxication
was discontinued. Normalization of the force ratio of the conditioned motor
reaction to the sound of the bell (strong stimulus) and to the appearance of a
red light (weak stimulus) began on the 14th day of the recuperation period.
Figure Z (see page 43) is a graphic presentation of results obtjined with a
higher nervous activity test in rat No.5 exposed to 5. 7 mg/m of NOZ during
the periods of inhalation and recuperation. Curves in Fig. Z also show that
beginning with the 19th day of inhalation there appeared disturbences in the
ratio of motor conditioned reactions magnitudes in response to weak and
strong stimulation; paradoxyca1 phases also appeared; on the 54th day of in-
halation the conditioned reflex to the red light stimulation fell out. Changes
in the cortical activity became c1earcut on the 5th month of intoxication and
appeared as lowered response on the part of the motor conditioned reaction
to light. as reflex falling out and as phase phenonema. The latent period of
conditioned reflex response to the light. or to weak stimulation. was charac-
terized by some fluctuations from the average throughout the entire period
of the intoxication. Differentiation disinhibition appeared more frequently.
especially during the first month of exposure. Changes in the conditioned
reflex activity of rats in t~at part of the stereotype which followed differen-
tiation were much the same as above described but they occurred more
frequently. Observations over the process of higher nervous activity normal-
ization were continued after exposures to the effect of NOZ had been termin-
ated. The period of convalesence extended over 34 days. Cortical activity
returned to normal 1 week after the exposure was discontinued. Data 'regard-
179
-------
'''','':
2:
..2:
.
co"
z- 1717
8.. IdO
...~ ~1$
, 0::; ~~~
No W~ 110
;~, DW If a
o =>CI< 90
...IQ :: CI< ~g
CI< ,..0 617
~ffi ~ ~ is
~N E~ JU
217
117
. 0
1-00
2:Qw ..
~; ' U 11717
-0 \&.I""" ~oO, ,..
~c.o DLIJ to '.: ,if
. 0 ,=a: 70 .: . .
-lei: ~ 60 . -;
C:~ =~ ~$ .
u..N "'... JU
;: ~*, 1S
~ ~
; J.~ . " . :.. . i\ !.," t,. .
~:O' f ' ,.." \," '.: '..'" ""'......-l.j \. .~: ~: \..' "".... '". '
. D
1-"
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..... I 2' r- ~
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r-o
-8 i-4z:
; :r: 0 fTI > ..... ID
,c,,>=.....,.., .
r- n-zGt
'~n-to-t
-40-z ::0
- Z 0'. "'8 fTI
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:z- :::or-
8at~ -",
Z 0><
3 ..
o ~ ::g'
.... ITI 0", .
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o no:
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1111 8",1
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.. '
{/2":5 BID~ '2 I.q 29 J7 M ,~.' 525.9 II &0 .9. 'DJ '" ':!U l.iO l.1&i{,/l.fS!5.,7 7 fI I.J '.9 2J ,77.71.74
BEFORE .EX~O$URE "',RECUPERATION'
EX~O$UR_E ~ERIOD ".' ,. HRIOD
- SOUND .... LIGHT !DII'FERENTIATION IN'iilllTION IN
OF DELL . RE$~ONSE TO IUZZER:"$OUND
: ,} ,
FIG. 2.- EFFECT OF 5..711&/,.,3 OF NITROGEN DI:bXrdEON'THE CONDITIONED REFLEX
. ACTIVITY OF R~J£ NO.5
ing the higher nervous a~tivity changes':in Rat No. 12, which was exposed t.o the
inhalation of O. 84 mg/m of nitrogen di~xide are listed in Table 2. (see page
44); this rat belonged to the group having a strong balanced neuro-pattern.
(See Fig. 2 and Table 2.) Data listed inTable 2 under experiments No. 158
show that on the 32nd day of nitrogen di:?,,:,ide inhalation no changes were
noted in the rats conditioned relfex activi'ty, and that the force ratios re-
ma'ined normal; thus, the average of the conditioned motor reaction force
in re sponse', to the sound of the bell and to the appearance of the light ,prior
to the buzzer signal were correspondingly 160 and 140, and after the :buzzer
sound 150 and 135. A normal correlation between the two forces was also
, '
noted during the latent period of conditioned reflex response. i
On the 7lst day of NO inhalation shifts appeared in the higher hervous
activity. Phase conditions Became manifest and the average conditiohed
motor reaction to the sound of a bell and,to the appearance of a red 1-~ght
prior to the buzzer signal were corres~pondingly 95 and 135, and after Ithe
buzzer signal 110 and 130. The latent periods of conditioned reflex r'esp<:>nse
to the sound of a bell and the appearanc'e: of light were corre sponding1y 1. 5
and 2 sec. ~efore the buzzer signal ahd' O~6and 2.1 sec. after the bu~zer
signal. The disturbances in the highe~,'n~rvous activity, as described: above,
became more pronounced on the l65tl,1 day of N02inhalation. The avEirage
magnitude of conditioned motor reaction, t"o;tb,e sound of the bell and to the
180
-------
i
J:'
~ :1:1
.. :Zl
z -:"c 1
o "/JC
u ~!'J(,
*= :~'~{'~I"
-~. ~ ~ s~. . .
b.I CQ..... ~'\, ,,4'
'" - '" ... "\I
:::;' ~ ~ ~ i
...... ~O Jll
CO '~ ~ "C
. ,,"
...aU .
zo,,", "
au-CO -i-
I- a:: J
cWZ Z
-18-- I
-~i "
..
"":z
z- 17~
o '6
uz '"
...~W1
0>- II.'!J
U ffO
....~ '00
"'..... ~o
"'~ ;:'" ~,o
Z 0 -c:
-II) :z0
~ "'>-
00: ~o
-J... ,~I:
-J ...
0'"
~:.~ i
; J J
~ ~ $
'. #
>-""
.. -
.j
TA B LE 2
CONDITIONED REFLEX ACTIVITY OF RAT NO. 12 DURING EXPOSURE TO THE
INHALATION OF 8.8-4 MG/M3 OF NITROGEN DIOXIDE
TEST No.l59 OF TEST No.l75 OF TEST No.219 OF
9/X/I959 2$"XI/I958 17/111/1959
32 EXI'OSURE DAY
71 EXI'o DAY
\65 EXI'. DAY
a
.....
G')
.
,a:
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";.. :....-w
o >-
:zX", J: Z~
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STIHUUTIN8
AGENT
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- - :..... -w 0
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= ~:~I.Z:~;
::a U...I-j.)C-
!; .~ ~!:~~~
t- I- G: &. 't&., -c
CJ) C .'",wl: ,"'"
.-J Ia: '" :c ' (/J
>-
<
-J
=>
:E:
a
If) 00
:z z.
~ fT1 CD
... c-
o :xI3
:z ..... If)
01 .....~,
.-3
(J) fT1 UI
~ ><
3 0
'" >-..,
C')
; = ~ ~
<-I
- -:xl
'"' -10
-
..., .....
- 02:
CD .....
. C
:xl -
N ~~
II)
a: z
. ,oze: 0
~ i~-=
~:~~%:~~
(,,) -'- :)(-
14..11: :wl-"-
.""'lI.I ;-,(,)0
t-cr:L ,~~ ....
'"II( ."''''2: ,en
-J a: 0: z:
>-
.
-J
=>
J:
BELL 784 0,3 160 874 0,3 165 1089 1 1140
n 785 0,2 180 875 1 120 1090 1,5 150
LIGHT 687 3,4 140 759 2 130 93\ 1 140
" 688 4,2 140 760 2 140 932 1 150
BELL
BUZZER 786 0,4 140 876 2 70 1091 0,5 100
~ELL 146 3,3 160 164 4 60 207 0,5 60
" . .. 787 0,2 150 877 0,5 130 1092 0,2 140
II 8IT 788 0,2 150 878 0,7 90 1093 0,5 90
" 689 1,9 130 761 3 140 933 1 120
690 2,8 140 762 1,2 120 934 1,5 160
\ ~,,:.. i : 1 t\
\:' \ 1\ !V\..l\8 J \
.. "".. .. . ..
. :
-
-
-
:.,.#.
.
-.1
. .. '"".
t. A
- ..
. 5
d
5
2: C
0rT>
.
o
...,z:
. -I
:c
rT>
,.'to ~
\! v.,
.. '..
\;
2 8 10 7 15 2J.12 #1 "5 5766 158" .9J10"fOlf7IZ7fJ7IU'55f551 5 .9 15 172f 25 2.9 Jf
BEFORE EXI'OSURE !'ER I OD RECOVERY
I'ERIOI
EXI'O~BELL ....L,GIIT ! DIFFERENTIATION ,HH'l'TloN IN
. RESI'ONSE TO IUZZER SOUNI
appearance of the light were correspondingly 125 and 145 before the buzzer
signal,and 115 and 140 after the buzzer signal, while the latent period of con-
ditioned reflex response to the strong and weak stimulation amounted to 1 sec.
- .
: .. ..." lit
. .
.'
.'.-. II
., .. .
181
-------
before t~e buzzer signal and to O. 35'andl. 25 sec. respectively after the
buzzer sIgnal. See Fig. 3 (page 44) and Table 3 below.
TABLE 3 '.
TABLE SUMMARIZING CHANGES IN CONDITIONED REFLEX ACTIVITY OF WHITE
, . RATS AFTER SIX MONTHS INHALATiON OF NITROGEN DIOXIDE
I
Z , -Q J. z
O:ilZ: =w '0-2 101- '::;-
.... z a: - ... -... "'=>1
>- a::: -c ..0100 >- 0 10 100... ....
':kJ(I.)Lr.J 0- ,-<>-- ",... .""'.J a:: ......
TY~E OF H'!:HER Q \&.. -L "'-1- -."" 0"' '''''' '" ..
II. ..... o"'- ....w . ... .
. NERVOUS w- ... "".. WII.IL.CD 111:... iloilo.. 20
o ACTIVITY a:QZ 1--- "'.. ... will 0 . _1-
:z => oz Z t- z: ::I,""C: " ....
'" :c - 0 ...:ez 111 111-0 IIIWI-
t- L -..... a: a::: CO' L-..... Z.. ..~" K 2z
... KO:: w... - M:... :c X:O ... 0..
0: UJ ::. ,.... a........ ...,,,...."" a. =>::r... ...a.._'
" '.. ....- - -._- zU)o ~~...
s.. 7 H!:/1130F N02
.-...-.-.--.-- -----'-.---.
I
., 2 STROH;
D "LUCES 10 48,7 62/19 43
4 STRONG
BALANCES 6 30,7 25/13 24 5/10
5 STRON;
UNBALANCED 28
STRONG 18/22 34 0/5
,6 BALANCED
WEAK TVI'E 6 37 24/16 41 0/2
13 4 38,4 1.5112 46 1/5 '
.. "~"'. ---~
0.84 I1G/"3 OF N02
._,--~_.-
7 STRONG ",
. UNBALANCED 32 15,3
STRONG 93/44 . 14 0/1
8 UNULANCEI
STRONG 17 26,9 105/41 ' 17
12 GALANCED .,
STRON!: 21 30,7 110/88 17 On.
17 IULANCEIi
WEAK nl'E 42 25,6. . 93/20 ' 24
16 21 33 '5/5 38 4/4
CONTROL,
3 STRONG
UNULANCED 30 6 5 0/ I
14 STRONG
UrlULANCED 2 3 111
Curves in Fig. 3 show changes in the high nervous activity, of rat No.7
of group 2. On the basis of its neuro-pattern this rat belonged to the type of
strong high nervous activity. The curves in the figure indicate th~t in the
course of the first month of N0z. intoxication no characteristic disturbances
in the conditioned reflex activIty of t~is rat became manifest. At the end
of the second and beginning of the third month of inhalation exposure the
force of the motor-conditioned reaction)n response to stimulation with light
and to the sO,und of a bell were the same, prior to and 'after exposure to the
~02 inhalation. . In the course of the th~rd month of exp~~ure to NOz i,nhala-
hon the paradoxIcal phase became mari1fest and the condItioned reflex In ,
182
-------
response to the appearance of red light fell out. The latent period of response
to the sound of a bell combined with the appearance of red light at the end of
the period of intoxication became relatively reduced,and in response to the
sound of a bell only became increased. . Differentiation inhibition became mani-
fest. On the 5th day following the te rmination of NOZ inhalation the highe r
nervous activity of rat No.7 became normalized. Similar changes, with minor
variations, were noted in all rats of this group.
Table 3 (page 45) presents a sum~ary of data regarding changes in the
conditione"d reflex activity of rats exposed to NO inhalation for 6 months in
the concentrations indicated. Studies cii: Gonditio~ed reflex activity of white
rats subjected to 6 months chroni<3 NOZ ,intoxication showed that concentration
of t.h~ gas am~unting to 5. 7 f1g/m ~li.cited n.otab.1e shift~ in the higher ne~v:ous
" actlvlty; NOZ m 0.84 mg/m also ehclted shlfts m the hlgher nerv0:fs actlVlty
but to a lesser degree; accordingly, a <;:oncentration of 0.84 mg/m of nitro-
gen dioxide must be regarded as active.. .
Cqnclusions
1. Chronic exposure of white rat~ to the inhalation of 5.7 mg/m3 of
NOZ for 6 months elicited clearcut cha~es in their conditioned reflex activity,
as shown by the appearance 6f phase states, differentiation disinhibition, and
falling out of conditioned reflexes in re~ponse to weak stimulators. .
Z. Chronic exposure of white rat~ to the inhalation of NO in 0.84 mg/m3
concentration elicited less clearly expr~ssed changes i~ the higfier nervous
activity, indicating that such aconcentr,ation of the gas must be regarded as
acti ve.
3. The data presented in this report were insufficient, and additional
data must be secured before a l~mit of ~l1owable NOZ concentration in atmo-
spheric air can be established with any Hegree of certainty. It is recommend-
ed that supplemental studies be conducted.
183
-------
BIBLIOGRAPHY
A f 8 H " HuE. 1(. C60pHHK HaY'IHblX TpY.D.OB l(y6aHcKofO Me.
.D.HUHH~KOfO HHCTHTYTa, 1957, T. XV (28), CTp. 32. .
A n e K C e e B a M. B.. I1H. <1>. 3pHcMaHa, 1958, CTp. 30.
A II " B A H H H. K:. B KH.: I( KJlHHHKe H npmjJHJlaKTHKe HHTOKCH-
KaUHA XIIOpOM H OKIICJJaMH a30Ta. I1HCTHTYT fHfHeHbI TpYAa H npo-
aa60J1eBaI!Hi'l JIeHfopa.n.paBoT.n.eJ1a. JI., 1939, CTp. 134. .
. B H f .n. 0 p 'I H K H. A., A HAP e e B a E. 11.., MaT Y C e B -
B H 'I 51. 3., H H K Y II H HaM. M., <1> P Y M H H a JI. M.; ill T P H-'
T e p B. A. B KH.: I( KJlHHHKe H npoHJlaKTHKe HHTOKCHKall.lIii XJlO-
pOId H OKHClIaMH a30Ta. I1HCTBTYT !'HfHeHbI TPy.n.a H npo3a6oJleBaHHii
JIeHfOp3.D.paBOTAeJla. JI., 1939, CTp. 88.
B H H 0 K Y P 0 B n. Jl.., I( 0 coy p 0 B C. H. B KH.: npe.n.eJlb'
110 .n.onycTHNble KOHueHTpaUHH aUlOcepHblx 3afpll3HeHHii. nOA peA.
B. A. PII3aHOBa, 1952, B. I, CTp. 50. .
I( 0 T II II P e B C K H H JI. 11. )KypHaJl BhI'cweii liepBHoH AellTeJlb-
HOCTH, 1951, T. I, B. 5, CTp. 739.
. JI a sap e B H. B. XHMH'IeCKHe Bpe.D.Hble Bew,eCTBa B npOMblWJleH-
HOCTH, 1951. 'I: II, CTp. Ill. . .
. JI blK 0 B a. A. C. Jl.oKJlap' Ha BcecoJ03HoA KOHepeHlI.HH no ca-
HHTapHoA oxpaHe aTMocepHofo B03p.yxa 26-30/V. . KHeB, 1959. .
M HI! HOB H q M. A. CoJlH a30THoi'l KHCJJOTbi (HHTpaTbI). M., 1946,
CTp. 60 H 145. .
H a 8 p 0 11. K a II E. M. OCTpoe OTpaBJleHHe P'BYOKHCbJO a30Ta
(9KcnepHMeHTalIbl!Oe HCCJJeJJ.QB8HHe). Jl.HCC: KaH.a.. XapbKoB, 1945.
. H a B po UK H A B. 1(. Y'IeHble 3anHCKH. T. XXV (HcCJJe,noBa-
HHe no npoM. TOKCHKOJIOfHH). XapbKoB, 1948, CTp. 97.
HOB H K 0 B. 10. B. B c6.: npe.a.eJlbHO p.onycTHMble KOHueHTpa-
U.HH 8TMOCepHblX 3afpll3HeHHii, 1957, B. 3, CTp. 85.
.' P II 3 a HOB a (CoJlHlI.eBa) M. C. B KH.: Tpyp.bI nepMcKofO MeAH-
U.HlfCKOfO HHcTHTYTa. nepMb, 1938, B. XI. CTp. 7.
PSIS a BOB 8'. A., B Y m T Y e B a K. A., HOB" K 0 8 10. B.
I( MeTOAHKe sKcnepHMeHTaJlbHOfO o60cHoBaHHII npep.eJlbHO AonycTH-
YbiX KOHlI.eHTpaUHA anlOcepHblX 3afp1l3HeHHA. MeP'fH3, 1957, B. 3,
CTp. 117. . .
- P R 3 a HOB B. A. CaHHTapHali oxpaHa aTMocepHOfO B03AYxa.
MeAfH3, 1954, CTp. 193.
II 10 pH <1>. H. 11. e p H H K . BpeAHble faabl. M., 1938,
CTp. 211.
II 0 P 0 B 10. n. BbicmaR HepBHall AeRTeJlbHOCTb np" TOKCH-
Kosax. Me.n.fH3, 1944.
r e B A e P co H H X a f a p A. Bpe.D.Hble fa3b1 B npoMblWlIeH-
BOCTH (nepeBOA C aHfIIHHCKOfO). M.-JI., 1930, B. I, CTp. 117.
L u d wig .M 0 s e f. Die Reindarstellung von Gasen ein Hilf
ffir das Arbeiten im Laboratorium Verlag von Ferdinand Enke in
Stuttgart, 1920,
184
-------
The Effect of Low Phenol Concentrations on the Organism
~f Man or Animals and their Hygienic Evaluation
B. Mukhi tov
From the Department of Community Hygiene of the Central
Institute of Post-Graduate Medicine, Moscow
Phenol is widely used in the preparation of synthetic aromatic com-
pounds, medicinal substances, antiseptics, tanning substances, synthetic
resins, plastic materials, explosives, pe rfumes and in the preparation of
many important dyes and disinfectants. Phenol penetrates into the organis m
through the intact skin, through the lungs, the gastrointestinal tract, the
chest and pleural cavities and open wounds; it entered the urinary bladder
and other organs, as was shown by Deichmann, Oettingen, Evans and Jackson;
Phenol is a narcotic poison which attacked primarily the central nervous sys-
tem, and upon application to the skin caused acute irritation and burning,a~
described by N. V. Lazarev. Cases of chronic phenol poisoning occurred in
plants produ~ing bakelite, where phenol con1entration in the air ranged between
18-15 mg/m in the winter and 20-48 mg/m in the summer. Examined work-
ers complained of muscular weakness, fatiguability, sweating, salivation,
irritability, vertigo, digestive disturbances, labored res piration, rapid heart-
beat and pain in the epigastrium, as described by L. S. Rozanov. Rabbits and
white mic3 exposed to the inhalation of vapors of cold-tar containing O. -02 mg/li
(20 mg/m ) or higher 1 hour daily for 23 days showed no visible symptoms of
poisoning. Autopsy of the animals showed extreme plethora of the internal
organs, a slight thickening of the vascu~ar walls, inflammatory infiltration
anq. hemorrhagic areas surrounding the blood vessels and bronchi, as described
by E. E. Grigor'ev. It should be noted that studies of the toxic effect of phenol
to the animal organism were conducted with low phenol concentrations. No
special studies were found in the USSR literature devoted to the determination
of low phenol concentrations effect on the organism, i. e. concentrations fre-
quently encountered in the atmospheric air.
The limit of allowable phenol concentration in the atmospheri3 air, or
the so-called single 0.3 mgfm3 and the average 24-hour 0.1 mg/m concen-
trations were approved by the USSR State Sanitary Inspector as recommended
by K. G. Beryushev in 1955. Studies conducted by A. A. Itskovich and V.A.
Vinogradova were limited to the determination of threshold phenol odor per-
ception unde r laboratory conditions and to-the study of the sensitivity of the
olphactory analyzers of the population residing in the proximity of a large
coke chemical plant. The limit of allowable phenol c~ncentration in the
atmospheric air proP<3sed by the author as O. 1 mg/m for the single concen-
tration and 0.5 mg/m for the 24-hour average concentration was accepted
and approved by the USSR State Sanitary I~spector.
185 .
-------
,-
The Committee for the Sanitary Protection of Atmospheric Air ass_?~ia-
ted with the USSR State Sanitary Inspectorate took no definite action at that
time in relation to the problem of rechecking the validity of the above re-
commended limits. The present author recognized the fact that the data
available for making a final decision were inadequate due to the fact that at
that time practically nothing was known regarding the effect of low phenol
concentrations in the air on the organis m of man or animal. Therefore, he
undertook first to determine the threshold concentration of phenol odor per-
ception, using as indexes the effect of odor on such functions of the human
organism as the emotional state, capacity for work, gas metabolism, vas-
cular system tonicity, and muscular stimulability. From the viewpoint of
the 1. P. Pavlov concept of odor perception the processes taking place in the
brain cortex constituted the primary factors. It was known, for instance, ,
that unpleasant odors were 'frequently accompanied by neuro-vegetative re-
flex reactions, such as holding the breath, nausea, headache, vomiting, etc.
Vegetative shifts occurred in reflex form not only in response to unpleasant,
but also in response to pleasant odors. The fact must be borne in mind that
atmospheric air constituted the medium which served as the basis for the
perception by man of different types of odor, consequently, the air medium
can be useful only if masking odors were eliminated, since such odors would
only lead to misinterpretation of odors present in the air, as was described
by V. A. Ryazanov. The method recommended by the Committee for the
Sanitary Protection of Atmospheric Air described by V. A. Ryazanov, K.A.
Bushtueva and Yu. V. Noulkov was used in the determination of threshold
phenol odor perception concentrations.
. Phenol determination in the atmospheric air was made by the method
based on the reaction between phenol and diazotized paranitroaniline in carbon
dioxide medium, which produced a red or greenish yellow color in the pre-
sence of small concentrations, or a reddish brown color in the presence of
large phenol concentrations. Sensitivity of the method is 0.2 Y or O. 0002 mg
in 5 ml of the medium. The method is nonspecific, since cresols interferred
with the reaction,as was shown by M. E. Alekseeva. In cooperation with M. E.
Alekseeva the preparation of diazotized paranitroaniline was changed as
follows: 0.01 g of paranitroaniline was dissolved in 1 ml of hydrochloric acid
of 1. 9 sp. gr. and to this 10 ml of.the distilled water was added, followed by
the addition of 1 ml of 25% solution of sodium nitrite. The mixture was allow-
ed to rest for 15 min. The volume was then adjusted to the same level in all
tubes, and 0.2 ml of the prepared diazotized paranitroaniline added to each
of a series of the standard scale tubes. This modification improved the
stability of the color and made possible the use of the standard scale for 2
days. This modification had no effect on the original sensitivity of the method.
According to A. A. Itskovich and V. A. Vin~vgradova the threshold odor
perceptio~concentration for phenol was 3 mg/m , for cr3sol - phenol it was
0.2 mg/m , and for black carbolic acid it was 0.1 mg/m. These values were
checked using 14 test pe rsons and 568 determinations; each concentration w'as
checked on 2-3 separate days. Checks on the mixed air entering the inhala-
tion cylinder were ,made 2-3 times a day during each determination. Data of
186
-------
this experiment are present-
ed in Table 1. Data in the
Table show that the threshold
concentration of phenol odor
perception in the air ranged
3
between 0.022 - 0) 184 mg/m
The 0.0175 mg/rn phenol
concentration was non-odor
perceptible. Thus, in 9 of 14
odor sensitive persons the
concentration of thr.eshold
phenol odor ~erception was
0.029 mg/m and in 2 highly
odor sensiti'3e persons it was
0.022 mg/m .
It has been shown on pre-
vious occasions that non-per-
ceptibility of an odor at a
given concentration did not
necessarily mean that such a concentration of an odor emanating substance had
no effect on the reflex reaction induced by the receptors of the respiratory
organ. This proved particularly true of reflex changes in the sensitivity to
light on the part of the optical analyzer. Experiments were conducted using
adaptometer A. D. M. Between the 15th and 20th minutes of adaptation to dark-
:-ness the test person was given to inhale clean air during the first three test
days. Only data regarding eye sensitivity to light, the values of which proved
. sta~istically reliable were accepted as basic, as shown in Table 2. Also see
Jfi~u~~_s- 1 and 2.. (page 51) .anc:!Jigure 3 (page 52)
T AS LE I
"NIT! ALS OF
TEST I'ERSON
CONCENTRATIONS OF THRESHOLD PHENOL ODOR PERCEPTION
..- PHE rlOl CONCN. III HG/1131
NUHIER OF ' I
I'ERSONS MI N. PER-. MAX. PER-
TE5T£I. CEI'TIDL~. CEI'TlDlE:
. . . . . . . .
L. SHe
G. I.
,R. U.
V. A.
YU. A.
I. G.
A. B.
A. P.
K. A.
E. V.
, T. M.
L. F.
N. N.
. . . . . . . .
,. . . . . . . .
. . . . . . . .
I. . . .
I. . . .
. . . . . . . .
. . . . . . . .
. . . . . . . .
. . . . . . . .
. . . . . . . .
i' . . .
,
43
43
43
43
39
39
41
33
39
43
43
33
43
43
-----~---,- - - - - -- - -.
-- .-.- - ---
0,029
0,029
0,029
0,029
0,029
0,029
0,029
0,184
0,073
0,022
0,029
0,160
0,029
0,022
0,022
0,022
0,022
0,022
.0,022
0,022
0,022
0,160 .
0,058
0,0175
0,022
0,130
0,022
O,()\75
TAB LE 2
AVERAGE MAGNITUDES OF EYE SENSITIVITY TO LIGHT, DURING INHALATION OF DIFFERENT PHENOL
CONCENTRATI ONS, I N PERCENT OF 15TH MI NUTE RESULTS
:;DTH HINUTE 25TH HI NUTE
I NIT I ALS OF PURE . PHENOL CONCN. IN 1110/113 ! PURE PHENOL CONCN. III 1110/",3
TEST I'ERSON '
AIR AIR
- I ' ., - I I
0,022 I 0,0155 0,0/25 0,022 0.0/55 0,0125
A. P.
R. U.
A. B.
. . . . . . . .
. . . . . . . .
. . . . . . . .
166
114
124
H>6 (b)
167 (c)
151 (c)
188 (c)
128 (C)
132 (b)
178 (0)
115 (0)
123 (0)
195
126
130
216 (c)
174 (c)
166 (c)
207 (0)
127 (0)
128 (0)
264 (c)
227 (c)
240 (c)
NOTE: DEGREE OF RElI481LITY: 4 - 95}!:; . - 99(.; C - 99.9%; 0 - UNRELIULE
- Phenol concentratio~ of 0.022 mg/m3 elicited a c<3nsiderable rise in eye
sensitivity to light in all test persons; the 0.0155 mg/m concentration was the
minimum active, or the threshold concentration, and the 0.0125 mg/m3 con-
centration was non-active. The results are summarized in Table 3, (See
.page 52). Data in that Table show that phenol odor threshold concentration
affecting eye sensitivity to light was 1. 8 times below that of the odor perception
187
-------
f$ 000
'" 17000
'10000
... f 5000
~ (/) fMOO
- 0- {3000
... :; 12000
o ::> flOOO
0- ... WOOO
~:: JOOO
- 0- 8000
:: ~ 7000
0-'" 5000
; "'. 5000
~ 4000
en 3000
2000
(OOO
o
~PURE AIR
--- o,OZZ ~
-.- 0,0155
.oaDD O,Oli5
5
1/1
15 2/1 25 JO
TIME IN MINUTES
FIG. I - EFFECT OF DIFFERENT PHENOL VAPOR CONCENTRATIONS
ON EYE_SE~~~VIT!~__LI GHT OF T~_~.r~E_~~~_~.P._-
28000
27000
2bOOO
25000
2U)OO
23000
22000
2{OOO
ZOOOO
z 1.9000
18000
~ 17000
- ~ fZOOO
= ;:. If 000
~ <10000
;:. ~. ;000
- a:. 8000
~ I 7000
'iI) ! 5000
.5000
, f.000
.- 3000
2000
(000
o
1',
I \
I \
I \
I \
I ,
I
I /.-.-.'
I .'
I I
I /
. I /' ..,
I ",' ....,.
fL,' .
- PURE AIR
-- 0,022 Ale/A(-
-.- o.O(55He!A(-
, .
000'. 0.(/(25 MI/A':
5
(0
. 15 20 25
TIME IN MINUTES
9IJ
..
FIG. 2 - EFFECT OF DIFFERENT PHENOL VAPOR CONCENTRATIONS
ON EYE SENSITIVITY TO LIGHT OF TEST PERSON R.U.
concentration and amounted to O. 155 mg/m 3 in all test pe rsons. Thus, the
phenol concentration which proved odor non-perceptible was able to affect the
light sensitivity of the optical analyzer.
Phenol effect on electrocortical reflex activity was studied by the method
described by K.A. Bushtueva, E.F. Polezhaeva, A.D. Semenenko, V.A.
Gofmekler, Yu. G.Fel'dman in 1960 and by G. E. Solomin, R. Ubaidullaev,
and by Lee Shen in 1961. Electrocortical activity was recorded by means of
an 3 lead Kaizer electroencephalograph.' Experiments were performed
using 5 medically examined normal test persons with clearly defined alpha-
rhythms. The test persons were allowed to become adjusted to the experi-
mental surroundings, and final tests were initiated after the test persons
188
-------
JIOOO
30000
ZP 000
uooo
27000
25000
25000
24000
2J 000
22000
Z Z I 000
20000
~ IgOOO
... II) IBOOO
:; ~ 17000
o : 15000
I- 15000
> ~ 11>000
I- - 13000
;: !; 12000
- .... (1000
!: ~ (0000
~ g 000
'" . BOOO
en 7000
6000
5000
4000
JOOO
2000
1000
o
A
I \
I \
I \
I \
I \
, \
I \
I .-.-
I /' '-.
I /
I /
I .
I /
I
~~
~:'
~~..,
...~.
.~~.
:-~.
- .PURE AIR,
--- 0.022 Alz/ftfJ
--- 0.0155 HZ/AlJ
-un 0,0125 "'tiN,]
(5 ZO ZS
TIME IN MINUTES
FIG. 3 - EFFECT OF DIFFERENT PHENOL VAPOR CONCENTRATIONS
ON EYE SENSITI VI TY TO LI GHT OF TEST PERSON R. B.
TABLE 3 i
i
SUf'f1ARY TABLE OF CONCENTRAT IONS OF THRESHOLD PHENOL VAPOR ODOR'
PERCEPTI ON AND REF LEX EFFECT OF PHENOL VAPOR ON EYE SENSI T I VI TY :
TO LIGHT.
;THRESHOLD OF ODO~' I THRESHOLD. OF EFFEr;T O. N .
PERCEPTiOn -- SENSITIVITY TO ~~~!!T__--.:
PHENOL VAPOR CONCN. IN M6/M3 .
MI N. PER- I MAX. NON- I HI N. PER"'; I Mu. NON- ;
CEPTIIU I PERCEI'TIILECEnJlLE . .llpERCEPTIILE.'
I
of
(0
30
J5
.1,0
. I H/TIALS OF
. TEST PERSONS
A. P.
R. Yu.
A. B.
MoST SENSI-
TIVE PERSONS
0,073
0,029
0,184
0,058
0,022
0,160
0,0155
0,0155
0,0155
0,0125
0,0125
0,0125
0,022
0,0175
orientation reaction to the surroundings became extinct.
Light was used as the unconditioned reflex stimulator which elicited de-
sychronization of the alpha-rhythm, and inhalation of different phenol concen-
trations was used as the conditioned stimulator. Inhalation of the phenol-v9-por-
air mixture was continued for 15 sec. with the light stimulator switched in during
the last 5 sec. Desychronization of the alpha -rhythm was taken as the basic re-
action indicator used in evaluating the effect of phenol, only if the desychroniza-
tion appeared after more than one simultaneous appearance of the conditioned
and unconditioned effects prior to switching in the light stimulator. T~e phenol
air concentrations thus studied were 0.024, 0.0156, and 0.0137 mg/m. Two
tests were made with each concentration. See Table 4 (page 53).
189
-------
TABLE 4 .
CorIO I T I ONED E LECTROCORTI CA L REF LEX ELI GI TED BY PHENOL VAPOR
I NHA LA T 1 ON
I NIT I ALS
OF TEST
PERSONS
PHENOL VAPOR COUC. III MG/M"
O,02~ 0,0156 0,0137
REFLEX RESPIRA- REFLEX RESPIRA- REFLEX RESPIRA-
FORMA- 11011 FORMA- TIOII FORMA- TIOII
TIOII SKIFT TJOH 5111 FT TIOII SHIFT
r
lo u.
YD. Bo
S. O.
18, 19,20 19, 20
7,8,9. 8,9,13,
10.13,14 14
6,7,8. 8,9
9. 10
13,14,15. 14. 18
17. 18
ISOLATED
EFFECT
13.14,15
15
Yu. So
G. I.
13, 15,
14. 16
18. 19, 22 18. 19
15
NOTE: NUMERICAL DATA INDICATE THE ASSOCIATION IN ORDER AT WHICH
CONDITIONED REFLEX APPEARED AND RESPIRATION SHIFTED.
DASKEO INDICATE NO CONDITIONE9 REFLEX FORMATION.
-- ----.--..----------- -- _.~ - _..
,'~~-
. ......",.......
."",
~~f
i<#."""~~"",,-*.
-
-
~.......~...... A",\ £~; ':
"#~\~~,..4,~~~\irN-~~~~J
. --..~ .
~...J,
0\'..... ,
-4 ~~ .
~~~~:,'..I!\'k,~M'.'. ~. ~'--W\~~.f
--.----- -.....---.. .--.
liLl.Lld.uud.'.JdJL...vu'L..kl.u~'L--k.hJ.u,,--k1U~
---'''"J----''-~~~
$
.f
F I G. 4 - E LECTROENCEPHALOGRAMOriEST 'PER'SON G:.I~ -AN-I SOiA'TEO '
INSTANCE OF 00024 MG/M PHENOL VAPOR EFFECT.
I, 2, 3, 4, AND 5 - ELECTROENCEPtiALOGRAMS OF DIFFEREIIT
OIOCURRENT LEADS; 6 - ..TIME OF PHENOL VAP!'R I,NHALATlOIi.
Data in Table 4 show that the 0.024 mg/m3 concentration of phenol
elicited the formation of conditioned electrocortical reflexes in 4 pe rsons.
In one person this concentration produced an isolated effect in the form of
unconditioned reflex alpha-rhythm desychronization; therefore, desychroniza-
tion of the alpha-rhythm was not used in this case for the formation of the
electrocortical reflexes. This case is illustrated in Fig. 4. Conditioned
reflexes were3elicited in 3 of the test persons with a phenol concentration of
0.0156 mg/m. Graphic results obtained with one of the 3 persons arefre-
sented in Fig. 5 (see page 54). The graph shows that the 0.0137 mg/m
phenol concentration was inactive. The electroencephalogram of one test
person is presented in Fig. 6'1s'ee page 54). Thus, it was shown that phenol
concentration of 0.0137. mg/m . had no reflex effect either on the eye sensitiv-
ity to light or on the test person's electrical brain activity.
190
-------
...,. ... ~ - /Ir ~ ~ "'.11> iN"''' .....
....'" 1
1
""II/IIW'.'~I/i'f.~-"" --"'-- .~J
~~~('v..~'~'-
-. ~~" '-
. .
I -.....vo..._,,-
, -wr. s
. ~~+. -~
J,-0~lJ~~JJU...-k.J.~LJ.".
.~J~
6
. FIG. 5 - ELECTROENCEPHAlOGRAM OF TEST PERSON G. I. CONDITIONED
. REFlEX DESYNCHRON.IZATION ON THE 1ST. ASSOCIATION WITH
0.01515 "t/~ PHENOL VAPOR I NHA LA T ION.
I, 2,3,4, 5, Allie AS II FII. 4
1 fJlbl1. ." ~ ...............~ -" .
1_- .....1111_""~ ............... . ~ '-
J rj'tjJ,... "~~l..""'''.,'' . ~...,.
.4 ..-...-. ...~~~ .,..4
--~
.w
.......
- - ... ~ ~fI
.-
.f ....... . .. .'. ~ .,.
14~a"
-i.
. .,..~ ~.t
I~
-
FIG. 15- ELECTROENCEPHALOGRAM OF TEST PERSON G.I. NO CONDITION-
. ED REFLEX FORMED EVEN ON THE 201'11 ASSOCIATION WITH THE
'NHALATI ON ~ 0.137 "1/"3 PHENOL VAPOR CONCENTRATI ON.
1,2,3,4,5, AlII 15-.A8 II FII. 4
. .
. K. G.. Beryushev recommended 0.5 mg/m3 of phenol as its limit of single
allowable concentration in atmospheric air, basing hi~ opinion on the fact that
the maximal single p~eno1 concentration of 1-3 mg/m was found at consider-
able distances from the source of phenol discharge and which were the cause
of complaints of specific unpleasant odor. .
A.A. Itskovich and V. A. Vinogradova were of the opinion that the low-
est threshold odor perception c~centration of phenol containing substances
equivalent to O. 1 and 0.2 mg/m .of phenol shoulti be recommended as the max-
imal single concentration 6f the vapor in atmospheric air surrounding a phenol
discharging coke chemical plant. Such phenol concentration predominated in
the' residential zone of 1000-2000 m belt surrounding the plant, and the odor of
the vapor was clearly felt in that air. It seems that the above recommendation
lacked scientific basis and was inherently self contradictory. Hygienic eval-
uation of the resuits obtained with low phenol concentration in connection with
their affect on the human organism was based on the position taken by V. A.
. Ryazanov that the crite'rion for the determination of an allowable concentra-
tion of a foreign substance in the air should rest not only on the absence of
visible or otherWise preceptible affects, but also on the subsensory affects
. .
191
-------
of inhibiting as :rell as stimulating characters. Therefore, it was suggested
that 0.91 mg/m concentration be accepted as the limit of allowable phenol
concentration in atmosphe ric air.
On the other hand, it has been known that reflex effects were accom-
panied by other general effects caused by the resorption of harmful substances.
In this connection, the study of resorptive effects is of great interest since it
enables the determination of limits of ave rage pollutant concentrations in
atmospheric air, as was shown by V.A. Ryazanov. With this in mind chronic
experiments were performed with small laboratory animals by subjecting them
to continuous 24-hour pollutant exposure for 61 days. The chronic experiments
were performed with 60 white male rats weighing 150-260 g. The rats were
divided into 4 groups of 35 animals each. Rats of group 1 were exposed to the.
inhalation of 0.01 mg/m phenol concentration, or the equivalent of the suggest-
ed limit of allowable si~gle concentration; rats of group 2 were exposed to the
inhalation of 0.1 mg/m phenol concentration, adopted by the USSR State Sani-
tary Inspectorate as the limit of all~wable average 24-hour concentration; rats
of group 3 were exposed to 5 mg/m phenol vapor concentration, which was the
equivalent of the limi't of allowable phenol vapor concentration in the air of
working premises. Animals of g:roup 4 were used as controls. Animals were
exposed to inhalation of the different phenol vapor concentrations in experimen-
tal chambers of 100 li capacity. Air containing different phenol vapor concen-
trations was run into the exposure chamber at the rate of 15"'20 Ii/min.. Sam-
ples of the mixed phenol vapor and air were taken once or twice daily for check
purposes. Fluctuations were insignificant. The average concentration in
chambfr No.1 was 0.0112 :f: 0.0014 mg, in chamber No.2 o. 106 :i: 0.0324
mg/m , in the 3rd chamber 5.23:i: 0.44 mg/m3; pure air was run in at the
rate of 15 -20 li min. into chambe r No.4 housing the control animals.
In the course of the chronic experiments, records were kept of the
animals I general condition, their weight, muscle antagonists motor chronaxy,
porphyrine metabolism and cholinesterase activity. Throughout the period of
exposure to the phenol vapor animals of groups 1 and 2 and of the control
gr~up were in a satisfactory condition, as shown by their active behavior.
Animals of group 3 were less active, somewhat sluggish and sleepy. No
dearly discernible or regular changes were noted in the weight of animals of
groups 1, 2 and of the controls. On the other hand, animals of group 3 mani-
fested statistically reliable gain (probably means loss) of weight when checked
on the 52nd and 60th day of exposure. Such shifts in weight persisted through
the period of recovery. See Table 5 (page 56). Changes in the right hind leg
muscle antagonists motor chronaxy of the rats were used as indicators of
effect of different phenol concentrations on the functional condition of the
central nervous system. Determinations were made once every 10 days under
similar experimental conditions in 5 rats of each of the 4 groups, using the
electronic impulse stimulator ISE -0 1. Average flexor and extensor chronaxy
values of the experimental animals are presented in Table 5. Also see Fig. 7
(page 57). Data listed in Table 5 and curves presented in Fig. 7 show that no
changes appeared in the motor chronaxy of rats belonging to groups 1 and 4.
192
-------
.' , EXTenSORS
FLEXORS
DAY OF RAT GROUI'S M (AVERAGE
EXI'OSURE Mo - MK ' Mo-~ M (AVERAGE Mo -MJ( Mo - MJ( ,
TIME) T... T...
Mcp TIME) Mcp
\
3)TII F'RST 0,164 -0,014 1,07(0) 0,14-4
SECOtlD -0,014 1,2(0)
THIRD 0,176 -0,002 0,1 (0) 0,148 -0,010 0,2(0)
.' FOURTH 0,152 -0,026 2,0 (0) 0,200 +0,042 4,5(b)
0,178 :
3OT" FIRST - - 0,158 -
0,168 -0,002 -
SEcon 0,5 (0) . 0,152 +0,004 0,7(0)
THIRD 0,114 -0,056 7,5 (c) 0,154 +0,006 0,7(0)
FOURTII 0,162 -0,008 1 ,0 (0) 0,176 +0,028 4,3(b)
'<401"' 0,170 - - 0,148 - -
FIRST 0,162 -0,012 1,7(0) 0,146 -0,006 1, 2(0)
SECOND 0,124 -0,050 6, 4( c) 0,162 +0,010 1 ;3,0)
THIRD 0,138 -0,036 5, 3( c) 0,182 +0,030 5,I(c)
FOURTH 0,174 - - 0,152 - -
~TH FIRST 0,166 -0,006 0, 4(0) 0,154 +0,002 0,2(0)
SECOND '0,138 -0,034 3,3(b) 0,164 +0,012 1,4(0)
THIRII 0,128 -0,044 4,4(b) 0,160 +0,008 '0,9(0)
FOURTH 0,172
- - 0,152 - -'
6On. F '" ST 0,180 +0,004 0,54(0) 0,158 +0,008 1,0(0)
SECONI 0,118 -0,058 8,6 (c) 0,154 +0,004
TH'RD 0,5(0)
FOURTH 0,122 -0,054 a,05(e), 0,156 +0,006 0,8(0)
, 0,176 - - 0,150 - - -
TABLE 5
AVERAGE EXTEtISOR AND FLEXOR MUSCLE CHRONAXIES OF THE EXPERIMEtlTAL AND COtlTROL RATS
NOTE: RElIA81LITY - . - 9Q%; C -' 99.9%; 0 - NOT RELIABLE; M~AVERAGE CHRONAXY OF
EXI'ERII1ENTAL RATS; Mx - AVERAGE CHRONAXY OF CONTROL RATS; Mc,-AVERAGE OF ALL
CHRONAXIES; T - TII1E.
Motor chronaxy changes appeared in rats of group 2 beginning with the 30th day
of exposure to phenol vapor inhalation, which persisted to the end of the ex-
periment. A reverse muscle antagonists chronaxy ratio appeared as a result
of a considerable shortening in the extensor muscle chronaxy while the flexor
muscle chronaxy remained normal. Changes in the motor chronaxy of rats
belonging to group 3 appeared on the 20th day of exposure to phenol vapor in-
halation manifested as reverse ratio of muscle antagonists chronaxy, which
persisted through the entire period of exposure, During the first 20 days the
ch~nge was the result of increased flexor chronaxy, and later the result of
shortened extensor chronaxy. Analysis showed that the chronaxy changes
were statistically reliable.
Changes in .porphyrin metabolis m were used as indicators of the chronic
phenol effect on the animal organs. Not much is known of the mechanism of
:p-o'rphyrin metabolism in the organism. M.1. Gusev was the first to study
JPorp~yrin metabolis m in rabbits subjected to the inhalation of lead oxide in
10 mg/mj concentration 6 hours daily for 6.5 months, which resulted in the
appearance of porphyrinuria. Yu. K. Smirnov was of the opinion that por-
phyrinuria in lead poisoning was the result of depressed or inhibited enzyme
systems which elicited changes in the cell metabolism of the nervous system,
liver and bone marrow. G. 1. Solomin found a sharp drop in 'copropor_pI:yrin- r'
in the urine of rats subjected to chronic inhalation of 10 and 0.2 mg/m", con-
centrations of dinyl. Lee Shen noted that reduced rate of coproporphyrine
eliminatio~ with the urine occurred in rats exposed to the inhalation of 50 and
0.5 mg/m concentrations of styrol.
193
-------
. V)'Ol.5
g'
'::
o
...
...
CIJ
-' 0
. = 0. 20
.J:
z'
, -
>-
~ 0. 1.5
::
o .
""
:I:
O.
-----
0.20
z
0.15
I
I ~ 4---
I . ,~
----1----------"'- I ....-
I ~-:-------------~---
I I .
,
I
I
o
,0.20
" RECUPER-'
," '''.. t; ATiON ;
I " "------', : ~~_D_' ..
I: , ''''', I
, .. ,
----t-.---- .':---1---
,
,
I
I
I
d
, NHALA TI ON'
EXPOSURE.
o I
I .
,
I
.-.-.-_.-----'-~~~l--
I
I
; 0
0,20
I --
----.....-~- .............
I "....--
. 1 .
I
I
I
.'
O,fS
a
! -- ~.:
-----.-----"..", -----+--.
I ...... ----"'-.. .-- I --...
I ,-... ~-..--- I
I I
I I '
I NHALATION ','
EXPOSURE
o
o
'0
- {XTE';:S-OR --
20 .J!J I,J
TIME IN DAYS
- . --
---- }LEXO~=!
50
50
(If)
- ----- --
-- -- -- -----
FIG. 7- AVERAGE MUSCLE CHRONAXY IN RATS INHALING PHENOL VAPOR
A - GROUP I; B - GROUP 2; C - GROUP 3; D - GROUP 4
~-_.- --- --
- ----- ~- -
Coproporphyrine concentration in the urine was determined spectro-
photometrically. Quantitative determinations were made on the basis of
optical density at 402 - 404 m,u as determined by spectrophotometer SF-4.
Urine was collected from 5 rats of each group at the same time for 24 hours.
Results of determinations are listed in Table 6 (see page 58). Data in that
Table show that no changes were noted in the 'porphyrTn:- metabolism of rats
belonging to groups 1 and 2. Rate of coproporphyrin elimination sharply
dropped in the urine of rats belonging to group 2 beginning with the 22nd daX
of phenol vapor inhalation, which pe rsisted throughout the expe riment with
the exception of a one time rise at the end of the inhalation experiment.
Changes in porphyrin metabolis m in rats belonging to group 3 we re noted \
beginning with the 11th day of exposure to the phenol vapor inhalation. No
194
-------
clearcut re gularity was noted
in the change of coproporphy-
,rin elimination rate over any
considerable length of time;
the changes were of a wave-
like character representing
inte rmittent rise and fall.
However, beginning with the
52nd, and especially the 60t~
day of exposure, the increase
in coproporphyrin elimination
with the urine became per-
sistent. The porphyrin meta- :
bolism returned to normal in
rats of all groups beginning
with the 10th day of the re-
cupe ration pe riod.
Cholinesterase activity in
the whole blood was determin-,
ed chemically by the method of
A. A. Pokrovskii, as modified
by A. P. Martynova. The prin-
ciple of the method is based on
the determination of time re-
quired for a change in the in-
13 27 Ifl 55 (8)
TUIE IN lAYS dicator color as a result of
FIG. a - CHOLI NESTERASE ACTInVITY- OF RAW WHOLE BLOOD shifts in the pH occurring
n~. during acetylcholine hydrolysis.
The physiological importance of cholinesterase is closely related to the activity
of the central nervous system. The mechanism of narcotic substances action on
the central nervous system may be the result of disturbed processes in the
chemical stimulation transmission to brain synapses, as was shown by M. Ya.
Mi'khl'son. No reliable changes in cholinesterase activity were noted in rats
of groups 1 and 4, as shown in Fig. 8. Increased cholinesterase activity was
noted in rats belonging to group 2 on the 41st day of phenol vapor inhalation,
which persisted to the end of the experiment. Increased cholinesterase activ-
ity was noted in rats belonging to group 3 beginning with the 13th day of expos-
ure to phenol vapor inhalation. Statistically the data presented in Table 7
(see page 59)' were found reliable. Cholinesterase activity returned to normal
beginning with the 8th day of the recovery period. ,
Thus, it was shown that conti~uous 61 day chronic exposure of white .rats
to the inhalation of 5 and O. 1 mg/m of phenol vapor elicited clearcut shifts in
the motor chronaxy, in the porphyrine metabj>lis m, and in the choline s te rase
activity. Results indicated that 0.01 mg/m concentration of phenol in the
atmospheric air was inactive. The limit of allowable 2J-hour concentration
of phenol vapor in the atmospheric air, i. e. 0.1 mg/m , approved by the State
TABLE 6
COPROPORPHYRI NE I N THE EXPERIMEIITAl AND CmITROL RATS
. RAT PERIOD OF I~VESTIGATION
GROUPS BEFO~ DAYS OF INHALATION EXPOSURE I PER'I-OD'.
E~=~ 11TH I 220 I 320 I 420 1 50TH 160TH OF RE-
COVERY .
GROUP ONE 3.06 2.95 3,74 3,36 3,54 4.00 3,98 3.21
GROUP 1....0 2.97 4.02. 2.08 1.70 3,12 1,72 6.54 3,08
GROUP THREE 2,74 5.66' 3,15 4,35 2,41 4,83 6,95 3,49
GROUP FOUR 2.88 3.40 3.47 3,63 4.79 4,44 4,12 3.46
CoO
....
...
:>
~ 20
:E:
:z
~ 30
U)
.)-
-'
o
:: ~o
)-
z
....
..
:50
o
:z:
u
-'
)-
1;;' 50
u
..c
10
, 'EXPOSURE 'RECOVERY' "
I PER 10D 1 PER I OD
I I
: -'\
I ---- 1\
I ,." I \
II ,.,,.,-- '/"-'-"1 ".\
'" / , ,\
I ~ /' I . \
~ J'-'-' I ' \
=::.:.-~ "-"~................~.....:~..
I I
I I
I I
I I
I " I
J ..... GROUP ONE I
I -.- GROUP TWO I
I --- .GROUP THREE I
I - GROUP FOUR I :
o
195
:.
-------
Sanitary Inspectorate of the
: USSR' in 1955 and adopted on
the basis of calculation was
the equivalent of 1/3rd of the
.limit of the allowable sing11
concentration of 0.3 mg/m '.
Results of above desc ribed
chronic experimen~s suggest-
ed that 0.01 mg/m could be
recommended as the limit of
allowable average 24-hour
concentration of pheno13vapor
in the air. 0.01 mg/m phenol
vapor concentration tested by
the continuous 24-hour chronic
exposure of rats elicited no-
---- . 39,4 shifts in the motor chronaxy,
NOTEr RElIAnII:ITY: C - 9909%; a = UNRELIABLE; M -CHOLINESTERASE . .
. ACTIVITY AVER. OF EXPERIMENTAL RATS; MK ~gHOLINESTERASE no changes 1n the porphyr1ne
ACTIVITY OF CONTROL RATS; Mcp -AVER. OF ALL CHOLII/ESTERASE metabolis m or in the cholin-
ACTIVITIES; T - TIME.
. - -. .' .' . estras.e activity, and was,
the refore, regarded as an inactive concentration.
Phenol is extensively used in such industries as the coke chemic~l,
phenol producing, in the manufacture of plastic, etc. and is the frequent
cause of atmospheric air pollution. Coke chemical plants are probably the
greatest offenders of air pollution with phenol, benzene, napthaline, and other
organic substances which imparted to coke chemical discharges unpleasant
specific odors. Hydrogen sulfide and phenols are generated and thrown into
the atmos pheric air during coke -quenching; this is especially true of plants
in which coke -quenching is done with phenol-containing waste water. This
proces s was introduced for the purpose of breaking the phenol down; the fact
is, howeve r, that only a s mall fraction of the phenol becomes thus broken
do~n, and that the greater part of it entered the atmospheric air in its orig-
inal state resulting in extensive air pollution. D. N. Kalyuzhnyi, L. M. Vol ova
and £.S. Turetskaya found the following phenol concentrations in the air during
coke -quenching with phenol-containing waste water. See Table 8.
Thus at 1000 m from the coke
chemical plant phenol vapor
concentrations in the atmo-
spheric air exceeded the limit
of allowable single concen - 3
tration of phenol (0.01 mg/m )
by 500 -600%. A. A. Itskovich
and V. A. Vinogradova studied
the concentrations of phenol
vapor in the air surrounding- a
coke chemical plant and found
that maximal single concen-
T AS LE 7
AVERAGE TIME OF CHOLINESTERASE ACTIVITY IN MINUTES
DAY OF '.
. RAT M (AVERAGE Mo-MIS Mo-MK
E~POS~RE GR au p TIME) T= Mcp'
-
. 13TH FIRST 37.0 - 0.8 0,4(0)
SECOND 35.8 - 2,0 0.8(0)
TH IRD 30.8 - 7.0 6.5(e)
FOURTH 37,8 - -
27T1I FIRST 40.0 + 1.4 0,9(0)
SECOND 39.6 + 1,0. 0.8(0)
THIf.1J 26,2 -12.4 8,8(e)
FOURTH 38.6 - -
415T FIABT 39.4 + 1.0 0.5(0)
'SECOIID 28.2 -10,2 8.9(e)
-TH I RD
FOURTH 22,8 -15,6 13,2(e)
FIRST 38,4 - -
55TII SECOt/!! 39,8 + 0,4 0.2(0)
~. THIRG 28.4 -11.0 8. 7(e)
FOURTH 19,0 -20.4 15,0(e)
.--
- -
TAB LE 8
, -
PHENOL CONCENTRATION DURING COKE-QUENCHING WITH
PHENOL CONTAINING WASTE ~~TER
MAXIMAL SINGLE COt/CNo IN MG/n3
M FROM DRYING
TOWER
PUNT No.1
I PLANT No.2
0,150
0,10
0,060
0,068
HeT
100
300
500
1000
2000
0,350
0,189
0,068
0,050
HeT
196
-------
trations at 2000 m from the plant ranged between 0.40 and 0.97 mg/m3.
Such concentrations are considerably in excess of the limit of allowable
phenol concentratibn in the atmospheric air.
The present "author studied the degree of city air pollution in the vicinity
of a plan(producing insulation material and which discharged phenol vapors'
into the air. The plant produced hetinax aid textolite which required the use
of lacquers mostly BBf. In its aqueous solution BBf contained phenolform".lde --
hyde resins containing 15% free phenol; oth~r lacquers contained 69% free
phenol. The preparation of the raw material saturated with the above sub-
stances was passed through 13 machines, all housed in one workroom equipped
with drying tiers. The material passing through the saturation processes was
dried at 100 - 1200 and liberated phenol vapor in high concentration into the
atmospheric air at the rate of 30 kg per hour. Hygienic investigations of the
air were made during June and September of 1960 and during September of
1961. Each investigation was conducted at a different stage of the insulation
material preparation. Results of the investigations are presented in graphic form
in Fig5 9. The graphs in that figure show that phenol concentrations of 0.01 .
mg/m were found in the air at 1000 m from the point of discharge. They
were somewhat lower at 1300 m. These determinations were made prior to
the installation of phenol catching equipment; after the installation o~ such
equipment phenol vapor concentration in the air exceeded O. 1 mg/m at 500 m
from the point of discharge and somewhat less than that at 750 m from the
point of discharge. At full operation of the phenol catching equipment the above
concentrations were noted at 400 m and 500 m correspondingly. Thus, the in-
stallation of the phenol vapor catching equipment 10we red the pollution of air
with phenol in the vicinity of the investigated plant. It must be noted, however,
that the existing sanitary clearance zone was only 100-150 m wide, whereas
its width should have been not less than 500 m.
AlOVE
0,5
---- 1ST OISERYATION
---- 2110 n
-.- 3RI n
C"\:
.
...
~ o.s-O,I
z
...
~ BELOW
~ ~O, .1
-----
-.-
. \
\ \
. \
\ ,
. ,
\ '
. ,
\ "
. "
\ "
. ..
, ..
. ..
, "
" ",
II)
:z
o
t- 0, (-O,OJ
~
'"
t-
z
&II
U
~ 0.03-0.0'
u
I I I I I I I I I I I I
, I , I I I I I
I'~ III'~'''I:-'
o 100 200 .100 400 500 000 100 800 900 (00011001200 (JOO
'. - - .
METERS FROM THE ~LANT
FIG. 9- MAXIMAL SINGLE ATMOSPHERIC AIR PHENOL VAPOR CONCENTRATION
: IN THE VICINITY OF THE PLANT MAKING INSULATION MATERIAL.
197
-------
Conclusions
1. The concentration of phenol threshold odor perception in most odor
.sensitive persons was 0.022 mg/m3; the threshold c~ncentration of reflex
reaction of eye sensitivity to )ight was 0.0155 mg/m , and of electrocortical
reflexformation 0.156 mg/m. Phenol con~entrations of 0.125 and 0.01.37
mg/m had no reflex effect eithe r on the eye sensitivity to light or on the
electrocortical activity. . .
2. The limit of allowable single Ifenol vapor concentrations in atmo-
spheric air should be set at 0.01 mg/m .'
3. Phenol vapor con~entrations ~f 5 and 0.1 mg/m3 were active accord-
ing to results of chronic expe riments of continuous 61 days exposure; this was
made clear by the fact that they elicited motor chronaxy changes, induced
changes in the ~o_r?h'yrin metabol is m, and affected cholinestrase activity;
the 0.01 mg/m concentration was not active according to the results of the
chronic expe riments. .
4. Results of chronic experi~ents indicated that O. ~1 mg/m3 of phenol
vapor in the air should be recommended as the limit of its allowable concen-
tration in atmosphe ric air. .
BIB LIOG RAPHY
Are e B a . M a H K 0 B a O. f. 060H!lTeJlbHblH a HaJlll3aTOp 'B
Y'IeHHH aKa.ll.eMHKa 11. n. naBJlOBa II ero KJlHHH'IeCKOe 3Ha'leHHe.
BecTHHK OTOpHHOJlapHHro.10rHH, 1961, N2 3, CTp. .8.
A JI e K C e e B a M. B. Onpe.ll.eneHHe aTMoce-
Hona B B03.l1.yxe HaCeJleHHblX MeCT. B KH.: npe.ll.eJlbHO .lI.onycTHMble KOII-
u,eHTpau,HH aTMoclj>epHblX 3arp!l3HeHHH. Me.ll.rH3, 1955, B. 2, cTp.81.
I) Y w T y e B a K. A., no JI e}K a e B E. CI>., C e M e H e H -
K 0 A..n:. 113Y'leHHe noporoB peneKTopHoro .lI.eHCTBHJI aTMoclj>epHblx
3arpJl3HeHHH MeTO.ll.OM 3J1eKTp03Hu,elj>aJlOrpaonorH'IeCKHe 113MeHeHIIJI B
opraHax H TKaHJlX B yCJlOBHIIX XpOHH'IeCKOfO 3KcnepHMeHTa. B KH.:
npeAeJlbHO .lI.onycTHMble KOHl\eHTpall,HH aTMoceHona B aTMoclj>epHoM n03.l1.yxe. Te3HCbI .lI.oKnaA08
HaY'IHoA CeCCHI! HOBOCH61!pCKoro caHHTapHoro HHcTHTyTa, 1956. .'
K a n JO }K H hi Ii .n:. H.,B 0 n 0 Ban. M. H T y P e 11, K 8 !I
3. C. I1ccneAoBaHHe aTMOc
-------
BIBLIOGRAPHY - Cont'd.
n :1 3 ape 8 H. B. C%leHOJl. B KH.: BpeAHble Be~eCTBa B npO'
NblWJleHHOCTH. fOCxHMH3AaT, 1954, 'I. I, CTp. 318.
n H ill 3 H. MnepHaJlbl K o60cHOBaHHIO npeAeJJbHO Jl.OnYCTHwoA
KOHueHTpaUHH CTHpOJla B aTMo~epHOW B03Ayxe. fHrHeHa B caUBTa.
pHR, 1961, N~ 8, CTP, 11.
M H X e JI b C 0 H M. 51. OCHoBHble CBoftCTBa XOJlHH'C:Tepaabl.
YcnexH COBpeNeHHOA 6HOJlOrHH. 1948, T. 25, 8. 3, CTp. 321. '
M Y X H TO B 5. I( Bonpocy 0 npeAeJJbHO AonYCTHloIoA KOHueHT'
paUHH «PeHOJla B aTMoccflepHoM B03Ayxe. 3ApaBooxpaHeHHe l(a3axcT8Ha,
1961. N~ 6, CTp. 65.
n 0 K P 0 B C K H A A. A. OnpeAeJJeHHe XOJlHH3CTepa3b1 B CbI-
BopoTKe H UeJJbHOA Kp08H. BOeHHO-yeAHUHHcKHA :lKypHaJl. 1953,
~ 9, CTp. 61. ,
Po 3 a HOB n. C. CaHHTapHo-rHrHeHH'IeCKHe ycnOBHII TpYAa
B npOH3BOACTBe H30JlIIUHOHHblX MaTepHaJlOB C npHMeHeHHeM HCXYC'
CTBeHHblX CNOJI. fHrHeHa H 3AopoBbe, 1942, ~ 10, CTp. 39.
, P II 3 a H 0 8 B. A. CaHHTapH3R oxpaHa aTMoccflepHoro B03AYU.
MeArH3, 1954.
P II 3 a HOB B. A., 5 Y W T Y e Bal(. A., HOB H K 0 B 10. B.
I( MeToAHKe 9KcnepHMeHTaJlbHOrO o60cHOBaHHII npeAeJ1bHO AonyCTH-
MbiX KOHueHTpaUHA aTMoccflepHblX 3arp1l3HeHHA., B KH.: npeAeJ1bHO
AonYCTHMble KOHueHTpaUHH aTMoccflepHblX 3arp1l3HeHHA. Mep,rH3, 1957.
B. 3, CTp. 117.
P II 3 a HOB B. A. 0 KpHTepHIiX OUeHKH AeAcT8HII NaJlhlX KOH-
ueHTpaUHA aTMoccflePlibiX 3arpll3HeHHii Ha opraHH3M. fHrHeHa H caHH-
TapHII, 1961, Ni 6, CTp. 3. '
Co JI 0 M H H f. 11. MaTepHaJlbl K o60cHoBaHHIO npeAeJ1bHO AO-
nycTHMoA KOHueHTpauHH AHHHJla B aTMoccflePHOM B03Ayxe. fHrHeHa
H caHHTapHII, 1961, Nt 5, CTp. 3.
C Ten a H e H K 0 5. H. I(ypc OpraHHQeCKOii XHMHH. MeArH3,
1955.
Y 6 a A A Y JI JI a e B P. MaTepHaJlbl K o60cHoBaHHIO npeAeJ1bHO
AonycTHMoA KOHueHTpaUHH IPypcflypOJla B aTMoccflePBOM B03Ayxe.
fHrHeHa H caHHTapHII, 1961. Hi 7, CTp. 3.
Dei c h man n W. R. Phenol and Phenolic Compounds.
Industrial Hygiene and Toxicology (under the editorship of F. A. Pat.
ty). New York - London, 1949, v. 2, p. 1023.
E van s S. J. Acute phenol poisoning. Brit. J. Industr. Med..
1952, v. 9, N. 3, p. 227.
J a c k son D. E. Experimental pharmacology and materia
medica. St. Louis. Mosby. 1939. p. 604.
o e t tin g e r W. F. Phenol and its derivatives: the relation
between their chemical constitution and their effect on the orga.
nism. Washington u. s. w. Gov. Priating Office, 1949, p. 3.
Pn I NT I HE! '
199
-------
An Autom~tically Regulated Apparatus for Chronic Toxicity
Experiments with Animals
B. K. Baikov and V. I. Shul'gin
From the F. F. Erisman Moscow Research Institute of Hygiene
The hygienic evaluation of atmospheric air pollution intensity is based
on maximal single and average 24 hours limits of allowable concentrations of
harmful substances. The determination of limits of aliowable average 24-
hour concentrations of a harmful substance in the air is accomplished with
the use of experimental animals, which in most cases are exposed to the
effects of pollutants for not less than 24 hours. Performance of such tests
is always accompanied by some difficulty because it required uninterrupted
presence of the investigator who must regulate the operation of the electric
motor, the rate of air supply, the ventilating equipment, etc. Interruption
in or improper operation of any of the controiling.conditions may lead to
non reliability of the final results or to death by asphyxiation of the expe ri-
mental animals. It is, the refore, essential that automatically and reliably
operating equipment be developed which might enable an individual investi-
gator to take full and uninterrupted charge of the experiment. It is hoped
that the apparatus herein described may meet the required condition.
z
8
I
/. .
,FROM THE AI R
HOWER
I
'.'
.'":
. . .
FIG. I - PLAN OF THE APPARATUS FOR CHRONIC TOXIC I NHALATION EXPERIMENTS WITH ANIMALS.
200
-------
The plan of the experimental arrangem~nt was designed'for chronic
animal toxicity experiments, and is schematically presented irt'Figure I,
(see page 63). The air is forced into exposure chambers (l)~each of 100 Ii
capacity, by air blowers operated by four motors connected .co,~,~es'pondingly
into right and left installation groups. "
The motors are of 1 kwt - capacity, each supplying an 'av~'rage of 75 li
of air per min. The air blowers are installed at distances of Z-O ~ from the
laboratory in a special housing. During the operation of the ,leff'side group
of air blowers air might escape from the system via the right side air blower
group and vice versa. The installation of special automatic corttrol valves (4)
prevented this from occurring by blocking reverse air currehts. 'Other im-
provements were installed to insure smooth non-vibrating and'continuous
operation of the motor blowers. The air was first passed th'rough the purify-
ing chamber (2); from there it entered into the distribution sys.tem which con-
sisted of a comb:"shaped glass arrangement (3), which enable;ti'i~~ simultan-
eOUs testing of several substances. It is pos,sible to increase ; the amount of
harmful substances supplied into the ,chambers by manipulating control valves
(4). The construction of the rest of the instrument usually dc:p~nded upon the
chemical and physical properties of the substance investiga,ted in any specific
instance. The present authors dealt with hydrogen sulfide a.nc.f.:carbon bi-
sulfide. The rate of air supply was regulated by rotameters :(5) which were
considerably smaller than the usual flowmeters. The rotameters were in-
, stalled in front of dosameters (6). (7). This was done to prevent the possi-
bility of any reaction taking place between their metallic pal'ts and the in-
vestigated chemical substances. Mixers (8) were used to obta~n desired con-
centrations of the investigated harmful substance.
The system of automatic apparatus operation is schematically presented
in Fig. 2 (see page 65). Section (a) presents the plan o.f a switch-board
equipped with a packaged circuit break (1), a voltmeter (2), a heat-shield (3),
regulating lamps (4) which indicate the group of motors in .()peration, a clock
mechanism (5) for the automatic switching in and out of the 'eh~ctric motors
at 'given time intervals, and two magnetic starters (7) equipped 'with heat
shields. Section (b) of Fig. 2 presents the plan of anautomat1.c motor regula-
tor consisting of 9 slave relays (9) of the M K U -48 type; e~9~:~t; the magnetic
starters (10) is equipped with three such slave relays. The'entire apparatus
is ope rated as follows: The packet switch on the control bo~,TCil ;is switched in,
and the current is sent simultaneously through the voltmeter 'and into one
of the magnetic control starters; this sends the -voltage into,'th~::operating
magnetic starters shown in the schematic plan of the automa~it:/motor regu-
lator, which switch in the slave relays and a corresponding gt-oup of motors.
In case of imprope r ope ration of the safety devices or of the In~tors, the
slave relays automatically switch the current over from one s'et of motors to
the other. When a' motor becomes overloaded and overheated,~",the heat shields
with which the magnetic starte rs are equipped, are automat~'a,lly set into ope ra-
tion, disconnect the ove rheated group of motors and automa:tic~Jiy switch in
.:.. "
201 ..
'...
" '
. ,'. -:'i"
. " :.' .
-------
a
3
:
'~UL;
4
50
I
5
1
----t;
I
I
I
I
I
I
J I
I
I
--..
..
d
ffl'J
'~2r
ro
13
~uu,g
Fll30 2 - PLAN OF THE AUTCt1ATlC CONTROL PANEL OF THE
APPARATUS FOR CHRONIC TOXIC INHALATION EX-
PERIMENTS WITH ANIMALSo
A - PLAn OF THE CONTROL PANEL; g - 'LAU OF
THE AUTO"ATIC RE'ULATOR
Conclusions
3
the other set of motors. At times
when no city current is available,
the apparatus can be operated by
storage batteries .via 3 slave re - .
lays .until such ti~s the city
current becomes available. Under
normal conditions of motor and
blower operation, shifts from one
. set of motors to the other can be
automatically effected every 12
hours with the aid of specia124-
hour operating.clocks connected
to a regulating switch. Twelve
hour intervals were adopted so
that the switching over from one.
set of motors to the other would
take place during the presence of
the investigator who could record
the rate of the air supplied to the
chambers. at that time. This is
es sential, since the switching of
one set of motors to anothe r could
change their rotation speed and the
tested gas concentration in the
chamber.
The apparatus is equipped with
a device which automatically con-
nected the motors. with a storage
battery in insfances when the city
current supply was discontinued
for some reason during ilie night
in the absence of the experimental
personnel. Thus, the described
apparatus enabled one investigator
to conduct the exposure experi-
ments.
:
The device described makes possible the following:
(a) Automatic switching in and out of the motor sets at given
- time intervals.
(b) Automatic switching over from one set of motors to another
- or from the city current to storage battery current in emer-
gencies.
(c) Automatic switching over from overheated motors to a new
- - -set of motors.
1.
202
-------
2. In the event of a breakdown in the original source of electrical
energy the motors ,become automatically connected with storage batteries
to insure the moto:ts I uninterrupted ope ration.
Methods for the Determination of Some Organic Atmospheric
Air Pollutants
M. V. Alekseeva and P. G. Tkachev
From the F. F. Erisman Research Institute of Hygiene, Moscow
Below are described methods for the determinat~on of aniline, xylol,
n-butyvinyl ester, and dimethylterephthalate in atmospheric air.
Determination of Aniline
Principle of the method:
Aniline is oxidized to indophenol by chloramine in the presence of phenol
and alkali. A blue color is formed which is compared with a standard color
scale. Ammonia and primary aromatic amines interfere with the reaction.
The sensitivity of the method is 0.25 u in 4.5 ml.
Apparatuses:
(1) Aspirator of 5 or 6 li capacity;
(2) U -shaped absorbers equipped with porous glass filter No.1;
. (3) Volumetric flasks of 50 or 100 ml capacity;
(4) Distillation flask of 50 or 100 ml capacity;
(5) 1 or 2 ml pipettes divided into 0.01 ml;
(6) 5 or 10 ml pipettes divided into O. 1 ml;
(7) Colorometric tubes marked at 2 or 3 ml;
(8) Reagent bottles, assorted;
(9) 2000 thermometer.
Reagents:
1. Standard aniline solution prepareq as follows:
Place 15-20 ml of 0.01 N solution of sulfuric acid into a 50 ml
volumetric flask. and weigh on analytical balance;
Add 2-3 drops of freshly distilled aniline and weigh again. The
difference represents the amount of aniline added;
Add 0.0 1 N of sulfuric acid to the mark and calculate the amount
of aniline per ml of the solution in the voiumetric flask;
use this as the aniline stock solution for the preparation of
203 .
-------
the standard solution containing 10 tL
of aniline pe r 1 mI.
2.
Absorbe r solution prepared as follows:
Take O. 1 N sulfuric acid solution and dilute
0.01 N solution;
Chloramine, 4% solution; dissolve the chloramine in water at
30-500 and filter;
tenfold to obtain
3.
4.
5.
Phenol, 30/0 solution prepared from -freshly distilled phenol.
Sodium hydroxide, 20/0 and O. 1 N solutions.
6.
Sulfuric acid, O. 1 N solutions.
Collection of air samples:
For the determination of the maximal single concentration in atmo-
spheric air aspirate the air through the U -shaped absorber equipped with
filter No. 1 and containing 4 ml of the absorber solution. Aspirate the air
at the rate of 1 li/min. for 20 minutes. For the determination of an average
24-hour concentration aspirate the air for 24 hours through the same U -shap_-
ed absorber equipped with Filter No. 1 containing 5 ml of the absorber solu-
tion. As pirate the air at the rate of 0.3 li/min. Keep the absorber solution
volume constant by replacing the evaporated water with fresh distilled water.
STANDARD $OLUTION IN HL
ABSORBER SOLUTION IN HL
MIU! OF AN I L UIE
Analytical Procedure: ,
Take 3 ml of the solution from the absorber and place into a coloro-
metric tube. Simultaneously prepare the standard color scale in a series of
8 tubes as described in Table 1. Add to each tube of the color scaleO. 3 ml
of O. 1 N alkaline solution as
a neutralizer; add to each of
the 8 tubes 0.5 ml of the 40/0
solution of chloramine, 0.5
ml of the phenol solution and
0.2 ml of the 20/0 NaOH solu-
tion. Shake' the tube and
leave rest for 10-20 min.;
compare the color with the
colors of the standard scale.
Calculation of results: ,
20 Ii of the air were aspirated at 100 and 766 mm of mercury; after ad-
justment to normal temperature and atmospheric pressure this would amount
to 19.4 li. The absorbe r volume was 4 ml, of which 3 ml WaS taken for th~
final determination. The color intensity in the test corresponded to the color
intensity of the 3rd tube in the color scale which contained 1,.,. of the ani-
line. Accordingly, the entire sample contained 1 x 4/3 = 1. 3 ,tL, and the
concentration of aniline in the air was 1. 3 x 1000/19.4 = 67 IJ. =
0.067 mg/m3.
TEST TUBE NOo
TABLE I
STANDARD COLOR SCALE FOR THE QUANTITATIVE DETERMINATION OF
ANI LI NE
I I \ I \ j. \ . \ : I &
'0 J\2I:1\4IiJl~l~
I I I , I I !
o 0.025,0.05,0.1,0.2IO.4,0.6jO.8i1.("
3 2 .975!12.!J5.2.!Ji2 .8r612 .412 .2'12.0
° 0,25 0,5 , 1 i 2 I 4 6 I 8 10
~
204
-------
Dete r.mination of Xylol
Principle of the method:
Xylol is nitrated to trinitroxylol. The trinitroxylol is the.n extracted
with butanone. Upon alklinization the trinitroxylol solution acquires a
yellowish -orange color. Othe r aromatic compounds inte rfe re with the re-
action, making the method nonspecific. The sensitivity of the method is
1 J.L in 2 ml.
Apparatuses:
(1) A water aspirator of 5-6 li capacity or a Kachora aspirator;
(2) U -shaped absorbers with porous filter plates No. 1, 10 mm in
diamete r;
50 ml volum~~ric flasks;
Erlenmeyer flasks of 50 or 100 ml capacity;
1 or 2 ml pipette sdivided into .0.01 ml;
5 or 10 ml pipettes divided into O. 1 ml;
25 or 50 ml buerettes equipped with a glass stopper;
50 or 70 ml separatory funnels;
Colorometric tubes marked at 2 or 3 ml, with ground to fit
s toppe rs ;
(10) 1000 thermometer.
Reagents:
1.
4.
(3)
(4)
(5)
(6)
(7)
(8)
(9)
2.
Xylol, C6H4 (CH3)2' taken from the plant in which the tests
are to be made, due to the fact that different xylol isomers
yielded different reaction colors.
Standard xylol solution. Prepare stock solution as follows:
. Place 20 ml of acetic .acid into a 50 ml volumetric flask and
weigh; add 2-3 drops of the xylol and weigh again; the differ-
ence between the two weights represents the weight of the
added xylol; add acetic acid to the mark and mix thoroughly.
Dete rmine the amount of xylol per 1 ml of the stock solu-
tion. Place 10 ml of the nitrate solution into a 50 ml
volumetric flask; add to it a volume of the stock xylol
solution which would represent 5 mg of xylol. Mix and
submerge into boiling water for 30 min. or until the xylol
becomes nitrated. Remove the flask, cool and fill with
distilled water up to the mark. 1 ml of this standard solu-
tion should be equivalent to o. 1 mg or 100 fL of the xylol.
3.
Prepare the nitration mixture as follows: .
Place 100 ml of sulfuric acid of 1. 82-1. 84 sp. gr. and add to
it 10 g of ammonium nitrate.
25% solution of ammonia.
205
-------
5.
40% solution of sodium hydroxide, or 20% of potassium
hydroxide.
Butanon~, or methylethylketone, (CH3CO C#I s) freshly
distill~d. colorless and having q. boiling point of 74-800.
Used Dutanone can also be employed after proper purifica-
tion. The final colorless butanone solution should remain
colorles s upon alkalinization.
6.
7.
Lacmus or litmus paper.
Collection of Air Samples:
For the determination of maximal single xylol concentration in the air
aspirate the air through a U -shaped absorber containing 1 ml of the nitration
mixture at the rate of 0.5 Ii/min. for 20 min.
For the dete rmination of average 24 -hour concentration aspirate the
air through the absorber containing 2 ml of the nitration mixture, 12 times
for 20 min. at equally distributed time periods in the course of 24 hours and
at the rate of 0.5 Ii/min. .
Analytical Procedure:
Place the entire sample into an Erlemeyer flask, wash the U -shaped
absorber with 6 ml of water and add to the same flask; cool the solution and
carefully neutralize with 25% ammonia. As a preliminary step titrate 1 ml
of the nitration mixture 2-3 times in the presence of lacmus paper in order
to determine how much of the ammonia solution must be added for the neu-
tralization without running into an excess. Excess of ammonia might result
in a premature appearance of the color in the determination solution. For
this reason add the ammonia in a volume of 0.5 mlless than required for the
titration or 1 ml of the nitration mixture.
Simultaneously prepare the standard solution of butanone as follows:
Place 6 ml of water into a small Erlemeyer flask and carefully add 1 mlof
the standard solution of the nitration mixture containing O. 1 mg of the xylol.
Cool the solution and neutralize with ammonia as previously described. This
step is necessary to prevent the premature appearance of the reaction color.
Cool the faintly acid solution and pour into a separatory funnel to which
add 10 ml of the butanone and vigorously agitate for 5 -1 0 min. until the ni-
trated xylol has 'been extracted. Allow the solution to separate completely
- - . . TABLE 2 and carefully decant the
STANDARD COLOR SCALE FOR THE Q[!ANTlTATIVE DETERMINATION OF XYLOL lower layer into another
I I I ] I I I glass flask through the
TEST TU/JE No. 0 I 2 .3 4. 6 6 separatory funnel stem;
pour the uppe r butanone
layer through the funnel
1.0 1,5 2,0 opening into a tube marked
1,0 0.5 0 at 10 ml; add butanone to
the 10 ml mark. One rol of
the solution in the tube will
R STANDARD IUTANE
SOLUTION IN ML
ML OF . UT AIlE
MKG OF XYLOL
. EQUIVALENT
o
2
o
0.1
1,9
0.4 0.7
:.6 I ~,3
I
10
15
20
206
-------
contain O. 1 mg or 10 ~ of xylol; prepare the color standard so"1utions as shown
in Table 2 (see page 69).
Place the ne\utralized sample into a separatory funnel, add 2. 5 ml of
butanone, shake w~l1 for 3 -5 min. and leave rest until the two layers clearly
separate; pour the 'lower layer into a glass flask through the separatory funnel
stem and the upper layer through the opening of the funnel into a tube. Add
to each of the color scale tubes 0.5 ml of 400/0 solution of NaOH. Shake the
tubes well and compare the yellow-rose color with the colors of the standard
set after 5 min.
Calculation of results:
1. 10 li of the air were aspirated at 200 and 741 mercury column.
Adjustment to standard temperature and pressure reduced
the volume to 9 li. For the final determination the entire
sample containing 2!J. was taken:' Accordingly, the xylol
in -the air was as follows:
3
2 x 1000/9 = 222 ~ = 0.22 mg/m
Determinati~n 'of n~butylvinylester .
Principle of the method:
This method was developed by N.N. Kuz'micheva. It is based on the
fact that n-butylvinylester hydralyzed in acid' medium; one of the hydrolyzed
products namely, n-butyl alcohol is then subjected to condensation with p':-"
dimethylaminobenzaldehyde which develops orange color. Higher alcohols
interfer with the re~ction. Acetylene does not interfere with the reaction.
The sensitivity of the method is 5 ~ in 2. 7 ml. ---'- ,
Apparatuses:
(1) An air blower equipped with a flow meter registering 0.5 -
1.0 Ii/min., or an aspirator; .
(2) U -shaped absorbers equipped with porous plates No. 1;
(3) Colorometric tubes. flat bottom, marked at 2 -3 ml with
ground-to-fit stoppers;
(4) 10, 5. 2 and 1 m1 pipettes;
(5} Waterbath;
(6) Tube support;
(7) 500, 100, 50, 25 ml volumetriC flasks;
Reagents:
1. Sulfuric acid of 1. 94 sp. gr.
2.
Absorber solution made up of strong sulfuric acid and
water in 1:1 ratio.
207
-------
1- -
3.
Standard solution of n-butylvinylest~ris prepa,red as follows:
Place 10 ml of sulfuric ,acid into a 25 ml volumet~ic fl~sk and
weigh; add 1-,2. drops of the ,ester and weigh ,a,gi?-in; add the
1: 1 .sulfuric acid solution to the mark and compute the amount
of n-butylvinyl ester per 1 mlof the so~ut~on. This is the
stock solution from which prepare a standard solution,! p-ll
of which. contained 100'/.1. of the' n-buty~v~nyi e~ter; ke~p the.
two solutions in the refrigerator or prepa're a fr~sh solution
each time the test is performed.
1 % solution of p-dimethylaminobenzaldehyde in 1: 1 ratio with
H2S04' .,
4.
Collection of Air Samples: ..
For the determination of maximal single concentration of'the este r in
the air aspirate the air for 20 min. through two U -shaped absorbers equipped
with porous glass filters No.2; each of the absorbers should contain 3 ml. of
the 1:1 H2S04 solution in water. .
For the determination of the average 24-hour concentration aspirate the
air through 2 U -shaped aspirators 12 times in 24 hours at equally spaced in-
tervals (duration of aspiration is not specified, but is usually 20 min.)
. STANDARD
$OLUTION
IN ML 0 0,05 0,1 0,2 0,4 0,6 0.8 I,
AD80R-ER -
SOLUTION 0.2 0
IN ML 1 0.95 0.9 0,8 0,6 0,4
MKG OF THE
ESTER 0 Ii 10 20 40 60 80 100
Analytical Procedure: ...
Take 1 ml of the aspirated solution from each of the aspirators for final
determination. Simultaneously prepare the color scale as shown in Table 3.
. . 'TABLE 3' Add to all tubes of the color
scale 1. 5 ml of the sulfuric
acid and 0.2 ml of the p"-
di me thylaminobenzaldehyde.
Mix the tubes and place them
into lightly boiling water for
30 min. An orange color
will develop which is com-
pared with the colors of the
scale.
o
STANDARD COLOR SCALE FOR THE DETERMINATION OF N-BUTYLVINYL ESTER
: TEST TUDE No.1 0 I. I 2 I 3 I . ~
Calculation of results:
20 Ii of the air was aspirated at 200 and 750 mm mercury. . Adjustment
to standard conditions reduced the 20 Ii to 18.4 Ii. One -third of the samplej
was taken for the determination, the result of which amounted to 10 l.t. "
Accordingly, the entire sample contained 30 Il of the ester; therefore,
the concentration of the ester in the air was. as follows.:
, - 3
30 x 1000/18.4 = 1630 Il = 1.63 mg/m
208
-------
Determination of Dimethylterephthlate
Principle of the me~:
This method was also developed by M. N. Kuz'micheva. The dimethyl-
terephthlate is hydrolyzed resulting in the development of methyl alcohol. The
latter is oxided to formaldehyde which is determined with the aid of chromo-
tropic acid. The presence of formaldehyde and methyl alcohol interfered
with this reaction. The sensitivity of the test is 1'6 /.L in 6,6 ml.
Apparatuses:
(l) Air blower with flowmeter to measure flow of 10 li/min.;
(2) Metallic adapter recommended for the collection of solid
substances in the air;
(3) Colormetric flat bottom tubes with ground-to-fit stoppers
marked at 5 and 10 ml;
1, 2, 5 and 10 ml pipettes;
25, 50, 100 and 1000 ml volumetric flasks;
25, 50 flat bottom Erlemeyer flasks;
Waterbath;
(4)
(5)
(6)
(7)
Reagents:
1. Sodium hydroxide, 2.5% solution.
2.
Standard solution of dimethylterephthlat.e ester containing
O. I mg/ml. which is prepared as follows:
Place 0.01 g of the ester into a 25-50 ml Erlemeyer flask
and add 10 ml of 2.5% solution of KOH; boil over a water-
bath for 30 min., pour the solution into a 100 ml volumetric
flask, wash with 2.5% solution of KOH and add the KOH
solution to the mark. 1 ml of the final- solution should con-
tain O. I mg or 100 u of the ester.
50% by volume of sulfuric acid.
3.
4.
2% solution of potassium permanganate.
5.; Sulfuric acid, 15 M (loo ml of water and 900 m1 of Hz S04
of 1. 84 sp. gr.)
6.
7.
3% solution of fre.shly prepared sodium sulfite.
acid in 4 ml of distilled
flask and fill to mark with
Dissolve O. 1 g of chromotropic
wate r in a 100 ml volumetric
15 M HzS04.
Ash-free filter paper, boil in 10% KOH solution for 30
then wash with hot distilled water till the wash water
becomes neutral, and air dry.
min.
8.
209
-------
Collection of Air Sample s:
Collect air samples through ash-free filter ,paper placed into
adapters aspirating the air for 20 min. at the rate of 8-10 li/min.
Analytical Procedure: .
After the air sample collection has been completed place the filte'r paper
into a colorometric tube to which add 5 ml of 2.5% KOHsolution and submerge
into boiling water for 30 ~in., cool and add KOHsolution to the 5 ml mark,
and take 1/2 of the 'sample volume for analys.is.' Similar colormetric tubes
are used for the preparation of the standard color scale as shown in Table 4.
Add to all of the tubes 6f the
TABLE 4 . color scale 2 inl 6f the 50%
H2S04 so'lution; mix and add
O. 1 ml of the 2% potassium
permangante to each tube.
Five minutes later add 1 drop
of chromotroI?ic acid." An
excess of'sodium sulfite
should be scruplously avoid-
0,05 0.1 0,2 0,4 0.6 0,8 1,0 ed. Mix the tubes and sub-
me rge into boiling wate r for
2.5 2.45 2.4 2.3 2.1 1,9 1.7 1.5 30 min. A rose-violet color
will form which is compared
with a color intensity of the
standard scale.
STANDARD COLOR SCALE FOR THE QUANTITATIVE DETERMINATION OF
DIMETHYLTEREPHTHALATE (DMTPH) ,
TEST TUBE No.1, I 2 I "3 I 4 '\ 5 " 6 I 7 I 8
I
. STANDARD
TMT P SOLN.
CONTAINING I
100 HKG/I1L
2.~ NAOH
SOLUTI ON
IN "L
MKG OF
DMTP
o
20
60
80
100
40
10
o
5
metallic
Calculations of results:. .
200 Ii of air was aspirated at 210 and 768 mm of mercury. Adjustment
to standard temperature and pressure condition$ reduced it to 184 Ii. Color-
metric comparison showed that the c_olor intensity of the sample corresponded
to 10 t.L; since only 1/2 of the sample was taken for analysis, the final re-
sult would be 10 x 2 = 20 mkg and accordingly'the concentration of dimethltere-
phth1ate in the air was: 3
20 x 1000/184 = 108.7 t.L = O. 109mg/m
Determination o'f Phenol with 4-Aminoantlpyrine
Principle of the method:
This method wa~ developed by V. A. Khrustaleva. Phenol reacts with
, 4-aminoantipyrine in the presence of potassium ferricyanide K3Fe(CN)6 in
medium of pH 9.3 producing a rose color. Benzene, isopropylbenzene,
peroxide of isopropylbenzene, acetone, dimethylphenylcarbinol, d-metllyl-
styrol, dimethylphenyl I-cresol did not interfere with the determination.
Acetophenon in excess of 20 t.L interfered with the reaction. Cresols inter-
fered with the determination. The sensitivity of the method is {). 2 t.L in 2 ml.
210
-------
Apparatuses:
(1) Kachora aspirator;
(2) U -shaped absorbers equipped with porous glass plate No.1;
(3) A modified Zaithev absorber; -
(4) Catcher-absorber of the Petrie type with a shortened inner
tube, inserted between the Kachora aspirator and a silicagel
absorber;
Colorimetric tubes marked at 2 or 3 ml;
1 or 2 ml pipettes divided into 0.01 ml;
5 or 10 ml pipettes divided into O. 1 ml;
25 or 100 ml volumetric flasks;
2000 the rmomete r.
(5)
(6)
(7)
(8)
(9)
Reagents:
1. .Absorber solution consisting of 0.5 M. solution of sodium
tetraborate (borax) (Na2B404. 10 H20.) Place 19.1 gof
this salt into a 1 Ii-volumetric flask and add water to the
mark.
2.
Standard solution of phenol (C6H 50H) of 1810 melting point.
Prepare the phenol stock solution by.using colorless freshly
distilled phenol; place 15-20 ml of the absorber solution
into a 50 ml volumetric flask and weigh. Place into the
flask several crystals of the phenol and weigh again; the
difference in the two weights represents the weight of the
phenol; now, add absorber solution to the mark. and mix
well; compute the amount of phenol per 1 ml of the final
solution; use this as the stock solution from which the
. standard phenol solution is prepared so as to contain 10 IJ.
pe r 1 ml. Prepare a fresh solution for each new
determination using the same stock solution; -
Silicagel ASM, granules 0.25-0.50 mm in diameter. Wash
the silicagel with hydrochloric acid diluted with 3 times its
volume of water, then wash with pure tap water Jollowed by
a second washing with distilled water until the chlorine ion
is completely removed, as shown by tests with silver
nitrate. Dry the silicagel and activate in a muffle furnace
at 3000 for 30 min. Store in ground to fit glass bottles.
3.
Collection of Air Sampies:
Aspirate the air through a solution of sodium tetraborate or through
activated silicagel. In the former case place 6 ml of the sodium tetraborate
(borax) into a U -shaped absorber equipped with a porous glass plate No. I;
aspirate the air at the rate of 2 Ii/min. for 20 min. When u'sing the dry sili-
cagel place 2 g of it into 2 modified Zaitsev absorbers and connect in succession
with a catcher for the purpose of trapping loose silicagel gra.nules. Aspirate
211
-------
the air for 10 mm. at the rate of 5-10 li/min. through the silicagel column.
: \
Analytical Procedure:
Determine th~ phenol in the air sample aspirated through the sodium
tetraborate solution as follows: place 5 ml into acolorometric 'tube;" simultan-
eously prepare the standard color scale as shown in Table 5; place 0.1 mlof
TABLE 5 the 4-aminoantipyrine solu-
'tion and O. 1 ml of the potas s ...
" STANDARD COLOR SCALE FOR THE QUAtITlTATIVE DETERMINATION OF PHErlOL ium ferricyanide into each of
I I I I I \ I \' \" the standard color tubes;
TEST TUIE No. 0 I 2 3 . 5 6 1 8 shake for 5-10 min. u:Qtil a
rose color developes; com- .
pare with the color intensity
in the standard series. De-
te rmine the phenol in the
silicagel as follows: transfe r
the silicagel into tubes with
ground-to-fit stoppers; add
" 2 ml of ethyl alcohol and
leave stand for 30 min. ; add to the tubes 2 ml of the sodium tetraborate solu-
tion; shake the tubes vigorously, and .allow the silicagel to settle down. At
the same time prepare the
color standard scale in 2 ml
volumes, as shown in Table
6; add to each tube of the
standard scale and of the
test O. 1 ml. of the 4-amino-
antipyrine solution; mix well
and add O. 1 ml of O. 1 % of
the potassium fe rricyanide
solution; shake well and make
colorometric determinations.
I -
,ML OF
ETA/I04RD
PHENOL 0,05 0,1 0,2 0,4 ~0,6 0,8 1.0 1,5
BOLUTI ON 0
ML OF
U50RDER 5 4,95 4,9 4.8 4,6 :4,4 4.2 4,0 3,5
SOLUTION
Mltll OF
PHENOL 0 0,5 1 2 4 6 8 '.10 15
TAB LE 6
STANDARD SCALE SOLUTION FOR THE QUANTITATIVE DETERMINATION OF
PHENOL
TEST TUDE No.1 0 II \2 I 3 I 4 I 5 I 6- 11 I 8
ML OF "
ST ANDARI :f
PHENOL .
SOLUTION 0 0,02 0,05 0,1 0.2 0,4 0,6 0,8 1
ML OF
USORDER
SOLUTION 2 1,98 1,95 1,9 1,8 1,6 1,4 1,2 1
MICe-oF
PHENOL 0 0,2 0.2 1 2 4 6 8 10
Calculation of results:
40 li of the air was aspirated at 220 and 750 mm mercury.' Adjustment
to standard temperature a~d pressure reduced the volume to 36.8 lie The
volume of air samples amounted to 6 ml, and only 5 ml was taken for the,
analysis which contained 0.5 J.L of phenol. Accordingly, ,the samples con-
tained 0.5 x 6/5 = 0.6 J.L . -. The refore, the concentration of phenol in the
air was: 3
0.6 x: 1000/36.8 = 16 LL:: 0,.016 mg/m
.- '. I
212
-------
Determination of some Air Pollutants by th~ Spectrophotometric
Method in the Ultraviolet Region of the Spectrum
M. D. Manita
Department of Community Hygiene of the Central Institute of
Post-Graduate Medicine
Absorption of ultraviolet rays by organic substa:nces offers the possi-
bility for the development of highly sensitive, exact and rapid quantitative
methods for the determination of atmospheric air pollutants. The principle
of the spectrophotometric method of analysis is based on the determination
of degree of light absorption in a narrow band of the spectrum correspond-
ing to the maximum absorption by the investigated solution.
The quantitative method of spectrophotometric analysis is used on the
Lambert-Bear law which is based on the postulate that similar layers of a
substance, other conditions being equal, absorbed the same section of the
light-band falling upon the substance. This law does not take concentration
into consideration. The effect of concentration is covered by another law
formulated by Bear, which postulates that light absorption is proportional
to the number of molecules of the light-absorbing substance through which.
the light band had passed; in other words, the degree of light absorption was
proportional tothe molar concentration. This relationship between degree -
of light absorption, the thickness of the solution layer and the molar concen-
tration is expressed by the Lambert-Bear law whieh is used in most instances
where quantitative determinations made spectrophotometrically.
The principle. expressed by the law of Lambert applies to practically
all cases of quantitative spectrophotometric analysis, but the law of Bear has
many exceptions. Thus, many acid, basic and salt solutions did not behave
in accordance with the law of Bear as the result of their high ionization -in
solution, since light absorption by ionized substances differed from light
absorption by non-ionized molecules. In addition, it is known that fluoresence
of a solution, the nature of the solvent and some other conditions may effect
significant deviations from the law of Bear. Therefore, - in making absorption
analysis it is necessary first to verify the applicability of Bear's law to any
particular case under consideration.
The following terminology is used at present in most cases of spectro-
photometric analysis:
(a)
(b}
optical density (extinction), which is usually denoted by E. ;
molar extinction coefficient (MEC) usually denoted by (epsilon),
and which is equal to the optical- density of the mo1ar- solution
of the substance under study in a given solvent layer of 10 mm
thickness;
213 -
-------
(c)
wave -length at which light absorption is at its peak and
.. which is known as m~ximum absorption, symbolized by
.' the Greek letter A max.
Spectrophotometer SF -4 has been used widely in the Soviet Union in the
study of light absorption or optical density of liquid and solid substances in
the visual and partly in the infrared section. of the ultraviolet spectrum.
The principle of the SF-4 spectrophotomete"roperatlon
In using spectrophotomete r SF -4: the optical density of the tested sample
is compared with that of the standar-d, the light pas sing capacity of which is
taken as 100% and the optical density as zero. The standard and the samp'le'
under study are consecutively interposed in the line of a.ligJ:1t b~am of known
wave length. The ratio between the light stream intensity which h~d passed
through the sample under study and the intensity of the light which had passed
through the standard is found on an optical density record~ng potentiometer scale.
The application of the spectrophotometric method to the determination of a:tmo-
spheric air pollutants in the ultraviolet section of the light spectrum falls into
two categories.
Category one:
This category is limited to the analysis of atmospheric air containing a
single pollutant. In such cases the light absorption by the investigated sub-
stance in a suitable solvent is determined after the optical density of the sol-
vent had been established, and the concentration of the investigated substance
is calculated in terms of mg per unit volume of the air. In making the final
calculation the molar extinction coefficient (MEC) of the chemically pure sub-
stance is taken into consideration; the MEC -of any chemically pure substance
dissolved in a given solvent has a charaCteristically constant: value, and the
sensitivity of the spectrophotometric determ.j.nation varies in direct propor-
tion to the magnitude of the MEC. MEC values had been established for many
substances, and published in pertinent journal~. 1£ the MEC value of a sub-
stance under study is known, the investigator merely has to define the 'con-
ditions of the spectrophotometric analysis, and the conditions of the air sample
collection. If the law of Bear embraces the studied s'ubstance dissolved in the
known solvent then the concentration of the substance (A) can be determined
with the aid of the following general formula:
. . 3
A = E x a / P x Yo (mg/m )
in which E - represents the optical density of the solution under study as
recorded on the apparatus;
a - represents the volume in m1 of the investigated solution;
P - represents a constant obtained by dividing the MEC by the
millimole of the investigated substance, i. e. the optical
density of the substance concentration in /.L pe r 1. ml;
y - represents the volume in li of the aspirated air adjusted to
o standard temp. and atmospheric pressure.
214
-------
Where data on MEC are not available the spectral characteristic of the
studied chemical substance should be determined in a series of different sol-
vents, a procedure which may present difficulties in some instances in con-
nection with the chemical purification of the substance. For the final dete r-
mination, select that solvent which yielded the highest" optical density, and
construct a graduated. standard curve based on plots of concentrations of the
substance in the selected solvent and of the corresponding optical densities.
Concentrations of the substance in the selected solvent are determined with
the aid of the constructed standard curve and the concentration of the sub-
stance (B) in the air, computed with the aid of the following formula;
B = C x a / Vo (mg/m 3)
in which C - repre sents the substance concentration in U. pe r 1 ml, as
shown on the graduated standard curve; .
a - represents the volume in ml of the investigated solution;
Vo- represents the volume in li of the aspirated air, adjusted
to standard temp. and atmospheric pressure.
Category two:
This category includes more complex cases in which two air pollutants
existing simultaneously are to be determined. Spectrophotometric deter-
minations of air pollutants in such cases are based on the fact that complete
extinction of a given mixture is equal to the sum of extinctions of the in-
dividual components. The method of Firordt (Phyrordt) has been used widely
in instances where two chemical components were present simultaneously,
and the individual extinctions of which had been previously established.
Standard curves are constructed of the absorption of both chemical compounds
at two wavelengths, selected so that the absorption intensities of the two sub-
stances presented a maximum variation at one wave length and a close approx-
imation of high absorption intensities at the other wave length. A system of
equations is then derived having two unknowns (X and Y); by substituting six
known E-magnitudes into the two equations, for"mulas can be developed for
the determinations of the X and Y concentrations in 1J. per ml (C); with the
aid of these formulas the concentrations of these pollutant components in the
air can be determined in ml per 1 m3.
Spectrophotometric determi.nation of Naphthalene in Indoor Air
Principle of the method:
The method is based on the" determination of the optical density of a"
naphthalene solution in ethylol at'" max. 220 uin a tube containing a 10 mm
column of the naphthalene solution, using spe"ctrophotometer SF-4. Sensi:-
tivity of the method is O. I /.L/ml"; benzene and its homologues do not inter-
fere with the determination.
215
-------
Reagent:
Ethanol
96%.
Collection of air sample:
Aspirate 0.1 - 1. 0 li of the air at the 'rate of O. 2li/min~ through an
absorber equipped with a porous glass plate of 100 .:. 300 mm wate:r column.
resistance and containing 10 ml of eth~T1ol; the volume'o'f air to be aspirated'
will depend upon the anticipated naphthalene concentration.in the air.. Keep
the original ethanol volume constant by replacing loss by evaporation. '
Analytical procedure:
At the completion of the air collection pour the ethanol fr
-------
Collection of samples:
a) Aspirat~ tpe air at the rate of 0.5-1. 0 li/min through 2 consecutive]
connected absorb~I;s equipped with a porou~ glass filter. each absorbers COn-
taining 5 mf of eth~pol. Aspirate between 10 and 20 li. depending upon the
anticipated acetophenone concentration in th.e air.b} The air can also be
aspirated at the rate of 4 Ii/min. if two consecutively .connected Zaitsev
absorbers are .used containing 2 g of silicagel as the vapor absorbing mater-
ial. .
Analytical procedure:
a) Pour the content of each absorber into separate tubes to a column of
10 mm and establish the optical density (E) atA max. 244 ml.t. using electro-
spectrophotometer SF-4; use eth;~l.nol as the, standard control or comparison
medium. Compute the acetophenone concentration (D) with the aid of the
following formula:
D - (El x 5) / (0. 132 x Yo ) +. (E2 x 5) / (0. 132 x Yo ) (mg/m3)
in which E
5
- represents the optical density of the solution from the
first absorber;
- represents the optical density of the solution from the
second absorber; .
- is the volume of absorbe r solutions in m1 in each of the
two absorbers;
- is a constant factor derived by dividing the M8C of
acetophenone at A max. 244 mM in ethylol (15 850)
by millimol of acetophenone (120 144) i. e. optical
density of acetophenone in tL /mi concentrati0l1.
Hence. 15850:120144 :. 0.132
E
0.132
b) Pour 5 ml of eth~no-l into each of the silicagel-containing absorbers
and shake at short intervals for 30 min. Pour some of the ethanol from
each silicagel absorber individually into separate tubes to 10 mm columns;
determine optical density (E) of each solution at A max. 244 m~t. using
electrospectrophotomete r SF -4; suspend fresh silicagel in et~~nol, pour
the eth?-noloff and determine its optical density for control purposes. Com-
pute final result using the formula presented under (a).. .
Note: This method was developed by M. D. Manita and N. B. Imasheva.
217 .
. h- ----
-------
----- ~-
< .,.
Spectrophotometric determination of Isopropyl Benzene in the Air
Principle of the method:
This method is based on the dete rmination of the optical density of
isopropylbenzene solution in ethylol at A max. 212 mU. of a solution layer
10 mmthick, using spectrophotometer SF-4. Sensitivity of the method is
1 jJ./ml. The method is not specific in the presence of isopropylbenzene
hydroperoxide and other substances possessing absorption properties at
212 mu wave length.
Reagents:
1. Eth~nol 96% the optical density of which did not exceed 0.3 at
1.9 mm slit;
2. Isopropylbenzene of 99.5% purity having a specific gravity of
0.8600 at 200.
Collection of sample:
Aspirate 20 Ii of the air at the rate of 0.5 li/min through 10 ml of
ethylol in an absorbe r equipped with a porous glass plate. .
Analytical procedure:
At the conclusion of air aspiration transfer the absorber solution into
a tube to a column of 10 mm and determine its optical density at A max.
212 mu, using electrospectrophotometer SF-4. Use ethanolas the control
standard solvent. _Determine the isopropylbenzene concentration (C) in the
. solution in Il, using a special standard curve constructed with the aid of
a standard scale--of solutions containing 0, 5, 10, 20, 30, 50, and 50 L.L .
in 10 rnl of ethanol the optical densities of which we re determined at A max.
212 mu as previously desc ribed; plot the isopropylbenzene concentrations
along the abscissa and the optical densities along the ordinate..
Calculation of results:
.. / 3 .
Compute the isopropylbenzene concentration in the aIr In mg musIng
the following formula: .
Isopropylbenzene or IPB 11- :: . (G x 10) / Yo
in which C' - represents the concentration of IPB in u Iml as found
on the constructed standard curve;
10 - is the solution volume in the absorber;
Yo - represents the volume of aspirated air in li, adjusted to
standard temp. and atmospheric pre.ssure.
Note: By this method of 0.2 - 1. 0 mg/m3 of IPB were determined in the
air of experimental exposure chambers. .
218
-------
Spectrophotometric determination of Styrol in the Presence of Dinyl
in the Air.
Principle of the method:
The method is based on the determination of the optical density of an
alcoholic solution of a mixture of styrol and dinyl wave lengths A max. 211. 5
and 246 m!J' in a 10mm solution layer, using spectrophotom,eter SF-4.
Sensitivity of the method is 0.25 mkg of styrol per ml. The method is not
specific, since other substances with absorption properties at A max. 211. 5
and 246 m~ wave lengths interferred with the determination.
Reagent:
Ethylol 96% having an optical density not exceeding 0.3 with a 1. 9 mm
slit.
Collection of the sample:
Aspirate .the air at the rate of 2.0 - 2.5 li/min. through two consecu-
tively connected absorbers equipped with porous glass plates, each of the
absorbers containing 5 ml of ethylol. Keep the ethylol volume constant by
replacing any of it which evaporated during the air aspiration and keep the
temperature of the absorber solutions below 23°.
Analytical procedure:
'..
Pour the content of each absorber into separate 'quartz tubes to column
height of 10 mm and determine the optical density (E 1) at A max. 211.5 mU. .
and E'2 at A max. 246 mIL; use ethylol as the standa-rd Gontrol background'
solution. Determine the styrol concentration (A) 'in u/ml in each' abs'orber
individually with the aid of the following formula: (1)
A. (0.122 E2-0.05 El) /0.011 (u/ml)
(1)
Styrol air concentration Al in J.L, can be arrived at with the aid of
the following formula:
Al = (Cl x a) / Yo + (C2 x a) / Yo (mg/m3)
, ,
in which C - represents the styrol concentration in ,.,. /ml in the firs t
absorber determined by using formula (1);
C2 - represents the styrol concentration in the. second absorbe r
determined by using the same formula (1);
a - represents the volume in ml of the solution-tested;
Yo - represents the volume in li of the aspirated air, adjusted
to standard temp. and atmospheric pressure.
219
-------
(1)
The calculation formula was deyeloped on th~ba,sis of experimental dat"a
obtained with spectrophotom..::ter SF-4 following the me'thod ~f Fi~ora:t
(Phyrord). using a \99% pure styrol of 0.906 sp. gr. at 200 and double distill-
ed dinyl. . .
BIBLIOGRAPHY
r II .~ .1 e M A. II ill T e p H E. 3.1eKTpOHllblC cnCKTpbl nor.1ow.e-
HIIH opraHII4eCKliX Coe.D.HHeHIlH. H3.D.. HHOCTpaHHOH .~IITepaypbl.' M..
1957. . .
TaT a e D C K II A B. /1\. CncKTpocKonllH. l-b.D.. MfY. /1\.. 1951.
\l Y.II a 11 0 n C K II A B. M. Bne)le1lHC B' MO.lleKYJlHpHblA CnE'KT-
paJlbHblli aHa.1113. fOCXIIMII3;J.8T. M.-J1.. 1951.
-..--- ._----"
220
-------
APPENDIX
At the recent WHO Symposium '')n Air Quality Criteria, Pr.' R. A.
Ryazanov made available a tabulation of the latest USSR issuariee of allow-'
able concentrations of atmospheric polutants as used in the c'ountry.
This
latest tabulation is he re reproduced for the readers I ii:uorm~tion.
Professor
Ryazanov explained also at the Geneva meeting that the values'w;hich are
-listed as "Maximal Single Concentrations" refer to a sampling period of
20 minutes.
LIM[TS OF ALLOWABLE CONCENTRATIONS OF
ATMOSPHERIC POLLUTANTS.
Air Pollutants
Maximal allowable 3
concentrations (mg/m )
Single 24 -hour
concn. concn.
1.
2.
3.
4.
5.
6.
7.,
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
Ace tone
Acetophenon
Acrolein
Amylacetate
Aniline .
Arsenic and its inorganic compounds
Benzene (bensol)
Genzine (as C)
Butylacetate
Carbon disulfide
Carbon monoxide
Chlorine
Chloroprene
Chromate (as C r0:3 )
Dimethylfomamide-
Dichlorethane
Dinyl (Diphehy1 Diphehyloxide)
Dus t (nontoxic)
Ethy1acetate
Fluorine and its compounds (as F)
0.35.
0.003 .
0.3
O. 1
0.05
0.35
0.003
O. 1
O. 1
0.03
0.003
0.8
1.5
0.1
0.01
1.0
0.03
0.08
(as As)
2.4
5.0
O. L_~~~.
0.03
6.0
O. 1
0.25
0.0015
0.03'"
3.0
0.01
0.5-
O. 1.
0.03
0.03
1.0
0.01
0.15
O. 1
0.01
221
-------
Air Pollutants
Maximal allowable 3
concentrations (mg/m )
Single 24 -hour
concn. concn.
21. Formaldehyde 0.035 0.012
22. Furfurol 0.05 0.05
23. Hydrogen chloride 0.05 0.015
24. Hydrogen sulfide 0.008 0.008
25. Lead and its compounds (as Pb) 0.0007
26. Lead sulfide (as Pb) 0.0017
27. Manganese and its compounds (as Mn) 0.03 0.01
28. M'~rcury 0.0003
29. Methanol 1.5 0.5
30. Methylacetate 0.07 0.07
31. Methylmetacrylate O. 1 O. 1
32. Nitrogen Oxides 0.30 0.10
33. Phenol 0.01 0.01 f
34. Phosphorus anhydride 0.15 0.05
35. Soot 0.15 0.05
36. Styrol 0.'003 0.003
37. Sulfuric acid 0.3 O. 1
38. Sulfur dioxide 0.5 0.15
39. To1ui1endiisocyanate 0.05 0.02
40. Viny1acetate 0.2 0.2
I . .
.'
222
uscm']":-DC-52,060-40
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