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    ••v       • ^ • . .
 fnhaled aef.osols of the rare metals which affected mostly the upper respira-
 tory" -tracts^  the bronchial system, etc.  Physiological observations made
»dice'ctly. in the plant under actual working conditions indicated that many
^ *  '  i5f ; ."Y'v, - ^-  «&•'  -/-•
 workers in such industries as are mentioned above developed some function-
 al 3?e'spii;rSt?ory disturbance manifested as respiratory insufficiency.  Thus,
 44 Of'57 examined worker patients had pulmonary hyperventilation, 52 show-
 ed a lowered maximal pulmonary ventilation (15 - 20%), and in  23 of the ex-
 amined Workers the vital lung capacity was  reduced by more than 15%.
( O'. .Ya Mogilevskaya showed in 1956 that  some employees with work records
"of ;triahy;iyears developed pneumoconiosis as the result of inhaling highly
 dispersed nAotybdenum aerosol particles and its oxides.  Surveys made at
 the I.' M.^Seche no v Institute and other research institutes showed that many
 employees of the metallurgical industries showed  signs of, what appeared as,
 process of pneumoconiosis.   This could  only be verified by further  and more
 detailed clinical examination.

        Investigations conducted by the present author indicated that there
 existed many industrial and  manufacturing processes which generated rare
 metal aerosol.condensates,  the inhalation of which produced in the workers,
 especially under certain conditions,  functional disturbances of  the respira-
 tory organs.  However, the  above recorded observations failed to firmly es-
 tablish whether condensation aerolsols of tungsten, molybdenum and rhenium
 affected the organism in a manner different from  aerosol  particles  of the
 same  metals generated as a result of friction or grinding.    Rational sani-
 tary hygienic standardization of air  polluted with aerosols of the three rare
 metals required additional detailed information on the degree of the aerosols
 dispersion and their physiological effect on the organism.  N. V. Mezemtseva
 in 1957 and O. Ya. Mogilevskaya in 1950 and 1952  arrived  at reliable data on
 tungsten and molybdenum aerosol effects on the organism, on the basis of
 which the office  of the U.S.S.R. Chief Sanitary Inspector'adopted maximal
 allowable tungsten and  molybdenum aerosol concentrations in the air.  This
 served as a sound basis for  the present authors investigations along similar
 lines.

        No information  relative to the toxicity of rhenium aerosol in the air
 has been found in the literature; therefore, this phase of the investigation
 had to be'initiated individually.  Investigations have been conducted on the
 basis  of atximal experimentation.   The object of the investigation was to ob-
 tain data regarding the  comparative pathogenicity of the different aerosol
 types  iriider conditions  which would insure complete comparability of experi-
 mental results with previously obtained results and with the results found in
. the  literature.  To attain this, investigations have been conducted with white
 male  rats weighing 180-250 g using the blood-free method of intratracheal
 administration'of the metallic particles suspended in saline.  The usual dose
 of 50  mg was used at first,  but this proved too toxic with the molybdenum
 trioxide condensation aerosol, which killed most of the test animals during
'the  first f£w hours of the experiment.  Microscopic examination of the lungs
 6f/:the de&d animals showed wide spread hemolysis, hyperemia, extensive
       * '•'•'  1 '                      - 81 -

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 localized atelectasis.  Following this, molybdenum irio^ide Aerosol was ad-
 ministered to new rats twice; at tfje rate of J6 mg 10 days a,part. Here, as
 in the case of the condensed aerosol,  a.n4 as in the case of highly dispersed
 rhenium, morphologic changes developed in the internal organ? of the ex-
 perimental rats.   The ,aclH}intstra$ioi> oi rare  metals,  as above described,
 developed bronchitis and chronic interstitial pneumonia accompanied by dif-
 fuse sclerosis of the pulmonary tissues in all experimental animals.   Histo-
 logic examinations indicated that pcleros>is was well defined in all cases.
 A well defined protein dystrophy w?.s  observed  in all the parenchymatous  or-
 gans.  In the case of rats administered rhenium aerosol, there also appeared
 a hepatic and renal fatty distrophy.

       Administration pf tungsten condensation aerosol elicited more clear-
 ly expressed changes thaja in the two previous   experiments with molybdenum
 and rhenium aerosols.  This  was particularly true of the reticuloendothelial
 system and of the connective  tissue elements.   Results  of general tissue and
 organ examinations  2, 4 and 6 months after the metallic aerosols adminis-
 tration showed that the condensation aerosols had a considerably higher toxic
 potency than the,metallic disintegration aerosols. The  morphologic changes
 produced by the two types of rare metal aerosols were of similar character.
 Results clearly indicated that tungsten and molybdenum condensation aero-
 sols possessed fibrogenic properties, especially in relation to lung tissue,
 and had toxic effects on the parenchymatoua organs of the experimental ani-
 mals. Tests were,  then, conducted to determine whether aerosols of these
 rare metals had an unfavorable effect in concentrations adopted as maximal
 permissible for coarsely dispersed tungsten and  molybdenum.   Accordingly,
 parallel with morphologic investigations more refined experimental proce-
.dures  were used. The pathogenic effect of rhenium has been established  and
 previously described; therefore,  the same concentration was used in the new
 experiment.

       In the hope of simulating practical conditions, experiments were con-
 ducted on a chronic inhalation basis, as described on numerous occasions by
 other authors for similar investigations.  The rare metals condensate aero-
 sols were prepared by burning pure metallic electrodes in a voltaic arc for
 2 hours every other day for 18 weeks.  The aerosol concentration was main-
 tained at approximately 6 mg/m9, with fluctuations within the  limits of 10%
 and with  p ~ 0.05, which corresponded to the maximal  permissible tungsten
 and molybdenum condensation aerosol concentration in atmospheric air.  Ten
 animals were subjected to the inhalation of air containing tungsten aerosol.
 Two of these died after two months.  Ten  white rats were exposed to the in-
 halation of molybdenum and 10 to the inhalation of rhenium aerosols.   All 20
 animals survived.  Animals were observed between exposure  periods; noth-
 ing noteworthy was observed  in their behavior or general appearances; how-
 ever,  their body weight fell below that of the control rats.  No substantial
 changes had been noted in the blood indexes during this phase of the study,
 except for slight drop in blood hemoglobin concentration in rats which had
 been exposed to the inhalation of air containing aerosols of molybdenum and

                                   ^ 82 -

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 ";, flieniufri.

        • Papeif slectrophoretic studies of the blood serum proteins of the ex-
 '•t.p$rj. mental animals were conducted to determine what effect, if any, the in-
••' haled, rare  metal aerosols  had on the intracellular biochemical reactions,  and
.  in swfi.at .marine r have they interacted,  if at all,  with the blood serum proteins.
 .'A dyspVoteinemia was noted towards the end of the inhalation tests, expressed
  ;a$ a drop in the  total protein and a parallel rise in the a- and Y-globulins.
3'> These changes were more  clearly defined in rats exposed to the inhalation of
•."•I Air containing molybdenum aerosol, as can be seen from the data presented
  £|i Table 1.    The dysproteinemia was not associated with sulfhydryl group
  blocking; in fact, a reverse tendency appeared as a rise in  the number of
  sulfhydryl groups, which in the case of tungsten aerosol inhalation amounted
  to 41. 5%.  The rate of amino   nitrogen elimination via the urine of rats which
  inhaled molybdenum aerosol increased to twice that found in the control rats,
  indicating that the  normal course of protein metabolism was disturbed.

          Table 1.
           Average Blood Serum Protein and Protein Fractocna Content and Albuiain/Glocul in
                                    Coefficient

Index

) of total protein
% of total a 1 bun in
% of total globulin

y
Albunin/globul in coefficient
- - so3
Baford Aftoc
e«prt.
6,93
35,6
64,4
24,6
23.4
16,5
0,576
13063 1 Ro207
Boforo
oaprt foaprt.
7,84
32.4
67.6
25 9
19.6
22,0
0,488
8.28
45.1
56.9
17.9
25,1
11.9
0,864
Control
Af terlBofot-JAf tar 'Before After
oaprt laapptjoxprt , exprt. exprt
8,88
31,9
68.1
27.2
18,3
22,5
0,482
8,28
o9,6
60.4
25,3
19,4
15.7
0,684
7,68
36.2
63,8
23,7
20.9
l'J,2
0,580
7.26
38.2
61.8
24.0
19 2
19,7
0,622
7 80
37,0
43,0
22.5
23,4
17,1
0,614
          Having obtained information regarding disturbed protein metabolism
   in the. organism as the result of tungsten, molybdenum and rhenium aerosol
   inhalation, as shown by the results of previously discussed morphologic
   studies, the investigation was directed into a study of protein regeneration,
   which pertained to the total and reduced  glutathione level in the blood serum.
   Results showed that normal levels of total and  reduced blood serum alula-
   thione remained undisturbed in the experimental animals, which  -MH.K it: fav^f
   of the protein biosynthesis processes,  creating tissue protein re Hour <•.<;•,.   .',,
   addition, a drop in alkaline phospbatase   activity was noted in all fixp«.:rJmen-
   tal animals, especially in rats exposed to the inhalation of molybdenum aero-
   sol.  This is significant, since alkaline phosphatase is an enzyme associated
   with vital liver activity.  The morphological studies disclosed  a chronic in-
   terstitial pneumonia accompanied by a progressing sclerosis, which was mort
   p"renounced in rats which inhaled air containing tungsten aerosol,  and which
   was also accompanied by a tension in the reticulo-endothelial system and in
 >.      '"            •                 . 83  -

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 the connective tissue elements.  A mild protein dystrophy was noted in the
 parenchymal organs.  Generally speaking,  the intensity of rare metals'toxic
 effects accorded their solubility in fluids of different pH, as shown by the
 data presented in Table 2.

        Table 2.
        Solubility of finely di*p*r*,t(t WQ3 CoOj «fld •»• in Liquid Media of Different pH
                 (Gpncentr»ti
2.4 >
«3, | "T-
"slT
s •
5 »
0.5 »9
0,75 «
0,5 f
After 30 d»y« exposure
"«*3 1 *°3 I '"*
7.82 1.9
4,59 >
2,35 »
~ Tp,
10 »
5 >
1.25 »8
3 >
1,25 >
        Results of the investigation illuminated the true nature of the toxic
effect exerted by highly dispersed aerosol of molybdenum, tungsten and
rhenium^ which could not be brought into light by the histo-morphological
investigation of the experimental animals' tissues and  organs.  Results of
the investigation led the present author to an important practical conclusion,
namely, that high di§persion of molybdenum, tungsten, and rhenium aero-
sols considerably-enhanced their toxic properties.   The investigation also
demonstrated that inhalation of air containing highly dispersed aerosols of
molybdenum, tungsten and rhenium in maximal permissible concentrations
adopted for coarsely dispersed particles  of the same metals  may prove toxic
to the organism.

                               Conclusions

        1.  Many metallurgical industrial  processes generated tungsten,
molybdenum and rhenium condensation aerosols resulting from high  tem-
peratures to which ground granules and powders of these metals are heated.

        2.  Inhalation of air containing highly dispersed molybdenum, tung-
sten and rhenium aerosols under certain conditions disturbed the normal
functional state of the respiratory organs. Inhalation of tungsten, molyb-
num and rhenium condensation aerosols developed chronic interstitial
pneumonia accompanied by pneumosclerosis, tension of the endothelial sys-
tem and dystrophic changes in the parenchymal organs.

        3.  Condensation aerosol of molybdenum and rhenium elicited mor-
phologic changes in the body organs, disturbed the process of protein metab-
olism,'  eliciting dysproteinemia, and a rise in the rate of amino nitrogen
elimination with the urine towards the end of the  experimental period,  and
lowered the activity of alkaline phosphatase.
                        :             - 84 -

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       4.  Inhalation of air containing equivalent concentrations of mechani-
cal and condensation aerosols showed that the latter had a higher toxicity
parameter.   Therefore, the maximal permissible' tungsten,  molybdenum
and rhenium crude aersol concentrations cannot be applied  to the condensate
aerosols of the same rare  elements.

       5.  In attempting to determine the maximal permissible rhenium dust
concentration in  the air consideration must be given the fact that rhenium in
its metallic form,  or in solution,  is less toxic than tungsten or molybdenum
in the form of mechanical dust; at the same  time it was shown that in the form
of the condensate aerosol rhenium was more toxic than  aerosols of either of
the  other two rare  metals.   Therefore the maximal permissible concentration
in the air of rhenium in the form of its condensate aerosol must be set below
the  ones set for tungsten and molybdenum.   Accordingly, it is recommended
that such concentration for rhenium condensate aerosol be set at 4 mg/m3 .

                                 Bibliography
           H3pa3/ibcoH 3. H. PHP. H can., 1953, M. 12, CTp. 36.—O H see. TaM JKC, 1954.
       jY» 4, c?p. 50.—MeaeH ueaa  H. B. TaM  we,  1957,  Nfe 4,  cip.  25.—M o r H ji e B-
       cKaa O. fl. TaM we, 1950,- M> 12, crp. 18.—Ona we. Tan  we, 1952, ffe 3, crp. 23.—
       F a i rh a 11 L. T. et al.. Pub. Hlth. Rep. (Wash.), 1949, v. 64, p. 485.
        Toxic Properties of Manganese Cyclopentadienyltricarbonyl
                           Antiknock Substance
                                 pp. 29 - 32

          O. G. Arkhipova, M0 S. Tolgskaya,  and T. A. Kochetkova
       (From the Institute of Labor  Hygiene and Occupational Diseases
              of the U.S.S.R.  Academy of Medical Sciences)
       Manganese Cyclopentadienyltricarbonyl has the chemical formula of
C5H5Mn(CO3).  It has been used as an antiknock substance for internal com-
bustion engines instead  of tetraethylead.  No reports have been found in the
literature dealing with the  toxicity of this compound. This new antiknock
agent exists in the form of a bright yellow crystalline powder which subli -
mates at 75-77°.  It is water insoluble, and is soluble in alcohol,  benzene,
and oil.  The antiknock  property of this compound is stronger than that of
tetraethylead. At the same time, it is more easily manipulated and is  less
harmful than tetraethylead.  In the course of its production the new antiknock
substance finds its way  into the  organism through inhalation and through the
oral route by ingesting food inadvertently contaminated by careless handling,
and by inhaling air-suspended dust. Therefore, the toxic  properties of the
new antiknock compound were studied by the method o. direct gastrointestinal
                                    -'85 -

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administration.  Changes in the state of the nervous system in the peripheral
blood circulation, as well as in the functional state of the liver and kidneys,
were determined pathomorphologically by examining internal organs of ex-
perimental animals.  Manganese cyclopentadienyltricarbonyl was administer-
ed to the animals by a gastric tube .in 1 ml quantities in sunflower-seed-oil
solution,,   Control animals were administered sunflower-seed-oil alone.

       Results of the tests indicated that gastrointestinal administration of
200  mg/kg of the preparation killed all the animals and constituted the ab-
solute lethal dose, while the administration of 150 mg/kg killed 60% of the
experimental white mice and was regarded as close to the L, D50 dose.  Oc-
casionally experimental white mice died following the  administration of 100
mg/kg0  None of the experimental white mice died which received doses be-
low  100 mg/kg,,  White  rats proved the  most sensitive to the  effects of the
new  antiknock substance, as shown by the fact that 120 mg/kg proved to be
the L DIQO dose; 80 mg/kg killed 60% of the experimental animals; 40 mg/kg
was  the minimal lethal dose, and 20-30 mg/kg was the maximum tolerance
dose.  It should be noted at this point that animal experimental tests made
with samples of 4 batches  of the antiknock substance yielded identical results,
showing that they possessed identical toxic properties.

       Experimental animals which survived the test  several days mani-
fested the  following symptoms of intoxication: bloody  exudation from the
nasopharynx, the animals  appeared sluggish and indifferent to some types of
external stimulation.  In the later periods of intoxication and shortly before
death the animals developed clonic spasticity.  Some of the experimental ani-
mals developed paralysis of the hind legs 5-7 days  after the  antiknock sub-
stance administration„  As previously mentioned, mice proved less sensitive
to the effects of the new antiknock substance than rats. Autopsies performed
on white rats which perished within 24 hours after the antiknock  substance ad-
ministration disclosed  that the  blood was of a raspberry color, and the liver
and  kidneys acquired a brownish tinge.  Histological examination of the inter-
nal organs of autopsied animals showed sharply defined vascular disturbance
in the form of extreme plethora,  brain hemorrhages,  perivascular and peri-
cellular edema.  There also appeared localized necrotic gastritis and fatty
liver cell dystrophy.

       Autopsy of white rats  which perished 24 hours  after the antiknock sub-
stance administration in lethal  doses showed changes basically identical with
those previously described.   Experimental animals which had been subjected
to the acute effect of the new antiknock substance had been tested for the
threshold of  electric neuro-muscular stimulability.  No deaths had occurred
among white mice which received 70 and 50 mg/kg of the new antiknock sub-
stance; however, the threshold of electrostimulability dropped from 9-10 mA
with an average  of 9. 6 mA to 5-7 mA with an average of 5. 5 mA.  It was,
thus shown that a single administration  of the  new antiknock  substance elicited
changes in the activity  of the nervous system manifested as spasticity and lo-
                                   - 86 -

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wered threshold of electric neurostimulability;  the latter was also noted in
experimental animals which received the new antiknock compound in doses not
otherwise visibly toxic.

        The occurrence of unusual changes in the blood color led to the as-
sumption that the new toxic substance possessed erythrocyte lytic proper-
ties which induced hemosiderin accumulation in the tissues. Several crystals
of the new antiknock substance had been injected into the  blood system of
fresh animals.  Observations showed that the new antiknock substance pos-
sessed some hemolytic activity which could result  from the effect of the pri-
mary substance or from its conversion products, basically from  the cyclo-
pentadiene which split off from the original molecule.  This observation led
to  the determination of the osmotic  erythrocyte resistance in white rats.
Results showed that following the administration of the new antiknock sub-
stance in 40 mg/kg dose the red blood cell resistance dropped.  Under normal
conditions red blood cell hemolysis  began atNaC10849%,  and complete hemo-
lysis occurred at NaCl 0.38%.  Red blood cells  of rats which received the new
antiknock substance showed beginning hemolysis at 0.73% NaCl, and complete
hemolysis at 0.48%  NaCl.

       A single administration of the new antiknock substance to  rats in le-
thal doses increased the animals' permeability, which resulted in punctate
and infarctlike bleeding,  and in acute and uneven plethora of the internal or-
gans, and also in the appearance of periovascular edema.  The  total picture
of results obtained,  as above described, clearly indicated that manganese
cyclopentadienyltricarbonyl belonged to the group of substances possessing
polytropic toxic properties.  Experiments  were conducted with white mice and
rats to determine the effect of repeated injections of doses which upon single
administration produced no toxic results.  The antiknock  substance was ad-
ministered to the  experimental animals repeatedly  intragastrically in the form
of its sunflower-seed-oil solution in  doses of 25 mg/kg.  The manganese com-
pound was thus administered to white mice on 18 successive days  in 0. 5 ml of
its  oily solution.  No toxic manifestations appeared in the mice  during the
first 3 days of the repeated administration.  On the fourth day some of the
animals perished  and at the end  of the  repeated  administration 8 of the 20
mice died.  In a similar series of  experiments, rats had  been administered
daily 10 mg/kg doses of the manganese compound.  Two of the rats died af-
ter the 5th administration of  the poison while the remaining rats  were still
alive at the end of the second week.  The external appearance of the animals,
their general behavior and gradual loss of weight indicated that  the animals
were unfavorably  affected by the toxic properties of the new antiknock sub-
stance.  Results of these  experiments clearly indicated that the new anti-
knock substance,  or the products of its  conversion, accumulated in the or-
ganism upon repeated injection,  resulting in the intoxication and death of the
experimental animals which received doses,  a  single administration of which
produced no death and no  intoxication symptoms.

       Chronic intoxication experiments extending  over considerably long
                                     - 87 -

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period of time were  then conducted with the experimental animals adminis-
tering 5 mg/kg of the organic manganese compound.  Experiments were con-
ducted with 20 white  rats which received the above  mentioned dose of the man-
ganese  antiknock substance  as  described in previous experiments  for 2 month
periods.  Fourteen control rats received 0. 5 ml of sunflower-seed-oil only
daily for the same period of time.  Determinations  of the neuromuscular
stimulability threshold showed that it dropped slightly below the normal level.
Blood tests showed fluctuations of  positive and negative values in the hemo-
globin concentration  and in the number of erythrocytes.  Shifts in the red blood
cell osmotic  resistance  ,/ere of more significant values.  Thus,  under nor-
mal conditions the minimal resistance of rats'  red blood cells were within the
range of 0, 52-0,48%  of NaCl, and  the maximal within the range of 0, 36 and
004%o After repeated administration of the  manganese  antiknock substance,
erythrocyte hemolysis appeared at 0,6-0.56% of NaCl,  and in some cases
even at 00 7%;  in the  animals administered the antiknock compound the NaCl
concentration range was 0, 38-0,42%,  Evaluating the data of the above ex-
periments,  it can be  stated that repeated administration of the antiknock sub-
stance to the experimental animals lowered the osmotic resistance of red
blood cells.

       Repeated administration of low doses of the  new antiknock substance
lowered the animals  resistance to infection as a result  of inflamation which
developed at points of subcutaneous administration, where purulent processes
develop as a rule.  No such phenomena had been observed in experimental
animals which received single skin injections of the new antiknock substance.
Results of daily subcutaneous injection of the antiknock  substance  in small
doses for a period of two months indicated that 20 mg/kg could be regarded
as the maximal tolerance  dose under the conditions of the experiment.  Con-
trol animals received a single 20 mg/kg dose without the preliminary injec-
tion of the small doses.  Following the injection of  the provocative dose  the
experimental animals began to lose weight rapidly.   They appeared slovenly
and dirty, showed external signs of intoxication, and died within 10 - 12 days.
Histologic examinations disclosed  signs  of acute gastric polyemia, lympho-
citLc infiltration of the submucous  membrane, and a marked eosinophilia;
processes of catarrhal desquamation appeared in the  duodenum; necrotic
changes, bleeding, polyneuclear infiltration, granular tissue proliferation
appeared in the cutaneous and subcutaneous layers.  Peritoneal wall muscles
showed necrotic spots surrounded by leucotytic infiltration.  Brain neuro-
cells became edematous  in f"he cortical and subcortical regions; the neurocell
protoplasm showed signs  of vacuolization, karyolization accompanied by the
appearance  of neuronophagia.  The lungs showed signs of acute polyemia and
of catarrhal bronchitis.   Some vascular lumens showed leucytic stasis, and
the blood vessels were surrounded by round cell infiltration.  The spleen ap-
peared acutely polyemic and showed disappearance  of lymphoid tissue pulp,
and deposition of a brown pigment.  There were also  many hepatic and renal
pathologic manifestations.  Histologic  examinations of gastrointestinal tissue
showed signs of pathology similar  to the ones described above  for other body
                                    - 88 -

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 organs.  Results of the above investigation indicated generally that the ad-
 ministration of the new antiknock substance to experimental animals in low
 doses elicited no noted changes in any of the organism's functional systems;
 however, they seriously upset the organism's biological balance.

       The total picture resulting from the  s'tudy warrants the conclusion
 that the investigated new antiknock compound was  actually a toxic substance.
 Samples taken from  different batches of the new antiknock substance showed
 different types of toxicity which most likely was due to differences in its
 purification.  This fact should be given special attention and should be taken
 into serious consideration when making standard sanitary and hygienic evalu-
 ation of this product.  Emphasis is placed on the fact that acute and subacute
 intoxication stages showed the predominance of symptoms related to damage
 done to the neurovascular system and to the  gastrointestinal tract.  It should
 be remembered that dystrophic changes had  also been noted in other organs
 and  that the compound manifested marked cumulative and hemolytic proper-
 ties.
                 Determination of Small Thorium Quantities
                          in Biological Specimens
                                 pp.  48 - 52

                N. A. Pavlovskaya, T0 N. Cherkashina, and
                              R. K.  Yunisova
   (From the Laboratory of Radiation Hygiene, Institute of Labor Hygiene
     and Occupational Diseases, U.S.S.R.  Academy of Medical Sciences)
        The use of thorium in the USSR national economy has been progress-
 ively increasing.  Therefore,  the present authors undertook to develop a
 method for the determination of small thorium quantities in biological speci-
 mens.  The existing methods for the determination of small amounts  of thori-
 um  frequently fail to serve the basic purpose of the analysis.  In 1948 S.  V.
 Tokmakova and A. D. Turkin presented a, so-called, emanation method;
 however, this method could not be applied to determination of  thorium in
 biological specimens, where a high degree of sensitivity was required.   The
 spectrometric and spectroscopic methods for the determination  of thorium
 in biological specimens proposed by Hursh in 1957, by Tilton and Perkins
 in 1956,  and by  others are characterized by insufficient  sensitivity, or they
 require almost  complete removal of other metallic salts present in the ana-
 lyzed specimen; this considerably complicated the analytical procedure  and
 made it prohibitively time consuming. In 1959 B. N. Belousov andS. A.
 Potapova proposed a highly sensitive method based on the extraction of thori-
 um from the solution with mesityl oxide after each mineralization, which was
."T~~".	                     -VST-" .

-------
 then followed by nephelometric estimation.  However, the presence of titani-
 um and zirconium interfered with this determination, and the fact that the
 extraction of thorium must be  done with  freshly prepared mesityl oxide made
 this method cumbersome and inapplicable to the determination of titanium in
 biological specimens.

         In developing the method for  the determination of small thorium
 quantities in biological specimens the present authors chose thoron and
 arsenazo III, which were first recommended by V. I. Kuznetsov and S. B.
 Savvin in 1961 for the determination of thorium in  ore.  Thorium combined
 with arsenazo III to form a stable complex substance of an emerald greenish
 color; the newly formed substance remained stable in a 6 N solution of hydro-
 chloric acid.  The  complex resulting from the  combination of thorium with
 "thoron" was less stable; therefore, determinations had to be  made in 0.05 -
 0009 N solution of hydrochloric acid. The reaction sensitivity of thorium
 with "thoron11 is 0. 5 |0> of thorium in  1 ml.  The reaction beteen thorium and
 arsenazo III proved more sensitive,  amounting to 0.02  M.  of thorium in 1 ml.
 Preliminary tests showed that  the presence of phosphates, sulfates, titanium,
 zirconium,  and large quantities of iron interfered with  thorium determination,
 whereas in the case of thorium and arsenazo III only titanium, zirconium and
 fluorides interfered with the determination.  Thus, thorium with arsenazo
 III can be determined by the fractional method in the fluid obtained after  min-
 eralization of the biological specimen.  Separation from admixtures may be-
 come necessary only when  the biological material is suspected to contain ad-
 mixtures of titanium,  zirconium or fluorides.  Preliminary separation of co-
 existing ions is required in all cases of thorium determination by the  "thoron"
 method. Thorium  can be separated  from the interfering  elements chromato-
 graphically with the aid of  cation  K U-2, as recommended by Yu. A.  Chernik-
 hov, V0  F.  Luk'yanov and A. B.  Kozlov in I960, or by  the ionoexchange,  us-
 ing the  highly acid   resin No. 1 tested by the  present authors.  As shown in
 Figure  1, it was brought out that thorium could be separated quantitatively by
 ionoexchange resin only in hydrochloric acid solution in  which thorium pre-
 cipitated up to  90%, or more,  regardless of its  concentration.  Thorium
 separated from nitric and sulfuric acids,  by  precipitation only  within the
 range of 30 - a maximum of 80%, independent of acid concentration.  It was
 also shown that the  presence of Ti4+ and POf~  ions in 100:1 ratio to thorium
 and Zr4"1" And Fe3+ in 1000:1 ratio  to thorium did not interfere with the ad-
 sorption of thorium by ionoexchange resin No.  1, nor did it interfere  with
 its  final determination.

~~      Thus determination of small thorium quantities in  mineralized biologi-
cal specimens can be made  by the  differential method with arsenazo III, or by
the preliminary chromatographic separation of the admixtures, followed by
the determination of thorium by the "thoron" or arsenazo III methods.   The
biospecimens to be analyzed, such as muscle  tissue, internal organs,  blood,
urine, feces, in quantities of 50-200 g should be mineralized by a mixture of
concentrated H2SO4  and HNO3 .   The mineralized light yellow fluid is placed

                                     - 90 -

-------
 Fig.  1                        into a Erlenmeyer flask followed by the addi-
—.                            tion of twice the volume of distilled water.  It
                              is then neutralized with concentrated NH4OH
                              which is  added at  first drop at a time until the
                              reaction  range is  between pH 6.0 - 7.0.  The
                              precipitated hydroxides are filtered off and
  >tOO
   90
  \80
   W
 •. so

 5 30
 H- 20
                              washed clean of SO4~ until no turbidity develops;
                              upon the addition of BaCl3.   In the course  of
                                                \3-
                              this step part of PO4  is lost in the form of
  .  .   '   '   •'—'— '  ' '  • '-  i   (NH4 )3PO4 which interferes with the chromato-
    V  (MfUl/fft UiUlH   iff • £& aff
        •Concentration of acids     graphic partitioning of thorium.  The washed
	L		precipitate is then dissolved in 10-20 ml of 6 M.
Effect of hydrochloric, nitric end
sulfurio acids concentrations on the   hydrochloric acid solution.  Further determina-
onantity of thoriua separated by iono-  ..    ,. .,           •,       •,  •        £ .,   .u
••chang* rosin Mo. I.              tion of thorium can be made in one of the three
                              ways.

       Thorium determination by the fractional  method is based on the for-
mation of  a stable  thorium-arsenazo III complex in a 6 N HC1 solution.  The
determination can be made colorimetrically or photoelectrocolorimetrically.
The colorimetric procedure is as follows:   prepare a standard scale con-
sisting of 10 colorimetric test tubes by placing into the tubes in successive
order, 0,  0.1,  0.2,  0.3,  0.4, 0.5,  0.6, 0.7, 0.8, 0.9,  1. 0 ml of a standard
solution containing  10 p, of the thorium per ml of 6 N HC1 solution; add  6 N
HC1 solution to  the  tubes to make a volume  of 4.  8 ml,  then add 0.2 ml of
9.05% arsenazo III  solution to a final volume of 5 ml in each tube of the se-
ries.

       Prepare the solution to be analyzed  as follows:  add 1-2 ml of the
solution to be tested to a standard colorimetric test tube; add 6  N HC1 solu-
tion to make 4.8 ml, then add 0.2 ml of the arsenazo III solution.  Appear-
                                                     3 -t-
ance  of a  yellowish color indicates the presence  of Fe   ,  in which case add
5-10 mg of ascorbic acid.  Compare the color of this tube with the colors of
the standard scale.   The sensitivity of the colorimetric method is 0. 5 p/ of
thorium in 5 ml.

       Less time consuming determinations can be made with the aid of a
photoelectrocolorimeter, in which case the final estimation is made with
the aid of a calibrated  normogram constructed on the basis of a previously
prepared  standard scale.  Two such  calibrated curves  should be prepared,
one for solutions ranging from 0.1 to 1 p. and another for solutions ranging
from 1 to  6 li, as shown in Figs.  2 and 3.  Both scales  are prepared simi-
larly. Determinations are made in 10 ml colorimetric cups at 680 p.p, wave
length using a red light filter.  The  thorium determination solution is pre-
pared as previously described for the colorimetric method.   Sensitivity of
the test is 0.1 p, in 5 ml.  The lowest thorium amount which can be deter-
mined by  the colorimetric method is 2. 5 p.,  and by the  photocolorimetric
method is 0.5 p..  In either case the determination error is below 15%.

                                      - 91 -

-------
Fig. 2.
            0,070

            0.060

            ff.ffSff

            0,010

            0.030

            0,020

           0.010
 Fig. 3.
O.ZSO
0.200
O.ISO
0.100
O.OSO
              0 0,U,i'ffj'0.4/xj J.50.70A0.9 !
                , of thoriua
   0  J	7  3
     |JLof thoriua
            ThoriuQ calibratod curve,,
                O.I te 1.0 j,
 Calibrated thoriua
 from  1=0 to 6.0 PI
The colorimetric method is adequately sensitive,  possesses a low experi-
mental error, and  is interfered with only by the presence of titanium,  zir-
conium or fluorides in ratios  of 10:1 to thorium.

       The second  and third thorium determination methods are based on
the chromatographic partitioning of thorium from the  co-existing ionic ad-
mixtures and differ from one  another with respect to the ionoexchange  re-
sins used (K U-2 and highly acid resin I).  The fluid obtained after dissolv-
ing the precipitated hydroxides is diluted in both instances with  twice the
volume of distilled water to obtain a 20% HC1 solution by volume and 5 ml
of 20% tartaric acid is  passed through the ionoexchange resin column.

       Before using cationite KU-Z resin  it must be  thoroughly purified
and placed  into a special glass cylinder 15 cm high and  0. 5 cm in diameter.
The solution to be analyzed is passed through the  resin column twice  at a
rate not exceeding 30 drops per minute.  This will insure a more thorough
separation of thorium from the solution.  The column is then  washed with
20% by volume  of HC1 and the acid wash water is discarded.

       The thorium adsorbed by the  resin column is eluted with a saturated
solution of (NH4,)2C204.   The eluate is evaporated to dryness and is  treated
with 4 ml of concentrated HN03 ,  and again evaporated to dryness over  a
water bath.  The dry residue  is then dissolved by the  addition of 2 ml of
0.05 N HC1 solution and  determined colorimetrically by the  "thoron" method.
The residue can also be  dissolved by adding 5 ml of 6 N HC1 solution and
determined colorimetrically or photocolorimetrically by the arsenazo III
method, as described above.  The lowest amount of thorium which can be
determined in this way is 1 p..  In this case titanium, zirconium, fluorides
and phosphorus did not interfere with the thorium determination.   The de -

-------
termination error is  20% or less.
       In the case of the highly acid ionoexchange resin I it is necessary to
use a cylinder 3 cm high and 3 cm in diameter.  The fluid exchange rate
should not exceed 20-30 drops per minute.  The test solution diluted to con-
tain 20% HC1 by volume is passed through the ionoexchange column three
times.  This is followed by passing 15 ml of 20% tartaric acid solution
mixed with 5 ml of 20% by volume  of HC1 solution  through the ionoexchange
column,  which is then washed with 15 ml of distilled water until the pH of the
wash  water becomes neutral.  The thorium is eluted from the ionoexchange
material by aspirating through a solution of (NH4)2C204 at 60 - 70  to which
strong HC1 of 1.17 sp. g.  has been added, or at the rate of 20 ml of the
(NH4)2C204  per 5 ml of the HC1.  The elution is done 3 times.  The alter-
nate use of ammonium  oxalate and of hydrochloric acid brings about an al-
most  complete elution of the thorium from the resin column.   The eluate is
then treated with the cationic KU-2.  The lowest amount of thorium deter-
mined by the "thoron", method is 1  (A and by the arsenazo III method is 0.05 p.,
with a loss of less than 25%.  The  tests have been checked by making thorium
determinations in muscles,  internal organs,  blood  and feces.  Results  are
presented in the Table  following and show  that the procedures proposed for
the determination of thorium in biological specimens yielded satisfactory
results.
D«t«n»ination of thoriua in biologic*! si*ci-
••ns (BUM l*s, '"Jf^S' organs, experimental.

Th^H- «
-------
                                 Conclusions

        1.  The following 3 methods for thorium determination in biological
 specimens have been described:  the differential  method with the aid of ar-
 senazo III, and 2 methods based on chromatographic partitioning of thorium
 from admixtures on  cationic reagent KU-2 and strongly acid ionoexchange
 resin No,, 2, followed by final colorimetric or electrophotocolorimetric
 determinations.

        2.  The lowest amount of thorium which could be determined by the
 differential  method was 2. 5 p. using the colorimetric method, and 00 5 p. us-
 ing the photoelectrocolorimetric method.  The lowest amount of thorium
 that can be determined in a biological  specimen with the aid of cationic res-
 in KY-2 was 1 p., and with the aid of the highly acid ionoexchange I it was
 0,, 5 p. using  the "thoron" reagent; it was 0.1 p, when arsenazo III reagent was
 used.

        3o  The error in determining thorium by the differential method was
 within the range of 10-15%.  Interfering factors in this method were zircon-
 ium,  titanium and fluorides.  Determination of thorium in biological speci-
 mens with the aid of ionoexchanges resins I and KY-2 following specimen
 mineralization was free from titanium and zirconium interference.

                                   Bibliography

             BejioycoB  B. O., hotanoBa C.  A. B KH.:  C6opHHK  pe&epatOB no paaBa-
            nofi MeflHUHHe sa 1958 r. M., 1959, crp. 144.—Ky ineuo B  B. H., Ca BBH H C. B.
              iMHfl 1961  T. 3, B.  1,  crp. 79.—CfSopmw paAHOxHMHiecKHx H floaHMerpHHecKEui
           ,««^. M.', 1959,' crp. 140—T OKwaKoaa E. B.. TypKHH A. fl. MCA. paflHOA, 1958,
         & 3. crp. 61.—M e p H H x o B K). A., Jl y K b a H o B B. ., Ko 3 Jt o B a  A. B. M.  aHa-nnT.
         XHMHH 1960 NO 4, crp. 452.—6.  LUsaftKOBa M. fl. Cyfle6Has XHMHH.   M.. 1959,
         CTP 276—Hursh J. B., Stead man L. T. et al.. Acta radiol.  (Stockh.), 1957, v. 47,
         n 481 -P e r k i n s R. W., K a 1 k w a r f D. R., Analyt. Chejn.,  1956, v. 28. p. 1989.-
         THton G. R., Aid rich L. T.,  Ing hram M. G.. Ibid., 1954, v. 26. p. 894.
           Prevention of Air Pollution in Gas Equipped Apartments
          (With reference to the  Proposed Sanitary Regulations for
                         Gas Equipped Residences)
                                  pp.  60 -  62

                               F. F. Lampert
     (From the A. N. Sysin Institute of General and Community Hygiene;
                  the U.SoS.R. Academy of Medical Sciences)
        Gas is gradually replacing hard fuel in the USSR,  which affects favor-
ably the population's living conditions..   On the other hand,  lack of develop-
                                       - 94 -
-------
ment or improvement in gas burners has resulted in frequent air pollution
in houses and apartments which had been equipped with gas.  This was noted
in 1945 by L.I.  Los and 1949 by D. N. Kalyuzhnyi,  and by many others.  Gas
burning generates  such air polluting products as carbon monoxide, carbonic
acid, hydrocarbons, etc; it also raises the surrounding air temperature  and
humidity,  easily detecte'd even after the gas has been used for  1 hour.  Thus,
rise in air temperature up to 10  and rise in relative humidity up to 20-30%
have been noticed by the investigators above referred to.  As a result of
such conditions, Kh. V. Storoshchuk (in 1951), M. N. Troitskaya in 1958,
S. F. Sorokina  (in I960) and many others found cases of chronic carbon mon-
oxide poisoning upon examining inhabitants of gas equipped houses and apart-
ments.

        The above clearly points to the need of regular sanitary inspections
for the purpose  of  establishing the factors which caused air pollution in gas
equipped homes.  In this connection past examinations have indicated that
imperfect gas burners  and gas plates used for cooking constituted a basic
factor in the pollution of indoor air in gas-equipped dwellings.   Another im-
portant factor is the complete lack of organized  ventilation, imperfect con-
struction, installation, and operation of existing ventilation systems, of the
improperly planned room arrangements.   S.  P. Sladkova demonstrated  in
1955 that the imperfect gas burners were responsible for breaks in the con-
tinuity of gas burning and in the consequent appearance of incomplete com-
bustion products in the indoor air.  She also noted that the exhaust ventila-
tion system installed in the average present-day residential house or apart-
ment was either faulty  or inadequate to bring about complete removal of  the
gas 'combustion products. D.  G. Devyatka noted in  1959 that the operating
ventilation system  in gas-equipped residences lowered the carbon monoxide
concentrations in the kitchen air by only 22%.  Kh.  A. Zarivaiskaya  found
in 1962 that the usually planned  and installed exhaust ventilation system
brought about kitchen air exchange in one-room apartments to the extent of
60.4% of the required minimum,  and only to the extent of  31% of the required
minimum, in two and three room apartments.

       Comparative studies conducted  in differently planned gas-equipped
living quarters indicated that where living rooms were connected  directly
with the kitchen, intensity of air pollution with carbon monoxide, and other
products of gas  combustion, was  greater in apartments in which the  kitchen
was isolated from the  living room.  The above indicated facts clearly point
to the channels along which modern engineers, planners, architects, and
hygienists must direct  their attention for the rational solution of the  air pol-
lution problem in future construction  of gas equipped residential houses and
apartments.  Present day attainments in sanitary technique and  in the  per-
fection of typical residence plans offer abasis for the solution of  this impor-
tant problem, and urgently call for the formulation of mandatory  regulations
arid specifications applicable to the planning of gas installation in  residential
homes.  In this  connection complete gas combustion by home utilities or gas

                                    - 95 -
-------
installations is a basic requisite.  This presupposes a steady and even gas
flow of homogeneous composition under a regulated, constant pressure into
properly computed and constructed gas burning  utilities.  K. N. Pravoverov
and others have developed gas burners and kitchen gas plates which produced
a, so-called, flameless or invisible combustion with an  overhead flue which
removed the gas combustion products including the resulting water (humidity)
and the increased air temperature directly into the atmospheric air.

       L0  M. Pinchuk, N.  M. Porubinovskaya of the Moscow City Sanitary
- Epidemiological Stati on demonstrated that carbon monoxide concentration
in the air of premises where the, so-called, flameless burners have been
used did not exceed 2 mg/m3.  According to S. P. Slabkova carbon monoxide
concentration in the kitchen using the flameless  gas plate was reduced by
several times and according to F. F. Lamport and V.  E. Konstantimova
(1959) no carbon monoxide presence could be detected in the other living
rooms.  Naturally,  most efficient from the  viewpoint of  carbon monoxide
and other gas combustion products elimination was the direct exhaust ven-
tilation of such products through a properly constructed  flue.    M. N.
Troitskaya found in 1962 no carbon monoxide in the air of kitchens which used
the P.  Akuz'min gas burning plate.  Under such conditions of gas combustion
no increase in the humidity of  the apartment house air could be detected.
This shows that proper gas burning utilities are at present obtainable and
that proper plans for their installation can be  proposed.   Therefore, it is
urged that construction and planning engineers in sanitary organizations
should make proper use of the available home gas equipment.  It is also sug-
gested that for the  purposes of proper sanitary safety gas burning utilities,
particularly those used for water heating, should be equipped with automa-
tic safety devices which would stop the gas flow  as soon  as unfavorable con-
ditions developed in the exhaust  flue.  Naturally, the same applies to gas
burners used in water heated houses.

       Installation of boilers directly under living quarters, and especially
under institutions for children, must be mandatorily forbidden.  Particular
attention should be paid to the  properly planned and properly functioning ven-
tilation systems.  Official sanitary hygienic  and  engineering specifications
should be formulated as guides for the calculation, construction, and proper
installation of the gas-equipped dwelling ventilation system according to
principles outlined by L. B. Chernin, Kh. A.  Zarevaiskaya, and others.
Generally speaking, the hygenic  requisites and specifications related to the
volume and dimensions of gas  operating rooms,  such as  kitchens, etc.
vary with the type and dimensions of the apartment or other dwelling, with
the character of kitchen equipment, and with the nature of other house fa-
cilities.    It is  recommended  that an air exchange of 5 m3 should be pro-
vided for each plate gas burner.   Wherever  possible the  kitchen, equipped
with gas burning cooking facilities, should be  completely isolated from the
rest of the living space.  A general educational  campaign must be instituted
along these lines and a rational sanitary hygienic inspection  and control
         «                           - 96  -
-------
                          concentration had increased.  No substantial im-
                          provements in the temperature-humidity condi-
                          tions had been noted.  However, the fact that ex-
                          periments  conducted with gas burning plate L.-15
                          OPS yielded no desirable results should not dis-
                          courage other investigators  from continuing this
                          type of work.   It is  possible that the principle of
                          using direct carbon monoxide removing devices,
                          which in our opinion is basically rational,  may yield
                          favorable results in future  appropriately planned ex-
                          periments.
 Scbeaatic plan of gas plate L-15
           OPS
                                   Bibliography
             HeBHTKa  A. I. Bpn-i. awio, 1958, Ns 10, cr6. 1093.—OH JK e. Fur. 11 can., 1960.
         N° I, crp. 90.—/I a M n e p T . 1>., K o H c T a H T H H o a a B. E. PHP. H can., 1959. Ns 4.
         rrp. 15.—j*I o c b A.  P., C a a o B H H K o B a .'I. H. Tpyau CaparoBCK. oGjiacTfioro nayMHO-
         Hccnea. caHHTapHo-r«rHennMecKoro Mii-ra, 1948, T. 4, ctp.209.—M a p T u H 10 K B. 3., Jl H (})-
         UIHH M. H. THP. H can..  1951. Ns  I. etp. 9.—CTopouiyK X. B. Bpa-i.  .ue.no, 1951.
         N? 11. CTO. 1015.
                                  NO.  5,  MAY
             Experimental Data as a Basis for the Determination
               of the Maximal Permissible Amylenes (Pentenes)
                       Concentration in Atmospheric Air
                                   pp.  3 - 8

                       M. I. Gusev and K. N. Chelikanov
       (From  the Department of Hygiene of the 1. P. Pavlov Ryazan
                              Medical Institute)
       Amylenes,  or as they are generally known, pentenes, represent a
mixture  of 6 olefin isomers.  Olefins are saturated hydrocarbons which con-
sist of carbon and hydrogen.  They contain a single double bond.  Olefins

                                      - 99 -
-------
 make up the homologous order of ethylenes.  Amylenes are synthesized
 basically by the dehydration of amyl alcohol with aluminum oxide at 380-
 450°,  or by a 65% sulfuric acid solution at 90-110°,  or by the pyrolysis of
 amyl acetate at 500-700° .  Amylenes can also be  synthesized by dehydrating
 amyl alcohol solutions of fusel oils by means of zinc chloride.  They are
 also contained in  the light amyl distillates,  mostly in the low boiling frac-
 tion of petrolic ether  obtained in cracking or pyrolysis of crude oil.  Techni-
 cally, amylene has a  b. p.  of 39-40, Sq df 00 6509, pj° 1.3783 and is,  a mix-
 ture of all amylene isomers including isopentene.  The main source of air
 pollution with olefins  is exhaust of automobile gases.  According  to data pre-
 sented by Hutchenson and Holdane of  Los Angeles, California,  automobile
 exhaust gases  contained 88% of olefin.  Other investigators of  Los Angeles
 found the percentages to range between 70 and 80, and those of San Francis-
 co found the olefin concentration to be 60%.

        Olefin poisoning appears in the form of narcosis accompanied by pro-
 fuse salivation, a considerable drop in  arterial pressure, tachycardia, renal
 disturbance, such as  uremiat   proteinemia and appearance of cylinders,
 also spasticity of the glottis.  100-120 mg/li of olefins constituted a narcotic
 dose,  if inhaled for 2 hours; 140-250  mg/li constituted a lethal dose.  Rab-
 bits exposed to the inhalation of air containing up  to 0.15 mg/li of olefin for
 7 hours daily for  20 days developed marked leucocytosis and paralysis  of the
 hind legs.   No noteworthy anatomical abnormalities had been noticed by N. V.
 Lazarev upon autopsy, as reported by him in 1954.  Lately, olefins, (es-
 pecially pentenes  and hexenes) attracted investigators' attention by the  fact
 that they were factors in the formation  of smogs,  as noted in Los Angeles.

        The present authors investigated the  affect of low amylene (pentene)
 concentrations on animals in chronic  experiments, and also conducted some
 observations on the affect of amylene on man. Amylenes  were determined
 in the air by the Morozov method, which is  based on the fact that unsaturated
 hydrocarbons reacted  with bromine at  the double bond, as shown by the fol-
 io-wing formula:

                        CH3—CH=CH2+Br2->CH3—CHBr-CHoBr.


The amount of bromine entering into reaction is used as the basis for the de-
termination of the unsaturated hydrocarbon concentration, and computed as
pentenes according to M. V. Alekseeva.

       The  threshold odor perception of amylenes was determined by the
method recommended by the Committee on Sanitary Protection of Atmos-
pheric Air affiliated with the Government Sanitary Inspection of the USSR.
Test volunteers were students  of the medical institute, 20-36 years of age.
Before beginning the experiment, the  students were familarized with the
specific odor of the preparation under investigation.  Students  were examined
for possible disturbances of the odor perception organs.  Tests were con-
                                     - 100 -
-------
 'ducted.for .10 days.  Results of the first 3 days investigation showed that 3. 58
 jhg/m  represented the average minimal olefin concentration perceptible to
 all the testers.  The following set of odor perception tests indicated that at
 1.79 mg/m of the olefin,  the odor was still perceptible.  However, at 0.75
 mg/m  the olefin  odor was perceived by none of the student testers.
               / J i_l  9 13 151719211 379 fJ 15 t'/'1123 25 JQ.2.4 6
                    February           March            Apr-i
                       i   Araylena concentrations curing
                             the exposure raonths
        The next step of the investigation was devoted to experiments with
 rats.  Thirty young white rats weighing 94-160 g were divided into 3 groups
 of 10 animals.  The investigation was conducted on the basis of  chronic ex-
 periments.  Rats were exposed to the inhalation of the olefin-containing air
 24 hours daily for 75 days.  Work was conducted in exposure chambers of
 100 li capacity.  As indexes of toxic effect the authors used the  animal's
 general conditions of behavior, changes in their body weight, coproporphyrin
 elimination with the urine, in blood serum and in erythrocyte colinesterase
 activity,  the number of luminescent leucytes,  changes in reflex activity, and
 results of pathoanatomical examination of the internal organs of autopsied
 animals.

        To facilitate the maintenance of constant amylene concentrations in
 the exposure chambers, the tube through which the amylene  entered the
 Chamber was submerged into a constant temperature waterbath  of 29-31°.
 Fluctuations in the concentration of amylene vapor in the exposure chamber
 during the chronic experiments are  graphically plotted in the following Figure.
 The  average amylene concentration  in the air of chamber No. 1  was 9.8±,
 0.51 mg/m .  The amylene concentration in the air of the second exposure
 chamber was 1. 9±, 0. 22  mg/m3, with a maximum of 4. 86 and a minimum  of
 0.0 mg/m .  Experimental animals of Chamber No. 1 began to show devia-
tions from their normal behavior pattern 10-12 days after the beginning of
the exposure period,  which was supposed to  last 15 days.  The experimental
                                  .   - 101 -
-------
animals appeared highly agitated,,  At the same time, animals in exposure
Chamber No, 2 presented a general behavior picture which in no way differ-
ed from the behavior pattern of the control animals„  The agitation noted in
animals in exposure Chamber No. 1 gradually abated, and the rats appeared
to have adjusted themselves to their environmental conditions, as shown by
the fact that their behavior returned to normal,,  Body weight records  of all
animala kept in the course of the inhalation exposure experiments showed no
significant deviations; therefore,  it was concluded that the inhalation of air
containing olefins had no effect on weight gaining in animals of the two  ex-
perimental groups.  Observations conducted during the recovery periods
showed that rats of Groups 1 and 2 began or continued to gain weight, at the
same time the weight of rats belonging to the control group remained con-
stant.   The reliability of the observations was confirmed by statistical ana-
lysis.   The general impression was that inhalation of low amylene vapor
concentrations enhanced the rate of weight gain in experimental animals.

        The effect of amylene inhalation on porphyrin metabolism, as a means
of determining maximal permissible  concentration of the substance in atmos-
pheric air,  was studied by procedures of M0 I.  Gusev,  G.  I. Solomin  and
T. Mo  ShuL'ga . (1961) and Li-Shen (1962).   This type of investigation was con-
ducted with rats exposed to the inhalation of air containing different amylene
concentrations under conditions of chronic experiments.  Twenty-four  hour
urine specimens were collected once every week.  Corproporphyrin was  ex-
tracted from the urine by the Fisher  method, and qualitative and quantita-
tive  determinations  were  made spectrophotometrically using electrospectro-
photometer SF-5. In this  way 10 tests were made with the urine of animals
exposed to the poison inhalations,  and 3 urine specimens were tested during
the recovery period.   Results  are  listed in Table 1.  Data in that table  show
that  chronic  24 hour exposure  of white  rats to the inhalation of air contain-
ing 9. 8 mg/m3 of amylene vapor resulted in increased porphyrin metabolism,
computed on the basis of 100 g of rat body weight.  The increase in the por-
phyrin metabolism amounted to 25%,  which statistical analysis established
as reliable.  Increased  coproporphyrin elimination with the urine continued
for more than 30 days after exposure inhalation was stopped. No changes in
porphyrin metabolism had been noted among rats chronically exposed to the
inhalation of air containing 1. 9 mg/m   of amylene vapor.

       Effect of inhaling air containing different amylene concentrations  on
blood serum and erythrocyte cholinesterase activity in rats was determined
by procedures previously described by G. I. Solomin, R. Ubaidulaev,  Li-
Shen, and others.  The analytical procedure was described in detail by
A. A.  Pokrovskii in 1953,  and modified by A. P. Martynova in 1958.   Cholin-
esterase activity control determinations were made  once before inhalation
exposures, at 6 intervals during the period of inhalation, and twice during
the recovery period.   Results  are  listed in Table 2.   Reliably significant
drops in cholinesterase  activity appeared beginning with the 23rd exposure
day in  rats of Group 1, which persisted through the  entire period of exposure
to chronic inhalation.  Cholinesterase activity returned  to normal in rats of
                                  - 102 -
-------
                                     this group only on the 25th day of the
                                     recovery  period.  No statistically re-
                                     liable or significant results have been
                                     obtained indicating either a rise or
                                     fall in the activity of this enzyme.  Ac-
                                     cordingly, an average 1. 9 mg/m3 amyl-
                                     ene concentration in the air elicited no
                                     changes in the blood serum cholinester-
                                     ase activity of the experimental animals.

                                         A. D. Semenenko was the first to
                                     apply  the principle  of leucocyte lumin-
                                     escence analysis to the standardization
                                     of harmful substances in atmospheric
                                     air.  He conducted his experiments at
                                     the Central Institute of Post-Graduate
                                     Medicine.  The present authors used
                                     this method  in connection with the in-
                                     vestigation herein reported.   Blood
                                     specimens were taken periodically
                                     from the experimental rats,  and the
                                     percentage of luminescent leucocytes
                                     determined as described by A. D.
                                     Semenenko.   Results are  listed in Ta-
                                     ble 3.  Statistical processing  of the at-
                                     tained results indicated that 37 days
                                     after inhalation initiation  the blood of
                                     rats belonging to Group 1 showed an
                                     increase in the number of luminescent
                                     leucocytes,  as compared with the  con-
                                     trol animals.  This condition  persisted
                                     for 30 days,  after which the number of
                                     luminescent  leucocytes gradually re-
                                     turned to normal and remained at  that
                                     level to the end of the inhalation period
                                     and through  one month of the recovery
                                     period.  No  changes in the number of
                                     luminescent  leucocytes had been noted
                                     in the  blood  of rats,belonging  to the
                                     second group.

                                         Effect of chronic amylene inhala-
                                     tion in different concentrations on the
                                     established  pattern conditioned reflex-
                                     es was conducted by the method of Yu
.V.  Novitov, N. F. Ismerov and others.  Experiments were  conducted with
10 white male  rats weighing 10-160 g.  Four  white  rats were  placed  into ex-

                                    - 103 -
;


i— i
43
n$;
-^-
«
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Hi >
1 I

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O

0 '
O '
L.
•a
S
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9 .

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f.
«• .
*•
s
e ]
? i

1
£
21
3

^
^
2
 •
s. s
i
•#*
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a.
s >
* It

M
CO
>
5r

S-
. -
tp1
"2 i

*' 1
21
! 	
O • "
& -
ui 	
to
-
8
_

-
o























s^
«•-

SOi
CO .

mo
• — •<»•
tn ^
CO — "
gg
IN —
"*$
CO — '
OHO
t^ (O
CO —


S3
CO —
c*> oo ^
(N — e
(D OO §5
— 
(~. CO
co —


0000
'"* OO'*'
IN —
r>
S •* 00
•»• COIN
a> - -
a 
1

•S
o
—
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"8

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*2
U L.
18.
c c
L U
4'ii

O 0
a. a.
§•§•
oo
-------
posure chamber No. 1,  the air of which contained a low concentration of
amylene.  Similarly 4 white rats were  placed into Chamber No,  2,  the air
of which contained amylene in high concentration, while  2 control white rats
were placed into Chamber No.  3 containing clean air.  Conditioned reflexes
had been developed by the L. E.  Kotlyarevskii  rapid method, as described
by Ya Go Dvoskin0  A sterotype conditioned reflex pattern was developed in
the experimental rats, which consisted of responses to two positive signals,
bell-light,    light and belL  Slight changes in the conditioned reflex activity
were noted only in the rats which inhaled air containing 9. 8 mg/m3 of amylene.
Disturbance in the higher nervous activity appeared as slightly prolonged la-
tent periods of response to the  sound of a bell and to the  flash  of light.   Occa-
sionally,, a falling  out of reflex in response to light,  and the appearance of
phase states had been notedo  These changes in the conditioned reflex activ-
ity began to appear on the 5th week of the poisonous vapor inhalation.  The
functional activity  of the brain cortex returned to normal in the  experimental
rats 2 weeks after discontinuation of exposure to amylene inhalation.

          Table  2.
                  Clholo bleed chol onootoraoo activity on rato (in ainutoe)
. 3
Ofl/Q



Centre)
1.9
t
9,8
t
Jofeiro
aapo-
CWPO
25/1

38.4
38,0
0,44
39,4
Enposurs par tod


I3/II
38,6
39,0
0,84
38.5
1,30| 0,32


23/11
38,3
39,5
1,68
40,4
2.73a


8/III
39,7
40,7
0 92
46,0
«>o7(to


3/111
39,5
41.0
1,23
48,0
6.5»»c
i

4/IV
39,0
40,4
2,15
57,0
I2ol5c

17/IV
40.2
41,0
1.43
60,0
Recovery
pec too


27/IV
40,0
40,6
0,78
43._4
e.isc s.isc


IO/\
41,0
39 4
2.08
40.0
2.0
reliability
                                        Q-95?!,, b-99i$0 c-99.94
          Table 3.
                         Percent of  luoinescont loucocytoo

as/o3
Control
1,9
t
9.8
t
Bofos-o
oap®-
ouro
24/1
4,5
3,4
0,90
3.6
0,17
Enpcouiro porood
12/11
3,4
4,0
1.36
2.8
0,57
22/H
•1,2
3,5
0,65
5.1
0,64
7/111
2,8
3.2
0.-I9
11,6
5.30c
22/111
2,6
2,3
0.26
7.5
5.30c
3/IV
2,3
1,6
0.50
5,6 	
2o68o
17/IV
2,8
2,2"
0.40
2,2
0.39
Rocowery
pariod
27/IV
3,4
1,0
1.07
1.7
1,43
10/V
2,6
1.8
1.29
1.9
1.13
        Autopsies had been performed on some of the animals, and their in-
ternal organs examined macroscopically and microscopically.  No macro-
:scopic  changes had been noted in any of the animals.  Pathohistologic changes
                                     - 104
-------
 were rioted in the organs  of rats which chronically inhaled air containing
 9. 8 mg/m  of the amylene vapor; most clearly defined were signs of bron-
 chitis, perybronchitis, localized and confluent catarrhal and interstitial
 pneumonia, emphysema accompanied by minor bleeding and vascular ple-
;;thora. •'•              •

                                 Conclusions

        ,1.  It.was established that 1. 8 mg/m3  of amylene in the atmospheric
 air represented the concentration of threshold odor perception of the sub-
 stance.                                                        :

        2. .Continuous 24  hour exposure  of white rats to the inhalation of air
.containing 9. 8± of 0.51 mg/m  of amylene for 75 days elicited statistically
 significant enhanced porphyrin metabolism,  lowered cholinesterase  activity,
 and increased number of luminescent leucocytes.  In addition, the animals'
 p'attern of established reflex responses had become disturbed;  Some micro-
"scopic histologic changes had been noted in the organs and tissues of autop-
 sied rats,  most noteable among which were pathologic lung changes.

        3.  Exposure of rats to the inhalation  of 1. 9±,   0.22 mg/m  of amyl-
 ene under similar  experimental conditions elicited none  of the above enumer-
 ated changes, with very slight postmortem exceptions.

        On the basis of the above discussed results, it is  recommended that
 the maximal permissible  amylene concentration in atmospheric air be set
 at 1. 9 mg/m3 .

                                 Bibliography
            A.icKi'eeaa M. B. Onpi'.ie.iemie aiMoci)>epiii>ix MrpH.-weHHH. M., 1959. — B e .1 \i . K. B MI.: KpaiKasi MiMinuvKan 3HiuiKflono;inn. M., 1961, T. 1, crp. 168. — HBOC-
        KHH H. T. I'lir. can.. 1961. Ns 10. cip. 41. •— McpKOB A. M. OGmaa TCOOIIH n MetoaiiKa
                  iicTii'iiH-Koro )Ki-.nc;ioBaniisi. M.,  1960. - • P n :t a H o B B. A. PyKOBo;icTBO  no
                  rnrnciip. M., 1961, T. 1.
            Effect of Combined Radiation and High Air Temperature
                                 on Animals
                                 pp. 24 - 29

                               A.  F. Guriev
 (From the Department of General Hygiene, The I. M. Sechenov First Moscov
                     Order of Lenin Medical Institute).
      .  A- study of hygienic working conditions with radioactive substances
 ini thfe .petroleum industry must not be limited to the effect of ionizing radia-
      '    .,   '-,
:•..    '  •                      -    - 105 -
-------
tions5  but must take into consideration other environmental factors,  such as
temperature increase of the surrounding air.  According to N. I.  Rykov
(I958)t Po A. Milonov (1959), and others one single total exposure of animals
to X-ray  of 250-600r  at increased surrounding air temperature enhanced the
gravifcy of acute radiation sickness.

       The  present author studied the effect of increased surrounding air
temperature on the appearance and development of radiation sickness caused
by exposure to  rapid neutrons radiation.  The investigation was conducted
with 20 male rabbits,,  divided into four groups; the first group consisted of
8 rabbits; the second, third, and fourth of 4 rabbits each.  During the initial
6 weeks (January - February) the normal physiological patterns of all animals
had been  established.  During the following 20 weeks (February -  July) the
animals had been irradiated and studied on definite days and at definite hours.
The  months of July and October constituted the recovery period,  during which
experimental and control rabbits had been kept in  the animal room under
usual conditions.

       Animals of group 1 had been irradiated by fast neutrons of  polonium -
beryllium at normal surrounding air  temperature; (15-17°).    Animals were
transferred to special radiation cages where they  were kept in a fixed posi-
tion.  Four  rabbits had been irradiated at the same time0   The posterior-
anterior longitudinal body axis of the irradiated rabbits was in accommoda-
tion with the radial direction of the fast neutrons emanation.  The distance
between radio-emanation source and  the closest point of each animal exposed
surface, that is the hind part, was kept at a constant 8 cm.   Each experiment
lasted  2 hours.  Irradiation lasted about 59 minutes during the initial period
of the experiment,  when the  activity of the source  was approximately 1. 107
neutr/seco

       Subsequently the exposure  time was in proportion to the drop in ac-
tivity of the source.  Irradiation was made every other day attaining a maxi-
mal weekly  tissue dose of 0.4rd.  The total dose of radiation for each rabbit
was 806 rd.  The radiation dose was  controlled by means  of a portable radio-
meter  which measured the emanation of fast neutrons (KPN-2S RPN-l), and
by calculation.  The instruments had been calibrated in a  special laboratory
using a polonium-beryllium source of known activity; the measurement error
averaged  20% of the nominal scale value.

       Rabbits of the second group had been irradiated similarly at  surround-
ing air temperature raised to 37-39°.  This was done in an exposure chamber
specially  constructed for such studies.  The rabbits were kept at the increased
temperature for 2-30 min. before being irradiated.  Rabbits were kept at the
increased air temperature for a total of 2 hours,  after which they were return-
ed to the laboratory animal room.

       Rabbits of the third group had been placed into a chamber, the air of
                                    - 106 -
-------
 which was raised to 37-39° without being irradiated.  Rabbits of the fourth
•^'group served as controls.  Records were kept of all animals general condi-
 tion, behavior, appearance,  appetite, and changes in  body weight.  Deter-
r mihations were made  of the following:  1) number of erythrocytes  2) hemo-
;;gldbln content 3) number of reticulocytes and thrombocytes  4) ratio of mor-
 phologic blood and plasma elements and their volumes,  5) osmotic resistance
 ,• stability of erythrocytes   6) sedimentation rate 7)  catalase activity  8) total
 leucocyte number  9) leucocytic formula  10) phagocytic  leukocyte activity
 11) blood coagulation time 12) prothrombin time and 130  heparin tolerance.
 Erythrocyte and leucocyte counts and the leucocyte formula  were determined
 "weekly. , All the other indicators were checked fortnightly.  Resulting data
 •w^'re a'tialyzed statistically.

        No external signs  of radiation sickness appeared during the entire
 time (4-1/2 months) of irradiation and during the 3 months of recovery.  All
 rabbits appeared healthy and lively; they fed normally and gained weight.
 Some blood indexes declined as  compared with the  initial values and with
 those of the controls.  This decline was lowest in the  erythrocytes.  All ir-
 ra9iated rabbits showed a wider fluctuation range in the number of erythro-
 ' cytes and reticulocytes in the  13-15th week of the test  as compared with these
 ilidicat&Jfs in the controls. Changes were more pronounced  in rabbits ir-
 radiated-at higher  surrounding air temperature.  At the end of the irradiation
 the color  index decreased by 15-20%, as compared with  the initial data, while
 it changed only slightly in rabbits of the first group.  The average erythrocyte
 volume, the red blood cell resistance and their sedimentation rate changed
 only slightly in irradiated and control animals. The number of thrombocytes
 decreased slightly in some rabbits by the middle of the irradiation period;
 the decrease was most pronounced in some animals of the second group (up
 to 70, 000 in 1 mm3 of blood) at the end  of the irradiation.  The number of
 such cells rapidly increased later and reached the  initial level 45 days after
 irradiation discontinuation.  All animals manifested during the experiment
 significant catalase number fluctuations,  which were more pronounced in
 rabbits irradiated at increased temperature.  The  catalase index was con-
 siderably reduced toward the end of irradiation in rabbits  of the second group.
 The number of leucocytes, the leucocyte formula,  the phagocytic activity of
 leucocytes, and some  blood coagulation indexes showed  greatest changes.

        Number of leucocytes began to increase during the first weeks in all
 irradiated animals of groups  1 and 2.  Leucocytosis was more pronounced in
 rabbits under the action of neutrons  at the higher temperature, amounting to
 13,000- 17,000 leucocytes in 1 mm3 of blood (the average control number for
 this group was 7400 leucocytes). The number of leucocytes  increased mainly
 at the expense of the increase of the relative and absolute  quantity of lympho-
 cytes (Fig. 1).  These indexes did not change substantially in control animals
 throughout the entire experimental period.  Animals of groups 1 and 2 showed
 ah increased number of leucocytes at the end of the ninth week of irradiation,
 a''-shift to  the left in the nuclear leucocytes, which were  more pronounced in
 rabbiti irradiated at increased temperature (Fig." 2)0  This  shift to the le/ft
       -" -    '-•                    --107 -
-------
 was  caused mainly by the increase in the number of neutrophiles  with
rod=shaped nuclei  and decrease in the number of  young forms.
Fig0  !„
               ff
                              ?      3      4      /

                              Months of  i era di a to en
             Ceuireo of chongoo  in tho abc©Iuto nuabar ef  lyophocy taa in  the peripheral
             blocd o? tho_oaiDaLm_(.Llustsjaii®>. 1 Soots tsl  aworogo otatistical waluao
                                                     P<0.05).	
            0-AtfSo nuobor of lyaphocytos in anoraalo  ioradiatod at noraal taroperatures;
            OD-ditt©  in cnioalo irt-adiated at tho boater toapafuture ef the ourround-
           • iing airj  ODD - ditto on onoDalo (topt  at  caoa tooporaturo of the surround-
            ing air but not irradiated; 0V -
 Figo 2.
                                    of irradiation

                   of chongeo in  loucccyto phagocytoc activity  ow anionlo of all  groups
                                     oist>e3^otnt5atical walaoo . P <" 0.05).
             0-Wuctaar rf>6ft  in anionls  orrodiotod at ncrool tcoporatuyoj  10  - ditto in
             anioalB irradiated at highar tooporoturo of ournBundong oorj  111  — ditto i.i
             onioalo at highor toopofotuiro of cur rounding aip0 but Rot orradiatodj 0V-
             dotto in anioais of tho central gr^up

                                                -  108'-"
-------
  Values of nuclear shifts to the left amounted to unity or more in some rab-
  bits as compared with 0.1 - 0.15 of the controls and 0. 3 - 0.35 of nonirradi-
  ated;rabbits kept at increased room temperature.   Phagocytic leukocyte ac-
•  "tiyity/was studied by  the Platonov method.  Results  showed that the irradia-
v  'tiott of rabbits by fast neutrons at normal temperature  gradually decreased
  the; htimber of phagocytic neutrophiles beginning with the fifth week of irradia-
vtaoft {
-------
 fcial and control values in the irradiated rabbit.  Most substantial changes
had been observed in rabbits  irradiated by rapid neutrons at increased sur-
rounding air temperature, that is, in rabbits  of the second group, in which
heparin tolerance time increased by 50% and more as compared with their
initial normal time, and with time of the control rabbits.  Irradiation of rab-
bits at normal temperature extended  heparin tolerance time by 25-30% as
compared with the initial background values.  The fact that the discussed in-
dex changes manifested in rabbits of the first and particularly of the second
group tended to return to their initial normal values during the recovery
period is of particular significance and interest.

                                 Conclusions
       T^o-  Changes of several indexes in the red and white blood cells and in
the blood coagulation time had been observed in rabbits irradiated by fast
neutrons with the maximal tissue dose of 0.4 rd weekly to a total of 8.6 rd
irradiation.

        2.  These changes appeared more  defined in rabbits chronically ir-
radiated by fast neutrons at increased surrounding air temperature  (37-39°).
The effect of increased surrounding air temperature intensified the  harmful
effects  of fast neutrons.
          i

        3o  In planning  means for the protection of employees working at
processes connected with sources of fast neutron emanation, serious con-
sideration should be given to the possibility of  a rise in the temperature of
the working premises.

                                  Bibliography
           EejieHbKHfi M. JI. SjieMCHTbi KOJumectBeHHoft OUCHKH tpapMaKojiorHqecKoro 3$-
        (beKTa  PHra, 1959. — M H Ji o H o B Fl. A. B KH.: COopimK naymiux pafiot Xapi.KOBCK. Mf.i_.
        HH-xa' 1959  CTD 113 — PbDKOB H.  H. B KH.: namnonmeCKaH i})H3iio.iorHH octpoH
        jiyieBofi 6o.ne3HH. M.. 1958, cip.  315. — 111 an b H o B M. H. TKaiieaan Aosa nefitponoB.
        M.. 1960.
               The Toxicity of Low Styrol Vapor Concentrations
                                 pp. 29 - 35

                                N. S0 Zlobina
           (From the Central Institute of Post Graduate Medicine)
       Styrol is used extensively in the production of high molecular com-
pounds such as synthetic rubber and different types of plastic materials.  It
is a benzene homologue with one unsaturated bond (C6H5 CH=CH2); it is a
                                     -110 -
-------
 colorless liquid having a characteristic odor, a specific weight of 104.14,  a
 b. p. of 146  ; it is soluble in water up to 0. 03% by weight.  Styrol is an un-
- saturated hydrocarbon which easily polymerizes and copolymerizes.  Accord-
 ing to reports found in the literature styrol,  a benzene homologue, belonged
 to the group of narcotic hydrocarbons which irritate the  respiratory passages.
 According to H. S. Faustova the concentration of a single styrol dose for
 rabbits was 0.62 mg/li,  and according to M. L0  Rylova  0.25-2 mg/li. Ac-
 cording to the latter author 0,02 mg/li was also the concentration of thres-
 hold mucous membrance irritating effect, while Li Shen (1961) established it
 at 0.00002 mg/li.

        The concentration of chronic styrol vapor effect was investigated by
 L. F. Larionov and E. I.  Nusel'man (1936),   They exposed white mice and  '
 rabbits to the inhalation of air containing 3-15 mg/li of styrol for 10-45 days.
 Records were kept of inhalation effect on the  cardiovascular  system, on the
 peripheral blood,  on the liver and kidney functions, and on the hemopoietic
 system.

        Results of M. L.  Rylova's tests with 3 mg/li of styrol showed a loss
 of resistance in rats to unfavorable environmental effects and a drop in
 physical work capacity in white mice.  Microscopic examination of the in-
 ternal organs showed the presence of abscesses and pneumonia in the  lungs,
 and of hyperplasia in  the spleen.  T. A. Blinova exposed rabbits to air con-
 taining 1 mg/li  of styrol vapor and detected changes in the peripheral blood.
 The chronic action of 2 mg/li styrol vapors (A.S, Faustova,  1961) elicited
 functional liver disturbance.  Spencer, Irish, Adams, (1942) of the  USA
 studied the lasting effects of different styrol vapor  concentrations on several
 animal species.  Most sensitive were Guinea pigs; inhalation of air contain-
 ing styrol vapor severely irritated the eyes, nose and mucous  membranes;
 the animals became sluggish, their fur became ruffled, and 10% of the ani-
 mals died. At  9. 3 mg/li styrol concentration the above condition became
 more aggravated.   Patho-morphologic liver  and kidney changes were found
 in guinea pigs which inhaled air containing 11.6 mg/li of styrol vapor.   The
 above presented literature survey clearly shows that all previous studies of
 styrol effect on the organism had been conducted with high concentrations.

        Reports found in the literature on the health of workers coming in
 contact with styrol vapor showed that inhalation of air containing 42. 5 mg/li
 of styrol vapor was harmful and even fatal.  (L/efaux, 1955).  The concentra-
 tion of 3.4 mg/li  produced irritation of the mucous  membranes of eyes and
 upper respiratory passages, apathy and somnolence (Carpenter,  1944).
 Workers temporarily exposed to the inhalation of 1. 85  - 2. 97 mg/li styrol
 concentrations developed signs of "styrol sickness", such as nausea,  gener-
 al weakness and  loss of appetite (Rodgers, 1955).  Barsotti and others found
 in 1952 that 0.8 mg/li of styrol applied externally produced skin irritation.

       In 1961 V.A. Pokrovskii examined 100 persons exposed  to the inhala-
-------
tion of air containing 0.6 mg/li of styrol vapor.  Clinical examinations dis-
closed functional central nervous system disturbance,  atrophic and  hyper-
trophic changes in the mucous membranes of the upper respiratory tracts,
changes in the genital system and in the blood.  Employees with long work
records in styrol  plants developed toxic hepatitis,  the  gravity of which be-
came intensified.  Development of pathological liver changes was also ob-
served  at 001 mg/li concentration (N.I. Shumskaya,  1956).

        Liver function disturbance and toxic hepatitis,  as a liver syndrome,
were found during the clinical observation in workers exposed to  the per-
missible maximal concentration or  close to it.  (E. I.  Drogichina,  1959).
Arterial pressure dropped to 100 mm, and below, in 33% of the examined
workerst  and the  gastric secretory  function was disturbed in some,  accom-
panied by complaints of dyspeptic disorders.  Blood changes appeared in the
form of moderate  leukopenia, lymphocytosis, and a type of thrombocytopenia
and reticulocytosis.   Results of the  clinical examinations  indicated that most
characteristic manifestations of styrol vapor effect resulted from its hepato»
tropic action, changes in the central nervous  system,  and in the blood and
the cardio-vascular  system.  Irritation of mucous  membranes of the eyes
and of the upper respiratory tract were caused by higher styrol in air con-
centrations.

        Results of  the above described investigations, particularly the clini-
cal examinations of workers exposed to the inhalation of low styrol vapor
concentrations prompted the present author to study the effect of  low styrol-
in- air  concentrations, notably those below the permissible  maximum con-
centration limit.   The studies were  centered on the block and emulsion poly-
styrol production, where styrol vapor was the predominant  harmful factor
in the surrounding atmosphere.  The studies had been  conducted for several
yearso  Results indicated that the stvrol vapor content in the air fluctuated
in the range  of thousandths  of milligrams in 1 m3, which is below  the per-
mitted maximum of 0005 mg/li.  Observations showed that styrol concentra-
tions during  the winter and  summer months of 1962 (about 1000 analyses)
ranged  in the block polystyrol production department from 00002  to 0.0093
mg/li and in the polystyrol  emulsion production department from 0. 0004 to
000068  mg/li.  Styrol vapor concentrations were equal to or exceeded the
0005 mg/li permitted maximal concentration in some air samples collected
in the polymerization sections during apparatus cleaning as  a prophylactic
inspection measure.

       Thus, the  above sanitary hygienic survey of the plant established that
styrol vapor concentrations in the air of the working premises were below
the~oT05~mg/li adopted maximum.   In this connection a statistical study  was
made of morbidity types which occurred among the workers of the entire
plant and loss of work time. Some  of the data are  listed in the Table below,
which show  highest  morbidity in hepatic  and gall bladder  diseases.  Half of
the workers  in the block and emulsion polystyrene  production department

                                   - 112 -
-------
 lnd«x«3 of Liver and Gal I Bladder Ducts Morbidity
             (Fora 3-1)
                                       complained .of frequent headaches, sub-
                                       costal pains on the right side (38%),
                                       irritation of the mucous membranes  of
                                       the upper respiratory tract (dryness,
                                       rasping feeling, aches  - 44%), pains
                                       in the heart region (21%), and in the
                                       epigastric region (19. 5%).  Arterial
                                       blood pressure determined in non-se-
                                       lected workers (20 from the  block and
                                       20 from the emulsion polystyrol de-
                                       partments) was as follows: the pres-
 sure level fell in workers connected with the polystyrene emulsion  produc-
 ti'&i from 105/65. 7 to 93/57.5 mm, (Fig. 1).  It  returned to normal during
 off days.  No such arterial blood changes were noted in workers  of the con-
 trol group,  according to E.  A. Kapkaev,  Relative peripheral blood albumin
 fell below the normal level in some workers of long contact with  styrol vapor.
 Thus,  characteristic changes appeared in employees of long contact with low
 styrol vapor concentrations, indicating that the concentrations of styrol va-
, pors occurring in the investigated industry unfavorably affected the workers'
 health.
•».' '/ :
'"' . !' . :~V
' J •*': '' .'
•*/•
'in the pi art t generally „
. in polystyrol block
' production ......
In *au)Sloh poly styrol
". " -?i •*
Morbidity por 100
1959
1,7
6,7
2,9
I960
2,7
9,7
6,4
1961
2,1
7,5
5,5
Fig. 1.
           I	  )
           Days
                              The above conclusion had to be confirmed ex-
                           perimentally. Accordingly, toxicological tests
                           had been conducted with two groups of white rats.
                           Rats of the first group were exposed to the inhala-
                           tion of styrol vapor concentrations averaging 0.049
                           mg/li. within the range of 0.046 to 0.070 mg/li.
                           Rats of group 2 were exposed to the inhalation of
                           styrol vapor ranging between 0.004-0.0072 mg/li,
                           with an average  of 0.0055 mg/li.  The two experi-
                           mental and control groups consisted of 15 rats
                           each.   The rats  were exposed to the styrol vapor
  -=r-.—-;	, .     .     ,  ~in 100 liter chambers  5 hours daily for 6 months.
  Blood praasure in workers produc-                                  '
                           Effect of styrol vapor inhalation on  the rats was
                           determined by examining changes brought about
                           in the following indexes:  glycogenic function,
                           changes in blood serum albumin fractions, patho-
 anatomic changes, states of cardiovascular and nerve  systems, changes in
 body weight, weight ratio of body organs, rate of coproporphyrine elimina-'
 tion with the urine, and histology of post-mortem internal organs.   No signi-
 ficant changes were noted in the  animals' behavior during the exposure to
 styi?ol inhalation.  Hyperemia of the nasal and eye mucous membranes de-
 veloped in rats of group 1 during the early days of exposure to styrol vapor
 inhalation;  rats of group 2 became sluggish towards the end of the experi-
 metit&l styrol vapor inhalation; epidermal and subcutaneous abscesses de-
                                     - 113 -
   ing poly«tyrol

 2 I
-------
Jfltftop 60
 veloped in 5 rats of the first group, toward the end of the exposure.  The
 wounds healed slowly, pointing to lowered resistance.  Dynamics of the
 weight Increase in rats of the first and second group remained unaffected
 and unchanged.

        The effect of 0. 05 mg/li styrol vapor inhalation on the glycogenic
 liver function of rats was studied next.  Quantitative liver glycogen deter-
 minations were made in the experimental rats at the end of the styrol vapor
 inhalation, and 30-60 days of the recovery period,,   Results showed that the
 initial 20  32% of glycogen was reduced to 0,82% after the period of styrol va-
 por inhalation.    Return of glycogen to its original normal levels occurred
 at the end of two months,  amounting to 2. 52% in the test rats and to 2. 62%
 in the control animals (Fig, 2).

                           Blood serum albumin fractions were determined
                       monthly by the  method of paper electrophoresis.  Re-
                       sults showed a  relative  albumin decrease and a cor-
                       responding globulin increase in rats of groups 1 and
                       2 on the third month of exposure.   Peripheral  blood
                       albumin fell at the end of the inhalation exposure
                       period from 410 8  to 310 7% in rats of group 1, and
                       from 39»5 to 33.2% in rats of group 2, while it rose
                       to higher levels in the control rats. Results of serum
                       globulin fraction analysis presented no clearcut
                       change regularity except for a relatively persistent
                       increase in the y-globulin in rats of groups 1 and 2.
                       One  month after the end of exposure to styrol vapor
                       inhalation the relative blood albumin fraction return-
                       ed to its  original  level in rats of group 1.  Macro-
                       scopically, the liver in  rats  of group 1 appeared
                       flabby and of yellowish-brown color,,  The micro-
scopical examination disclosed turbid edema, granularity, and vacuolization.
Similar, although less pronounced changes appeared in rats of group 2.  Au-
topsy examinations performed at the end  of the experimental styrol vapor in-
halation showed increased weight and enlargement of the liver.  Thus, the
study indicated that the chronic effect of low styrol vapor concentrations pro-
duced toxic changes of pathologic character in the experimental rats as de-
scribed in the preceding paragraphs.

        Effect of styrol vapor inhalation on the activity of the central ner-
 vous system was determined by the chronaximetric method establishing the
 rheobase  and the chronaxy ratio of the right hind leg muscle antagonists be-
 fore and after styrol vapor inhalation.  Rheobase changes  presented no con-
 sistently  regular pattern.  Changes in the chronaxy  ratios of the muscle an-
 tagonists  appeared to be  of a compensatory character and occurred at the
 same time without substantial difference.  Before exposure and  during the
 first t&iree exposure months chronaxy fluctuated between 0.08 and 0.09

80 3.0
a
.0
i>^'
!>
-------
rn/sec.  in rats of all groups.   Chronaxy ratio changes were most pronounced
ill" ratlS* of group 1.  Beginning with the third exposure  month occasional rats
of this "group manifested delayed chronaxy,  while in all other rats such mani-
festations appeared during the 5th-6th month, reaching average values of 0.21
*- 0.22 trf/sec.  Delayed chronaxy was manifested occasionally among rats of
group 2  on the 5th and 6th month of exposure, attaining a maximum value of
0.15 fh/sec.
Fig. 3.
    Effect of styrol vapor inhalation on
the vascular system was determined
from records made of arterial blood
pressure, before,  during and  after rats'
exposure. Arterial pressure  began to
drop one  month after the start of the ex-
posure in animals of the first  group and
decreased from an average of 99 to 69
mm.  Blood pressure continued  to drop
sharply during the  months following.
The blood pressure began to fall later
in rats of group 2,  and the drops were
less pronounced.  Return to normal
blood pressure proceeded slowly in
rats of group 1 and 2, reaching their
initial normal values at the end of  the
second month of the recovery period.
             liv.r change* in \he r»t»
                                        Rate of coproporphyrin elimination
                                    with the urine was determined in 5 rats
of each group.  Daily urinary voidings of each of 5 rats were collected and
the coproporphyrin extracted by the Fisher method and determined spectro-
photortetrically.  Accumulated data were irregular and of inconclusive char-
acter. . - Histologic examinations of internal organs of both test group rats
disclosed pathologic liver and spleen changes such as hyperplasia and lym-
phoid folliculitis.  Thus, results of clinical examinations of plant workers
and results of experimental animal tests verified the previously expressed
assumption that the officially adopted maximal permissible styrol  vapor con-
centration was too high and should be revised downward.

                                Conclusions

       1.  Statistical comparative  evaluation of morbidity and work time loss
records  of workers employed in plants producing polystyrol disclosed high
rates of liver and  gall bladder morbidity,  fall in arterial  blood pressure and
a variety of complaints characteristic of systemic intoxication with styrol
vapor.  Since the  prevailing styrol vapor  concentration in the air of the  plant
was ~ be low the permitted 0.5 mg/H concentration, it was assumed that  the
official limit was  set too high.          .  '
    -•
        '
-------
        2o  Chronic experiments with animals exposed to the inhalation of
 0005 mg/li of styrol  vapor impaired the glycogenic liver function, the liver
 parenchyma and brought about many other pathologic functional and  morpho-
 logic changes in the experimental animals.  Some of the pathologic changes
 were reversible, others were permanent,,

        3o  Results of tests performed with rats indicated that 0.005 mg/li of
 styrol vapor concentration constituted its  threshold of harmful effect for rats,

        It is recommended that 00 005 mg/li of styrol vapor be adopted as the
 maximal permissible concentration in the air of working premises.

                                  Bibliography
                   ea T. A., Pujioaa M. Jl. B, KH.: MarepHajibi no TOKCHKO.IOPHH eeiuecTB,
                   B npoHSBOflCTBe tuiacTHiecKHx Mace H CHHTCTHiecKHx KayqyKOB. 71., 1957,
         crp. 6. — .UporH i HHa 3. H. H ap.  PHP.  tpyfla,  1959, J* 3, crp. 10. — Jl a p H o-
         H o B Jl. 0. B KH.: SKcnepmueHTajibHue Hcc^eAOBaHHn no npOMuuiJieHHUM naaM. Jl., 1936,
         crp. 104.—H yce/ibwaH 3. H. IBM xce, crp. 95.—IT o KJ> o B c K H A B. A. Fur. rpyaa,
         1S81, JV& 5. CTp. 3. — PuflOBa  M.  Jl. TUT. H cau., 1955, J* 5, cip. 2\. — Tapa-
         A H H H. H., K y 3 H e u o B a B. H. B KH.:  Bonpocu cepflewHo-cocyflHCTofl naro^orHH,  FH-
         rweHw rpyAa H  npocjjsaeo.'ieBaHHft.  Boponew,  1957,  crp. 15.— a y c T o B A. C. TeaHCW
         noun. BoponewcK. (pHflHajia nayMHoro o-aa rHPHeHHCTOB H caHHrapnux apaieft, 1961, B. I,
         CTp_ 6. — 111 y M c K a H H. H. TesHChi O.OKJI. KOHt^epenuHH MO^oaux naymiux paSorHHKOB
         MH-TS rHrHCHH rpyaa H npoeccHOHa,/ibHHX aa6o^eBanHfl AMH CCCP. M., 19"6 ctp. 37.—
         Barsotti  M.,  Parmeggiani  L.,  Sassi C.,  Med. d. Lavoro,  U52, v.  43,
         p. 418.—Carpenter C.  P., Shaffer  C. B., Weil C. S.  et al., J. industr. Hyg.,
         1944, v. 26, p. 69. —Lef aux R., Arch. Mai. prof.,  1955, v. 16, p. 554.— Rogers J. C.
         et at., Arch, industr.  Hlth, 1955, v. 12, p.  470.—Spencer  H. C., Irish D.  D.
         A d a m s E. M. et al., J. industr. Hyg., 1942, v. 24, p. 295.
            A Photoelectrometric Method for the Determination
                    of Low 3, 4-Benzpyrene Concentrations
                                    pp. 47-49

            P. A.  Krotkov, N_ N. Serzhantova and V, B.  Timofeev
      (From  the Ukrainian Research Institute of Community Hygiene).
        The report published by P.P. Dikun in 1961 contains a quantitative
spectrophotometric method for the  determination of low 3, 4-benzpyrene con-
centrations.  The sensitivity of the method makes possible the determination
of 10  jj, of 3, 4-benzpyrene in 1 ml of solution.  The quantitative analytical
procedure  previously recommended by the same author which was based on
fluorescent 3, 4-benzpyrene spectra at  low temperatures  and on the use of a
photometer as described by F.  Weigart in 1934; V. K0  Prokof'ev,  1951;  by
that procedure 1,12-benzperylene was used as the inside standard.  The
spectra were recorded  photographically.  The present authors increase the
method sensitivity  and rapidity by  recording  spectral intensities, photo-
                                        -  116" -
-------
 electrically.  The plan of the photoelectric spectrometer is schematically
 presented in Fig. 1.


      *• .    x        .                   The outlet aperture was placed in
                                      the focal plan  of the camera objective.
                                      The photoelectronic multiplier FEU -19
                                      (N.O. Checkik and co-workers, 1954),
                                      served as the receiver of light.  The
                                      photoelectric multiplier was fed by the
                                      electronic stabilizer of the type "Orekh".
                                      The photo multiplier signal  was conveyed
                                      to the entrance of the amplifier of the
                                      direct current.  A micro-roentgeno-
            _________ _______  meter of the  type "Kaktus", having the
6*slc pi**.3 of t'h« photoelectric s^ectrophotooato r  sensitivity of 3. 10"1 2 amps (division at
                                      WMch the ionization Camber receded)
                                      861™1 aS ^  intensifier'  while the  siS-
           |ji pUced tho tube containing  tho  na^ was conveyed on the screen of the
           '* '»lz- b««P*nrl«=n« MIHOI 4 -  double electrometric lamp  2E2P.  The
             !•«««, S - Sfwctrogreph I6P-5I      ...            ,.     , ,.    .    ,
           e»»er»                       continuous recording of the signal was
carried out by the self-recording electronic potentiometer.  The shifting of
the spectrum was accomplished with  the help of the mechanical revolving of
the little prismatic tube of the spectrograph,  syncronously with  the unrolling
of the potentiometer roller.

        Fig. 2 shows the  recording of the fluorescence spectrum of the  solu-
tion of 0,1 microgram per ml 3, 4-benzpyr ene andl microgram per  ml 1,12-
benzperylene in  n-hexane in the spectral intervals of 4000-4100  A.   The solu-
tion was frozen in liquid nitrogen.
   »nt».
 .
pro i««ti«a
•ith • 270 a*
Fig. 2.
            w
          __ t__.
F li»«r«sc«i>e«-«p«cTra I
    ina 6f'« Soln.'to
            irt
of
•i» «t
                        The maximum X2 = 4060 A the line of the 1,12 benz-
                     perylene.  The recorded response corresponds to the
                     spectral slit width of 1, 9 A.   The spectrum in question
                     is slightly altered by the spreading of the spectral sensi-
                     tivity of the photomultiplier.  The  spectrum of the same
                     solution, together with the recording of the spectral sen-
                     sitivity of the photomultiplier is shown in Fig. 3.  The
                     computations show that the recording of the  spectral ac-
                     tivity deforms the curve represented in Fig.  2  with-
                     in 4-5%, because the registered spectral section is
                     rather narrow.  Hence, in the farther measurements,
                     the selectivity of the spectral sensitivity of the photo-
                     multiplier can be henceforth neglected.

                         The  determination of the 3, 4-benzpyrene is carried
                     out from the comparison of intensities in the maxium of
                     the line  Xi = 4021 A  of the  3,4-benzpyrene and X2 = 4060
                                      -'117 -
-------
A of the 1,12-benzperylene (see Fig.  2).  The reading of the intensity in the
maximum of the line of the 3, 4-benzpyrene J3>4 is made from the short wave
ground of the intensity, which depends  on the spectral width of the slit.  To
determine accurately the intensity of the line of the 1,12 benzperylene,  it  is
necessary to consider the contribution  given by the fluorescency of the  3,4-
benzpyrene under the maximum X3 = 4060 A of the 1,12-benzperylene (see
Fig0 3).  The carried out measurements of the fluorescence spectrum of
the pure 3, 4-benzpyrene, frozen at 77°  K,  in concentrations from 3 to  0.01
7/ml showed that this contribution amounts to 11% of the intensity maximum
Xi = 4021 A at the spectral width of the slit of 1. 9 A0  Its magnitude changes
slightly with the change of the spectral width.
Fig0 3.
             MS
 Floerooeoroeo opoctiruo of
 oolatoen ceatainong 00t V/al
 e? 3(>'5-&c3Bpyroao end 0,1
  Y/al e? bonspoey I ono0 tak-
 ing apoetrol photoool t ipl ooc
. oosiootow 6 ty onto ceneodora-
 tocTto  Cifoloo indicate dio-
 tfobutSeiv ef tho f laopooconco
 opoctira!
                             For determination of unknown concentrations of
                          the 3, 4-benzpyrene, it is necessary to know in
                          advance the intensities J3  4  and Ji>ls of the fluor-
                          escence line Xi = 4021 A of the 3, 4-benzpyrene, and
                          X3 = 4060 A of the 1,12-benzperlene, reduced to the
                          unit of  concentrationso  For  this purpose measure-
                          ments were carried out at wide intervals of concen-
                          trations of 3, 4-benzpyrene and 1,12-benzperylene
                          (between 10 and 0.005 -y/ml.) The results are con-
                          tained in the table.   See next page for table.

                             The data in the table show that at the  indicated
                         interval of concentrations we do not encounter any
                         concentration extinguishing of the fluorescence.
                         Therefore,  the intensity of the fluorescence of the
                         3, 4-benzpyrene and 1,12-benzperylene is propor-
                         tional with the respective concentrations.
        intonoity ©f 3^-
         ot raoninal 1 jno A2
                             The relation of the intensities J3)4/Ji 13 of the
                         photometrically measured  fluorescence lines of the
                         3, 4-benzpyrene and 1,12-benzperylene was found to
                         be 4.55 for equal concentrations.  The obtained re-
sult agrees with the data of the photographical method of P.P. Dikun (1961).

       To determine the unknown concentration of Cx of the 3, 4 benzpyrene
at known content Ci 13 benzperylene in a solution,  it is necessary to measure
the intensities J3 4 and Ji  i2 of the respective  lines Xi = 4021 A and X2 =
4060 A.  Then the  sought for concentration of the 3,4 benzpyrene can be com-
puted from the relation
                            i.i2
                           4,55
                                                "3-4
                                                7
                                                 1.12
        The sensitivity of the photoelectric method was  equal to 5.10

                                      - 118 -
                                                                    ,-io
-------
    l.  1?he accuracy of the analysis is not less than 12%.
             Determination results of mhnosn 3p|i-bonzpynsne concentrations
Con ens. of
3$ 6-eSz-
Con ens. of
1,12-
>enzpery-
|n " YA»t (10" 9/"0
iA
' 2:,
-' . 2 L<
••• ' 2-
2
0,5
0,5
. 0,5
0 c;
01
0 1
0,1


1
2
4
.10
0,5
. 1
2,5
10
n i
0,2
0,5


Max. fluorescence
intensity ratios
of photometric
(See note be loo)
4,4:1
4,5:1
4,0:1
4,2:1
4,0:1
4,0:1
4,1:1
4 *}• !
50. i
5 O'l
5,0:1


Ccncns. of Can ens. of M-JU f,uoresceBee
38<« bonz- 1.12- i . . ., < .
pyrOTO bon^ryJ "»*«»'t» f.tios
C, . leneCi,i2 1 of photometric














On Y/°l (10~ 9/Ql) (See note be lo«
0,1
0,01
0,01
0,01
0,01
0,005
0,001

1,0
0,01
0,02
0,05
0,1
0,01
0,005

Avo. intensity ra-
tios of oa«. flu-.
ofascant IgneSo
I §@s noto bol®^j

5,1:1 >.
4,0:1.
5,0:1
5,1:1
4,9:1,
4,1:1
5,9:1





4,55:1
Hotel  oh tn« basis of  30ll-bcnzpyrene and
(This note was introduced
                                            P2 banazpery lene unit concentrations.
                            by QO t© cut tho earns openO ing  insortoons shorter  BSL)
                                    Bibliography
            BeflrepT .  OnrHiecKHe MeTo.au B XHMHII. Jl.,  1933. — Zl H K y H  H. Fl Bonp
        OHKOJI., 1961, ^f9 7, cip. 42.— On >K e. Taw we, 1955, M> 4, crp.  34; Nt 5, cip. 24.—
        JlyKbanoB  C.  K). oiorpa-
        
-------
computed by subtracting results of the second determination from the results
of the first determination.

       For this purpose O. D.  Khalizova and L0 S0  Chemodanova (1953)  de-
veloped a method by which the bases are absorbed by a sulfuric acid solution,
then broken down by the Kjeldahl method, and the formed ammonia deter-
mined colorimetrically by the Nessler method.  E. A. Peregud and B. S.
Boikina in 1954 and L<» A0 Mokhov and B.  A.  Malyshkin in 1959 proposed titri-
metric methods, based on the binding of amines by a standard solution of sul-
furic acid, and the excess of  the latter determined by idometric or alkaline
solution titration, using a suitable indicator.

       Picric acid has been proposed for the colorimetric determination of
amines in biological products by Richter in 1941, Dyer in 1945 and in sewage
by Yuo Yu0  Lure in 1961.  Other nitro-compounds have been used for this
purpose by Inekova in 1954, Mathewson in 1955,  and others.  The present
author studied different indicators,  including tri-, di-, and mononitrophenols.
Best results were obtained with o-nitrophenol, which has been recommended
for the determination of total aliphatic amines in air0  The method is simple
and highly sensitive,,   Aqueous  solution of o-nitrophenol in 0.1% has a narrow
absorption band and a maximum at 420 mn.  In the presence  of amines the
maximum shifts in the direction of the longer waves.  The spectral character-
istics are represented in Fig. 1.  In making colorimetric determinations it
was found advantageous to select a light filter having a narrow transmission
band at 440-450 m(j, to avoid large loss of light as the result of light absorp-
tion by the nitrophenol solution. Use distilled water in making the absorp-
tive solution,  since mono-, di,  and trimethyl and ethyl amines contained in
the air are easily absorbed by water. Tests made with three amines and
ammonia established that o-nitrophenol formed colors of same optical den-
sity with solutions of the investigated bases in equal molecular concentrations.
Therefore, in analyzing a mixture of lower amines,  their total  molar quan-
tity can be determined, regardless of their composition (See Fig.' 2,  curve 1).
For Figs. 1 and 2 see next page.

       Since O-nitrophenol is the indicator,  the presence of acid gases and
vapors and also of ammonia,  interferes with the analysis. Acidic impuri-
ties can be eliminated by aspirating the  test air through ascarite or a 5-30%
alkaline solution.  It  was experimentally established that aliphatic  amines
passed through these absorbents quantitatively.   Absorbents,  such as soda
lime, KhPI,  or  barium hydroxide cannot be  used in this case, since they ad-
sorbed microquantities of amines.

       Ammonia is determined in parallel samples by the Nessler method
and the results obtained subtracted from the  results of the total determina-
tion.  Aromatic amines do not interfere with the determination.

       The optical sensitivity of o-nitrophenol reaction with the bases is only

                                    - 120 -
-------
 negligibly affected by changes in its  concentration within the limits of 0.1 and
 0.25%,  and only slightly by temperature,  differing  in this  respect from
 many other indicators which  change  color upon reaction with amines, includ-
 ing pTnit'rophenol.' The o-nitrophenol solution is stable.   It reacts with bases
 instantaneously and the formed color does not change with time.
         Fig.  1.
  Fig.  2.
                             X m|J.
          Spectral characteristics
         T3f.fjr solution of o-nitro-
         phvnol in I «2j I »3, li^p 185
         ratios in relation to eatar -
         Solutions of o-oi trophenol
         derivatives in relation to o-
         riitrophonol  at layer thictj-
         no»» of 50 oil, oero as fol-
         io«Si 2 - lOM-M/lij 3-20
         .M- fe/li;  l» - 50 |i bl/li| 5 -
         IOO^U/1 i
                                      Quantity ef ooinp in sample in
                                              Co Iibrotad curves
I  — CffilororaotHc dotorooaQt6tcn of araoont* and aaines
in tho e-mtrofthcinel oolutocn using FEC-H-57 at 50 a*
layer thicbnoss tnd oith Hjht filter 3j 2 - colori-
raotroc Qinioonoa dotoroonatien aith the M«asler-Fo! in
reagent uoong c«>l oroBotof FEC-8-67e  at 50 ma layer
tMeitnoss  end uoirag light filter 3j circular black
diocs - ooncoothylooona, square black disn* - di-
BothYlaninOj tiriongular black discs -  triMthy l«
-------
2) 0.1% solution of O-nitrophenol prepared at 40-50° with intermittent stir-
ring; 3)  Nessler-Folin solution, prepared from potassium iodide, iodine,
mercury, and alkali^as described by D. T. You in 1935;  4)  standard  001
millimolar (O.ljj, mole/ml) solutions of aliphatic  amine and ammonia,  pre-
pared by hundredfold dilution of 0.01 M stock solutions,  using ammonia -free
water;  check by titrating 100 ml of the 0001 M amine solution with a standard
001N HC1 solution using methyl red as the indicator; 5)  ascarite granular 2-4
mm in diameter.

       Photoelectrocolorimeter FEK-N-57 was used in  performing the anal-
ysis. Determinations were made using light filter 3, having a narrow trans-
mission band and a maximum at 453 m|j,.  Now proceed as follows;  set up
a series of 16 photo colorimetric cups 30  mm high.  Place into the first cup
0. 5 ml of the 0.1 millimolar amine solution, 1. 0 ml into the second cup,  1. 5
into the third cup; continue to progressively increase the values until cup 16
will contain 8.0 ml;  add ammonia-free distilled water to the first 15 cups to
make a volume of 8.0 ml.  Add 4 ml of 001% standard o-nitrophenol solu-
tion to all 16 cups and shake gently,,  Make colorimetric  determinations and
plot the results as shown in the curve of Fig. 2.

       Set up another series of 16 colorimetric  cups 30  mm high; place into
the first tube 1.0 ml of the  0.1 millimolar ammonia solution; continue to  pro-
gressively increase the volume by 1. 0 ml until cup 16 will contain 16  ml  of
the standard ammonia solution.  Add  ammonia-free water to the first 15 cups
to make a volume of 16 ml; add 4 ml of Nessler-Folin reagent; make colori-
metric determinations and  plot results as shown in curve 2, Fig. 2.

       Make air  tests as follows: aspirate 2-5  li of the  air  successively
through  a 5  ml U-shaped tube filled with  ascarite and through a coiled ab-
sorber containing 40  ml of  ammonia-free  water, or through two successive-
ly connected Richter  absorbers, each containing 16 ml of ammonia-free dis-
tilled water.  Pour the contents  of the coil or Richter absorbers into  a glass
flasko  Remove 8  ml  of the water from the flask, place into  a colorimetric
cup, add 4 ml of the Nessler-Folin reagent and proceed as above described.

       On the basis of the optical density data,  and with the aid of the stan-
dard curve,  and of Formula 1 compute the total  concentration (Ctot> )  of the
amines and ammonia in the air in moles  per liter.   Take 16 ml of the
sample and place  into a colorimetric  cup,  add 4 ml of the Nessler-Folin re-
agent; make  colorimetric determination; on the  basis of the  data and with the
aid of the corresponding  standard curve compute ammonia concentration
      ); in moles  per  liter,  using the same formula.
where (a)~ denotes M. moles of total bases in terms of ammonia found by using
curve 1 or 2 corresponding to optical density data; (b)  denotes ml of volume
-------
of solution in the absorbers (in the given case 40 or 32 ml);  (d) denotes ml
of the sample taken for colorimetric determination (in this case 8 ml for the
total bases and 16 ml for the ammonia);  (V )*" denotes li of air aspirated
through the absorbers, reduced to standard temperature and pressure.

        Concentration of amines in the air was computed on the basis  of to-
tal bases minus ammonia concentration,, To convert ml to li of a given amine
multiply by M/1000, where M is the molecular weight of the given amine.

                      C    .   = (C    -  C ___ ..   M/1000 mg/li
                       amine     tot    NH3)    '       &

        The value of M/1000, in the case of methyl amine is 0. 031; for di-
methyl or ethyl amine it is 00045,  and  for triethyl amine, 0.101.  The method
is accurate to 0.02 p- mole in the colorimetrically analyzed volume; for
methyl amines  and ethyl amine it corresponds to about ly,  for di- and tri -
ethylamine 2y,  and for ammonia 0.4Y per sample volume.

        The method was applied in practice and yielded satisfactory results
in determining  content of aliphatic  amines in the air of working premises and
in experimental animal exposure chambers.

                                Bibliography
            BopoK M. T. B KH.: ABTOiaaTHiecKHe  raaoaHajmsaTopu. M.,  1961,  cip. 307.—
        BropoB B. F., KajiMaHOBCKHft B. H. Tanc we, cip. 325. — Fl o y R. P. OOTOMCT-
        pHieCKHft XHMHMeCKHJ) 3H3.1H3. M., 1935, T. 1, CTp. 469. — MOXOB  JI. A., M 3 JI bl Ul-
        K H H B. A. THF. H can., 1959, Ni 9, crp. 82. — Fl e p e r y n E. A., B o ft K H H a B. C. B KH..
        Pei|>epaTbi Haymtux paCox HayMHO-Hccnefl HH-TB nirneHbi tpyaa H npo3a6o;ieBaHHft 33
        1953 r. HmpopMauHOHHbift 6K>nae-reHb. Jl., 1954, crp. 213. — X a a H 3 o B a O. fl., Hi M o-
        .naHOBa JI. C. THF. H can., 1953, K° 4, crp. 51.                        ~^
            The Accuracy of a Colorimetric Method for Determining
                   Toxic Dinitrophenols in Biological Matter
                                  pp.  53 - 58

                              G.A. Khokhol'kova
                      Candidate of Biological Sciences
        (Kiev Institute of Industrial Hygiene  and Occupational Diseases)
        The use of dinitrophenol (DNP), dinitro-o-cresol (DNOC), dinitro-
sec-butylphenol (DNSBP), and dinitro-iso-propylphenol (DNPP) in agricul-
ture  as insecticides and herbicides is progressively increasing.   These
preparations are highly toxic  to man and farm animals, and continuous con-
tact with them can induce acute and chronic poisoning.  Therefore, a method
had to be developed for the detection of dinitrophenols  in biological specimens.

                                    - 123 -
-------
Such a method must be highly sensitive, satisfactorily reproducible and easy
to perform. In this connection the present author examined the following re-
actions:

       !„  Anger's  drop reaction for nitrobenzene derivatives (I960).  The
authors  stated that 2, 4-dinitrophenol also produced this reaction.  Tests
were made to determine the possibility of applying this method to a study of
the toxicity of dinitro derivatives,particularly DNP and of DNOC.   A blue
color appeared as soon as diphenylbenzidine was dissolved in 80% sulphuric
acid; the color disappeared during  subsequent stages of the  reaction and  did
not reappear upon boiling even in the presence of large amounts of tested
substances.

       2o  Meyer's reaction (L. Devern,.  1934)  was modified and described
by Petrascu and Grou in 1955.  Check tests made by the present author show-
ed that this reaction gave positive  results only in the presence of 50\i/g  or
more»  Therefore,  this reaction was also unsuitable for the purpose.

       30  Lead dichloride reaction (L. Deverri,   1934)  This reaction was
tested with all four  preparations.  Its sensitivity was very low,,  A faint,
yellowish color appeared in the test tube in the presence of  20^/g or more
of the preparation,  which was not sensitive enough for the purpose.
         j
       40  In 1956 Zeumer described the Yanovskii and Bose methods for
the  determination of dinitro -compounds 0  A check of these methods showed
that only Bose's  reaction yielded positive results in the presence  of 100 to
500 jJ,/g of the toxic  preparations.   Yanovskii's reaction failed to produce
colored solutions even with 100|J./g of the preparations.  Therefore, these
methods  were not suitable for the determination  of dinitrophenols  in biologi-
cal  specimens.

Table 1.
            Eatonctoen of OMPh0 DROC0 OtJSBPh erad DWPPh solutions Jn 3 ol of tha
                       toot oooplo of dotffoPOBt  |J,g cent ant


M>8 of tho
subs tan co

0,5
1,0
2,5
5,0
10,0
12,5
15,0
20,0
25,0
50,0
Extinction E
SuJjetoneo

OKPh
0,002
0,005
0,015
0,035
0,067
0,080
0,092
0,120
0,140
0,237

DMOC
0,002
0,005
0,010
0,020
0,037
0,046
0,053
0,069
0,088
0,152

DHSBPJ*
0,001
0,007
0,015
0,030
0,055
0,071
0,084
0,108
0,138
0,244

DMPPJi
0,002
0,006
0,010
0.020
0,042
0,053
0,063
0,080
0,097
0,157
                                  - 124 -
-------
        5.  Parker's method for the determination of DNOC in urine  (1949).
 This method was described by M.P. Slyussar and I.E. Kogan in 1958.

        6.  Harvey (1952) developed a method for the determination of DNOC
 in 6.1 ml:'of blood serum.  This method was based on the principle of Par-
 ker's method.  Drops of finger blood were collected in a weighted 5-10 ml cen-
 trifuge tube equipped with a ground- to- fit stopper containing an anticoagu-
 laiit. -Th^fe centrifuge tube was then weighed  again.  Blood traces  on the cen-
 trifuge tube'walls were  washed down by a  piece of filter paper saturated with,
 a 1% physiological  solution. The filter paper was then placed into the  centri-
 fuge'tube containing  the blood,  and 2 ml of methyl ethyl ketone  and an  excess
 of physiological solution added.  The entire  contents was shaken well for
 five minutes.  The methyl  ethyl ketone extract  turned yellow in the presence
 of DNOC in the blood serum.  Other steps of the investigation  were carried
 out by means of a spectrophotometer.

        The aim of the study was:  1) to investigate the possibility of using
 the Harvey method for the  determination of DNP, DNOC, DNSBP,  and DNPP
 in biological specimens; 2) to find optimum conditions for the determination
 of the above-mentioned substances in urine, feces, blood serum and internal
 organs  and tissues; and 3)  to determine the sensitivity and accuracy of the
 proposed method.  Results of check tests showed that the reaction could be
 used in determining toxic dinitrophenols in biological specimens.  The accur-
 acy  of the Harvey method was  determined by introducing known quantitites of
 DNP, DNOC, DNSBP,   and DNPP  into specimens of urine, feces,  blood serum,
 and  internal organs and tissue.

        Determinations in urine: Use 3 ml of the urine; add 50  ^/g of the
 test substance, 1 g anhydrous sodium sulfate, and 3 ml of methyl ethyl ketone.
 Shake the contents  vigorously and centrifuge  for 10-15 minutes.    Examine
 the upper yellow colored methyl ethyl ketone  layer for color intensity using a
 photoelectrocolorimeter.  Evaluate the concentration of DNP, DNOC,  DNSBP,
 or DNPP with the aid of a calibrated curve, previously plotted  as follows:
 let the abscissa represent p. of the preparation per unit volume  of the urine,
 and  the   ordinate the solution extinction (E)  as  shown in Table  1.

        Sensitivity of the method is 0.001 mg  per sample volume.   Curve in
 the figure below exemplifies the procedure used in constructing a calibrated
 curve for the determination of dinitrophenol in urine.  Calibrated curves for
the determination of  other dinitrophenolic derivatives in biological specimens
are constructed similarly.   The figure is on the following page.

       Accuracy of the method was checked by introducing known quantities
of  DNP, DNOC, DNSBP, and DNPP into urine specimens.  Results were pro-
cessed  statistically by the M. L, Belen'ki method and expressed in percent.
Data in Table 2 show the accuracy  to which DNP can be determined in  urine.
The  accuracy of the method for other dinitrophenol derivatives  is  as follows:
-------
  Qtff-

110,0
83,7
86,0
86,0
83,7
100,0
86,2
96,0
94,2
97,0
69,2
74,6
82,0
76,4
1225,0

A'



n=14;
X=87,5












"X-X

+22,5
-3,8
— 1,5
— 1.5
—3,8
+ 12,5
—1,3
+8,5
+6.7
+9,5
— 18,3
—12,9
—5,5
— 11.1


(X-A)'

506,30
14,44
2,25
2,25
14,44
156,30
1,69
72,25
44,89
90,25
334,90
166,40
30,25
123,20
1559,81
       The accuracy of the method was determined as follows:  50)0. of a
dinitro derivative was added to a fecal specimen, and completness of it's
extraction by methyl ethyl ketone was determined.  Accuracy of the method
for DNP is 84. 6±7.12%, for DNOC- 92. 0±5. 92% for DNSBP-  92. 0±5. 54% and
for DNPP- 101.0±4.22%, per specimen before making corrections.  However,
corrections based on control tests were necessary, since some fecal control
specimens were  of a slight yellow color.

Determination in blood serum.  Add the test substance to 0«1 ml of blood
serum,  add 0. 1 g anhydrous NagSC^ ,  and 0.2 ml methyl ethyl ketone.  Shake
for 10 - 15 min. ,  and centrifuge.  Wash sediment with  0.1 ml methyl ethyl
ketone and centrifuge   three times.  Determine the concentration of the toxic
                                    - 126 -
-------
derivatives vising a calibrated curve constructed as usual and a photoelectro-
colb'ri fneter.  Data in Table 3 show that the method sensitivity was  0.0005
mg for DNP, DNOC,  and DNSBP,  and O. 002 mg for DNPP in 0.1 ml blood se-
rum.
                   S=
                   S= ±
1559-81 = ±V 120,0= ± 10,95;
  13
       » f\ f\f
              ± 2,39;
                                   3,742

                                  X~ = 87,5 ± 2,93.
Table 3.
            Extinction road in 3 3 of DNPhp DP30C,, OtdSBPhp and DtdPPh solutions of
            blood serura ooaplas having different CCT contra to en a of the substances
                                     Extinction E

A noun t
in M-9
0,5
1,0
1,5
2,0
2,5
5,0
7,5
10,0
12,5
Substoraeo
• DNPh"
0,007
0,010
0,012
0,013
0,015
0,025
0,032
0,041
0,050
oMc
0,003
0,005
0,007
0,008
0,010
0,018
0,025
0,033
0,040
Ot3S8?h
0,004
0,006
6,0085
0,009
0,010
0,015
0,020
0,028
0,030
OK?Ph
0,003
0,003
0,003
0,005
0,007
0,010
0,0125
0,018
0,020
        Accuracy of the method was determined by adding 12. 5 or 25p. of test
 derivative to the blood serum specimen.  Statistical data processing showed
 the following degrees of the method sensitivity: for DNP-  77.6 ± 3.16%; for
 DNOC - 70. 8 ± 3. 82%; for DNSBP  - 61. 6 ± 2. 58%; and for DNPP - 77. 6 ±
 5.15%, per blood serum specimen.

 Determination in internal organs.  To a weighed amount of tissue or organ
 add an equal amount by weight of anhydrous Na2SO4 and grind to complete
 homogeneity.  Place 2 g of the homogenate into a test tube; add the dinitro
 derivative,  followed by the addition of 0.4 ml of methyl ethyl ketone, ex,-
 tract for 10-15 min. and separate by centrifuging the sediment 4-5 times with
 0.2 ml of methyl ethyl ketone. Determine the concentration  of the test sub-
 stance in the supernatant methyl ethyl ketone,  using a photoelectrocolori-
 meter and a calibrated curve  constructed on the basis of data in Table 4.

        Data in Table 4 show that the method sensitivity in  the case of in-
< '       '     ,                        - 127 -
-------
internal organs was 0,0005 mg for all four dinitro substances.

Table 4.
            EntoncUon of DHPh0 DMOC0 DKSB«tp end OHPPSi oelutftcao depending upon
                         cencontpotjsn in Sfltoraal ergons
                 of
                                       Extinction E
                                        Swbotanco
oobotanco
0,5
1.0
1,5
2,0
2,5
5,0
10,0
20,0
50,0
DfOPh
0,004
0,006
0,008
0,010
0,012
0,022
0,040
0,070
0.152
DBOC
0,005
0,007
0,009
0,010
0,011
0,014
0,020
0,040
0.095
DKSBPh
0,002
0,0025
0,0045
0,007
0,012
0,016
0,026
0,046
0,095
DCOPPh
0,003
0,005
0,008
0,009
0,010-
0,016
0,021
0,032
0,060
        Data in Table 5 show that contents of any dinitroderivative  in internal
organs and tissues can be determined accurately.  It was previously shown
that this was equally true of dinitroderivatives in urine,  feces, and in blood
serum.

Table 5.
         Accuracy ef aothod for tho dotoraonaUen of Of3Php DMOCB DMSBPhB and DMHPh
                              in internal organ toocaos
                                                     of aothod
	 	
• TJoouo ©P ©pgon





MOQPt 0000000,00000

QoOaOOO oooooooooooo

SefbstancQ

OMPh
72,3+4,52
75,4+4,67
82,1+6,04
78,9+4,78
84,8+5,82
69,8+4,44
84,7+6,90
82,2+6.15

ONQC
95,1+2,74
90,7+1,87
97,0+2,72
93,1+2,54
92,8+3,24
95,5+2,30
94,1+2,89
94,8+3,69

ONSBPh
74,6+4,55
73,9+4,08
83,8+3,37
72,0+5,59
78,5+4,38
72,3+4,58
82,2+4,63
70,3+5.90

DNPPh
88,4+5,17
82,6+4,99
91,5+2,41
85,4+5.37
83,6+6,28
81.4+4,49
88,8+4.59'
85,9+4,48
                                  Conclusions

           The sensitivity and accuracy of the proposed method for the de-
             of toxic dinitrophenol derivatives in biological substrate had been
           Accuracy of the proposed method for the determination of DNP,

                                      - 128 -
-------
 DNOC,  DNSBP,  and DNPP in living organisms ranged between 0. 005 and
 0.002 mg per specimen, which is considered high,

        3.  Accuracy of the proposed method for the determination of dinitro-
 'derivatives  ranged between 6L 6 ±  2. 58% and 95, 5 ± 2. 3%.
   "*      :           «
*  •  ,                            Bibliography
              Ee.ieni. KHH M. Jl. S^eineHTbi KOJiHiecTBeHHofi OUCHKH  c a p b M. n., Koran H. B. KoJiHMecTBeHHoe onpe^e-
          .temu' ,iHHHTpoopTOKpe30;ia B B034yxc H 6Ho^orHMecKHx cyficrparax.  XapbKOB, 1958. —
          Anir« r V., Mikrochim. Acta. 1960, N 1, p. 58. — I d e m, Ibid., 1960, N  5—6, p. 827.—
          Harvey D.  G.,  Lancet, 1952, v. 1, p. 796. — P a r k e r V. H., Analyst, 1949, v. 74,
          p  M6. - P e t r a s c u  S., G r o u E., An. Inst. Cerec. agron., 1955,  T.  22, crp. 509.—
          7 .-urner H., Zr. ahaiyt. Chem., 1956, Bd. 148, S. 403.
                     Mine Waters Use for Dust Abatement
                                   pp» 91-94

                         M. A. Frolov and R. I.  Frolova
                   From the Novocherkask Polytechnic Institute
        Data available regarding the water resources and water supplies in the
Novoshakhtinsk administrative region of the Rostov oblast, where the mines
of coal trust "Nesvetal-Antratzit" are located, suggest that in approaching
the problem of dust abastement in the mines, the possibility of utilizing the
mine waters  should be given first consideration, provided  that such mine
water can satisfy some important technological and sanitary basic require-
ments.  In this connection the Novocherkask Polytechnic Institute investi-
gated the conditions under which  the dust  was generated in the mines  and the
type of dust and character of the  mine waters in  the Institute's Ventilation
and Mine Dust Laboratory.  First under investigation were the V.I. L/enin,
A.M.  Gbr'kii and No. 5 mines, where the problem of dust abatement was
most acute.  The cleaning and preparatory faces in these  mines had no pro-
visions for dust abatement,  and the dust density  in the air  was frequently
between 10 and  100  times  in excess of the  permissible maximum.  The i
coal vein of the  mines is  only 0.55-0065 m wide; therefore, in working
it, it became necessary to break up,  load and deliver to the surface a consid-
erable  amount  of surrounding rocks, of which approximately  75% are sand-
stones and aleurites, which  contain 20-70% of free silicon  dioxide.  It was
hoped that results of analyses of  the V.I.  Lenin, A.M.  Gor'kii and No. 5
mine waters could  serve  as  reasonable bases for the judgment of  water
quality of other Nesvetaev region mines of considerably heavier coal veins .

       It was mentioned above  that only water which fulfils certain sanitary

                                     - 129 -
-------
and technological requirements should be used in dust abatement.  The
technological requirements pertain to qualitative indexes which might af-
fect the dust catching capacity of the water and also the water distribution
system,  such, for instance, as the presence of mechanically suspended
matter, hardness, etc.  The sanitary requirements pertain to  such qualita-
tive indexes  as pollution which may be harmful to health, or factors which
may unfavorably affect the atmosphere in mine shafts  and mining spaces;
the pollution may be  of a bacteriological,  toxicological,  or organoleptic
character, especially in relation to odor.  Mechanical suspensions in the
water are regarded as an  obstacle, since they can cause  clogging and ob-
structions in the spraying system and in the water flow regulating device.
It was  also noted that certain types of particles suspended in rapidly flow-
ing water had abrasive  effects on the distribution system pipes and their
fittings.  Data presented by N,!, Kurenkov indicated that suspended parti-
cles of less than 0,05 (J. in diameter had no destructive effect on the water
distribution system,  nor did they cause sediment deposits or clogging of
even small orifices through which  the water passed, as,  for instance, in
the case of spraying  or sprinkling  equipment. In accordance with Kurenkov's
observations, it is recommended that the presence in  water  used for dust
abatement of suspended particles the diameters  of which  exceeded 0.15 p>
should be regarded as undesirable  and prohibited.

       Water hardness had no substantial effect on its dust abating proper-
ties, however, the use  of  such water for dust abatement should be restricted
in the presence of certain wetting agents,,  It is recommended that in the
presence of iron compounds  in the  water, its pH should be kept within the
6,0-8,5 range,, if it is to be  used for mine dust abating purposes by sending
it through the mine water pipes and into the spray distribution  system; it is
also recommended that the water Fe concentration should not exceed 1 mg/li.
Careful determinations should be made of the free silicon dioxide in the
mineral sediment of the water, and its content should  be  taken into considera-
tion in regulating the water quality with respect  to its  suspended mineral
matter content in order to avoid erroneous conclusions.   For example,  the
temporary directives applicable to humidification of underground working
spaces issued in 1952 specified unconditionally that the water used for mine
dust abatement must  contain not more than 50 mg/li of suspended mineral
matter] actually this  limitation should be instituted only for water the  miner-
al suspended matter of which contained 10% of free silicon dioxide; for
waters in which the silicon dioxide content is below 10% the above specified
limitation is  excessive.  This statement is verified as follows:  the maximal
mineral suspended matter in water used for dust abatement can be  deter-
mined by the following expression:


                         n = 1000 ptq  mg/li

where   p  represents the permissible sanitary  norm  of mine  atmosphere
           dust density in mg/m3	
                                  - 130 -
-------
       q   represents the maximal permissible content of atomized
           water in the mine air in ml/m3


       As a. rule the .value of (q) never exceeds 40 ml/m  ; actually under
present'conditions   of mine  air humidification the value of (q) is below
12 ml/m3.  Assuming that (q) had the value of 40 ml/m3 substitute for (p)
and (q) in the above expression their values, find that the permissible norm
of suspended mineral matter in the  above cases could be assumed equal to
250 fng/ii.  Accordingly, depending upon the percent of free silicon dioxide
contained iTn the water-suspended mineral matter two limiting suspended
matter norms .should be set, one at 50 and one at 250 mg/li.  The need for
limiting the wate.r bacterial  density in such cases is self evident.  And yet,
even in this respect the existing sanitary specifications were also excessive.
According to the same 1952 temporary directive not more than one E. coli
organism pe'r 300 ml must be present in the water used for underground dust
abatement.

       Determination of the  mine water quality in places -where the coal vein
iz was being worked was based on the following indexes:  1)  the water pH;
2) mg/li  of mechanical suspended matter;  3) mg/li of suspended mineral
matter;  4) % of free silicon dioxide in the  suspended mineral matter; 5) per-
cent of fractions with diameter greater than 0.05 M-,as determined by the
Sobanin method,  and 6) Fe3  and H2S content in  mg/li.  Water samples for
the above enumerated  determinations  had been collected in the spring season
from central and gradient water collecting points, and from  troughs which
delivered water to  points of  drift mining.  In addition, summer pH deter-
minations were made of the  A.M0 Gor'kii and No. 5 mines.  Results showed
that the summer pH ranged between 6.4-6.8 and the winter pH between
6. 6-8. 7 H3S traces were found in isolated  samples of water  collected from
the A.M.  Gor'kii mine.  Data related to the mechanical water  suspended
matter are presented in the table.  See Table next page.  Records  of the
Sanitary-Epidemiological Station showed that the bacterial pollution of the
mine waters was on the  level of river Don pollution during the summer months.

       The  present authors concluded that mine waters having up to 250 mg/
li of suspended mineral  matter and a coli titre  of 0,1 could be used for the
purpose of mine dust abatement.

                               Bibliography
                     K y p e H K o B H. H. PacMet UIBXTHUX
                     peaepeyapOB H BOAOc6opHHKo&
                                  - 131 -
-------
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                               NO. 6, JUNE
       Experimental Data as a Basis for the Determination of Maximal
              Permissible Toluylene Diisocyanate Concentration
                             in Atmospheric Air
                                 ppo 8-15

                              V. Ao Chizhikov
     (From the Department of Community Hygiene,  the Central Institute
                        of Post Graduate Medicine)
        Toluylene diisocyanate has the chemical formula of CH3CSH3(NCO)
                                                                       o
                                                                        2 •
It is a light yellowish fluid having a sharp unpleasant odor, a b. p. of 246
and solidified at 4-6 . It is used as raw material in the manufacture of
polyurethane foam-like plastic materials.  It is synthesized by interaction
between toluylene-diamine dissolved in chlorobenzene and phosgene.  Most
frequently used in the national economy and in industry is  a mixture of  2,4
and 2,6 isomeres of toluylene diisocyanate known abroad as "desmodur T".
Industrial plans which use  or produce toluylene diisocyanate may become
sources of atmospheric air pollution with this compound.  Little information
has been found in  the literature concerning the toxicity of toluylene diiso-
cyanate, and practically no information was  found regarding  it as an air
pollutant or its effect on the human and animal organisms  in low concentra-
tions.  Acute toluylene diisocyanate poisoning has been encountered and
described by several investigators as an irritant of the conjunctiva and
mucosa  of the  upper respiratory tract.  Toxic effects of the preparation
have been described as cumulative.  Some authors believed that toluylene
diisocyanate possessed active allergic properties.

       Tests for the determination of toluylene diisocyanate concentrations
in the air had been conducted by the present  author by the  method described
by  Tubina in I960, and modified by M.  V. Alekseeva of the F.  F. Erisman
Institute.  Sensitivity of the method is  2 H in the studied sample volume.   The
method is based on interaction between toluylene diisocyanate  with sodium
nitrate.   In the presence of toluylene diisocyanate,  a dark-orange color
appears which reached maximum intensity in 60 minutes,  and  persisted for
another 60 minutes.  Acute affect of this produc-t in low concentrations on the
human organism was studied beginning with the concentration of threshold
odor perception.   Zapp found that  0.4 ppm  in the air, or its equivalent 2. 8
mg/m   was the concentration of toluylene diisocyanate odor perception
threshold.  The present author conducted experimental toluylene diisocyan-
ate threshold odor determinations according to the procedure recommended
by the Committee  for the Sanitary Protection of Atmospheric Air.    Three -
hundred ninety-five  (395) determinations have been made with  13 different
toluylene diisocyanate concentrations.  Results presented in Table 1 show

                                   - 133 -
-------
that 0. 2 mg/m3 was the concentration of minimal perception  for most odor
sensitive individuals,  and 0015  mg/m  was the maximal nonperceptible tol-
uylene diisocyanate concentration.
Table 1.
 Doternjnat Sen of toluy lonodi i oocyonato
              odor poircoptoen
Mesiios- of
"ftk-flo0**

2
3
3
5
5
2
11
tig/a of ttoo subotaneo
U to Soot
COTOOptHbllo
0,2
0,3
0,35
0,45
0,6
1,0
2,6
daaooal ncn-
poireoptSblo
0,15
0,2
0,3
0.35
0.45
0.6
2,0
    The next step in this study was to deter-
mine the effect of low toluylene diisocyanate
concentrations on electric brain activity.
This was done with the aid of an 8-lead Kai-
ser electroencephalograph by the usual pro-
cedure employed in electroencephalography
and adapted to the study of maximal  permissi-
ble concentrations  of harmful substances in
atmospheric air.
                                  The procedure is briefly as follows:
                              An electroencephalographic record is made
of the test individual's  response to rhythmic stimulation with light; the elec-
troencephalographic record thus produced enables the investigator to study
the  character of the tested person's  adaptation to the stimulating light rhythm
during the entire experiment.  Several control experiments are made  first
with the person inhaling clean air; then,  without the test person's awareness
"known~coneentrations  of the pollutant are introduced into the inhaled air
and experimental encephalographic records made with the different  concen-
tration of the pollutant.  Results of such tests made with toluylene diisocyan-
ate  are shown in Table 2.   Data in Table 2 show that 5 minutes inhalation of
low toluylene diisocyanate concentrations affected the electric  brain activity
of different individuals differently.  Thus, in the case of female A. I.  statis-
tically significant changes in the electrocencephalogram were obtained only
upon the  inhalation of air containing 0.2  mg/m3  of the tested pollutant, as
shown in Fig. 1. In the case of 2 other test individuals  the concentration was
Ool5 mg/m3,  and for 2 others it was 0.10 mg/m3. It  should also be noted
that in the experiments here described,  changes in adaptation to the rhythm
of light stimulation extended in the direction of increased and decreased
adaptation rhythm amplitudes.  0,2  mg/m3 toluylene diisocyanate concen-
tration depressed the brain electric activity in every  case, while in 001
mg/m3 concentration  most test persons  manifested a brief rise in the  adopt-
ed rhythm amplitude,  followed by a  depression.  Each test individual was
given to inhale toluylene diisocyanate in  4 different concentrations,  making
a total of 100  experimental tests.  All concentrations were below the thres-
hold of toluylene diisocyanate odor perception.   Based on the results of
this investigation the present author proposes  0.05 mg/m3 of toluylene
diisocyanate  as its maximal permissible single concentration in atmospheric
air.   The maximal permissible 24 hour toluylene diisocyanate concentra-
tion in atmospheric air under chronic experimental conditions was determined
by exposing white rats to the toluylene diisocyanate containing air daily for
24 hours.  Sixty male rats weighing 110^13Q_ g were divided into 4 groups of
                                    - 134 -
-------
15 specimens.  Rats of group No. 1 inhaled air containing 2 mg/m3,  rats of
group No. 2-0.2 mg/m3,  and rats of group No. 3 - 0.02 mg/m3  of the
toluylene diisocyanate, while rats of Group No.  4 served as controls.  Checks
for the  toluylene diisocyanate concentrations in the exposure chambers were
made 3-4 times daily in exposure Chamber No.  1,  and 1-2 times daily in
Chambers Nos. 2  and  3.  The average toluylene diisocyanate concentration
was 1. 951± 0.223 mg/ma in Chamber No.  lp  0.2036± 0.18 mg/ma in Chamber
No. 2,,and 0.0207± 0.038 mg/m3 in  Chamber No. 3.    Chronic experiments
under conditions described extended over 84 days.  Evaluation of effects
was based on changes  noted in the behavior of the animals,  their general
state of well being, favorable or unfavorable changes in body weight,  changes
in muscle-antagonists  motor  chronaxy, cholinesterase activity, blood serum
protein  composition,  and in rats of coproporphyrin elimination with the
urine.
Table 2
         Determination of tofu/lenedfisoeyanato
         threshold effect on olactrical braon
                    activity
           Nuaber
Mg/a  of the compound
tost
Persons
2
2
t
£1 iciting
activity
changes
0,10
0,15
0,20
El letting no
changes
0.05
0.10
0,15
Fig. 1.
          Experiment duration in ninutos1
           in the established amplitude rhytho
     in teat persona. A. I. upon  inhalation of
     different t luy Idi ieocyanate concentrations
     I -response reaction - pure air» 2 -ditto
     0.05 «a/«V33- 0.10 ng/«3l *» - 0.15 Bg/a3|
     B cyanate vapor adwinietration
    Results of chronic toluylene
diisocyanate exposure experiments
showed that the general condition,
appearance and weight of rats be-
longing to group 1 have been unfavor-
ably affected.  Rats of Groups 2 and
3 behaved and appeared like the  con-
trol group rats.   Rats belonging to
Group 1,  which inhaled air contain-
ing an average of 1. 951 mg/m3 of
toluylene diisocyanate manifested
changes in their general behavior
beginning with the first few days  of
inhalation;  the rats were restless,
irritable, and showed signs  of nasal
mucous  membrane  irritation.  The
negative  signs abated after  a few
days.  However,  the signs  reappear-
ed in a more aggravated form after
the second half of the inhalation  ex-
posure.   The rats became sluggish,
indifferent to food,  and consumed
less of it.  Their nasal mucosa and
conjunctiva were  irritated,  the fur
became  shaggy,  and one of  the rats
died before the termination of the
experimental period. Resistance to
experimental starvation became con-
siderably reduced in rats of group 1
which inhaled air containing 2 mg/m"
of the pollutant.   (Fig. 2).
                                     - 135 -
-------
        Many authors believed that motor chronaxy size depended upon the
state of the cortical regulatory function and that chronaxy changes served as
an objective and sensitive indicator of functional disturbance in the central
nervous system;  among such investigators are Yu.  M. Uflan'd (1941), A.N.
Magnitskii (1934), A.F,, Makarchenko (1952) and many others.  This served
as a basis for the application of this method in many toxic or dynamic in-
vestigations.  Accordingly,  study was made of  hind leg muscle antagonist
motor chronaxy of 5 rats  in each group, once every 10 days, at the same
hours  of the day,  and  under similar experimental conditions.    Results in-
dicated that rats of group 1 showed reverse muscle antagonist chronaxy  ra-
tios  at the end of the first month,,  Similar manifestations appeared in rats
of Group 3 later in the inhalation exposure.  Return of normal muscle  an-
tagonist chronaxy ratio  appeared during the recovery period first in rats of
Group 2o    No statistically  significant or reliable changes  in the motor
chronaxy ratio had been noted in rats of Group 3 and in the control rats.
All results were statistically processed and found reliable.

        Cholinesterase activity was determined by the method described by
A. A. Pokrovskii in 1953 and revised by A, P. Martynova in  1957.  The method
is based on determination of time required for the hydrolysis of added acetyl-
choline, which changed the medium pH, as shown  by color  changes in the ex-
perimental test  tubes.  Such tests had been conducted at 15 day intervals.
Animals of Group 1, which inhaled air containing 2 mg/m of toluylene diiso-
cyanate, showed35-40% increase in Cholinesterase activity.   Cholinesterase
activity of rats belonging to Group 2  increased to a lesser extent.  In both
groups  the Cholinesterase activity levels rapidly returned to normal. (Fig. 3).

        Many authors  noted that animals exposed to the chronic effects of
some harmful substances developed changes in protein metabolism, as in-
dicated by lowered albumin concentration and increased concentrations in the
blood serum globulin fractions.  This was particularly true  of animals which
had been exposed to the chronic effect of low furfural concentrations.  There-
fore, studies had been conducted by the method of electrophoresis to deter-
mine what effect,  if any,  toluylene diisocyanate had  on the blood serum pro-
tein picture in 5 rats  of each group.  This was done  at 20 day intervals.   No
changes had been detected in the blood serum protein concentration of any
rat during the entire observation period.  Because of the highly dispersed
character of the values obtained, the data had been processed statistically
in a preliminary manner; the results confirmed the validity of the above re-
corded impression.  Data in Table 3 show that albumin fractions showed
greatest changes; this was followed by changes in  P-globulins.  No changes
of any kind had been noted in the Y-globulin fractions.  Changes in the  above
indicated protein metabolism phases of the rats were most expressed in
animals of Group 1, and less so in rats of Group 2.  The protein metabolism
picture of rats belonging to Group  3 was practically the same as of rats be-
longing to the control group.  Maximal changes in the different phases of pro-
tein metabolism appeared at the end of the exposure period,  the levels of
•which persisted throughout the recovery period.
                                    - 136 -
-------
 Fig. 2.
Fig.  3.
               _..
              D»tes of weighing
  Otngee in *ni««l mights in tha couroo ef chs-e!»5o
   expoaur* to to Ivy I d i i eocy anate
  I -  Aniftala of Group Ij 2 - Group 2} 3 - Grcq? 3j
  l» -Control| 5 - Exposure
              Do tea. of eeighing
 Effect of toluy Idioaocvonato on blood chol in-
 ooterasa activity of the rats .
 I - Rats of Group 15 2 - Group 2j  3 - Group 3j
 4 — Control group
 Table 3
         Blood «*ru» protein fractions of changes of rats oapesod to tho effect of toluyl-
,- 	
Blood protein
fraction
Tooo of Dotoraifioticn
1 	
A Ibunins
0! -Global ins
fuGlobul ins

Y-Globulins
















Aniaal Group
Ona
40,83
32,11
34,75
18,45
21,16
20,30
24,81
29,11
27,97
16,10
18.0
16,95
T»o
40,83
36,69
39,25
18,45
17,46
21,80
24.81
27,47
24,65
16.10
18,41
14.28
Three
40,83
37,14
38,38
18,45
18.84
18,11
24,81
26,22
26.0
16,10
17,77
17,45
Control
40,83
39,19
38,40
18.45
19.67
18,16
24,81
26.0
27,80
16,10
15,0
15.60
        Tests were  then conducted to determine possible changes in  copro-
porphyrin elimination with the urine.  The mechanism by which harmful sub-
stances affected the rate of  coproporphyrin elimination under conditions of
chronic experiment had not been clearly understood.  Many suggestions have
been offered in the  way of explanation,  but none has been verified.  In the
present study, 5 rats of each group had been set aside for the coproporphyrin
elimination investigation.  Tests were  made with 24 hour urine specimens of
                                       - 137 -
-------
rats which were kept in cages specially constructed for the collection of
urine0  Porphyrin had been extracted from the urine by the Fisher method;
qualitative and quantitative determinations of coproporphyrin were made
spectrophotometrically in the region of 400-410 m^i wave length,,
Beginning with the  fourth week of experimental inhalation exposure,  the
rate of coproporphyrin  elimination with the urine increased in  rats of Group
Ij this increase persisted throughout the entire exposure period, and return-
ed to normal only at the end of the  recovery period. Slight, but statistically
significant changes  in the rate of coproporphyrin elimination with the urine
had been noted in rats of Group 2.  However, enhanced levels of copropor-
phyrin elimination  with the urine noted in rats of Group 2, rapidly returned
to normal, as shown in Fig. 4,  No statistically significant changes in the
rate of coproporphyrin elimination with the urine had been noted in rats of
Group 3o
Fig. 4o
       _/	£ 3  6_ S  ff  T B __ ^	# //
        T8oo of oapoHoont on ten-da/s	
 Efffooft of toO«jy I Jndoicesyanato ea tho rato of
            Q| ioSftottOT aith tteo uc-Sno ©f
       onpofooontal  d»6to pa4o
 - Rato of fit-cap 10 2 - Group 20 3 -
 -Central) oroaoR CesregetTjEtwfira otooinQtod pop
      In sumrtiary,  it can be stated that
  continuous chronic exposure of white
  rats to the effects of toluylene diisocynate
  of 2»0 and 0.2 mg/m3  concentrations  for
  84 days elicited toxic symptoms  in the ,
  experimental animals, such as loss of
  body weight, increase  in cholinesterase
  activity, changes in muscle antagonists
  .motor chronaxy ratios,   changes in some
  phases of protein metabolism,  and in  the
  rate of porphyrin elimination via the
  urine.  As previously  mentioned, no such
  changes occurred in experimental rats
  which chronically inhaled toluylene diiso-
  cyanate in 0. 02 mg/m3 concentration.
  Accordingly,  the  present author  recom-
  mends  that 0,02 mg/m3  of the air pollu-
3? tant be accepted as its maximal permis-
  sible average 24 hour  concentration in at-
  mospheric air.
       In the next step of the investigation the present author attempted to
obtain a general  picture of existing atmospheric air pollution with toluylene
diisocyanate.   This was done in the vicinity  of a plant which used toluylene
diisocyanate as the  raw product in its manufacturing processes.  The investi-
gation was conducted in September,  1962 when 107 single test air  samples had
been collected.   The plant around which the studies had been conducted lack-
ed  the necessary purification installations,  and all harmful side  products
had been discharged into the atmosphere without preliminary purification.
The plant operated in two shifts, and  was organized so that the final product
had been completed during the  first  shift, whereas the second shift made all
necessary preparatory operations.    Data in Table 4 show that toluylene
                                    - 138 -
-------
 diisocyanate concentrations in the atmospheric air surrounding the plant
 under investigation became rapidly dispersed, reducing the pollutant con-
 centration as it floated away from the plant in the higher atmospheric layers,
 so that  300 m from the plant the  concentration of this air pollutant did not
 exceed the maximal single average 24 hour permissible concentration.  It
 must be noted, however,  that under different  conditions of technology or
 different arrangements in the working shifts,  and especially with an increase
 in the production volume, the situation may change, so that the density of
 air pollution with toluylene diisocyanate may rise to levels exceeding the one
 just indicated.  It is suggested that the investigated plant should be surround-
 ed by a sanitary clearance zone the width of which should be determined on
 the basis of dominant and important factors.

        Table 4.
Atmospheric air peHutien aith
                                              o iseeyonato


en
0 f.
«. o a
i. S.
ggs
•H 'O

* a
75
200
300
No. of coliactod
Air oaaplao
Soap 1 OQ
	 	
Total



25
50
32

above
netted
oenoo-
tiwity
18
22
1
Ceneontratoien
on Dg/o^
^

OnaoDQl



0,075
0,024
0,006

a '
a
e




—
—
Saopla ceacantratien distri-
butoen on ogfo^

Abevo
i 0.05



6
—
—


O.Oi-0,02



10
4



Bejloo 0.02



2
18
1
                                Conclusions

        1.  The concentration of toluylene diisocyanate threshold odor per-
 ception for most  sensitive persons was experimentally established as
 0.2 mg/m  and the maximal odor nonperceptible concentration was estab-
 lished at 0.15  mg/m3 .

        2.  The concentration of toluylene diisocyanate threshold effect on
 electric brain activity was established at 0.1 mg/m3, while 0.05 mg/m3
 concentration  elicited no changes  in the electric brain activity.

        3.  The maximal single permissible toluylene diisocyanate concen-
 tration in atmospheric air should  be set at  0. 05 mg/m3.

        4.  Exposure of white rats to the inhalation of air containing 2. 0 or
 0.2 mg/m3 of toluylene diisocyanate 24 hours daily for 84 days caused the
 animals to lose weight, brought about increased cholinesterase activity,
 changed muscle antagonists motor chronoxy, and disturbed the protein frac-
"tipn ratios, and the process of -porphyrin metabolism. In 0.02 mg/m3 con-
                                    -  139 -
-------
cenfcratioxip  toluylene diisocyanate had no observable unfavorable effects on
the organism of the exposed experimental rats0


        5o  Based on the results of the present investigation, it is recom-
mended that 0,02 mg/m3 be accepted as the maximal average 24 hour toluyl-
     diisocyanate concentration in atmospheric air,


                                    Bibliography
             KOUITOHHU X. C. MSB. AH CCCP. CepHH 6noji. nayx, 1945, Ns 2, crp.  170.—
         MarHHUKHft A. H. B KH.: CyCopAHHaitHH B HepsHofl cHCteMe H  ee anaieHHe B (pH3HO-
         norHH H namnorHH. M., 1948, crp. 5. — MaKapneHKo A. . Bpaq. aeJio, 1952, N° 5,
         cr6. 390. — MapruHOBa A. H  THC.  rpyaa,  1957,  N° 4,  crp. 23. — n o K p o B-
         cKHft  A. A. BoeH.-wefl. «., 1953, N°  9, crp. 61. — CnepaHCKHii P. H., FI p a T y c e-
         B H i IO. M., K o p w H. H. ROM. AH CCCP, 1960, T. 131, Mi 6, crp. 1472. — CypaaeA-
         KHHa  Jl. H. B KH.: C6opnHK TpyaoB ApxaureflbCK. nea. HH-ra, 1956, T. 14,  ctp. 78.—
         Ty6HHa A. H. B KH.:  Onpeae^eHHe epenHbix aemecTB B BO3ayxe npoHSBoaciBeHHux
         noMeuieHHft. FopbKHft, 1960, crp. 239.—V  n a H a K). M. TeopHa  H npaKTHKa xponaKcn-
         MetpHH. Jl.,  1941.—V 6a ft a.y n n a es P.  THP. H caH.,  1961, W» 7,  cip. 3. — Frie-
         bel H., Luchtrath  H., Arch. exp. Path. Pharmak., 1955,  Bd. 227, S. 93. —Gra-
         nati  A., Scavo D.,  Montervino  C., Folia med., 1956,  v.  39, p. 763. — H a-
         m a G., Arch,  industr.  Hlth. 1957,  v. 16.  p.  232.—J o h n s t on e Rutherford T..
         Industr. Med. Surg., 1957, v. 26, p.  33.—Rein 1 W., Zbl. Arbeitsmed., 1953,  Bd. 3,
         S.  103. — S w ens so n A., Holmquist C.—E., Lundgren  K.—D., Brit. J. indust.
         Med.,  1955, v.  12,  p. 50. —Zap p J. A., Jr., Arch, industr. Hlth, 1957,  v.  15, p.  324.
             Labor and Sanitary Health Conditions in Phthivazide
                           •  Manufacturing Plants
                                   pp. 24-28


                               Mo  Mo Ostrovskii
               (From the Department of Hygiene, the Leningrad
                       Chemo-Pharmaceutical Institute)
        Pharmaceutical products such as  PASC,  phthivazide,  metazide,
larusanp  and others are now being manufactured on a commercial scale.
Literature contains insufficient information regarding the processes used
in the production of anti-tuberculous pharmaceuticals, especially in rela-
tion to sanitary hygienic labor conditions.  In this paper, the author re-
ports  on  a study conducted in plants producing phthivazide with  special em-
phasis on sanitary-hygienic labor conditions.   The report presents observa-
tions made in a plant producing isonicotinic acid, which  is an intermediate
product of phthivazide manufacture,   Phthivazide results from the  reaction
of isonicotinic acid with thionyl chloride which  forms first chloranhydro-
isonicotinate hydrochloride  which is converted  into ethyl-nicotinate-hydro-
chloride; the reaction mass is neutralized by  an  alkaline solution,  which
yields amyl  nicotinate; from which hydrazide of isonicotinic acid is formed
upon the  addition of hydrazine hydrate,  Hydrazide of isonicotinic acid is

 I                                       - 140 -
-------
 used in the final synthesis of phthivaside.  The resulting mass is centri-
 fuged, desiccated, sifted and  filtered.  In the production of isonicotinic
 acid and phthivaside the air in the working  premises may become polluted
 with vapors of picolines and o~f hydrazine hydrate; in some cases the air
 may also contain nitrogenous gases, sulfur dioxide,  and fine particles of
 phthivaside and nicotinic acid.   Table 1 presents concentrations in which
 the above mentioned pollutants can be found in the surrounding air.   The
 method described by Dolgopolva and ogloblina in 1961 was used in this in-
 vestigation.  Picoline vapor was found in the air of the room  in which
 Y-methylolpicoline was synthesized from components of  P-picoline fractions
 used in the production of the intermediate products.   Results of 8 analyses
 showed the presence  of 0.012-0.032 mg/li of picoline, which is 2-6 times  in
 excess of the maximal allowable concentration of this substance, and in one
 instance the concentration was 0. 058 mg/li,  or 12 times  in excess of the
 maximal allowable concentration.  A thorough investigation disclosed that
 picoline vapor was generated where 3-picoline fraction ^components had been
 utilized in synthesizing the final product.  Employees working at such points
 complained of continuous coughing. To obtain some  relief the workers  open-
 ed the doors which helped to disseminate the harmful substance and disturbed
 the temperature and humidity conditions in the working premises, especially
 during the fall and winter months.

        Table 1.
             Concentrations of poicenouo 3ases> and »opora 5n the air of working premises
Harmful ccapononto

Hydrazine hydrate vapor . . . „ .


«r
•s. o
•1
o a
o a
& 0
10
19
24
20
Socploe
sithin
BflC
listts
0
0
17
17
Concentrations in wg/li
Baaioal
0,007
0,00016
0
0
Binim.l
0,058
0,008
0,03
0,06
MAC
0,005
0,0001
0,005
0,02
       Air pollution with hydrazine hydrate vapor was noted in the room
where hydrazide-nicotinate had been synthesized.  Analytical results in-
dicated that most air samples contained the hydrazine hydrate pollutant in
concentrations considerably exceeding the maximal permissible limits.
Further inspection showed that the technological organization of some interme-
diary production stages was faulty; it was equipped with leaky vapor con-
duits,  and constituted the main cause of surrounding air pollution with hydra-
zine'^hydrate vapor exceeding the maximal permissible concentration limit
10-25 times.  This was further aggravated by the fact that the  entire  «ystern
of hydrozideisonicotinate production  was antiquated and primitive.  Thin
was particularly true of the hydrazine-isonicotinate paste unloading which
was done  manually. This  was equally true of the paste  centrifugation.

       Nitrogenous gases were formed_as side products in the process of
                                     - 141 -
-------
Y-methylol picoline mixture oxidation which was done in a properly isolated
installation,,   Most of the generated nitrogenous gases were trapped by pass-
ing them through a special absorption installation and the nonabsorbed resi-
due was discharged into the atmosphere through a stack 50 m high, which
adequately dispersed the original pollutant gas concentration.  Chances for
vapor leakage into the atmospheric  air appeared during sample collection,
loading of the activated charcoal, etc.  Results of analyses established
that where such operations had been performed the nitrogenous gas concen-
tration  in the immediate air ranged between 0.01-0,03 mg/li, or 2-6 times
in excess of  the maximal permissible concentration.. Results of some analy-
ses showed nitrogenous  gas concentrations not exceeding the maximal per-
missible limit.  Sulfur dioxide was  generated during halogenation of the
isonicotinic acid with thionyl chloride and during the thionyl chloride hydroly-
sis.  It was present in  3 of 20 analyzed air samples in 0.03-0.06 mg/li, or
2-3 times in excess of the established norm. In all the instances observed,
sulfur dioxide leakage occurred through the aggitator vacuum boxes.   General-
ly speaking,  making the  production  techology leakproof had a favorable effect
and only on rare occasion was serious leakage noted.

        Air pollution with particulate matter was noted mostly during the final
stages of the antibiotic production.  Analytical results showed that the par-
ticulate_matter concentration in the  surrounding air ranged between 8.2-20
mg/ma  when the dry isonicotinic acid was poured from  the drying pans into
the collecting bags. Such a dust density prevailed only  during the pouring of
the final product which usually lasted between 15 to 20 minutes; when opera-
tion time was prolonged, the dust density in the air reached the concentration
of 7201  mg/m3.  Phthivaside dust concentration in the drying room air ranged
between 9,1-33.5  mg/m3, in the sifting room  between 5.1 and 60.1 mg/m3,
and in the packing room  between 7.8-37.5 mg/m  .   Highest phthivaside dust
concentrations were found in the air during manual unloading of the driers,
which usually lasted up to 30 minutes.   Other operations, although manually
performed, generated lower dust densities, probably due to the fact that the
final product under those conditions contained considerable moisture. Where
the open manual operations  were of very short duration,  phthivaside dust den-
sity in the air was also slight.  Phthivaside dust  of considerable density was
found in the room  of the  shaker sifters where its range  was 20.6-60.1 mg/m3.
The sifting operation in the  plant under investigation was done  manually in the
open.  In some instances the sifters were  jacketed.  This somewhat reduced
the phthivaside dust concentration in the air, but added  little  to the solution
of the basic problem.

        Effect of phthivaside and isonicotinic acid dust on mucosae of the  up-
per respiratory tract was studied next by examining some female employees
who worked in the drying and packing rooms.  Examinations consisted of an-
terior rhinoscopy, of the oral cavity,  of the glottis, and of laryngoscopy.
All workers were  tested for taste and odor acuity.  Results are shown in
Table 2.  Data in  that Table show that no hypertrophic changes of the nasal,
oral and throat  mucosa  had been noted in any of the examined workers; on
                                   ~~ - 142  -
-------
 the other hand, subatrophic rhinopharyngitis was found in practically all
 women who worked in the plant 3-6 years.  Six of the women workers had a
 lowered odor perception. The data here presented and discussed are not
 sufficient to warrant final conclusions, but they can be  used as orientation.
 values for more detailed future investigations.  Picoline and hydrazine hy-
 drate were the most  toxic of the vapors generated in the phthivaside produc-
 tion complex.   Picoline vapor toxicity is rated as high as that of pyridine
 vapor, and, as was indicated by M0 L. Rylov in 1951, it also unfavorably and
 irreversibly affected the central nervous system.  Hydrazine hydrate vapor
 produced anemia, hypocholesterolaemia and changes in the arterial blood
 pressure.   The vapor also caused inflamatory processes  in the conjunctiva
 and in the nasal pharyngeal  mucosa, and occasionally produced temporary
 blindness.  The above presented data and their discussion clearly point to
 the urgent need of adopting and introducing means of sanitization in the work-
 ing conditions of the  industry, aimed primarily at the prevention of air pollu-
 tion with picoline and hydrazine hydrate vapors.

        Table 2.
          Mucous aetabrana changes in the uppar respiratory and nasal passages of nonen
              working  in an ataosphere of phthivazide end nicitinic acid dust
->
Initials
Ch
t
I
B
(T
K
K
U
0
1
Ago
«6f-h
Record
Years
32
45
47
46
56
44
32
38
30
20
6
6
4
3
6
3
3
2
2
2
Nature of Duct

9 son 1 cot in tc
Acid Duet
'
Phthivaside .
duot
Uucous Moiabrane Changes
Mesa!
c
a
c
c
c
a
c
Pharyn-
geal
c
c
c
c
a
c
Laryn-
geal
c
c

Odor
Perception

Norn* 1
Hyposnia
»
Norwal
» »
Hyposnia
»
»
Barest
               _e±  a - «trophic changes  c - subatrophic changes
       In conclusion it is suggested that the crystalizer installations in the
hydrazide isonicotinic acid synthesis room should  be metallically encased
and connected by means of conduits to the local ventilation system.  It is
also suggested that the presently existing  general ventilation system be
thoroughly modified and improved to accord with the  latest principles of
modern type of industrial space ventilation.

       Repeated analyses had shown that hydrazine hydrate vapor concen-
trations in the air could be considerably reduced by improving the existing
system of local ventilation.  However,  such reduction still failed to  satisfy
the official standards of air condition in working premises.  Therefore,  it

                                    - 143  -
-------
is suggested that the following basic changes be instituted in the phthivaside
producing plant with undue delays  1.  Isolation and encasing of equipment
used in the utilization of P - picolinic fraction components used in the inter-
mediate steps of phthivaside production? ,   2, Installation of an interdepart-
mental pneumatic system for the distribution of isonicotinic acid and soda;
3o  Introduce the use of automatic  packaging machines in the final phthiva-
side production operations.

                                  Bibliography
              Be-nJiHHr  E. H., FlpeoGpaweHCKaR  A. A.  FHT. rpyaa,   19fti  Ns 8.
          CTp.  27.—Jlo.nrono.noBa B. 3., Or.no6.nHHa P.  H. B KH.:  C6opmiK nayMHt>ix
          pa6oT HH-TOB oxpamj TpyAa BUCOC.  M., 1961, Ns  1,  ctp. 103. — P bui o B a  M. J\.
          <&apM3Koji. H TOKCHKO^., 1950, Jft 3, cip. 20. — C o n o B b e B a T. B. B KH.: Onpeae^e-
          HHC  speaiibix Beiuecre B soaAyxe (noA peA. 0. fl. XajwaoBofl). M., 1957, crp. 89.—
          H.naTOBa B. C., M p 11\ B c K a a  A.  M., CM Hp HOBS B. P. B KH.: MarepHa/iu no
          BonpocaM THrHeHU rpyaa H MIIHHKH  ripocpeccHOHaflbHbix Oofle'sHeft. PopbKHfl, 1956, C6. 5.
          crp.  94. — 0 A P H T Jl., 0 r r B. XHMHH rHApaaHHa. M.,  1954. — T e m p s k i J>, 0 I s z e w-
          a k a Z., Przegl. derm. Wener., 1956, T. 6, crp. 29.
              Hygienic Aspects of Methylmercaptophos Spraying
                                 by Airplanes
                                   pp.  28-34

                              T. A. Asribekova
       (From the Government Research Institute of Civil Aeronautics)
        Mercaptophos, a highly toxic insecticide, has been used as a cotton
plant insecticide  spray since 1955»   In most instances the cotton crops have
been sprayed with mercaptophos  from the air by specially equipped air-
planes,  Mercaptophos is  a member of the phospho-organic group of com-
pounds which includes metaphos, thiophos,  carbophos, octametphyl, M-81,
M-82, phosphacol, acetylurate, and many, others.  According to some USSR
and foreign investigators mercaptophos is a neurotropic  poison which at-
tacked particularly the parasympathetic system. It was  hoped that  methyl-
mercaptophos would possess effective insecticide properties and lower the
general toxicity to man and animals; and, indeed, many investigators proved
that this was the  case.

        In 1961 the present author studied the hygienic aspects of crop spray-
ing with methylmercaptophos by means of specially equipped airplanes.  The
studies had  been conducted  during the  months of April and May, which is the
period of orchard spraying in the Crimean region,  and in July and August,
which is the cotton crop spraying time  in central Asia,  Methylmercapto-
phoss  similar to  mercaptophos,, is a mixture of two isomeres, - thionic
and thiolic,  the formulas of  which arenas follows.
                                      - 144 -
-------
                     CH,0    S
                        X
                     CH8O    OCH2CH2SC2H6    _,TKy«mic I
                     CH8O    O
                           //
                          P
                           <	 __
                     CHSO'    SCHzCHzSC-Hs     —'Thy Ionic iocosir


The technical concentrate of  methylmercaptophos is a light to dark-brown
fluid which emulsifies in water.  It contains 30% of the thiolic and thionic
isomeres and 70% of a surface  active substance  trade-named OP-7.  In the
process of isomerization the  thionic isomer becomes converted  to the more
toxic thiolic isomer; isomerization proceeds much faster in methylmercapto-
phos than in mercaptophos.  Temperature increase  and polar catalytic
agents markedly enhance the  rate of methylmercaptophos polymerization.
Methylmercaptophos concentrate is distributed by the chemical industry in
20 li containers.

       Methylmercaptophos crop spraying is done by airplanes An-2 and
Yak-12 and by helicopter Mi-I0   The airplanes  have been equipped with 2
types of spraying systems. In  system No. 1 the  spraying is done  with the
insecticide previously prepared for the  purpose.  In the second system in-
secticide mixture preparation and the spraying are done simultaneously in
the air.  Investigations made by the present author (1958-61) showed that the
second method of atomized spraying was  the more  sanitary and offered more
protection to the airplane and helicopter operating personnel.  Orchard and
cotton field spraying was  usually done during the morning hours of 6  - 9,
and in the evening during the hours  of 17-20, when the wind velocity was be-
low 4 m/second* The working emulsion  contained  002-0.3% of active methyl-
mercaptophos and was  applied at the rate of 100 li  per hectare,  or the equi-
valent of 700-1000 g of the methylmercaptophos per  ha.  The airplane and
helicopter tanks were  filled with the spray material by motor driven pumps.
Other tank filling operations were done  manually in the airplanes and in the
helicopters.    (See  Fig.  l)

     .  Flights over the sections to  be sprayed extended between 5 to 15
minutes, depending  upon  the distance from the aerodrum to the field to be
sprayed.  All personnel which participated in  the crop  spraying had been
supplied with means for protection against spray inhalation; however, only
the laborers made complete use of such protection  equipment (see Fig.  2).
Pilots and aviation technical personnel did not take advantage of the protec-
tion facilities  because such equipment has been designed without taking into
consideration specific work conditions.   The rubber gloves were crudely
designed and were too large.    They lacked elasticity, and could not be used
in finer operations usually performed by pilots and technical aviation per-
sonnel.   Respirator F-46 was poorly designed and  markedly reduced the
pilot's field of vision.  Technicians and manual workers were in contact with
                                     - 145 -
-------
the insecticide most intimately and for longer time in the course of a work
day.  Methylmercaptophos could enter the workers1 system through inhala-
tion or through skin absorption.  The  same routes of the insecticide  entrance
into the organism applied to the pilots, though to a lesser degree.

Fie
* •*• b • *•
                                 .  .  '   ••  %   ;:
                                     .  '
             Filling the •t«tion«ry (fi»*d) »pr«y  tank of *«ropl»r»«
                           ••thy(••rcaptopho*  Mid. »«t«r
                                                                              .
Fig. 2.                                Determinations had been made also
                               	   of the methylmercaptophos vapor con-
                                    centrations in the air of the airplane and
                                    helicopter cabins and in the air surround-
                                    ing other technical aero workers.  One
                                    hundred and eighty test flights had been
                                    made, during which 300 air samples had
                                    been collected.  Face and hand skin wash
                                    water samples  had also been collected
                                    and tested for the amount of the insecti-
                                    cide deposited per unit  area  of the face
                                    and hand skin.  Skin wash water samples
                                    had been collected before and after the
                                    air had been degased by spraying with an
                                    alkaline solution.  Determinations were
                                    also made of the amount of methylmercap-
                                    tophos which may have  settled  upon the
                                    compartment floors of the  airplane or of
                                    the helicopter.  This was done before and
                                  -  after the floors had been degased with a
         I porUbl* lr«MV«fcl«) ipr«y t«nk of         .    ......
         An-2 «ith ««thy(••rccptopho* wid   suspension of chloride of lime.
                 mttr
       Twelve pilots,  10 aviation technicians and 10 manual workers had
been examined clinically and physiologically.  Tests included  reviews of
previous illnesses, complete  opthalmological examination,  sensitivity to
light and to convergence,, changes in the dermographic  reaction, in body
                                    - 146 -
Fit lin
     o \*
     i«M
                                                                                     '
-------
 temperature, in arterial blood pressure, and in the  Aschner eyeball-
 heart reflex phenomenon, and other pertinent tests.    Complete determina-
 tions were made of the morphologic and chemical blood pictures, including
 checks for prothrombin  and cholinesterase activities.  Chemical analyses
 of the air samples showed that the air in the airplane and helicopter cabins
 contained methylmercaptophos in concentrations exceeding the  maximal
 permissible 0.0001 mg/li.  The actual concentration of mercaptophos in the
 air  depended upon the temperature,  as  seen from data presented in Table 1.
 Results also showed that mercaptophos concentration in the air depended to
 a considerable  degree upon the velocity  of the  flight,  especially so in the
 case of the helicopter.  Thus, when the  helicopter flew at the rate of 30
 km/hr, the methylmercaptophos concentration in the cabin ranged between
 0.00006 and 0.00979 mg/li, and when its flight velocity ranged between 50-
 60 km/hr, the methylmercaptophos  concentration in the helicopter cabin
 ranged between 0.00019 and 0.00041 mg/li,, as shown in Table 1.    Methyl-
 mercaptophos vapor concentrations  found in the air of the actual workroom
 are  listed in Table 2.  The data show that in 77% of the tests the mercapto-
"phos concentration in the air of the airplane and helicopter operating rooms
 exceeded the  concentration in the cabins by 150 - 860%,  and in  one  case  it
 was 460 times as high. This was probably due to the  nature of the operation
 which required opening of the  canisters  containing the insecticide.   Other
 contributing factors may have been complete absence  of mechanization  and
 of leakage preventing improvements.

        Data yielded by analyses of the face and hand  wash water showed  that
 methylmercaptophos was present in all such samples  in concentrations rang-
 ing from hundredths to thousandths of mg.  Amounts  of mercaptophos found
 per  unit of face or hand skin surface indicated that the material settled upon
 the skin not as a result of careless handling of the  toxic material, but as a
 result of methylmercaptophos vapor condensation upon the  skin.  A certain
 amount of mercaptophos was found in the wash water even before the air-
 plane and helicopter began actual spraying,,  Wash  water of external and  in-
 ternal  airplane and helicopter surfaces  and from instrument and panel sur-
 faces contained tenths of mg of methylmercaptophos.   Protecting devices
 failed to completely protect some surfaces  from becoming  polluted with con-
 densed mercaptophos vapor, although the concentrations of the  insecticide
 were somewhat reduced.

        Work ground surfaces  contained 0.00039-0.01560 mg of  mercapto-
 phos per 1 cm  of soil.  Greatest insecticide concentrations were found on
 grounds where methylmercaptophos. was stored and loaded into the airplane
 and  helicopter.  Soil samples  collected at one of the insecticide storage
 grounds 15 days after degasing contained 0.00073 - 0.04953 mg  per 1 cm3 of
 soil.

        Most aviation air spraying workers  complained of headaches, vertigo,
 general weakness, heavy sensation^n_the_head, restlessness, irritability,-

      •                             - 147 -                               i
-------
                                                                                                                               Table 1.
                           Bothy Jaarcnptc^hea cereecntratie« in tho OOP of ooTOpOcno  end  teot iccptoir cobitso during orchard
                                                        ond cattera fSoOd opiroyirag tfcia  ttao oBir
Typo of QQroplano or hoi o copter
A crop 1 en o A«v-2 equipped eith & rooovable spray
tomh
i
Aoe-opdoroo to-2 oquippod oith a otationary
spray tank '
Aorcptoito to— 2 oquoppod with a rcnovablo !
oproy tofjb
AoropSano Yob— J2 oquiprod oith reooveblo s^re/
tank
AcP®plcnaTQB— !2 oquJpjad oith statesnary
sproy torab {
AoirosloRO Voh— !2 aquippod oi th reaowablo oprey
tana
HoMeoptor U»-|
B n
Hothy Hoof coptopJiieia ora ag/H j
Cabin :
Pilot
0,00023-0,00056
0,00020-0,00679
0,00011-0,00098
0,00018—0,00034
0,00016-0,00471
0,00013-0,00044
0,00006—0,00979'
0,00019-0,00041
Spray operator ;
0,00015—0,00244
0,00014—0,00114
0,00045—0,00134
0,00017—0,00042
0,00018—0,00570
0,00022—0,00058
—
—
Muobor ©f dotno.
Pil®t»o{
Cob en
9
11
14
12
35
25
33
10
Opora-
tor'a
Cabin
9
11
11
11
25
10
—
. —
$ of cir
oaraploc
moth
Indi-
cated
concnoJ
100
100
100
52
57
100
100
100
flog ion and reason for air
spray ing
Air spraying of Croaem
orchards
Air eprayisg ef Criooon
orchards
Air oproying of ccatiral Aoi®
cotton plantaticno
Air spraying ef Oioesra
orchards
Aor oproying of Crioosn
erchordo
Air spraying ®f central Aoiar
Gotten plantations
Air spraying ot Crioeen
orchards
Air spraying of central Asian
cotton plantations
00 !
-------
   MethylMrcaptophoe cencontratiejso 5n tfco air ©f
   •orkin9 grounds during air oppoyomg e>f ofchas-do
             and cotton fto)do

Points of air stop I e cotJoctaen
M«thyli»ercaptophos 8toragan.n-
Aeroplano parking grounds
Methy loercaptophoo loading .
M«thyl»«roaptophos loading
grounds «hcn DO thy loorcap—
tophos is poured into aero-
plane spray tanko
Hg/H c
DO ire
ElOOB-
DOll
Troco
»
»
»
if oothyl-
aj/toptaco
Baaoool
0.0460
0,00862
0,00273
0,00416
tic. of
dotar-
oina-
toono
13
3
6
12
Table  2.                                 uncontrolled salivation, sleepless-
                                         ness,  loss of appetite, nausea, ab-
                                         dominal pains,  sharp pains in the
                                         eyes,  skin scaling and many other
                                         similar symptoms.  The complaints
                                         were more persistent.and more con-
                                         stant among workers using methyl-
                                         mercaptophos than among workers
                                         similarly employed in field and
                                         crop spraying with mercaptophos.
                                         Results of clinical and physiologi-
                                         cal examinations of the workers, as
                                         previously described,showed that
                                         most of the examined personnel had
                                         a drop in their maximal arterial
blood pressure by 10-30 mm, and in the minimal by 10-15 mm. The pulse
rate was reduced by 2-18 beats per minute, and body temperature dropped
by 0.1-0.8 degrees.  Localized dermographic reaction became more per-
sistent} there appeared symptoms  of increased stimulability of the sympa-
thetic nervous system, and a lowering in  the stimulability threshold of the
parasympathetic branch of the nervous system,,   The total symptom-complex
yielded by the clinical and. physiological investigation indicated that workers
employed in the airplane  and helicopter spraying of crop fields with methyl-
mercaptophos showed some  pathologic changes in their central and vegeta-
tive  nervous  systems.  Morphological and physical chemical blood changes
were as follows: increase in the number  of erythrocytes, in hemoglobin con-
centration, and  in the color  index; number of reticulocytes increased  in some
and decreased in others;  the number of blood platelets also increased.   The
number of stab-form neutrophiles  and of segmented nuclear neutrophiles in-
creased in most of the pilots and avioteclinicians, and the number of leuco-
cytes aHcf lymphocytes decreased.   In employees engaged in the aviochemi-
cal phase of field-crop spraying the symptoms became reversed, i.e., the
number of stab-form and segmented neutrophiles were reduced, while the
leucocytes and lymphocytes  increased numerically,,  Blood coagulation time
was  shortened in most of the examined persons,  accompanied by an increase
in the prothrombin concentration.  Red blood cell sedimentation time  was
shortened,  Cholinesterase activity  fell by 10-30%.

                               Conclusions
       1.  Noncompliance with safety regulations in field work with methyl-
mercaptophos may lead to intoxication of the central and vegetative nervous
systems accompanied by  changes in the morphologic blood composition and
in its physico-chemical properties.  Accordingly, those -who work with
methylmercaptophos  must be provided with,  and must be compelled to wear,
devices of individual  protection against occupational intoxication.

       2.  Medical examination of pilots and chemical and technical workers
                                   "-"149 -~
-------
 engaged in crop spraying must include blood cholinesterase activity deter-
 minations.  No one should be assigned to work in chemical field and crop
 aerospraying with  methylmercaptophos from  the air without a preliminary
 medical examination,

         3.  Air field and crop spraying with methylmercaptophos should be
 done from airplane A-2 and YAK-12 which must be equipped with removable
 tanks containing the insecticide concentrate.   All equipment of airplanes used
 in field and crop spraying must be mechanized and made leakproof.

         4.  During field,  and crop  aviospraying the kolkaoz and sovkhoz ad-
 ministrations  must provide workers  employed on the chemical storage  and
 distribution  grounds  with properly fitting individual devices for their protec-
 tion against  the toxic effects of the insecticide spray or vapor.

         5,,  Airplanes and helicopters built for field and crop spraying with
 insecticides  must be  equipped with air conditioned  systems for the  removal
.©,£ neutralization of the toxic insecticide vapor.

         6,  R A-59 is at present the best type of apparatus or respirator de-
 signed for the  protection of workers  against the inhalation of active chemical
 poisons.

                                  Bibliography
             K a r a H K). C. B KH.: Pm-neiia, TOKCHKOJIOPHH H KJiHHHKa HOBUX HHceKTo4>yHrHUu,ao&.
         M.,  1959, crp.  187. — OH we.  B KH.: Hoeue HKceKTO^yurHUHAu  H rep6nUH.au. M.,
         1960, crp.  107. — K a ji row H u H  R. H., Me ABC Ah Jl. H., MorHJieB-jHK 3. K.
         OcHOBHue Bonpocw  rHrneHbi cejia. M., 1961.—Mease a. b Jl. H. Tni-Hena rpy.ua npit
         npHMeneHHH HHceKTO
-------
ary, tertiary amines from ammonia -were developed specifically  for the iden-
tification of large ammonia quantities.  Thus,  Francois developed a method
in 1901 which was revised by other chemical investigators;  the method was
based on the property of yellow mercuric oxide to bind ammonia.  However,
it was found later that ammonia absorption by yellow oxide of mercury was
accompanied by secondary factors which gave rise to considerable determin-
ation errors.  For this  reason, present attempts to use yellow oxide of mer-
cury in the separation of ammonia traces were unsuccessful.  Leone pro-
posed in 1925 that ammonia be precipitated with sodium cobalto nitrate.
this method was perfected by K.  G. Mizuch and A, Ya. Savchemko  in 1940,,
However,  the precipitate thus obtained had to be washed, which made the
procedure cumbersome and time consuming.  Guinot, Bellier,  and  Isham in
i$$Ht/developed a method for the separation of primary and secondary methyl-
airlines from ammonia based on the property of formaldehyde to react in sol-
ution with  primary and secondary amines, but not with tertiary amines.  Am-
monia was precipitated  as hexamethylenetetramine and the trimethylamine
and dimethylamine aldehyde derivatives were removed by distillation
ever, monomethylamine formed a practically nonvolatile compound with for-
maldehyde which  could not be separated from ammonia,, In this connection
S. Kolosov showed in 1936 that hexamethylenetetramine was formed in a
mixture of gaseous formaldehyde  and ammonia.

        The present author found that inactive tertiary ethylamine was not
the only one which failed to react with formaldehyde vapor on short contact;
primary and secondary  ethylamines, if  present in the air in traces,  also
failed to react with formaldehyde vapor  present in the air in high concen-
trations.   Under similar conditions ammonia reacted with formaldehyde
quantitatively.   This property of differential .reaction with formaldehyde
formed the basis of the  method here described for the separation of  alkyl-
amines  from ammonia.    The schematic drawing in Fig. 1  illustrates the
principle of the method.  By this method the air to be analyzed entered the
apparatus  at (2) and continued in the direction indicated  by the  arrow,  while
formaldehyde vapor entered the apparatus at (3) and also in the direction in-
dicated by  the arrow.  The two gases entered mixing chamber  (1).  This  con-
verted ammonia present in the air into hexamethylenetetramine.  As the re-
action mixture passed through absorbers (4),  containing an alkaline solution,
the formaldehyde excess and acid air vapors  became trapped and the ammo-
nia containing air entered the air analyzers.  Purification of ethylamine from
ammonia and other air  admixtures is accomplished in an apparatus schema -
tically illustrated in Fig. 2.  The air to be analyzed entered the T-shaped
tube, divided into two currents flowing in opposite directions,  - one  part to
be analyzed, and the other  to react  with formaldehyde.

        The air to be analyzed moved at the rate of 70-80 ml/min.  along
channel (l) then through  flowmeter (3), through capillary (4)  entered gas
mixing bulb (5) of 30 mm diameter.  Capillary resistance at (4) helped to
maintain the required ratio of flows.  The air which was to react with
formaldehyde was aspirated at the  rate of 150-180 ml/min,  through channel
                                       ~~"~
-------
 (£),> through flowmeter (6) and column (7) filled with silicagel,  where it
 was freed from ammonia,,  It then entered glass tube (8)  equipped with  a
 porous glass plate 40 mm in diameter, and was bubbled through  35-40%
 formaldehyde solution;  here it becamed absorbed by or mixed with the for-
 maldehyde and entered mixing bulb (5).   From mixer (5) the ammonia-free
 gas mixture was aspirated through spiral shaped absorber (9) filled with
 300-400 ml of 30-40% sodium hydroxide solution; it then  entered  another
 cylindrically shaped  ascarite-filled container 30 mm in diameter and 70 mm
 higho  After passing  through stopcock (1) it entered absorber (12),  contain-
 ing wafcer>  for final analysis.  Air samples were collected as follows:  the
 air was drawn through the stopcock and glass container (13) for 5-10 minutes.
 The air may  be  analyzed directly, quantitatively, for the amines by mixing
 it with a solution of o-nitrophenol,  and making final determinations colora-
 metrically.

 Figo 10                                  Indoor air samples should be col-
                                     lected with the aid of an air pressure
                                     device installed at the  outgoing end of
                                     the apparatus connected via a T-shaped
                                     tube to absorber (12) and glass tube (13)
                                     in which the entire system is under ai_*
                                     pressure.  The special air pressure de--
                                     vice may not be required.  All parts of
                                     the apparatus should be made of glass
                                     or transparent plastic  material,  and
                                     the entire assembly must  be absolutely
                                     leakproof.  The flowmeters  should be
                                     filled with mercury or with sodium
                                     hydroxide.  Application of lubricating
                                     material must be  scrupulously avoided.
  1                                   If all described specifications of appar-
 atus construction and assembly have been  complied with, then the time
 necessary  for collection and analysis of an air sample  should not exceed 5
 minutes?.in plants which operated on the basis of single shifts,  reagents in
 the analytical apparatus should be changed only once, or  at  the most twice
 a month.  Absorber (12) can be replaced by an automatic  colorimetric gas
 analyzer constructed by  M. T. Borok in 1957, replacing the working fluid
 with 001% solution  of o-nitrophenol.  In this way continuous control deter-
 minations can be conducted for amine concentrations in the  air.  Air purifi-
"cafcion check tests should be  made with the aid of specially prepared gas-air
 mixtures containing mono-,  di-, triethylamines and ammonia.  The mixtures
 must be prepared with pure  chemicals (gases) kept in steel  cylinders,,  All
 precautions and preliminary surface drying and cleansing steps must be
 taken  to ensure  proper storage of  the prepared gas-air mixtures.  Amines
 are easily  adsorbed by  metallic surfaces; therefore,  an excess  of the gas-
 air mixture should be run into the cylinder upon first filling.   Desorption
 of the amines will become noticeable when the pressure in the  steel cylin-
         drop to 20-10 atm.  Concentration of amines and ammonia released
                                    ""152"-""
      picas ®f cwot6n«ouo pure?ocatocs etf
     orao ftraeoo firca troeoo ©tf aoccaoo
cad coid BQOOO in aiir cuprontBo
I) - 600 aoaoe-j) 2 — tmbo tfoir 4t»o do! 6vcs^
off GiaOysod OOFS 3 — tuba for tbo doHwopy
  tfcraaddobydoB >3 — obcsxTbopa f 60 Oot^ oith
       cKiotcneoj 5 - •ft©o
-------
 from the 'steel cylinders at 100-20 atm0  pressure remained constant regard-
 less of storage duration.  Each gas-air mixture  was analyzed by the combined
 and direct methods after passing through the purification installation.

 Fig.  2.
            Plan of laboratory apparotuo f©r tho pwof oeotisn ond oaQolo c© I I ac-
              tion for tho detorotnat ten of tho aor con to on od QthyOansnes
            I - Delivery of air f©p csnolyajo} 2 - doOovory of air carrying form-
            aldehyde) 3 - flea Dotor; t> - eapol tary tuba; 5 —900 obaer; 6 -
            flow meter; 7 - cylinder  cento in omg so I 06090(5 8-0 bubbles- con-
            taining fontaldohydog 9 — olttolo containing absorbers 10 — oscarite
            containing cartridgej  II —Q 3—aay stopcocks 12 — obaorbar for
            amines; 13 - a glass container
        Samples  had been taken from  the compression steel cylinders  by
 carefully opening the  fine regulating petcock and by releas ing the examined
 air at a slow rate for 60-90  minutes, thereby avoiding errors caused  by the
 adsorption of amines  and of  ammonia by the valve surfaces.  Air samples
-intended for combined analysis were  released from the steel cylinders
 through U-shaped glass tubes filled with ascarite,  and then through absorbers
 containing distilled water.  Total quantity of bases was determined colori-
 metrically with the aid of o-nitrophenol; ammonia concentration was  deter-
 mined by the Nessler method, and the amines were determined by difference.

        In making direct  analysis the  steel cylinder was connected to the pre-
 viously described analyzer and the gas-air mixture was passed through it in
 the direction of glass container  (13) for 10  minutes.  Then stopcock (11) was
 turned so that the gas flow passed through absorber (12)  which was filled
 with ammonia-free distilled water.  At that time the timer recording  seconds
 was  switched into the system.   The amount of analyzed air was recorded by
 the flowmeter and the  stop watch0  It amounted to 2-5  li;  6-15 li of air was
 passed at the same rate  through absorber  (12).    Then petcock (11) was  again
 turned so that the air flow passed through  glass  tube (13),  or through an ab-
 sorber installed in  the place of it, and the time was recorded in seconds.
-------
Concentration of amines in the absorber was determined colorimetrically in
8 ml of the sample to which 4 ml of 0.1% o-nitrophenol was added.  Results
obtained by the direct and combined analysis of the same gas-air mixture
consisting of monoethylamine>  ammonia, and air are listed in Table  1.

Table .1.
                 dcnootbylooirao dotoraonatiea in a6e- csntaoning
Ceaboraod cnalyeis atthout tho af.>aretuo


SooplQ Woo
1
2
3
4
5
6
7
Averages • • •

|JH/IJ of booao
Total baooo
pica Illy
oith ©-
0,60
0,62
0,62
0,63
0,61
0,63
0,64
,62


Total by
Wesolar
ciothod
0,18
0,19
0,20
0,20
0,21
0,22
0.22
0,20
(0,0034 Og/jj

Aainoa by
dofforencQ
0,42
0,43
0,42
0,43
0,40
0,41
0,42
0,42
(0,019 og/) 6
Direct analysis upon
1 QDcruence frca the
Qpparatue

; B 3E '
1
2
3
4







p,t£/li of tffiino,
coloriQotrieel-
Ijr otth o-
n>tr«phenol
0,42
0,40
0,41
0,43



0,42 .
(0,019 og/li
        Data listed in Table 1 show that deviations in separate direct colori-
metric determination magnitudes yielded by the combined analy-
sis;  in either case the magnitudes were  within the limits of experimental
error.  Average values of 4-8 analyses made by both methods in each of the
investigations are listed in Table 2.
Table 2.
E thy lea PRO dotootainat oe?i in air containing aacuioo
Ccaposotoen of
bases in tho air
QHjNHj+NH, . . .
C^NHj+NH., - . .
(C2H6)2NH+NH8 . .
(QHjJzNH+NHs . .
(C2HS)3N 	
(C-H^sN 	
(QH6)sN+NH8 . . .
NH3
NHS 	

; CsJiecnifot oen of boooo on tho air
(oworogoe ©f 
-------
Delta, in that Table show that ammonia present in the air alone and in combina-
tion with amines in  0.03 - 100 7 jiM/li (000005 - 0.182  mg/li) was quantita-
tively absorbed during the  air  sample aspirations while the three ethyli-
amines, including the most active primary member,,  passed through the ap-
paratus quantitatively and could be determined colorimetrically when pre-
sent in the air in 0.42  -  3.20 ^M/li (0.019 - 0,144 mg/li concentrations.
In one instance only did the  difference between the direct  and combined de-
termination procedures amount to 4, 9%»

                                 Conclusions

        1.   The brief simultaneous presence in the air of low ammonia con-
centrations and of formaldehyde vapor excess elicited an interaction between
the two substances which resulted  in the formation of hexamethylenetetramine.
No interaction occurred  between mono-, di- and triethylamine and formalde-
hyde gases simultaneously present in the air.

        2.   On the basis of the above  described differential reaction a pro-
cedure and a laboratory  apparatus have  been developed for the continuous
quantitative purification  of "$he examined air and for the separation of ethyl-
amine from ammonia simultaneously present in the air.

        3.   Direct single or continuous automatic  ethylamine determinations
in the air   can be made by the new analytical procedure" and apparatus.

                                 Bibliography


            6 op OK M. T.  ABTOMa-nmecKHe rasoaHa^Hsaropbi. M., 1961, crp.  307. — J3, o J\-
        runa A. H., SaBejibCKHfi fl. 3., KpHqesuoB B. K.  B KH.: Meroflbi aHajiHaa
        a;iHaTHMecKHX aMHHOB.  M.,  1957, ctp.  3. — Ko.no COB C.  HOBOCTH TexHHKH,  1936,
         ;iH<>aTHMecKHX aMHHOB.   .,    ,  ct.  . —   .     B   .  OBT  T,    ,
         S 40 — 41, crp. 42. — Mnayq K. T., CaBMCHKO A.  fl. FIpOM. oprammecKoA XHMHH,
        1940, T. 7, Ns 1, cip. 24. — VoKep fl. . OopMa^bflerHfl. M., 1957, crp. 315. — Ekla-
        dius L., King  H.,  Biochem. J., 1957, v. 65, p. 128. — F r a n  2, 657, 237.  1953 rofl. — L e o n e P., Chem.
        Zbl., 1925, Bd. 2, S.  1781. — Pug h C.  E. M., Quastel J. H., Biochem. J, 1937.
          31, p. 283.
            Method for the Determination of Carbon Tetrachloride
                               in Intestinal Juice
                                   pp.  55-56

                                Vo V. Lebedev
                     (From the Yakutsk State University)
        Carbon tetrachloride (CCl^) is a heavy colorless fluid which has a
sp. gr. of 1. 594 and a b. p.  of 76. r ; it is widely used in the chemical in-
-------
dustry.  N. V.  Lazarev described carbon tetrachloride as a toxic substance
•which caused grave damage to the liver and kidneys. Carbon tetrachloride
frequently contained admixtures of carbon disulfide, hydrogen sulfide, hydro-
chloric acid,  and organic  sulfide s0  The toxicity of carbon tetrachloride and
its accumulation in the animal organism are reasons for its frequent  deter-
mination in biological specimens.  In this paper the author reports on at-
tempts to develop a method for the determination of carbon tetrachloride in
intestinal juices.  A search of the literature indicated that no such method
has been developed and described.

        It is well known that chlorinated hydrocarbons reacted with pyridine
in acetone at alkaline *pH,  producing a colored compound.   This reaction
formed the basis of the present investigation. Intestinal juice has been ob-
tained from animals in -which an experimental intestinal fistula had been pro-
duced.   The intestinal juice was filtered and centrifuged to remove adventi-
tous material.  The procedure was as follows:  3 ml, or less, of intestinal
juice was placed into a test tube to which 1 g of NaCl was added, and the test
tube vigorously shaken until the NaCl saturated the intestinal juice.   Then 3
ml of acetone was added,  and the test tube centrifuged  for  5 minutes  at
3000 rpm,  or the  tube was allowed to stand for 60 minutes until complete
separation had taken place.  The upper  acetone layer was then carefully
poured into another test tube to which 2 ml of 20% NaOH and 2 ml of pyri-
dine were added.  The test tube  was then heated to 70   in  a water bath.
After the solution has  cooled and the rose color has developed,  the inten-
sity of the  color was compared with a standard color scale.  The standard
six-tube scale was prepared from a stock solution of 10% CCI& in acetone.
The first tube contained no CCL,; the second tube contained 0.005,  the third
0, 01, the fourth 0, 02,  the  fifth 0, 04 and the  sixth 0, 06 mg of CCl^, .  The
sensitivity of the reaction  was 00005 mg CCl^, in one ml of acetone.   Chloro-
organic compounds interfered with the  reaction.  The standard color scale
should be prepared by using as  the diluent an analogue of gastrointestinal
juice free from carbon tetrachloride and from other chlorinated hydrocarbons.

                               Conclusions
        1.  A method has been developed for the determination of carbon
tetrachloride in gastrointestinal juice, based on a reaction the sensitivity
of which is 00 005 ml of CC14 in 1 ml of acetone.

       2.  Chlorinated hydrocarbons interfered with the reaction,

       3.  The test can be performed with 3 ml of the gastrointestinal juice.
Carbon tetrachloride should be  extracted from the juice with acetone and
NaCl| the formed precipitate should be removed by centrifugation.
                                   - 156 -
-------
    Experimental Study of Atmospheric Air Pollution with 3, 4-Benzpyrene
                           in Industrial Sections
                                 pp0  65-69

           Zh. Li. Gabinova,  A. A. Vasil'eva, N. Kh. Sklyarskaya
                             and M0 D. Manita
         (From the Moscow City Sanitary-Epidemiological Station)
        Recently atmospheric air has been investigated for the presence of
 cancerogenic hydrocarbons by the fluorescent-spectral analysis.  Such
 studies have been conducted mostly for the detection of 3,4-benzpyrene  in
 the air. The earliest studies for the detection of 3, 4-benzpyrene  in atmos-
 pheric  air had been conducted in the USSR in 1948 by B.  P.  Gurinov and
 others.  In the winter of 1954-1955 P.P., Dikun,, L_M.  Shabad, and V. N.
 Norkin conducted similar detailed investigations in Leningrad.  However,
 these investigators  restricted their studies to the detection of 3, 4-benzpy-
 rene in sedimented  air dust samples.  Results of tests previously conducted
 by the fluorescent-spectral method showed that the concentration of 3,4-
 benzpyrene ranged between 0.018 and 0,08 Y  per 100 ma  of atmospheric  air.

        The purpose of the present investigation was to obtain more complete
 and up-to-date information on the state of Moscow atmospheric air pollu-
 tion with 3, 4-benzpyrene,  on the basis of which rational sanitation means
 could be developed for the protection of atmospheric air against pollution
 with 3, 4-benzpyrene.   The work was conducted under  the supervision of Prof.
 L.M. Shabed.  The  first investigation  was centered around industrial enter-
 prises which had been only slightly surveyed with regard to the presence  of
 3, 4-benzpyrene in the air and which,  by the nature of their processing  and
 production, lent themselves to the introduction of appropriate sanitization
 measures.  3, 4-benzpyrene determinations were  made  by the P.  P. Dikun
 fluorescent spectral method in the following order:  in the primary raw  ma-
 terial,  in the intermediate and final products, in dust  settled  from the at-
 mospheric air, and  in dust collected by aspiration.  Analyses were conduct-
 ed in the physico-chemical laboratory  of the MOSCOW Sanitary Epidemiologi-
 cal Station.

        The raw material used in the investigated plants  contained different
 quantities of tarry substances and presumably contained 3, 4-benzpyrene in
 varying concentrations. Tests for the  presence of  3, 4-benzpyrene were made
 with pitch, crude  oil bitumens,  different types  of soot, crude  oil coke, heat
 processed  anthracite,  many other intermediates, by-and end-products of the
 plants under investigation.  The number of examined products amounted to 31.
Samples of coal tar  and pitch  collected at different  plants contained 3, 4-
 benzpyrene in the range of 0.1 - 1,2%.   No 3, 4-benzpyrene was  detected by '
 the analytical method in the crude oil bitumen.   Ten types of soot had been
 examined,  and it was found that 6 types contained 3, 4-benzpyrene in the

                                     - 157 -
-------
 range of 0.005 - 000003%, which included lamp black, gas soot,  and furnace
 soot.  No. 3,4-benzpyrene was detected by the method in the remaining 4
 types of industrial soot.  3,  4-benzpyrene was also found in the crude oil
 coke, in pyrolyzed anthracite, and in several other by-products.  Results
 also showed that crude oil coke of different trademarks used in the same in-
 dustrial plant contained 3, 4-benzpyrene ranging between 0.0008 and 0.007%.
 The same was true of 3, 4-benzpyrene content in differently labeled  soot of
 the same  plant.

        The above results caused the present authors  to assume that the
 plants  under investigation discharged into the atmospheric air some con-
 centrations of 3, 4-benzpyrene0   Maximal 3, 4-benzpyrene concentrations
 were found in the  dust discharged by one of the  plants into the atmospheric
 air. Survey was made of atmospheric air pollution with 3, 4-benzpyrene at
 different  city sections, where dust sedimentation samples had been collect-
 ed  in locations of the  "Tol'prom" electrode plant, the "Krasnyi Bogatyr"
 rubber  plant, and the like.    Settled samples had been collected during the
 months of April and May,  I960,  from cracked windows and other breaks and
 openings of nearby dwellings.  Most samples had been collected inside the
 dwelling rooms.

        Results showed that greatest air pollution with 3,4-benzpyrene
 occurred in the proximity of processing and production plants which used
 coal tar and  crude oil coke as their raw materials. It was found that the
 maximal 3, 4-benzpyrene concentration was  contained in dust settled from
 the atmospheric air in the vicinity of plants which used the above mentioned
 products in their production  and manufacture.  Thus, the dust settled in
 the proximity of the "Tol'prom" plant contained 0.009 - 0.049% of 3,4-
 benzpyrene,  and the dust settled in the vicinity  of the  elctrode plant  contain-
 ed 000013 - 0,01% of 3, 4-benzpyrene.   Concentrations  of 3, 4-benzpyrene
 were considerably lower in  dust which penetrated into the Moscow  Sanitary
 Epidemiological Station, probably due to the fact that' no production  or manu-
 facturing plants of the above described character existed where  the Station :
 was located.7 In summary, it can be stated that 3, 4-benzpyrene concentra-
 tions varied  in the settled dust samples  from thousandths to hundredths of
 per cent,  depending upon the  nature of the existing air pollution  sources.
On the basis  of  the first investigation stage sanitization measures have been
 recommended for some of the plants which had been instituted by order of
 the  Chief Physician of the Moscow Sanitary Epidemiological Station.  As a
 result,  the  "Tol'prom" plant discontinued the use of  3, 4-benzpyrene-con-
 taining  raw products, replacing them with 3, 4-benzpyrene-free  raw mater-
ials.  Other  air pollution protection measures have also been instituted.

       In the second stage of the investigation tests have been conducted for
the direct determination  of 3, 4-benzpyrene in the air.  Investigations con!-
 ducted in England in  1949-1951 had shown that annual  3, 4-benzpyrene con-
 centrations in the  air ranged between 10 3 and 4. 6 Y per  100 m3 of air.  At
-------
such concentrations the quantitative determination of 3,4-benzpyrene  in the
air by the fluorescent-spectral analysis  required the aspiration of thousands
of cubic meters of air for a single analysis.  It was also necessary to catch
the most highly dispersed air dust which contained 3, 4-benzpyrene.   This
could not be done with the usual type of cotton or filter paper aspirators, and
required the preliminary testing of many samples  of synthetic tissues.  A
specimen labeled FPA-15  gave  the desired positive results.

        A special aspirator was installed in the Moscow Electrode Plant for
the collection of highly dispersed dust.   This plant used pyrolyzed anthracite,
crude oil coke,  soot, coal tar and graphite as its  raw materials. The techno-
logical  procedures consisted in grinding the anthracite or the crude oil coke.
The ground material was then calcined in gas heated furnaces  at 1300° . The
dust formed in this process was caught by a filter-bag  installation.  After
the heated  crude-oil coke had cooled to 80 it was ground repeatedly to a
fine powder.  Dust generated in this process was  trapped by  a filter  bag
installation.  The fine coal powder was  mixed with other materials to form
the final production mixture,,  The air in this production department was
passed  through a purification system consisting of a cyclone and bag filter
or electric  precipitator.  The previously prepared basic powder was  then
mixed with  thick coal tar or coal pitch at 120 „  and was then directed  into the
hydraulic press department for final manufacture of the electrodes.   After
this the electrodes were calcined at 200-1300 ,  and coated by a layer  of fine-
ly ground coke.   The assembly in which  the foundry coke powder was  prep?.red
was equipped with a bag filter installation.  Dust and sublimated tar  particles
formed in the furnaces were trapped by 4 electrostatic  precipitators.   The
final electrode shaping was done mechanically.  The dust thus generated was
trapped by a two-stage cyclone and bag filter installation or by wet scrubbers
and returned to  the production department.

       The aspiration installation is schematically shown in Fig. 1 and photo-
graphically in Fig. 2.  As mentioned before, the Petryanov filter tissue
FPA-15 was used in this dust trapping apparatus„  Its filter area is 314 cm2.,
and the  air  is aspirated at the rate of 10-20 m3/hr, or  at the rate of 0. 5-1
li/min.  per 1 cm2.  Id. Gusarov and V0K. Lyapidevskii found in 1948 that  at
air aspiration rate of 12.1-12. 8 li/min, per 1 cm8 through filter tissue FPA-
15 there occurred an 8.4% slip-through of the air suspended dust.  In  the
present investigation the air was aspirated through the  synthetic tissue at a
rate of 0. 5-1 li/min.  per 1 cm3, so that  the amount of slip-through dust was
negligible.   The installation used in this investigation  possessed the  advan-
tages of uninterrupted operation over long periods of time usually required
for the aspiration of great air volumes even at  higher temperatures with a
high degree of reliability.    It  was  necessary  to aspirate 2000-3000  m3 of
air over a period of 5 days in order to obtain an adequate sample for  a re-
liable quantitative 3, 4-benzpyrene determination in the aspirated air.  The
amount  of dust collected during such an aspiration ranged beteen 0.2  and 1  g.
-------
 Fig. 1.
                                               Fig.  2.
   Plan of •Biwratu* "fir the O»ll«oti«n of «ir
    wi.pl «• polluted «ith 3,<«-*««ip)rr«n«
   I - Electric v«nt lUting fw» 2 - <•••  Mter
    PS - W| 3 -  Funnol »*.p«d »ir bl«wr
                                                6«n«r»l vi«« of
                                                  •••pi* coI'acti*«
     R«Milt* »f ••pirttion coll«ct«d «t«o«-
            ph»ric «ir •*•[*!••
        During the months of August-November of 1961, 13 samples had been
collected as above described.  Data in the Table show that 3, 4-benzpyrene
concentrations were within the range of 0.4 and 2. 33 Y per 100 rna  of air.
Data in the Table also show that in only 4 of the 13 samples was the 3,4-
                                      benzpyrcne concentration below 1 Y  per
                                      100  ma of air.  In most cases the 3,4-
                                      benzpyrene range was between 1  and
                                      2. 33 Y per 100  ma of air.  It is signifi-
                                      cant that the increase in  percent of  tar
                                      was paralleled by an increase in the
                                      amount of 3, 4-^enzpyrene  in most  sam-
                                      ples.  The 0.4-2.33 Y of 3,4-benzpyrene
                                      per  100 m* of air considerably exceeded
                                      the 0.018  - 0.08 Y per 100 ma found by
                                      B. P. Gurinov in 1957 in Moscow air.
                                      This can be explained by the fact that the
                                      sample collecting device  used in the pre-
                                      sent investigation was of higher per-
                                     formance efficiency.

SM I.
N—
Q«

1
2
3
4
5
6
7
8
9
10
11
12
13

i Ti»« of Air
•••pi*
col Uction

21/V1I— 2/V1II
2/V1II-10/V1II
10/VIII-19/VI1I
19/VI11— 24/VII1
24/V1I1— 29/V1II
29/VI11— 4/IX
4/IX-15/IX
21/1X-26/IX
26/IX-2/X
2/X-7/X
7/X— 12/X
18/X-24/X
24/X-31/X

-3 	 ;
3,H~
tn"?pyr*??

1.10
0,94
0,54
1,59
0,40
2,10
1,10
1,60
1,90
1,90
0.52
0,10
2,33
. _
* of Ur in

phoric »ir
dw.t

3,20
1,80
4,30
1,00
5,20
—
_
9,50
7,54

8^46
9,30
Hot*. Rang* of air M»pl« eolUctioo t !•• 12* -
  215 hour*. K«n«« of »«piri.t«d «ir 735 - 29VJ m
                                                   Conclusions
                                         1. It has been established that some
raw materials, intermediate and final products used or  manufactured by the
investigated industrial plant contained detectable quantities of 3, 4-benzpyrene;
samples of settled dust collected in the proximity of the investigated plants
also contained detectable quantities of 3, 4-benzpyrene.

                                    - 160 -
-------
        2.-  Samples of aspirated atmospheric air collected on the electrode
 plant grounds during August-November of 1961,  contained 3, 4-benzpyrene
 in 0.4-2. 33 Y per 100 m3 of air.
        3.   On the basis of this orientation investigation I -
 examinations, certain sanitization arid air pollution protection means have
 been recommended and instituted in the investigated plants.  The present
 report presents  results of the first stage of a general investigation to be con
 ducted in the future on a broader and profounder scale.

                                 Bibliography
            FypHHOB 6. H, 3opa B. A., H ;i b H H a A. A. H A?. THF. H caH., 1953, :Ns 2,
        cm. 10. — FycapOB H.  H.,  Jl a n H Ae BCKH ft B.  K.  THF. H  can., 1958, Ns 10,
        crp. 10. — AHKVH FI.  H. LLIa6aA  Jl. M., HOPKHH  B. Jl. Tam we, 1956, Ks  1,
        crp. 6. —HOBHKOB  K).  B., TOAOBHI M. Jl. FHF. H  can., 1960, Ks 11, ctp. 47.—
        Ul a 6 a A Jl- M., Jl H K y H Fl.  FI. SarpasHeHHe aiMocfJiepHOro Boaayxa
        eemecTBOM 3,4-6eH3nHpeHOM. Jl., 1959.
                  The Toxicology of Refrigerant Freon - 12
                                  pp0  95-97

                               V. A.  Shugaev
                                 (Leningrad)
        Freon-12, which is dichlorodifluoromethane (CF2C12), is widely used
as a refrigerant.  The advantage which this reagent possesses fro.m a practi-
cal viewpoint lies in the fact that in addition to its thermodynamic properties
it is characterized by chemical inertness and noninflammability, as shown by
G.  Z. Yakovkin in 1956.  Freon-12 is a gas which possesses a slight speci-
fic  odor, It becomes odor perceptible in concentrations of 20% or more by
volume, or 1080 mg/li.  Freon-12 decomposes at a temperature exceeding
400° with the formation of hydrogen chloride, hydrogen fluoride, and a small
quantity of carbonyl chloride, as shown by O. D. Khalizova and E.  I. Voront-
sova in 1952. It is generally believed that  freon-12, being an-inert  gas,  pos-
sessed no toxic properties under normal conditions of use, but in concentra-
tions  exceeding 30% by volume1*, or 1620 mg/li it manifested early signs of in-
toxication, not as the result of its own toxicity, but as the result of created
oxygen insufficiency in the surrounding air.  At the same time,  some reports
appeared in  the literature pointing to some toxic  properties of freon-12.   Les-
ter, Greenberg and others reported in 1950 that freon possessed certain nar-
cotic  properties, while Brenner in 1937 concluded, on the  basis  of his  ex-
periments,  that freon-12  was a central nervous system depressant.  DaL?  -r
harnm in 1958 and Mendilhof; in 1952 reported on cases of intoxication with
products of freon-12  decomposition which resulted in fatalities.  This may
have been caused by  some source of temperature rise which resulted in the

                                   - 161 -            ;
-------
decomposition of freon-12 into the previously mentioned components.  Fro on.
poisoning also occurred during the repair of freon operated refrigerators,
during the use of acetylene torches,  and during the use of insecticide  bombs
in which freon-12 was used as the spraying agent.

       The aim of the present study was to investigate the toxicity of  freori-
12 in the absence of  oxygen insufficiency.  For this purpose experimental
conditions have been created under which oxygen concentration had been
maintained at 20-22% by volume.    White male mice weighing 20 g were
placed into 100 liter exposure chambers.  The oxygen and carbon dioxide
concentrations in the exposure chambers were kept under control at 19. 5-
22. 3 and 0. 38-00 8% correspondingly.  The air in the exposure chambers
was kept in constant motion by small fans.  Mice were exposed to freon-12
vapor for 3 hours in experiments designed for the  determination of its
lethal concentration, and for the determination of its threshold effect  con-
centration, as indicated by the loss  of  conditioned defense reflexes during
exposure  to inhalation.  Early signs  of poisoning appeared in the  experi-
mental mice at freon-12 concentration   30% by volume,  or 1620 mg/li.
Freon-12  inhalation  in concentration of 30% for 15 to 20 minutes elicited in
the experimental animals motor stimulation followed by immobility.   The
animals became placid, and respiration became rapid. At freon-12 concen-
tration 40-60% by volume,  or 2160-3240 mg/li, the clinical picture of poi-
soning became sharply defined.  The stimulation period was shortened to
1-3 minutes.  The experimental mice soon developed a tremor, and fell into
a narcotic sleep which  persisted to the end of  the experiment.  At 61% by
volume,  or 3294 mg/li of freon the animals  died. L/D5O at 3 hours exposure
amounted to 62% by  volume, or 3348 mg/li;  under similar conditions  66% by-
volume,  or 3564 mg/li of freon was  the LDioo dose.  Results of these ex-
periments clearly showed that freon-12 per se possessed toxic properties arid
proved lethal to experimental animals  even  in the  presence of oxygen suffi-
ciency in  the surrounding air.

       Effect of freon inhalation on positive and negative conditioned  reflexes
was tested by the procedures described on numerous occasions by previous
investigators.  Results showed that in  10-20%  by volume, or 540-1080 mg/li,
freon-12 elicited clearcut disturbance in the experimental animals condi-
tioned reflex activity, as shown  by the lowered percentage of response to
conditioned stimulation.  At 5% by volume, or 270 mg/li, no break was no-
ticed in the conditioned reflex activity  of the exposed experimental animals.

                               Conclusions

       1.   Information  found in the technical literature regarding the biologi-
cal inertness  could not be  confirmed scientifically.   Experiments with  white
mice showed that freon-12 elicited shifts in the organism's functions follow-
ing a single exposure to the inhalation  of air containing  6% by volume,  or
324 mg/li, of freon  or  more, even in the presence of complete oxygen suffi-
ciency.
                                  - 162 -
-------
                                  Bibliography
            A Ji e K c a H fl p o B  H  C.. 14. H 6 H H a M. f. Tpyaw HaytHo-Hcc.ne;i.  MH-TZ.
         rpy;;a  H npo(f>3a6oJieBamiii. JI.,  1947.  T. 2, M. 1. cip. 48. — ripaniiyia TCXHHKH
         IIOCTH  Ha  xo.noflii.ibiibix yi-ranoBKax.  paOoraioimix  na (})peoHe-l2.  M.,  1960. — X a J\ n
         3 o B a  O. Zl. B o p o ii u O'R a E.  H. fur H can., 1952, K? 4, crp. 44. — fl K o B K n H T. A.
         Opeoiiu. CBOHCTBB n npiiMeiiemie. J}.,  1956. — B r e n n e r C., J. Pharmacol. exp.  Ther.,
         1937, v. 59, p.  176. — D a Ih am n T.,  Nora. hyg. T.,  1958, v.  39. p. 105. -l.es
         tor D., Green berg L. A., Arch,  induslr. Hyg., 1950, v. 2, p 335.-—M a r t i  T.,
         Arch. Mai.  prof.,  1948. v. 9, p. 356. — M e n d c 1 o f f J.,  Arch,  imluslr.  Hyg., 1952.
         v. 6, p. 518.
                                 NO. 7, JULY
         Hygienic Determination of Sanitary Clearance  Zones Between
           Residential Developments and Animal Husbandry Farms
                                   PP. i  - 11

                     V. A.  Kononova and V.  B.  Aksenova
      (From the Saratov Scientific-Research Institute of Rural Hygiene)
        Agricultural industries, including extensive animal husbandry farms
have been recently moving into residential regions.    Some kolkhozes and
sovkhozes have already begun  to construct facilities for the maintenance c:
800-1000 cows  and 5000-15000  hogs.   The present 200/m standard is appli-
cable to sanitary hygienic clearance zones between residential developments
and animal husbandry farms is based on a maximum of 400 heads of cattle.
Therefore.it becomes imperative to define new standards for sanitary clear-
ance zones in relation to animal husbandry farms of the size and capacity
which are now  in the process of development and organization.  It is reason-
able to assume that the increase  in size and capacity of  animal husbandry
farms will be followed by worsening in the environmental conditions.  A.  A_
Kirpichnikov noted in 1957 that the unpleasant specific odor emanating from.
large swine-breeding farms  extended over an area of  700 m radium.  M. M.
Uvarov and  L.  F. Tulyakova noted in 1961 that the sanitary clearance zones
for large animal breeding farms should not be less than 500-1000 m wide.
In searching for a solution of the problem related to rural sanitary clearanc ;
zones factors of economics  and convenience must be taken into consideration.
It cannot be  doubted that the  localized development of a village has its posi-
tive aspects since the shortening of water supply, sewage,  and other en-
gineering systems  of roads  and other communication means add to the  com-
fort, convenience and efficiency of village  dwellers.  The fact that it is mov

                                     - 163 -
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difficult to manage and operate distantly located farms, especially in bad
weather,  should also be given serious consideration.  Nevertheless,  the
width of a sanitary clearance zone must be based primarily on basic sani-
tary hygienic considerations.

       In this connection it was felt that recommendations  made regarding
the width of sanitary hygienic  clearance zones for farms of different pro-
file and different numbers of cattle heads must  be based on a knowledge of
the zonal air and soil pollution distribution in the proximities of hog breed-
ing and dairy farms organized within  the last several years.  Such investi-
gations had been conducted in 24 animal husbandry farms in the Saratov,
Volgograd,  and Moscow regions.   Soil samples and air samples  had been
collected at distances ranging  between 50 and 1000  m for the determination
of maximal single ammonia concentrations.  Sample collection and analyti-
cal procedures were conducted by the usual methods.  Records were  kept
of the temperature, wind direction and velocity; simultaneously organoleptic
tests were made to determine  distances  to which perceptible ammonia odor
spread over the entire neighborhood.

       Bacteriological studies  of the  air had been conducted by the Krotov
aspiration method  and by the open Petri dish method.  A total of 156 bac-
terilogical air tests had thus been made.  Soil samples collected at the same
points were analyzed for the presence of ammonia, nitrites,  nitrates, arid
chlorides. At the same time,  special questionaires had been distributed
among 500 persons residing in the vicinity at different distances from the
farm.  Distances  to which flies migrated from the farm were determined
by the luminescent method.  Flies were trapped inside of village residences
with the aid of strategically placed fly paper. The  investigated stock farms
were divided into 4 groups.  Hog  breeding farms of up to 100 heads belonged
to group 1} farms of 1000 to 3000 heads belonged to  Group 2, and those of -1-000
-13000 heads belonged to Group 3.  Cattle breeding farms usually pastured
200-800 heads and were classed in Group 4.  It was noted that farms  of
Groups  3 and 4 were well-organized,  well-mamaged,  and the animals were
kept in a relatively clean and sanitary condition.  However, sovkh'ozes
"Krasnokutskii" and "Vol'novsk"  made no special provision for manure dis-
posal;  it was merely piled up  close to the cattle barn.  The pasture grounds
of hogsovkhozesi "Temp" and "Vydvizhenets" were heavily covered with hog
manure and flies freely proliferated in the farm surroundings.

       Analyses of atmospheric air showed that within a. radius of 400 m of
farms belonging to Group 1 ammonia concentration  was considerable.  Maxi-
mal concentrations in the air of farms belonging to Group 2 were found in
the 400-600 m zone,  while in farms belonging to Group 3 maximal  ammonia
concentrations were found in the 600 m  zone, as shown by curves in Fig. 1.
Lowest ammonia concentration in the air was found in the vicinity of the
sovkhozes "Belaya Dacha",  which was the most extensive,  the best man,\ ..
and the  most sanitarily maintained.  As the distance from the farm incre •-. ..
the ammonia concentration in the  air  decreased,  so that at  a dis'ance o

                                   - 164 -
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800-1000  m from the farm only a trace of the ammonia could be detected.
But the specific  odor of ammonia was still  perceptible at 1000 m from the
farm.
            Group I
                     N
                                      .In the case of farms classed as Group
                                   4 slight concentrations of ammonia had
                                   been found in air samples collected at a
                                   distance of 200 m, from the well main-
                                   tained dairy farm "Zarya Kommunizma".
                                   On the other hand, the manure piles ac-
                                   cumulated in the sovkhozes "Vol'novskii"
                                   and "Krasnokutskii" seriously affected the
                                   sanitary condition of the atmospheric air,
                                   as shown by curves in Fig.  2. Air sam-
                                   ples were collected in some sovkhozes
                                   along 2  radii from the farm.  One of the
                                   radii crossed the green sanitary clearance
                                   zone. Analysis of air samples showed that
                                   air pollution seldom extended beyond the
                                   green zone.  Organoleptic tests showed no
                                   perceptible traces of odor coming from th*.
                                   animal breeding farms.  A.  A.  Kirpichni-
                                   kov showed in 1957 that the presence of a
                                   sufficiently wide green clearance zone re -
                                   duced the specific farm odors by 17-20%.
                                   Residents of sovkhozes verified the posi-
                                   tive effect of green sanitary  clearance
                                   zones and stated that  the unpleasant odor
                                   became  non-perceptible as soon as the
planted trees reached sufficient height.  Results  of the tests and observa-
tions,  also answers to questionnaires clearly indicated  that the proper man-
agement, cleanliness,  and general maintenance  of a farm,  plus the  intro-
duction of a green sanitary clearance zone,  played a substantial role in lower
ing the air  pollution around the residential area.
  200
      400    600   800
       0 istanc* in meters
                       1000  1200
Ammonia concir t rut i on in atnospher ic
>, \T near the hoy firm.
I Fi.rm, *nd territories maintained in
poor sanitary  condition} 2 — S»niti>ry
conditions oe'.ter than in I j 3 —
sanitation cnci cl ebn I ineRi*
                           Good
Fig. 2.
                                      As previously mentioned, bacteriologi-
                                   cal investigations had been conducted in ih:
                                   atmospheric air surrounding tha animal
                                   bvy'-din."' (arms bv ch-e u* pi r .id. or. c-.n.-i .-;<--!;-
                                  contained thousands and evc-.r,
                                  thousands of microorganisms per 1 rr *
                                  air, as  shown by the  aspiration method,
                                  and per 1 m2 area,  as shown by the sedi-
                                  mentation method.  The suspended bac  -r
ial counts became lower at 800 m from the farm.  Results of similar hi-cix- -
                                     - 165  -
                Ois-tance in meter:;
        concentr.ition in atmospheric air
  in the proximity of Milk farms.
  Designations are trie sane a a in Fig.  I
  above
-------
iological tests conducted in surroundings of smaller hog breeding farms
showed the presence oi: hundreds and thousands of microorganisms in the
air.  In the case of poorly managed and improperly maintained hog breed-
ing farms bacterial air contamination extended even beyond  1000 m.  Counts
of thousands and tens of thousands of microorganisms per 1 m3 of air had
been  recorded at distances of 100-200 m from the dairy farms.  However,  in
the case of well-managed and sanitarily maintained dairy farms  the bacterial
air density dropped considerably at a distance of 400 m from the farms.  No
such  reduction in the bacterial air population was noted 400-600  m from  farms
in which the  manure was stored improperly.

       Atmospheric air pollution with microorganisms,  with ammonia, and
other unpleasant odors caused especially by poorly maintained hog breeding
farms created unsanitary and unpleasant living conditions to the  surrounding
urban population, a condition which must be corrected by instituting appro-
priate sanitary hygienic measures.  Answers to the  previously mentioned
questionnaires contained many complaints of unpleasant odor and fly infesta-
tion coming from the animal breeding farms.  Such complaints came from
practically 100% of persons residing 200-400 m from the investigated farms.
Number of complaints became reduced with increase in the distance from the
farms under consideration.  Fluorescent-marked flies were found in large
numbers in the 400-600  m zone and occasionally  fluorescent-marked flies
were found within a, radius of 800 m from the animal breeding farm.

       Chemical analyses of soil samples collected  on the animal breeding
farms showed high concentrations  of chlorides, ammonia, nitrites,  and ni-
trates, clearly pointing  to intense  soil contamination with fecal matter.  Tlu;
intensity of such soil pollution abated as the distance from the farm increased.
At 1000 m from the hog breeding farm the soil contamination became negli-
gible. It should be noted at this point that the radius of soil contamination in
the well kept and properly managed hog  farms of sovkhozes "Belaya Dacha"
and "Petrovsk" was relatively limited.  In the case of the dairy farms  sub-
stantial soil pollution reduction was noted at 50-100 m from the farm, and be-
yond  200 m the soil showed practically no signs of unusual contamination.

                               Conclusions
       1.  Animal breeding farms are sources  of regional atmospheric air
and soil pollution: (a) small farms with an animal population not exceeding
1000 heads and which are improperly managed and poorly maintained caused
intense air and soil pollution within a radius of 400 m, while farms with an
animal population of 3000-6000 heads under similar conditions showed ir.-
tense soil and air pollution in the 1000 m zone;  (b)  in farms with a hog popu-
lation  of 4000-13000 heads which were relatively well managed and sanitar-
ily maintained the above mentioned  types of air and soil  pollution were noted
within the zone of 600-800 m;  (c) in properly maintained dairy farms air  and
soil pollution, as above described,  was  noted in the limited radius of 200  rn.

                                    - 166 -
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        2.  It is recommended that 600  m be adopted as the absolute  minimal
 sanitary  clearance zone for large well managed and properly maintained hog
 farms.

        3.  It is recommended that 200 m be specified as the minimal sani-
 tary clearance  zone for large dairy farms which are well managed and pro-
 perly  maintained from  the sanitary viewpoint.

        4.  The above recommendations mandatorily imply forestation of the
 sanitary  clearance zones.

                                Bibliography
           K H p n M M H H K o D  A. A. PHP. H CMH., 1957, .N° 7, crp. 78. — V K a p o B  M. M..
        !' y .1 fl K o B a Jl. O. B KH.: Plocci6ne no rHnieiic n.'in ce.'ibCKiix yiacTKOHhix » caimrapHbix
           eft. M., 1961, crp. 5.
       Experimental Data as a Basis for the Determination of Maximal
          Permissible  Porophore ChKh  3-5 Concentration in  the Air
                            of Working  Premises
                                  pp. 18-23

                               M. V. Aldyreva
   (From the Department of Industrial Hygiene, the Central Post Graduate
                               Medical Institute)
        Light porous or foamy synthetic materials are being used on an in-
creasing scale by different brances of USSR industries.  Porous or foam
rubber and plastic materials are produced with the aid of gas  formers of
an organic  or inorganic nature.  Best results for the production of evenly
distributed pores and materials of lowest specific gravity are obtained with
the organic pore  or foam formers known as  porophores.  Organic  povc-
phores of varying chemical structure are being synthesized by  many in-
stitutions by different chemical processes.  A sulfohydrazide  preparaii.
known as porophore ChKh 3-5  is widely used in the USSR; it is a p-m.eu.vl~
urethanebenzylsulfohydrazide of the following structural formula:
                                  CSO,NHNH,
                              HC1^  ,'CH ^°
                                 CNHC--OCH..,
                                 - 167 -
-------
It is a light crystalline powder practically insoluble in water, soluble in acids,
ethanol  acetone and in NaOH solutions.  At 160-170° one g of the porophore
decomposes generating approximately 115 ml of gas, known as its gas number.

       Working conditions under which ChKh3-5 is produced were studied at
plant Mosplastkozh and at combine Iskozh of Kalinin City.   The commercial
product  is in the form of a coarse powder; contains considerable moisture;
it must be dried,  reground and sifted before being used in the production of
foam rubber or porous plastic material. In the process of drying and grind-
ing to a fine powder,  much of the material  becomes suspended in the air of
the production premises,  mostly due  to grinding and sifting on shaker screens,
especially those manually operated.   Work with finely powdered porophore is
of short duration, amounting generally to 2-25% of the sifter's operating
time, and depends largely on the rate of its daily consumption. The workers
use gauze masks, or other types of masks  over their mouth and nostrils as
protection against inhalation of the porophore powder.

       The commercial use of the porophore preparation is gradually in-
creasing, yet practically nothing is known concerning its effect on the
organism.  The present author conducted special experiments for the de-
termination of the porophore toxicity  parameter by administering same  to
white mice and rats intragastrically.    Experiments had been conducted in
ten series of acute tests, using 100 experimental animals which received
different  doses of porophore powder suspended in water and starch medium.
Results of the investigation established  the following toxicity parameters to
both animal species:  LD.ioo was 0.5 g/kg,  and LD50  - 0.35 g/kg, while the
maximal  tolerance dose was 0.2 g/kg.  Experimental data had been process-
ed by the Miller and Teintner method.  Administration of lethal porophore
doses elicited in the animals profound convulsion states followed by death
several hours after the porophore administration.  Some of the animals died
two days  after the substance administration.  Application  of an aqueous poro-
phore paste to the skin of rabbits had  no unfavorable effect  on the organisms.
Under industrial working conditions the air-suspended porophore dust enter-
ed the workers' organisms basically through the respiratory route; accord-
ingly, 4 series of experiments had been conducted in which white male rats
had been  exposed  to the inhalation of air containing different concentrations
of suspended porophore dust.  A total of 82 white male rats had been ex-
posed to inhalation of the porophore preparation in the following concentra-
tions:  20-30, 7-10, 2-4,  and 0.6 mg/m  .  Experiments had been conducted
in inhalation exposure chambers of 100 li capacity,  into which air containing
porophore dust was supplied on a constantly exchanged basis.  Results of the
first 2 series of inhalation tests with high porophore concentrations produced
grave intoxication pictures and established the upper toxicity parameters.
Each group of the  two series consisted of 12 male rats.   Control groups
consisted of 10 rats.  The rats were exposed to the inhalation of lower porc-
phore concentrations  for 4 hours, while exposure to the higher concentra-
tions was limited  to 1 hour.

                                   - 168 -
-------
        During exposure to the porophore dust inhalation the rats became rest-
less, and some remained lying in a lateral position.  Respiration rate of all
experimental animals rose to 60-90 per  minute,  and all animals showed signs
of hyperhidrosis.  At the end of the exposure period clonic and chronic spas-
ticity appeared in the animals accompanied by disturbed motor coordination ,
restlessness and motor stimulation.  Between states of convulsion animals
fell into a state of  collapse.  Death ensued within several hours after the on-
set of convulsions  or collapse.    Five of the 12  rats exposed to inhalation of
air containing  7-10 mg/m  of the porophore and  8 of the 12 rats which in-
haled 20-30 mg/m3 perished.   The surviving rats showed  changes  in the
nervous system expressed as convulsions, slight or complete  paralysis of
the hind legs; the blood showed an increased number of Heinz bodies, which
was still in evidence 2  months  after the brief exposure to the  polluted air.
Thus,  a single exposure to inhalation of  20-30 and 7-10 mg/m3 of the poro-
phore  killed 13 of the 24 rats and developed signs of toxicity in the surviving
experimental rats.

        The purpose of  the third series of exposure tests was to determine
the effects of longer exposure to the action of porophore at concentrations
of 2-4 mg/m3.  These  were subacute experiments.  During these experi-
ments a test was developed for the colorimetric  estimation of decomposed
porophore  ChKh3-5 molecules in the air. Twelve white rats had been ex-
posed to the inhalation  of the porophore dusts 4 hours daily for 45 days.  Be-
tween inhalation  periods rats were kept in individual specially constructed
metallic cages to obviate the possibility  of inhaling porophore  dust during
intermittent or rest periods.   Appropriate controls had been conducted as
previously described.  Rats began to die on the  3rd or 4th day following ex-
posure  to the  porophore containing air.  All test animals died  during 45
days of the experimental period.   Observations conducted through the ex-
perimental exposure period showed gradual loss of weight with a final loss
of 30-95 g, which pointed to profoundly disturbed metabolic processes. Five
of the 12 experimental rats showed an increase in their erythrocytes from 11
                             «3
million to 17. million per 1 mm  of  blood.  Osmotic'erythrocyte resistance
fell to considerably lower levels,  and the number of Heinz bodies in the
erythrocytes markedly increased.  The leucocyte formula  shifted as a re-
sult of increased number of neutrophiles. Incomplete and complete paraly-
sis set  in;  latent period of conditioned  reflex response  became shortened.
Some rats  showed signs of urine retention and hyperhidrosis.  Rats died
manifesting grave symptoms usually noted in acute poisoning experiments.
Macroscopic examination of autopsied  animals showed acute plethora of all
organs  which appeared of raspberry color.  The  liver   and other organs de-
veloped acute pathology signs;  signs appeared of other anatomical disturb-
ances.  Thus,  inhalation  of 2-4 mg/m3 of porophore ChKh3-5  for 45 days
killed all experimental animals as a result of profound  functional and mor-
phological  pathology.

        An analysis of symptoms elicited in the  rats  exposed to inhalation 01
air containing concentrations of porophore ChKh.3-5  clearly indicated that  ex-

                                   - 169 -
-------
perimentn.1 animals developed a pathologic picture  of hypoxia, and animals
apparently died as a result of oxygen hunger.  To verify this  conclusion, a
fourth series  of experiments had been  conducted for the purpose of deter-
mining the chronic effect of low porophore ChKh3-5 dust concentrations on
the organism,  and to obtain data on which to base recommendations for max-
imal permissible  porophore dust concentrations in the air of  working prem-
ises.  Experiments had been conducted with 36 white male rats 12 of which
served as controls. A regulating system was established by  means of which
it was possible to maintain an average 0.63 mg/m   porophore concentration
in the  exposure chamoer with maximal/minimal fluctuation 0. 3-0.9 mg/m3.
This experiment extended over 6 months,  and was  followed by a recovery
period of 45-90 days.   The general technique of these experiments was iden-
tical with one   previously described.  At the end of each 30  days, the ex-
perimental animals' functional state was tested,  by procedures usually em-
ployed in similar  'investigations.   Changes in the red blood picture began to
appear during the  first and second inhalation months.  As in the case of the
subacute experiments, substantial fluctuation in the number of erythrocytes
began to appear, as shown by the  fact that in 8  of the 12 animals the number
                                               -a
of red blood cells  rose to  10 - 13 million per mm  during the  first 2 months
of exposure.  The color index and hemoglobin per cent also rose  periodical-
ly in the control group.  Curves in Fig. 1 show changes in the number of
erythrocytes in experimental rat No. 9, as comparted with a control  rat.
As the number of  erythrocytes increased,  their diameters decreased. Heinz
bodies were seen  in the erythrocytes of some experimental rats.    No pro-
gressing changes  were noted in the erythrocyte inclusions during the  re-
maining 4 or 5 months of the chronic low dose porophore inhalation experi-
ments.

Fig. 1.                         Osomotic erythrocyte resistance dropped to
                             0.62-0.7% of NaCl during the first 60 days,  but
                             the upper maximum limit remained unchanged.
                             At the  end of the experimental exposure period,
                             erythrocyte resistance rose to higher levels,
                             the minimal ranging between 0.56-0.46, and
                             the maximal between  0. 38-0. 30% of NaCl.
                             These  changes point to the hemolytic porophore
                             effect and to the appearance of young erythro-
                             cytes,  which possessed a higher osmotic resis-
                             tance.  The number of reticulocytes in the blco:.
                             of experimental rats  fluctuated  within the ran;?e
of 10-40%,  pointing to some periodic stimulation in the production of  erythro-
cytes by the brain marrow.  Microscopic slide examinations  indicated that
at the  end of the porophore inhalation period the experimental animals ex-
hibited slight increase in the red cell elements which returned to normal at
the end of the exposure  period. No clearcut changes have been noticed in the
number of leucocytes  or in the peripheral blood picture.  Chant><;s in  dv.
cardiovascular system appeared during the 1st month as a drop in the ;. ri.':r-
ial blood pressure  in the  experimental animals,  which persist.*:'! th rouf
-------
the exposure period in all the experimental rats.  (Fig. 2).  Blood serum
and red blood cells cholinesterase activity rose to higher levels which per-
sisted in all experimental animals through the entire exposure period.  The
latent period of the motor reflex response became slightly shortened dur-
ing the first 5 months of exposure,  but returned to almost normal on the 6th
month, as shown by curves in Fig.  3.    No substantial changes had been
noted in the weight and general  behavior of the experimental rats.  Recovery
of the different  functions occurred at different periods in  the experimental
animals.    Longest recovery period of 3 months was noted in the arterial
blood pressure. Other functions  returned to normal within 30-45 days.
       Fig.  2.
Fig. 3.
         a          Months
         Average ctianges in arterial pressure.
         Other designations as in Fig. I  pre-
         ceding .
          Mon t hs
Average changes in latent i-eriod of
motor ref leu resf-onoe
Other eiesignat ions as  in Ki; I pre-
ceding.
       According to results of this investigation, most pronounced changes
occurred in the red blood cells  and in the arterial blood pressure.  However,
in evaluating the true effect of the  concentrations used in  the current study,
consideration must be given to the time in which  the animals recovered
their initial indexes.  Accordingly, 0.6 mg/m3 of porophore should be re-
garded as a near threshold concentration.  Changes in the nervous  system,
as indicated by shifts in the latent  period of the motor  reflex  response  and
by the cholinesterase activity, were slight and returned to normal within
a short time,   Histologic  weight, and behavior changes showed no substanti.i. >
deviations from those in rats of the control group.

        Taking into consideration the high toxicity of porophore  dust, its
limited toxic parameter,  the development of shifts in the  functions  of erythrc
cytes and arterial  pressure under  conditions of chronic experiments,  the
present author decided  to introduce a substantial safety coefficient  of 12.
The  0.05 mg/m3 porophore ChKh3-5 concentration in the  air of working
premises recommended by this author as the maximal permissible norm wa-:
accepted by the committee of the USSR Ministry of Health.
                                     - 171 -
-------
                                Conclusions

        1.  Toxicity parameter of porophore ChKh3-5 was determined by ad-
ministering the substance  to experimental animals intragastrically.  Re-
sults showed that LDi00 equalled 0.5 g/kg,  LD5O equalled 0.35 g/kg, and
the maximal tolerance dose equalled 0.2 g/kg.  The closeness between the
tolerance and lethal dose characterizes porophore as a substance having a
narrow toxic activity  zone.

        2.  Experimental inhalation of porophore in 20 - 30 and in 7 - 10
mg/m  concentrations for a short time,  and in 2  - 4 mg/rrT  concentrations
for a long time killed the experimental animals,  clearly indicating that poro-
phore ChKh 3-5 was a highly toxic preparation.

        3.  Results of the investigation brought out the dominant effect of
porophore ChKh 3-5 on the  erythrocytes  and on  the  central nervous  system,
the first being in the nature of hypoxia and the second in the nature of pro-
found pathomorophologic changes in experimental animals which died as a
result of the porophore administration.

        4.  Chronic effect of porophore dust inhalation in average concentra-
tion of 00 6 mg/m  elicited reversible functional shifts in the red blood cells
and in the arterial blood pressure;  slight functional changes in  the nervous
system and in  cholinesterase  activities were trancient.

        5.  Based on the  experimental data it is  recommended that 0. 05
mg/m" of porophore ChKh 3-5 in the air of working premises be adopted as
its  maximal permissible concentration.

                                Bibliography
           AjiAbipeoa M. B. BBCTH. TCXH. H aKOiioM. HH(popM.-iuiiii, 19C2. N» 7—8. crp. 152.—
        Posoua H.  tt.. TesHcu flOK.i. 17-ii nayino-npaKTimi'CKoii KuiKJiepiMiuiin no
                  ninienbi. M., 1961. erp. 16.
                                     - 172 -
-------
            Labor Conditions Prevailing in Spraying Cotton Crops
                     with Phospho-organic Insecticides
                                 pp. 24-27

                              A. Ya. Yakubox
     (From the Dusharibinsk Institute of Epidemiology and Hygiene and the
         kiev Institute of Labor Hygiene and Occupational Diseases)
        Phospho-organic compounds have been recently used as insecticides
on an increasing scale regardless of the fact that they were highly.toxic to
man and warm blooded animals.  Many reports have appeared in foreign
literature describing cases'of poisoning  with phospho-organic insecticides
during their application in agriculture.   I. A. Kryuchkova reported in 1959
several cases of phospho-organic poisoning in the UzbekSSR.  Kh. Z. Lyn-
betskii  and  T,  M. Efendiev reported in 1961 on similar cases in  other USSR
regions.   The present author made a direct study of the  sanitary hygienic
labor conditions  prevailing in the application of phospho-organic insecti-
cides to agriculture in different climatic USSR regions.  The first stage of
the investigation was concerned with the application of phospho-organic in-
secticides to cotton crops and was conducted at the Kurgan-Tuvin, Ordzhoni-
kidzabad and in the Khodzhantsk  regions of the TadzhikSSR,  Local  condi-
tions in the Tadzhik SSR, in some instances, are not favorable to the insecti-
cide treatment of cotton  crops  by airplanes, so that crop spraying has to be
done from the ground using tractors.  In some cases the  spraying  was done
entirely manually.  Agricultural workers came in contact with the insecti-
cide (a) during its transportation, (b) during the preparation of  the aqueous
insecticide  emulsion, (c) during the cotton  crop spraying,(d) in  repairing
and adjusting and cleaning the spraying equipment .
Table 1.
Phospho-organic insecticide concentration in the air of «or».in£ ^cncs of
      different methods of cotton field spri, my (average data;

Spray in j method and narking zone

Air Spray Method
Insecticide distribution point . .
Dispatcher's breathing live! . . .


Ground Spraying Method
Trie tor workeru' breathing level .
Breathing level of wornerii using
back carrying spray pumps . . .
Merceftophos
No.of
senpls
on
7G
78
r


...
*3/li

Merlfptophos | Intr.tnion
No.of
Mg/l. «o.of
sanplsj isaopla
i
0,0007
0,0009
n ()(i(V^
•

""
28
10
0,1


'27

! "


0,001
0 000'^


0.0007
•j'j
18
31
H>

«9/»i


0 . OOO."-
o.ooof.
0 ()00">
n i w if 1 1

1C.
0.00 IK.

)?, 0.000'J
       Data in Table 1 show that insecticide concentrations in the air 01 ai]
investigated areas exceeded the maximal permissible norms.  High insecti-
cide concentrations were found in the air at the breathing level of most agri-
cultural workers connected with cotton crop spraying during opening the in -
                                    - 173  -
-------
sccticide pressure containers,  measuring and preparing the reagent, .filling
the airplane and tractor insecticide containers,  etc.; the insecticide spray
fell on the worker s face,  eyes, hands and clothing, and skin of other open
body parts.'

       The airplane method was the most advantageous from a hygienic and
economic viewpoint because it enabled the operator to spray crops  within a
relatively short time with few workers.  However, under present local con-
ditions,  the airplane  cotton crop spraying had certain limitations,,  The tem-
porary airplane landing was below standard from a sanitary viewpoint; the
spraying was done  mostly during the hottest part of the day accompanied  by
enhanced insecticide  evaporation, and resulted in plugging and stopping up
of the sprayers. Cotton crop spraying was done usually with insecticide
doses of 1. 5 and 2 kg per 1 ha,  which created high insecticide concentrations
in the air of working  areas.  The treatment of cotton crops growing in close
proximity to residential areas heavily polluted the surrounding air with the
phospho-organic insecticides.

       The present author noted that methylmercaptophos  and intrathion
concentrations in the air surrounding residential areas did not exceed the
maximal permissible concentrations.  Cotton crop spraying from the ground
resulted in an intense pollution of the air  at the working level, and in addi-
tion the sprayed insecticide became deposited on the workers' unprotected
skin and on their garments.  In addition, the manual spraying method re-
quired considerable physical exertion during the hottest hours of the day.
This was considerably  aggravated by the lack of individual means of protec-
tion against  high air temperature effects.  The  rate of phospho-organic
insecticide  evaporation from the sprayed crops had to be determined.   This
was of considerable importance, since 'Tadzhikistan fields had been usually
irrigated the day following the  spraying.  This  raised the  content of the
phospho-organic insecticide  suspended in the air to concentrations exceeding
the permissible maximum; thus,  during 6-12 hours after  spraying the in-
secticide concentration in  the air was within the range of 0.0001 and 0.001
mg/li, and only after 2-3 days did the insecticide  concentration abate  to
traces.    The personnel connected with the phospho-organic insecticide
spraying of cotton  crops during I960 and 1961 had been examined medically
on a parallel basis.   Under observation were 77 workers.  It had been pre-
viously established that phospho-organic insecticides possessed cholinergic
properties; therefore,  particular attention had to be given  to the  determina-
tion of the vegetative  nervous system condition and to the  blood cholinester-
ase activity which was  determined before,  during and after the workers'
contact with the insecticide.  Results in Table 2 show that  cholinesterase ac-
tivity was  lower in 11 of 16 investigated summer personnel 20 days after con-
tact with the poison.  In 7  of these cholinesterase activity was lowered by
22-33%,  and in the  remaining 4 the drop ranged  between 5  and 16%.  The
average drop amounted to  24%.

                                   - 174 -
-------
 Table 2.
                   concentrations of |:hosj.no-or9«n ic insecticides in the- air ol
                •orkm.j zones at dtferent nethoos of cotton field spraying
Personnel
"•! ' "



Tractor workers . .
Persons operating
"Automax" Man-
ual sprayers. . „
No. of
anal -
y sea
29
;54
54
30
45
Choi inester»se activity
bef ore exposure -
444b±166(100%)
4349+136(100%)
.4118+121 (100%)
4150±152(100%)
3998±123(100%)
In the courts
of -.exposure
3 391 ±162 (74%)
3874±143(89%)
3986+121 (96%)
3250±134(77%)
2810± 82(70%)
• At the .end of
»pra.y in.g . ;
•3560+ 80 ( 80%)
3 988+1 21 ( 92%)
4134+112(100%)
4020±156( 96%)
3925+150(100%)
       It should be noted that summer spraying was usually done with the
more toxic mercaptophos. preparation.  Blood cholinesterase activity was  re-
duced in 8 of 18 tank filler workers.  The reduction ranged between 20 and
30% in 5 workers and  31 and 41% in 3 workers.  These workers had been in
contact with the insecticide for 10  to 15 days.  Three of the 5 workers who
showed a 20-  30% reduction in blood cholinesterase activity worked with
mercaptophos.  Four  of 18  examined signal workers showed  11-25% cholin-
esterase activity reduction.  Results  obtained with the remaining 14 signal
workers were statistically-analyzed and found not significant or not reliable.
The signal workers generally had  been in contact with the insecticide for
2-5 days, which was  too brief for the development of significant functional
changes  under the ^yevailing working conditions.  Blood  cholinesterase ac-
tivity in tractor worker's associated with the ground method of insecticide
crop spraying fell by an average of 23%,and in workers who operated sprayer
VAutomax", the average cholinesterase drop was 30%.  Seven of 10 examined
tractor workers shdwed a 15-37% range of reduction in cholinesterase ac-
tivity.    Cholinesterase activity dropped by 34-37% in 3  workers exposed to
the effects of  mercaptophos for 24 days.  Blood cholinesterase activity was
determined in 15 workers who applied the insecticide manually;  lowered
cholinesterase activity was found in 13,  of whom 5  showed a reduction of 17 -
28%, 4 showed a reduction  of 30-40%, and 1 showed a reduction  of 50%.  All
such workers  had been engaged in the intrathion  crop spraying.  Results of
the investigation showed that maximal reduction  in blood cholinesterase ac-
tivity was found in workers associated with the ground method of spraying, and
during the hot summer months in workers  associated with the airplane  method
of cotton crop spraying.

        Data in  Table  3 show that cholinesterase activity was-affected nega-
tively to different  degrees by different phospho-organic  insecticides.  Maxi-
mal effects were noted in persons  working with mercaptophos in whose
cholinesterase  activity drop  averaged 19%, as compared with an average of
12. 5% in workers  handling  methylmercaptophos and intrathion.  Eight to 10
days after contact with phospho-organic insecticides, cholinesterase began
to rise gradually; recovery was considerably slower in workers exposed t.o
the effects of mercaptophos than in workers exposed to the other two insect!-
                                   - 175  -        % -  '
-------
cides.  Recovery of cholinesterase activity to normal levels was generally
complete in persons exposed to the effects of insecticides  other than mercap.-
tophos.  Most examined workers showed a persistent red dermographia and
a slight hypotonia.  Some workers complained of headaches, thirst,  hyper-
hidrosis and a sensation of heat. Skin temperature determination  showed a
rise in the skin parallel with increase in the atmospheric air temperature.
At 24-25  air temperature the  skin temperature was  32.1°;  at 38-39° of
surrounding air temperature the upper temperature limit of skin of the fore-
head,  the back of the head, of the hands, the chest, and etc. rose  to 35°.
No changes were  noted in the general body temperature.

Table  3.
         Average results of chol incsteruse  hydrolyjed tcet/l chol ine ,*r I ml  of thole
         olo-xi in 30 rain, in cn^loyees «orkiny aith different types of phospho-organic
                                insect icides
Insect icides
Mercaptophos. ...
Methyl raercei'topnos
No. of
anal-
yses
82
40
')()
Prior to expos-jre
In |JLg
4 338 i-76
3771 '-46
4 02.1 '-87
In 5
100
100
100
'Sf^SBFP
In ^9
3581+65
3330 + 57
3550+134
In '!,
81
87
88
At the end of Aork
In U-g
3 784 M 34
3966 + 126
3900 + 95
In ;t
86
10n
99
                               Conclusions
       1.  Cotton crop spraying with phospho-organic insecticides created a
considerable insecticide  concentration in the air at working level. Results
of most analytical tests showed an insecticide  air concentration exceeding
the maximal permissible limit.  Most appropriate method from the view-
point of lower air pollution was the airplane method of crop spraying.

       2.  Studies had been conducted for the determination of negative
effects produced by air suspended insecticide on physiological indexes of
workers engaged in cotton crop spraying with phospho-organic  insecticides;
results  established  that workers connected with cotton crop treating by  man-
ually operated sprayers were more  vulnerable  to the effect of the insecti-
cides.  The same can be said of tractor-hose spray workers, of signal work-
ers, and of the  repair  men employed in  the aviation method of insecticide
crop spraying.

       3.  Some of  the physiological changed noted among the workers,  .  r
as hypotonia, thirst, hyperhidrosis,  etc. ,  may have been the result of hig-i
air temperature or  other environmental causes-  It is  suggested that under
climatic Tadzhik SSR conditions, coupled with high temperature and ex-
cessive solar radiation,  the combined effect of the insecticide and of the hi /
air temperature should be taken into consideration in making  final sanit.ii->,
hygienic evaluations.

                                    - 176 -
-------
                                Bibliography


            K ;> 10 >i K n n ;i B A. B KM.: rnnirii;i. TiihriiKi>.-ionin n K.-NIINIK;I iioiiux IIIHVK Hiijr. urn
         iin/ioii  Vv, l!).r)!», iTp !U.  • .'I in fir UK ii ii X.  X B f n i-c |>e K ;i 11 X. H. I'nr.  u i""i .
         !!)(»!, X"' II, rrp. :«i. - H i|> c- n ;i no n T. M  KJIHII. Mi1.!., litlil. Nv I. <"ip. I-1'
                   Experimental Study of Grain Dust Harm
                                  pp. 28-32

                     M_ I. Karpova and S.  A0 Stepanov
       (From the Saratov Scientific-Research Institute of Rural Hygiene)
        Labor and health conditions  of workers engaged in the grain industry
have been investigated only slightly.  Morbidity due to bronchitis and neural-
gia is  rather high among grain elevator workers.  In fact,  such morbidity-
rates are higher among grain elevator workers than among other personnel
connected with the grain industry, as was shown by M. I. Karpova in 1962.
Investigations conducted by the present authors in 1958-1961 on working con-
ditions in grain elevators and at  mechanized grain conveyors in the Saratov
region showed that the laborers were subjected to the effects of high grain
dust concentration which in many instances  amounted  to hundreds  of mg per
1m  of air.  The installation of grain cleaning machines in electrically oper-
ated and mechanized grain conveyors considerably improved working condi-
tions due to  the fact that grain cleaning installations reduced the grain dust
density in the air to 82-86  mg/m ,  as was shown by M. I. Karpova.

       It was shown that air grain-dust density in Saratov region grain ele-
vators exceeded the maximal permissible dust concentrations 9-120 times.
The highly dispersed fraction, particles of less than 1 (J. in diameter,  con-
stituted 11.2-38.9%.  while  the fraction of particles measuring 1-5 p. in dia-
meter  amounted to 59-98.8%, and the fraction of particles  above 5 M- in dia-
meter  ranged between 2.4-17.4%.  Meteteorological conditions during the
winter months were unfavorable in the grain elevators; the air temperature
inside  the elevators was practically the same as the outside air.  The air  of
the grain drying rooms  contained carbon monoxide which came from the gas
burning room.   Carbon  monoxide concentration was  13 times  above the  maxi-
mal permissible limit.  According to the previously mentioned author,  the
noise at the working levels of the grain elevators also exceeded the maximal
permissible  decibel intensity.  Analysis of settled dust collected at differ-
ent grain elevator working levels showed the presence of vegetable particles
in large  quantities.  Amorphous loam clay and coal particles were practi-
cally absent, and when present in an occasional sample, did not exceed 20%.
Chemical analysis  showed  that the grain dust contained 62-70% of organic
substances and 3.5-17% of  free silicon dioxide.  In addition the dust con-
                                      - 177 -
-------
tained large quantities of fungal spores.  Mycological sprouting tests made
with the grain dust yielded an abundant growth of different fungi.

        The effect of grain dust on respiratory organs of animals was studied
experimentally.  As shown above, grain dust contained large quantities of
fungal spores,  some of which might have been pathogenic to man. There-
fore, the experimental study also included a determination of pathogenic
changes which the grain-dust and the fungal spores could produce in the
organism.

        Settled grain dust was collected in the Saratov region grain elevators
and sterilized to kill all fungal  spores.   The dust was sifted through a series
of sieves followed by partitioning in N. I. Smetanin separator.   The highly
dispersed dust fraction, of particles less than 5 ^ in diameter, was  then
used in the  experiment. White  rats were administered the dust intratra-
cheally by the Gorodenska method and also by the  V. B. Latushkina  inhala-
tion  method. The grain dust was triple steam sterilized at normal pres-
sure.  Fifty mgof the dust was  then suspended in 6 ml of physiological solu-
tion  and stirred until the suspension became evenly distributed.  Forty-nine
white rats were used in the first series of experiments; 50 mg  of the steri-
lized grain  dust was carefully administered intratracheally to each rat under
narcosis.  Ten of the  49 rats died of pulmonary inflamation two days after
the intratracheal administration of the sterilized grain dust.  Surviving rats
were killed 10 days, 4 and 6 months after the dust administration.  In the
second series of experiments,  12 white rats  had been exposed to the inhala-
tion  of air containing 200 mg/m3 of the sterilized grain dust in suspension
for 2-1/2 hours; such  a dust concentration corresponded roughly to the
average concentration of grain  dust in the air of grain elevators. Four and
6 months after the dust inhalation, the rats  were decapitated.   Lung tissue
was  studied histologically  and histochemically using a polarizing microscope.
The  chest cavity was opened under sterile conditions and material was taken
to determine the presence of fungi. The incubated plates developed  a growth
of monotype fungi cultures  similar to those  previously mentioned.  Thirty-
two plate innoculations made from rats of the control group yielded  peni-
cillia in only 4 of the inoculated plates.

        Outwardly,  no difference could be detected between the  behavior and
general appearance  of the  experimental rats and the control rats. It must
be noted, however,  that during  the first  10 days following  the grain dust in-
halation, experimental animals  began to  lose weight.  Later, all  rats gained
weight steadily over a period of 2 months,  after which the rats again began
to lose  weight.

        Microscopic tissue  examinations  showed that 10 days after the dust .
inhalation and intratracheal dust administration pulmonary ceulluar  granu-
lomas developed around the anchored mineral and vegetable dust particles.
The  granulomas measured 10-30 \i in diameter and were distributed  predom-
inantly subpleurally, at times within the  bronchial walls and around  the
                                    -~17 8 -
-------

bronchi and vessels.  They consisted of large cells with engulfed dust parti-
cles, of epthelioid, lymphoid and polynuclear giant cells, as shown in Fig. 1.
There appeared signs of subpleural interstitial pneumonia in the form of in-
durated alveolar septi,  disturbed alveolar lung tissue structure and an in-
creased number of histiocytes in the septi. The differentiation of vegetable
from mineral particles,  which permeated into the lung tissue,  was made by
the microscopic examination of stained sections for the detection of polysac-
charides with the  aid of a polarizing microscope.  Vegetable particles nor-
mally showed the  presence of polysaccharide stained red-violet by the Schiff
stain. Fungal hyphae isolated from grain dust and from the lungs of experi-
mental animals could also be stained by the Schiff reagent

Fig.  1.                                   It has been known that some or-
                                      ganic substances and mineral parti-
                                      cles such as corundum crystals  be-
                                      came illuminated under polarized mi-
                                      croscopic examination, but they did
                                      not stain by the Schiff reagent.  On
                                      this differential  basis  it was possible
                                      to establish that the cellular reaction
                                      in lung tissue, in the form of granules
                                      conglomenated around mineral and
                                      vegetable particles and around fungal
                                      spores and hyphae.  The bronchial
                                      mucosa showed signs of catarral des-
                                      quamation in the early stages of the
                                      experiment,  which later developed into
                                      chronic and purulent bronchitis.  Simi-
lar,  and more clearly expressed,  lung changes were noted in rats sacrificed
4 months after the grain dust administration.  Cellular granulomas occurred
more frequently in tissues of rats belonging to this experimental basis.   Par-
allel  sclerotic changes were more  clearly expressed in animals of this group.
Rats  sacrificed 6  months after intratracheal grain dust administration showed
localized  peribronchial pneumonia, accompanied by purulent bronchitis,
bronchiectasis and abscess forming pneumonia,  as shown in  Fig. Z,   The
presence of foreign particles on the bronchial mucosa elicited in the early
and late  stages following the dust inhalation, proliferation of the cylindrical
epithelium, lymphoid infiltration of the bronchial walls, and  considerable
constrictions  of their lumens. The finer  bronchi became  obliterated.
  Cellular gr«n^lom« "fiicn dtv«lu|.*n around th
   foreign particles
   Hecutoxy I in-eoam st*in. Obj. Hi/,  Ocul. o

        Lung tissue of rats sacrificed during the early and late periods fol-
lowing the intratracheal administraion of the  sterilized grain dust showed
monotypical changes; however, suppurative bronchitis, bronchiectasis,  and
abscesses were noted frequently.    Lung changes in the rats which inhaled
grain dust were less clearly defined than in the rats which received the  grain
dust intratracheally.  In this case,  changes were characterized by the pre-
sence of cellular granulation, interstitial pneumonia, pulmonary emphysema,
catarrahl desquamation of the bronchial mucosa.
                                    - 179 -
-------
 Bronchopnemonii ana abtte&sea d«v«lot,«d »ft«r
  !-.«« months of intratr«che«l ad* in i at rat ion of
  ra« grain dust.
   Henatoxy I m-«osin »t*m«d 3bj,  10  Ocul. 8
Fig. 2.                                  Thus, intratracheal administra-
                                      tion and inhalation of grain dust by
                                      the experimental animals elicited pul-
                                      monary lung changes which were more
                                      clearly defined and more sharply ex-
                                      pressed in the rats which received
                                      grain dust intratracheally.  In the
                                      early stages these changes resulted
                                      from the formation of cellular granu-
                                      lation around the vegetable and miner-
                                      al particles, interstitial pneumonia,
                                      pulmonary emphysema,  and catarrhal
                                      desquamation.  In the later stages,  the
                                      above changes became superimposed
                                      by purulent lung processes,  such as
                                      purulent  bronchitis, bronchiectasis
and abscess forming pneumonia.  The enumerated pathological processes
were not the results  of fungal action.  Such changes, including  the purulent
processes,  had been observed frequently in rats which had been administered
or inhaled sterilized grain dust, although the changes occurred less frequent-
ly and  were less clearly defined.  Nevertheless, consideration must be given
to the fact that it was possible to  cultivate  monotypical cultures of fungi from
smears taken under sterile conditions from surface cuts of lungs.  Fragments
of hyphae and fungal  spores had also been seen  in lung tissue sections,  which
were accompanied by the formation  of cellular nodules.  There appeared some
evidence that  the effect of grain dust on respiratory organs, and the formation
of cellular granules in lung tissue differed with the grain dust composition,
its origin, with the type of mineral and organic particles, and with the  fungal
spores and hyphae present in the  dust.  The morphologic changes noted in the
lungs of the experimental  rats cannot be effects of mycotic flora only.  On
the other  hand,  the effect  on the animal organism of toxic fungal products
cannot be entirely excluded.

                               Conclusions
        1.  Grain dust is composed of approximately 70% organic and inor-
ganic substances and 17% of free silicon dioxide; it also contains spores
of different fungi.  Grain dust suspended in the air of  grain elevators and of
mechanized conveyors consists mostly of high dispersion particles measur-
ing less than 5 M- in diameter.  Actual  concentration of the latter, according
to analytical results,  varied between 82.6 and 97.6%.

       2.  Experiments with rats  showed that the effect of grain dust on
respiratory organs was due to the presence in the dust of mineral and or-
ganic admixtures, and to the presence of  fungal spores and hyphae.

       3.  Intratracheal and inhalation administration to rats of natural and
sterilized grain dust  elicited in the  animals catarrhal and purulent bronchi-
                                   - 180  -
-------
tis,  interstitial, peribronchial and abscess forming pneumonia, and the for-
mation of nodular granules consisting of epitheliod, histioid,  lymphoid and
giant cells.

        4.  Progressively changing mechanization of technological processes
in grain moving and storing increased the air pollution intensity in grain ele-
vators  and in mechanized conveyors creating an urgent need for a thorough
hygienic  evaluation of labor conditions and a study of morbidity among work-
ers employed in the grain industry.   Results of such investigations should
serve as  a basis for the recommendation of sanitary hygienic improvements
in working conditions  of the grain industry.

                                Bibliography


           P o p . 51. — O n a  Hi c.  >Ko.ri.\o:)noe npoiBBonrrno.  1961, .V? 8.
        CT[>. '12.- -O n a >K c.  I'nr. M can.,   1962,  ,N? 1,  crp. 89.—'1 a T y ui K n 11 a B. B  Hoisan
        ycT.'iiirniKa a/in •iKiMiopHMciiTa.ii.noro ncc.'icAonannH AIM"ICTHIISI  npOHSuoacTuciiHoii IIM.TH iia
       •opramuM. M.,  1956 -  1.1 n n 3 e p ;i n n r A. B. Ap.\. nai , I960, n. 2, crp. 76.
      Colorimetric Methodsrfor the Determination of Sulfamate in the Air
                                  pp. 45 - 46

                               T. A.  Lazareva
       (From the Saratov Scientific Research Institute of Rural Hygiene)
       Sulfamate has the formula of NH4,SO3NH3 .  It is a herbicide  used in
the forest industry.  It is a white or yellowish crystalline substance having
a m.p. of 125°; it decomposes at'160''  or above.  It is hygroscopic and is
easily soluble in water.   It can be stored for a long time in a dry atmos-
phere  at normal temperature.  It is not inflammable, not explosive,  but
possessed corrosive properties.  The development of a method for the
determination of sulfamate in the air was conducted on the basis of 2 color
reactions which characterize the NH^  : (a) with Nessler reagent, as de-
scribed in COST 5606-50, Group Zh-29; (b) with phenol and sodium  hypo-
chlorite,  as described by M.I.  Poletave and N.A. Andreev  in 1959.  In the
presence of sulfamate,  the Nessler reagent produces a complex of a yellow-
ish-brown color.   The reaction  sensitivity  is 6. 7 n of sulfamate in 10 ml of
solution.   The reaction between phenol and sodium sulfamate in the presence
of hypochlorite yields a substance of a blue color.  A minimum of 3.  35 JJL
of sulfamate in 5  ml can be determined by this method.  In both determina-
tion methods the intensity of the color produced is directly proportional to
the amount of sulfamate present.  In the elimination  of brush wood the  latter
is sprayed with a sulfamate solution which  may remain suspended in  the air
as a yellowish aerosol.  Air samples for the  determination  of sulfamate
                                    - 181 -
-------
 aerosol are best collected with the aid of fabric filter FPP-15 fastened in-
 side a metallic holder.  The filter is placed into a small glass beaker washed
 several times with small volumes of ammonia-free distilled water for the re-
 moval of the trapped sulfamate aerosol.  The filter paper is then pressed by
 means of a glass rod to remove the  residual sulfamate solution; all the wash
 fractions are poured into a cylinder graduate.

        For  analysis with the Nessler reagent, proceed as follows: place 10
 ml of the sample containing absorber solution obtained as above described,
 into a  colorimetric cup; prepare the standard scale as follows:  set up a
 series of 11  test tubes;  place none  into Tube No. 1, into tube No. 2-0.1,
 tube No.  3-0.2, tube No. 4-0.3,  tube No.  5-0.4,  tube No. 6-0.5, tube No.
 7-0.6, tube No. 8-0.7, tube No.  9-0.8,  tube No.  10-0. 9 and tube No. 11-1.0
 ml of standard sulfamate solution, each 1 ml of which contained 67.13 (a, of
 the reagent.  In this way, the standard scale will  cover a range of 6.7-67.13
 10.  of sulfamate,  as shown in the Table below. Now, add ammonia-free dis-
 tilled water to each of the 11 tubes to the 10 ml mark.  Then  add to all tubes,
 including the one to be tested,  0. 5 ml of the Nessler reagent. Mix the tubes,
 and after 10  minutes make the colorimetric determination.
                     Standard scale for the deternin&t iosi of sulfanate
Tube no»
St&nderd solution
Ml of QBitron lo-fret eater
4i of aqueous phenol
Sodium hyf.ocnl ori to . .
M-9 of

1
A
5

l!
2

4,95

3,35
3
n
4,9

0,7
4
On
4,8

13,4
5
ft i
4,7
X
20,
6
ft A
4,6
0,5
26,8
7
C\ z.
4,5
» X
33,56
8
1 1 fi
4,4
*
40,27
9
A 7
4,3
»
46,99
10
n ft
4,2

53,7
u
n Q
4,1

60,4
\'j
\ n
4

67 , i ,i
        For the determination of sulfamate, by the phenol and sodium hypo-
chorite method, collect the sample as described under the Nessler method.
Remove the trapped sulfamate from the tissue filter FPP-15 as described for
the Nessler method.   Then place 5 ml of the air sample solution into a color-
imetric  cup.   Prepare the standard sulfamate solution so that each 1 ml con-
tains 67.13 p. of the sulfamate. Then add to the tube containing the 5 ml of
the air  sample solution 1 ml of 4% phenol solution and  0. 5 ml of the sodium
hypochorite solution previously prepared by the method described by Poletaeva
and Andrdeva.   Shake, and after 10 minutes compare the intensities of the
blue color with the intensity of blue colors developed in the  standard scale.

       Check tests were  conducted as follows:  samples of air containing
given sulfamate aerosol concentrations were collected from experimental
animal exposure chambers and tested on a parallel basis by the 2 described
methods. The  difference in the results of the  2 methods ranged between

                                    - 182 -
-------
 0.001 and 0.006 mg'of sulfamate, indicating that the 2 methods were of-near-
 ly equal sensitivity.  In view of such results, it is felt that either of the
 methods  could be used for the determination of sulfamate aerosol concentra-
 tion in the air under conditions of agricultural application.
                    Micro Dose Gas Delivery Apparatus
                                  pp.  46 - 48

                               V. D. Bartenev  -     •      ;
         (From the Leningrad Toxicological Laboratory of the State
        Scientific-Research Institute of Polymerized Plastic Materials)
        In conducting toxicological studies based on the continuous supply of
gas into an exposure chamber there arises the need for delivering small gas
doses at one minute intervals; this applies in particular to studies conducted
with gases  #nd vapors under chronic experimental condictions.   The present
author developed a simple micro dose  gas delivering apparatus which oper-
ated on  a continuous  basis delivering 100 ml of the tested gas up to  tens of
thousands  ml per minute.  The apparatus consists of a medical type syringe
which intermittently sucked in and forced gas out. This pneumatically closed
system is  schematically illustrated in  Fig.  1.   The studied gas is first col-
lected into  a suitable  collapsible container from which it passes through a T-
shaped connection into a system of tubes equipped with valves o.r pinch-cocks,
which automatically control the flow direction of the gas.  Valves marked (3)
and (4) are arranged so that when piston of syringe (21) is moved in  the direc-
tion of the arrow, valves (3) open and valves (4) close.  This brings two pro-
cesses into simultaneous action:  in process No.  1 air is sucked into syringe
(21) from the collapsible container and is forced out from  syringe (2") into
the mixer.  As the pistons of the two syringes touch the bottom of the cylin-
ders,  valves (3) automatically close, while  valves (4) open so that the gas is
forced out of syringe  (2') and is  sucked into syringe (2").

                                     The apparatus is mounted on a metallic
                                  plate as shown in Fig.  2;  it consists of a
                                  direct current motor SL-281 of  24v and
                                  26w; it is equipped with a selenium recti-
                                  fier,  a laboratory regulating autotrans-
                                  former LATP-2, a reducing gear  23; 1
                                  ratio.,   a  crank gear and a valve -type con-
                                  necting mechanism, and 2 syringes.  By
Plan of the pneumstic microdose gas delivery means of  a  reducer and a crank gear con-
               -                       .              ...          ,  ,.
i  - coota.ner .ith tn. 9as under *n«iys,sj 2' necting rod the  original motor  rotation is
u"n°cf!!j'rl
-------
  two hollow trunions fixed to a special frame.  At the lower end of the frame
  two syringes are firmly attached parallel to the  horizontal  rod,  but in op-
  posite positions; syringes of different sizes can  be inserted whenever re-
  quired.   Two holders are affixed to each end of the horizontal rod into which
  the piston handles can be firmly inserted and through which the horizontal
  rod  transmitted its in and out movements to the syringe pistons.   One crank
  brings about a complete piston cycle during which given volume of gas  is
  sucked into and forced out of the syringe cylinder.  The valve containing ap-
  paratus part is in the  form of an unevenly balanced water carrying beam, one
  end of which contacts  the circumference of the crank gear and the  other ex-
  tends  into the metallic frame between the two parts of the tubes as shown in
  Fig. 2.  The long shoulder of the beam is attached to the  base or  metallic
  plate  by means of a small spring.  In such position the valves of one pair of
  the tubes are  closed.  The first end  of the beam rolls  along the inside of a
  peripheral semi-circular groove on  the crank gear.  When the extending part
  of the  crank gear comes close to this end,  the position of the unevenly  shoul-
  der beam becomes reversed  and the previously open valves close. As the
  crank gear makes a 180
  original position.
  Fig. 2.
turn the unevenly shouldered beam returns to its


              '
             •
                           u«n«rkl vi<* of the
                                            micronna ly /er

       The speed at which the small gas-dosing apparatus operates depends
upon the speed of the motor and the size of syringes used at the time.  The
speed of the motor can be regulated by means of a laboratory autotransformer.
Maximal rate can be obtained with the autotransformer set  at 24 v.  With this
apparatus it is possible to vary the rate of gas supply within a wide  range.  Gas
supply rate can be  reduced or increased by using a poly staged reducer instead
of the monostage.  The apparatus construction is a simple  one.  It  has no com-
plex detail parts  and can  be assembled in  any laboratory, and can be easily
set to deliver any desired gas volume at any  desired time intervals. The mode!
here described has been used in the author's  laboratory in studying  the chronic
effect of toxic gases on experimental animals.

                                      - 184 -
-------
       Dust Discharged by Plants Producing "Cold Asphalt",  and its Effect
               on the Sanitary Conditions  of Residential Localities
                                  pp. 62 - 64

                        O.  B. Perov and D.  M.  Boris
       (From the Department of Hygiene  of the Ternopol Medical Institute
            and from the Regional Sanitary Epidemiological Station)
  s      The large scale production of improved road paving materials began
 •fJ!|r~the USSR in 1927.  This led to a substantial increase in the production of
 «•** '*?•*   ,-•>-'                                             •
  asphalt, including the preparation of "cold asphalt".  In 1931-1932 plants for
 .''the pfeduction of road paving materials made  of asphalt and ce^ment had been
  opened up in Leningrad, Moscow, and later in the Ural Mountain region, in
  Povolzh'e, in the Ukraine, and in many other  regions.  Plants which pro-
 " dueed "cold asphalt"  operated through the year.

  , ^    "Cold asphalt" is a viscous mixture of finely ground rock and bitu-
  men  or as^phaltl'*'  "Cold asphalt" is manufactured in stationary plants or pro-
  duction departments which use the same production methods; this type of
  asphalt can also.be prepared in the open,  creating unfavorable sanitary hy-
  gilnic working and living conditions in  nearby residential and industrial areas,

         The mineral filler used in the production of "cold asphalt" can be
  sedimented deposits or'crushed or ground igneous rock.  Limestone and
  dolomites are usually most suitable for the manufacture of "cold asphalt".
  The filler particles must not be larger than 8  mm in diameter,  and can be
  as fine as 74 \i in diameter, usually obtained by grinding the original filler
 ••material to a powder. Such filler material is  generally prepared in advance
  and is kept in the open until needed.  In the final operation, the mineral pow-
  der is poured into the dose supplying installation from which it is taken in
  'given quantities and poured into the mixer containing the asphalt.   The tem-
  perature of the mixture is then, raised  to  90-100 .  The powder and the as-
  phalt are mixed to homogeneity and the  mass transported to the storage place.
  In the process of rock crushing and grinding a considerable amount of dust is
  generated which permeates into the surrounding air.  Where "cold asphalt"
  is prepared in the open,  the mineral dust  persists in the atmospheric air for
  a  long time, and is also carried with the air currents to distant and extended
  areas.   The dust pollution pattern of any given territory can be studied by the
 'combination of aspiration and sedimentation methods.

         Data obtained in connection with studies  at asphalt  processing plants
  show that in dry weather the  density of dust in the air over the rock crushers
  and dryers amounted  to 1360-1550 mg/m .  The  air over the mixers at times
  contained 2400 mg/m3 rock dust.  The air  of territories surrounding plants
  producing dry asphalt were severely affected by the generated filler dust.  .
; .Data  Obtained by the present authors, show that through  the year, and depend-
'*• <-  '•'"                    •
                                   - 185  -
-------
 ing upon the wind pattern, the greater part of sedimented dust was found in
 the 100-500 m zone.  Data obtained from dust distribution studies made in
 the proximity of the Skala-podol'sk asphalt plant are listed in the Table below.

                Oust  distribution of the Skala-Podol >sk Asphalt plant
                         (averages of 5-6 detenu met ions)
In the direction of
t»St .....0......
Northeast ..........
North ............






lg/ffl-3 of dust in 24 hour;.
F»ll-flinter ,eriod
Meters
100
4,6
6,1
3,2
4,2
6,3
11,2
7,8
7,8
200
4,0
4,7
2,9
3,0
3,1
6,6
4,5
4,7
frwi t
r,oo
3,7
4,3
2,0
2,0
3,0
6,2
2,3
3,1
rte soul
1 000
2,7
3,1
1,2
1,5
2,7
4,7
2,0
2,3
Spring -Sunner period
"ce of dust formation
100 j 200
1
12,0
7,0
6,3
7,1
7,9
17.3
15,7
20,4
9,3
6,0
3,1
5,4
7,8
12,5
10,8
16,6
r.OO
8,0
5,8
2,3
4,5
7,8
12,3
7,8
11,0
1 Odl)
6,0
4.0
1,«
3,0
7,6
5.H
ti.3
7,1
        Data in the Table show that in the 100 m zone surrounding the asphalt
 plant the dust settled during the dry season of the year on the windy side of
 the plant and amounted on the average to 12 g per 1 m.^ per day; the rate of
 dust sedimentation per day per m2 of area amounted to 20.4 on the windy side
 of the  plant. At a distance of 200 m from the plant the corresponding rates
 of dust sedimentation were 9. 3 g and 16.6 g per 1 ms per day.  At 500 m from
 the asphalt plant, dust concentration in the air was still high, and its sedi-
 mentation rate reached 12.3 g per 1 m3 of area.  At 1000 m from the  dust
 pollution source the  sedimentation rate was still within the range of 1.2-4. 7
 g per 1 m0 per day during damp seasons of the year, and 1.8-7.6 g during
 dry seasons of the year.

        The high dust concentrations generated by plants producing "cold as-
 phalt" and the extensive spread of the dust over the  plant territory and
 neighboring residential areas  created  the following unpleasant conditions:
 the workers' bodies and their  clothing became heavily covered with dust;
 the sanitary condition  of many residential sections in the proximity of the
 "dry asphalt" producing plant  were negatively affected by the dust;  the yards
 and even the inside of residences suffered heavily of heavy  dust settling;
 domestic wash hung out to dry in the open air became coated with the filler
 dust,  and seriously affected,  and in some instances even killed, ornamental
 and other vegetation.

        The following  recommendations have been proposed as means for
improving the above  mentioned deteriorated sanitary conditions.  It was
 recommended, first,  that rock crushing and filler grinding by the  dry  me-
thod should be discontinued during the spring and  summer months  and  re-
placed by a wet  process.  Observations have shown that this change had not
                                    - 186 -
-------
affected the technological aspects of this,.project, while it had considerably
lowered the dispersion of. the. mineral filler and its spread over the territory.
At the point of crushing and grinding  air dust density was  reduced by 50%,
and its. rate of sedimentation, over the. working platform did not exceed the
one usually prevailing'during.'"the: ^al'l a-iid.1 wintey-seasons'.? • -It,.-was recommend-
ed next that the crushing and^grli£d'i'n"g-install                             ,
leak-proof metallic-housings',; aridv.l&at'the; groundjma,terial should be {stored
in dugouts. Observation indicated that :ericasirigthe? crushing arid grinding
installations failed to completely-'atop dulst  dissemination; 'on..the. other hand
storing of the ground mineral fill'.er in. djujgiput's \prpved effective iand prevented .
the stored material from becoming dispejrsed .by.> ai,r >cucrents.; ,f I't..wa*s also
noted that the metal  or other; mate'i?iaiiUS,e'^^
ing and grinding installations rapid.fy deteri'prat^d^Vand; tfe "air^dust density.
gradually returned to the •o.riginaldevelv ^
that the asphalt-cement plant shouldbe:" mb\£ed .".tf'p)^ location'5 m£|e.distant.from
residential areas, and that".it be :sur.ro.uhde.d'.:by.;a/sanita'ry Clearance, zone not
less than 500 m wide.   . However, the most rational way appeared to be to
discontinue production of "cold asphalt" in  the 'Open, and to move all its  oper-
ations inside^pf an appropriately .planned and; construe ted building equipped
with necessary dust'abating  or 'eliminating  installations and 'adequate  fresh
air circulating .ventilation systems. •.It 'was also recommended-that the sani-
tary clearance zone  be implanted with leaf  bearing trees.

                                Bibliography   .

             K p hi >K,.'a ii o B o K a H M.. B., H r H a T b c B a T.;K. -Bpa'i. ACJIO, 1961, M» 7, • CTU  110.
                              NO, 8,. AUGUST-   ./
         Correlation between 3, 4-Ben±pyrene arid Carbon Monoxide
                Concentrations in Automobile'Exhaust Gases
                                PP: 3V8--^.-'     .  •

          V. A.  Gofmekler, M.  D.  Manita, ,Zh. V.. Manusadzhants
                             arid Li.L.  Stepanoy   ..      .    , ;
      (From the Connmunity Hygiene Department^of the-.Central Institute
                       of Automotive Transportation)      .
       One of the most widely.occurring cance^rogenic -s.ubstances in ambienv.
air,   3,4-benzpyrene, is als'o. a component of automobile exhaust gases.  Kr,-
-------
tin and his collaborators demonstrated in 1954 that highest 3, 4-benzpyrene
concentrations were discharged by slow moving auto vehicles.  This is also
true of carbon monoxide;  seemingly, there exists  a correlation between the
formation arid discharge of 3, 4-benzpyrene and  carbon monoxide, as both
may result from incomplete liquid fuel combustion. It was hoped that a bet-
ter understanding of this 3, 4-benzpyrene and carbon monoxide correlation
might  be  of value in dealing with the problem of sanitary protection of atmos -
pheric air.                                                                •

        Concentrations of 3, 4-benzpyrene in auto exhaust gases were deter-
mined by the  spectral-fluorescent method which consists  of the following 4
steps:  extraction,  chromatographic partitioning,  qualitative determination
by fluorescent spectra,  and quantitative determination by absorption spectra,
as described by P. P.  Dikun in 1955. Many authors, namely Sawick and
others, demonstrated in I960 that 3,4 benzpyrene was found in the air in the
solid phase  of exhausts.  Accordingly, samples  of automobile exhaust soot
were collected using synthetic fabric filter FPA-15, which is an acetyl-
cellulose product of low pressure drop and high filter  retention.  It is insol-
uble in organic solvents such as benzene, dichio roe thane and the  like. Two
types of filter holders were used.  The first type was  conically shaped and
had a base diameter of 12 cm.   The above mentioned filtering material was
placed between two copper wire screens  and fastened into the filter holder.
The  smaller end of the conically shaped holder was fastened to the automo-
bile  exhaust pipe.  For sample collecting convenience th^ exhaust pipe can
be extended into  the automobile interior.  By this method, samples of soot
had been collected from an automobile truck trade  marked ZILi-164 as it
travelled over a  distance of 24000 km; the  automobile  was equipped with a
carburetor marked ZH->-120.   Second grade gasoline A-6^6, of the same
batch,  was used  in all experiments.  Gas analysis  was performed using the
Orsa apparatus.  The pressure  drop created by the filtering assembly  \v-is
80-100 mm at the testing speed,  and exceeded 600 mm  during idling.  How-
ever, this difference in pressure drop was not accompanied by any noteable
change in the  carbon  monoxide content of the exhaust gases at the time of
soot sample collection; immediately after, the filtering assembly had been
disconnected with the engine running at the same speed.

       Three series  of samples had been collected as above described,  The.-
amount of soot collected per sample varied between 50 and  300  mg.  The de-
termined 3, 4-benzpyrene .ranged between 0.24 and 45 M. per sample. 3, 4--
benzpyrene concentration in the exhaust soot of  an idling automobile r.-ii.^e..
between 9.00015  and 0.0022%.   The color of the  filter  after sample  collec-
tion  varied from yellow to deep velvety black.  The first series coiisisted of
6 samples collected while the auto truck  was idling at  400-1200  rprv...  During
the collection of  samples for this series  the carburetor was under control
and performed evenly and efficiently so that in the  10 minutes of sample col-
lection only a slight greyish soot deposit accumulated,  which gave either very
slight or no positive tests for 3, 4-benzpyrene.
                                    - 188 -
-------
affected the technological aspects of this,.project, while it had considerably
l«owered the dispersion of'the mineral-filler-and its spread over the territory.
At the point of crushing and grinding air dust density was  reduced by 50%,
and its rate of sedimentation, over the, working platform did not exceed the
one usually prevailing'during, the; fall; and.1 winter:-se.asons^ v ItVwas recommend-
ed next that the crushing and;grinding ihsti'allat'io.his^shduld'b'e enjclbsed in
leak-proof metallic -housings, andv1&at'the, ground^material should be ^stored
in dugouts.  ObservatipnHndiCated/that^ericasmg ;thej crushing arid grinding
installations failed -to completely 'atop du;st dis.semination;!on,,the, other hand
storing of the ground mineral fille'r^in/diugouts,proved effective land prevented
the stored material from becoming dispe;rs:e.d'b'y> ai,r.cur-rents.••'..• rt.,wa*s also
noted that the metal or 6ther.:rriat^Eial4u-s.^:'d''$i3r-;:the/e'nca'S.ement''of the crush-
ing and grinding installations irapidTy det'eriorafejd^a.nd the ;'air\,dust density
gradually returned to thevorigihal leve.i/'Xhe.rerfore^ it was xecommended
that the asphalt-cement plant should be rnbyed t'p|a:. location'' rriprje distant.from
residential areas, and that.it be sur.ro.unded by.';a ;sanita'ry.. clearance zone not
less than 500 m wide.     However, the most rational way appeared to be to
discontinue production of ."cold asphalt" in the'Open, ahd:to move all its  oper-
ations inside%pf an appropriately ..planned and; constructed building equipped
with necessary dust'abating or'eliminating in'stallati'ons and adequate fresh
air circulating .ventilation systems. : It .was also recommended  that the sani-
tary clearance £one  be  implanted with leaf bearing  trees.

                                Bibliography .".'•"••
                   I    •    * ':    ••-...           •  ,.   .._  -.-...
             K p H JK/.'a n o B t K a H M. B., H V H a T b c B a T. .K.-Bpa'i.  ae.no, 1961, j\r» 7,-cTO  110.
                              NO, 8,. AUGUST-
         Correlation between 3, 4-Benzpyrene and Carbon Monoxide  •
                Concentrations in Automobile: Exhaust Gases
                                pp: 3 .- 8        '             .

          V. A. Gofmekler, M..D.  Manita, ,Zh. V.. Manusadzhants
                             and Li . L.  Stepanov   /  p   .    : • ••
      (From the Community Hygiene Department of the-,Central Institute
                       of Automotive  Transportation)      ..
       One of the most widely, occurring cane erogenic 's.ubstances in ambient:
air,   3|4-benzpyrene, is als'b. a component of automobile exhaust gases.  K;--

                           ' •-• '  .'• '   -.187''-: '•••-'•   '-•  ..    ,'  .'.' •
-------
tin and his collaborators demonstrated in 1954 that highest 3, 4-benzpyrene
concentrations were discharged by slow moving auto vehicles.   This is also
true of carbon monoxide;  seemingly, there exists a correlation between the
formation arid discharge of 3, 4-benzpyrene and carbon monoxide, as both
may result from incomplete liquid fuel combustion.  It was hoped that a bet-
ter understanding of this 3, 4-benzpyrene and carbon monoxide correlation
might  be of value in dealing with the  problem of sanitary protection of atmos-
pheric air.

       Concentrations of 3, 4-benzpyrene in auto exhaust gases were deter-
mined by the  spectral-fluorescent method which consists of the following 4
steps: extraction,  chromatographic  partitioning, qualitative determination
by fluorescent spectra,  and quantitative determination by absorption spectra,
as described by P. P. Dikun in 1955. Many authors, namely Sawick and
others, demonstrated in I960 that 3,4 benzpyrene was found in the air in the
solid phase  of exhausts.  Accordingly, samples of automobile exhaust soot
were collected using synthetic fabric filter FPA-15,  which is an acetyl-
cellulose product of low pressure drop and high filter retention.  It is insol-
uble in organic solvents such as  benzene, dichloroethane and the like. Two
types of  filter holders were used.  The first-type was conically shaped and
had a base diameter of 12 cm.  The above rnentioned filtering material was
placed between two copper wire screens  and fastened into the filter holder.
The  smaller end of the  conically shaped holder was fastened to  the automo-
bile  exhaust pipe.  For sample collecting convenience the^ exhaust pipe can
be extended into  the automobile interior.  By this methodj  samples of soot
had been collected from an automobile truck trade marked ZIL-164 as it
travelled over a  distance of 24000 km; the automobile was; equipped with a
carburetor marked ZIL-120.   Second grade gasoline A-6;6, of the same
batch,  was used  in all experiments.  Gas analysis was performed  using the
Orsa apparatus.  The pressure  drop created by  the filtering assembly  was
80-100 mm at the testing speed,  and  exceeded 600 mm during  idling.  How-
ever, this difference in pressure drop was not  accompanied by  any noteable
change in the  carbon monoxide content of the exhaust gases at- the time of
soot sample collection; immediately  after,  the  filtering assembly had been
disconnected with the engine running at the same speed.

       Three series  of samples  had  been collected as above described, The
amount of soot collected per sample  varied between  50 and 300  mg.. The de-
termined 3, 4-benzpyrene .ranged between 0.24  and 45 M. per sample,  3, 4--
benzpyrene concentration in the exhaust soot of an  idling automobile ran^e:.
between  9.00015  and 0.0022%.  The color of the filter after sample collec-
tion  varied from yellow to deep velvety black.  The first series consisted  of
6 samples collected while the auto truck  was idling at 400-1200  rpn..  During
the collection of  samples for this series  the carburetor was under control
and performed evenly and efficiently so that in  the 10 minutes of sample col-
lection only a slight greyish soot deposit accumulated, which gave either very
slight or no positive tests for 3, 4-benzpyrene.
                                    - 188 -
-------
 Table 1.
           3,4-benzpyrcne and carbon monoxide concentrations in autonofti It exhaust
Enyine operation
Transmission
SP«ecl | .;- rp-ben/pyrcne
.Mg/«3' «9/««n
Carbon monoxide
Abs...
9/«3
                             :      . Id I ing engine

                  First series «ith carburetor in good condition










'400
'• 600 .
''800
1 000 •
I 200
1
• 1
•'2
1
1
0,00
0,00
• 0,00 :
0,80
0,89
_

- v
•0,60
1,07
Second series Carburetor at cruising speed
























400—500
600
800
1 000
1 200
1 400
1 600
1 800
2000
2200
2400
2600
1
1
o
2
2
2
2-
'2
2
2
2
1
0,00
0,06
0.41
0.04
2.22
0,10
(),UO
0,00
0,0)
0.00
0,05
0,55
	
0,02
0.22
O.U3
1 .80
U.09
~_
0,06
—
—
0,10
1,10
                                                              0,8.
                                                              0,8
                                                              0,<6
                                                              0,4.
                                                              0,3
                                                              0,4
                                                              1,0
                                                              2.8
                                                              5.it
                                                              -.2
                                                              I!o
                                                              0,8
                                                              1,0
                                                              0,5
                                                              0.5
                                                              2.2
                                                              2,8
                                     In nation

                         Third series with carburetor at cruisiny speed
                                                            10.0
                                                            '10.0
                                                             7.5
                                                             5.0
                                                            3,75
                                                             5.0
                                                            12,5
                                                            35.0
                                                            (V2.5
                                                            27,5
                                                            12,5
                                                            10,0
                                                            ,12,5
                                                             7,5
                                                             6,3
                                                            26,9
                                                            35,0
11

"I

IV— V
Ditto
» »
» »
0—15

10-30

30
40
50
60
400-250.)
Accelerated
1 400—2 hOO
Accelerated
1 UOO-1 20' i'
1 400—1 lid)
1 800—2 ! 00
2 200—2 400
1

' 1

2
2
2
2
26,70

8,57

3,90
1,80
1,30
0,50 •
75,00

'31,30

2.90 .
2 , 50
2,50"
1 .50
4,'i

2.7

1,6
1.2
.0,7
'0,9
61.3

33,8

19,4
14,4
• 3,8
10,7
        Twenty-one samples were collected in the second series of tests un-
der all auto truck operation systems.  Two samples were collected with the
engine operating at each of the following speeds: 400,  600, 800,  1000, 1200.
1400,  1600, 1800,  2000, 2200,  2400 and 2600 rpm.   Concentration (C) -,f tl,>
3, -I -benz.pv'rene was  computed with the aid of the following forr/j^i;;.,
                                            I <»jO
in which S~ denotes 3, 4-benzpyrene concentration in the  sample in ;J<; r-.'.
denotes the volume of exhaust  gases in m ;  15- is the conversion coefficient;
0. 74- is the sp.  gr. of the fuel; P- is ml  of fuel consumed.
mula:
Carbon monoxide concentration was computed by the  following for-

                         C = a-1,25-10 e/M\

                             -  189  -                 '   :    '
-------
in which (a)- denotes volume percent of carbon monoxide; 1.25- is the weight
of 1 ml of CO; 10- is the conversion coefficient.  Determination data of the
series are presented in Table 1.  Data in the Table show that changes in 3,4-
benzpyrene concentrations in the exhaust gases were accompanied to a de-
gree by corresponding  changes in the carbon monoxide concentrations,  which,
as shown in the  Table,  ranged between 5  and 62.5 g/m"J.  The correlation
coefficient  of 3, 4-benzpyrene and carbon monoxide concentrations amounted
to 0,42,  which was twice the value of the average experimental error.

       Twelve soot samples were collected in the third series at different
motor speeds, using the same carburetor as in the second series.  Two
summary samples had been collected under different motor  operation condi-
tions  during a 1  km drive. The different  operations included the start,  even
motion and use of brakes. The 3, 4-benzpyrene concentrations in the two
samples were correspondingly 3.28 and 3.87 (J./m° , which from the practi-
cal viewpoint, can be regarded as identical.  Higher 3,4-benzpyrene con-
centrations were obtained when the motor operated in second gear; as the
motor speed increased, the 3, 4-benzpyrene concentration gradually abated
to a mere trace, as shown by the data listed in Table 1.

       The carbon monoxide concentrations expressed in g/m  practically
paralleled the 3, 4-benzpyrene concentration curve.  The correlation coef-
ficient between 3, 4-benzpyrene and carbon monoxide concentration in this
series of experiments amounted to 0,96 and was  32 times greater than the
average experimental error, which indicated high reliability of the correla-
tion coefficient.   However,  the working area of the soot collecting filter
used under above described conditions was relatively small  and created a
high pressure drop.  For this reason, following  series of experiments had
been performed  with a  soot collecting filtering apparatus of  a considerably
lower pressure  drop.  The filter holder was in the form of an elongated
cylinder.   One end of it was tightly sealed. Synthetic tissue FPA-15, measur-
ing 30 x 94 cm,  or of 2820 cm"0 working area,  was wrapped  around the cylin-
der.   The tissue was held in place by a wide gauge copper netting.  This
assembly,  together with a water  cooling device,  was attached directly to  the
exhaust pipe of an automobile truck of mark GAZ-51A.  Soot  samples were
collected as the  motor truck was driven 122-127 km along a level section of
the Leningrad highway.

       Records  were kept of gas fuel consumption,  time of sample collect-
ing, conditions  of motor operation, partial vacuum created in the air suck-
ing tube, resulting pressure drop,   and carbon monoxide concentration in the
exhaust gases, as indicated by a  device developel at the Scientific Research
Institute of Autotrarsportation, known as  NIIAT, with 0.1% accuracy.  This
filtering device  created a pressure drop of 30-40 mm of water column at  low
motor speed, not exceeding  140-160 mm  at high  rpm, and at 60 km/hr speed
as shown in Table 2.   Such a low pressure drop had no effect on the normal
motor operation.  It had no effect on the initial carbon  monoxide content in
                                   - 190  -
-------
 the exhaust  gases,  nor did it have any effect on the degree of negative pres-
 sure  developed in the air sucking pipe, or collector, which is'a true'reflec-
 tion of the condition of  the  motor operation.

 Table 2.
           Effect of soot sample tailing on the operating efficiency of motor GAS-51
Operating conditions
Resistance '
(.pressure drop )
in KB of *ater
column
Discharge in
suction collector
ffith 'ftitneut
filter , the
device | device
CO in g/B3
it t h ' Ji triout
th«. the
device device
                              Carouretor He II regulated
        Loed «>..5 - 3.J ton
        tV trinsroia* ion 20 km/hr.
         »  '  »   40  »
         »    »   60  »
30
40
70
270-280
200—220
70—80
•
2SO
21 '0- -220
70—80
-------
with the carburetor properly adjusted, and from 88.2 to 2 |J./min in the
second period of experiments in which the  carburetor had not been well ad -
justed, as shown in Table 2.
    10
  v
  s
  *."
  N

  I"
  "* U-
    /

    f-
                         so  60
          IS
                                                Conclusions

                                         1.  Carbon monoxide concentration
                                     in automobile exhaust gases ran in cor-
                                     relation with the concentration of  simul-
                                     taneously occurring 3,4-benzpyrene;
                                     accordingly,  CO concentration can
                                     be used as an indicator  of the rate at
                                     which 3,4-benzpyrene is discharged
                                     into the atmosphere with the automo-
                                     bile exhaust gases.

                                         2.  Automobiles with properly ad-
                                     justed carburetors generated and  dis-
                                     charged into the atmospheric air less
                                     carbon monoxide and less 3, 4-benz-
                                     pyrene.

                                         3.  The highest concentration  of
                                     3, 4-benzpyrene and of carbon monox-
                                     ide  was discharged with exhaust gases
                                     coming from automobiles operated at
                                     low rpm,  usually at the time of start-
                                         or accelerating.
 txhttust of 3,4-ben*pyrcr>* by different auto-
 mobiles at different operation conditions
 I  — 211-16*4 "ith  carburetor poorly adjusted;:
 2 -GAS-SI »ith carburetor well adjusted;   :
 3 - GAS-SI with carburetor poorly adjusted
                                         4.  Atmospheric air pollution with
                                     3, 4-benzpyrene and carbon monoxide
                                     can be reduced substantially as follows:
by controlled carburetor operation at all times,  particularly when starting
and moving into line with the traffic,  and most of all by keeping the  car-
buretor clean and well adjusted; by reducing to a minimum the number of
stops and starts  at cross sections and light signals.  This can be  done by
proper manual and signal traffic regulations and  by instituting overhead
and underground auto routes which would allow automobiles  to travel witho-n.
m.»khi£ in.-uiy stops.

       See  page 193 for Table 3.
                                     - 192 -
-------
Table 3.
            ;l4—benzpyrene end CO concent rat i one in exhaust jases of autweooile GAc. 5IA
Operttm.,
conditions
meaion
Ko/nr
No. of
s»ople?
. . 3,H-Wipyren«, .
.9/-3
( *
' CarLon aono»ioc
Abbl. ,(,
;
First series^ carouretor sell «o justed t
11

III

111
. IV
IV
IV
0—20 Ac-
eel oration
15-35AC-
celeration
Ditto
20
40
• 60
2

1 .

1
1
1
1
1,45,'

0,83,

' Traces
» '.
»
1,52
• 4,3$ ' '•••

; . 0-47 •:.',.

Traces"- .x
»
»
4,40
' 	 :
'.
—
«
, . '_ —
•^"0 1
-------
tioned pesticides may unfavorably affect the organism's resistance to differ-
ent diseases, thereby raising the rate of different morbidity types among
workers coming in contact with such pesticides; and in fact, E. N. Burkats-
kaya, G. A0  Voitenao, E. P. Krasnyuk and others have shown that morbidity
of different types was more frequent among workers engaged in the produc-
tion of chemical pesticides.

       The present author studied the effect of HC1CH Y-isomer, a com-
ponent of hexaclorane, on the immunobiological properties  of the animal
organism.  Hexaclorane,  a trade name  for HC1CH, is widely used in agri-
culture as  an insecticide;  it consists of  several stereoisomers of which
only the Y-isomer is of practical value.  Technical hexaclorane contained
12-13% of Y-isomer.  However, the production of hexaclorane containing
60-90% of Y-isomer and its application are gradually increasing. The
Y-isomer of  HC1CH is a polytropic poison which acts on the central nervous
and vegetative nervous, systems.  LDBo  of this isomer for rats is 120/mg/kg,
according to some  authors, and 190 - 200 mg/kg, according to other investi-
gators.  It possesses  no well defined cumulative properties; however,  daily
administration of this preparation in oily solution to rats at the rate of 20
mg/kg for  22 days  resulted in the rats'  loss of weight and appetite, drop in
the liver glycogen level, and in fatty liver degeneration.

       The clinical picture of Y-isomer HC1CH poisoning, is as  follows:
stimulated central  nervous system, hyper salivation,  tremor, convulsions,
emaciation,  blood picture  changes, etc. The maximal permissible Y-isomer
concentration in the atmospheric  air was set at 0. 00005 mg/li.   The  effect of
Y-isomer HC1CH on the immunobiological reactivity was  studied using rab-
bits  and cats as experimental animals.  The preparation was administered
to the rabbits daily, for 3  months at the rate of 10 mg/kg.  Experimental cats
were exposed to the inhalation of air containing 0. 002 mg/li of the toxic sub-
stance in specially constructed chambers four hours daily for 2 months.  Of
4 such experimental series 2 were performed with the HC1CH y-isomer, us-
ing 5 rabbits and 5 cats, and 2 control experiments of 5 rabbits and 3 cats.
Experimental animals of all series were triple immunized with typhoid vac-
cine containing 1 milliard  micro -organisms per ml.  The vaccine was ad-
ministered subcutaneously to a total of  2.5 ml in the following order:  0.5 ml
the first injection,  and 1.1 ml each of 2  following injections at weekly  inter-
vals. Seventy-five days after the exposure, the animals  were revaccinated
subcutaneously with 1  ml of the vaccine. Tests for the  determination  of  the
animals' immunobiological reactions were as follows:  agglutination titer
after the typhoid vaccination, blood complement titer and leucocyte phago-
cytic titer.   The latter was checked for  phagocytosis intensity based on the
average number of phagocytized microorganisms per phagocyte,  and by es-
tablishing the ratio between phagocytically active and nonactive polynuclear
leucocytes.  The phagocytic activity of  leucocytes was determined as  follows:
using a micro-.pipette, O.I ml of 2% sodium citrate solution was placed into
a centrifuge  tube followed by 0. 2 ml of whole blood and 0. 2 ml of typhoid

                                    - 194 -
-------
 fever diagnostic agent which contained 2 milliard microorganisms  per ml.
 The centrifuge tube was  rotated between the hand palms for 2-3 minutes until
 the suspended bacteria became evenly distributed.  The centrifuge tube'was
 then incubated for 30 minutes and centrifuged.  The leucocytes  separated
 into a layer were drawn  off with the aid of a:Pasteur pipette, deposited on a
 microscopic slide,  spread, fixed with ethanol,,1 stained by the Giemsa method,
 and examined microscopically under the oil immersion lens.

        As indexes of Y-isomer HC1CH effect on the animal organism the
 present author used body weight and temperature, appetite, general animal
 behavior;  blood Sedimentation changes were  noted and recorded in the case
 of cats. Results showed that 'the above indexes were practically the  same  in
 the experimental as in the  control ariimals which  were immunized  by the
 typhoid vaccine but not exposed to the effects 6f the Y-isomer.   The study in-
 dicated that immunobiological indexes of cats and rabbits  possessed species
 specific characteristics.

        The aggultination titers of the  experimental and control  rabbits,
 prior to having been immunized,  varied between 1:20 and 1:40, as  shown in
 Table 1.  One week after the first immunization,  the aggultination titer in the
 experimental rabbits  increased 12 fold, and only 8 fold in the control rab-
 bits.  Following the second immunization the aggultination titer rose 80-fold
 in the experimental animals and 18-fold in the control animals.  Continued
 administration of the  toxic Y-isomer to the rabbits had no effect on the blood
 aggultination, which retained its final enhanced titer.  This  indicated that
 •rabbits subjected to the action of low Y-isomer  concentrations during the
 first  stage of poisoning became immunologically more reactive  and produced
 larger  quantities of antibodies in response to typhoid vaccine.  Following re-
 vaccination the aggultination titer rapidly rose in the control rabbits to an
 average quadruple intensity of the original.  At the same  time.the post-'re-
 vaccination aggultination titer remained practically the same in the experi-
 mental rabbits.  The  complement titer dropped to lower levels during rab-
 bits chronic exposure  to the effects of the HC1CH Y-isomer to the same de-
 gree as in the control rabbits.  However,  7 days  after revaccination there
 appeared a  notable fall in the complement titer of the experimental rabbits '
 and a considerably lesser drop in the  control rabbits;  in the experimental
 rabbits the drop amounted to 50%, and in the control rabbits only  to 12%.

        On the basis of the results it can be assumed that prolonged exposure
 to HC1CH Y-isomer  after the first period  of defense mechanism activation
 in the living organism elicited the appearance of depressed immunobiologi-
 cal activity in the form of arrested agglutination titer increase,  and in a
 drop in the complement titer. Aa B. Sakhnovskii noted similar  changes in
 lead poisoning.   He observed that the  organism's  defense  functions in lead
 poisoning could be expressed so intensely as to conceal from observation the
 phenomenon of bactericidal  depression.  However, long exposure to lead poi-
 soning  brought   about changes in the-phases  of bactericidal activity, point-
ing to a rise in the organism's defense properties.  No changes  have been
                                    - 195 -
-------
 noted in the indexes of weight, body temperature, appetite, general animal
 behavior,  etc.  This led  to the assumption that changes in the immunibio-
 logical reactivity of rabbits exposed to the toxic effect of HC1CH y-isomer
 under  chronic conditions appears as the only early symptom of intoxication.
 It should also be noted that rxo changes appeared in the phagocytic activity of
 leucocytes under conditions of the experiment,  and so visible sig,ns cf .;,,!
 i-'oxicn'taon a!^pvsaivM! in  ®>e animals s*posed to  the .a.,ctioa c: HCiCH •• -.'.»u;r.vr v
 for  3 months.   The total amount of HC1CH y-isomer received  by all the
 experimental rabbits amounted to 8  lethal doses (LD100).

 Table 1.
                  Agglutinative titr«e of rtbbtts •xpo«ed to chronic inhalation
                          of hvxBChlorocyclohexone  Y-'sooer v«por


An in* Is


Immunized «nd
exposed to in —
h«l«t ion of
HCICH Y -*•«•«•
v.por }nh»U-
tlon
Av«r«9«e
Controls




Averigos
e
*
J
e
*.
24
25
26
27
28

17
18
19
22
23
A
— * —
•
•D
4
*
j;
:40
:.20
:20
:20
:20
:40
:40
:20
-.40
:40
1:40
I ig
a .=
a'a a
>,— H
s
i^-S I
1 : 320
1:320
1:80
1:240
1:240
1:240
1:400
1:240
1 : 3"Q
1:3-1
1:3
1:320
»iS
9-« •««
5^.5
"* e S
N.-f •
1 : 1 600
1 : 1 £00
1:800:
1:2401
1 : 1 1.00
1 : 1 600
:32C
:320
:640
:1 600
:800
1:730
I * C
t*. a H
«•-•-
|S9
U §
K-S a
1:600
1 : 3 200
1:100
1 : 1 600
1:1600
1 : 1 600
1:6(10
1 : 400
1 : 400
1 : 1 600
1:800
1:760
"S»S
• •**
•W-
«-S
<&*
1 : 1 400 '
1:800
1 : 1 600
1 : 1 600
1 : 1 6' 0
1 : 1 600
1:600
1-200
1:200
1:600
1:400
1:360
i i
*. u
* * 6
^
' <».£
(S.-M U
1 : 1 600
1 : 1 600
1:800
1:800
1 : 1 600
1 : 1 600
:2400
:800
: 1 600
:1 600
: 1 60U
1:1600
*• u
• c
f!i
a- • -
— *• u
1 : 1 600
1 . 1 600
1:1600
1 : 2 400
1 : 800
1:800
1:2400
1:1 600
1 : 1 GOO
1 :2'100
1 : 1 600
1 : 1 900
       Agglutination titer changes in experimental cats exposed to the inhala-
tion of HCICH y-isomer were similar to those manifested in the experimental
rabbits.   The initial 1:40 titer of the control cats rapidly rose to an average
of 1:6400, while in the experimental cats the  titer rose from initial 1:60 to
1:1280.  In two of the five experimental cats the agglutination titer dropped to
1:100 before they died. The complement titer of the experimental cats did
not differ significantly  from that of the control rats.  In the light of the pre-
sent findings  blood serum complement cannot be used as the determining
indicator of the organism's state of immunoreactivity.  V. K. Navrotskii
studied the  effect of low SOg concentrations on the immunobiological reac-
tivity of  rabbits; he also noted that changes in complement titers were poor-
ly defined and insufficiently characteristic. The phagocytic activity rose
significantly in 4 experimental cats, as shown by pertinent averages listed
in Table 2.     Comparison of the results showed that the phagocytic number
rose by 0.04 in the control cats as compared with 0.35 in the experimental
cats, or more than 4  times as high as in the control cats.  Phagocytosis in
the experimental cats was  also four times  as extensive as in the control cats.
                                     - 196  -
-------
 Table 2.
               Average (.htgocytic activity values in cuts exposed to chronic inhalation
                                of HCICh Y-»«»»er inhalation

Animals



InMiunized «nd
exposed to
HClCH Y'°"—
raer inhklt—
t ion
Controls

a
° B
• .V
o c

5



3


Index



Phagocytic number
Ph«gocytic extan—
sivcness. . , .

Phagocytic number
t'hatjocytic exten-

—
•• 9
• *m (9
C "O

0,78

0,27

0,8
0.3
i
^•s
ft •»

3fcrf^ ^

yi
1.13

0,33

0,84
0,32
^B§
K -.-
I/I 0 *
>VM N
* .-
"«f
t~.~t
1,26

0,35

0,94
0,32
1 1 C
* 5 -
a a*o
>.<*! "
a •—
•o i. c
V 3
I--.H 8
1,29

0,39

1,09
0,31
i "
« B ^
» •*
l l
•S2S
> *
a?rri s ' ^ ^ *
5 - : • c
0 41 §
'O "H C
1.14

0,3

1.11
0,3
0 fc-i
vu
f1^ -»^
1,16

0.39

1,14
0,40
W- 0
* *K
> O
v> it -
»% t *j

*i.£
3- H-> 0
1 .0

0,35

1,0
0,36
        Phagocytic activity rose to higher levels in the experimental cats with
each successive immunization, a  phenomenon not noted in the control cats.
The rise in the phagocytic activity of the experimental animals seemingly re-
flected stimulated activity and development of the defense processes.   No
further  clearly defined  phagocytic activity changes  had been  noted in  either
the control or experimental animals during the remaining 45  days of the ex-
periments.  At the end of the experimental period there appeared a rise in
the  erythrocytes and leucocytes sedimentation rates of the cats.  Two cats,
which died two months after  exposure to the inhalation of the  poisonous
Y-isomer, developed symptoms of apathy, loss of appetite, loss  of weight,
tremor  and convulsions.
                                   Conclusions

        Prolonged effect of HCICH Y-isomer in the doses used elicited changes.
in the organism's immunobiological activity,  particularly in the agglutination
titer.   The latter first rose to higher and then dropped to lower levels.   The
agglutination titer dropped to lower levels as  the result of HCICH Y-isomer
effect only after revaccination of the experimental animals, which points to
the phase character of the changes,  namely, a rise in the immunobiological
organism reactivity during the early intoxication period followed by activity
depression.

                                   Bibliography

            R v p K a n K a H V.. II., B o fi T e n K o F. A..  K p a c H K> K E. II.  PHP. H can., 1961,
        .Vo 9, rip. L'4.--R y p K a u K a si E. H.  OapMaKo.i. n  TOKCMKOJI.,  1959, N> 3, cip. 272. —
        K ii p si M K o 13.  A. B.iiifliuic xpoiuniecKoro OTP.-IH/ICHHSI cmmuoM iia  nMMy>io6»o.noni'ip-
        CKVIO poaKTiinnocTb opramoMa >KHBOTHbix. I"nrnena H caiuiTapnfi, 1957, .No 8, eip. 30. —
        HanpouKHii B. K. Fur. H can.. 1959, N° 8, cip. 21. — C a x H OB c K H ft fl. H. O 6aK-
        rcpimi&iioc'iii  cunopoTKii npii  cinuiuonoM oipan.ieHMii.  Tpyju N KpaiiHi-Koro niuMiiiyia
        paOo'ioif Me.iitHiiiiiJ  1920 crp. ;J2 --TilRiier S..  Naumvisi'nsclKii'U-n.  I'.i"".  li'l. l'^-
        -S. 259.
                                       -  197  -
-------
    Colorimetric Method for the Determination of Monoisoprophydiphenyl
                                 in the Air
                                pp. 40 - 41

                              M.  I. Poletaev
                                 (Moscow)
       Monoisopropyldiphenyl (MIPD)

                                              CH.,
                             	     	       I

                                              CH3

is a transparent liquid of a yellowish color, having a characteristic  aroma-
tic odor.  Its  m.p. is 270°-297°. sp.  gr.  at 20° is 0.9865, and its flash point
is 117°.  Ninety-five  per cent of the final product consists of isomers  ortho-,
meta-, para-, and 5% of diphenyl.  It is  used as  a heat carrier and in the
production of  snythetics in many branches of the  USSR industry.  The pur-
pose  of the present paper is to report on attempts to develop a method for
the determinati on of MIPD in the air of working premises.  This author used
the method based on  the colorimetric determination of MIPD by the Yanov-
skii reaction.  Air samples were collected by the aspiration method using the
Polezhaev microabsorber which contained 1 ml of a nitro mixture consisting
of 10 g of ammonium nitrate in 100 ml of sulfuric acid of 1.82-1.84 sp. gr. ;
the air was  aspirated through this medium at the rate of 0.2-0.4 li/min.
Where the concentration of MIPD is  suspected to be high,  air samples can be
collected by the vacuum method into special containers of 100-200 ml capa-
city.   Two ml of the  nitro mixture is added to the air sample containing ves-
sel, and let stand for 1 hour periodically washing the walls of the sample con-
tainer with the nitro  mixture.

       Perform the analysis as follows:  remove 1-2 ml of the nitro mixture
absorber and  place  into a separatory funnel marked at 50 ml to which 2 ml
distilled water had been previously added;  wash  the absorber   with 4 ml of
distilled water and add to the separatory funnel.   Further procedure of the
MIPD  determination  can be accomplished either by extracting the polynitro
compounds with acetone from alkaline solution,  or by ether from the acid
nitro  mixture. In the first case,  proceed as follows?  neutralize the content
in the  separatory funnel with 30% NaOH to slight  alkalinity, using litmus as
the indicator.  Then  add 0.5-1.0 ml  more of the alkaline  solution,  add  3 ml
of acetone,  and shake vigorously  several times.  Allow the mixture to sep -
arate into layers.   Remove the  upper aqueous-acetone layer into a colori-
metric tube with a  ground-to-fit  stopper, which  should yield 5.5-6.0 ml.
If at this  point there  occurs a separation of salts in crystalline  form, heat
the separatory funnel in hot water up to 40-45°.   Use a  previously prepared
                                    - 198 -
-------
scale of MIPD preferably produced at the plant the indoor air of which is be-
ing investigated.

        Place about 15-20 ml of the nitro mixture into a 25-50 ml volumetric
flask and weigh on an analytical balance; add 1 drop of the MIPD and weigh
again.  The difference between the two  weights represents the weight of the
added MLPD.  Mix the solution and leave rest for 1 hour, then add the nitro
mixture up to the mark.  Compute the amount  of MIPD contained in each 1
ml of the final solution.  Now,  adjust the  solution by the well-known analyti-
cal procedure,  so that each 1 ml of the nitro mixture will  contain 0.1 mg of
the MIPD, Prepare the standard scale as follows:  set up  a series of colori-
metric  tubes 120 mm high and 15 mm in diameter.  Add to the first tube 0.03,
to the second 0.06, to the third 0.1,  to the fourth 0.2, to the fifth 0. 5,  and
to the sixth 1. 0  of the standard MIPD solution;  add to each of the tubes
enough  of the nitro mixture to make  a final volume of 1 ml.  Use a control
tube which contains only 1 ml of the nitro  mixture.  Now,  treat the tubes of
the scale series the same as above  described for the sample containing tube.
After 30 min. standing compare the  intensity  of the developed yellowish-
brown color with the  intensity of the sample in the usual manner.

        Prior to final extraction of the polynitro compound from the acid
solution of the nitro mixture cool the separatory funnel under running tap
water; add 5 ml of ethyl ether and thoroughly shake  several times.  This
phase of the work should be  done preferably under a chemical hood,  and
away from open flames.  Remove the top  ether layer and place into a colori-
metric  tube equipped with a  ground-to-fit glass stopper.  Add an  equal  vol-
ume of  acetone,  then add a 1:1 ether-acetone  mixture to  make a volume of 9
ml.  Finally add 1 ml of 40% NaOH.  Make colorimetric comparison  20
minutes after the addition of the alkaline solution.  Prepare a standard scale
from the same MIPD solution which  was used in the extraction of the nitro
compounds in the alkaline medium,  i.e. 1 ml of which contained 0.1  mg of
the MIPD.

       Add to a series of colorimetric tubes 0. 02, 0. 05,  0.1, 0.2, 0.5, and
1.0 of the standard solution and bring volume in each tube  to 1 ml by adding
nitro mixture.  Treat the series the same as the air sample.  The control
tube should contain 1  ml of the nitro  mixture alone.  The scale range extends
over 2-100 |i  of MIPD.  Make final comparison of color intensities visually
or photocolorimetrically using a green light filter of 450-600.my-  wave length.

       Experiences indicated that the first extraction removed 92-95%  of the
nitro compound by the described procedure.  It is felt that a second  extrac-
tion would not add materially to the determination precision.  The minimal
amount  of MIPD determined by the acetone-alkaline  medium extraction was
3 |Ll in colorimetric volume,  and by the ether extraction in acid medium, the
minimum was 2 jU. In the presence of other aromatic  substances, the
method  is nonspecific.

                                    - 199  -
-------
     Experimental Hygienic Evaluation of Combustion Products Discharged
          into the Atmospheric Air by the Smelting Department of a
                            Metallurgical Plant
                                 pp. 58 - 59

           G. M.  Kuryndin, G. B.  Orlovskaya and I.  G. Dinkevich
      (From the Dnepropetrovsk Sanitary-Epidemiological Station of the
                          Krasnogvardeisk Region)
       The smelting department of the plant is located in a residential block.
It  has one smelting furnace which burns 7 tons of fuel and produces 20 tons
of pig iron per day.   The hygienic investigation included a sanitary inspec-
tion of the territory over which  the discharged smoke extended, and labora-
tory examinations of atmospheric air samples collected at given intervals.
Air samples had been collected  beginning with the month of May and ending
with the  month of December, a period during which  the north-western and
north-eastern winds prevailed in the vicinity.  Air samples were tested for
dust, soot and sulfur trioxide.   Samples were collected in yards bordering
on the  plant grounds at the time  the smoke plume  spread over the yard at a
distance of 12-30 m from the pollution origin.  Sample collection was made
by the  aspiration method.   Analytical results are  presented in the Table below.
               Dost,  soot, ana SO- concentrations in atmospheric air on the lee
                            «   side of the plant
Meters
of







from source|
discharge

12- 20
22-30

12- -20
22 - 30


12—20
•:•:— 30
No. of air »anpls
Dust
17
30
Concentration in n^/K
Uaxinal
9,0
8,9
Minimal
1,6
2,6
Soot
22
15
0,42
0,43
0,21
0,1
i i
Sulfur Dioxiae
18
24
0,94
0,32
0,12
0.15
       Data listed in the Table show that maximal single soot concentration
was 2.8 times as  high as the maximal permissible concentration in atmos-
pheric air at a distance of 12-30; the dust concentration at 12-30 was 18
times as high at its  maximal permissible concentration. Minimal single dust
concentration at 12-20 m was 3.2 times as great, and at 22-30 m distance
5.2 times as great as the maximal permissible concentration in atmospheric
air.   The discharged smoke contained predominately fractions exceeding
                                    -  200 -
-------
 10 M, in diameter.

        The maximal single CO3 concentration at 12-30 m was 212 times as
 high  as the maximal allowable concentration for atmospheric air.  The min-
 imal single concentration of CO3 was within the  permissible limits.  Answers
 to questionnaires distributed among the residents  contained complaints of
 headaches, general ill feeling, and a burning sensation in the throat.  Leaves
 of trees growing at points of sample collection appeared wilted, yellowish
 and of stunted growth.   Results  of this  investigation caused the sanitary
 authorities to order the smelting department to move outside the city limits.
 In compliance with such order,  the plant administration  began to move the
 smelting department in 1962 with the expectation of its complete removal
 from its old location to the  new  one in 1963.
                 Radioactivity of Some Building Materials
                                 pp. 94 - 95

          Z.  P. Barlyaeva, A. A. Velicho, and N. G.  Prokof'eva
     (From the Department of Hygiene, the N.I.  Pirogov Second Moscow
                             Medical Institute)
       B.  Hultkvist and A. I. Shafir investigated 6 types of radioactivity in
14 types  of building materials.  According to data presented by them,  highest
radioactivity was emanated by clay, loam,  granite, clinkers  or slags,  and
bricks;  lowest radioactivity  came from chalk and chalky materials and  from
limestone.  The present authors investigated the a- and (3—activities of 16
types of  building materials generally used in Moscow and its surroundings.
The  materials studied had been ground and sifted,  ot- activity was deter-
mined by a B-2 installation equipped with a scintilating device; 3-activity
was  determined  using  same  installation B-2, but one equipped with an end-
counter, and a parallel cylindrical counter AC-1.  When the end-counter was
used 0.5 g of the investigated material was evenly distributed over a round
target and placed into a lead  housing.  Ten samples of each material had
been thus tested and the results averaged.

       P-activity determinations with counter AC-1 were made with the  aid
of a  special cylindrical double walled paper container. The inside wall  of
this  container fitted closely over the counter surface with the  outside wall
creating an 0.5 air space.  In this way the studied material was  distributed
around the counter in an even layer  0.5 cm thick.  The entire material  under
study, depending upon its sp.gr. ,  weighed between 20 and 35 g.  Determina-
tions of individual samples of the same material made by this method  were
identical so that only 2 determinations were made and averaged by this me-
thod.  Each determination lasted one hour.  The radioactive background wa.i
                                   - 201 -
-------
 determined immediately prior to making the material determination  and
 lasted 30 minutes instead of 1 hour,  and immediately after the experimental
 determination also for 30 min.  Absolute activity of the investigated samples
 was determined by comparison with  the activity of a standard irradiator,
 such as  KC1, under identical conditions; results were  processed statistically.

       A comparison of results obtained in determining the radioactivity  of
 the building material samples by the cylindrical and end-counters leads to
 the assumption that orientation determinations of building material activi-
 ties could be made by either count method,  but that the results of the cylin-
 drical method were more precise, as shown in the Table below.
                         Radioactivity of Structural Material*




Materials


Cenent 6T
Reinforced concrete
Porous clay and pebble
concrete
Port Ian 6 ceaent
Crushed granite
Crushed stone

Ceramic clay
Sand
Gypsum
Bricks
F 1 o or tile
Glazed tile
Slag
Cenent mixture »ith ground
slag




Obtained fr««




Karacharovq, Mosco* Region . . .
Factory Gigant, Voskreswisk . . .
Vencvsk Region, Uosco* Oblaat • -
Akadeoiche&ki i kar'er.


Tuchkovsk Region, Moscow Ob last .
Oanilov A labaster Plant of





	

<\j

>.
«*
'>M
r-
e

•S"oo
'> •5""
5B5
ca |
>>
! 0 CM

*• 0 ft
1*7
s.ss
i— 6
O3.B" 1
Curie/g
0,44
0,42
0,63
0,61
2,10
0,60
0,55
0,64
0,56
0,21
0,43
0,70
2^49
1,38
1,37

15,2
2,7
8,0
12,5
23,3
17,'.)
8 2
30,5
10,8
9,8
21,8
18,8
10,9
26,5
43,7
25,1

4,0
5,5
11,4
10,2
26.2
2,4
6,0
30.0
6,9
1,3
21,3
17,5
14,0
31,5
46,1
18,0

        Data in the Table show that cinder materials possessed higher radio-
activity than any of the other type materials, which is  due probably to the en-
hanced concentration of the radioactive substances originally present in
hard coal.  Relatively high radioactivity was noted in gravel and in porous
clay used as cement, also in bricks and in facing and floor tiles.   The rela-
tively high radioactivity of the mentioned building materials may be due to
the fact that they were products of processed clay,  which is one of the
natural materials possessing  high radioactivity.  Lowest radioactivity was
found in gypsum and  in sand; relatively low activity was found in pure <•„*:me.-.?.,
However,with the addition to the cement of high radioactive components   th»-
activity of the cement naturally rose.  Data in the Table show that materials
possessing high a-activity  also possessed high &-activity.  Therefore, it'
can be assumed that  granite and brick buildings  emanated a relatively high
                                    -  202 -
-------
radioactivity as compared with buildings constructed of wood materials and
concrete.  In the light of above statements, consideration should be given to
type of components added to the cement base,

        A study of a-activity emanated by building materials  may lead to in-
formation regarding the effect of building material dust inhalation on the
health of workers engaged in processing building materials.  In this connec-
tion,  the present authors  computed the radioactivity emana.ted by the  com-
bustion of coal originally  possessing high a-activity.  Results showed that
air containing such cinder dust in 10 mg/m concentration emanated a radio-
activity equivalent to 2.49 *  10~17  curie/li, which is considerably below the
maximal permissible radioactivity for working premises processing a-ac-
tivity emanating raw building materials.  The maximal permissible concen-
                                                  ™" 1 ft        /
tration of a-activity for working premises  is 2 x  10     curie/li.  It should be
noted at this point  that the combined a-  and $-activities under similar condi-
tions  would amount to 3.4 x 10     curie/li.  According to data presented by
G. I.  Rumyantsev  in 1961,  radioactive dust concentrations in the air under
some working conditions may be as high as 210 mg/m  , and the intensity of
radioactivity would be equal to 7<,14X10~  "  curie/li, which is considerably
above  the permissible concentration limit.  In other words, the radioactivity
intensity emanated by 59 mg/m3  air dust concentration would exceed the max-
imal permissible concentration.   Therefore, it is suggested  that in process-
ing building  materials which generated considerable amounts of radioactiv-
ity into the air of working premises the sanitary inspectors should take these
factors into  consideration, particularly in  making recommendations for the
introduction of rational sanitary protective measures.

                               Bibliography
            P y M n mi e B I". H. I'HP. rpyna, 1961, JVs 9, crp. 39. — X y A i, T K H K c T B. Homi-
        supyiouiee  H3JiyieHHe  ecTecTBennux HCTOMHHKOB. M.,  1959. — III a 4> u p  A. H. 1 HP.
        H can., 1961, No 6, crp 14.
                                     - 203 -
-------
                           NO. 9,  SEPTEMBER
     Radioactivity Level of Moscow Ambient Atmospheric Air in 1957-1961
                                 pp. 5 - 11

           A. S. Zykova,  E. L. Telushkina, G.  P.  Efremova,  and
                             V. P.  Rublevskii
                                  (Moscow)
       Nuclear armament tests have been polluting the atmospheric  air, the
soil,  plants, food products, etc.  Considerable data have been accumulated
during the past few years on the intensity of radioactive fallout at different
seasons  of the year.  V. P. Shvedov and his collaborators (1959) Hvinden
(i960), Martel (1959),  and  others found that the amount of radioactivity has
been  gradually increasing,  reaching maximum in 1959; thereafter the amount
of radio  fallout was  significantly reduced.  Considerable data have also been
accumulated showing that concentrations of fB-active fallout have been chang-
ing.  Peirson and his collaborators (I960) presented data which show that con-
centrations of  (3-active substances in the atmosphere paralleled the intensity
of radioactive fallout.  A drop in the level of radioactive fallout and in the
concentration of radioactive substances in the air was noted beginning with
the second half of 1959  following the moratorium on nuclear test explosions
in 1958.

       The present  authors followed and recorded  the amount of radioactive
fallout and concentration of radioactive substances  in the air surrounding Mos-
cow during 1957-1961.   Determinations of  radio fallout intensity in relation  to
long-lived ^-active aerosols were  made by the snow sample method and by the
open  pan method.  The first method was  used during the month of March,
when  the snow began to fall. Snow samples had been collected every year at
the same 20 points.  The snow was melted and the  water evaporated. The
residue was ashed,  and the ash  placed upon the counter target and deter-
mined by means of B-2 apparatus equipped with counters T-25, BFL and
SI-2B by the thin layer method.  The count error did not exceed ±20% and
the final results were  expressed in terms of millicurie per 1 km . Quanti-
tative twenty-four hour determinations  of atmospheric radioactive fallout
were  made by the open collection method  using containers 50 x 10  cm.  The
containers were lined with filter paper for better aerosol retention.  Samples
were  collected at twenty observation points  continuously in the region under
study. Radioactive  fallout  catch containers were changed every 10 days at
all points.  Radioactive material accumulating upon the filter paper was pro-
cessed as previously outlined and determined  by the method described for
snow  samples.

       Samples intended for the quantitative determination  of long-lived
                                   - 204 -
-------
 radioactive aerosol in the atmospheric air layer close to the ground were col-
 lected by the aspiration method,  using filter FPP-15 and aspirating at the rate
 of 100-150 li/min through a 140 cm2.   The total aspirated air ranged between
 100-180 m „   The filter paper with the radioactive  fallout material was ashed
 in a muffle furnace at  300-400° .  An average of 4-6 samples had been thus
 collected per month, and between May of 1957 and  December of 1962 the to-
 tal of samples amounted to 237.  Strontium-90 was determined by a method
 of precipitation with fuming  nitric acid,  as described by E. I. Orlova in 1959.
 Cesium-137 was determined by the method of isomophic precipitation in the
 form of a practically insoluble cesium phospho-molymbdate salt as described
 by E. N0  Belyaeva in 1959.  The  group of rare earth radioactive isotopes
 were determined by the method of precipitation with oxalic and hydrofluoric
 acids with a consequent formation of practically insoluble oxolates and fluor-
 ides, also as described by E, N. Belyaeva in 1959. Cesium-144 was deter-
 mined by isolating it from the mixture of rare earth isotopes by the carrier
 separation method, in  the form of cesium iodates, after preliminary oxida-
 tion of trivalent cesium to tetravalent,  as described by E. N.  Belyaeva in
 1959.

       Ground snow  samples were studied annually during 1956-1957, in-
 cluding winter of  I960 and 1961.  Radiometric  determinations showed that,
 despite careful adherence to prescribed steps  of technical procedures,  re-
 sults varied considerably.  This  may have been due to uneven thickness of
 snow layers  at sample collection points, resulting from drifts which carried
 the snow from place  to  place.  Under such conditions,  reliable results
 could be obtained only from an adequately large number of samples  collected
 at many points.  Data presented in Table 1 are averages,  which characterize
 intensity of P-active  substances in the snow samples collected  during 1956-
 1961.  Results show that the amount of radioactive fallout increased  each suc-
 ceeding year up to and  including 1959,  after which the  fallout sharply dropped
 to 1/8-1/12 during the period of 1959-1960,  and to 1% of the original during
 1958-1959.
Table 1.
                   Anount of p-actiwe substances in sno»

Year
1956—1957
1957—1958
1958—1959
1959—1960
1960—1961

No. of
soaples
16
17
19
19
17
Aoount of P-Qctivo substoncQs in
B.-.O.,
17
28,5
35
2,9
0,15
Men ooal
150
118
120,
12'
1,56
Average
49-i-0,83
58,5-1-5.8
73,0-*-7,9
6,2-1-0,6
0,56+0.097
        Rate of P-active fallout was determined by the collection method
from February, 1957 to January, 1962,  amounting to 59 months.  Sample
                                    - 205 -
-------
collecting distribution was as follows: 541 during 11 months in 1957; 674 dur-
ing 12  months in 1958;  783 during 12 months in 1959; 655 during 12 months  in
I960, and 674 during 12 months  in 1961,  making a total of 3327 samples in 59
months.  Final results indicated that the total fallout of long-lived P-active
substances  amounted to 1047 microcurie/km"* for the 11 month period in 1957;
it amounted to 1114 microcurie/km2 for the  12 month period in 1958; 998 micro-
curie/km2  for the 12 months in  1959; 45.88  microcurie/km2 during the 12
months of I960; and 220 microcurie/km2 for the  period of 12 months of 1961.
Curves in Fig.  1 graphically represent the quantitative course followed by the
long-lived P-active fallout substances.  The curves show that during 1957,
1958,  and 1959 there appeared 2 maxima annually,  one during the spring-
summer period of April-May, and the other during the fall period of Septem-
ber  - October.  No fall maxima had been noted in  1959 or during the spring
of I960 and 1961.  Absolute values and the character of radioactivity fall
curves during I960 and 1961 differed markedly from those recorded the pre-
vious years.
Fig. 1.
 400
 300
 200

100
 80
 60
          I
          L
          »
          Q.
 20
             .
          2  6
          L.
          3
                         fMfV Z3S2 I E V W US 1  i 7 E7 SS I  i 7 W S
                         a sviwi wn ffvwx js a ffwwz w s u wwx
                                   onths                    "
                   ISJ?       I35B       /SJS        1360       1961
               Fall-out of  3-active substances «nu fciwospheric frecipt tation in
                        Uosco* in I y 37-1% I according to months
                   Curve represents atmospheric precipitation and blocks radio-
                                active fa(l out
        Beginning with January and through September of I960, and from
January through August of 1961 the monthly radioactive fallout had been prac-
tically the same, ranging from 1. 3 to 3 microcurie/km  .  In September of
1961,  coincident with the resumption of nuclear bomb tests,  the amount of
radioactiive fallout rose sharply,  reaching 30 microcurie/krn^ .   'Jin: ri :-,<:
continued during the following months,  and rose to 80 microouri <-./\- ra"  i.-,
December.  Thus,  92% of the  radioactive  fallout of  1961 occ'irrc'i 'iunr.;'
the last 4 months  of the year.  Maximum  radioactive fallout of 300 rnic.ro-
curie/km0 was noted during May of 1959, and minimum of 1. 3  mic rocuri t:/krn'
was noted  during March of 1961.  A parallel study of monthly radioactive
                                      -  206 -
-------
fallout with simultaneous  atmospheric precipitation, pointed to a degree of
correspondence between the two indexes,  particularly during the months of
April-August and October-November, 1957-1959, as illustrated by curves
in Fig. 1.   The total picture appeared different in I960 and 1961.  For ex-
ample, the amount .of radioactive fallout during January,  February,  March
and April of I960  was approximately the same, while the amount of atmos-
pheric precipitation during January-February was 7 times as high as during
March-April,  showing that the correlation between radioactive fallout and
the atmospheric precipitation was not of a definitive quantitative character.
It was noted that the  amount of radioactive fallout depended not only upon the
absolute amount of atmospheric precipitation, but also on its general char-
acter  and duration,  etc.

       Some of the samples collected by the open pan  method during 1959-
1961 were analyzed radiochemically.  Records were  kept of radioisotopes
playing a part  in biological investigations, such as strontium-90,  cesium-
137, and the rare  earth elements.   Twenty radiochemical analyses were
performed in 1959, the results of which are listed in Table 2.  Atomic wea-
pon tests had been resumed in 1961. As  a  result, the amount of strontium-90,
cesium-137, and of rare earth metals  falling  out from the atmosphere had
increased as compared with those found in I960.  The  ratio between cesium-
137 and strontium-90,  according to the data obtained in this investigation
averaged 2.1 in I960  and 1.6 in 1961.  These results coincide with values
found in the literature.   Average monthly concentrations of radioactive
substances found in the atmospheric air during 1957-1961 listed in Fig. 2
show  that radioactive substance concentrations in most instances had been
found in the limits of n x  10"16 curie/li,, Maximal radioactive substances
were  found during the spring and fall, which is in agreement with observa-
tions  made by  the open collection method.  Highest radioactive substance
concentrations were found in the air in March, 1958, when it reached 9  x 10
curie/li.  Beginning with July, 1959 the level began to drop,  and in 1961, the
concentration fell to  9.2 x 10"   curie/li  which amounted  to a hundred-fold
drop.  Results of air  samples collected and analyzed during  each  month of
1960-1961 are presented in Table 3.

Table  2.

          Amount of radioact owo substoncne on soapOoOpCol Ooctctl t>y tnc
                           pethod (on ocuiroo/hQ')
                                                          dieh
Samplo collodion data
7— 23/V1H 1958 	
a 25/X 1958 T
17/XII— 2/1 1959 •.'....
13 29/1 1959 	

Strant«ua-*W
During
le?|feS-
poiriod
0,14
0,145
0,044
0,066
AvQirago
2k hourt.
0,0088
0,0085
0,0028
0,0041
Coaoua-l 37
During
cw-
[iorioe:
0,194
0,1
0,085
0,092
Uurmc
col iot-
tocn
' period
0,012
0,059
0,053
0,058
Totool of rcaio-
QCtowo alamcnto
,ia nepiioA
OTfiopa
5,06
3,7
1,28
2,14
Aworji,e
2<« hours
0,32
0,28
0,08
0,134
                                     - 207 -
-------
Table
                 Amount of  radiooctov« fall-out  during IV60 «nd  l%l  in ncurit/kn
Months













Totals . . .
Strontiun-UO
1960
0,067
0,146
0,037
0,032
0,077
0,093
0,08
0,031
0,047
0,063
0,056
0,73
1961
0,021
0,021
0,047
0,047
0,084
0,166
0,05
0,075
0,22
0,111
0,45
0,39
1,68
Cosiun-137
1960
0,04
0,022
0,072
0,16
0,16
0,255
0,218
0,065
0,046
0,119
0,083
1,24
1961
0,043
0,037
0,113
0,093
0,203
0,27
0,083
0,171
0,17
0,089
0,37
0,29
1,93
Rktio of Cs-
!37/Sr-90
I960
0,6
0,15
2,0
5,1
2,0
2,6
3,6
1,6
1,0
2,2
2,6

1961
2,0
1,8
2,4
2,0
2,4
1,6
1,6
2,3
0,8
0,8
0,8
0,7

Cerium-!1*1*
Hrtseod/nium
M
1960 ' 1961
0,48
0,85
0,41
1,05
1,0
1,86
1,56
1,14
0,7
0,53
0,75
10,33
0,177
0,2
0,161
0.26
0,33
0,411
0.17
0,42
2,95
2,7
8,67
18,35
35,0
Fig.  2,
              10
               Curie/li

               2

               .-it
              10
               2

             IOIS
               8
               6
               4
               J
               2
             10
               'n

                          ft\
                               Uwi
                                                                       V.
                   r m i n s IP m mi  ms s ^sw i  HI n.  N v vni YU ir Ninwx w
                   WEuimvwiziiiinvwiiiii M v w ax? / M 7 wg g
                    IS 31
1958
Months
  1359
                                                      1960
                                   1961
            Concentration of  (3-active fall-out froa the air over Moscow in lvi>7 - 1961
                                          - 208 -
-------
        Average annual radioactive substance concentrations in the atmos-
 pheric air, based on results  of 31 samples collected in 1957,  amounted to
 3.5 ±0.30X 1CT1B curie/li,  and in 1958 based on 52 samples, it amounted to
 4.8 ± 0.45 x ICT15  curie/li; in I960,  52 samples had been collected which
 gave an average of 0.64 ± 0.086 x 10~15.  Finally the  51 samples collected in
 1961 gave an average of 1.1 ±  0.01X 10"1B  curie/li.  Average concentrations
 during the period of January  - August, 1961 (34 samples) amounted to 0.13 x
 10  , and during the period of September-December (17 samples,  the average
 amounted to 3.1X  10"6.  Thus, the average annual radioactive substance con-
 centration in the atmospheric air for the 3 years of 1957-1959  remained prac-
 tically the same, which ranged between 3.2X10~1C curie/li.  This level
 dropped to one-fifth of the one given for I960.

        The hygienic atmospheric air pollution evaluation during 1961 must
 take into consideration not only average annual concentrations, but also aver-
 age concentrations determined during January-August, prior to the  resump-
 tion of atomic weapon tests,  and during September-December, following the
 resumption of such tests.   Average radioactive substance concentration in the
 atmospheric air during January-August of 1961 amounted to 0.13 x  10~l0 curie/
 li, indicating that it continued to fall from the levels of previous years.  The
 average radioactive substance concentration in the atmospheric air sharply
 rose with the resumption of the atomic weapons test in September of 1961 and
 amounted to 3.1X 10~15 curie/li.   Thus, atmospheric  air pollution with radio-
 active  substances was of the  same level at the end of 1961 as it was during the
 period of 1957-1959.

                               Conclusions
       1.  The present investigation extended over 6 years and yielded data
which illuminated the course of changes in the levels of Moscow atmospheric
air radioactivity.  Highest level of radio activity was recorded during 1957-
1959 in the first 6 months of 1959 and at the end  of 1961.    Results  showed that
the radioactive substance concentrations in the air in the fall of 1958 retained
their high levels after the resumption of nuclear weapon tests in the fall of
1958 for  6-7 months.  This  was followed by a substantial fall in the radio-
activity level, reaching a minimum at the end of 6  months.  Average monthly
radioactive substance  concentrations in the  atmospheric air ranged between
lx 10~16  and 1 x  10-14  curie/li during die period 01 observation.

       2,  Results of radiochemical analyses showed that 0. 73 microcurie of
                                                         f~f
strontium-90, 1.24 microcurie of cesium-137 fell per 1 km  of ground surface
in 1960; 1.68 microcurie of  strontium-90 and 1.93 microcurie of cesium-137
fell per 1 km2 of ground in 1961.

       3.  Results of the present investigation point to the occurrence  of
spring and fall  maxima of radioactive  substance fallout from the atmospheric
air.  A degree of correlation appeared to exist between the amount of radio-
                                - 209 -
-------
active fallout and atmospheric precipitation.

        4.  Results  of atmospheric air investigation made  by the method of
snow samples,  open pan collection procedure, and aspiration  method were
in good agreement and reflected the course followed by atmospheric air pollu-
tion with radioactive substances in Moscow environs during the 1957-1961
period.
                                Bibliography
           BejiHesa E.  H. B KH.: C6opnnK paAHOXHMHiecKHX  H AO3HMeipHMecKHx
       M., 1959, crp. 62, 66, 70. — O p Ji o B a E. H. B KH.: COopuHK pannoxHMHqecKiix n A
       MexpimecKHX MeroflHK. M., 1959, crp. 57 — III B e n o B B. FI., E .n H H o B B. A., Feaf-
       OHOB  Jl. H. n ap.  \AroMHafl  sHeprHH,  1958, T. 5, B. 5, crp. 577. — Hvinden T.,
       Hvending D., li'l leg raven  A. et al., Nature,  1960,  v.  185, p. 805.— Mar-
       tell E. A., Science, 1959, v. 129, p. 1197. —P e i'r so n D. H.,  Crooks  R. N... Fi-
       sh er E. M. R., Nature, 1960, v. 186, p. 224.
     Labor Hygiene Problems in Plants Manufacturing Construction Glass
                                  pp. 23-30

           N. Ya.  Suponitskii, F. M. Shleifman,  E. P. Tupchii,
                           and E.  D.  Bakalinskaya
        (From the Kiev Scientific-Research Institute of Labor Hygiene
                         and Occupational Diseases)
        The state of labor hygiene in glass making factories was first in-
vestigated by  Ya.  Kuritskii and by A.  P. Flerovskii in 1927,  by I. I.
Matusevich and E.  A. Peregud in 1933,   and again by Matusevich in 1934.
Many reports  have appeared of late which presented some data  regarding
labor conditions in the glass making industry and dealing with the state of
health  and morbidity among the workers.  Among the authors of such re-
ports were Milev (1957),  Berdan,  Pafnote, and Vaida (1959), E. E, Vish-
nevskaya (i960), R. Sh Samitova (1961),  V. S. Bodyako, G.  I. Pashkovskaya,
N.  S. Irger (1961),  Z. S. Gavrik,  I. G.  Gulitz, and M.  Ya Suponitskii (1959)
and K.  K. Vrochinskii (1961).  Reports of the above  authors dealt primarily
with labor conditions in glass packing and glass bottle making plants.  None
of the above mentioned authors included in their  investigation the study of(
labor conditions in construction glass making plants.  The present paper  is
a report of labor conditions and morbidity noted  among  workers of several
construction glass  making plants.
                                                                           r
        Construction glass  making consists of the following  steps or stages:
preparation of the glass making mixture  in the composition department,  mix-
ture smelting  in the glass furnace, vertical drawing out of the glass  or hori-
zontal glass blowing,  glass cutting into given sizes,  sorting and packing.  The
                                     - 210 -
-------
 above steps in making construction glass have been largely mechanized with-
 in recent years.  This applies particularly to the  loading and unloading of
 the raw materials,  their grinding, drying, sifting and mixing of the compon-
 ents for the preparation of the final mixture, which is also mechanically load-
 ed into the glass smelting furnaces.  Many plants have also mechanized the
 control  of the smelted glass mass levels  in the  furnaces, the furnace temper-
 ature, and several other production steps.  The mechanization and automation
 of the basic construction glass making steps  led to considerable improvement
 in the working conditions of the employed  personnel.   Nevertheless,  there
 still remained some phases of the work which have been and still are con-
 ducted under favorable labor conditions from a hygienic  and strictly physical
 viewpoint.  The most important of these is the suspended dust in the air of
 some working premises, unfavorable temperature, humidity, noise and vi-
 bration.  Data in Table 1 show that dust density  in the air of the composition,
 dose measuring and mixing departments was 10-fold and hundred-fold as
 great as the maximal permissible dust  concentration limit.   High air dust
 concentrations had also been noted during  loading and conveying of the in-
 dividual components  and of the final mixture.  Cleaning of the work premises
 was done manually using a broom which also created air dustiness of high
 densities.  In such instances, the dust was  of a  highly mixed character.  Dis-
 persion determinations, showed that 86.4-100% of the dust particles measured
 up to  5 ju in diameter,  of which 51-92. 2% measured up to 1. 3 jU in diameter.
Table 1.
                   of dust on the air of compound dspartiaonto ecrnin;, points ot
                            different preductien •">'"•"is«»»*.
Production procoseos and oorhing peonto
Unloading of coS, sis-lfale rojatutr.;, soda.,
Crush or* 3 and sifting of components (d»J oroi tep
LoadtMy ana unloading of diryjny drums ft » »


Hg/o3 ef dusti
MoHOQOl
610
555
72
227
620
MiniDol
10
30
2
72
2
       Air dust concentrations between 16-66 mg/m3 had also been noted
in other  production departments, and an air dust concentration between 100
and 103 mg/m3 was noted at loading of  glass plates onto the transportation
wagons,  due to glass breakage.  Air dust concentrations at other sections
of the mechanized  vat department did not exceed the  maximal permissible
concentration.  The dust in this  department consisted entirely of particles
measuring up to 5 fj, in diameter, 82. 4-91. 6% of which measured up to 1. 3 p.
in diameter.  Temperature and humidity conditions of the construction j./!;,•,•
production department were the most unfavorable from the viewpoint of
labor hygiene. Data in Table 2 show that the air temperature at all point:,
of this department  was high  during  the warm season of the year.
                                   - 211  -
-------
 Table 2.
Air temperature on 3 relative hunidity  in t*»e oach ino aivJ tne aeltt.Vj v +2°
Air temp.
in
dejrees
Maxi-
mal
20,0
22,0
21,0
23,0
39,0
19,0
Mini-
aal
7,0
8,0
6,0
4,0
17,0
5,0
J of rela-
tive
hurt i d i ty
Maxi-'
nal
43
44
54
61
39
53
fiini-
inal
20
17
21
11
7
17
The maximal air temperature at certain points exceeded the maximal out-
door temperature by 3-22° ; particularly high air temperature had been noted
close to the glass smelting furnace and to the vertical glass drawing-out.
The air temperature in this department fluctuated considerably at different
points during the cold period of the year:  at some points the temperature was
the same as it was outdoors, at other points it varied from the  outdoor air
temperature by 10-18°, whereas at other points,  it was uncomfortably high
even during cold winter months,  as shown in Table 2.  In  addition, consider-
able air temperature fluctuations have been noted at one and the same  depart-
ment sections on different days.  Air temperature fluctuations at different
sections of the department varied with the distance of. the working spaces
from the heat generating sources.

       Operational periodicity of heat producing processes also played a
part in the temperature fluctuation.   Thus, during the summer  months the
indoor air temperature fluctuated between 10-33  at the same working  point,
while the outside air temperature fluctuation did not exceed 8° .  During the
winter months, when the outdoor temperature  fluctuation stayed within the
range  of 6-8°, the indoor temperature at such working points fluctuated in
the range of 7-30°.  The glass melting furnace and the vertical glass drawing-
out machine constituted sources of high temperature radiation.   The radia-
tion intensity  coming from the melting furnace reached 7 cal/cm / min at
1  m, and 3-1 cal/cm  /min 5 m from the glass  melting furnace,   (see curves
in Fig. 1). The extensive insulated furnace surface radiated heat of 90-190° .
The heat radiating from the furnace surface at a distance of 1 m amounted to
0. 75-2. 5 cal/cm2/min, and at 4 m from the furnace it amounted to 0. 3-0. 6
    /   S /                            _
cal/cm /min  as shown by curves in Fig.  2.

       The walls, ceiling and floor of the building housing  the plant acted as
secondary sources of heat emanation, and the  temperature of such surfaces
ranged between 40-68° .  The inside wall temperatures of the building ranged
                                    - 212 -
-------
 between 43-55° during summer months.   Intensive heat.also radiated from
 the vertical glass drawing machine  pits; thus, the heat radiation 1 m from the
 machine pit ranged between 1.5-2 cal/cm2/min.  Intensive heat came from
 the final glass plates and glass fragments accumulated during glass cutting.
     Fig. !„.
Fig. 2.
0
c
4L r
§
"7? 6'
0
.£ S
•*-*
| 9


S
—
^








*
V
\\
\

\

N











\
\.
'v
<-

s.











k

— I

^












^















v_



*-*-











*• .



' — .















-«•


                                         r
               vat heater
                              5
      Mstars fr«js> fvirficcQ stacKing opening.
      infrareo rudiaUan intensity  betoeen
      too melting vet  burners (b/stew Mo. I)
      a — bet.-seen 1st,  2d, 3dp and  Uth ourn-
      crsj b — between  4tf» ana 5tn  burners;
      c — tjetnoon 2d and 3d burners; d - t>e—
      tuean i>tr> one 6th nurners with
 Infrared radiation intensity  at tne
 space c* tne mechantJOu melt in j de!.art»«o t
 in the iaro«ioity o» each melt in j wet
       l)
                                        a — one notor firoia the uumorj b - I! waters
                                        from tho Durnar; c - 3 meters frwj the turner

The glass plate had a temperature -of 100-140° as it entered the  vertical glass
drawing machine^ and 1 m from the machine it radiated heat ranging between
0.6-1.26 cal/cm^/min.  He'at also emanated within the department confines
during the glass plates transportation to the cutting tables.  All such sources
of heat emanation contributed to the formation  of the heat and moisture char-
acter  of the local department micro climate.  Production noise  is an impor-
tant factor which affected general working conditions.   Measurements es-
tablished that the general noise  prevailing j.n the glass making  department
ranged between 60-67 decibels.  The  noise intensity created during loading
of the  crushed material into the thin layer loader ranged between 95-97 deci-
bels.  Dropping of broken or cracked glass into the bunker produced a noise
of  100-108 decibels, while loading the plate glass upon the transport wagons
produced a noise of 110-115 decibels.   The  exhaust fan  and motors in the com-
position and melting departments produced a noise of 80-82 decibels.  Thus,
the conclusion is that  the general noise in  the glass producing department was
of a high decibel,intensity.
                                     -  213  -
-------
        Examination of workers' physiological functions disclosed a lowered
sense of odor perception caused by dust accumulated on the nasal mucosa.
Workers employed at points of unfavorable temperature and humidity condi-
tions developed tension of the thermo-regulation function,  particularly dur-
ing the  summer months,  as shown by increased temperature of the  forehead
and the chest skin by 2.5-3°,  of the palms by 2-4.5°, and by excessive pers-
piration.  It was estimated that glass smelters lost between 2.8-5.9 kg of
weight through perspiration, including water taken in during the working
hours.  Workers employed at  the vertical glass drawing machine  lost be-
tween 3 and 5 kg of weight, and the glass cutter between 2-5.8 kg of weight
through perspiration during working hours.  The pulse rate rose by 16-24
beats per minute,  especially  during physical exertion at high air tempera-
tures.   The systolic blood pressure frequently dropped by 10-15 mm at the
end of a working day.  Not withstanding the high heat elimination, particu-
larly caused by intensive perspiration, the organism retained enough heat
to cause a body temperature rise by 0.3-1°,  or higher in some  cases.  In-
crease in skin temperature and in cardiac  contractions were less pronounced
during the winter months.  Loss in body weight due to profuse perspiration
was also less pronounced during the winter months, ranging between 1-4. 3 kg
among workers employed at different production processes.  Sharp tempera-
ture fluctuations noted in the machine-bath departments elicited drops in the
organism temperature, especially during  winter months.  Glass smelters,
machinists,  and other workers stated that they preferred to spend most of
the time close to the glass  furnace and machines during the winter months to
avoid the  cold.

       An estimation of the heat balance by the formula of W. K.  Vitte show-
ed the following: if the heat radiation in the immediate proximity of a heat
emanation source exceeded the heat lost by the body, then the air tempera-
ture will be 7.7°, radiation will  be nill, and the air  current rate will be
                                                  /   55 /
0. 95 m per  second, the heat balance will be 2. 5 cal/cm /min,  and at a
distance of 8 m the air temperature will be 2°, the air current  rate will be
1. 7 m/sec,  and the heat balance  will be 4. 36 cal/min.  Workers operating
the glass  drawing machines, and their helpers, generally move from points
of high heat emanation to points at which loss of body heat increases; they
usually subject their organisms to sudden cooling which is conducive to fre-
quent common cold development.

       A  thorough study was made of the morbidity rate and of  loss of work
time among workers  of construction glass producing  plants.  Results indi-
cated that the high morbidity and loss  of work time noted during the investi-
gation was closely related to unfavorable labor conditions.  Elaborate statis-
tical analysis verified this  conclusion.  Morbidity rate among workers of
specific occupational groups had been compared with average morbidity rate
among all workers  of the glass producing  plant.  Results showed that aver-
age morbidity of workers operating at most unfavorable working conditions
was higher than the average morbidity of'the plant's total working personnel.

                                   - 214  -
-------
The differences were noteworthy and significant.  Thus, average morbidity
among workers employed under conditions of high temperature and heat ra-
diation exceeded the  average morbidity among the workers of the entire
plant by  65%, and among workers employed at points of dust generation,  the
morbidity rate exceeded the average morbidity rate of the plant as a whole
by 75%,  etc.' Rates of morbidity also varied with the length of employment
at a particular occupation.                   .  •

       A clinical study was  made of 570 workers connected with the  high
.temperature and high dust generating phases of construction glass manufac-
ture. Res.ults clearly pointed to a direct connection between the employees'
state of health and the sanitary-hygiene of  labor conditions. Medical ex-
amination of workers engaged in the high temperature* occupations showed a
lowered  arterial blood pressure more  often than an increase in the blood
pressure. Such workers also  showed symptoms of myocardial dystrophy
as a result of unfavorable working conditions, particularly high air tempera-
tures. Chronic bronchitis was found frequently among workers operating
under -conditions of continuous high temperature heat radiation and high
air dust  density.  The same was true of gastrointestinal and digestive mor-
bidity.  Fifty-three per cent of such workers showed disturbance of the per-
ipheral nervous system in the form of radiculitis, neuritis, neuralgia,
neuromyositis,  etc,,  Affected conjunctivae were noted in 15% of workers
engaged, in dust generating'phases of the work,  and in 18%  of workers opera-
ting under conditions of high air temperature.  Considerable eye,  ear, nose
arid throat changes had been noted in 60% of workers operating under un-
fc^vorable air temperature and humidity conditions, and in 50% of workers
operating under conditions of high air dust density..

       An important  phase  of the present investigation was the  development
of means suggested for the  sanitization of working conditions in the construc-
tion glass making plants.  Some of the suggestions have already been insti-
tuted in some plants.  The developed and recommended suggestions can be
outlined  as follows:'  (1)  it was .recommended that  the transportation, loading
and unloading of the components used in the final mixture should be complete-
ly mechanized and properly  enclosed to prevent any dust from  getting into
the air;  in this  connection,  the vacuum transportation system  or,  the so-
called, pneumotransportation, was  regarded as the most efficient from the
sanitary-hygienic viewpoint;  moistening the crushed material  intended for
transportation was recommended as a  temporary sanitization measure;
(2) it was also recommended that the crushing and grinding machines should
be equipped with appropriate dust catching  and dust aspirating  installations;
it was noted  that the  presently existing equipment was inadequate and ineffec-
tive  to accomplish the intended purpose; (3) it was recommended that sifting
of the ground components and of the final product should be done under leak-
proof housing, and that opening of the housing whenever necessary should  be
done after proper care had been taken  to prevent any dust from getting into
the surrounding air;  (4) it was recommended that the dosing apparatus and
    component mixer should be enclosed by a leakproof housing; from the
                                    -  215 -
-------
sanitary viewpoint,  mixing apparatus C-10,  or the like, appeared to be the
most rational; (5) manual cleaning of the working premises and dust blowing
off or dusting with the aid of brooms or similar equipment must be forbidden,
and mechanized up-to-date cleaning and dust removing apparatuses should be
installed throughout the  plant;  (6) appropriate  measures should be taken at
the recommendation of experienced  engineers for the control of humidity
and heat emanated by some of the production processes; this can be attain-
ed by the use of heat insulating materials, by appropriate ventilation systems,
and the like;  as stated above, this should be done at the recommendation and
direction of experienced engineers in the pertinent field of sanitation; (7)
measures  should be introduced for the  prevention of sudden temperature
drops  in the winter and undue temperature rise in the  summer; the existing
construction  glass manufacturing technology should  be  thoroughly examined
and analyzed by trained  industrial construction engineers  and  production
specialists and where necessary should be improved or replaced so as to
create more favorable labor conditions from the physical  and physiological
viewpoints.

                                Bibliography


            D a p x a A B. H AP, THF, rpyAa, 1960, N° 8, crp. 13. — B o A H K o  B. C, PI a tu-
        KOBcKan  f. H., Hprep H. C. FHF. H can., 1961, N°  12, crp.  82.— B H tu H e B-
        CK3H E. E. SApaaooxp. BeJiopyccHH,  1960, Ns  11, crp.  50. — B p o i H H c K H ft  K1. K.
        PHF. H caH., 1961,  N° 4,  crp. 61. — FaspiiK  3. C.,  f y a i u  I.  P.,  CynoHHtib-
        K H ft M. H-  Te3H AOK. 6-ro cbisAy ririe.HicTiB,  eniAenioJioriB,  MixpoCio/ioriB ta IH^CK-
        uioHicTia. VKpaHHbcK. PCP. KHIB, 1953,  erp. 28. — CaMHToaa P. III. B KH.: CCopHHK
        uaymibix paOor HH-TOB oxpaHU rpyAa BUCFIC. M., 1961, Ks 2, crp. 49. — M H .n e B M.
        SApaBHO AWIO, 1956, >f» 5, crp. 61. — Berdan C., Pafnote M.,  Vaida 1., Jgiena
        (Bucur.), 1959, T. 8. crp. 195.
         Acetylene Determination in the Air by Infrared Spectroscopy
                                  pp. 51 - 54

                     R. V. Lindval and I. V. Yermakova
              (From the Kazan Chemo-Technilogical Institute)
        Acetylene  vapor is present in the air of working premises in the
production of calcium carbide, in the air of acetylene stations and of plants
which use acetylene in their production processes.  No maximal permissible
concentration of acetylene vapor  in the air  has as yet been established.   The
All-Union Congress dealing  with  problems  of industrial ventilation recom-
mended that 0.5 mg/li (0.043% by volume)  of acetylene vapor in the air should
be adopted as its maximal permissible concentration.  A colorimetric method
for the determination of acetylene in the air has been developed by M. S.
Bykhovskaya, S. L, Ginzburg, O. D.  Khalizova in 1904 which enabled the de -
                                                                          !
                                    - 216  -
-------
 tection of 0.003 mg/ml of the tested solution.  However, determination of
 very low concentrations of acetylene vapor in the air by this method required
 the collection of large volume air samples, which is time consuming.  In ad-
 dition different samples are characterized by different color shades which
 makes precise determination at times  difficult, if not impossible.  By the
 method here  described it is possible'to determine minute quantities of
 acetylene in the air with the aid of infrared microscopy.

        Fig. -1 shows that the acetylene spectrum has a wide absorption  band.
 at' 730 cm x due to the fluctuations in the H-C triple'bond group,  as shown by
 G.  Gertsber'g in 1949.   With the aid of  a single illumination infrared spectro-
 photometer and using a standard gas tube  of 1608 cm thickness it is possible
 to determine  0.023 mg/li or 0.002% by volume of acetylene concentration.
 Spectroanalysis was made in the region of  700-800 cm"1 using a sodium  '
 chloride prism.  The gas containing window was  also made of sodium chlo-
 ride.  The working width of the  slit was 400 microns. The effective spectral
 width of the slit was 3.4 cm"1 .  Dispersed light in the 730 cm"1 region was
 accounted for by measuring the  intensity of the dispersed light which passed
 through a film of lethium fluoride and which was equal to  7. 5%.  Correction
 factor for light dispersion was also determined by making a spectrum for
 pure acetylene (p = 766 mm of mercury) in this region.  In this instance the
 light dispersion amounted to 4%0  The latter method appeared more reliable,
 since the lethium fluoride incompletely absorbed rays of the given wave  length.

•Fig- I-
                              1500 11001300 KM 1100 1000
                                                                15
                        Infrarod spectrum of acoty I eno .
                        Pressure in ram of nercury, ns in
                         at curves
       Impurities were removed from the acetylene by passing the sample
through solutions of sodium bichromate in concentrated sulfuric acid and
dried by passing it through concentrated sulfuric acid containing calcium
chloride. ,  A graduated standard, curve was constructed by obtaining spectra
of gas mixtures containing 0. 050,  0.040, 0.030,  0.020,  0.010,  0.008,  6.006,
0.004, and 0.002% of acetylene  by volume.   Prepare acetylene concentra-
tion gas mixtures as  follows:  fill the  gasometer with dry nitrogen gas  and
add a given volume of acetylene. Raise the pressure in the gasometer to  2
                                    - 217'-
-------
atmospheres by adding nitrogen gas.  The acetylene concentration thereby
becomes equal to  5% by volume. Reduce the pressure to 76 mm of mercury
and again raise the pressure in the  gasometer to 2 atmospheres,which will
reduce the acetylene concentration in the air mixture to 0.25% by volume.
Again reduce the  pressure in the gasometer to 400 mm of mercury, and again
raise it to 2 atmospheres by adding, dry nitrogen gas,  which produces a 0.05%
by volume of CsHa .  Force this gas mixture into the  gas pipette up to a pres-
sure  of 1 atmosphere.  After the spectrometric   determination ot this mixture
has been made pump a part of it out from the pipette  and replace  by dry
nitrogen gas which again lowers the acetylene concentration in the gas mix-
ture container. In this way, spectra can be prepared for reduced acetylene
concentrations down to 0.02% by volume.  Determinations of acetylene band
intensity at 730 cm"1  was made by the Wright basic line  method (1941).
Straight line curve in Fig. 2 is a calibrated curve of ratios between optical
density in the band of minimum absorption  at 730 cm 1 and acetylene con-
centration in the air.   The straight line character of the  curve shows that in
this instance the Lambert-Beer law prevailed.  The value of molar extinc-
tion coefficient (e) at a given band is equal  to 529 li/cmx mol.  The relative
error of acetylene determination in the concentrations interval of 0.002-
0.050 by volume is  characterized by the data shown in Table 1.  Compara-
tive determinations of different acetylene concentrations were made by the
spectral and colorimetric methods; results are  listed in  Table 2.  Acetylene
concentration in the initial gas was determined by the method of A. E. Volkov
(1953) using gas analyzer VTI, and determination of acetylene concentration
in the gas mixture was made by the method of M. I. Bogdanov (1959).
Fig. 2.
               a
               o
                     D
                  0,200 •
                  0,/SO
                  0.100
0,050
                    0 V.
                                  0,3?    0.0?
                                ', an c*n t r » !. i w> «
                              (JJl'l
                     /-o
                            j -
                Calibrate: curve for tn<5 aetar»< 141 t«v of «i»t/l'»>i» > t •">«• «•'
                I -First expert nen t«l aeries; <;  - second e*p«'i»ent«l se'ie!.»
                3 -  thira ex .eriiaent*! series; H  - feurf* et^ar inty, :a] series.
                                    - 218 -
-------
        Table 1.
Table  2.
           f'recfsicn of acatylene dotoroo.!-
                 atisn in the air
Aoatf 1 enc'
concentra-
tions dop-
ing mix-
ture prop-
orat i an
Acoty 1 eno
can centra
to. 3ns as
doterain-J Deviation
ed lay coV,
ibratod [
, curve . i
AbsoUS
0,006
0,010
0,020 '
0,030
0,0354 '
0,040
0,047
0,006
0,012
0 ,,023
0,030
0,034
0,041
0,048
0,000
0,002
0,003
0,000
0,0014
0,001
0,001

i of
relative
error


0
20,0
15,0
' 0
4,0
2,5 .
2,1
Results of spectral and color i-aetn c
   datoroinations in absolute  J
Acetylene •
ccncantre-
tixns dup-
in g', a Da-
tura prep-
are tim
0,005
0,037
' 0,041
0,042
0,050
*
Results of
spectral
detos.


fie&ults of
co lor no.
delis-

".

0,036
0,041
0,0425 .
—
0,003
.0,028
0,028
0,028
0,021
        Data presented in Table 2 show that the colorimetric method yielded
somewhat lower  results.  However, a detailed comparison of the charac-
teristics of the 2 methods in relation to acetylene trace quantities in the air
is now in the process of study.  Thus,  in this paper a method was described
for the quantitative determination of low acetylene concentrations in the air;
it was developed on the basis of infrared spectrophotometry and is  sufficient-
ly sensitive to determine acetylene vapor in the air within the limits of
00 002-0. 05% by'volume,
   >.
                                 Bibliography
         M - J1  1953 B 2 crp  175 — K o p UJ M IT SauoflcK.  .ia6op.,  1957, T. 23, M> U.
         CTO  1299'—repu<5epr P. KV>.ne6aTe.nbHbie H  BpamareJibHwe ciieKrpu  MHoroaroMHbix
         MO^KYJI. M., 1949, cip. 212.-Pier son R. H., Fletcher A. N. Gantz  E S  I...
         Analyt Chem., 1956, v. 28, p. 12l8.-Wri ght N., Industr. Engng. Chem.  1941,  v.U,p. I.
    Some Principles Underlying the Determination of Maximal Permissible
            Dust Concentrations  in the Air of Working Premises
                                   pp.  88 - 94

                  B. K. Katsnel'son.and B. T.  Velishkovskii
(From the Sverdlovsk Institute of Labor-Hygiene and Occupational Pathology)
        In I960 the Soviet Union adopted a new list of maximal allowable con-
centrations for poisonous gases,  vapors and dust in the air of working prem-
ises.-  According to the old concept, air polluting dust was classed as toxic
and nontoxic,  for  which two corresponding  maximal permissible pollution con
                                      - 219 -
-------
centration had been adopted.  Only dust containing free silicon dioxide was
regarded as  toxic.  At present  there exists an extended list of maximal per-
missible concentrations for dusts of different kinds.  In establishing the new
list of maximal dust concentrations, the Committee on Maximal Limits had
taken into  consideration not only the presence of free silicon dioxide but also
other factors.  The most important factor was percent of free silicon dioxide
in the dust.  On that basis the Committee established three grades of pneumo-
noconiosis potentialities, depending upon the amount of free silicon dioxide
contained in  the dust.   The Committee had also lowered the maximal allow-
able concentration of silicon dioxide containing dust up to 1 mg/m3, and es-
tablished lower maximal permissible concentrations for some silicates, in-
cluding asbestos,  and considerably lowered the number of instances in which
10 mg/m3  could be regarded as the maximal permissible concentration in the
air of working premises.

       Comparison between results obtained by the gravimetric and the
particles'  count methods can be only of an approximate nature,  nevertheless,
results presented by Elkins in 1961 may prove of considerable interest.
Elkins had analyzed the count coefficients of Drinker and of Hatch and  came
to the conclusion that the maximal allowable concentrations recommended in
the USA for different mineral dusts were 2-9  times as high as those corres-
pondingly adopted in the Soviet Union.  The recommendations made by USA
investigators have been in use in many other industrially developed countries
which had  adopted the  principle of hygienic air standardization.  This clear-
ly indicates that the maximal allowable dust concentrations in the air  of
working premises adopted in the USSR insured safer hygienic conditions for
the workers.  On that point, the present authors express no difference of
opinion;  however,  they believe that the principle underlying the classifica-
tion of dust as  "nontoxic" A 'or  "tuxic to varying degrees", should be dis-
cussed more thoroughly. In fact, many investigators  of this  phase of sani-
tization are still analyzing  the principles upon which the new classification
is based.

       In the first place, doubt arises in the minds of the  present authors
regarding  the necessity of excessive breaking up into many standards of the
interval between present concepts of maximal and minimal permissible con-
centrations of different dusts,  thereby introducing fine distinctions between
the degree of dust "harmfulness".  It is,indeed,  difficult to select a single
principle  on which to base  such interval breaking up.  On the one hand,
different maximal pei-missible concentrations have been adopted for group?
of dust which were of almost the same degree of pneumorioconiosis poten-
tiality.   Such, for instance,  as artificially abrasive dusts for  which  5
mg/m3 was adopted as the  maximal permissible concentration, and loam
cement and other mineral dusts which are free from silicon dioxide, and for
which 6 mg/m3 was adopted as  the maximal permissible concentration in
the air of working premises.  On the  other hand, the same 2 mg/m'3  concen-
tration was adopted as the  maximal permissible concentration for dusts  con-
                                    - 220 -
-------
 taining 10-70% free silicon dioxide, despite the fact that dusts containing
 15-65% of quartz possessed high fibrogenosis potentialities, indeed, higher
 than those possessed by the dusts mentioned just above.   The fact that the
 new list  of standards contained maximal permissible dust concentrations  of
 1,  2,  3,  4, 5, 6, 8, 10 mg/m" create,s the imp cession that medical science
 is  iai  possession of precise quantitative data on which to base such fine dif-
 ferentiations between  the effect of,  so-called, nontoxic dusts on .the organism.
 It  may give rise'to the idea that the task of establishing maximal permissible
 concentrations for some,  so-called, nontoxic dusts is in a^more advantageous
 position  than- poisonous gases and vapors,  in as much as  the  latter differ  from
 one another most frequently only by the order of magnitude,  as is shown by
 the fact that 115 of the  168  inacted or adopted maximal permissible concentra-
 tions  fall within the range of 1 x 10~   and 5 x  10"  mg/li.
        The present authors  believe that such impressions are erroneous.
 It is well known that degrees of toxicity as determined by experimental data,
 and on which the adoption of maximal permissible concentration is based did
 not agree with the results obtained by experimental studies of pneumonoconio-
 sis.  Dust  inhalation by experimental animals produced visible changes in the
 lungs only  when dust concentration in the air of the experimental chamber was
 substantially above the adopted maximal permissible concentration limit.
 Intratracheal  dust administration to experimental animals, which is the  most
 frequently  used method of evaluating the effect of different substances on the
 organism,  cannot by its very nature yield da.ta for the direct or  computed
 determination of maximal permissible dust concentrations in the air of work-
 ing premises.  Finally, data obtained as a result of medical examination and
 general observation of  large groups of workers, who had been exposed to the
 effects of low dust concentrations for many years,  could be obtained only in
 exceptional cases and with considerable  difficulty.   It should  be noted, how-
 ever, that  maximal permissible concentrations of 1 and 2 mg/m3 have been
 arrived at  by  just such a method in the case of quartz containing  dusts.

        It is only natural that under such unavoidable conditions all new maxi-
 mal permissible concentration values adopted in the new list  should be based
 on qualitative  and semiquantitative comparisons of the nature  and degree of
, dust effect on the organism, whether experimentally or clinically arrived at.
 Although, this approach to the standardization of dust concentrations in the
 air of working premises appears to be the only  possible one,  it must  be  ad-
 mitted that it  can not be used as a rational basis for the fine distinctions in
 the standards  adopted in the new list.  Despite that, the present practice in
 developing "precise" sanitary dust standards follows basically the precedent
 established by those who recommended and adopted the new list of investi-
 gated dust  concentrations.  In fact,  it is sometimes extremely difficult to
 decide which of the dusts elicited'si'mulating pathosymptomatic pictures on
 the basis of which maximal permissible  dust concentration of 5 or 6 mg/m"3
 should be adopted.  Such difficulty presents itself even  after a complex  histo-
 pathologic  picture has  been obtained for  a dust of low toxicity experimental  .
                                     -  221 -
-------
It should also be born in mind that such a procedure of determining maximal
permissible dust concentrations is basically oriented around previously
described evaluations of the organism's reactions as seen by other investiga-
tors and not as  presented by the direct observation of the studied material.
By the above described  procedure of sanitary dust concentration standardiza-
tion the quantitative evaluation of the fibrosis reaction, elicited by the dust
under experimental conditions, is not given due consideration.  The present
authors found this to be  particularly true with regard to many experimental
investigations which had been  used as bases for the adoption of the new  maxi-
mal permissible dust concentrations in the air of working premises.  On the
other hand, it would be  erroneous to expect that other methods, such as bio-
chemical evaluation of the degree of experimental fibrosis,  should yield basic
results applicable to the differentiation between dusts  requiring 4 and 5,  or
5 and 6 mg/m°  as the maximal permissible air concentrations, since even
the results  of most carefully controlled biochemical experiments are reliable
only within  certain limits.  Results obtained by the gravimetric method of
dust concentration determination in the air also show that the fine  differen-
tiation in maximal permissible dust concentrations incorporated into the new
list were not based on rational foundation.   Thus, in making duplicate air-
dust concentration determinations by the aspiration  method, one test may
yield a concentration of  5 mg/m3 and a duplicate concentration  of 6 mg/m3 .
According to COST specifications the  maximal allowable dust concentrations
should be a single one but according to the new list the determinations require
2 levels of maximal permissible dust  concentrations.  In addition, it is well
known that dust density in the  air of working premises at any particular point
may vary within wide  limits in short time periods.  For instance, a dust con-
centration fluctuation between  4 and 6 mg/m  frequently occurs in many plants
without any apparent cause, but under the system presented by  the new list
such variations in air dust  concentrations cover 3 levels of the  newly adopted
maximal permissible  air dust  concentrations in working premises. In this
connection,  it is of interest to note, that only 3 maximal concentration levels
have been established in the USA  for 16 types of mineral dust in the air, name-
ly,  5,  20,  and  50 million parts per cubic foot of air.  It should be added,
however, that,  whereas  the present authors regard the levels of maximal
permissible dust concentrations adopted in the USA as inadequate for the
sanitary protection of workers, they,  nevertheless, agree with the basic
principle of 3 levels.

       On the basis of the above discussion, the present authors suggest
that the new list of maximal permissible dust concentrations be reviewed
and revised in  the following way:  that 1 of 3 permissible dust concentrations,
namely 2, 5, and 10 mg/m3 be adopted as the maximum for  nontoxic mineral
organic or metallic  dust, with the exception of dust containing more  than
70% of free  silicon dioxide,  for which the  present 1 mg/m3  maximal per-
missible concentration  should be retained.   The present authors base their
reasoning on the fact that 1 and 2  mg/m" concentrations have been adopted
as maximal for dust containing a  considerable  amount of silicon dioxide, arid
                                   - 222  -
-------
 that no evidence had been presented requiring positive or negative changes
 in the upper (10 mg/m ) limit of dust concentrations.  Finally, the above
 stated  considerations present reasons for the selection of only 1 intermedi-
 ate  level between 2 and 10 mg/m  as the maximal permissible concentra-
 tion.  For the same reason the present, authors suggest that the  selection ot"
 maximal permissible limits of all types of dust; as recommended in the
 newest lists, be limited.  This suggestion has no relation to dust possess-
 ing frankly toxic and irritating properties, nor  to dust possessing radioac-
 tive and. cancerogenic properties.  It is suggested that in establishing maxi-
 mal .permissible limits of dust'concentrations in the air of working premises
 the following be taken into consideration:                  s

        (1) that 2 mg/m  be 'adopted as the maximal  permissible  concentra-
 tion of dust possessing clear-cut fibrogenic properties, -as evidenced by re-
 sults of laboratory experiments  or clinical and  microscopic examinations;

        (2). that 5 mg/m3 be adopted as  the maximal permissible concentra-
 tion of dust possessing some degree of fibrogenisis, as shown by experimen-
 tal data, but the intensity of which was below that possessed by quartz and /
 or dusts which elicited development  of  pneumonoconiosis in persons exposed
 to such dust for long periods of time, but the intensity of which was  lower
 and  the occurrence less  frequent as compared  with the development of sili-
 cosis;

  •»      (3)   that 10 mg/m3 be adopted as the maximal permissible concentra-
 tion for dusts which experimentally produce  only slight cellular  reactions or
 a barely perceptible  reticular fibrosis around points of dust accumulation,
 but which produced no fibrosis even  in as long a period as 18-24 months
 after intratracheal or inhalation administration of high dust concentrations;
 this includes  dusts which after the inhalation  of high concentrations over a
 period of many years under working conditions produced  symptoms of
 pneumonoconiosis and of pneumosclerosis  in  only occasional well estab-
 lished and  properly diagnosed cases.

        The present list of .maximal permissible dust concentrations rests
 on dusts grouping on the basis of silicon dioxide and silicate per cent they
 contained;  such a grouping limits the criterion of  standardization to  the
 capacity of  dust to elicit  pneumonoconiosis of predominantly interstititial
 and fibroplastic characters.  However> it is  known that "Instructions for
 the Application of the List of Occupational Diseases" approved by the USSR
 Ministry  of Health in 1956 permits to class as occupational diseases cases
 of chronic   diffuse bronchitis and pulmonary  emphysema,  which develop in
 pers.ons of long work records  under  conditions of  intense air-dust pollution
 even in the  absence of roentgenological evidence of pneumosclerosis.  The
 present authors regard this position taken by the Ministry of Health  as of
 great significance  and as basically rational.  Records accumulated  in the
Sverdlovsk  Institute, and pertinent references found in the literature, clear
 ly indicate that pneumonoconiosis was  not only  the effect  of dust,  but that
                                    -  223  -
-------
it was also an occupational disease accompanied by the develop merit of
bronchitis and symptoms of pulmonary emphysema.  This disease  ' way
noted among workers  who had roentgenologic symptoms of dust pneumonoco-
niosis, which may be lacking in some cases. In any case, such workers must
be diagnosed as having an occupational disease frequently accompanied by
considerable functional disturbances.  It should be remembered  that con-
siderable bronchial changes had been seen in persons exposed to dusts of
low fibrogenic  potency, or in the absence of any fibrogenisis,  as the case
may be iii persons exposed to the inhalation of dust consisting of elemental
silicon.  In the light of what was said above, the determination o.f maximal
permissible  limits of  dust concentrations should be based not only on  the
previously mentioned  criterion of fibrogenisis, but must also take into con-
sideration their effect on the bronchi, since statements  regarding  the etiology
of occupational diseases have been officially recognized as pertinent docu-
ments.

       In this connection the following must be recognized assuming that
the  differential approach  to dusts of different chemical  origin as factors
in the  etiology  of  pneumonoconiosis was a correct one,  then dust as a fac-
tor  in  the production of bronchitis  is still looked upon as undifferentiat.ed.
Proper dust  differentiation in relation to  chronic bronchitis etiology must
be based on data derived  from extensive  clinical and  experimental investi-
gations pertinent to  this problem.  In this connection the present authors
wish to emphasize the urgent need for such investigations.  At the moment,
and in the  absence of the  necessary data,  the present authors suggest that
5 mg/m   be  adopted as the maximal permissible concentration of dust which
causes undoubted wide spread occurrence of dust bronchitis.   Included in
this category should be dusts which produced low intensity fibrogenosis.
If this viewpoint should be adopted,  then  10 mg/m3 as the maximal permissi-
ble  concentration for  some dusts of vegetable and animal origin, even when
free from  silicon dioxide, could not be accepted as rational.  Tne  adoption
of a single theoretical approach to the standardization of maximal  pirmiss-
sible air dust concentrations presupposes the use of unified and standardized
methods  for  the study  of dust effects, on the organism,  particularly in. ex-
periments with animals.  Such methods can be  developed only with the parti-
cipation of workers  engaged in different phases of laboratory investigations.
In arriving at unified and standardized methods for the  study of maximal per-
missible limits of air  suspended dusts special consideration should be given
to the  following phases of the investigation:  species and  age of the  experi-
mental animals,  their number,  dose, concentration and route  of dust  admjn-
istration,  dust dispersion,  duration of exposure and observation periods,
minimal parameters of morphological investigation,  means for quantitative
determination of dust  accumulation in the lungs,  chances of fi.bros.ls forma-
tion and statistical data processing.   The adoption of unified investigation
methods  should not preclude the freedom to conduct supplementary investiga-
tional  procedures,  and should be regarded as the minimum necessary for se-
curing an adequate basis  for the determination  of maximum permissible  dust

                                 - 224 -
-------
concentrations in the air.                            •
                                                          i
        The discussion would not be complete without defining the maximal
permissible, concentration as the  maximal single concentration indicated in
the introductory part of the latest list.  Such an approach to the concept of
maximal permissible  concentration elicited controversies even with regard
to toxic  substances.  The controversies become profou.oder and more acute
when the. above  mentioned concept is applied to dusts which elicit pathologi-
,cal conditions only upon chronic exposure to their effect.  Theoretical con-
siderations and experimental evidence indicated that the accumulated dust
deposits in the lungs over a long period of time are  determined, all other
conditions  being-equal, not so much by the dust concentration in the. air,
as by the duration of daily exposure to dust inhalation. Therefore, it is
suggested that .maximal permissible nontoxic dust concentrations should be
regarded as average concentrations prevailing at specific processing posi-
tions during the work  day.  Where the air dust density significantly fluctu-
ated during the  day, due to changes in technology or other similar causes,
the maximal permissible dust concentration  must be compared with the
average of the fluctuating daily concentrations.  This  means that air dust
concentration determinations must be made in a processing room or depart-
ment every time the technological procedure is changed.  Neither  the dura-
tion of the  changes, nor brief peaks of dust concentration will have any signi-
ficant effect on  the value of the,so-called,  maximal single concentration.
        The above discussion  does not exhaust the many problems which
rriay arise  in arriving at maximal permissible dust concentration limits.
There are  also  other factors,  such as volume and rate of air inspiration
and the  problem of simultaneous presence  of dust and gas, etc.  But for the
present the authors prefer to limit their discussion  to the above presented
pointSo  The problems raised by the present authors and their concrete sug-
gestions are controversial; it is not expected that they will be treated as
proposed;  however, it is hoped that the discussion will lead to the develop-
ment of unified and standardized theoretical and practical methods of  ap-
proach  to the problem of standardizing maximal permissible dust concentra-
tions in the air.

Notes:

(1)
The  term in quotes, "nontoxic", has been officially  adopted by sanitary coco
N 101-54; like many such terms in biology it  represents an arbitrary designa-
tion.  However,  it serves its  purpose from a practical viewpoint.  For this
reason, the authors continue  to use it in discussing  the subject  of maximal
permissible concentration limits.

(2)
Many authors designate this disease by the term of "miner's" disease and
believe  it to be widespread.  Some authorities do not regard it as an occu-
                                   - 225 -
-------
pational disease.


(3)

Assume that there has occurred a 10-minute  rise in quartz dust concentration

MAC/mg/m3,  Assume also that during a 6 hour work day the basic dust con-

centration was  0.5 mg/m3.   Solve equation  (10 x-t-350 x 0.5)/ 360 = 1 and

find that the permissible concentration during the 10 minutes would be only

18.5 mg/m3.  Under practical conditions and longer periods  of dust concen-

tration the permissible maximum  would be of even lower value.


                                  Bibliography



             \ K o n a H O. A., E p a M a H C. I'. B KH.: MarepHa.iu naynHoA KOHepeHHHH HH-ia
         rMrnem.1 rpyaa H npO(p3a6o.ieBaHnfi.  EpcaaH, 1961, crp. 17. — B p ro K n e p Jl., POCMH-
         .1 i H.  Fur. rpyaa, 1962, Jv° 2, crp. 52.—A a 111 T o H H A. K- B KH.: MarepHa^w HayiHoii
         K«H(pepeimiiH Hn-ra ninieiibi rpyaa  H npcxpsaCojieBanHH. EpeaaH, 1961,  crp.  16.—Epa-
         M n H C. f., flaiuTOHH A. ;K., 5 a r n ii P. T. Tan we, crp.  13.—3 n c ,1 H H R. M. K.IH-
         nifKa CHJWKOsa B MCflHopyfliioft npoMbiiu;ieHHOcTH. AfliopeeJ).  AHCC. B.OKT.  TOMCK,  1961. —
         H a H a K a T n K a H A. O. yiiKUHOHa/ibHoc COCTOHIIHC flbixare^bHofl CIICTCMU npn HHCBMU-
         MiiiiKxiax H xpOHHtecKHX CpoiixHiax  nu^eBoft STHO^orHH n po^t HCPBHUX MexaH»3Mon B
         ••'» H.tMCHoiiiiRx. ABTOP«P. flHCc. AOKT. M., 1962.—FIpcae^bHo aonycTHMue KonueHTpaunii
         H.IUHHTUX  raaou, napoB H  ribi.m u noaayxe paOomix noMeweHHft.  M., 1959.— Car-
         stcns M., Brink mann 0., Lange H. J. et al., Arch.  Gewerbepathol. u. Gewcrbc-
         hyg., 1959, Bd. 17, S. 65.—Drinker P., Hatch T. F., Industrial dust. Hygienic signifi-
         cance, measurement and control. New York, 1954.—E 1 k I n s H. B., Arch,  environm.
         Hlth, 1961, v. 2, p. 45.-Higgins I. T. T., 01 d li a m P. D., Brit. .1. industr. Med..
         1962, v. 19, p. 65.—Wrights. M., Ibid., 1957, v. 14, p. 219.
      Effect of Natural Climatic Conditions on Atmospheric Air Pollution
                             Near Seashore Cities

                                     pp. 95 - 96


                                D.  B.  Gorkavenko
      (From the Far Eastern Scientific Research Construction Institute)
        It is  known that some cities located close to  the  seashore which had no
definite sources of atmospheric air pollution had a considerable air pollu-
tion fallout amounting  to 730-900 tons  per 1 km^ annually, and single air
pollution  concentrations 7 times as great as the  specified maximal per-

missible  air pollution  concentration.   This paradoxical  phenomenon can be
explained by specific natural local climatic conditions.  The topography
complex of near seashore cities  has  a considerable effect on the city's
local climatic conditions.   Cold air masses descending  along the hill slopes
produced disturbances in the vertical temperature gradient,  as a result of

which smoke failed to  rise and extended horizontally over the city, creating
heavy smogs consisting of gaseous vapor and  solid particulate substances.
These  conditions become considerably aggravated in the presence of temper-

                                        - 226 -
-------
 ature inversion.
        The vertical temperature gradient was analyzed on the basis of data
accumulated for the past 5 years at two meteorological stations  located in
strategic positions  favoring  such analysis.   Distortions in.the vertical tem-
perature gradient had been observed monthly throughout the year at differ-
ent recurrent frequencies.  Highest recurrence frequency was  noted during
the winter and spring months,  that is  during the heating period when the
smoke  discharge into the atmospheric air was greatest," as  shown by the
curves  in the figure below.     •'  •   .         .                   •

                                      The topography of city territories
                                      under  observation was complex in
                                      each case, so that the mouths of in-
                                      dustrial smoke stacks and of residen-
                                      tial chimneys were frequently on the
                                      level with streets and windows  of
                                      residences located at  the higher slope
                                      levels. Under such conditions  the
                                      smoke plume axis reached the breath-
                                      ing level immediately after its  dis-
                                      charge, that is at a time when the
                                      «moke pollution was at its maximum.
                                      For this  reason,  the measure adopted
                                      for the protection of the city's atmos-
                                      pheric air by raising the height of the
                                      residential chimneys and industrial
                                      smoke stacks proved ineffective near
seashore cities of a complex geological topography. In places of-complex
tapography, points of  contact between  the  smoke plume and the ground sur-
face depended, not only upon the smoke stack height and the horizontal dis-
tance from it,  but also on the steepness of slopes surrounding the locality;
for this reason the usual standard maximal permissible  pollution regulations
were inadequate for the  protection of atmospheric air cleanliness in cities
located in regions under present discussion.

        Historically developed plans for the construction of near-shor^: ci.ti *••-•.
arc characterised by iuf lexibilicy.  In  one such  city more than */'.. !!%  '.f ':h^
y -1
a

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8 ' .
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~[7 [n |/// i/7| 7 |w |w|w/|/r | x \n \in
         Months
 Repeated cases of vertical temperature;
 gradient invars inn in seashore cities ,
     ambient air in IV51* - I :^59
, I - Total  number of i.ivorsiensf
 2 — Casas of teraperatwirQ inversten

   .      .
der conditions of increased load while ascending  and descending--acn s,i
and required the  continuous use of brakes, especially during winter months.
The gases exhausted by automobiles under such conditions contained an in-
creased number of incomplete combustion products, and an  increased con-
centration of toxic substances.  The characteristic  distribution of atmos-
pheric precipitation according to annual seasons, constituted one of the fac-
tors which in the. case of near-seashore cities impeded the successful pro-
cess  of air'self purification.  Thus, the amount of atmospheric precipitation
                                     - 227  -
-------
during the cold winter months was 45-65% below that of the centrally located
cities, despite the fact that at such time the atmospheric precipitation in sea-
shore regions was supposed to be at its maximum.  Climatic conditions  of
cities located within the immediate proximity of the Pacific Ocean were
characterized by constant trade wind patterns which blew in the northerly
direction from the south during the summer months, and in the reverse  direc-
tion during the winter months.  Such seasonal changes in the wind direction
presented additional difficulties to rational planning of industrial  regions in
relation  to residential sites.

       Present code Sn 41-58,  p. 101 specifies that the average annual wind
pattern,  particularly during warm months should be the determining factor
in planning cities  and their direction of expansion. However,  such a speci-
fication could not  properly apply to construction of cities under above de-
scribed seasonal wind direction changes.   Atmospheric  air pollution con-
centrations are affected by natural climatic conditions,  particularly when
the fog season and consequent reduced natural ultraviolet radiation density
persisted for many days.  Under such conditions the prevailing climatic  con-
dition  strongly intensified concentrations of atmospheric air pollution.

       Analysis of meteorological observations made during the last 18
years in the  vicinity of near-seashore towns under study indicated that dur-
ing 1924-1941 the number of foggy days increased from 21 to 28%.   Examina-
tion of meteorological data accumulated by the city under investigation and
by a nearby meteorological station showed that the city lost annually 13-56,
with an average of 26, clear days.  The effect of atmospheric  pollution on
sanitary living conditions was studied in 1962 by the questionnaire method
specially prepared for this investigation.   The total number of questionnaires
distributed among inhabitants residing under different air pollution condi-
tions at different city regions was 829.  The questionnaires were  distributed
among residents of 9 city regions.  Results obtained in regions No. 1 and
No.  9 are briefly presented below.    Region 1 was the site  of a harbor and
of some industrial plants.  Inhabitants of this  region (17.5%) complained  of
damage and soiling caused by the air pollution to their upper clothing;
92. 2% of the  answers complained of the impossibility to dry the washed
clothing in the  open air.  Region No. 9 had the appearance  of a well-managed
section,  and  its air pollution was of a low intensity.  Accordingly, their  com-
plaints came from about 35 - 22% of the questioned residents.  Among the
predominant  complaints, were  unpleasant odor, headaches, nausea, cough,
and during the  still winter months also dense fogs.  Generally, the unfavor-
able climatic conditions occurred simultaneously, which enhanced the un-
favorable effect of the atmospheric pollution on the city  residents.

       Answers to the questions also showed that outdoor air  pollutants
penetrated inside the residences even with the doors  and windows closed,
a condition which most obviously must not be tolerated.   Row houses  facing
south or north suffered most intensely from the above mentioned  dust pene-
                                   - 228 -
-------
tration into the dwellings.  This was especially true with/rega.rd.to apart-
ments of the first and second building stories.  Under any set of atmospheric
and air pollution conditions the situation was generally more favorable in
region No.  9'than in region No0 1.

       Summarizing, it can  be stated that natural climatic conditions  of
cities located in close proximity to seashores contributed to the formation
of high pollution concentrations even when pollution discharges were rela-
tively low.  This fact makes  the problem of atmospheric 'air protection more
pressing in cities located in  close proximity to seashores.   The facts  dis-
cussed in this  paper must be taken into  consideration by authoritative  bodies
concerned with the planning and construction of near seashore cities.

                                Bibliography


           Mapsees A. H. KoMMyHa;ibHan nit-Hena. M., 1951. — ripaBHjra  H nopMbi n.iaHH-
       POBKH M sacTpoiiKH ropoflOB. M., 1958—PnsaHOB B. A;  CaHHrapnast oxpana aTMOC-
       cpepnoro BOMyxa. M., 1954.—\11  e n « H x o B c K H H T. B. 3aflbiM^enHe ropoflOB. M., 1949.
            Radiation Danger Presented by Surfaces Contaminated
                        with Alpha-Active Substances
                                pp. 101 - 103

                            Go  M. Parkhomanko
                                  (Moscow)
        Radioactivity intensity in premises assigned to work with radioac-
tive substances is affected to a considerable degree by radioactive contam-
ination of'the walls, ceilings,  installations and instruments.   Such surface
contamination with o?-active substances seldom, if ever,  affects the exterior
surroundings, but  is harmful to the health of persons employed inside such
radio polluted premises,  affecting particularly exposed body parts.  There
exists a definite connection between surface  radio contamination and the
concentration of radioactive substances in the  air, depending  upon the char-
acter of the  protecting coverings,  the rate of air  ventilation,  the general
dustiness of the premises,  and the  chemical and physical condition of the
a-active substances.  The rate at which radioactive substances  entered the
air also depended  upon the volume of air which passed over the  contaminated
surface.  Surface  contamination with a-active,  substances under similar con-
ditions is accompanied by a  greater entrance of radioactive aerosols into
the air than  in contamination with (3 and Y-active substances.  This is par-
ticularly true of such a-emanators  as Po, Ro,  and Pu, which are charac-
te,rized by aggregate emanation.  In addition, the  chemical composition of
                                    -.229 -
-------
the contamination also plays an important part, since it has been shown that
the volatility intensity of the same compound, or of the same radioactive ele-
ment, may differ.   This was shown by K. Bengal in I960, who noted different
degrees of air pollution in the laboratory when working with Polonium dioxide
and Polonium halide, which he explained on the basis of high volatility of pol-
onium halideso
        Effect of surface contamination with a-active substances on ambient
air has been studied by many investigators.  It was shown that in the presence
of a given surface contamination, and in the absence of known air contamina-
tion sources the formed air aerosol concentration was at the level of its
maximal permissible concentration.   Data presented in the  Table below show
that intensity of surface contamination effect on the condition of air was prac-
tically the same for different a-emanating substances, especially if differ-
ences in the maximal permissible concentrations in the air  were taken into
consideration.  Data obtained by Aizenbad did not support such an opinion.
This can be explained by the fact that Aizenbad and other investigators did
not have at their disposal data related to the rate of air ventilation in the
investigated premises,  a fact which prevented them from obtaining quanti-
tative relationships between the degree  of surface radio contamination in the
working premises and its concentration in the air.   The present author found
that by  complying with the specified maximal surface  contamination level
(500 a-particles per 150 cm3 per min.)  and by insuring an 8-fold to 10-fold
air ventilation per hour, the air  aerosol concentration could be reduced to
below the maximal permissible level.   Under such conditions a "reserve"
was created between the contaminated surfaces which conditioned the maxi-
mal permissible air aerosol concentration and the  maximal permissible
contamination levels specified by sanitary regulations.
          SarpasHCHHOCTb  paSoMHX noBepxHOCTefi, o6ycjioBJiHBaiomaH  npefle^bHo AonyctMMyio
                       KOHUeHTpaUHK) U-aKTHBHhIX BCUteCTB B B03fl,yXC          	


Active substance
Polaoi'JO-210
Radi'jn— 226
Radius -2^6
Plutoni ja-i:39
Plutoni^-239
MAC in the
air of
•orxing .
premises '
in cu/ 1 i
1 10-"
3- 10-"
3 10-"
2- 10-"
2- 10-"
(y-yart i clea
j,er 150 c«2
«hi=h deter-
mine the UAC
in the air
4000—10000
10000
100000
3300
6600



G. M.
G. M.
19
Eisen
V-.
Dunst
1:
                                                 Authors
                                         G. M. ParKhonenko,
                                             f'arkhoaenko, G. Ya. iv\ otukh jna,
                                             0
                                         tison&ua, Beat*, and Barry,
                                           I 354
                                         Dunstar, li*5b
                                         Chamberlain and Stan&ury,
               Cited from H. Sherwood, l%l
       The  present author is of the opinion that such a "reserve", or
safety factor,  was practical from the hygienic viewpoint.   It would be
erroneous to establish the maximal permissible surface contamination
                                     - 230  -
-------
  at a level requiring  a maximal permissible air pollution.  It must be remem-
  bered that work with radioactive substances is generally accompanied by
  other atmospheric air polluting causes which cannot be completely disregard-
  ed.  In addition, it has also been shown that a connection existed between
  radioactive surface contamination and degree of workers' skin of arms and
  of clothing surface contamination, which  must also be  taken int.o con^idera-
  tion in establishing surface contamination standards.  Determination of
  maximal permissible limits for radioactive surface  contamination must give
  consideration to the possibility of attaining same technically.  Experience
  indicated to the present author that laboratory work with a-ractive substances
  can be conducted so as to avoid intensity  of surface contamination, exceeding
  the permissible level,, Radioactive surface deactivatipn can be  markedly
  facilitated by rational planning of the work,  selection of suitable equipment,
  and installations, and many other sanitary protective steps.  Present sani-
  tary contamination controlling regulations specify  that  intensity of contamina-
  tion be determined before and after cleaning operations, It is obvious that
  such a radioactivity standardization procedure must apply to clothes of em-
  ployees whose work was  directly connected with radioactive substances.
  Radio contamination of surfaces should not exceed 500  a-particles/150 cm „
  In this connection, it appears  more rational to standardize surface contam-
                                 Q
  ination not on the basis of 150  cm  , as has been done before, but on the
  basis  of 1 cm , since many of the apparatuses used in  measuring contamina-
  tion have different transmitter unit areas, and adopting the 1 cm2 basis would
 , simplify measurement calculations.   The terms of fixed and non-fixed contam-
  ination, and the need for standardizing same are frequently mentioned.  In
  the opinion of the present author,  these are ill defined  concepts.

         A review of the literature shows that  radioactivity contamination
  levels have been adopted by many countries.  In work -with a-radiating sub-
  stances the permissible surface contamination varies within 3300 and 33300 .-
  a-particles per 100 cm2/min.   Different standards have been suggested for
  surface contamination in different laboratory sections  and for different con-
  taminated surfaces.   The  present'author is of the  opinion that limited con-
  tamination areas should be restricted to low contamination levels.  It has
  been demonstrated that localized radioactive contamination frequently served
  as a source of radioactive  substance  dispersion over the entire  working
'* premises; a gradual averaging of contamination has been observed in in-
  stances of poorly organized deactivation due to the carry over and spread
  of contamination to and over the entire  surfaces of the  floors or equipment
  during manual cleaning of the  premises.  This is particularly true of floor
  installations,  and apparatus surfaces.  In the light of what has been said
  above, different maximal levels of surface contamination should be estab-
  lished for different zones of some laboratories.  In other laboratories, where
  work with radioactive substances was conducted.at infrequent and short time'
  intervals it is possible to. set a limit  of permissible surface contamination
  5-6  times as high as  in other places.  Under presently prevailing conditions
  it can be safely stated that strict observance of surface contamination limits
  for -radioactive  substances adopted in the  USSR reduces the effects of sur-
                                     - 231 -
-------
face  radiation to safe levels.

                                 Bibliography
            IlapxuMCHKo I". M. B KH.: CGo.pHUK pe(})epaTon no paflHamioHHofl MeaiiUiiHe. M.,
         1961, T. 4, crp. 221. — IlapxoMeHKo T. M., 3oJioryxnna P. fl. FurHeHa Tpy.ua
         npH paGore c paflHew. M., 1960. — BsrHa^ K. XHMHH peaKHx paAHoaKTHBHux 3.ncMen-
         TOB. nojioHHH-aKTHHHfl. M., 1960. — Chamberlain A. C., Stanbury G. R.  UMT
         P. Rut. lUepsyfl. — III ep ay A P. flw. KpaiKHii Kypc sautHTU OT paflHoaKTHBHoro H3Jiy-
         M6HHH. M., 1961. — Dunster  H. J., Atomiqs,  1955,  v. 6, p. 233.—D u n st e r H. K.
         UHT. P. flxc. lUepayfl. —  Eisenbud M., Beatz H., Barry E. V., Nucleonics,  1954.
         v. 12, N 8, p. 12.
                              NO.  10, OCTOBER
         Toxic Properties and Biotransformation of Benzotrichloride
                                  pp. 30  - 34

         O. G. Arkhipova,  T. A. Kochetkova and B.  N. Shinkarenko
       (From the Institute of  Labor Hygiene and Occupational Diseases
                      USSR Academy of Medical Sciences)
        Benzotrichloride  (C7H5C13) is a transparent yellowish fluid which is
insoluble in water, partly soluble in alcohol,  benzene and ether.  Its. M. W.
is 194.48, sp. gr. is 1.37 and b.p. 214-220.   It is used in the production of
plastics and in the rubber industry as a vulcanizing catalyzer and as  an in-
termediate product in the synthesis of organic substances.   Knowledge of
its  toxic properties is incomplete.  N. V.  Lazarev, of the USSR, merely
states that it elicited eczema.

        The present authors studied the  toxic  properties  of benzotrichloride
by the methods of vapor inhalation and skin application.   Experiments were
conducted with white  rats and white mice placed  into special  chambers of
100 li capacity where they had been subjected to single, and also daily 2 hour
inhalations of different benzotrichloride vapor concentrations.  The daily in-
halation exposure lasted  60 days.  Concentrations of benzotrichloride in the
air of the  exposure chambers was determined by a procedure developed in
cooperation with Z.  M. Pimenova.  The benzotrichloride was decomposed
                                     - 232  -
-------
 in acid medium and the Cl determined with the aid of AgNO3 ,  Air samples
 were collected by aspiration using an aspirator devised by the institute;
 the aspirator  was filled with 10 ml of alcohol.  Upon completing the sample
 collection 1 ml of the alcohol was dilluted with 5 ml of distilled water to
 which 1 ml of 10% HNO3 were added.  A standard solution was prepared by
 dissolving benzotrichloride in alcohol.  Sensitivity of the method was 0. 005
 mg in a, given volume.  Results indicated that air  containing 1 mg/li  of the
 benzotrichloride  vapor was lethal to the  experimental animals.  Results  of
 acute toxic experiments produced the following  clinical picture: mucous
 membrane irritation,  dyspnea and general excitability.  These symptoms
 appeared almost  immediately following benzotrichloride inhalation and was
 followed by delayed motor activity.  No complete  narcosis was observed.
 Higher concentration of the vapor produced extensive dilatation of the
 peripheral vessels of the tail,  paws and  ears at the end of the experiment.
 Upon return to fresh air inhalation the delayed motor reaction disappeared,
 and the experimental animals entered into a brief stage of excitation.  In-
 halation of large doses elicited partial narcosis  which lasted 2-3 days.  Ben-
 zotrichloride concentrations up to  0.1 mg/li elicited irritation and stimula-
 tion.

        Death of white  mice caused by the inhalation of benzotrichloride in
 lethal concentration was paralleled by the appearance of sharp vascular
 disturbances  and irritation of the mucous membrane in the upper respiratory
 tracts.  Autopsies of the perished animals  showed vascular disturbances
 such as plethora  of the lungs, liver, kidneys and intestinal tract, brain bleed-
 ing of varying degrees; liver cells showed signs of diffuse fatty dystrophy;
 kidney  tissue appeared dull and the adrenals were enlarged and swollen.
 Histologic examination of internal organs of white mice and fats which died
 folio-wing a single 2 hour inhalation of air containing benzotrichloride also
 showed plethora of internal organs, extensive and small brain bleeding,
 swelling of cortical brain cells,  of the subcortical nodes and of the trunk.
 The lungs  showed signs 'of swelling and of catarrhal and desquamative bron-
 chitis;  micro droplet type diffuse fatty dystrophy appeared in the liver; the
 kidneys showed a faintly defined protein dystrophy of the convoluted  tubular
 epithelium.    Thus,  results of single benzotrichloride vapor effect  in differ-
•'ent concentrations showed that it possessed narcotic properties and  elicited
 considerable  irritation of the  conjunctiva and of the lining of the upper respir-
 atory tract,' it also elicited vascular dilatation and morphologic changes in
 the lungs, liver and kidneys.

        The chronic effect of benzotrichloride  on white  rats was determined
 by exposing the experimental animals to  the inhalation of air  containing
 benzotrichloride  in 2 concentrations in the  exposure chambers for 2  hours
 daily:   the first concentration was 0.03 mg/li which elicited  no toxic mani-
 festations  in the experimental animals upon a  single inhalation exposure;
 the other concentration 0.01 mg/li elicited general irritation and some delay
 in the  animal's motor  activity after a single inhalation exposure; the effect
                                   - 233  -
-------
was transient and of short duration.  Chronic experiments had been conduct-
ed with 30 rats of 170-200 g, of which 10 were kept as controls*  The gener-
al behavior and appearance of the experimental rats at first differed in no
way from those of the  control animals.  However, at the end of the first
week,  rats  subjected to the inhalation of air containing 0.1 mg/li of the
benzotrichloride  began to lose weight,  showed signs of malnutrition and
their external appearance reflected internal pathology.'  Animals became
aggressive  towards their cell mates and towards the laboratory service
personnel.  They refused to eat the food normally supplied to them but de-
voured rats which died in the exposure chamber.  Rats  subjected to repeated
inhalation of air  containing 0.03 mg/li of the benzotrichloride also showed
signs  of malnutrition and loss of weight, and at the end  of the experiment,
loss of weight in  individual rats ranged between  35-76 g.  No  such signs de-
veloped among the control rats which,  in fact, gained weight.  Despite the
developed unusual aggressiveness among the experimental rats, an  investi-
gation of their threshold of neuromuscular stimulability showed no signs of
unusual changes.

       Benzotrichloride is a derivative of benzene and chloroform and is a
CO-trichlorotoluol.  Accordingly,  the present authors made  a thorough
study of the experimental rats' peripheral blood picture.  Results showed
that generally the number of erythrocytes  remained within the normal limits
of 6 x 106  - 624 * 10a» hemoglobin also remained practically normal, ranging
between 12.8-11.9 g%.   On the other hand,  the number of leucocytes dropped
considerably to the range of 8,600-14,400, and some of the rats which ori-
ginally had  a leucocyte count of 12, 000 showed a count of 5,200 per 1 mm0.
Results of the Quick test showed a loss in  the liver function activity.  As
previously mentioned, a single acute exposure to the toxic effect of  benzo-
trichloride inhalation elicited liver vascular dilatation and repeated inhalation
of the poisonous vapor lowered the blood pressure considerably.  Thus, rats
with a  maximal arterial pressure of 90/110 mm manifested a blood pressure
of 60 mm after 2 months of daily benzotrichloride inhalation,  and in some
individual rats the arterial blood pressure dropped to 30-25 mm. Repeated
benzotrichloride  vapor inhalation elicited considerable changes in the mucous
membranes of the bronchi, brought about development of mucous bronchitis
and of focal purulent pneumonia; internal organs showed occult bleeding;
there  appeared some liver cell fatty degeneration, fatty degeneration of the
convoluted tubule epithelium and also  depletion of the superenal cortex.

       Extensive changes were noted in the nervous system,  especially in
the cortex and in the thalamo-hypothalamic  region.  Darkly stained cells
were noted  in the cortex, and there were also wrinkled cells, most of the
pyramidal type.  These were surrounded by cells with vacuolized protoplasm
and cariocytolyzed cells as shown in Fig.  2. Sharply defined vacuolized
protoplasm and cariocytolysis were noted in cells of the thalamo-hypothalam-
ic region*    These signs may explain the  appearance of clinical intoxication
in the  form of hyperstimulability and aggressiveness of the experimental
                                   -  234  -
-------
animals, while changes which appeared in the cells of the hypothalamic  re-
gion may-be regarded as  the cause of drop in the animals' blood pressure.
The investigation of benzotrichloride toxicity and of its toxical dynamic
properties have next been studied by a  follow up of its physical, chemical
conversion in the organism and the nature of its metabolites eliminated  by
the organism.  Some data indicated that toluol in the  organism underwent
changes similar to benzoic acid,  and that it  was eliminated with the urine
as hippuric acid.
Fig.  1.
' VA -U .*.*_, M>^«.hVrf.»
                        «                   »
             ,
                                           .
                                   Fig. 2.


                                                      , •  '  ••
      »*.' '*, . ' * • tv ** ••  '.  -Si •' T ,,-»• *»'• ,*'.»' - >
     :•••;  ' - -  ?•' •"~f,s"-->V •:-"•• '•«"• /"(/-.;<
      i- •-..-',    ' vtf:yv ,•:<" ,' • v.-•••/•; • •»
             •" -• ^>.^.-'^^--'v;r,r:»,^'I-"*^
        ,' ^'-. •A"''-'"-^':: ,:'yfl>T^
  flat «r«i.U depl.t.or. «f c»rtiMl lip«d          "«t br.in, c.ryocy t.l/«i« of cort.c.l
                . 8 x  10)                     c«IU
                             "
       It was indicated in one  of the preceding paragraphs that benzotri-
chloride was a CO-trichlorotoluol; therefore, the present authors  worked
on the assumption that benzotrichloride might also be changed in the organ-
ism chemophysiologically similar to toluol,  and that it, too, might be  elimin-
ated with the urine as hippuric acid.  On the basis of such an assumption the
following experiments  were perforrtned;  the  rate of hippuric acid elimination
via the urine under normal conditions was determined in a group of 10 rats.
This was done by the Quick method  as described by M. Ya.  Savina.  The ani-
mals were then placed into an  exposure chamber 2 hours daily for 20 days
and were subjected to the inhalation of air containing 0.03 mg/li of benzotri-
chloride vapor.  The amount of hippuric acid eliminated by  the experimental
rats prior to exposure to the inhalation of benzotrichloride vapor containing
                                     -235 -
-------
air ranged between 14-20 mg/day.  After exposure to the inhalation of air
containing 0.03 mg/li of-the toxic vapor for 20 days, the daily hippuric acid
elimination with the urine rose in individual cases to 47 mg as a result of
inhaled benzotrichloride conversion in the organism; one of the conversion
products was identified  as sodium benzoate which became converted to
hippuric acid. It  should be noted at this point that the possible formation
of other benzotrichloride metabolites cannot be excluded.  Thus, Stekol
found, in 1938, that chlorinated toluols having a haloid in their side chain,
could be transformed into benzylmercapturic acid.  In the next stage  of the
investigation, a study was made of benzotrichloride effect on the skin and
its possible penetration through the intact skin. In this  case,  experiments
were connected with  rabbits; benzotrichloride was applied to fur-free skin
at the rate of 1'ml, 3 times daily for 7 days.   Records were  kept of local
skin effects, effects  on  the peripheral blood picture, such as hemoglobin,
leucocytes, erythrocytes, reticulocytes and also on red blood cell resistance.
After the third benzotrichloride application to the depilated skin there de-
veloped bleeding skin erosions and cracks which later became covered with
scar tissue.  Rabbits showed signs  of pain sensation upon pressure applica-
tion  to such points.   The affected skin spots healed slowly, but developed
new  scar tissue after a  second application of the benzotrichloride to the
same spots.  The  fur, surrounding  points of the benzotrichloride applica-
tion, fell out and the bare skin acquired a dark pigmented color.  The ef-
fects of above described benzotrichloride application were not limited to
the skin; leucocytes fell from the original 14, 000 to  8-9,000  per mm3, and
the osmotic red blood cell resistance fell to lower levels.

                               Conclusions
        1.  Benzotrichloride is a toxic substance.  Air containing 1 mg/li
of benzotrichloride  vapor was lethal to white mice and rats.

       2.  Experimental animals subjected to acute benzotrichloride poison-
ing developed irritated conjunctiva and mucous membrances of the upper
respiratory tract, dyspnea and disturbances of the nervous system.  A sin-
gle exposure to the toxic effects of benzotrichloride elicited in the experi-
mental animals vascular disturbance in the internal organs and in the brain,
catarrhal desquamative bronchitis and focal purulent pneumonia,  also  dystro-
phic liver dysfunction.

       3.  Repeated benzotrichloride inhalation possessed the potentiality of
eliciting chronic intoxication paralleled by loss of weight, leucopenia,  and
fall in arterial blood pressure.

       Repeated benzotrichloride inhalation elicited in the experimental
animals  changes at the point of its entrance, of which purulent bronchitis
and pneumonia were the gravest along with changes which indicate general
resorption of the substance and its capacity to disturb the blood circulation
system,  to produce  dystrophic liver, kidney and suprarenal changes, as well
                                    - 236 -
-------
as profound changes in the cortical layers of nerves, ;and in the th'alamo,
hypothalamic region.                       .

        4.   Benzotrichloride is partly eliminated with the urine as hippuric
acid.'   .               -.        •      •,.•..•;•       -

        5.   Benzotrichloride penetrated through intact skin,  and elicited
symptoms of poisoning,  such as  leucopenia and alopecia.  Damage done to
intact skin by the direct  application of benzotrichloride healed very gradual-
ly.             -                       '        '"••  '.'•.;<•'.''.'

                                Bibliography                 .
                  oemecTBa B  upOMhiuj^eHHOCTH.  riofl pea. H.  B. Jlasapeoa. Jl:, 1954,
        r. 1, 2. — C a DIIH a M. fl.  THr. H can., 1963, KB 1, crp. 45. — S t e k o I J. A.,  J. bidl.
        Chem , 1938, v. 124, p. 129. — 1 d e m, J. hiol. Chem., 1939, v. 128, p. 199.
          Comparative Efficiency of Bacteria Catching Devices Used
              in Determining Bacterial Aerosol Concentrations
                                 pp. 45-48

            V. S.  Kiktenko, S. I. Kudryavtsev.and N.  I. Pushchin
        (From the Medical Department of the P. Lumumba University
                           of Peoples Friendship)
        Existing methods for the determination of aerosols are time consum-
ing, cumbersome, and are subjective,thereby yielding unreliable results.
The present authors attempted to use an objective method for the. determina-,
tion of bacterial aerosols using'a continuous flow ultramicroscope, to which
a special highly serisitive photoelectronic device and an electromechanical
c-ounter were attached,  making possible automatic counting- and recording of
aerosol particulates passing through the tube 'of the  continuous flow phoi
microscope.  Using this method, the present authors compared the effec-
tiveness of different bacterial catching devices including  cotton filtei-s soaked
in 3% gelatin solution or liquid vaseline.  All investigated devices and methods
were based on aerosol filtration through liquid or soluble solid filters and
also on aerosol precipitation.by a highly dispersed fluid.   The technique in
which such devices have been prepared and used accorded with the descrip-
tions and specifications described by the original authors.  Experiments were
conducted by the drop and solid aerosol fractions of  Chromobacterium
prodigiosum  strain No.  266 with particulate dispersion range  of 0.6 and
3. 4 jU,  and with Bac.. subtilis,  strain No.  8236 aerosol of 3 H average diameter.
The b'acterial suspensions contained 00 5 milliards of microbial cells  per ml
                                    - 237 -                                ;
-------
and were prepared with distilled water and physiological saline containing
a mixture of 15% of glycerol and 5% saccharose.  The chromobacteriutn
prodigiosum suspension contained a gelatin-phosphate buffer prepared as
follows:  gelatin-2g, NaaPO4-4g, distilled water-1000 ml, with pH adjusted
to 7.0,  A spore containing Bac. subtilis suspension was heated to 70-80°
and vigorously shaken for 5-10 minutes as described by Tyler and Shape.
Samples were collected simultaneously by four bacteria catching devices.
Ten li of air was passed through each bacteria catching device and the air
flow rate checked with an  air flow meter of R.S, -5 type.  Air samples col-
lecting time was 1-3 minutes.   Results are shown in Table 1.

Table 1.
              Comparative evaluation of bacteria trapping apparatus efficiency
                     based on averages of 32 e»i»eri»ental series
6«cteri« trapping apparatus
Construct ton of ap^aratusi



A* £« Verahi^ory .•..•..*•**•*.»*»•*•
Fiber filtersi

Dry cotton filters saturated *itn
Cotton fibers saturated with 3$

>act. pro'ii-
yiasum, Blood
5581
3189
3081
1 859
1 451
152
21
42
37218
oc eo,i

H*y b«cillu«
6286
4281
3862
2303
2402
1 922
861
893
42680
^1 871

                                                       number of bac-
                                                  terial per li »f »ir
        Data presented in Table 1 show that highest number of microorganisms
per 1 li of air was yielded by the impregnated cotton filter.  The nonimpreg-
nated cotton and glass wool filters trapped the lowest number of micro-or
ganisms, probably as a result of rapid dying off of the B.  prodigiosum. The
same was true of B, Subtilis. Consideration  should also be given to the fact
that "micro-organisms" are incompletely removed from cotton and glass
wool fibers and with considerable difficulty.  Data  presented in Table 1  v/erc
verified by results obtained in studying the retention capacity of the devu.^.s
by the oil aerosol method and by the retention capacity of B. prodigiosum.
The dispersion of the  oil aerosol ranged between 0. 31-0. 34 /I.
the investigation are presented in Table 2.
                                                               Results of.
        Data in Table 2 show that the greatest number of slip through parti-
cles was found in the bacteria retaining devices of different construction and
that lowest particulate retention  capacity was  possessed by the soluble geln -
tin foam filters which showed a slip through coefficient of  92-98%.  The dc -
                                   - 238 -
-------
 vice suggested by S.S. Kikenko had a slip through of 42-48%. .Simultaneously
 counts were made by the photoelectronic device.  Results are shown in
 Table 3.                                               ' .

 Table 2.                                         '     '-V
     •Oil aerosol particles ana bacterial aerosol si bp-tnrough coefficient  i.i different'
                                Spparatuses           ,       -
Fi 1 ter oade of
Gloss .100 1 (per 9)
Cotton f 1 1 ter (per g)
Glass aool (per 9} sat'd aith 3j sol'ra of
gelatin arid vasel ono oil (ai)
Cotton fiber (in g) sat'd as abovo
( in ml)
Bacterial trapplinj apparatus of different
c«nst ruction
Aaount of
cub st on co
10
5
10
12
5
12

SI ip-throuah,coef f » ci ent
Oil
Aerosol
2.1 ,
0,08
8,1
0,1
From 14? to^
98
Biicterial
aerosol
5.5.
1,05
0,35
0,025
—
The aerosol concentration was computed by the following formula:
n =-N/V = dx N/W, where N- represents the number of counted particu-
lates;  W-  represents the aerosol volume; d-  represents the constant of
a given diaphragm aperture in a given optical system,  and V-  represents
the aerosol volume in which the particulates were counted.

        Data presented in Table 3 show that the  aerosol concentration in the
counting chamber dropped to lower values 10 minutes after its dispersion by
only 5% of the original concentration as determined immediately following,the
aerosol dispersion.  It can be concluded, therefore, that no noteworthy change
occurred in the aerosol concentration  during the sample collection.  Counts
made by the photoelectronic counter could conceivably contain some aerosols par-
ticles-free from micro-organisms ; therefore,  the present authors considered
it desirable to determine the approximate  count of bacteria containing par-
ticles per unit volume.  This was done by desiccating the drop  phase of a
bacterial aerosol  by a silicagel desiccating column.  In such instance the
bacterial suspension was free from glycerol particles.  The  concentration of
bacterial particles in an aerosol; that is the hard core drop-nuclear fraction,
determined by the photoelectronic particle counter,  amounted to 43, 250 per 1
li of chamber air  during the period of air sample collection  by'the devices,
amounting to 3% of the  total number of aerosol particles.

        By determining the number of  particles  in a microorganism contain-
ing aerosol  by the method described,  and by considering the results  obtain-
                                   -  239  -
-------
Table  3.
       B

       CM
a
            :C
            O
            CN
           !X>
           C)
           O
   9
       e
       in
       ~  I
           CO
           O
           00
           o
           :O
           CO
           O
           CO
           CM
                   from a comparison of the effectiveness of the bacteria
                   catching devices,  it is possible to determine the approxi-
                   mate efficiency of the bacteria catching devices under in-
                   vestigation.   Thus, by examining data in Table 1, it will
                   be found that the bacteria catching device based on  the
                   principle of  cotton filter impregnated with the 3% mixture
                   of dissolved gelatin and vaseline oil,  amounted to 89% of
                   all micro-organisms present per unit of  chamber air vol-
                   ume.  The bacteria catching capacity of the other devices
                   fluctuated within the limits of 0. 3-14%.  In  conclusion,  it
                   must be noted that the per cent of microorganisms  which
                   lost their viability during the process  of  dispersion and at
                   the moment  of sample collection had not  been taken into
                   consideration in this  study.

                                        Bibliography
                     BepiiJHropa A. E. Bpai. ae/io, 1957, npmiow., cr6.  106. — H b a K o n o B I~I. FI.
                 Tup. Tpy.ua, 1925, B. 3, cip. 117. — KHKTCHKO B. C., C a (p p o H o B K). n., K y A p H fl-
                 ues C. M. H zip. Piir. H can.,  1961,  N» 2, cip. 47. — KHKTCHKO B. C., K a 111 a H o-
                 Ba H. H., K y A p K B u e B C. H. n a.p. /K.. MHKPOGHOJI., 1961, Ns 7, crp. 6. — P e 4 M e H-
                 •c K H ft  C C K npoSjieMe BoaayujMux  HHtpexuHH. M.,  1951. — Tyler M.  E.,  Shi-
                 pe E. L., Appl. Microbiol.. 1959, v. 7, p. 337.
      I

      •o
.2  I
t
1
      1.
      41 TO
                                      - 240 -
-------
          Fluorine and Hydrogen Fluoride Determination.in.the Air
                            •with a Solid Sorbent
                                pp.  48-50

          S. N. Suvorova, A. M.  V.orob'ev, and/G. V. iV'abovskii
                                (Moscow)  !          .    .,..; f  ..
       No simple and adequately sensitive methods have been described for
the determination of fluorine and hydrogen fluoride.  Therefore,  the first
step in this investigation was to select a substance.,which might completely
absorb both components.  Tests were made with water, solutions of alkalies,
carbonates, sodium sulfite, hydrazine, hydroxylamine, and other substances.
After some preliminary tests the following absorber solution was selected;
Na2S2O3-7, KI-4,  and methyl (p-methylaminophenol sulfate) 0.1  per cent by
weight.  However, successive determinations of the fluorine-ion in this  ab-
sorber mixture by highly sensitive procedures proved very complicated.  In
a.ddition,  the liquid absorber presented some difficulties when used in the
field under conditions of low temperature.  For this reason,  the  present
authors decided to use solid absorbers.  The first absorber thus  tested was
silicagel trademarked MSK of granule  sizes  ranging between 260  and 300 mg,
which  were impregnated with an aqueous solution of triethanolamine.  The
silicagel was clarified and decolorized by boiling it in 6 N solution of hydro-
chloric acid.  It was then washed in distilled water, dried at 100-120°, cooled
and saturated with a 3% aqueous solution of triethanolamine  in a 1:1 ratio by
weight, and again dried at  room temperature.  The silicagel thus prepared
was then placed into a ground-to-fit glass stoppered bottle.  The  silicagel
thus prepared can be stored for a long time.  Best results were obtained with
2 g of  the silicagel in  a Yavorov or in a U-shaped tube as shown in the Figure
below.
             - Stopper
      U-shaped rir absorb or
 Preliminary tests were then made to de-
 termine the effect of aspiration rate on the
 complete fluorine  or hydrogen fluoride ab-
 sorption by the silicagel. Some 'results
 are presented in Tables  1 and 2.   For the
 determination of possible fluorine or hydro-
 gen fluoride slip through  a second Yavorov
 or u-shaped absorber was attached to the
 first one.  Fluorine determinations were
.made  colorimetrically by the thorium-
 thoron method after it had been extracted
 from the silicagel.
       Data in Table 2 show that complete fluorine absorption varied with
its original concentration in the  air.  At fluorine concentration in the air  of
0.02 mg/li, its slip through began to appear at 0.6 li/min. aspiration;  at
                                    - 241 -
-------
 fluorine  concentration in the air of 0.003 mg/li its  slip through was noted
 at aspiration rate of 2 li/min.  Such data indicate that in instances where
 the  fluorine concentration in the air  was only slightly above  the maximal per-
 missible level, the air could  be aspirated through the  silicagel as described
 at the rate of 2 li/min. However, since the method sensitivity is 0. 0001 mg
 of fluorine in the test volume the aspiration rate can be  reduced further.
 Additional tests showed that temperature changes within the range of 25-303,
 had no effect on the original absorption properties of the silicagel.
 Table 1.
           Effect of aspiration r»te go the completeness of Hr absorption by si I icajel
Concentra-
tion in
»ih»
0,020
0,020
0,020
0.020
0,020
0,015
0,015
0,015
0,003
0.003
0.003
Aspiration .
rate in
ral/min
100
?50
500
600
1 000
2000
3000
5000
1000
2000
5000
Win. of
aspirat ion
10
4
2
1,6
1
5
5
5
5
5
5
.
Theoretical
aaount
• <> ag
0,02
0,02
0,02
0,02
0.02
0,150
0,225
0,375
0,015
0,030
0,075
Observed
amount
iri rag
0.019
0,020
0 , 020
0,018
0,017
0,135
o.ni
0,170
0,015
0,027
0,045
Hem*rK8


SI ip
through 10%
ir>";,
10%
15%
r>r,%

10%
40%
 Table 2.
             Absorption rate of F and HF mixture by silicate) at 0.5 li/'nin.
                               aspiration rate
                                                  Found F~ as HF
                                                     0 i'It,
                                                     O.Pl.T
                                                     0.016
                                                     0.1)17
                                                     0.020
                                                     0.01!)
Amount of fy
i.i the
mixture

O.OM
0,012
o.oio
0 010
0.010
0.009
0,008
Amount of HF
in the
mixture
In
0.003
0,001
0.005
O.OOG
0.0.17
0.010
0.010
Total ' •.
HF and F
R|
0.017
O.OHi
0,015
0.016
0.017
O.Ol'.i
: 0.018
        Simultaneously present fluorine and hydrofluoric  acid in the air  an.-
determined as follows:  place 2 g of the  silicagel saturated with 3% solan jr.
of triethanolamine inho  a Yavorov or U-shaped absorber.  Aspirate the air
at the rate of 0.5- 2 li/min.  The volume  of air to be aspirated and the  rate
at which it is to be aspirated vary with the anticipated fluoride and hydrogen
fluoride mixture concentration in the air.  If only elemental fluoride is  to
be determined then the air  can be aspirated  through a separator containing
sodium fluoride. The fluorine-ion is eluted from the silicagel with distilled
water.  This is accomplished by placing the silicagel into a test tube coated'
                                     - 242  -
-------
on the inside with parafin; 5 ml of water is then added.  Leave stand for 20
minutes and remove 1 ml of the solution and place into a colorimetric cup.
Simultaneously,  prepare the standard scale as follows: set up a series of 11
colorimetric. tubes  and place into the second tube a volume  of NaF standard
solution containing 0.0002 mg of  the fluorine.  Now, add to the. third tube
the standard solution of NaF containing 00 004, to the fourth containing
0.006,  0.008 mg of the fluorine,  etc. continue adding  so that the volume
added to the last tube contained 0.002 mg. of the fluoride.  Add to all tubes
0.02  triethanolamine solution  so  as to make  a final  volurrie of 1 ml.  Then
add to all the tubes  of the standard scale and to the  tubes containing the sam-
ples, 1 ml of thorium nitrate, 0. 25 ml of 1 N  HC1 and 3 drops of 0. 05% thoron
solution.  The thorium nitrate  solution should contain 0. 024 mg/ml of the
reagent.  Leave  stand for 5  minutes and make colorimetric determinations.
As stated above, the method sensitivity is 0. 0001 mg °* fluorine-ion per test
volume.
               Characteristic of Natural Ultraviolet Radiation
                               in Vladivostok
                                pp. 58  - 61

                              B. A.  Fedorets
                                 (Moscow)
        Prevention and elimination of ultraviolet insufficiency symptoms or
 consequences presupposes a thorough knowledge of natural ultraviolet radia-
 tion under different climatic zones on the basis of -which hygienists can ar-'
 rive at and formulate zonal, or local, standards of hygiene.  A knowledge of
 natural ultraviolet radiation in zones of prevailing sunshine is  also of con-
 siderable importance to hygienists.  In this connection V. S. Svarichevskii
 and O. Ya. Khomeriki observed in Tashkent and in Tbilisi (formerly Tiflis),
 for example, considerable losses in ultraviolet radiation, which was re-
 flected in the development of ultraviolet insufficiency symptoms among some-
 population groups.  It is  only natural that the problem of ultraviolet radiatior.
 and consequent compensatory processes, should appear most acute in the
 northern latitudes of USSR, as was noted by N. F. Galanin and  also by N. ivl.
 Kaikov.  A survey of the  literature made by this  author failed  to find any
 records dealing with  ultraviolet radiation of Vladivostok or other regions
 of the USSR extending along the shore of the Pacific Ocean.

       .The latitude location of Vladivostok is  much the same as the location
 of populated areas extending along the Caucasian  Black Sea  shoreline, for
 instance, Sukhumi and Sochi.   Maximal solar  altitude  recorded locally,  ac-
 cording to months were as follows:   January  - 25.4  , February - 33.5  ,
 Ma,rch -44. 2°, April - 56° , .May - 64.8°,  June - 69.3°, July  - 67.5°, Au-
                                      - 243 -
-------
gust - 60°,  September  - 49.1°, October - 37.6°, November - 27.6°, and
December - 23°.  Duration of solar radiation in most of the inhabited areas
of the Northern hemisphere changes in proportion with the solar position,  so
that maximum solar radiation duration prevails during the summer solar
period and minimal during the month of December,  The average annual solar
radiation duration of Vladivostok differs only slightly from other regions of
approximately the same latitude, but the pattern of solar radiation distribu-
tion according to months has  its specific characteristics.  The present author
studied the  data accumulated  at the Vladivostok meteorological observatory
for 15 years,  between 1945 and 1959,  and found  that the shortest solar radia-
tion hours occurred in  the months  of June, July and August, amounting cor-
respondingly to 30, 26, and 37%  of the possible maximum.  It was also noted
that during  the month of June, which is theoretically  the month of longest
solar radiation, actual solar  radiation duration was 1.2  -1.8 times less than
the solar radiation hours during the other months of the  year.  Longest solar
radiation hours prevailed during the month of September, with an average of
57% of the possible maximum.

       These specific characteristics can be explained by  the distribution of
seasonal foggy and cloudy days.  Thus,  during  the months  of June, July, and
August the foggy and cloudy days ranged between 60 and 90%, according to
meteorological records of many years,  as compared with only 10% during the
other months  of the years.  Total cloudiness during the summer months as a
rule measured 7-10 balls (arbitrary units), while during all other months'
cloudiness rarely exceeded 6 balls.  Maximum number of cloudy days occur-
red during May, June,  and July, amounting to 43-57%; minimum occurred
during January and February, amounting to 2-3%.   Such data, taken from the
meteorological observatory records explain why the duration of solar radia-
tion in Vladivostok is greater during the winter instead of the summer months

       Natural U-V radiation prevailed in Vladivostok during September in
I960. Intensity of U-V radiation was determined by the oxalic acid method
proposed by N. M. Danzig, and  Z. N. Kulichkova.  Despite the shortcom-
ings noted by  A. A. Generalov,  this method is  the easiest  to perform.  De-
terminations were carried out at three points in the city during  the frost-
free period.  Data had  };>een obtained on the courses of seasonal and daily
U-V radiations, half-daily radiation,  short-wave and dispersed radiation,
total daily radiation,  and loss of U-V radiation due to smoke and dust.  A
total of 1000 determinations have thus been collected  and processed.  The
data indicated that highest average daily total U-V radiation during 1961
prevailed during May (11.57 mg/cm ).  During  June and July U-V radiation
fell to 10.04 and 8.77 mg/crrT5 correspondingly. During the winter months,
when the  solar altitude is lower, U-V radiation fell to 6 mg/cm";  it was
generally lower in 1962 than in 1961.  It was  noted that seasonal U-V radia-
tion course  generally ran parallel  to the solar  radiation duration,  as shown
in the following diagram.  Curves  in that diagram show  the characteristic
difference between the  actual course of U-V radiation and radiation prevail-
                                   - 244 -
-------
 ing during cloudless days:  under prevailing Vladivostok conditions  maximum
 U-V radiation had not been noted during summer months at highest  solar al-
 titude.,  It is of interest to note in this connection that monthly U-V  radiation
 in Moscow, Kazan, Kiev,  L'vov, Gurzufe, and Tashkent changed with the
 height of  the sun, i. e. its maximum occurred in June and minimum in  the
 winter months, a condition which had not been noted in Vladivostok  for the
 above mentioned reasons.  Considerable U-V  radiation fluctuations  were
 noted here on different days of the same month.  Thus,  recorded data show
 that in 1961 daily U-V radiation fluctuated in the range of 7 - 12 mg/cm2 in
 March, 3 - 7. 5 in April, 3» 5  - 18. 5 in May,  6,5 - 17. 8 in June,  2,5- 13. 8
 in July, 3.0  -  16. 5 in August,  3.1- 15. 7 in September,  5.5  - 14 in October,
 and 2.6- 10. 7 mg/cm3 in December.
             20

             w

             IS

             f-1

             12

           I  fff
           3
           O
           x  8

             6

             4



     S  x
•20 5.
o
•IU m fjj
NC
i
X
Hn
. ll.lkfk.rh.rv, 	 	 ,

       /  ff
                        ff 7 W !ff
                         ounsh me
a
s si
n a ff 7
Ultraviolet
 vf m s
rooiation
                           xz
Hours of sunshine anci intensity of ultraviolet radiation ,per
                        VI ndoxostok
                                                            per oay  «n
            I - Hours of sunshine and conputcd ultrovielet raaiQt9on  intenaity aurinj
            clear atraos^here; ;; —Hours of sunshono ccrofuted on the basis o*  a*t«i of
            oan/ x«ars» ana actuol ultraviolet intensity  in I9ol — l%2.
                    Nuaoer of cloudy onys    fiuabor  of fojgy days
        A study of daily U-V radiation course had shown that the oxalic  acid
test begins to be  positive about 60 to 90 minutes  before sunrise, and con-
tinues for about 90 minutes after sunset.   Maximum U-V radiation was re-
corded during midday hours, amounting each midday hour to 10 - 13% of to-
tal daily radiation, and summarily to more than  50% of total daily radiation
Dispersed U-V radiation amounted to 30  -  50% of total daily radiation dur-
ing bright sunny days, total daily U-V radiation dropped considerably during
cloudy days,  while dispersed U-V radiation rose to 70 - 90%0  A  study  of
the specific intensity of short wave U-V radiation (290-350  m|i)led to the
conclusion that it diminished as  the height  of the  sun receded.  Thus, in July
the short wave  radiation constituted 33.8%, in August 28.5%,  in September
                                     - 245 -
-------
27„ 3%, and in October 25. 2% of total daily radiation; average absolute daily
short wave U-V radiation values during the same months were corresponding-
ly as follows:  3.4, 2.4, 2.9,  and 2.2 trig/cm"3,,  Results of U-V radiation
determinations made in different  Vladivostok sections  yielded information
on radiation loss caused by air suspended dust and smoke.  The  air was
cleanest in region close to the city limits,  where industrially operating
plants were few and,  consequently, sources  of smoke were few.   Compared
to such regions U-V radiation of the city center was on the average 23 - 25%
below,  the radiation loss  fluctuating between 8 - 70%; the data here present-
ed ran a close parallel to the number of smoke and dust sources existing in
the city's central sections, U-V radiation losses in the southend and eastend
of the  city were intensified by fogs most frequently  coming from the south-
east.

        Analyses of seasonal changes in U-V radiation and of such meteoro-
logical factors  as fogs and cloudiness, indicated that lowered U-V radiation
which prevailed in Vladivostok the greater part of the year created conditions
not conducive to the development  of resistance to rickets.  During the winter
months the U-V radiation intensity was low and the winter apparel allowed
only 5% of the  body to be exposed to solar radiation. During the summer
months more of the human body surface was exposed to solar radiation  and
hours of exposure were markedly  prolonged. However, during each month
the number of  gloomy, cloudy  and foggy days noticeably increased, consider--
ably lowering the intensity of the  U-V radiation.  Thus, the, so-called,
period of low U-V radiation level in Vladivostok prevailed through the longest
part of the year.  Therefore, it is only natural to assume that  under such
conditions some population groups, namely children, workers  employed in-
doors and in mines,  etc.  could easily develop symptoms of U-V  radiation
insufficiency.  Accordingly,  the entire problems of U-V radiation in Vladiv-
ostok must be  investigated systematically and thoroughly from the clinical
viewpoint and prophylactic measures  should  be developed and instituted for
the prevention of rickets and similar  clinical conditions among Vladivostok
inhabitants and other similar regions of the Southern Seashores.

                                Bibliography
           r a ;i a H H H H. . PHI-. H can., 1955, Ws 5, crp. 54. — T e H e p a ji o B A. A. TaM «e,
        1956, N<; 10, cip. 15.— A a HUH r H. M. B KH.: y.tibipacpHOjieTOBoe in.nyiiemie n nirne-
        Ha. M., 1950, crp. 141. —KafiKOB H.  M. Tnr. H can., 1959, Kb 3, crp. 76. — K y .n n t-
        Koea 3. H. B KH.: y^bTpac()noJieTOBoe  Ha.nyMeiwe  n rnrneiia. M., 1950, crp.  147.—
        C B a p n M c B c K n ft B. C.  TpyAhi Koncpepeimmi no 6no.nornMecKOMy  neiiCTutuo yjibrpa-
                Ha-ny'ienim.  /I., 1960, c6. 4, crp. 29. — Xo me pun a O. H. TaM we, crp. 2G.
                                   - 246 -
-------
                       The December Fog in England
                                pp. 71 - 72
                              V.  A. Ryazanov
       Corresponding Member of the USSR Academy of Medical Sciences
                                (Moscow)

       USSR newspapers reported that in December 1962 a dense fog spread
over the country which seriously affected that Country's life; but the report
contained no information regarding the degree of the fog toxicity.  The report
which appeared in the journal "Smokeless Air" No. 125, 1963 threw some
light on the subject.  The fog persisted through 3 - 7 of December 1962, vary-
ing in its intensity through the 5 days in different regions of Great Britain.
Similar to  the fog of 1952, the South-Eastern part of the island was affected
most seriously, especially London and the Thames valley.  The fog soon
turned into a smog,  similar  to the one which occurred in 4 - 9 of December
1952.  The 1962 fog lasted longer than the one of 1952, it also was denser and
more consistent.  The inversion height was  approximately the  same, ranging
between  300  - 400 feet,  or 9 - 12 meters. Tall buildings, such, for instance
as the  Royal Military Academy (College), appeared as though they were pierc-
ing through the fog  coat, but the air temperature was somewhat below the
temperature of 1952.

       The fog density was great enough to bring to a stop all interurban
transportation.  Transportation over the roads of England in general suffer-
ed 20, 000 automotive accidents in 5 days. More than 100 large seagoing ships
were anchored in the London harbor due  to inability to sail out into the open
sea. Air communications also came to  a complete stop.  Aviation  companies
lost 500,000 pounds sterling.

       Air analyses showed  that density of suspended soot in the air during
the 1962  fog amounted to only 60% of the air  suspended soot observed during
the 1952  fog.  This  was due to basic changes  which had taken place in the
interim in  the methods  of home and house heating in England, such as central
community heating  systems, use of smokeless fuel in the place of coal,  etc.
Despite that, maximal soot concentrations in the air during the fog days
reached  2.8  mg/m3 ,  which was 7 times in excess of soot concentration in
the air prevailing during winter days in  normal times.  The SO2 concentra-
tion in the  atmospheric air of  London during the 1962 fog exceeded the maxi-
mum concentration recorded during the  1952  fog.  Thus, during the 1952 Lon-
don fog it amounted to 3.8 mg/m  , while during the 1962 fog SO2  concentra-
tion in the  atmospheric air was 4.2 mg/m .   The Journal in which the report
appeared explained it by the  fact that the 1962 winter was considerably colder
and, therefore,  more fuel was burned.  It should be noted in this connection
that modernization  of combustion  chambers  does not lead to a drop in SO2
formation; on the contrary, more of the fuel  containing sulfur becomes oxi-
                                   - 247 -
-------
dized, so that less of the sulfur remains in the slag and more of it is con-
verted to SO2 thrown into the atmospheric air.

       Analysis of total inhabitants' mortality occurring during the fog pre-
vailing days  showed an increase of approximately 340 cases;  persons below
70 constituted  33.4%,  and persons  older than 70 years constituted 66.6% of
the dead.  The mortality curve crest was recorded on  the third day of the
prevailing fog, 5/XII/1962.    Statistical study showed this increase was due
primarily to increase in bronchitis  cases.  Rate  of general morbidity also
increased.  Thus,  records showed that  during the period of foggy days  mor-
bidity,  a.s  the cause of loss in working days,  rose to levels exceeding those
of preceding and following periods by 50%.     However,  morbidity rate
during the  1962 foggy days was below that  of the 1952 foggy incidence, despite
the fact that  intensity of atmospheric air pollution with  SO2 was greater in
the 1952  days.  The report in the English Journal ascribed that to the facts
that atmospheric air pollution with soot and dust  in the fog days  of 1962
was considerably below that  of 1952, and that conditions of personal hygiene
in 1962 wvre  on a higher level than in 1952, and also to  the propaganda con-
ducted by the Society for the Protection of Clean Air.

       These assumptions deserve  attention,  since experimental  studies,
especially those of M. Amdur in the USA indicated  that aerosol adsorbed
gases, specifically sulfur dioxide, manifested enhanced toxic activity,  in
comparison with free gases.  Accordingly, it  is  reasonable to assume  that
the lowered soot concentration in  the atmospheric air in 1962 lowered the
total toxicity of adsorbed SO3 in the air. However,  this is a mere assump-
tion,  since no data had been  collected on the amount of SO2 present in London
air during  the fog of 1962.  This is to be regreted for it might have proved of
considerable help in the search for  an explanation of this or other similar
phenomena.  K. A.  Bushtueva of the USSR demonstrated that the transition
of free SO2 to the  aerosol state depended upon meteorological conditions.
It can be reasonably supposed that under conditions of identical SO2 concen-
trations, the H2SO4 aerosol  concentration or dispersion in the air over London
in 1962 profoundly differed from the same in 1952, which may have been the
reason for the lowered fog toxicity.   Reports of medical authorities indicate
that the latest December fog had seriously affected  many industrial centers of
England.  Thus, an increased respiratory organ morbidity was reported in
Birmingham  during the period of the last fog.  The  latest fog was especially-
dense in Leeds, where  respiratory  organ  morbidity also rose, although not
as high as  in Birmingham.  In Glasgow  where  the fog lasted only one day
(5/XII),  increased pneumonia and bronchitis morbidity  was noted  among the
oldsters.  The toxic smog of England elicited  many comments in the press
and was  the subject of parliamentary discussion.  As for us, in the USSR,
the following is clear:  measures  taken  in England for the ten years between
1952 and 1962 proved to be far from adequate to bring to a  stop the periodic
occurrence of toxic fogs which carry off large numbers of human  lives.

                                    - 248 -
-------
                            NO.  11, NOVEMBER
        Maximal Permissible Concentration of Hexavalent Chromium
                            in Atmospheric Air
                                pp. 9-16

                             E. F. Cooperman
 (From the Sverdlovsk Institute of Labor Hygiene and Occupational Diseases)
        It has been established by many toxicologists in the USSR and abroad
 that hexavalent chromium compounds were the most toxic of chromium com-
 pounds.  The toxic properties of hexavalent chromium had been studied most
 frequently under experimental conditions of brief inhalation of air containing
 comparatively low concentrations of the compound;  some tests have  been made
 by the intragastric, intravenous administration and by skin application.  A
 review of the literature failed to disclose reports dealing with the effects  of
 chronic hexavalent chromium inhalation in low concentrations.   Little infor-
 mation was found in the literature regarding air pollution with hexavalent
 chromium compounds.  The present author knows of only one report present-
 ed by Bourne of the USA in 1950, which dealt with such ambient air pollution
 in'the vicinity of a chromium processing plant.

        The present author conducted his studies of  air pollution with hexaval-
 ent chromium in the proximity of two largest USSR  plants producing  chromium
 compounds.   A study of the technological processes and of the ventilation
 systems showed that the plants discharged into  the atmospheric  air rnono-
 chromates, bichromates, chromyl  chlorides, and the like, in the form of
 gases,  vapors, and aerosol condensates.  Much of such pollution also came
 from sources commonly designated as  "nonorganized".  The exhaust air of
 one of the plants was subjected to preliminary 70% scrubber purification.   It
 has been  estimated that between 700 and 800 kg of hexavalent chromium com-
• pounds had been discharged by the  plants into the atmospheric air at a height
 of 10-15 m.

        Chromium oxide was produced in the other plant by the sulfur-
 chromium method.  By such a method hexavalent chromium could be used
 only in solution, which reduces the  discharge  of the hexavalent  chromium
 into the air from  700-800 kg to 150-200 kg per day.   Air  samples were  collect-
 ed within a radius of 2 km from  the plants, usually  on the side  of the wind
 direction. The air was aspirated through membrane filter No.  2, or through
 textile  filter FBP-15 fastened  inside of a "dust cartridge".  A single sample
 required  the aspiration of 30 li of air at the rate of  1 li/min.  Hexavalent
 chromium in  the air was determined by the method  of Gurvits and Sergeeva,
                                    - 249 -
-------
modified by the present authors to make possible the collection of small air
samples and to increase the  sensitivity of the test to 0.0001 mg/li.

        Curves in Fig. 1 graphically represent results of hexavalent chromium
determinations in the atmospheric air surrounding the investigated plants.
Fig. 1.
  a

t* 35
                          MAC
                             Si
                                  0.8  I
                                  Km froro plant
                VIas in*I  single concentration of hexavalent chrewijm t.i the
                 air surrounding tie plant (jroducinj cnroaiun coa
                I — Pervoural criromiunt plant} 2 — Aittubirt cirotaiun
Procedures used in the determination of maximal permissible hexavalent
concentrations in the atmospheric air were those described and recommend-
ed by the Committee for the Sanitary Protection of Atmospheric Air.  Hexa-
valent chromium condensation aerosols were obtained by heating portions of
chromic anhydride in a tubular electric furnace,  schematically illustrated
in Fig. 2. The gas mixture containing a given aerosol concentration was i-un
into inhalation cylinders installed inside a special exposure chamber,. Deter-
minations were made of concentrations  producing irritation, and also concen-
trations representing the threshold of hexavalent chromium reflex effect on
the functional state of the cerebral cortex.   The concentration of chromium
threshold irritating properties was determined by the usual method described
by many investigators  testing ten practically normal volunteers.  Two hundred
and fifty determinations were made with 12 different chromium aerosol con-
centrations in the range of 1.5 and 40 Ji/m3.  Results indicated that inhala-
tion of air containing 10-24 p./m3 of chromium, even for a brief period of
time,  elicited the sensation of sharp irritation in the nostrils; inhalation of
lower  chromium concentrations elicited slight irritation of the upper respira-
tory tract.  Lowest perceptible  chromium concentrations for the entire group
of test volunteers ranged between 4-2. 5 mg/m° .   For most sensitive of the
volunteers 2.5 M/m3 of chromium represented the  concentration of threshold
perception;  1.5 H/m3 was below the perception threshold  of  the entire group
of test volunteers.
                                    -  250 -
-------
Fig.  2.
                      Plan of the experimental apparatus
           I - Air blower; 2 - aolicadelj 3 - activated charcoal} M  - electronic po-
           tentiometer} 5 - electric ovenj 6 - a nuarti boat; 7 - f lo.».neters  S _ ratxe
           y - odo-- testing cylinder} 10 -screen} II -exposure chamber
        Tests  for chromium concentration of threshold reflex effect on sensi
tivity to light  were conducted by the  method of dark adoptation using adapta-
meter ADM.   Results are  shown in the Table below:
              Average values of eye sensitivity to lijjht in the course o* <•>-
              haling different chromium vopor concentrations, ii —on the 15th
              minute
Tester's initials

*
(_ 	

2vth rain.
Clean
air
150
'118
129
Chromium in
p.i/™3
2,5
198
266
162
1.5
149
118
124
2i>th «>r».
Clean
air
205
. 149
ItO
Cnroaijro tit
M-9/B^
2.5
184
238
128
1.5
205
129
153
Tests were conducted with 3 volunteers whose threshold of chromium irri-
tation effect had been previously determined.  Two  courses  of dark adapta-
tion were tested first with clean air for control purposes  and then with air
containing 2. 5 and 1. 5 jLt/m3 of chromium aerosol.  The fresh air and the
aerosol air mixtures  were tested  at 15 minute intervals for 4, 5 minutes,
making triplicate tests for each concentration.  A total of 60 dark adapta-
tion tests have thus been made.
        Inhalation of 2. 5 H/m"*  of hexavalent chromium for a short time <:
siderably  enhanced eye sensitivity to light in all test persons on the 20th
                                      - 251  -
-------
minute.   Adaptation to the dark failed to return to normal even on the forti-
eth minute.  Statistical processing of experimental data showed that the adap-
tometric changes  elicited by the inhalation of 2. 5 Ji/ma of chromium were
significant and reliable.  Chromium aerosol concentration on 1.5 M/m3  had
no effect on the process of eye adaptation to the dark or on the eye sensitiv-
ity to light.  This is  shown by curves presented in Fig.  3.

Fig. 3.
                 IS   10  IS
                  Minutes
   Effect of different chroraijn concentrations on
      eye scnsiii'iiy to lijht.of tester L
   I - Cl««n air, 2 - 2.i JJ.9/"-* of chroniunj 3 -
                                         Thus,  experimental results indi-
                                      cated that the threshold reflex effect
                                      of chromium on the functional state of
                                      the cerebral cortex, as determined by
                                      the adaptometric method, coincided
                                      with  the concentration representing
                                      the threshold of its irritating effect,
                                      which is characteristic of substances
                                      affecting the trigeminal perception
                                      apparatus.  In summary it can be
                                      stated that 1.5 M-/m3 (0,0015 mg/m3)
                                      of hexavalent chromium was a sub-
                                      threshold  concentration as established
                                      by each of the two methods.  This con-
                                      centration is recommended as the
                                      maximal single permissible concentra-
                                      tion of hexavalent chromium in atmos-
                                      pheric air.  It was adopted by the GSI
                                      of the USSR November 14, 1961 in code
                                      No.  221-61.
                                         Chronic experiments for the
                                      determination of prolonged inhalation
                                      of hexavalent chromium in low con-
centrations were conducted by exposing laboratory animals to continuous
20 hour inhalation daily for a period of 90 days.  Experiments were conduct-
ed with 45 white male rats weighing 90-120 g which were divided into 3  groups
of 15 rats each. Rats of group 1 inhaled air containing 30 H/m3 of the hexa-
valent chromium,  which is only  33-35% of the maximal permissible concen-
tration of hexavalent chromium in working premises;  rats of group 2 in-
haled air containing 1. 5 /1/m3 of hexavalent chromium, which is on the  same
level as  the recommended maximal single concentration limit; animals of
group 3 served as controls.  Air in the exposure chambers was tested four
times  daily.  The  average hexavalent chromium concentration in the chamber
occupied by rats of group 1 averaged 29± 0.3 (J./m3 .  In chamber No. 2  the
average  hexavalent chromium concentration was 1. 31±,  0.026 (i/m15,.  The
hexavalent chromium aerosol concentration in the  air mixture consisted of
particles 90% of which measured 1 \i in diameter.   All through the exposure
                                    - 252  -
-------
period,  records were kept of the animals weight, changes in muscle antagon-
ists motor chronaxy, activity of blood enzymes,  such as carbonic anhydrase,
and of the blood morphology picture.  No changes were noted in the  external
appearance of the animals,  except for a  slight loss of activity in the animals
of group 1.

        Changes in the chronaxy and rheobase of  the extensor and flexor
muscles of the rats right hind leg were measured by the GIF chronaxy-
metric condenser daily under similar conditions. Rats  of group 1 which in-
haled air containing 30 Jl/m3 of the chromium aerosol showed delayed
chronaxy of the extensor and flexor muscles two  weeks after exposure  to
chronic  chromium inhalation.  At the  end of the second recovery week,
the chronaxy  returned to its original level.  The  effect of chronic hexavalent
chromium inhalation by rats presented a more clearly expressed picture
when the animals had been observed individually, and not as a group.   Under
such conditions it was noticed that some  animals manifested paradoxical and
reverse chronaxy ratios. No changes in the chronaxy ratios  were noted in
any of the rats belonging to  group two, throughout the course of continuous
hexavalent chromium inhalation.  This conclusion was verified by statisti-
cal processing of the experimental data of this group. See Fig.  4.

       It has  been demonstrated repeatedly that  many toxic substances
strongly inhibited  blood carbonic anhydrase.  The present author used the
colorimetric  method for the determination of carbonic anhydrase in  whole
blood.  The method was originally developed by N. E. Ponomarenko and
is based on the determination of CO2 hydration rate in the presence  of bi-
carbonate and sodium carbonate.  Carbonic; anhydrase activity was deter-
mined in 3 rats of each group, and the results graphically presented in Fig. 5.
Fig. 4.
                  aan-,
                  0.013'-
                  C.OH'-
                  O.OOS-
                  0.00?-
                ^ 0005-
                i.
    nat 4
Lxposure
                      T~t  3  i  5678  S  toll K 13 14 15 IS i? !S !i W

                  R015-,                        Rat  b
                  0.013-
                  O.Oli-
                      /  I  3  4  S 6 ? 8  9  1(1 n K 13 H 15 K I? IS IS ^0
                              Observation ti.»e in »ee«s

                Muscle antagonists  notor chron»«y  in r«ts Noo. 4 and  S of
                Uroup I (30  IJa/"-*) Defers exposure, gunny exposure ana
                during the roeovery period. I  - Extensorj  'i -fl««or.
                                   - 253 -
-------
 Fig. 5.
       a   >i3   t   s   6.
            Observation tino in ten-oay

  Whole blood car ban i canny dr.se activity of rat* before anu
     during exposure and during the recovery period
  I -futa o« fcrout, I, 3J   IV«3, t -r«t» of Group i!, 2.5
              M-9/»3> 3 - control rat*

manifested by rats of the control group.
                                               Prior to hexavalent chromium
                                               inhalation,  the c arbonic anhv-
                                               drase activity average of the
                                               9 rats was  8-9 sec.  As  the
                                               experimental exposure to the
                                               inhalation of hexavalent chro-
                                               mium extended, the time of car-
                                               bonic anhydrase activity grad-
                                               ually became longer and at the
                                               mid-point of the experiment,
                                               the time of  COg hydration ex-
                                               tended to 15-20  sec.  in rats of
                                               group i.  The carbonic anhy-
                                               drase activity time of rats be-
                                               longing to group 2 (1.5 mg3)
                                               were practically identical with
                                               the carbonic  anhydrase time
       No changes were noted in the number of erythrocytes, leucocytes or
in the hemoglobin concentration; however, the  blood leucocyte formula in
rats belonging to group 1,  which inhaled 30 pl/m'3 of the hexavalent chromium,
showed an increase in the number of stabnuclear neutrophiles up to 6-8%,
paralleled by the appearance of young forms.   There also appeared a small
number of neutrophilic myelocytes.  These changes pointed to a decided  shift
to the left of the leucocytes reflecting an irritation in the hemopoetic organs
produced by the hexavalent chromium.  No blood changes were noted in  the
rats of group 2 which inhaled air containing 1.5 jLt/m3 of hexavalent chromium.
At the end of the 3 months continuous exposure to the inhalation of air con-
taining hexavalent chromium, the  rats were autopsied and their organs ex-
amined histomorphologically by the usual staining procedures.  Tissues of
                                     /   *5
rats which inhaled air containing 30 /Ll/m of hexavalent chromium, showed
many changes, particularly in tissue of the respiratory organs.  Tissue of
the trachea showed lymphoid infiltration into the cells of the mucosa parallel-
ed by intensive hyperemia.  The sinuses were  dilated,and hemorrhages ap-
peared in the paratracheal lymphatic nodes.  There was  also thickening  of
interalveolar septa and signs of emphysematous processes and of perivascu-
lar and peribronchial diffuse sclerosis.  There were some clearcut changes
in the parenchymal  organs.

       The absence of complete changes in the nasal septa in many of
the animals  is of particular interest in this case.   This  was also noted by
V.  P. Lukanin in his experimental rabbits, which were exposed to  the in-
halation of sodium bichromate.  In the experiments conducted by the present
                                     - 254 -
-------
 author, absence of such-changes in .the nasal septa of the experimental rats
 may have been due to the fact( that they were exposed to the inhalation of
 lower chromium concentrations,  and also to the fact that the aerosol was of
 a high dispersion  and more easily, penetrated into the higher  sections, of the
 respiratory apparatus.  No noteworthy.histppathelogical;'changes"'were ob-
- served in tissues  of rats^belonging to. group 2. which inhaled 1: 5 \i/rr? of hexa-
 valent chromium.  In fact,, their tissue pictures were indistinguishable from
 tissue pictures of the experimental animals.V.A-study of chromium accumula-
 tion and distribution  in organs of the  experimental animals; showed  that' in
 rats belonging to group 1,  which inhaled"air\ containing SOr/ii/m? of .chromium,
 the chromium-ion content in the lungs determined by''the- spectral method was
 1%, computed as ash, which i's 30 times'in.excess of chrqrniurrv similarly de-
 termined in the  lungs of the control rats.  The same trend,  though  at.lower
 levels, appeared in the kidneys, the spleen,  the liver, and. ih^ the cerebrum.

        Based on the  data yielded by the chronic experiments, it can be recom-
 mended that the maximal permissible average  daily conpentration of  hexa-
 valent chromium in the atmospheric air should be the same  as the maximal
 permissible single concentration previously recommended,  which is  1.5 jLi/m° ,
'. This concentration-of hexavalent chromium  in the air elicited no functional
 changes in the organism, of man or  laboratory animals.  The experimental
 data which point to the harmful effect of. 30 jU/m3 of hexavalent chromium in
 the air, strongly point to the need of  re studying the concentration of this
 toxic component in the air of working premises with a view to lowering the
'present maximal permissible concentration of  100 jU/m".

        A comparative analysis of hexavalent chromium concentrations found
 in the atmospheric air surrounding the  investigated plants'with the  proposed
 maximal concentration limit indicated that at a distance of 0. 5 km from  plant
 No.  1,  hexavalent chromium concentration in the air was 10-30 times as high
 as its maximal permissible limit.  At  1.5 km  its concentration in the atmos-
 pheric air  was still 3'times as high as the maximal permissible concentration
 limit.  At 2 km, the air contained a lower hexavalent chromium concentration
 than the one now officially enforced, as shown  by results of all analyzed air
 samples.   In the case of air, surrounding plant  No. 2 the hexavalent chromium
 pollution was  even of greater intensity. Hygienic evaluation  of conditions
 surrounding the two chromium processing plants as sources  of air  pollution
 suggest.that a sanitary clearance zone 1-2 km wide should be established
 around each plant.

                                Conclusions

        1.   A  concentration of 2. 5 jU/m  of hexavalent chromium in the air
 represented its  threshold of irritation action;  the same 2. 5 H/m3 concen-
 tration represented the threshold of reflex chromium ae-rosol effect on the
 functional state  of the cerebral cortex,  as determined by the  adaptometric
 method for persons'of highest perception  sensitivity.    "                  '
      ...                        - 255- -
-------
        2.  L 5 H/m  of chromium, as determined by the above mentioned
procedure,  produced no unfavorable  effects on the organism,  and should be
regarded as the nqnactive or subthreshold concentration.
                                           /  «a
        3.  Hexavalent chromium in 30 Ji/m  concentration chronically inhaled
for a period of 90 days, as described in the text, elicited  in the experimental
animals, changes in their motor chronaxies,  in  the  carbonic anhydrase activ-
ity,  and in the morphologic component of the blood.  Some definite histologic
changes were noted in the tissue of internal organs.

        4.  Under similar chronic conditions, inhalation of air containing
1.5 Jl/m3 of the hexavalent chromium produced no  statistically significant
changes.

                                        /  *^
        5.  The concentration of 1.5 /1/m  computed  as CrO3 can be adopted
as the maximal single, and also as the 24 hour,  hexavalent chromium con-
centration in atmospheric air.

        6.  The following sanitary clearance zones are recommended  for
chromium processing plants:  for plants  which discharged 200 kg of hexa-
valent chromium into the air,  the sanitary clearance zone should be not less
than 1000 m, and for  plants which discharged  1000  kg of hexavalent chromium
into the air daily,  the sanitary clearance  zone should be not less than 2000 m
wide.

        7.  The existing maximal permissible hexavalent chromium concen-
tration in the  air of working premises, now 0.1 mg/rrT ,  is regarded,  in the
light of the present investigation,  as  too high  and should be revised to a lower
level.

                                 Bibliography
            Ee.nneBa /I. H. B KH.: Bonpocu rnriieHU, npon,Tro;iorHH H npoMbitu^eimofl TOK-
         CHKO.FIOI-HH. CeepfljioBCK, 1959, T. 5, CTp. 302.— F p y uj K o fl. M Bonp. OHKCWI., 1961, M> I,
         crp. 100.— E p ui o B B. n. Pur. ipyaa. 1962, K? 2, crp. 3.— Jl y K a H H H B. Fl. Tpya H
         aaopoBbe  pa6omix xpoMmiKOBoro sasofla. CBep;uioBCK, 1930.— O a fi a u 111 E. B. B  KM.:
         CaiiHiapHaH  oxpana BonoeMoa  or sarpnaHeitHn npoMbiiu^eHHUMH CTOMHWMH  BoaaMH. M.,
         1954, B. 2, cip. 70.—OH a we. Fur. H can., 1960, ^9 7, crp.  10.—Bourne H. G.,
         Industr. Med. Surg.,  1950. v. 19. p. 568.—K i b a S., Fukuoka  acta med.,  1959. v. 50,
         p. 514.— Lehmann K.. Die Bedeulting der chromate (iir die  Gesundheit  der  Arbeiter.
         Berlin, 1914.— L e r 7. a P.. Folia Medica (Napoli),  1957, v. 40, p.  100.—Mane uso T. F.,
         Industr. Med. Surg., 1951, v. 20, p. 393.
                                       - 256 -
-------
       Orientation Data for the Determination of Maximal Permissible
             DDT Concentration in the Air of Working Premises
                                pp. 36 - 39

                   E. N.  Burkatskaya and G. A.  Voitenko
    (From the Kiev Institute of Labor Hygiene and Occupational Diseases)
       DDT,  which is 4, 4-dichlorodiphenyltrichlorethane, also known as
pentachlorine, is  a pesticide widely used in agriculture.   It is also used as
a pesticide in homes. Its use is progressively increasing;  yet the toxicity
of DDT to the organism upon entering via the respiratory route has not been
adequately investigated.  Literature reports a number of DDT poisoning cases
occurring in the production of the pesticide which contradict the heretofore"
existing notion of  this pesticide's low toxicity.  During its application, DDT
can be inhaled by  the worker or by  persons close by causing intoxication of
different intensities.  Some  authors also believe that the effect of DDT is
cumulative.  Other authors expressed the opinion that persons  working with
DDT in many instances become sensitized to the effect of the preparation.
There have also been noted effects  of species and of individual  sensitivity
to the effects  of DDT.  Results of numerous investigations established that
man was more sensitive to the effects of DDT than laboratory animals.  Thus,
according to tests,  the lethal dose of DDT to animals was in hundreds of mg
per kg, whereas,  in man, the lethal dose measured in tenths of mg per kg.

       DDT inhalation experiments were  conducted with cats which, accord-
ing to S. G. Serebryabnaya and others, are the most sensitive  of all labora-
tory animals to the effects of this preparation.  Twenty cats were used in
two series of experiments.  The first series was used to study DDT toxicity
under acute experimental conditions, and  consisted of 13  cats exposed to DDT
inhalation for 6 hours.  Seven cats  of the  second series were used in deter-
mining the toxic DDT effect  under conditions of chronic experiments, in
which the cats were exposed to the  inhalation of  the DDT 6 hours daily for
75-90 days.  Experimental animals were  exposed to the inhalation of DDT  in
2 exposure chambers. ,In one, the  preparation was introduced  into the air
in the form of finely particulate talc containing 10?o of the  DDT; in the other
chamber, the DDT was introduced into the air in the form of a  1-5% highly
pulverized aqueous  DDT emulsion.   At the conclusion of. the acute and r.h-onic
experiments,  the  animals  were kept under observation for 2 weeks,  after
which they were sacrificed and their organs studied histopathologically,   Re-
sults  showed that  0.0007 mg/li of DDT elicited no visible intoxication in the
acute experiments.  At DDT concentrations of 0.005 mg/li in dust form, the
animals began to lose activity, became indifferent  to the  surroundings, their
hemoglobin concentration fell  and they developed a slight leucocytosis.  Cats
exposed to the effect of 0. 02 mg/li  DDT  suspended in the air in the emulsion
form  for 6 hours  developed symptoms of toxicity such as salivation,  slug-
gishness, muscular convulsions, vomiting, nausea, ataxia,  tremor, frequent
defecation, and urination,  Animals ate only, part of  their daily rations. The
                                    - - 257 -
-------
blood picture showed leucocytosis,  rapid red blood cell sedimentation,  and
hyperglycemia.  The urine contained albu?Tdn,  and urobilin.  Inhalation of
air containing 0.08 mg/'ii of DDT dust clinically showed the sarr\e signs of
intoxication as in the case of inhalation of lower  DDT concentrations in the
air, but the severity of the symptoms was considerably greater.  Experi-
mental animals subjected to the acute inhalation of DDT in  0.005-0.08 mg/li
concentration, in addition to the clinical  intoxication manifestations, showed
morphorlogical changes in the cerebrum and in the internal organs.  There
appeared slight blood circulation disturbances  and slight dystrophic changes
in the brain, the liver, the kidneys  and in the heart muscles.  H^inodynamic
changes developed in the lungs.  All above symptoms were  paralleled by
swelling of the argyrophilic fibers.    The enumerated  symptoms increased
in gravity with increase in the DDT concentration in the air.  Chronic in-
halation o:f 0.008 mg/li of DDT by the 3 experimental cats for "5 months,
developed well defined pictures of intoxication  at the  end of the second ex-
perimental week. Two of the cats showed blood in the fecal matter and in
the vomitus beginning with the fourth week.  All cats showed the presence of
albumin and urobilin in their urine at the  end of 2 weeks.  The albumin con-
centration rose progressively  as  the experimental period progressed.   The
blood picture  showed reduced number of erythrocytes,  lowered hemoglobin
concentration,  rapid red blood cell  sedimentation and hypoglycemia.  The
body temperature of 2 cats considerably dropped at the midpoint of the ex-
perimental period, and one cat developed spasticity of some muscles,  gen-
eral tremor and ataxia.

        Following the discontinuation of inhalation the toxic  manifestations
began to abate,  but the flabbiness and general indifference, as well as loss
of appetite persisted.  The presence of albumin and urobilin in the urine,
the reduced number of erythrocytes and increased rate of red blood cell
sedimentation persisted.  Macroscopically, autopsies showed discolored
swelling venous plethora of the internal organs, and uneven pulmonary blood
distribution,  localized emphysema and occasionally small hemorrhagic foci.
Four cats were exposed to the inhalation of 0.015  mg/li of DDT dust in the  ~
air for  75 days.  The cats developed signs of grave intoxication, the clini-
cal picture of which in its character and gravity was  similar to the one  de-
veloped by cats which inhaled DDT emulsion in 0.008 mg/li concentration.
Results of above.investigations- led the present authors to conclude that  in-
halation of DDT p»ra4uce£ it* il^-eX|pe1rita£6taV a,nlmals general intoxication.
Thus,  results-;of--th'e'al^pii^%^4-riblft!d^^'^iM.ments verified the observations
made by V. A. Kaganovich and others  (1956) under actual working  condi-
tions in plants producing DDT  regarding the effect of DDT inhaled in 0.001
mg/li concentration.
                                                                        i
        The present authors also investigated the sanitary-hygienic working
conditions prevailing in  the synthesis of DDT and in making,-'the insecticide
mixtures of this preparation.  Results showed  that: the air of premises where
DDT has been synthesized and mixed contained DDT vapor in concentrations
                                    -  258 -             •      •
-------
ranging between 0.0017-0.008.'") with an average of 0.003 mg/li, and that the
Suspended DDT dust in the form of a 10% mixture ranged between 13 and 272
    /  2                          / *^
mg/m ,  with an average of 23 mg/m  which was the equivalent of 0.0023
mg/li of the  DDT proper. Workers exposed to the  inhalation of air contain-
ing DDT in the form of vapor or dust in the  above indicated concentrations
manifested clearly discernable disturbances of their general health; the
central nervous system developed an asthenic syndrome and vegetative
dystonia.  The nervous system disturbance  was  of a diffuse character, but
pathological  processes were localized predominately in the  region of the
cerebellum and its sinuses,  usually paralleled by arterial hypotonia.  The
above picture was frequently associated with disturbance in the peripheral
nervous  system as polyneuritis, which agreed with observations recorded in
the literature.

       Changes in the internal organs appeared  frequently as myocardial
distrophy, physical liver changes, chronic gastritis and,  less frequently,
as changes in the respiratory organs.  Examined workers also showed the
presence of hypochromic anemia, leucopenia, eosino-and neutropenia, a
moderate lymphocytosis, throbocytopenia, and changes in carbohydrate
metabolism.   It was noted,  unmistakably, that the above conditions increased
in gravity with length of employment.    This is  particularly true of myo-
cardial dystrophic liver changes and of toxic polyneuritis.

       On the basis of above presented experimental data and  observations
under conditions of actual production and processing, and taking into con-
sideration data found in the literature regarding the toxic effects of DDT, the
present authors arrived at the following conclusions and recommendations
regarding the maximal permissible DDT concentration in the  air of working
premises; the threshold DDT concentration in inhaled air was 0.05 mg/li
and its toxic  concentration was  0.02 mg/li.   The toxic zone of perorally ad-
ministered DDT was a narrow one; the lethal 200 mg/kg dose exceeded the
100 mg/kg minimal toxic dose only by 100%.   DDT  Is a strongly cumulative
poison.  The ratio between the total amount  of cumulative DDT administered
daily and which resulted in the death of the animal and its lethal  dose, as
determined by acute experiments, was 0.75 and pointed to a super accumula-
tion of the DDT.  Results of chronic inhalation tests conducted by the present
investigators verified the above statement,  Intensity of DDT  toxicity was the
same whether administered as dust or emulsion.  In other words, it varied
only with its  concentration in the air.  Under industrial production conditions
the inhalation of air containing an average of 0.003 mg/li of DDT produced
frequent  disturbance of the central and peripheral nervous system, of the   j
cardio-vascu.lar system, of the gastrointestinal  tract,  of the liver and kidney
functions, and of the blood morphology and enzymic activity.   Based on the
results of the present investigation, the authors  recommended that 0.0001
mg/li or  0.1  mg/m3 of DDT  in the air of working premises  should be regard-
ed as its  maximal permissible concentration. This recommendation was
officially inacted by the  Chief State Sanitary USSR Inspection Office, and was
incorporated into code No. 388-61 December 30, 1961.
                                   - 259 -
-------
                                 Conclusions

        1" DDT inhalation proved toxic to warm blooded animals.  The minim
toxic DDT concentration in the air under conditions of  acute experiments was
0.005 mg/li for cats and toxic effects were produced by 0.02 mg/li.  In
chronic experiments 0.008 mg/li of DDT in the air elicited sharp symptoms
of intoxication and 0.15 mg/li proved to  be the LDBO for cats.

        2.  Inhalation of air containing an average of 0.003 mg/li of DDT was
harmful to workers' health,  the gravity  of the poisonous  effect increased
with the DDD employment record.

        3.  It is recommended that the maximal permissible DDT concentra-
tion in the air of working premises be set at  O.OOOi mg/li or 0.1

                                 Bibliography
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        crp.  M.--13 y p K a u K a H II  H., B o fi T e H K o F.  A.,  K P a c tno K I:. II. Fur .11 can.,
        1961, J^B 0, crp. 24.—K a H n u B H H B.  A., H c q a e a'a T. A., PVCCKHX  A  A. B KM.:
        MaTtpna.'iM  no aonpocaM ninmiiM Tpy.ua M  K.;IMIIHKH iipcx^Oo.nerniCH.  rupi,Kiu'i, I'Jfm.
        crp  f.2.-—FI e T RO B a T. P.  Fwr. n can., 1(J55, Nb 8, cip. 51.— C c: p e fi p n M a .M r  r
        4>apMaK.o.n. it TOKCIIKO^., 1950, .Jvf? 3, c?p. 38.— O p e ft A M a n  C. ,1., Ij i; H .1 o p
        Field F. G. S.,' Nature, 1946, v. 157, p.'658.—T Ii o in a s O., L a f o n I a i n e'A., Para-
        silica, 1955, v.- 11, p.-126.
                     The Toxicology of Metallic Antimony
                                  pp. 39 - 44

                               G. G. Scherbakov
   (From the Department of Sanitary Hygiene, the Kirgiz Medical Institute)
        Antimony is used in the manufacture of high quality steel to which it
imparts the property of antifriction important in the production of ball bea.r-
ing.   The property  of antimony to expand with the lowering of temperature,
accompanied by its hardness,  makes it  of considerable value in typography.
Antimony is also used in the preparation of lead antimonate, of babbit, of
battery plates, in the rubber industry,  in the preparation of enamel paints,
of fire  resistant fabrics,  and in many other industrial processes.   As a re-
sult of the wide antimony use in the national production and processing indus-
try many workers are exposed to the inhalation of antimony vapor and dust,
                                     - 260 -
-------
 Fairhall and Hyslop of:,'the"USA,showed in 1947 'that the number of workers  con-
 nected with i'he production.and processing of antimony and its compounds was
 nearly 100,000 prior to the Second World/yVar.;  Despite  that,' the toxic anti-
 mony proper-tie's have not been adeq>iat;elyihyestig.ated0i J,M.o;st reports-.dealing
 with,the  subject have been-;devoted'.tovthel>study\of'e'asily  soluble.} organic an.ti-
 niony compounds ,»used :p'ri"marily iri, the medical ahd veie rina''ry practice s.
 Only, few studies haye been devoted "to the deteTminatipn  of'.biological effects
 of inorganic -antimony compounds, arid only; 1 report was'.fou'rid, in'the; litera-
 ture which,.dealt-with the toxic effe;ct'.of ahtirripny. ;This  was -a .Report'by
 Bradley  and, Frederick Which'appeared .in 1941 in the foreign literature.
 No report of this type ^was tf qundr.iri the USSR literature.. ;--. ,--'  /. -

        Inyestigpto-rs who studied the  toxicity of antimony compounds always
 inserted.notes 'pertaining to the roleV'plaiyed by arsenic,, lead, bismuth, iron,
 and other constant antirkony admixtures,  always emphasizing the importance
, of arsenic  and leadj other investigators are inclined to ascribe no particular
 significance to such antimony  admixtures.  However, theT opinions of either
 group of investigators are not based on any experimental evidence,  and,  as
 such,, were mere  suppositions.  The  present author undertook to determine
 the  toxic properties .of, metallic antimony and the effect which the above
 enumerated.admixture elements had on the basic toxicologic properties of
 metallic  antimony. "Tlie -present.study was conducted with  metallic  antimony
'of 3-different trademarks,  - Sbooo » Sbo and Sb3 , which differed only in the
 degree o'f their purity. • Metallic antimony of the highest  purity  - Sbooo -
 contains  admixtures in thousandths of a per cent and includes lead and ar-
 senic,  the .total" amount of which is equal to 0.0008%; this  can be completely
• disregarded, since the amount of antimony present in the human body varies
 between  50 arid 200 mg/kg of body weight.  According to  N. V. Lazarev (1954)
 the  toxic doses, of the  admixture elements  are in the tenths  of mg for arsenic '
 and tens  of mg for lead..  Antimony of trademark Sbo .contains approximately
 Q. 5% of admixtures including 0.4% of lead and 0. 016% of  arsenic. In the
 case of Sb3 the admixtures amount to 2. 3%, half of which is lead and only
 one tenth is arsenic.  Tests were  made for the determination of metallic Sb0
 solubility in different  media.  Results are presented in Table 1 as averages
,,of ten successive  tests in buffer solutions, and of 50 successive  tests in each
 of the other media.-            i

        Data in Table 1 show that antimony is readily soluble particularly
 in body fluids of neutral "arid alkaline  reactions despite the  fact that  up to
 the  present investigation, antimony was regarded as an insoluble metal.
 Toxic-antimony  properties were investigated using white rats weighing be-
 tween 230 and'320 g.1 .Experimental groups of animals consisted of  20 rats
 of which'10 were male and 10 female.   The toxic  properties of the above speci-
 fied metallic antimony products were tested in .the following doses:
 50,  100,  150, and  200  mg/kg.   The mate rial was, administered intraperitoneal-
 ly as aline antimony powder suspended in apricot oil.  Control  animals simi-
 lar!^ raceived equivalent volumes of  sterile apricot oil.  The antimony powder
        '    ,                       -  261 -
-------
 was of the following fractional'clispeTsion:  up to 1 /i  - 51%, 1-2 jLt - 37%, above
 2   -  2%. Diameters  of the largest.particles measured 8 /Lt.   The antimony
 powder of the above indicated dispersion was obtained by grinding the metal
 in an  agate mortar followed by thorough washing.  Spectrographic studies of
 the  3  antimony types before and after washing showed that their physico-
 chemical properties were  not affected by the washing step.   Results of
 the  experiments had shown that administration of 50  mg/kg of the dispersed
 antimony by the route  de-scribed killed none of the experimental animals by
 any of the 3 trademarked antimony metals;  on the other hand, 200 mg/kg was
 absolutely lethal in the case of any of the trademarked antimony metals.   Re-
 sults  also showed that dose for dose experimental rats which had been ad-
 ministered the purest  (S.booo) antimony-died quicker  than-experimental ani-
 mals  receiving similar 'doses of other antimony types.  Administration of
 150  mg/kg also showed that Sbooo was.the most toxic judged by the greater
 number of animals killed within a shorter period  of time.  Results thus in-
 dicated that the toxicity of Sbooo was.greater than.the toxicity of Sb3 which
 had the greatest amount of admixtures.

 Table 1.
                Solubility of metallic anttMon/ it tyi at 37° v«v*r«3«»)
Tine in
wt.vjtes
10
30
60
360
-1440
Type of mad i u<*
buffered solvents - mediuB pH
M
3,10
3,98
4,28
4.52
4,52
2.0
3,36
3,94
4;30
4,40
4,80
5.0
4.44
5,58
5^2"
?•, 86
7,80
7.0
5,38
7.34
8,54
10,80
9,66
7,2
5,70
0,54
7,85
8, CO
6,08
1.2
6.04
6,74
8,04
8,87
6.26
• k
*s
'a!
5,02
6.30
8,04
7.06
5,50
"5 c
|3
u.
4, CO
5.95
6.77
8,48
7,49
"2 B
Is
ss
5,07
6,83
9,38
18. C8
23,20
Gistric.
Juice
3,91
5.08
5.92
7,78
8,04
Urtne
2,63
4,84
6,58
11, G7
—
        Data obtained in experiments for the determination of L-Dro  were pr m^/H/,  :'',.-•
Sl\3 - 110 ti\g kg, and for.Sb3 - 130 mg/kg.  "Bradley and FrrMe rici- ••i.nrrii :.,-.-
to red powdered metallic antimony  to experimental animals  and fo'irri IOC)
mg/kg as the LDso dose. It was not possible to establish clearcut toxicity
differentials between the '3 types of antimony metal on the basis of clinical
observations.  Experimental animals became somewhat excited between the
6 and 8 hours following the .antimony powder administration.  They lost their
avidity for food and drank much water; simultaneously, they developed  a
state  of anuria which led to body  swelling noted particularly over the head so
                                    - 262 -
-------
 that their eyes.became almost completely closed.  Six to 8 hours'later,  there
 appeared a sta'-.e of depression and a simultaneous lack of mobility and reac-
 tivity to external stimuli, superimposed later,  by disturbed motor coordina-
 tion, as shown by lateral body Iocomoti9n.  Respiration became labored and
 less frequent, and the stool of many.'animals became liquid.  Death ensued
 as a result of respiratory arrest with the experimental animals"'in  a convul-
 sive state.  It was noted however,, that .animals receiving Sb3 were not as
 profoundly affected by the metal administration as we're  experimental ani-
 mals wliich had been administered Sbooo or Sbo ^  Autopsy observation showed
 marked vascular hyperemia especially in the skin mesentery;and in. the in-
 ternal organs.   Vascular blood stasis varied',with the-antimony'dose.  . The
 liver was enlarged,- swollen, soft and flabby.  Macroscopic .-dystrophic changes
 had also been noted in the kidneys,  lungs,  mesentery and especially in the
 small intestine.    .                     ,                  :         .
                       \
        Surviving rats were kept under observation for an additional 30 days. .
 At .the end of  this period, the rats were decapitated.  Ldve.r,s, kidneys,' spleens.
 hearts, lungs, and brains of the dead and decapitated animals were weighed,
 after which sections were   made for histologic study.  It was  noted that the
 surviving animals  lost much of their fur during the 30 days observation.
'A hemorrhagic rash spread over the skin which became wrinkled and covered
 with scar tissue.  Changes in body weight of the control animals throughout
 the observation period were within the limits of normal fluctuation. Curves
 plotted  on the basis of weight  changes in experimental rats which  received
 antimony of different purity manifested similar characteristics.  In every  case
 there was an  initial loss  in body weight followed by a progressive rise in
 body weight.  However,  rats which received dust  of antimony Sb3 gained
 weight after their original loss of weight at a very low rate, 'reaching the
 initial weight  22  days after the administration of 100  mg/kg, and 24 days aftec
 the administration of 150 mg/kg.  Generally, however,  the data indicated that
 antimony contributed to the increase in the animals' body weight throughout
 the observation period.   This agrees with data found in literature and explains
 the long standing practice of hog  and geese breeders who added antimony to
 the rations of their animals and birds.
       It has been known for some time that, internal animal organs,  par-
ticularly the parenchyma,    were highly sensitive to the effects of many
poisons.  Such effects appeared as changes in the weight of the different
organs in a specific manner, and, therefore, in specific ratios.  Most pro-
nounced changes, which are also most  indicative, occurred in the  weights of
the liver and kidneys,as shown  by graphs in the Fig.   In such experiments
the weight of control animals is regarded as 100%.  Data obtained from weigh-
ing organs of the experimental  animals were statistically processed and
showed firstly that changes in the weight of organs in animals  administered
50 mg/kg of the antimony were not statistically significant and/or  reliable;
secondly, that organs weight changes were more significant in the animals
which died early in the experimental period, as shown  by the weight coeffi-

                                   - 263 -
-------
/Off-
120

ffffi.
so-
60
j






>'\

|_
"rH
\

I
V

X
V







• A

•3^

&
'$'•'>
:>;:
s •'






M
L ,)
-n~

w
&
i
%

1
$
&
Control

P5
K




fJC



So 030 Sb 0 Sb 3 Sb

,




c
;
>


r
/

'.
'.
•
i
000 SO 0 So
Liver Spleen
CZ3 t C^Di' C2SJ"
cients; and thirdly,  that the increase in the liver weight and fall in the wi:ii;lii
of the kidneys followed a regular pattern.

   •/,                                   Profound changes  in the liver and
                                   spleen were paralleled by corresponding
                                   differences in the antimony distribution,
                                   which is clearly indicated by data  pre-
                                   sented in Table 2.  Analysis of such data
                                   showed that most of the antimony accumu-
                                   lated in the liver and in the spleen and
                                   that during the early days of observation
                                   the amount of antimony accumulated in
                                   the liver was twice as great as the amount
                                   accumulated in the spleen. Whereas 30
                                   days later, or at the end  of the observa-
                                   tion period, the spleen contained 6 times
                                   as much antimony as did  the liver.  Anti-
                                   mony accumulation was also noted in the
                                   gastro-intestinal tract.  Data in Table 2
                                   also show that the rate of antimony ac-
cumulation in the body organs varied with the degree of the metal purity,
and intensity of toxicity.   This was shown by the fact that organs of experi-
mental animals which received Sb3 accumulated 50-75% less of the metal
than was found in the organs of experimental animals which received Sbooo >
and also in organs of animals which died during the early days of the experi-
ment, and also  animals which had been sacrificed at the end  of the observa-
tion period.  The large antimony accumulation in the bifurcated lymph glands
may have been the result of mechanical carrying over of metallic antimony
by the lymph flow.    See next page for Table 2.

                               Conclusions
  Ratio of organ in Body (eight  ii
 poisoned *i th So of different purity degree
 I - 53 ng/k3 of Sbj 2 - 103 mj/tcg} 3 - ISO
       1.  Metallic antimony possesses highly toxic properties as shown by
the fact that the Sbooo was more toxic to the animal organism than the dust
of the less pure antimony,  such as Sbo and Sb3 .

       2.  The belief that toxic properties of antimony were due to lead or
arsenic impurities was not substantiated  by the present investigation.

       3.  Metallic antimony is easily soluble in different body fluids.
Highest solubility was noted in human blood serum (23.2 mg%) at 37° in the
course of a day.  Solubility of metallic antimony increased directly with in-
crease in the fluid alkalinity and vice versa.

       4.  Antimony poisoning produced dystrophic changes in the parenchy-
matous    organs which explains the reason for increase in the  weight of
liver and loss in the  weight of spleen in the experimental  animals.  Antimony
                                    - 264  -
-------
accumulated in the liver and in the .spleen.   Changes in weight  coefficient of
other organs in the  experimental  animals  were  of lesser magnitude.


Table 2.
          OiitriDjt«on of SbOQO, SbO, and Sb3 in  organs »ia tissues of  *hite rats which
           died durin9 the e»rl/ days of the experiment and rats sacrificed ena
                           sied 30 days froa Oeainn«.ij of experiment
Organ






Seoul | intest ioe .....





Lyaphatic gland ....
Averages in tQ/IJJ 9 of org«n
Rats dead «ithin 5-8 days,
So 330
7,f2
16,02
4,43
Not
studied;
2,34
13,32
Not
s tud i ed
4,20
6.66
0,98
9,13
Nat
studied
Not
studied
5,86
SbQ
0,97
11 ,t,9
3,48
1,28
1,11
1,23
1,66
1,44
4,02
0,71
2,08
0.61
' Not
studied
"Nat
studied
Sb3
2,86
0,88
2,42
Not
studied
0.4,'
0,98
1,93
1,20
1.97
0.24
Not
studied
Not
studied i
5,85
7,69
30 days fro» be,) i in 113 of
experiment
SbOOu
6.0;
1,34 •
0,43
Not
studied
0,U3
0,42
1,33
2,41
14.95
0,34
I race
0,29
1,13
102,14
SbU
13.40
1,51
0,17
-. 0
Trace
0,12
0,33
1,45
2,23
0
"Not
studied
Not
studied
0,72
133,15
o&3
1.88
0,54
0.08
Not
Studied
0
0.03
Not
s tudiea
0 70
1,19
0
Mot
studied
0,14
0
68,36
                                         Bibliography
              r a a a c K H H a  H.  /!., Zl o 6 p a K o a a  H.  C, K p e n c  H.  . n up.  Pur. H caw.,
          1953, jN? 10.  cip.  23.— ,H y a H  H a A. B.  Maiepvia^u KJiiiHiiMecKoro H SKcnqiMMf-iira.ibH'.iro
          iiff.ieaonaHini no  aonpocy o BJIHHUHH Tpe.xoKHcii cvpi>Mi>i  na  Dep.xmie .flbi.xan.'.ihH.bie ny~}>
          B opranw cjivxa.  ABTopecj). flucc. KaHfl.  MIIIICK,  I9G1.— FI o T e p ji i; B a f.  I7.  1'nr  tpv;i.:,
          1958, .\r9 6,  crp. 22.—D e r n e h 1 C. U., Nau C. A.. Sweets 1-1.  H., J. imlustr.  ll\i:.
          1945.  v. 27, p. 256—Fair'hall  L.  T..  Hyslop F.,  Tht' Toxicolocy  of  Anlnr.Miy.
          Washintjlon, 1947, p. 13.—Fell M.  A..  Dresse med.. 1939, N 57,  p. 1133.—R o d i e r .1.,
          S o'u c  h e r e 0., Arch. Maladies prof., 1957, v. 18 p. 662.
                                             - 265 -
-------
          3, 4-Benzpyrene in Crude Oil and in Bitumenous  Products
                                pp.  71 - 73

        N.  Ya. Yanysheva,  I. S. Kireeva, and N.  N. Serzhantova
  (From the Ukrainian Scientific Research Institute of Community Hygiene)
       The task of cancer prevention can be considerably advanced by the
elimination or significant reduction of cancerogenic products widely used in
the nation's daily life.  Among such products are coal brickettes which are
used as a convenient fuel,  especially in rural districts.  The present technol-
ogy used in making brickettes from coal dust is based on the use of coal pitch
as the binding material; the cancerogenic properties of coal pitch have been
well demonstrated.  L. M0  Shabad and P. P. Dikun showed in 1959 that coal
pitch content of cancerogenic 3, 4-benzpyrene can be as high as 1.5%.  Data
close to the above were found by the present authors during their investiga-
tion of pitch products produced by different Ukrainian coke-chemical plants.
The present authors found that the  3, 4-benzpyrene concentration in differ-
ent coal pitch products ranged between 0. 98-1.4%.  By order of the Chief
Government Sanitary Inspector of the  R.S.F.S.R.  the use  of brickettes in
which coal tar pitch was the binder, for the population's daily needs was for-
bidden. In the place of coal-tar  crude oil binders had been recommended.
Evidence found in the USSR and foreign literature indicated that blastomo-
genic activity of crude oil products was of a considerably lower intensity than
of hard coal products.  Lately,  however, many investigators found the pres-
ence of 3, 4-benzpyrene in crude oil products. A study of the Groznesk and
of Lyuberetsk crude oil tars failed to  discover the presence of 3, 4-benzpyrene.
It should be noted in this connection that such studies  had been conducted by
spectrofluorescent method at room temperature.

       The present authors investigated the 3, 4-benzpyrene concentrations
in crude oil tars of different trademarks. The investigation aimed at finding
which of the products contained the least amount of 3, 4-benzpyrene so their
use could be recommended  in the place of other products which contained
higher cancerogenic hydrocarbon concentrations.  The investigation included
crude oil,  tar and pitch products trademarked BN-IV and BN-V,  obtained
from cracking residuals BN-V produced by the Kherson plant.  This plant
processed crude oil coming from the Ukraine and partly from Povolzh'ya.
Samples for the investigation came in a variety of forms of processed crude
oil, such as crude oil asphalt resulting from direct vertical crude  oil dis-
tillation, and  cracking residuals resulting from processing crude oil break
down products.  The composition of products resulting from direct vertical
crude oil distillation depended largely upon the nature of the crude oil,  and
the composition of cracking products characterized by high content of aro-
matic  polycyclic hydrocarbons is determined basically by the production
technology.  Trademarked crude oil bitumens  are distinguished by their melt-
ing point and viscosity.

                                  - 266 -
-------
                                  .
        Samples of crude oil-bitumen products weighing 0.1-0. 5 g were dis-
 solved  in 2. 5 ml of benzene and poured into a partitioning column of acti-
 vated aluminum oxide.  Chromatographic partitioning was made at first with
 petrolic ether and then with a mixture of petrolic ether and benzene and end-
 ing with pure benzene.   The.fluorescent fractions were collected under
 ultraviolet lamp PRK-4, the light of which  was passed  through light filter
 UFS-3.  3, 4-benzpyrene was identified by comparing fine structure fluores-
 cent spectra of different fractions with, the  spectrum of 3,' 4-benzpyrene  solu-
 tion.  N-hexane was used as the'solvent. .Quantitative analysis was made us-
 ing 3, 4-benzpyrene spectrofluorescence at a temperature of liquid nitrogen
 using 1,12-benzpyrene as the inside background.  The fluorescent spectra
 were reforded by the photoelectric method developed in the laboratory of the
 institute by N. N. Serzhantoya, V. B. Timofeev and P. A.  Korotkova.  Sensi-
 tivity of this photoelectric  method was 5xlO~l0 g/ml and the accuracy was
 within 12%. At firs.t the spectralfluorescent analysis of the crude oil  bitumen
 was conducted at room temperature, and no 3, 4-benzpyrene could  be detected
 in any of the 20 investigated samples.    Later, 3, 4-tfenzpyrene determina-
 tions were made at the temperature of liquid nitrogen.  Using this method it
 was possible to establish that,contrary to the prevailing opinion,  crude oil
 bitumen products contained 3, 4-benzpyrene, as can be seen in the spectra
 presented  in the  Figure.
                                   Quantitative results  of the investigation
                                   are presented in the Table.
                                     '
                                      Bitumen trademarked BN-V, prepared
                                   from crude oil tar residue also contained
                                   3, 4-benzpyrene.  However, in the  present
                                   study only 1 tested sample contained the
                                   cancerogenic hydrocarbon in a consider-
                                   ably lesser quantity  than in the  crude oil
                                   cracking residues.   This  is in agreement
                                   with information found in  the literature
                                   which indicated that  products  of distruc-
                                   tive crude oil  processing  contained more
                                   groups  of aromatic compounds than the
                                   products of vertical  crude oil distillation,
                                   as  was  shown  by B.  T.  Brooks and his
                                   collaborators  in 1959.   Results of  the
                                   presented investigation make  it possible
                                   to determine the cancerogenic properties
                                P- of different crude oil tar residues by de-
  - SUno*rd .%ii-b«nzpyr«n« toljtion I, 3, U,  termining the  quantitative content of 3,4-
 , 6, - crude „ i  «.«,,*,-«.. fr.el.on*.       benzpyrene.  Results indicated that even
the maximal 3, 4-benzpyrene concentrations  found in the crude oil tar  resi-
dues were considerably below the maximal concentrations of  3, 4-benzpyrene
fqund in coal pitch.   Therefore, it appears that replacing the coal tar pitch
                                   - 267'-

-------
as  a binder by crude  oil tar residue should reduce considerably the amount
of cancerogenic  coal  products in coal dust brickettes.  It should be remem-
bered, however,  that crude oil tar residue binders may contain cancerogenic
substances  other than 3, 4-benzpyrene,  the concentration of which  may be
different in different  types of the crude  oil binders.   In view of this, final
recommendations for the use of the safest crude oil residue bindei-s of differ-
ent trademarks should be  based on experimental studies with  animals.
                    3, ^-benzpyrenc concentration  i.i crude oils pro-
                            cessed by the Kherson plant
                    Crude oil tr«de a*rk
               BN IV of cracking residue
               BN V  of cracking residue
               BN V of crude oil tar residue
No. of
samples
	 9
. . . . J 4
due . . J 3
* of
rene
O.f
0 i
Non
3,*»-benip/-
m samples
>0<~M 1) 0075
xi' I n (i'j72
e found —
                                  Bibliography
            EpyKc B. T., Bypfl C. E., KypTti C. C. n up. XHMHH yrjieBoaopoaoB HCHJITH.
        M., 1959,"T. 2.—TopGoB B. A., OOMCHKO B. II. Fur. n can, 1952, ,Ns 6, crp. 10-1.•--
        FypHHOB B.  H. Y'len. samiCKn MOCKOBCK. iiaymio-ncc^efl.  IIH-TH  can. n nil'., 11)60,
        N° 6, crp. 3.—ZlHKyH R II. Bonp. OHKOJI., 1961, Ks  10, crp. 64 — tlJ a 0 a a J}. A\.,
        JlHKyH H. n.  SarpanHciiHe aiMOC(J)epHoro  eosayxa  Kaimeporciniu.M
        3,4-CeH3nnpeHOM. /!., 1959.
      Blastomogenic Properties of Crude Oils From Different Oil Fields

                      D.  D. Shapiro  and I. Ya. Hetmanets,
     (From the Ukrainain Scientific  Research Institute of Labor Hygiene
                          and Occupational Diseases)

          Gigiena i Sanitariya Vol. 27 No.  6 (June) pp.  38-41, 1962)
        The  machine building industry extensively uses  lubricating and cool-
ing fats and oils  of crude oil origin.  During machine operation the lubricat-
ing materials fly into the air of the working premises or become deposited
on the exposed skin and clothing of the workers in the form of a fine  spray.
The droplets finally permeate through the clothing,  come in contact with the
skin of the trunk and appendages.  The oils  generally possess irritating and
photodynamic properties.  Prolonged repeated skin contamination with the
lubricating oils and fats  frequently results in the appearance on the workers'
                                     - 268  -
-------
skin of wart-like growths. 'This justifies  the search of Ijlastomogenic poten-
tialities in crude oil proper.   '

        O. G. Prokof'eva experimented with white mice (1938) and found that
sulfurized mineral oils possessed cancerogenic properties. .  She  applied the'
sulfuric oil to the skin of the-white mice for 4 and'one-half months, at the
end of which some of the experimental rrdce' developed papillomas and some
developed cancers.  R. I.  Verkhovskaya performe-d similar experiments  with
emulsol and concluded that the substance contained slight blastomogenic prop-
erties, if any, since none of her experimental mice developed canqer growths.
Lubricating and cooling oils used in the. machine building industry are deriva-
tives  of crude oil.   Therefore, it is reasonable to determine  first, whether
crude  oil as  such possessed blastomogenic.properties.  A clearcut answer
to this question will predetermine the expediency of further investigations
with respect to blastomogenicity of crude  oil derivatives,  such as lubricating
and cooling oils.  The  investigation herein reported included  crude oil speci-
mens coming from 5 different oil fields.   Experiments were conducted with
groups of 6 rabbits,  by coating their  outer ear skin every other day with
crude  oil samples selected for the investigation.  Application of the oils to
the outer skin of the rabbits was continued for 10-17 months.  The skin of the
experimental rabbits' ears developed  slight erythematosis scaling,  follicu-
lar hyperkeratosis, and falling out of the fur.  The rabbits developed isolated
nodules around the ear periphery the size of a poppy seed,  and some  of the
rabbits, developed small flat isolated warts the size  of a millet seed.  Such
growth generally remained stationary and in  some instances expanded at a
very slow rate,  while in other cases  the warts became reabsorbed,  Warts
resulting from the application of the Bitkov and Gozhansk oil  fields were
generally more  numerous and of larger dimension and their development
could be easily detected.

        Histologic examination of skin sections with wart development pre-
sented a picture  of varying pathology, such as papillomatosis, acanthosis,
and predominately focal wart-like epithelial protrusions.   According  to re-
sults  of the investigation, most pronounced changes,  as above described,
were  produced by crude oil coming from the Bitkov oil field;  next in order of
intensity was the oil from the Gozhansk oil fields, then came the  crude oil
from  the Radchenkov,  the Rbmashkin, and lastly from the Kokhanov oil
fields.  The  samples selected for the  present investigation contained  differ-
ent concentrations of paraffin,  tar, and sulfur, as shown in the Table below.
                Percent of paraffin, sulfur, ana t«r in different tr.es of
                                 crude oil
                iu»stances    i Bytkof  Gozhwiel^ Ro»»sh- Radchen-  Kok-
                           I      >         kin  !  icov    nanov
                           I      I
             Paraffin .-...,  \.\   '   4
             Sulfur ......  j   o.;, !   :;,,-,:
             lar.' .'•	    :',:,  '   :W .
                                   '- 269 -
-------
       Results indicated that tar and sulfur in themselves could not explain
the cancerogenic properties of the crude oils, since the Kokhanov crude oil,
which possessed highest concentrations of the two substances, manifested the
slightest blastomogenic properties.  On the other hand, the Bitkov crude  oil
which had the lowest tar concentration, manifested blastomogenic properties
of intensity greater than did the  crude oil from the Kokhanov  oil fields which
contained 14% paraffin.  The data indicated that the intensity of blastomogenic
properties of the investigated  crude  oils abated with the reduction in the par-
affin  concentration.

       Supplemental tests were  conducted with -white mice and crude oil com-
ing from the Kokhanov,  Bitkov,  and  Gozhansk oil fields.  That is crude oils
which contained highest concentrations of tar, paraffin and sulfur.  Experi-
ments were performed with groups of 30 mice.  Experimental animals re-
ceived crude oil applications twice weekly over the skin covering the backbone
area in the neighborhood of the blades.  The applications were continued
10 months, amounting to a total of 80 applications.  Mice, the skin of which
was treated with the Kokhanov crude oil, developed alopecia and localized
hyperkeratosis.  One of the experimental mice treated with the Bitkov crude
oil developed a malignancy the size of an Italian plum on. the ninth month of
the crude oil application . Upon incision of the malignant growth a bluish
bloody fluid oozed out.   One of the mice treated with the Gozhansk crude oil
developed a malignancy the size  of an average plum on the tenth  month of the
crude oil application.  Macroscopically, it appeared as a nodular grayish
blue malignant growth  which easily  separated from the animals  skin and
muscles.  Histologic studies showed  that the two malignant growths consist-
ed of polymorphic cellular elements, the nuclei of which were of different
developmental stages and different maturity periods.   There was a large
number of polynuclear and giant mononuclear cells.  There were signs  of
nuclear and protoplasmic cell degeneration.  The stroma consisted of con-
nective tissue fibers visible in small numbers between the accumulation of
cellular elements.   The inside surface of the blood vessels was frequently
covered with a layer of sarcomatous cells,  and the malignant  growths pene-
trated into the intravascular spaces  accompanied by thrombosis.   Based on
the paranchyma and stroma appearances, the developed malignancy was
classed as angiosarkoma. Supplemental experiments  for the  determination
of the role played by paraffin in  crude  oil blastomogenisis were conducted
with white mice and crude oil  tar-pitch products  and cracking residues  of
Dolinsk-Bitkov and Tuimazinsk crude oil.  Crude oil from the Dolinsk oil
fields contained 0.37% of sulfur,  20% of tar, and 11.55% of paraffin; crude oil
coming from the  Bitkov oil field, as  noted previously,  contained 0.5% of
sulfur, 35% of tar,  and 14% of paraffin. The Tuimazin crude  oil contained
1.47% of sulfur, 40% of tar, and 5.9% of paraffin.  Cancers developed in two
of the 20 mice, the skin of which was treated with the  Dolinsk crude oil tar-
pitch product.  The  mice ultimately  died.  On the basis of histologic investi-
gation, the cancers  were classed as  angiosarcomas.   Twelve  of the 28 mice,
the skin of which was treated with the Dolinsk crude  oil  cracking residue,
developed neoplastic growths.  Histologic examination showed that 8 of the
                                  - 270 -
-------
 12 neoplastic growths were of a true cancerous nature.  Observation of mic.:,
 the  skin of which, was treated with Bitkov crude oil cracking residue, showe 1
 that 8 of the 13 surviving animals showed wart-like formations of different
 dimensions.  No wart-like or cancerous growth developed in the white mice,
 the  skin of which was treated with .the Tuimazin crude oil cracking residue.

        Results of experiments conducted with mice  by treating their skins
 with cracking residues  of Bitkovv Dolinsk and Tuimazin crude'oil  generally
 agreed with the  results in experiments with rabbits  and  verify the assumption
 that paraffin played an important part in the cancerogenicity of crude oil and
 of its  processed derivatives. .    "    '        .              .

                                Conclusions
        1.  Results of the above investigations show that crude oil coming
 from the Bitkov,  Gozhansk,  Romashkin, Radchenkov and Kokaanov oil fields
 possessed blastomogenic properties.

        2,  Results of the investigations, as reported in the present paper,show
 that the blastomogenic properties of the crude oils mentioned in Conclusion
 Nou 1,  and of their derivative products differed to. some extent with the con-
 centration of paraffin contained in them.  The results showed that the greater
 was the paraffin concentration in the crude oil,  the more intensive was its
 blastomogenic activity.  The same was  true of the crude oil tar-pitch and of
'the. crude oil cracking residue.

        3.  The blastomogenic  effects  of crude oil derivative  lubricating and
 cooling oils  may be'eliminated or greatly reduced; it is recommended that
 such oils be prepared from crude oil, the paraffin content of which
 originally was or was artificially reduced to  less than 1%.

                                Bibliography
                           A|l\. flll'l.l.
                               "
                                   -  271 -
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     The Role Played by Paraffin in the Blastomogenicity of Crude Oil
                                pp.  87 - 92

                             M.  M.  Gimadeev
        (From the Ufa Scientific Research Institute of Labor Hygiene
                        and Occupational Diseases)

(With reference to the paper of Prof.  D. D.  Shapiro and I.  Ya Hetmanetz
entitled "Blastomogenic Properties of Crude Oils from Different Oil Fields'
            which appeared in Gigiena i Sanitariya, 1962, No. 6)
                                pp.  38 - 41
       Prof. D.  D. Shapiro and scientific aide I. Ya Hetmanetz studied the
properties of crude oil from 5 different oil fields and found them to possess
blastomogenic  properties.  The question concerning the presence  of blastomo-
genic properties  in crude oil was not a new one.  Results of many investiga -
tions showed that crude oil of some oil fields possessed blastomogenic proper-
ties  of different intensities, as was shown by the investigations of Twort and
Twort in 1928-1933, by Combes in 1954, and by others.  Examination of work-
ers engaged in oil mining in different oil fields showed that a direct connec-
tion  existed between the  nature of the crude oil, conditions of contact with
same, and rate of skin cancer morbidity. According to data presented by
Schwarts and his  collaborator 146 of 743  workers engaged in the crude oil
industry of California had keratosis of  their hands, forearms,  face and back
of the neck, while 7 had  general skin cancer.  It is of interest that 5 of the
workers who had skin cancer had been  employed as underground oil well re-
pairmen,  which brought  them into intimate contact with crude oil.  Similar
examination of 330 workers employed in  the oil fields of Texas failed to dis-
close the presence of  skin cancer among them.

       The crude oil mined in the USSR has been regarded as practically free
from blastomogenic properties.  Thus, M. Yu'Gol'denberg, Yu. I. Faer and
M. D. Vesloguzova stated in the literature of 1956 that the USSR crude oil
was  generally free from skin cancer producing properties.  However, this
opinion was not held by all investigators.  N. V. Lazarev stated in 1954 that
as the mining of crude oil spread over  different USSR territories some evi-
dence appeared that the crude oil of some oil fields possessed blastomogenic
properties.   In this connection the position taken by M. I.  Fongaus in 1962
regarding the approach to the hygienic  evaluation of physical,  chemical crude
oil properties from the viewpoint of possible blastomogenesis is fully justi-
fied.  Indeed, reports which appeared in the literature during the  past several
years indicated that crude oil of some new oil fields, unlike those of the Cau-
casus possessed  blastomogenic properties.   Finally D.  D. Shapiro and I.Ya.
Hetmanetz verified the fact that the crude oil from Bitkovsk, Gozhknsk,
Romashkin, Radshekov and from  Kokhanovsk oil fields possessed  blastomo-
genic properties.  It should be noted that the paper presented by Prof.  Shapiro
and Hetmanetz is of considerable: interest, since it stimulated great interest
                                   - 272 -
-------
on the part of medical and technological and engineering workers in protect-
ing the skin of workers employed in the crude oil industry.  Nevertheless,
it is not enough to establish the fact that one or another type  of crude oil
was free from or possessed blastomogenic  properties.  Attempts should also
be made to identify the cancerogenic compounds  specifically and to demon-
strate the  presence in crude oil of other compounds possessing blastomogenic
potentialities.

        It has been known that crude oil coming from different oil wells
possesse  different physical properties and chemical compositions. In addi-
tion to different hydrocarbons crude oil contained sulfur compounds, oxygen,
nitrogen, etc.  What are the compounds  which supposedly possessed blasto-
mogenic properties?  Unfortunately, this question  ca'n not be answered cate-
gorically,  and opinions in  this respect differ,,  Generally speaking, no known
cancerogenic substances have been detected in crude oil.  On the other hand,
Cook and his collaborators found  several polycydic hydrocarbons in crude
oil of Kuwait, which supposedly possessed blastomogenic properties.   P. A.,
Bogovskii  expressed  the opinion in I960 that from the viewpoint of possible
cancerogenicity the group  of high molecular tarry substances, which are un-
saturated heterocyclic compounds were of considerable interest.  In our
present state of knowledge it is difficult  to say whether the above opinion was
right or wrong.

       It is an unfortunate fact that many of the investigators made no effort
to correlate the results of their experiments on animals with the physical
chemical characteristics of the crude oil.  In this respect the work of  D0 D.
Shapiro and I.  Ya Hetmenetz is an exception,  and advantageously differs from
investigations of other authors.  Shapiro and Hetmenetz found that blastomo-
genic properties of oils coming from different oil fields differed in  their in-
tensities .  The above authors put in the first place crude oil coming from the
Vitkovsk oil field and in the second place crude  oil coming from the Gozhansk
oil field, followed by oil coming from the Radchenkov and Romashkinsk fields,
and finally  crude oil coming from the Kokhknovsk  oil field. . They correlated
such data with  results of physical, chemical properties of the same crude oil
samples and carrie to the following conclusion: in cases where the concen-
trations of tar  and sulfur appeared of no importance, the paraffin concen-
tration proved  of exceptional Significance.  The correlative studies showed
that crude  oil from the Vitkovsk and from the  Gozhansk oil fields,  the  paraf-
fin content of which was  greater,  possessed more intensive blastomogenic
properties. However, no  such correlation was  found by these authors  in
the  case of crude oil  coming from the Romashkinsk and Radchenkov oil
fields.  On the contrary, the Romashkinsk crude oil contained paraffin up to
3% and was below the Radchenko crude oil with regard to blastomogenic ac-
tivity, despite  the fact that its paraffin content was only 1.6% or 50% of that
found in the Romashkinsk crude oil.  The blastomogenic properties of  all
the  5  crude oils are studied by the authors using rabbits and in  addition us-
ing  rats in connection with the Brickov, Gozhansk  and the Kokhanov crude
oils.  Results of experiments with the rabbits could be  arranged in  a specif-
                                   - 273  -
-------
ic succession (not specifically indicated by the authors) while the results of
tests made with the  rats were somewhat different.  Essentially, the crude
oil which contained approximately 4% of paraffin possessed a blastomogenic
intensity similar to  the Bitkov crude oil which contained 14% paraffin.  Both
types of crude oil elicited the same type of cancer.

       It has  been known for  some time that paraffin is a skin damaging sub-
stance.  In the second half of the  preceding century, Grotovskii described a
folliculitis type of skin disease developed among workers employed in the
production of  paraffin.  At one time a "paraffin disease" has been recognized
or spoken of as occurring among  workers  engaged in the production of paraf-
fin.  Reports  of paraffin cancer have been found in the literature elicited in
workers engaged in  the production of paraffin and its products.  N. N.  Petrov
(1931) listed paraffin cancer as an occupational disease.  According to Hen-
dricks and his co-workers cancer of the scrotum was frequently found among
workers employed in paraffin purifying departments.  This type of cancer
occurred among the  workers  at no greater frequency than in the general pop-
ulation.  However, among employees  whose work record exceeded 10 years
cancer  of the  scrotum was found  at a higher frequency.  On the other hand,
some investigators believe that paraffin as such had no damaging effect on
the skin, and  that the above mentioned harmful effects were the result of some
paraffin processing by-products.  Wood stated in 1929  that pure paraffin was
inert and harmless and that it produced no dermatitis of pholliculitis among
employees working in the paraffin industry.  B.  T. Brooks expressed a simi-
lar opinion in  1959.    He pointed  to the fact that from  the physiologic view-
point, paraffin was inert and,  as  a rule, produced no irritating  effects.  He
believed that the specific type of cancer which at times developed  in workers
connected with the production of paraffin was actually elicited by aromatic
hydrocarbons. In this connection, it should be mentioned that some investi-
gators established a clearcut connection between the concentration of aroma-
tic hydrocarbons including other high  molecular compounds, and the  paraffin
content in crude oil.  Thus, E. A, Robinson noted in I960 that an increase in
the paraffin content was paralleled by a reduction in the amount of high tem-
perature boiling aromatic  hydrocarbons,  and also a  reduction in the cyclic
nature of the molecules.  The blastomogenic or  cancerogenic substances
well known to  investigators belonged to different groups of chemical com-
pounds foremost among which are the aromatic and heterocyclic compounds,
as shown by L. M, Shabad in 1947, and by L. M. Shabad and P. P. Dikum in
1959, and by many others.

       In their paper on the  subject, D. D. Shapiro  and I.  Ya.  Hetmanetz
failed to indicate clearly whether  or not they have  taken the above mentioned
circumstances into consideration. It is difficult to comprehend why Shapiro
and Hetmanetz considered irrelevant data  regarding contents of different
hydrocarbon types in the studied crude oil samples,  while  they presented in-
formation concerning the contents of paraffin, tar  and  sulfur.  It is pointed
out above that crude oil coming from foreign oil fields could be  arranged
                                     - 274  -
-------
 in a definite consistent, order. . Thus, Combes noted in 1954' that crude oil
 coming from Venezula, Borneo, Rumania,  and.Iran possessed1 stronger
.blastomogenic .properties than crude oils coming from California,  Texas,
 Pennsylvania or from oil.fields of the Soviet Union.  According .to data pre-
 sented by some American investigators,, Pennsylvania,cr.ude; oil,represented
 the classical type of. so-called paraffin: crude oil,-,'while-the. MidrCpntinental  *
 crude'oil belonged to the .'same c-lass, whereas, .California crude oil contain-
 ed less of the paraffin  and the Borneo surface crude oil contained no hard
•paraffin and only as the .depth ofithe wells increased".the content of solid par-
 affin, began  td appe.a-r and rise.  In this  connection the following 'definitions
 are" generally used,.  'Crude .'oil containing up' to 3% of. paraffin is classed as
 paraffinic erude.oil,  and crude oil containing more  thari 3% is referred to as
; strongly paraffinic'crude oil. 'Below 1% the crude oil is usually referred to
 as paraffin-free.  E. A. "Robinson pointed out in I960 that crude oil corning
 from Pennsylvania and\ Borneo oil fields represented strong paraffinic as
 well as weak paraffinic crude oils.  Crude oils conning from Venezuela and
 Oklahoma oil fields, occupied an intermediate position,  with Venezuela oil
 being closer to  the Borneo oil, and Oklahoma oil  resembling more the Penn-
 sylvania crude oil.  A.'  F. Dobryanskii found that Pennsylvania crude oil
 contained approximately 2.5% and Texas oil 1.5%, California oil 0.1-0.6%
 and Rumanian oil 6-7% of hard paraffin.  A careful' study of the above pre-
 sented data clearly indicates that no direct  connection existed between the
 paraffin content of a  crude oil and its blastomogenic properties.
 t        t                 ;
     ^   D. D. Shapiro and I. Ya. Hetmanetz made a more elaborate study
 of the role  played by paraffin in relation to blastomogenic properties of
 crude oil.   They investigated the blastomogenic properties ^of crude oil tar
 products and crude oil cracking residuals using white mice as  the experi-
 mental animals. Experiments were limited to investigation of crude oils
 and their products  coming from the Dolinsk, Bitkov, and Tuimazin oil fields.
 In their studies  they  paid particular attention to the contents of sulfur, paraf-
 fin, and tar in the crude oils. The present writer believes that such a scope
 of information was utterly inadequate,1 for the  reason that crude oil consisted
 of many hydrocarbon groups.  It is also believed that data  presented by
 Shapiro and Hetmanetz regarding the quantities of paraffin, tar and sulfur
 in the original crude oil, failed to adequately reflect the true concentration
 of even these substances in the products .of the crude oil processing,  par-
 ticularly in the tar or pitch and in the cracking residues.   Up to the present,
 particular attention has been given to aromatic hydrocarbons in the crude oil.
 In this connection,  Twort and Twort stated in 1928:. "It has been stated at
 times that crude oil. contained no'aromatic compounds, or-a small quantity
 of same, pri'or to  its distillation, and that such products became synthesize:!
 during the process of distillation.  Such a supposition is  understandable, yet
 it can not be'denied that some samples  of crude oil are capable of eliciting
 cancer development in  animals even though it may be to a small degree. "
 Results of experimental series showed  that high temperature crude oil pro-
 cessing brings about a  recombination of the split products  which results in
              . .      .''             - 275 -
-------
the formation of aromatic cancerogenic compounds.  Kennaway (1925) tested
some California crude oil by applying same to the skin of white mice for 515
days without eliciting cancer formation symptoms. He,  then,  heated the
same oil to 880° in hydrogen atmosphere, after which the oil,  which pre-
viously was presumably free from cancerogenic properties,  possessed can-
cerogenic activity.  Similar experiments had been performed by other in-
vestigators. There are no data which would clearly point to the origin of
blastomogenic crude oil products; nevertheless, there are isolated indica-
tions  of same.  Thus,  Twort and Ing (1929) expressed the opinion that blasto-
mogenic effects were elicited by unsaturated aromatic hydrocarbons.  Ac-
cording to data presented by Fischer and his collaborators in 1951, high
boiling crude oil products may contain  a considerable amount of different
hydrocarbons.  This should have been reason enough to prompt D.  D. Sha-
piro and I.Ya. Hetmanetz to determine the exact chemical composition of
each individual product with special reference to aromatic compounds.  This
should have been necessarily done for no other reason than for the fact that
cracking residuals consisted of high condensation aromatic hydrocarbons,
and some other compounds; yet,  this was  not done by Shapiro and his collab-
orators.  It is generally known that values characteristic of paraffin con-
centrations, sulfur and other crude oil components did not always coincide
with values  characterizing their concentrations in other products.  Thus, -
according to D.  L. Nelson and his collaborators (1956) the ratio between
sulfur concentration in cracking residuals and its concentration in crude oil
ranged between 0. 7  and 5. 5% according to the  original oil field.  On the ba-
sis of their  proposed conception D. D.  Shapiro and his collaborator con-
cluded at the end of  their report that it was necessary to free crude oil from
paraffin or to reduce it to 1%.

       The  present  author believes that more  convincing data regarding
the part played by paraffin in the blastomogenic potentialities of crude oil
should have been obtained. The indications are that the two authors con-
tinue to pursue their highly important studies.  For if it were actually and
undoubtedly established that paraffin played an important role in the blasto-
mogenic potentialities of  crude oil, then it would become necessary to con-
centrate all effort in the direction of complete and general mechanization
and automation of crude oil treatment processes as well as their complete
leak-proof encasement wherever necessary.  M.  I.Fongaus found in 1962
that the use of high temperature in connection  with crude oil products may
form vapors of heavy hydrocarbons which upon cooling condensed to aero-
sols of solid or liquid phases forming paraffin aerosols or oil fogs, both
of whi ch..a r_e acutely harmful to the organisms of workers.  Such aerosols,
consisting of heavy polynuclear aromatic hydrocarbons,  act not only by
way of the respiratory organs but by  skin  permeation as  well.
N. M. Thompson showed in 1959 that the human organism eliminated
through the  skin 20 g of fat or oil  per day,  and under the protection of
the skin such oil can catch and retain and  even dissolve some substances
present in the air  as aerosols.  The possibility of paraffin entering the or-
ganism in a similar manner can not be excluded.
                                - 276  -
-------
       D» D.  Shapiro and his collaborator made an earnest attempt to ex-
plain the reason for or origin of blastomogenic properties of different types
of crude oil.  In their work, they made certain inaccurate assumptions which
to some extent invalidate their results, or lead to incorrect evaluation
ation of their  results.  It is hoped that the studies being conducted at the
Ukrainian Institute of Labor Hygiene and Occupational Diseases in connec-
tion with the Ufa Institute of Hygiene and Occupational Diseases will produce
data on the basis of which the problem attacked by Shapiro and Hetmanetz,
and which is discussed in this paper,  will be rationally resolved.

                             Editor's Remarks
       Commenting on the remarks made by M. M. Gimadeev regarding the
publication of D. D. Shapiro and I. Ya, Hetmanetz,  M. I.  Fongaus states at
the request of the editor that the paper was justly evaluated by Gimadeev,
both as regards its positive significance and  shortcomings.  The objections
presented by M.  M. Gimadeev are basically  sound  and convincing.  The ques-
tion of crude oil and crude oil products  cancerogenicity is occupying the at-
tention of increasingly larger circles  of sanitary hygienic investigators.  For
this reason,  the position adopted by Gimadeev in his evaluation of the paper
by Shapiro and Hetmanetz acquires special significance, since it can prevent
other investigators from taking the wrong positions in organizing and exe-
cuting future investigations in crude oil mining and crude oil processing
plants. On her part, M. I. Fongaus notes that M.  M. Gimadeev failed to
note and take into account some erroneous positions expressed in the paper
by Shapiro and Hetmanetz.  In her opinion, it is erroneous to regard all
mineral oils  as agents capable to produce warty growth on the skin.  In this
respect the authors contradict themselves.  Thus,  on  two occasions  they point
to the fact that cancerogenicity of crude oil products raised the problem of
blastomogenic  potentialities of crude oil proper; but the cancerogenicity of
raw crude oil is a problem by itself, and has no relation  to the cancerogeni-
city of the crude  oil products.  Employees engaged in  crude oil mining in
underground  repair of oil well casing  and  apparatuses, and in similar bran-
ches of the industry,  come in contact  with the crude oil only.   The cancero -
genicity of crude oil products likewise presents a problem of  its own, which
can not be disregarded even in instances in which the crude oil itself was de-
void of cancerogenic properties, since in  the course of its processing by
destructive distillation cancerogenic substances may come into being.  Under
such conditions the position assumed by the original authors has a disorient-
ing effect, on hygienists and sanitarians.

       Bibliography next page.
                                   - 277  -
-------
                                         Bibliography


                 AH TO HOB  A. M.,  JI y it u A. M.  Bonpocw OHKO.iornn, 1960,  N°  11. crp. 66.—Bo-
            roBCKHfl 11.  A. FIpo<}>eccnoHa;ibnbie onyxo.nn KOJKH, BbisbiaaeMbie npoAyKiaMH  nepepa-
            OOTKII roproMHx HCKonaeMbix.  M., 1960.— DpyKc  J3. T. B  KH.: XIIMHSI  yrvie.BOAopo.noB
            nci})TH. M., 1959,  T.  3, crp. 78.—B p y K  c b. T., B y p a C.  B..  Kyp-ru C.  C.,  Ill M e p-
            jiHHrJl.  (pen.).  B  KII.: XIIMHH ymenoAopoAOB ne(})TH. M., 1958, T. I.—F n M a nee B M. M.
            KaaancK.  MCA.  >K., 1962, N° 2, crp. 79.— FojibjiciiGepr  M. IO.,  Oaep rO. H, Bee
            ^orysona M.  fl.  BCVIKIHH KOJKH y  paOo'mx necpTRHofi  npoMwui^cHiiocni. flporoGui,
            1956.—flaeHAwa  FI.  Fl. FHT.,  fiesonaciiocTb H nai.  rpyaa,  1931, N?  9,  cip. 136.—
            flofjpHHCKHH  A.  .  FeoxHMiifl iiecpTH.  M., 1948.— K o n e c u H K o B H. M. Tpyau
            AaepfiafiAiKaiiCK. nn-ra MHi
-------
napthalene. Its b. p. is 160-163°.  It is water soluble and easily soluble in
organic solvents.  It belongs to the group of narcotics and possesses strong-
ly irritating properties.  Little information was found in the  literature on
the subject of a-methyl styrol toxicity,  and what evidence has been found was
of a contradictory nature.  T. A. Blinova exposed several species of experi-
mental animals to the inhalation of a-methyl styrol vapor in 1 mg/li concen-
tration for 106 days.  She reported in 1954 the following changes in the peri-
pheral Talood of the experimental animals:  hyperchromic anemia,' relative
leucocytic   reticulocytosis, which turned into  reticulopenia at the end of
the vapor inhalation exposure,  and a shortened  blood clotting time.: N. L.
Rylova (1955) exposed white rats to the inhalation of a-methyl styrol vapor
in concentration  of 3 mg/li for 9 months, and reported that the preparation
irritated mucous membranes and lowered the experimental animals' capacity
to perform difficult physical tasks.   She found that 0. 02 mg/li  of the vapor
constituted the concentration of threshold irritation to the conjunctiva  and to
mucous membranes of the respiratory tract, and also the concentration of
a-methyl  styrol odor perceptibility.   Using the  procedure of  Zakusova-
lnyablina, she determined that 0. 06 mg/li of the a-methyl styrol vapor repre-
sented the concentration  of threshold activity on the central nervous system
of rabbits.

       Experimental results obtained by T. A.  Blinova and M.  L/.  Rylova
led them to the conclusion that prolonged exposure to the effects of a-methyl
styrol vapor was toxicologically harmful.  Wolf of the USA came to the oppo-
site'conclusion in 1956.   He and his collaborators worked with  white rats,
guinea pigs,  rabbits, and Macacus rhesus,  male and female; these experi-
mental animals were exposed to the inhalation of air containing 2. 9 mg/li of
a-methyl  styrol vapor for 6 months, and found only slight changes in the  form
of arrested growth and increase in the liver and kidney weights; inhalation of
air containing 0. 97 mg/li of the tested vapor elicited no toxic symptoms in
any of the experimental animals.  Wolf and his  collaborators were of the opin-
ion that even under conditions ,of chronic exposure, a-methyl styrol failed to
manifest notable  toxic effects  usually characteristic of compounds of the
aromatic  series.  They emphatically denied, that a-methyl styrol vapor pos-
sessed myelotoxic properties.  Gerarde (1962),  Browning (1958), Batchelor
(1,927), Spencer and his co-workers (1947),  and,  other investigators expressed
the same  opinion in relation to the toxicity of benzene homologues.

       Such contradictory conclusions may be explained by the fact that the
authors used toxicity indexes of different natures.  In addition, the cited
USSR and foreign authors .based their conclusions only on experimental data,
whereas,  the practice of establishing maximal permissible concentration of
toxic substances  must be mandatorily based on  data obtained  experimentally
aind under practical conditions including  examinations of general health of
persons exposed to.the effects of the'investigated toxic substance in different
concentrations.

                                  - 279 -
-------
       Investigations of conditions prevailing in the production of divinyl
methyl styrol synthetic rubber in the Bashkir ASSR indicated that the basic
harmful factor in the production of the preparation was air pollution of the
working premises with a-methyl styrol vapor.  Results  of 1400 analyses of
air sarrrgles collected during 1960-1963  showed that concentrations of a-meth-
yl styrol were below the official permissible maximum of 0.05 mg/li ranging
between 0.01 and 0.03  mg/li.  At some points of the synthetic rubber produc-
tion,  such as rubber drying conveyors and other similar points, o?-i~nethyl
styrol vapor concentration in the  air ranged between 0.65-0.11 mg/li.

        Investigators who studied the sanitary conditions prevailing in some
branches of the organic synthetic industry noted that chronic exposure to
the inhalation of benzene and some of its compounds elicited symptoms  of
cardio-vascular poisons.  Therefore,  it appeared important to determine
what effect vapor of a-methyl styrol, which is a benzene homologue, had on
the physiological functions of workers chronically exposed to the inhalation
of air  containing low concentrations  of such vapor.

        The physiological reactions of some employees was  studied in the
course of a work shift and a work week.  Results pointed to a lowering in
body temperature, a drop in the systolic and diastolic arterial blood pressure
and a loss in eye sensitivity to light.  A comparison of results  obtained from
above  described investigations in 1960-1961 and  1962 indicated that there  was
a reduction in the values of index shifts according to reports in 1962. This
may have been caused by the development of a peculiar intoxication charac-
terized by a sharp drop in external manifestations  of poisoning.

        The observed shifts in the organism's functions basically accorded
with the results of clinical observations and examinations made on 224 work-
ers employed by the synthetic rubber producing plant.  Some workers mani-
fested disburbance in the functional state of the  central nervous system, such
as headaches,  tremor of the fingers and eyelids, disseminated red dermo-
graphy and a labile pulse;  24. 8% of  the observed and examined workers mar --
ifested atrophic changes of the nasal and glottis mucous  membrances.   In-
dividual workers also developed leucopenia,  thrombocytopenia,  a rise in the
pH of the gastric juice,  and a  loss in its digestive capacity.  Some changes
were noted in the liver of young workers, but no hepatotropic diseases;  the
liver size  increased, and its antitoxic function was impared,as shown by the
Quick  test.  A.  A. Orlova, G.  N.  Mazunina,  andE. A.  Solov'eva studied
the effect of o!-methyl styrol in the Krasnoyarsk synthetic  rubber plant;
their results were similar to those cited above.

        Results  of the above physiological, hygienic and  polyclinic investiga-
tions prompted  the present author to study the biological effect of a-meth\i
styrol  vapor under acute and chronic experimental conductions,  in order tu
secure basic data for the determination of the maximal permissible  fy-rru-t;hyl
styrol  vapor concentration in the air of production  premises.  Results ob-
                                    - 280 -
-------
rained under acute experimental conditions indicated that a-methyl styrol va-
por  possessed resorptive properties, and that it constituted no possible in-
toxication factor under industrial production conditions.  Exposure of mice to
a single 2-hour inhalation of the tested vapor failed to kill any of the experi-
mental animals probably due to the insufficient exposure chamber air satura-
tion with the a-methyl styrol vapor due to the low volatility of the  oily prepar-
ation.  Only slight sluggishness was  noted in the mice at the end of the in-
halation tests.  Intragastric a-methyl styrol administration in oily solution
in 1.5-9.0 g/kg doses irritated the gastrointestinal  mucosa,  elicited motor
agitation and a state of narcosis.  Experimental animals died within 1-2 days
in a state of clonic convulsions,  cyanosis,  lowered body temperature, paraly-
sis of the hind legs and uncontrolled  urination.  The absolute lethal dose was
7.0  g/kg,  and LD5O was 4.5 g/kg. The maximum tolerance dose  was 2.0
g/kg.  Dipping the tails of the mice into Gf-methyl styrol for 2-4 hours pro-
duced results similar, to the ones described above, strongly affected the
blood vessels, and killed some of the mice.  Autopsie   -howed acute hyper-
emia, areas of atelectasis and pulmona-^  hemorrhag:   injected blood ves-
sels, cerebral swelling and minute kidney  and  liver hemorhages.

        Chronic experiments were conducted with  33 male rats;  they were
exposed to the inhalation of air containing 0.05,  0.005 and 0.0001  mg/li of
a-methyl styrol vapor.  It should be  noted that 0.05 mg/li was the concen-
tration officially specified as the maximal permissible concentration in the
air.   Eleven rats were used as controls.  Experimental animals were placed
into, exposure  chambers the air of which contained the  respective  ex-methyl
styrol for 5.5 hours daily, excepting Sunday,  for 5 months.  Concentrations
of the  tested vapor were checked in the chambers  by the method of optical
density.  Results of daily analysis indicated that fluctuation from the intended
concentrations were statistically insignificant.  Throughout the period of
chronic intoxication, the experimental animals had been observed for their
general behavior, body temperature,  arterial blood pressure, muscle an-
tagonist chronaxy, blood serum protein composition, the thymol test, whole
blood cholinesterase activity, morphologic peripheral blood picture,  and,
oxygen consumption rate.  At the end of the chronic experiment the animals
became sluggish as compared with the control rats; rats which inhaled air
containing 0.05 and 0.005 mg/li  of a-methyl styrol vapor developed mucous
membrane irritation and bloo.dy nasal exudation.  These symptoms became
clearly discernible  at the end of 30 days experimental inhalation  exposure.
At the end of 60 days chronic inhalation of air containing 0. 05 mg/li of
/^-methyl styrol vapor,  the experimental animals  lost weight,  as  compared
with the controls, the values of which were statistically significant.  The
loss of weight by rats of this group persisted to  the  end of the  chronic vapor
inhalation.  Rats which inhaled air containing 0.005 mg/li of oi-methyl styrol
vapor lost weight statistically significant only at the end of 120 days of chronic
inhalation.   This loss in body weight was rapidly regained by rats of this
group after the  inhalation was discontinued.  Rats which inhaled air contain-
ing 0.001 mg/li of the poisonous vapor showed no  loss in body weight through-
out the experiment,  (see Figure 1)
                                  -  281 -
-------
Fig.  1.
                   Recovery
                   period
                                Rectal temperatures taken by the battery
                            type electrothermometer showed drops only in
                            rats of group 1.  The drop in rat's rectal temper-
                            ature was greatest at the end of the vapor inhal-
                            ation period.  Thus,  the drop in rectal tempera-
                            ture during the second  and third mouth,  ranged
                            between 0.68-106,  with an A\0.084-0.102 and average of 0.093, and 0.007-
 0. 087 with an average of 0. 82 m/sec.
                                    - 282 -
-------
       Statistically verifiable muscle antagonist chrortaxy prolongation ap-
peared in rats of group 2 on the fifth exposure  month less clearly defined and
less general in character.  In addition,  the central nervous control over the
neuromuscular apparatus was disturbed in rats of both experimental groups,
as shown by the close approximation between the two chronaxies.   Later
the chronaxy ratio became reversed.  Muscle antagonist chronaxies and
their .ratio returned to normal only at the end of the second recovery month.
Curves in Fig. .3 show that  0.001-mg/li of the a-methyl styrol had no sub-
stantial effect on the muscle antagonist chronaxies.  Accordingly,.  0. 05 and
0.005 mg/li of a-methyl styrol vapor affected the cerebral cortex, as evi-
denced by lowered response to electric stimulation.
Fig. 3.
                                                   B ~
                   Months of exposure
Month* of exposure
                      Courses of muscle antagonists chronaxies
            A —Flexors 6 —Extensors in the course of the chronic enj-eri-nen t.
                         Other designations as on fij, 2
        Recently accumulated data indicated that cholinesterase,  which
hydrolyzed acetylcholine, ''played an important role in transmitting stimu-
lation from the central nervous system, from the ganglia apparatus of the
vegetative nervous  system, and from the neuromuscular synapses.   The
present author determined whole blood cholinesterase activity by the  Ph-
buffer method  which is based on determining the amount of acetic acid liber-
ated by  acetylcholine hydrolysis, as shown by changes in the Ph-buffer solu-
tion.   This method  has  been described in detail by M. V.  Smitrieva.  Cholin-
esterase activity of rats belonging to group 1 dropped from  the original range
of 1. 80-2. 36,  with an average of 2. 08,  to 0.38-1. 18,  with an ave rage  of 1. 78
units at the end of the experimental vapor inhalation as shown in Fig, 4.
No statistically verifiable values  in cholinesterase activity  have  been found
in rats belonging to groups  2  and 3.

        Effect  of a-methyl stryol vapor on the hematological indexes was
investigated next.   Toxic vapor inhalation in 0.05 mg/li under chronic ex-
                                     - 283 .-
-------
pe'rimental conditions affected such indexes during the early vapor inhalation
stages, as shown by the gradual rise in the number of erythrocytes from
6.89X 106  -6.91*  106. with an average of 6.9 x  10a, to 8.11 x 106  - 8. 77 x
106 ,  with an average  of 8.44 x 10s .  This was paralleled by a slight rise in
the number of leucocytes during the first two months of vapor inhalation,
followed by a notable  ^tendency to drop.  Such fluctuations were more pro-
nounced in animals of group 1 than in animals of  groups 2 and 3, as shown
by the data presented in the following Tables.
 Fig.  4.
                               The  rise in number of erythrocytes in the
                           blood of rats of group 1, and the relative  stabil-
                           ity in the number of erythrocytes in the rats be-
                           longing to group 2 was paralleled in each case
                           by a loss in the hemoglobin concentration.  Thus,
                           the hemoglobin percent in the blood of rats be-
                           longing to group 1 fell from 75.4-81.4, with an
                           average of 78.4%, to 60.5-67.9, with an  average
                           of 64.2%.  In rats belonging to group 2, the
                           hemoglobin dropped from 76. 3-97. 7, with an
                           average of 81%, to 66. 3-72. 9, with an average
                           of 69.6%.  No  statistically verifiable data in
                           hemoglobin changes, were obtained in rats be-
                           longing to group 3.  Such changes as had  been
                           described above are regarded by the present
                           author as pointing to the development of hypo-
                           chromic anemia.  Rats  of groups 1 and 2  also
                           showed indications of developing reticulocyto-
 Cho«ii>a»ter.«e •ctivity in the ret* sis>  Data of the present investigation accord
 in the course of the chronic expert-    .                            °
           •«»t             with the opinion expressed by T. A. Blinova
 I - Control r«ta» 2 - R«ta of Group       ,.    ,,    ,,  .  .      .,  ,  .    ,     .,
        i, o.s ag/li          regarding the effect of a-methyl styrol on the
   T  "..""           :. "., .~7.'Z7~ general  blood picture.   Results  of the experi-
ments also show that the  assumption made by Wolf and co-authors,  and by
Gerard and others,  that a-methyl styrol possessed no myelotoxic activity
could not be substantiated by the present author; it is true however, that
the effect in the case of a-methyl styrol was less pronounced than in the
case of benzene and some of its homologues.

       Results of paper electrophoretic studies show that a fall in the blood
serum albumin concentration from 40. 9 to 35. c(8%  occurred in  rats belonging
to group 1 during the fifth month of chronic vapor inhalation.  This was par-
alleled by a slight rise in the  concentrations of a- and P- globulins.  Ac-
cordingly, the albumin-globulin coefficient dropped from 0. 7 to 0.52.
No changes were noted in the  turbidity degree of the thymol test, and no
significant histologic changes were noted in the liver tissue  of the experi-
mental rats; therefore, no  study was made of possible hypoalbuminemia as
an:index of damage caused  to the kidneys.  The above blood serum protein
fraction changes may have  been caused by the direct a-methyl styrol  effect
                                   - 284 -
-------
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on the tissue and serum proteins.  However, .since the
clinical symptoms pointed to liver damage,  the  possible
effect of a-methyl styrol toxicity  should be considered;
workers connected with  the production of processing
a-methyl styrol should be checked periodically for the
appearance of pertinent  liver damage symptoms.  Rate
of oxygen consumption in rats of group 1 dropped to less
than 50% at the end  of the vapor inhalation, period.  No
changes in the rate of oxygen consumption were noted in
rats belonging to groups 2 and 3.

    Pathologic studies  of internal  organs of  rats be-
longing to group 1 showed changes in the lungs,  kidneys,
liver,' and cerebrum.  The lungs showed the presencfe
of interstitial pneumonia, desquamative bronchitis, and
a well defined emphysema; the kidneys showed epithelial
degeneration of the convoluted tubules and dilated lumens,
The interstitial tissue  appeared friable, and the lumens
of the convoluted tubules were filled with a pinkish mass,
Some proliferation in the periportal connective tissue
was seen in  the liver and in Basse's spaces.  Cells of
the liver parenchyma were devoid of protoplasmic  glyco-
gen.  The cerebrum showed the presence of cytopykno-
sis and karyocytolysis accompanied by  the formation
of shadow cells and small anemic  areas. Acute swell-
ing was seen in the region of subcortical ganglia, also
gravely affected gangliar cells,  presenting a picture
of true neurophagia; the cerebellum showed  falling out
of Purkinje  cells  accompanied by acute light or pynkno-
morphic swelling of the Purkinje cells.  The pathomor-
phologic changes  in rats  belonging to group 2 appeared
as light pulmonary interstitial pneumonia and glycogen
depleted, liver.   Histologic investigations conducted two
months after  discontinuation  of the -experimental vapor
inhalation showed complete restoration of liver glyco-
gen and of cell structure in the cerebrum.   The lungs
showed residuals of emphysema and points  of resolving
pneumonia.

    Thus, the clearly expressed changes on the  part of
the central nervous system,  of the peripheral blood,
cholinesjterase activity,  arterial blood pressure, and
protein-forming liver function evidenced in  rats belong-
ing to group 1, and the  presence of organic changes in
their  internal organs incline  the present author to re-
gard  the 0. 05 mg/li a-methyl styrol concentration  as
an active one.  Rats exposed to the inhalation of 0. 005
mg/li of a-methyl styrol vapor manifested the above
               - 285 -
-------
described changes in a less  gravely expressed form in only a part of the ex-
perimental rats, and in no instance did the picture of changes include all the
investigated physiological systems; in addition,  such  changes  rapidly re-
gressed and returned to normal at the end of the  experimental  period.
Therefore,  0.005 mg/li of a-methyl styrol vapor is regarded by the  pre-
sent author as the threshold concentration, while 0.001 mg/li was  regarded
as entirely inactive.

       Results of the investigation showed that a-methyl styrol belonged to
the group of poisons characterized by a wide zone of toxic effects. It has
been established that in the case of substances characterized by a wide zone
of toxic effects, the maximal permissible concentration could be adopted
within the range of threshold concentrations.  Results  obtained  from a com-
parative analysis of sanitary hygienic investigation, animal experimental
studies,  and of physiologic and polyclinic human  observations led the pre-
sent author to recommend 0. 005 mg/li of a-methyl styrol vapor in the air
as the maximal  permissible  concentration.  The  recommended  concentra-
tion has been adopted by the  official authorities and was included in the ap-
propriate sanitary code.

                               Conclusions
       1.  Results of experimental, clinical and physiological studies had*
shown that a-methyl styrol had a definite effect on the central nervous and
cardiovascular systems; its action on the peripheral blood  produced mild
polychromic anemia.    Chronic exposure  to the  effects of a-methyl styrol
may produce trophic  and metabolic changes.

       2. Examination of workers in contact with a-methyl styrol vapor
should include arterial pressure,  mucous membranes of the upper respira-
tory tracts,  and the peripheral blood picture.  The presence of some  upper
respiratory diseases in applicant workers should be regarded as contra-
indicative to their employment requiring contact with a-methyl styrol vapor.

       3. Results  of clinical observations conducted in the studies herein
reported showed weakening of  the liver function; wherever this is the  case
workers  should  be carefully examined as a prophylactic measure against
any possibility of toxic hepatitis  development.

       4. It is  recommended  that 0.005 mg/li of a-methyl styrol be adopted
as the maximal  permissible concentration in the air of working premises.

       Bibliography next page.
                                   - 286 -
-------
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            aainiii  pafxiMiix  XHMii'iecKoii npoMuubiciiiiocni. Popi.Kiiii,  1959,  cip.  .S. .-. A ;i c K >: r •.• » a
            M. 13., Kpu.-ioHa H. A., X p y c T a ,i c n a  B.  A. Pur.  n  tan.,  1963. ArL> 1,  a p.  3!  -
            A Ji b n r  p n /I.  E. B  KH.:  CoBpc.MCMHhie nonpocu Hepnn:iMa »  (piniM.'iornH n iiaio.'iot nil
            M., 1958, crp. 41.  — Bejietii. KHI'I M. JI. C)JII:MI'IITI,I KOjiiiii CHKMIKII cp;i[p:.K!i'r>
            florwiccKoro 3eKTa.  Para, 1959. — 13 n n n o B a T. A. B KM.:  IJei|>cp;'.i 1,1  ii:iyiin.i.\ pan n
            /leHiuirpaacK. iiayMHO-Hcc.nen. HH-T;? VHnicnij rpy/ia >i npoipaaGo.ioHaiiHii  ta  I9.~»3,  I9rit.
            crp. 191.  -- f> H K o B K. M., B Ji a a H M H p o B P.  L7.., A e ;i o  n B '\l. n jip. y>icfinii:. linn'io-
            .loniii. M.,  1954, tip. 127; 565.  — KanKaes 3. A. Bocrii. SKUHOM. M rex H.  iim|?opM.-tiiH«
            PocKOMiiTCTa  no XHMHH Cnseia Mmmc-rpoB  CCCP. M..  19612,  7--S.  c~p.   MX. —K :i n-
            KatB 3. A. T'lr.  ipyna. • 196H,  j\Ts ;i, cip. 7.—K o UJ T o H  n u 1O. (.;.  H ;n. AH CCCP. Ce-
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            nm H  K.nmiiiKa  r'ipo4)3aOo.'iouamn"i XHMII'ICCKOM 3Tiio.T.>rnn. M.,  1962.  cip.  H.—.'] e V an'• i
            A. A. T:IM  >Kf.  crp.  'V -- JI 10 fi n  » n a F. H.,  K .n H ;i c K  a »  K. ('.., O .n 10 ii n n 1-1. B.
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            n o ii a A. A., M a 3 y n » H a P.  H., COJIOBI. eua H.  A. B MI.:  ripoMi.iiii.neiuiau  TMKTH-
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            P O H C K II ii B.  A. •.TllKCHKO.K'iTHH H  PHnieHa  HpOII3BOflCTIia  CHHTeTII'ICCKOro Kay;IVKt'i.  A\ ,
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            Hlth, I9.ri(i.  v. 14,  p. 387. — Gerard e H. W.,  Toxicology and Biochcmibiry of Anuna-
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            v. 7. p. 276. — Browning E., Toxicity of Industrial Organis  Solvents. London, 1953. -
            Spenser  H. C., Irish  D. D., Adams E. M. el  al., J. industr. Hyg.,   1942, v.  24.
            p. 295. — Q n a  s i e I J. H., T e n n e n b a u m M., W h e a t  1 e v, Biochem. J., 1936, v.  30
            0.  1068.
          Hygienic Evaluation of Dust from Vanadium Containing Slag
                                         pp.  23  - 29


                                       I.  V.  Roshchin
        (From the F.  F. Erisrnan Moscow Scientific Institute of Hygiene)
         Bessemer,  open hearth,  and blast furnaces yield considerable quanti-
ties  of slag.   Slag can be defined as a chemically inert fusion mass  of differ-
ent metal  oxides,  the composition of  which depends  upon the composition of
the original ore and  on the  smelting technology.  Slags are frequently re-
ferred to as  artificial minerals of great variety.  Many slags represent  con-
version products  which  are  used in additional future  reprocessing.  Slags  of
the ferrous  metalurgic industry have  found wide  application  in  the prepara-
tion  of-many building materials and as  base material in street and highway
road construction.   Some slags contain considerable amounts of phosphorous
and are finding increasingly wider application to soil fertilizers,  particularly
the open hearth slags.   Some Bessemer,  Thomas and open hearth slags  con-
tain  quantities  of  rare metals.   This  is particularly  true of  the  Bessemer  an-'

                                             - 287 -   .
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open hearth slags formed in processing pig iron obtained from the Ural
iron ores.  The latter contain titanium  and vanadium.  For the recovery of
the rare metals the slags must be crushed and ground to a very fine  powder
for the complete removal of the rare  metal.  The crushing and grinding is
usually conducted on a large scale, and it is natural that air susprnded dusl
be generated in concentrations  constituting a factor of occupational danger,
such as blast furnace slag dust, or open hearth furnace  slag dust,  the  factor
of primary hygienic importance is the presence of highly dispersed free and
combined silicon dioxide. On the other hand, in the case of  slags, the com-
position of which is chemically complex, and which contain considerable
quantities of highly toxic metallic oxides,  free and combined silicon  dioxide
is not the only  important factor from  the hygienic viewpoint; a special  and
broader study of the  toxic properties  of the  dust must be conducted,  due to
the presence of other toxic  metallic components, without which the deter-
mination of maximal concentration limits would be incomplete and ineffec-
tive .

       The  literature contains  reports  of foreign authors dealing with  the
effect of Thomas slag on the human organism (Thomas slag pneumonia)
due to the presence in such slag of phosphorus. Some investigators  studied
the pathogenic  role played by individual Bessemer slag components in  the
development of bronchitis and pneumonia.  However, all such  reports  lack
detailed descriptions of  the effect of metallic slags on the respiratory  organs
of the workers.  Therefore, the present author conducted industrial-hygienic
and experimental studies and also clinical observations  to determine the
mechanism  of action on  the organism  of dust from Bessemer slag, from
which vanadium is  extracted in the USSR.   The aim of the investigation was
to find means for workers'  protection against metallurgical occupational
diseases.

       The  technology of slag processing consists first  in crushing the large
lumps of fused slag by means of a heavy steel block; the slag pieces  thus
obtained are then crushed and  ground to a  fine powder by means of tubular
or ball-mill.   The slag powder is then  conveyed into rotating  furnaces, where
they are cinter oxidized in the presence of  NaCl at 900° . At this stage the
lower vanadium'oxides become converted to vanadium pentoxide forming
sodium  salts of vanadium, which are  easily water soluble and  can be extract-
ed from the powdered slag.  It is easily seen that considerable dust is  gener-
ated during  the breaking up, crushing, grinding, loading, conveying  and cin-
tering of the raw material.

       Air pollution  studies were conducted in 1949, 1962. In  1961, the air
dust concentrations were determined  by Yu.V.  Osipov.  At other times, dust
density determinations were made by  the city sanitary epidemiological sta-
tion.  Results  of 400 air sample analyses are  presented in Table 1.
Particular attention was centered on most frequently met concentrations
which constituted more than 50%.  The data show that dust concentrations

                                 - 288 -
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most frequently encountered at all production stages fluctuated within narrow
limits.  Processes  of cold slag breaking up were not organized as a unit, but
were widely scattered over  the plant; this seriously hampered  any attempt to
institute a centralized leak-proof enclosed dust removing system.


Table 1.


               Air dustiness and dust dispersion  at basic operations of slej
                                  processing
                  Production processes
                                            Minimal
m  of dust      I
   • - --, - -  •--•• ! .i of j.«r-
       Uccorrina. titles up
 Ma*i»al iooit fre-j to ijj, in
       | quently I diaraeter
        Slay crusting'• ..........
        Loading of crushed slag ......
        Unloading   ............
        Slag grinding ...........
        Slag mil I my to fioader ana magnetic
          separation ...........
        Calciniig of pondered slag  ....
        Leaching  .............
           These operations are done under one roof, other operations are done in differ-
       end ^remises.

This was true of the crushing and  grinding as well as of loading,  unloading,
conveyor transportation,  and of cleaning the working premises.   There were
other factors which enhanced the danger to the  workers' health,  such as pro-
longed intimate  exposure  to high concentrations of highly dispersed dust.
Results of chemical slag analyses are  shown in Table 2.
Table 2.
                XHMHieCKHfl COCT3B UIJlaKa (HO AaHHMM aHOJlHSOB 33  1958—1962 IT.)


Oxides


FeO

SiO2

VjO, (Computes as
Contents in I
Ground
charge
Mini-
mal
35,4

22,1

11,1
Ma«l-
•»'
37,1

25,6

12,9
CrjOs" <)-(l ; 1; -3
TiO,
MnO
A 1,0,

CaO
Other component
parts
6,7 | 7 7
3,7
2,21
0,8
0,75
1,9

5,8
4.0
1.6
1,4
3,2

Calcined
charge
Maxi-
mal
40,0

18,97

9,6
8.*"
5 8
3,07
2,66
0,72
0,85

M mi-
nt 1
48,4

22,4

11,8
9.52


Remarks


FeO converts to Fe_0, during calcin
ing f- 3
\ - 51 SiO^ is f0jnd in free stbte,
the remainder is bojnd
VjOj converts to NaVO^ after csilciri

7. -3,
5,D8
3,3
1,3
1,3




Is found oasically in the Fe com-
ponents

                                      - 289  -
-------
Data in the Table show that the slag dust contained oxides of vanadium,
chromium, manganese, etc. ,  all of which possessed well known toxic proper-
ties.  Dust concentration in .the air generally was considerable, yet,  no spe-
cific symptoms characteristic of each toxic dust components had been noted
in the workers probably due to the complex masking interaction between the
metallic oxides.  On the other hand, it should be remembered that hygienic
evaluation of dust and its standardization can not be based on the toxic proper-
ties of individual elements.

       Petrographic and roentgenostructural analyses of the slags made by
Ya. S. Umanskii, Ya. E. Samchuk,  A. Yu. Polyakov,  and V. T. Kolpakova
showed that vanadium was  present in the slag in the form of a trivalent
oxide.  The slag contained  approximately 67% of mineral spinel consisting
of iron,  chromium, and vanadium; 67% of the latter was in the form of
vanadium trioxide.  In addition,  the  spinel also contained oxides of aluminum
and of manganese.  No silicon was found in the mineral spinel. The iron, van-
adium   and chromium components were  firmly  embedded in the spinel
which prevented the components from acting as free oxides.  Silicon was
present  in the slag in the form of manganese, iron and calcium metasilica.te;
part of it was also in the form of fayalite.  The total amount of silicon diox-
ide in the slag ranged between 15-20%,  1-5% of which was in the  form of
tridymite, cristobalite, plus silicon in the form of silicon dioxide. During
cintering the mineral spinel oxidized to hematite and released pentavalent
vanadium; the latter possessed toxicologic potentialities, which were impart-
ed to the slag dust.  Chromium and manganese, together with some other
oxides, remained firmly bound and were unable to directly manifest their
toxicologic effects.

       Toxic  slag dust effects were  tested by administering intratracheally
50 mg of the dust to each of 20 white rats.  At intervals of 3, 6, 12 and 15
months rats had been sacrificed and their organs studied pathohistologically.
No clinical manifestations  of poisonous dust effects on the experimental
animals had been observed, and the  experimental and control rats gained
body weight steadily.  Autopsies showed only subpleural slag dust accumula-
tion.  Pathologic changes in the  respiratory organs appeared as serous-
desquamative bronchitis, enlarged lymphatic  folliculi,  and thickening of
the interalveolar septi as a result of round cell lymphoid and histiocyte  in-
filtration.  In addition, dust cell foci formed at the interalveolar septi and
the vessels.  There were also foci of epithelial cells and of coniophages
with phagocytized dust.  There were no giant cells and no signs  of narcosis
and no development of mature  fibrous  connective tissue.  However, many of
the animals developed concentrically distributed fibroblasts around the dust
accumulated foci, as shown in Fig.  1.   Van Gieson stained  sections showed
that the dust cell foci developed thickened interstitial tissue 6-15 months
after the intratracheal dust administration (see Fig.  2).  The dust cell  foci
appeared massive on the third month after the dust administration; their size
appeared somewhat reduced 12-15 months after the dust administration.
                                  -  290 -
-------
It appeared as though the amount of dust in the lungs  became redured,  but tin-
hardening of the inactive  tissue at the point of dust accumulation somcwhal
increased.  All histological sections  showed dust engulfing coniophages in
the bronchial lumens,  indicating that the dust  had  been systematically elim-
inated by the lungs.  Accumulations  of free and phagocytized dust  was noted
in the sectional lymphatic nodes.
 Fig. 1.
 Fig. 2.
   <
 Uuit-ce! 1 nadti in interalveolar tissue with con-
 centric*! ly distributed ficrobl»»ts in ao*e VJ»II
 nodes.  Tne rat *as sacrificed 3 months after the
 dust injection.  Magnif. b » a
Du-.t-cell node* in tht luigs «t points
of dust *ccu»jlat ion —indurated con-
nective tissue.  Hat n* sacrificed II
•onths after du*t  injection.
S « 8
        Detailed histologic investigation of pulmonary alveolar tissue fre-
quently showed alveoli in which the epithileum regenerated in the form of
glandular epithelium, probably as the result of prolonged chemical dust
action.  The coniophage  protoplasm showed signs of fatty infiltration, a
phenomenon which can be explained by the same fact as cited just above.
Thus,  the  slag  dust showed no clearly defined fibrogenic effects under ex-
perimental conditions; nevertheless,  it possessed the capacity to elicit
moderate development of productive changes.  Pneumoconiosis developed
on the basis of  chronic desquamative bronchitis.

        The slag dust affected the mucous membrane of the upper respiratory
tract.   This was shown by the  fact that among 45 workers  examined in the
clinic  hyperemia of the mucous membrane  of the upper respiratory tract
and hypertrophy of the nasal mucosa  appeared in all the  examined persons.
Subatrophic  rhinitis was noted in 11 workers of extensive employment records,
Nasal  mucous membrane erosion localized in the region of Locus kisselbachi
was  noted  in 10  workers  who had been in contact with slag  dust for 10 years
or longer.  In some,  the nasal mucous membrane  appeared bloody.  Some
workers exposed to the effects of cintered slag dust had perforation nasal
septi,  others had developed extensive scar tissue.  Thus,  results of the
                                   - 291  -
-------
investigation showed that the toxic properties of cintered slag dust were  more
pronounced. Nasal septi perforations may have been caused  by sodium vana-
date,  an assumption prompted by the occurrence  of perforated nasal septi in
several employees who worked with vanadium pentoxide; the perforations may
have also been caused by the chromium oxide contained in the dust in low con-
centrations. Chronic bronchitis was  found in 27 of 45 examined workers.
Practically all workers with a record of 5 years employment had  chronic
bronchitis.

       Clinical-roentgenological studies made by G. V.  Bulychev, V. B.
Usman, and by L.  M. Markova confirmed the conclusion arrived  at by the
present author that the investigated slag dust could be regarded as a conio-
sis causative agent.  Twenty-four of 45 examined  employees  with a work
record of more than 10 years showed  roentgenological changes; in ll of me
workers the changes were indicative of pneumoconiosis of I-II stage.  An
X-ray picture showed characteristic distribution of diffuse-sclerotic changes
over the entire pulmonary lobes, and other changes characteristic  of pneu-
moconiosis.   Unlike in silicosis, no extensive damage  was noted in the
lower  section of the lungs.   Enhanced and delineated pulmonary deformation
was seen  in 13 examined workers with 10 years or more  employment records;
this observation should be regarded as indicating the  possible presence  of
pneumoconiosis,  or early .manifestation of occupational pneumoconiosis.
Thus,  thorough observation  of the workers brought out the fact that prolong-
ed exposure to the  inhalation of slag dust elicited pneumoconiosis  which ap-
peared and developed on the  background of damaged mucous membrances  of
the upper respiratory tract complicated by the presence of chronic  bronchitis.
Pneumoconiosis belongs to the mixed diffuse sclerotic form of pulmonary
diseases. The roentgenological manifestations  of  slag dust pneumoconio-
sis simulated in some respects the general picture found in literature deal-
ing with silicosis,  but differed from it by the presence of damage  to the
upper  respiratory tract,  not generally observed in other types of  pneumo-
coniosis.

       Additional clinical investigations have been in process which might
elucidate  more profoundly the characteristics of slag dust  pne umonconiosis.
It was  shown that the changes enumerated above were well defined in persons
who had been exposed to the  inhalation of cintered slag dust,  and it  was  as-
sumed that the presence  of  free pentavalent  vanadium was the causative
agent.  It was also shown that general health conditions of  workers  coming
in contact with vanadium.-containing slag dust accorded with the data ob-
tained  in experiments  with animals.  Results of the present general investi-
gation  clearly indicated that  there was need for the determination  of maxi -
mal permissible concentration of Bessemer slag dust generated in process-
ing titano-magnetic ores  from the Ural Mountains. It was noted during the
investigation that the Bessemer slag dust containedlow free silicon dioxide
concentrations.  This, and other  observations and data,  led the present
author to  conclude  that the approach to the problem should be based not  only
on the  free SiO2 dust in the  air,  but that other factors should  also be taken
                                   -292 -
-------
 into consideration.  Measures adopted for the improvement in the production
. and processing tephnology are usually the most important factors in the pre-
 vention of dust disease.  In this  respect,  the  introduction of an integrated ^and
 leak-proof enclosed system in the slag grinding and calcining should be given
 primary consideration..  The  same.applies to . the conve'yor system "and to
.loading and unloading of the raw and. ground materials.'. 'Fused slag should  he
 delivered into the crushing machines, in smaller chunks •,  so that-the prelim-
 inary slag breaking up  by a heavy block could be completely eliminated.  All
 manual procedures should be replaced by .a'utpmatic,'ope rations .  Next in
 importance is the appropriate improvement in the • system of local and over-
 all ventilation.'    ,             .          .-"'";'     . ,.   \
           i             ,        :     -         '••           *
        Workers exposed to 'Bes:semer slag dust inhalation should  be manda-
vtorily examined clinically periodically arid systematically.  The examining
 board should consist of an otolaryhgologist,, a therapist,  a roentgenologist,
 and a general practitioner.  Only persons found free from-diseases  of the:
 respiratory tract and of the cardiovascular system should be-employed in
 work which includes  contact with vanadium containing slag dust. .

  .                 .            Conclusions
                                                  t>
    1.   It has been proven,  experimentally, that Bessemer slag dust formed
 in processing Ural titano-magnatites chronically inhaled in concentrations
 of 30-100 mg/m  or more,  may elicit pneumoconiosis.  Productive  changes
'developed only moderately and the process is a relatively benign one.  Pneu-
 moconiosis development is usually preceded by well defined changes in the
 mucous membrane  of the respiratory tract, and by chronic bronchitis eli-
 cited by  the slag dust.  The coexistence of moderate roentgenoiogical pneu-
 moconiosi's manifestations and of well defined damaged mucous membrane
 of the-upper respiratory tract, creates a picture of variable  subjective and
 objective systems which distinguished slag dust pneumoconiosis from other
 pneumoconiosis types.                     .

   2.  : Prevention of slag dust pneumoconiosis can be attained by  a  complex
 of special technical  sanitary hygienic and therapeutic-prophylactic measures.
      '    •        .
   3.   It is recommended that 4 mg/m3 of Bessemer slag dust be adopted
 as'its maximal concentration in the air.

                             Note from the Editor
        It is regretted that the-author failed to present data regarding the
 radioactivity of the investigated slag which lately had been regarded as
 one of'the important hygienic factors.

      ,  Bibliography next page.
 '  i ' •'     •'•'•/                 - 293 -
-------
                                 Bibliography
            K o n ii a u K H M M. A. CnJiHKaT03b!. M.—Jl., 1957 — P o m 11 H H. I}. B KII.: M;iTC'pu
        jiu 8-ii iiiiyiHofi CCCCHH  CBepjuioiicKuro mi-'ra riiniciiu rpyjia H npriipiruTp.ioniii.  lOIi.S.
        crp. III). — On we. Hn<}>opM. OKWW. MOCKOP.CK. nn-ra c.iiiirrapiiii n nmicnu, 1050, JV? 2-1,
        rp. fi',1. --  Klavis G., Kolcr H., Bister P., Arcli. f "n'wurliepjilli., (k-worlK-hyg..  I05ii.
        Bd. 14, S.  607. ~ S job erg S. G., Ada mecl. scand., 1050, Suppl. 238.
            A Method for the Determination of Industrial Aerosols
                      of Antimony and of Its Compounds
                                 pp. 50 - 54

                   G. A.  Gudzovskii. and G. G. Scherbakov
 (From the Department of Sanitary Hygiene of the Kirgiz Medical Institute)
        Existing methods for the determination of antimony proved inade-
quate for the study of atmospheric air pollution  made by the present authors
in the  surroundings of an antimony industrial combine, because such methods
were time consuming, cumbersome,  and inaccurate for the purpose at hand.
Therefore, the present authors investigated the  possibility of applying dia-
minotriphenylmethane dyes to the determination of metallic antimony and its
compounds in the air.  In 1927, Eegriwe proposed that small antimony quan-
tities should be determined by the rhodamine-B-reaction in the presence of
chloride ions.  V. I.  Kuznetsov made a thorough study of the reaction mech-
anism in 1947-1949 and replaced rhodamine-B with methylviolet which was
a considerable improvement in the procedure for the determination  of anti-
mony and its compounds.  Further improvements in the reaction were made
in 1956 by L. N. Lapin and V. O. Hein who replaced methylviolet with brilli-
ant green, a member of the basic diaminotriphenylmethane dyes.
The  pentavalent antimony ion (SbCls)  turned brilliant green solution  orange
in the presence of strong HC1.                               The authors
state that the chain of  reaction will proceed only in the presence  of HC1.
After the orange color has formed, a small amount of toluol, or  of its analo-
gues, is added and thoroughly shaken;  the toluol extracts  the newly formed
orange  colored antimony complex which acquires a bluish green color.   The
test  is highly sensitive and permits the determination of 0. 05y of the anti-
mony.  Any  other type of antimony ion must be converted first  to the SbCls
ion.   The Sb complex must be converted first to SbCl3, and then oxidized to
SbCls with the aid of strong HC1; in the  course  of this reaction the Sb com-
bines with the brilliant green ion to form a complex which is ultimately  con-
verted to a toluol blue complex.   Having made a series of check tests,  the
present authors recommend with confidence the  following method for the de-
termination  of aerosols  of antimony and its compounds:

        Aspirate the air  samples through cloth filter of trademark FPP-15
                                   -  294  -
-------
firmly held by a standard metallic filter device.  Aspirate  200-400 li; and
,whevn necessary 1 m3  of the air through the FPP-15 filter at the rate of 15-18
li/min.  Weigh the filter before and after aspiration of the  air, and determine
the amount of trapped aerosols contained in the air by the difference in the
two weights.  The air volume must.be  adjusted to normal pressure and tem-
perature.    Then place the filter inside a 100 ml Kjeldhal flask- containing
5 ml  of concentrated hydrochloric acid and 10 ml of sulfuric acid.  Heat  the
flask for about 15-20 minutes; the FPP-15 filter  will, turn into a small solid
round lump.  The double acid treatment has a dual purpose:  first,; the HC1
prevents the cloth filter from becoming digested  or charred by- the sulfuric
acid,  and second, the sulfuric acid enhances the  solution of the antimony and
reduces its loss during heating.   Two additional attempts were'made  to
treat  the FPP-15  filter with hot sulfuric7 acid without subsequent heating,
and with aqua regia which completely dissolves antimony.  The 3 methods-
produced approximately similar  results.

       Upon completion of the filter treatment cool the solution an'd transfer
to a 100 ml volumetric flask;  fill the flask to the 100 ml mark with a solu-
tion of 10% hydrochloric and 1% tartaric acid.  Rinse the Kjeldhal flask sever-
al times with some of this  solution and add the rinsings to the 100  ml volu-
metric flask.   The  FPP-15 filter residuals contain practically no antimony.
Depending upon the suspected concentration of antimony, place between 1-5
ml of the  solution into a 25  ml Erlenmeyer  flask for final reaction.. Add to
the Erlenmeyer flask 5 ml of  5 N hydrochloric acid solution and 0. 5 ml of.
1?0% tin chloride solution  in 5 N HC1.   Leave  the flask stand at room temper-
ature for  5 minutes then shake thoroughly at 1 minute intervals.  The penta-
valent antimony will  become reduced to trivalent; the trivalent antimony is
then converted to its pentavalent ion of Sb C15 by the addition of 0. 5 ml  of
N  sodium nitrite solution.

       Leave the flask stand for another 5 minutes, while free brown vapor
of nitrogen oxide  is given  off.  Carry, this step out under  a  chemical hood.
Decompose excess of sodium  nitrite by adding 1. 5 ml  of  10% urea in 5 N
hydrochloric acid.  In the presence of-nitrite excess shake  the flask for
about 3 -4 minute's.    The  reaction may be regarded as completed when
formation of oxygen nitrite bubbles discontinue.   Now,  a'dd  20 drops  of 1%
'aqueous-alcoholic solution of  brilliant  green.  Prepare the  dye by  dissolv-
ing-1 g of the substance in 25 ml  of ethanol over a water bath.  After the
dye has completely dissolved  make the volume up to 100 ml with  distilled
water.  Pour the  resulting orange-yellow solution into a separatory funnel
to which add 10  ml of toluol and  shake for 2-3  minutes.   If the solution  be-
comes colorless, add more of the dye  since it is essential that the dye be
present in the final product in an excess as shown by  the persistence  of the
yellowish-orange color in the  solution.  The separation can also be accom-
plished in test tubes.

       Where several such determinations are made simultaneously, the
                                  - 295 -  -
-------
separatory funnels can be suspended in a special rack as shown in the accom-
panying figure.  Complete separation into layers of toluol and water usually
requires 3-5 minutes.  Remove the  water phase and pour the bluish-green
toluol into test tubes containing a small quantity of disodium phosphate, for
the complete removal of any residual water.  Make colorimetric determina-
tions using photoelectriccolorimeter of trademark FEK-M, and colorimetric
cups containing 5  ml of the solution  and using a blue light filter.  One liter
of the standard solution should contain 0.2743  g of chemically pure  potassium
tartrate and 5 g of tartaric acid dissolved in 10% HC1 solution.  One ml of this
standard solution  should contain 100 Y of antimony. A graduated standard
curve can  be constructed by using 1  ml of this  standard solution according to
the generally adopted procedure.  Place the colored toluol into a series of
test tubes  in the following quantities: 0. 2,  0. 5, 1. 0,  1.5, 2. 0, and  2. 5  ml.
Add chemically pure toluol to make  10 ml in each tube and make final colori-
metric determinations.  The colorimetric scale should be equivalent to
2.0, 5.0,  10.0, 15.0, 20.0,  25. 0 fj. of antimony.  It should be pointed out
that in making  colorimetric  determinations of high antimony concentrations,
there may be a negative deviation from the Lambert-Beer law.  Where  the
antimony concentration is expected to be high appropriate dilutions  of the
original solution should be made first.  Sensitivity of the recommended
method is  9. 5 JU in 1 ml of the solution.

                                          The method described had been
                                      tested first under laboratory condi-
                                      tions, then under mining engineering
                                      conditions at the antimony combine.
                                     Series of check tests have been ap-
                                      propriately made. Results of deter-
                                      minations  made under above  describe;!
                                      conditions using cloth filter FPP-15
                                      are presented in Table 1.  Check tests
                                     •were made under industrial conditions
                                     using triple layer of filter FPP-15.
                                     Final determinations were  made  with
                                      each of  the filter  layers individually
                                      for the purpose of determining traces
                                      of possible slip-through.  Results arc
shown in Table 2.  Differences in the results of duplicate check tests ranged
between 10-15%.  The method is specific.  Arsenic did not interfere  with thv
determination of antimony.  Gold, gallium and  iron yielded similar reaction.
However,  these metals can  be  removed by the addition of urea used to re-
move excess of sodium nitrite.  As  shown above,  the method is highly sei.
tive, specific,  and accurate.  Therefore,  it is  recommended for use by in-
dustrial sanitarians during their air purity control examinations,  especialU
in the air of plants engaged  in the production or processing of antimony or
its compounds.  Laboratories which have no eleclrocolorimctc rs  us<  ;>  sivr.>
 of standard color  tubes prepared  as previously  described.
                                    - 296  -
A holder *-tn an •»senbly o< s*p*r«tory
     funnels r«»uj for *n«ly««s
-------
 Table 1.
                        &b determinations on cloth filter FPI--I5
Test
No.
1
2
3
4
5
6
7
a
9
10

Mg of Sb deposited on
filter
7,9
, 16, 0;
16,0
16,0
16,0
16,0
12,5
10,4
14,2
15,4
{, of average accuracy
Mg
8,1
16 ;0
14,0
15,0
14.7
14 2'
12.0
18,9
14,2
15,2

>b found
1
102,5
! 100,0
88.0
. 93 .8
92,0
88,8
96,0
97,4
100,0
98,7
95,7±2,1
 Table 2.
              Results of Sft determination an  FPP-li  cloth filters after
                               I 'JO I i of air at 15 li/nin.

Test
No .
1
2
3
4
5
•6
7
8



Metal lie
n
.11
H
An tin on/
n
An t i B on t
M


Suistance
So 	 	
\\
" . .
!!

n

ti

M
1st cloth
layer
3.0
9.(i
' 14 2
12.8
17,0
11 1
18 0
14,9

j f own d
2d cloth
layer
_
Trace
—
_..
Trace
	
Trace



3d rloth
layer
_
—
—
	
Trace
.
>
>

                                     Conclusions
                                                                                         /
         1.   A method is proposed for the determination of aerosol antimony
 and its compounds *-n the air using a basic dye  of the  diaminotriphenylmethane
 series.
         2,  Filter fab-ric FPP-15  retained  99.9% of the antimony and its  com-
pounds contained in-the aspirated air sample.

      .  . .1.  .The method is  precise, simple,  corn pa r;j.ti v:i y r :>-...'•.,  .,:.•: •••.-.  •.-
•-isoa i;-. making industrial  sanitary dete rminatior;s in  ?..-.-<:  ->.. r ',:' .,•,':-.•,.-  {,:•••••:
isos  by plant laboratories.
                                     •Bibliography
                   euOB  B. H.  >lv ana.'mr. XHMIIH, 1947,  B. 3, crp. 178. — On  >K t Vc
          XMMHM. 1949, B. I,  crp. 75 —/laiiHH-JI. H. Bonp. uen.. XHMHH, 1956. B. 4, crp. 309.—
       . .  .'I a n n i! fl. H, F e H n B. O. Tpyau KOMHCCHH no aHa.nnT»'iecKofi XHMHH. M., 1956, T. ~.
          cip. 217.
                                        - 297 -
-------
           Methods for Lowering Solvent Concentrations in the Air
                 of Plants Engaged in Dry Cleaning Clothes
                                pp. 71  - 73

           N.  V. Dmitrieva, A.  I. Dukhovnaya and I. S. Khazanov
         (From Moscow Central Institute of Post Graduate Medicine
                and the City Sanitary Epidemiological Station)
       Dry cleaning of every day and working clothes is being used more and
more extensively.   The present authors investigated the sanitary hygienic
conditions prevailing in 5 Moscow dry cleaning plants which used different
types of equipment.  The technological procedure  used in dry cleaning clothes
is generally as follows: (a) preliminary removal of unusually dirty spots;
(b) first step of dry cleaning with trichlorethylene or with perchlorethylene
in special wash drums,  (c) when necessary second removal  of persistent
dirty spots, (d) ironing. An examination of the  room in which the prelimin-
ary spot removal was done showed complete lack of standard equipment.
Preliminary spot removal and cleaning was done by spreading the clothes
over the usual type of ironing table; special tables for spot  removing were
seen in only one of the 5 examined plants.  For the removal of specially dirty-
spots, the following organic solvents  were used:  acetone, gasoline, benzene,
trichlorethylene, white spirits (a turpentine substitute). Spots are removed
as follows:  the suitable spot removing chemical  is applied to the spot manu-
ally with a saturated  cotton wad or saturated gauze.  The spot is  rubbed until
it disappears.  This is repeated using a clean solvent saturated cotton or
gauze wad.  This procedure of special spot removing was practiced in all
the 5  plants heavily polluting the air of the working premises at the level of
workers  breathing  solvent vapors.   Direct contact between  the solvent and
the skin is frequent under the above described conditions.  Trichlorethylene
vapor permeates the air of  other departments at  the time clothes  are delivered
from  one  department to another.  Results of air  analyses made in all the
plant's operating rooms verified this.

        Ventilation in some spot removing departments consisted of the  usual
mechanical systems which  exchanged the air 4-20 times. An exhaust fan usu-
ally installed  close to the ceiling  enhanced the ventilation of the work rooms.
Air analysis made in such rooms found an average trichlorethylene concen-
tration of 0. 04 mg/li and higher,  which is considerably above the adopted san-
itary hygienic maximum/ Thus, working conditions in the spot removing rooms
of the dry cleaning plants were highly unfavorable from the sanitary hygienic
viewpoint, due to the lack of efficient solvent vapor removing installations.
Vapor concentrations in the air of such rooms can be lowered to the pre-
scribed official level by installing ventilation equipment which would increase
the air exchange  rate.  It is suggested that manual spot removing as above
described be discontinued and that s ponge-stopper flasks be used instead of
saturated cotton or gauze wads.   In addition to remodeling the general ventila-

                                   - 298 -
-------
tion system,  local vapor exhaust devices should be installed close to workers
engaged in spot removal as above described.  Similar local vapor exhaust
devices  should be installed in other sanitarily strategic sections of dry clean-
ing plants.

        The final step of clothes dry cleaning is done in tightly 'dosed  revolv-
ing drums containing, trichlorethylene or perchlorethylene.. 'The operator
manually loads the revolving drum with 15-16 kg of .clothes,  .tightly closes
the drum and runs in the required amount of solvent through, a specially con-
nected inflow pet cock.  Each drum is connected via a closed communication
system with a distilling apparatus usually installed inside the operating  room,
arid with'a solvent supply tank installed outside the  operating room, from
which the required amount of solvent is  run into the cleaning drum once, a
month*   In the course of this month,  the solvent circulates via the above men-
tioned closed solvent distilling system.

       T-he worker who operates the clothes cleaning drum is stationed at
the control panel  and observes the dry cleaning process through an inspec-
tion-window.  A dry cleaning procedure  may last 20-90 minutes depending
upon the type of equipment used.   The operator generally loads and unloads
the rotating dry cleaning drum 3  to 10 times per working shift.  In the case
of drums SN-60 "Trilux" and "Spesima" the dry cleaned clothes are also
dried before being released.  The two mentioned machines are equipped
with exhaust ventilation devices which begin to operate automatically as  the
drum is  opened for unloading, and also when air is run into the drum during
the clothes drying operation.  Under such operation conditions the clothes
come out from the dry cleaning drum free of solvent and .have only a bare-
ly perceptible odor of trichlorethylene.  In the case of USA  dry cleaning ma-
chines the clothes drying and deodorizing is done in separate installations,
and the'operator unloads the solvent saturated clothes, loading them into
the revolving drying  drum  manually.  Air analysis made by different me-
thods indicated that trichlorethylene and perchlorethylene concentrations in
the air during unloading of clothes from the  different types of drying clean-
ing revolving drums  exceeded the maximal permissible limits; vapor con-
centrations  amounted to 0.15 mg/li in the air surrounding Czechoslovakia
built machines, 0. 08 mg/li in the air surrounding German built machines
and 0. 81 mg/li in the air surrounding American built machines.  The above
data represent averages of 98 air sample analyses.  The sanitary hygienic
conditions of air in dry cleaning plants equipped with American machines was
sanitarily the most unfavorable,  due to the fact that the drum had to be un-
loaded 10 times during  a single work shift,  resulting in the increase of tri-
chlorethylene or perchlorethylene vapor qoncentration in the air.

       Analyses made  of air samples collected at dry  cleaning plants  which
used different, equipment, and operated under  different technological condi-
tions  had been compared,  that is  effects of  different drying and airing peri-
dds. had been compared.  Results indicated that 30 minutes of clothes drying

                                    - 299 -
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 followed by 4 minute aeration created a trichlorethylene vapor concentra-
tion in the air at the time of unloading which was 100% above the trichlor-
ethylene vapor concentration resulting from a procedure of 40 minutes dry-
ing and 10 minutes  aeration.   Unorganized trichlorethylene air pollution was
a contributing air pollution factor.

       The general air exchange ventilation system in the working premises
under consideration ranged between 6 and 22 times per hour as compared
with the 13.5 times per  hour originally planned.  Exhaust fans operated at
the upper and lower air  levels with the final outlet close to the ceiling.  On
many occasions the air exchange rate was greater than the officially speci-
fied rate, ye{ results of air analysis indicated that frequently the solvent
vapor concentrations exceeded the prescribed maximal level.  This sug-
gested that in some of the plants considerable leakage from vapor of the
organic solvents came from the  equipment,  conduits, solvent pipes and from
dry cleaned clothes.  The amount of solvent vapor (trichlorethylene and per-
chlorethylene)  released into the air of working  premises  was estimated at
737 - 931  g/hr as compared with the originally planned  80-100  g/hr.  The
removal of such a large solvent  vapor volume from the air of working prem-
ises could be accomplished only with an air exchange rate of 284-233 times
per hour,  unattainable under  practical conditions and for technical reasons,
and also inadvisable for hygienic considerations.

                                Conclusions
       1.  Indoor air pollution with organic solvent vapors in dry cleaning
plants  constituted a hazard to the health of the workers.

       2.  The following air pollution sources were found in dry cleaning
plants:  open manual method of applying solvents in the spot removing de-
partment; non-observance of safety regulations,  primitive  and manual tech-
nological  procedures in loading and unloading the rotating cleaning drums,
unorganized leakage, etc.

       3.  The method used in  unloading dry cleaned clothes  from the solvent
containing drums constituted a  particularly hygienically unfavorable  condi-
tion.  Comparative evaluation  of equipment and  machines used showed that
highest solvent vapor air pollution was noted in  dry cleaning plants equipped
with USA machines.  Therefore, it is recommended that the use of Ameri-
can machines be  discontinued.

       4.  Prevention of air pollution with solvent vapors in dry cleaning
plants  can be attained by the following means: (a) strict adherence to most
advanced  technological defatting processes;  (b) elimination  of all leakage
sources,  especially in the pipes and conduits; (c) installation of a properly
planned up-to-date  overall ventilation system supplemented by the installa-
tion of local exhaust devices at points of workers  exposure to the inhalation

                                   - 300 -
-------
  of the solvent vapor polluted air.                 .

         5.  The present practice of manual spot removing from clothes in the
  open should  be  unconditionally prohibited, appropriate local exhaust ventila-
  tio'n devices  be installed; the rate  of. fresh air.infldw. should be increased.

        '6.  Employees of dry cleaning establishments should be examined
  periodically by industrial medical'personnel, arid persons  unfit'for such
  occupation should be replaced.     .   '           .•'••'•
   .Sanitization of Working Conditions in Chemical and Pharmaceutical Plants
                      which use Mercury as a Catalyzer
                                 pp. 73-76

                               M.  Z. G of man
   (From the I. M. Sechenov First M'oscow Order of Lenin Medical Institute)
         Metallic mercury and its  salts have been recently used as catalyzers
 in the  chemical and chemo-pharmaceutical industries.  During the past de-
 cade the chemical and chemo-pharmaceutical industries,  especially of the
 organosynthetic type, have been rapidly developing in the USSR.  The  tempo
 of such development will continue to progress,  and with it will increase  the
 use of metallic mercury and its compounds as catalyzers.

         The present author investigated the effect of mercury and its com-
 pounds as  catalyzers on working  conditions in the above mentioned manufac-
 turing industries*  This particular phase of labor hygiene and sanitation has
 not been studied adequately.  The aim of the present study was to determine
 the effect of mercury used as a catalyzer on >the air of working premises,  its
 absorption by wall,  ceiling and equipment  surfaces, and  to develop measures
 for the sanitary improvement of labor conditions in the above  mentioned in-
,* dustries.

         Mercury was determined  in the air, dust, and scraping samples  by
 the Polezhaev  colorimetric  method.  Hygienic investigations were conduct-
 ed at the "Akriquin" chemo-pharmaceutical plants producing promedol,  in
 which  the hydration process proceeded in the presence of mercury as  the
 catalyzer.  A survey of sanitary  working conditions prevailing in the produc-
 tion of promedol showed that mercury was one of the basic toxic  substances
 which  polluted the air of the working premises in which  successive technolo-
 gical chemical steps were accomplished.  Mercury concentration in the  in-
 door air exceeded its maximal  limit by 300-700%.   Analytical results  showed
 that mercury vapor was present not only in the  air of  the hydration room,

              .                       -  301 -
-------
where yellow oxide of mercury was used as the catalyzer,  but also in other
seemingly isolated work rooms in which other.types of production steps
have been carried out, such as cyclization and piperitone  vacuum distilla-
tion.  No mercury vapor was found in any of the work rooms in which chemi-
cal synthesis was completed.

       Mercury vapor was present in the air of the hydration room due to
imperfect hydration in which manual procedures were used in introducing
the mercury catalyzer and in other reaction phases, such as removing mer-
cury from the accumulation  wells, etc.  For this reason the hydration room
was equipped with a separate entrance which isolated it to a degree.  In the
opinion of the present writer,  the emulsified mercury salts  accumulated in
the reaction mass, and which were partially reduced to the metallic state, and
constituting the source of  air pollution in the cyclization and vacuum  distilla-
tion rooms,  which were separated from the hydration room  and from each
other.  Following the  completion  of the hydration process,  the emulsified
mercury salts failed to precipitate completely from the reaction mass.

       Observation  of the  residue formed in distilling off methanol from the
ketone mixture disclosed the presence of metallic mercury, indicating that
mercury was carried  over by the  reaction mass and by the incomplete pro-
ducts  of the nonprecipitated  salts  into the following technological  stages.
Thus, in the residues remaining after  piperitone extraction and vacuum dis-
tillation, metallic mercury was noted periodically.  This indicated that
emulsified mercury salts  present in the reaction mass became partially re-
duced to metallic mercury which was  carried over into the  succeeding tech-
nological stages; aided by  the ketone and solvent vapors contained in the
reaction mass,  the carried over mercury permeated through the  apparatus
doors and the flange couplings polluting the air of the working premises.
Mercury compounds,  or metallic  mercury,  could also  be carried  over by
the vapors of organic  solvents used in  processing the intermediary products
containing mercury  or mercury compounds.  Mercury  slurry  and distillation
residue are collected  in asphalt coated metallic drums and  are disposed  of
in the plant's dump.

       Results of laboratory ambient air  studies proved of  particular in-
terest from the hygienic viewpoint. Data of such a study are presented in
Table 1 which show that mercury vapor concentrations  in the air of the hydra-
tion,  cyclization,  and vacuum distillation rooms exceeded the maximal per-
missible concentration even hours after the reaction and distillations had
been discontinued, and the apparatus,  equipment,  and rooms had been thor-
oughly cleaned.  Mercury  vapor concentrations were higher in the air of the
cyclization and vacuum distillation than in the hydration room, which may have
been due to the fact  that no measures  for  the abatement of air pollution with
mercury  have been used in  this room, because mercury carry over by the
reaction had not been  suspected.  Thus,  it must be assumed that  pollution

                                    -  302 -
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 of indoor air"  with mercury vapor occurred during the noriope rational period
 as'a result of mercury desorption and evaporation from the building structur-
 al parts and from the  equipment and installation surfaces which became pol-
 luted with mercury during the operation of the production processes.
1 Table 1.
          Mercury vapor concentration in the a«r of production rouns of the proaeciol
                  partnent  6 - a months after aiscontinuatian of' tnc process
Points of air sample
col lection .
i

Cycle /at ion room ....
Vacuun distil latij'i rj^i

No. of
sara- •
pies
5
7
6
6
rag/nr of raorcury
v»;;or
Hini-
oai
0.007F
0.012
O.OQt.
N
(*»«•-'
oe 1
0,028
0 03
0,066
one f ot
Aver-
ago
0,01-1
0.022
0.026
mo
iurro'jndin 3 conditions
Exhaust ventilation o(.erbt-
ina
'Srs^br^^V^T5 at ""•
 Data presented in Table 2 show the degree to which the walls, ceiling,  and
 equipment artcfanstallation sufaces were  polluted with mercury.
 Table 2.
         Mercury polluted calls, cviljntj, ap^ar^tus and equipment surfaces after ,rocc.'.j-
                                iny »>as

Point of duct
sample col lee -
t ion
Hy a ra t i on
room



'
Cycl nation ' .
r (•om



Vacuum (list i 1 lo-
t i on room
Otner
roome
^ fl! Md of Hi} ir 100 3
o «
* .j.
1.0




9




6


5
of sample material
Mtni -
1,3




1,5




7,2

mcl
219




15




24 2

a '-•
46,5




7,4




l
.25
•o —
i. a
2 t
"S 0
14,4 11


None found
oc
a —
,0 0

Condi t ions under nhich polluted mate-rial
tae col lected and character of col lected
staples
Too oeeks after worn *as stup,;ee, 0«(
painted anrt Mastered «ai Is a.i, I .f,
epil 3 m above the flot,r. nhi t«- *ashtcl
ant! plastered ceil in., sections, Jil
p&intea apD«r « | so
ceiling tint tc— «a:-h.
' A/hi te— «ash from nails en a cc; line
It should be noted that mercury was found not only on the external coating
 surfaces, but penetrated through the entire depth o'f the  plastering,  as shown
 by the fact that 100 g of the wall plastering contained 1.3-5.1 mg of mercury.
                                      - 303 -
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At the same height from the floor, more mercury was found on the surface
of white washed than on the surface of oil painted walls.  The following sani-
tization measures were recommended by the present author and have been
adopted and executed by the plant managers:

        1. Surfaces of walls,  ceiling and equipment are to  be cleaned and
coated by a mercury nonpermeable paint.

        2.  The exhaust ventilation and fresh air intake systems are to be
rebuilt  in accordance with the latest principles of air ventilation for produc-
tion premises.  All work rooms  in which mercury or mercury compounds
were used should be equipped with individual local exhaust and fresh air in-
take ventilation systems.  Where required, the ventilation system should be
equipped with air conditioning apparatuses during the summer months.

        3.  Such apparatuses were placed in rooms where the production re-
action masses contained mercury.

        4.  Demercurization systems were installed throughout the  plant.

        5.  Based on the findings  presented in this  paper, official regulations,
applicable to the production of promedol, have been revised, and new regula-
tions and technological instructions have been issued.  Final sanitary inspec-
tion of the plant showed marked improvement in the sanitary condition of the
air in the plant's different processing rooms.  It was also  recommended, as
a final thought,  that special filters be installed for the trapping of mercury
vapor discharged by the plant into the air.

                               Conclusions
       1.  Mercury vapor was found in the air of production rooms of the
chemo-pharmaceutical industry producing synthetic drugs, and of the chemi-
cal industry producing technical organic synthetic  substances.

       2,  The presence of mercury vapor was not limited to the air of work
rooms in which metallic mercury or its compounds have been used as cataly-
zers, but also in the air of rooms assigned to the processing successive pro-
duction phases,  as a carry-over by the reaction mass, or by the  intermedi-
ary half-products.  In making sanitary evaluations of such plants this fact
should be taken into consideration; it should also play an important part in
making sanitary inspections of industrial production plants in which mer-
cury and its compounds are used as catalyzers.

       3.  Mercury desorption from walls, ceiling,  surfaces of equipment,
etc.  should be regarded as  a  significant factor in air contamination with mer-
cury vapor in processing  rooms of such production industries.  Coating aU
surfaces, including those of equipment, with  a mercury vapor nonpermeab  •

                                   - 304 -
-------
 varnish or paint will markedly reduce the amount of adsorbed and permeated
•mexcury vapor,  the concentrations of which will be still further reduced by
 the introduction  of demercurization of the working premises.

        4.  In planning new, or reconstructing and renovating previously
 existing industrial premises of the type  under consideration^ the location
 of technological  processes should be arranged so as to reduce  to a minimum
 air pollution with mercury vapor.  Manual operations should b'e automated.

        5.  All production processes which used mercuric compounds as
 catalyzers, and  all associated production states,  must be evaluated from
 the sanitary hygie,nic  viewpoint as industries which employ, mercury and
 which must comply with corresponding sanitary specifications.
               Biogeochemical Problems in Radiation Hygiene
                                pp. 81 - 86

           V.  V.  Koval'kii, V. I. Baranov, and V. E. Sinel'nikov
     (From the Institute of Geochemistry and Analytical Chemistry of the
     USSR Academy of Sciences and from the Institute of Medical Radiol-
                ogy of the USSR Academy of Medical Sciences)
        The level of radioactivity has been constantly rising in the environ-
ment due to the dispersion of nuclear explosion products and atomic in-
dustry waste products.  This raises the need for the determination of possi-
ble consequences to future generations  if the  rise in atmospheric radioac-
tivity should continue.  It becomes necessary to ascertain the nature of
somatic .changes which such a rise in atmospheric radioactivity level may
elicit in man of the present generation.  Scientists differ in their opinions
regarding the active  microdose of ionized radiation on the organism.  E, S,
London in 1920, Yu.  V. Sivintsev in 1950 and other investigators  expressed
the opinion that a natural  radioactivity  level is essential to the  normal de-
velopment of the animal   organism, in  support of which they point to the  part
played by radioactive substances in protein synthesis,  carbohydrate metabol-
ism,  and in the processes of growth and  proliferation. Opposed to that is
a group of other scientists, predominately geneticists,who believe that any
dose of ionized radiation was harmful.  Results of experiments  with animals
exposed to known ionized  radiation levels under experimental conditions
should not be used as a basis for the correct  evaluation of future conse-
quences,  nor should  they  be used as a basis  for the interpretation of possi-
ble results on  humans.  The number of observations thus far made on human
beings in radioactive polluted regions is too small and of too short duration


                                     -  305 -
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to be used as bases for the determination of a. safe radioactive microdose,
and for the determination of future consequences.

       A possible means for the solution of this problem is presented by or-
ganized observations in regions of abnormal natural radioactive backgrounds,
where man had been subjected to the effects of high level radiation for  many
generations, and where, as a result,  definite  somatic and genetic changes
have accumulated.   In this  connection, V. I. Vernadskii initiated a science
known as biogeochemistry, an original branch of geochemistry and biology
which analyzes the role played by organisms in the migration of chemical
elements in the external milieu, and of the effects which such  elements had
on the adoptive chemical or morphological changes in plants, animals and
humans.  In the words  of V. I.  Vernadskii,  organisms did not exist outside
the sphere of the earth's crust effects.  It is possible to delineate territories
over the earth's surface characterized by high or low content of natural radio-
active substances.   A.  P.  Vinogradov designated as "biogeochemical provin-
ces" regions characterized by a high  or inadequate content of naturally  radio-
active substances,  or by other chemical  elements which brought about  reac-
tions in the organism by their excess, or inadequacy. It is possible to  speak
of uranium, thorium, radon  biogeochemical provinces,  depending upon the
element present in the province in quantities sufficient to produce biologic
effects.  However, the  question of radioactive background effect on the  health
of a  population must be examined more profoundly and not on the limited re-
gional basis of known biological effects,  since the latter may frequently be
of an occult nonspecific character.  Thus,  the hygienic problem regarding
the remote consequences of radioactivity and the problem of maximal per-
missible radioactive element concentrations in the external environment be-
come intimately bound to the problem of  biogeochemical provinces.

       It has been  known that Y radiation emanating from soils into the  ex-
ternal environment, water  radioactivity and radioactivity emanating  from
other substances into the external medium in some territories was 5-10
times in excess of  the usual radiation emanation, and in some  instances ex-
ceeded the maximal permissible radiation level.  Studies devoted to  the de-
termination of uranium and radium contents in natural waters  of some  re-
gions indicated that the concentration  of such elements fluctuated widely de-
pending upon the  regional geologic characteristic of the locality, and also de-
pending upon the  general geodimatic  characteristics  of the region.  States
of Travankur-kochin and Kerala on the eastern and western shores of India
can serve as classical examples of extensive provinces,  the territory of
which is richly covered with placer deposits of monazite  sand; the monazite'
contained 5-11% of thorium and 0. 2-0.46% of uranium oxide and peroxide.
Natural radioactive substances  such as uranium, radium, thorium and others
belong to the class  of rare  metals and organic formations.  The natural ra-
dioactive effects  under  which the native population had lived  for many cen-
turies,  and the short duration effect of the  natural radioactivity on persons
of relatively brief residence and persons coming from regions of biogeochTH-

                                   -  306 -
-------
 ical provinces having a high radioactivity background offer the  possibility of
.establishing conditions  and degrees of adaptation to a given level of radioac-
 tive background.

        Of particular interest are biogeochemical provinces in which the con-
 tent of uranium  in sources  of drinking water exceeded 5 X10~5 'g/li; and in the
 soil exceeded  1 x 10" %,   and where the radium content in drinking water ex-
 ceeded 5 x  10    g/li.   The average Y radiation background of the central
 Soviet Union strip amounted to 8-15 m curie/hr. . The level of the .general at-
 mospheric Y background in territories of radioactive biogeochemical provin-
 ces is 3-4 times greater,  and in some regions reaches the level of 50-70
 m curie/hr, and even higher.  If the uranium content in source's of water
 supply of the Soviet Union black soil region is estimated as n x 10~G  g/li,  and
 its contents in the soil at n x 10 5%,  then it becomes clear that persons re-
 siding in the territories of radioactive biogeochemical provinces  are continu-
 ously  exposed, generation after generation, to the effects of radiation levels
 the dose of which per critical  organ is several times, and in  some instances
 10 times, in excess of the  usual level.   The reason for  this is in the follow-
 ing: as the uranium level of the  environment rises, the content of other ele-
 ments, which are  offshoots of uranium radioactivity, also rises.  That is,
 the content of radon  and its decomposition products  rises in the indoor air.
 Simultaneously,  the  soil Y emanation along with that of  natural  rocks and
 construction materials  also rises.  Therefore, under conditions  of radio-
 active biogeochemical provinces, determination of uranium is not the only
 factor of importance, but also the determination of polonium, radium, radon,
 and other elements of the uranium-radon family.   All these elerrents in their
 totality determined the  radioactive radiation dose to which the organism was
 exposed under existing  conditions.

        The science of biogeochemistry rests on the concept of  trace element
 migration in the system "water-soil-vegetables-animal organism-man".  This
 constitutes a unique  system in -which the significance of any individual  com-
 ponent can be understood only in connection with the other links of the  migra-
 tion chain.  This system has now been generally accepted in radiation  hygiene.
 In making recommendations for studies of an external environment, USSR hy-
 gienists emphasize the  necessity of investigating all biosphere  elements  and a
 determination of the  nutritional migration chains of  radioactive substances
 from the environment into the  human organism.

        The special branch of ecology,  known as geochemical  ecology,  repre-
 sents the development of biochemistry which attempts to elucidate the  inter-
 relation between organisms and geochemical environment under different
 biogeochemical conditions,  as was indicated by V. V. Koval'skii in 1958 and
 1962.  It has been established that organisms, including microorganisms,
 were capable of  adaptating to different trace elements existing in  the envi-
 ronment, such as a fall or rise in the concentration of cobalt, iodine,  copper,
 molybdenum, boron, nickel, strontium,  and lead.'  Such changes are usual-

                                   - 307 -                    '       •
-------
ly accompanied by specific changes in the metabolic role played by any spe-
cific geochemical factor, as for instance, the effect of cobalt on the synthe-
sis of vitamin Bia,  or the effect of molybdenum on the synthesis of xanthine
oxidase, etc.  Geochemical ecology acquires practical significance in its
application in radiation hygiene.  It shows that the explanation of radiochemi-
cal connection between the  radioactive environment and man presupposes the
determination of the radioactive substances distribution in the organs and
tissues under conditions prevailing in different biochemical provinces.  Such
an explanation will lead to the determination of interconnection between na-
tural radioactive elements  and such stable elements as strontium, calcium,
cobalt  and iron.  The  contents of such elements in the external environment
and in  the  organism are interrelated.  It is  essential that a study be made  of
functional  changes in those organs and systems, tissues and cellular  or-
ganella such as nuclei, mitochondria,  which concentrate the given element
within  themselves.  It becomes necessary  to determine with the aid of
metabolic  experiments the  individual balance of the natural radioactive sub-
stances in different groups of  residents living under conditions  of high and
low radiation.

       Up to the present,  effects on the organism of isolated external en-
vironmental factors had been explained, or  studied,  by classical hygienic
methods,  such as clinical and sanitary statistical studies, physiological ex-
periments, etc.   With the development of the  concept discussed above, new
methods developed by geochemical ecologists have been added to the old
classical procedures. Investigations  by methods of geochemical ecology in-
clude fine  analyses of radioactive substances distribution in different sec-
tions of the same tissue and in individual biological entities, such as  enzymes,
hormones, vitamins,  etc.  Such investigational procedures result in the ac-
cumulation of materials  on the basis of which it becomes possible to evaluate
the physiological characteristics inherent in radioactive elements and their
elimination from the organism in combination with stable elements.   For in-
stance, the present authors have been able to show that uranium accumulated
more in the erythrocytes than in the leucocytes, and that its specific  concen-
tration in bile was greater  than in urine.  In this way,  different branches of
science using existing procedures and methods, and approaching a problem
from different angles, reached a solution  for the same leading problem.

       At  the same  time, it must be realized that the  radioactive background
of any  biogeochemical province was complex consisting of many components.
The background determined by natural radioactive elements  such as uranium,
thorium, and calcium can be augmented by atmospheric fallout activity and by-
products of nuclear  tests and of the atomic industry disseminated over the
earth's surface.  Effect of  man on the  redistribution of radioactive  sub-
stances in nature is of considerable interest from the  viewpoint of overall ef-
fect of the  artificially  changed environmental  radioactive medium  on the
human organism.

                                   - 308 -
-------
       V.  I. Vernadskii calls man-changed biosphere "noosphere".  Changes
effected  by industry in the earth's natural radioactive background present an
example of man's influence on the earth's evolution. Under such conditions,
new regions  arise which can be regarded as artificial radioactive biogeo-
chemical provinces.   These come into being by man bringing to the surface
natural radioactive minerals  and organic compounds which are gradually de-
composed  through geochemical oxidation and other weathering factors and
become converted into mobile substances. Such regions may develop in the
proximity  of radioactive element sources, such as mines,  resulting in the
accumulation of radioactive waste products.  Radioactive element dissemina.-
tion from points of waste product accumulation results from the presence of
geochemical factors and of living organisms.   The participation of living or-
ganisms in the redistribution of radioactive waste products is closely connect-
ed with the formation  of the previously mentioned nutrition chains, which dif-
fer specifically in the soil, fresh water,  or in the seas.

       Geochemists in association with hygienists  must first concretely in-
vestigate the forms  of chemical compounds which make  up  the naturally radi-
oactive substances  present in individual objects of the environment;  they
obtain a  clear picture of their mobility and the part they played in geochemi-
cal processes.  For example, the different migration of compounds belong-
ing to humic substances with the mineral soil layers has now been well es-
tablished;  it  is known  that organic acids  eliminated by plants' root systems
played an important part j.n the migration of chemical elements.  Organic
a'cids eliminated by  plants' root systems  combined with  trace elements pre-
sent in the soil to form complex compounds,  the character of which depended
upon the  ratio existing between the acids  and the trace elements.  The degree
of trace  element assimilation by the plants depended upon such ratios.  For
this reason,  the rate of radioactive element migration from the  soil into
plants differed with  the character  of the  metal-organic complex  which  acted
as the recipient of the radioactive element.  Uranium formed firm complex
compounds with organic substances in the soil,  and,  as  a consequence, may
accumulate in the  soil in high concentrations in the course  of time.

       Distribution  of radioactive elements over territories of non-natural
biogeochemical provinces  usually  resulted from changes introduced by  geo-
logical explorations, mining, and  radio chemical industries.  Radiation
hygiene is  basically concerned with such artificially created radioactive ele-
ments distribution.  Basically, such artificial  distribution  of radiochemicai
elements follows the laws  discovered by biogeochetnists, although in in-
dividual  cases there may be characteristics specific to local environmental
conditions.  Best results can be obtained by investigating the problem of
biogeochemical provinces  through cooperative  studies of hygienists and bio-
geochemists. Radiation hygienists delineate territories  of artificial  biogeo-
chemical provinces which resulted from environment pollution by radioac-
tive by-products.  Chemical reagents and technologiqal  impurity admixtures,
together  with changes  in the aggregate state of the by-products can and do

                                  - 309 -
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affect the migration conditions in the external environment.  The study of
natural and artificial radioactive biogeochemical provinces must bring into
light the following data on which to base rational conclusions and practical
recommendations:  (l) information on the concrete content of individual radio-
active elements in the entire factor complex in the external environment of
the investigated territory; (2) specific biological effects elicited by enhanced
radioactive background in microorganisms,  plants, animals, and man; (3) the
specific fodder and nutrition changes under actual environmental conditions;
(4) information relative  to the internal distribution and accumulation of natur-
al radioactive substances in the  organs, tissues and cellular organella; (5)
computed doses of internal radiation used in connection with metabolic ex-
periments,  as shown by survival and postmortem radioactivity analyses of
the experimental animals' internal organs; computed doses of internal oi-
radiators concentrated in topographically delineated diffcr'cui.la.l LlooUe-and
cell sections, such as nuclei, mitochondria,  chloroplasts,  etc.; (6) medical
examination and statistically processed mortality data,  birth and morbidity
rates, anthropometric measurements,  and results of special physiological
and immunological tests.  Field studies of biogeochemical provinces must
make extensive use of topographical maps on 1:100,000 or 1:500,000 scale,
as well as geological, soil,  hydrological, geobotanical, and other large scale
local maps, outlines, or plans.  The  investigation should also include  de-
tailed descriptions  of landscape differences between the investigated and the
control regions, differences in their water regimes, in types of industries,
and in the population's living conditions.  The investigators  should  outline
courses for province investigations, which should, by necessity, include
most typical regions.  Soil samples should be collected by the  pocket-profile
method within the confines of the  micro- and mezzo- relief of the locality,
in pasture lands, in arable lands,  and in hay growing fields.  Soil samples
should be collected from special drilled wells and soil  dugouts.  More de-
tailed investigations should be conducted at  points of highest exposed radio-
active element concentrations.  Plant and vegetation samples should be col-
lected at known typical sections,  with particular reference to morophologi-
cal variability, appearance of deformed specimens and endemic species, time
and character of development according to vegetation stages.  A connection
should be established between the radioactivity in the external environment
and specific changes in the plants' metabolic processes resulting from adapta-
tion to the new environment,  or produced by pathological reactions. Reac-
tion to geochemical factors is usually less clearly expressed in man than in
animals, because social conditions lessen the effect of geochemical factors on
the living process.  For this reason,  the  direct effect of radiation on humans
can be noticed more easily among the rural population, which depended pre-
dominantly  on their own agricultural food products. The organism's adapta-
tion to different radiation conditions should be studied on a comparative basis.

        Data found in the literature on boron, cobalt, and copper in biogeo-
chemical provinces may be of aid in solving individual  specific questions re-
lated to the organization of hygienic studies in a radiation region.   In studying

                                  - 310 -
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the effect of radiation backgrounds on the population's health,  attention
should be centered  on the human organism; this has  not been done in the
usual biogeochemical investigations. Lately, biogeochemists accumulated
some experience from studies of element concentrations in different tissues
in the course of a life circle.  It has been known for some time that a specif-
ic hair protein easily bound and concentrated different trace elements.  Life
studies  can also be made with teeth obtained from stomatological and surgi-
cal clinics, as well as with urine and feces.  Such studies might present
data on the  accumulation of radioactive  substances  inside organs  and tissues
of men and  would  make possible a correlative evaluation between radioac-
tivity of external environment and similar data obtained in the study of man's
internal radiation.  In this connection, information supplied by section
studies  of radioactive organs might prove of considerable value.  Investiga-
tions conducted in provinces of thorium, radium, and uranium must include
determinations of radioactivity in the bones and parenchymal   organs;
similar determinations should be centered on the blood and expired air in
radon provinces.

       Studies of  biogeochemical provinces must aim at the development of
complete series of practical measures for the sanitary protection of nature,
specifically rivers, lakes and seas with particular reference to fishing,  to
the utilization  of algae,  seaweeds,  and  other fresh water and sea water or-
ganisms.  Such complex protective means must be  based on the principle  of
prophylaxis with regard to the effect of  high ionized radiation doses on the •
general population; it must include not only industries engaged in mining
radioactive  minerals but coal, nonferrous and rare metals,  fuel materials,
and construction materials,  because such substances are frequently asso-
ciated with  radioactive minerals and other substances. The possibility of
local rise in external environmental Y radiation, an increase in the concen-1
trations of radon in the atmospheric and indoor  air must be taken into con-
sideration in planning and constructing residential areas and in planning
water supply systems in localities where the water radon concentration a-
mounted to  hundreds of emans.  The radon factor played an important  role
in occupational therapy not only of miners engaged  in the  recovery of radio-
active minerals,  but also in  miners employed in the ordinary mines.  Radon
can accumulate in  the air in concentrations exceeding the permissible maxi-
mum in poorly ventilated mines not connected with  the radioactive elements.
Radon enhanced the development of silicosis in miners.  The amount of
radioactive  substances entering the organism can be  reduced considerably
by boiling,  technological treatment during grain  milling,  bread baking,
meat packing,  dairy products processing, etc.  Through the selection of
special  technical cultures, medicaments or edible vegetables and plants,
it may be possible to arrive  at a crop rotation and agricultural field working
system  under which the high content of naturally radiated substances con-
tained in the soil and in irrigation water would be retained to a lesser de-
gree by the  human or animal organism.

                                  -  311  -
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        Radioactive elements present in mining and industrial products  fre-
 quently transported over long distances contaminated territories  which had no
 detectable natural connection with geochemical provinces.  In this way new
 migration paths  come into being which hygienists must place under control.
 The biogeochemical concept  of "noosphere" viewed from a biogeochemical
 angle makes possible to investigate the role played by man and industrial
 pro'gress  in the rise of new foci and  zones of enhanced radioactivity,  and of
 their effect on the organism.  Therefore,  a study of  biogeochemical behavior
 or radioactive substances under "noosphere" conditions should be regarded
 regarded  as a most important problem in radiation hygiene.

                                  Bibliography
              BcpiiaflCKtifi B. H. BiioreoxHMimecKHe cwepKH, 1922—1932. M.~-Jl., 1940. — B n
                  B A. I~I. Tpyaw lofJH.icftHoft CCCCIIH AH CCCP, nocnniu. 100-Jicrmo co aim pow-
          ACHHH B. B, floxyiaeua. M.—/I,,  1949, crp. 59. — Ko B a n i, c K H H R. B.  Hoeue  tianpao
               n aaaa'iH 6no;iarn'iecKOH XHMIIH  ce.nbcKoxo3nftcTBcnnhix WMBOTHUX  B CBHSH c iny
                tiiinrooxHMii'irc-Ktix npoBiwuHrt. M.,  1957.  — On >K c.  (pea.)  MnKpo9.neMeHTbi u
                     c. M., I9(i2, ctp. 5. — 0 H « e. Me>Kflynapoflii. c/x >K., 1962, Ns 4, crp.70.—
          Jl on a OH E.  C. BCCTH. peinreHOJi., 1920, T. 1. B. 1—2, crp. 37. — Flepeae^bCKHfl
          A.  A. HTOPH HayKH. Biio^onmecKiie HayKH,  1957,  B.  I, crp. 379. — PaanauHOHHaq rurHe-
          na. M., 1962,  T. 2.—CHBHHUGB K). B. OOHOBOC  ofwiyieHHe le^ooeMecKoro  npraHn.iMa.
          M., 1960. — Mapefl A. H. CaHHTapHaa oxpaHa  otupbirbix BOAOCMOB or sarpasHenHH pa-
                     BcmecreaMii. M., 1958.
           The Problem of Sanitary Protection of Atmospheric Air
                                   in the USA
                                   pp.  87 - 96

       N.  F. Izmerov,  Chief State Sanitary Inspector,  RSFSR Deputy
        Minister of Health and Leader of the Visiting Group, and M. K.
       Nedogibchenko,  Chief State Sanitary Inspector of the Main State
               Sanitary Inspection of the USSR Ministry of Health
        Early in 1963 Soviet specialists in the  field of sanitary protection of
atmospheric air visited the USA in accordance -with cultural and scientific
exchange agreements between the  USSR and the USA.  USA specialists in
different phases of air pollution visited the USSR in September-October of
1962.  The visit of the USSR group was in the  spirit of reciprocal  courtesy.
The visiting group included Professor  D.N. Kalyuzhnyi,  Director of the
Ukrainian Institute of Community  Hygiene, Candidate of Medical Sciences,
O.  P. Shalamberidze, Deputy Director of the Research Department of the
Sanitary Hygienic Research Institute of the Georgian SSR Ministry of  Health,
and the  authors of the  present report.  During the  30 days the group spent in
the USA they visited 10 cities, which presented them with the opportunity to

                                      - 312 -
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 become acquainted with activities of more than 30 scientific research centers,
 laboratories, universities,  departments and bureaus engaged in the  study of
 .problems in the field of air pollution.

        Making laws regulating the sanitary  protection of atmospheric air in
 the USA is not a function of the Federal government. Such a function is
 within the immediate jurisdiction of each state.  Planned and directed work
 'in the field  of atmospheric air protection began in 1955,  after the U.S.
 Congress became aware of the need to investigate and study the causes  of
 atmospheric air pollution,  to  offer assistance  to the industry in work on this
 problem and in training pertinent technical and scientific personnel.  A
"special study was made in 1955, the results  of which indicated that atmos-
 pheric air pollution was found in 9500  populated localities  in the  USA.  The
 same year the Federal Government appropriated  five million dollars for the
 purpose of investigating the extent of the atmospheric air pollution problem,
 :.a P.H.S.  Division for the study of air pollution was organized at the Robert
 A. Taft Engineering Center in Cincinnati,  Ohio.  Work in  atmospheric air
 protection against pollution was conducted in 15 of the 50 USA states; these
 states  had adopted legal codes for the  protection of atmospheric  air.  Laws
 for the protection of atmospheric  air have also been adopted independently
 by some individual municipalities.

        Law-making in the USA can be divided  into two basic categories:
 a) punitive laws, designed to eliminate atmospheric air  pollution by  way of
 penalizing those guilty of discharging polluting substances into the atmos-
 pheric air; and b) regulatory laws, the purpose of which is to lessen the
 intensity of atmospheric air pollution by precluding the discharge of pollu-
 tants into the atmospheric air.  State laws,  as a rule, assign the responsi-
 bility for  compliance with the  laws to districts or cities.  Thus,  in the state
 of California a law is in force which creates special "districts" for the  con-
 trol of atmospheric air  pollution within different state regions; such "dis-
 tricts" existed in vicinities  surrounding Los Angeles and Santa Clara.   Dis-
 charge of "heavy smoke" (No. 2 by the Ringelman scale) in the state of
 California is limited to  3 minutes per  hour.  Regulations enacted in  Los
 Angeles in 1948 specify  that fly-ash concentration in smoke containing 12 7o of
 CO2  must not exceed 0.4 grains per m3, or the equivalent of 0.92 g/m3 .
 Maximal allowable limits have also been set for fly-ash or smoke discharged
 by industrial plants.  The standard limits are:  0.11 kg/hr at production rate
 using an average of 22.68 tons/hr of raw material to 18.4  kg/hr  at produc-
 tion rate using an average of 27. 216 T/hr of raw material.

        A  "smoke alarm system was instituted in  California in June 1955,  the
 purpose of which was to forestall excessive  accumulation of pollutants in the
 atmospheric air and to avoid catastrophic  results from high concentrations
 of toxic substances in the air  (Merril,  1956).  The Table below lists concen-
 trations of harmful substances calling for  signals or alarms of caution,
 alert,  and danger.
                                     -  313 -
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                                             Max.  allowable con-
                                       	centrations in ppm.
             Substances                Caution   Alert   Danger

           Oxides of nitrogen             3         5       10
           Ozone                         0.5       1        1.5
           Sulfuric anhydride             3         5       10
           Carbon monoxide             100       200      300

       Alarm No. 1 is  sounded when carbon monoxide concentration in the
atmosphere exceeded 100 parts per million, nitrogen oxides 3 parts per
million,  oxides of sulfur  3 parts per million,  and ozone 0.5 parts per mil-
lion.  Alarms Nos. 2 and 3 are sounded when these  gases reach concentra-
tions  exceeding the above indicated limits correspondingly by 50 to  100
percent.  These indexes  are  characterized as follows: alarm No. 1  indicated
merely an approach to  the maximal allowable concentrations which  consti-
tuted  no immediate danger to the population but were gradually  approaching
the danger levels.  Thus, alarm No. 1 called for the immediate adoption of
preventive measures; alarm No. 2 warned that the concentration level of an
atmospheric air pollutant or  pollutants constituted a health  hazard (alert
stage); alarm No. 3 sounded when the concentration of the air pollutant con-
stituted a positive health  hazard.  Alarm No.  1 was  in essence a call to
voluntary curtailment in non-essential automobile traffic and a  taboo sound
against certain  types of trash burning.  Alarm No. 2 covered items mention-
ed under alarm No.  1,  and, in addition, called for a stricter curtailment in
automobile traffic and for halting the operation of certain specified  indus-
trial production processes.  Regulation instructions advise  that realization
of the purpose of atmospheric air pollution protection,  as called for by
alarm No. 2,  must be accomplished as much as possible without resorting
to unduly  harsh measures which might upset the normal course  of local
economic life,  or cause financial loss to some branch of local industry or
trade. The sound of  alarm No. 3 called for action indicated by  alarms No.  1
and No. 2 and in addition, the Governor of the State could declare a state  of
emergency, giving the  proper authorities the right to effectuate preventive
measures stipulated by the laws in catastrophies. Data presented in the pre-
ceding Table show that the maximal allowable limits adopted in  the State of
California for the protection of atmospheric air  and which called for the
sounding of Alarm 1 were 19 times  as high as the corresponding allowable
concentration limits adopted in the USSR.   As stated previously in this re-
port,  discharge into the atmospheric air of smoke the density of which
exceeded  2 Ringelman units for 3 or more minutes per  hour was forbidden.
Sulfur compounds could be discharged into the air in concentration not
exceeding 0. 2% by volume.   Depending upon the  amount of fuel used, the
maximal discharge of dust or fly-ash  could not exceed 18 kg/hr.

       "Thick"  or "heavy"  smoke was defined in Pittsburgh as  smoke of 2
Ringelman unit  density.  The use of fuel containing more than 20% of vola-

                                   - 314 -
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 tile substances was allowed in Pittsburgh only where the fuel burning cham-
 bers were of the complete smokeless combustion type.  The regulations
 also prescribed conditions for the discharge of soot,  ash, harmful gases,
 vapors and fly-ash.  Locomotives had to use hard smokeless fuel,  or they
 had to be equipped with smokeless complete combustion type of fuel burners;
•'the1 discharge of "thick" or "heavy"  smoke by locomotives was limited to 1
 minute per hour.

        In l/X/1950 New York adopted standard allowable limits for fly-ash  dis
 charged by boiler installations and by electric heat and power stations.
 According to these standards the allowable  fly-ash concentration limit range
 was from 2.2 kg/T  of steam in small boiler operated plants  to 0.8 kg/T of
 steam in large electric power and heat generating stations;  the range of
 corresponding total discharge equivalents was 10  - 1450 kg/hr, which in turn
 corresponded to a concentration range of 0. 5 -  0.15 g/m3.   Maximal allow-
 able concentration of dust in flue gases coming  from boiler  operated plants
 differed with the city municipalities within the range of 0.9  and 1.2 g/m3.
 Some cities  prohibited the burning of coal having  a volatile substance con-
 tent in excess of 20-25%,  and of ash in  excess of  12%  by plants equipped with
 the usual (old) type fuel burners, unless such burners have  been modernized
 by the addition of devices to insure complete smokeless fuel combustion.
        In the Allegheny region,  which is the center of extensive steel produc-
 tion, the maximal concentration of volatile substances was set at 23% for
 hard fuel burned in non-automatic combustion chambers,  but there are some
 exceptions, especially with regard to some special technological processes
 or branches of the industrial production.   Special maximal limits have also
 been set for the ash content in the smoke discharged by plants of some pro-
 duction and manufacturing branches.                                         '

        Regulations adopted in St.  Louis forbid the use of hard coal having a
 23% content of volatile substances, or coal the lumps of which were less
 than 5 cm in diameter, if such coal contained more than 12% of ash and more
 than 2% of sulfur,  except in plants  equipped with complete combustion cham-
 bers of approved  original or modernized construction.  The discharge into
 the atmospheric air of smoke, the  density of which exceeded 2 Ringelman
 units was forbidden, except when the  chamber was being cleaned or during
 the start of furnace firing.  However,  even in such emergencies, the dis-
 charge of smoke the density of which exceed 2 Ringelman  units, could not
 exceed 6 minutes  per  hour; in such instances the smoke discharge could be
 extended to not more  than 9 minutes per hour if its density did not exceed  2
 Ringelman units;  even in such special instances the ash and dust concentra-
 tions in the discharged gases could not  exceed 1 g per 1m  of smoke.  All
 newly designed combustion chambers and old combustion chambers in the
 process of repair or reconstruction had to be approved by the smoke inspec-
 tor, who had the authority to stop  operation of any production,  manufactur-
 ing or processing plant in cases of non-compliance with the above regulations.

                                   - 315  -
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       A basic  shortcoming of the present day USA law-making procedure  for
the protection of atmospheric  air against pollution is the lack of a uniform
approach to the solution of the problem in relation to the Country as a whole,
which  results in the issuing of different codes,  rules and regulations by dif-
ferent states, and frequently by different cities within the same state.
Therefore,  it frequently happened that sanitary efforts exerted by one city
or state  in the  field of atmospheric air protection were negated by air pollu-
tants coming from a neighboring city or  state in which air purity protection
means were either inadequate or entirely lacking.

       Despite  the fact that laws existed in the  USA for the  protection of atmo-
spheric air purity,  the air of its cities was notably polluted by industrial
discharges, and more so by automobile exhaust gases and fumes.   This was
confirmed by numerous  complaints which came from private individuals
and from business people.  In 1962 New York City  authorities received
20,000 such complaints  and California authorities  received  25,000.

       The  structure  and  organization of the  service in the  field of atmo-
spheric air  protection.  The Division of Atmospheric Air Protection is a com-
ponent of State Services, an organization.of the Public Health Service  of the
Department of Health, Education,  and Welfare.  The Division of Air Pollu-
tion  was  made up of the  following sections:  1) scientific  research and per-
sonnel training,  the staff of which consisted of experts who  examined re-
quests for financing specific problems related to the study of atmospheric
air pollution and for the training of technical  and scientific personnel, etc.  ;
these experts also dealt with problems of publications, disbursement of
funds,  and use of facilities granted to investigators;  2) laboratory for medi-
cal and biological research devoted to the study of related problems in farm
economy, such  as damage  caused to crops by air pollutants, clinical,  phar-
macological and toxicological  problems of routine  and research character;
3) centers for the study of  air pollution effects at chosen points, staffed by
statisticians, epidemiologists, and biometricians;  and 4) an aerometric sub-
division;  studies have also been initiated in morbidity caused by atmospheric
air pollution, in the effect  of meteorologic factors  on air pollution and pos-
sible prognosis of same, etc.;  5) a laboratory for the  study of engineering,
scientific-physical and meteorological problems related to air pollution
reduction or elimination;  6) a section for the study of physical chemical
air qualities and related meteorological  aspects;  7) a technical and technolo-
gical section,  the function  of which was to assist states in training profes-
sional personnel, participate in consultations related to  problems of atmos-
pheric air pollution, etc.

       This section of the  Division of Air Pollution was  located not in Wash-
ington, but in Cincinnati,  Ohio at the Robert A.  Taft Sanitary Engineering
Center.   The Division of Air Pollution has a personnel of 400 employees,
including those  assigned to states; of the 400  employees  20 are physicians,
25 meteorologists,  about 60 engineers, approximately 60 chemists; then i

                                     - 316 -
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 there  are  physicists, mathematicians, statisticians, pathologists, etc.;  15%
 of the personnel were scientists who held different professional or scientific
 college or university degrees.  The entire personnel was financed by the
 Department of Health, Education, and Welfare.  The engineers were ac-
 tively engaged in sanitary-hygienic investigations.  Heads of the Division of
 Air Pollution believed that under conditions prevailing in present-day com-
 plex industry a technically adequate appraisal of the parameters of external
 environmental conditions could be made only by engineers trained to deal
 with problems of air pollution.

        It was briefly mentioned in the preceding paragraphs that the USA had
 adopted the municipal form of organization in the  control of atmospheric air
 pollution.  Each town or city could arrive at its own maximal limits  of air
 pollutant concentrations  discharged from smoke stacks.  Cities and towns of
 some  states were guided by principles adopted by their state while munici-
 palities- of other states preferred to guard their air environment independent-
 ly, and to establish their own standards of air purity,  and to use their pre-
 rogative in adopting means for the control of the city air purity in accord-
 ance with  their own regulations.

        The Division of Air Pollution of the Public Health Service of the De-
 partment of Health, Education, and Welfare developed and offered recom-
 mendations to sanitary law-makers; such  recommendations  may or may not
 be adopted by the states' health departments.  Furthermore the Division of
 Air  Pollution of the Public Health Service had no inspection authority,  ex-
•cept in cases governed by laws operating on a federal  level.  Money  assigned
 to the  Air  Pollution Division by the Federal government was intended specif-
 ically for  research purposes and for  the training of technical and scientific
 personnel.

       Scientific-research investigations in the fields  of sanitary protection
 of atmospheric air was conducted in many universities, engineering  centers,
 in research laboratories and in many  USA Government bureaus.  Local
 municipalities or State Departments of Health selected their research prob-
 lems according to local conditions and assigned them to appropriately
 trained and experienced  research investigators.  Research grants alloted to
 selected research experts in 1963 amounted to 3 million dollars, which
 covered the cost of 90 research projects.   This amount was raised to 4 mil-
 lion dollars for 1964.  The Department of Health,  Education, and Welfare
 financed 39 universities  and 18 scientific  research institutes; it also  engaged
 other Government organizations such  as the Weather Bureau, the Bureau of
 Mines, Bureau of Weights and Measures to conduct related investigations on
 a contract basis.  The Division of Air Pollution also subsidized 2 experimen-
 tal stations, one in Oklahoma and one in Pittsburgh, Pennsylvania.   Most of
 the air pollution research was conducted and financed  directly by the states.
 For example, the State of New York allotted 8 million  dollars for air pollu-
 tion research in 1963, which is  more than twice the amount spent in the same
 year by the Division  of Air Pollution  of the Public Health Service for the

                                   -  317 -
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 same general purpose.  (I was informed that this statement was incorrect -
 BSL.)  The division of Air Pollution of the  Public Health Service also issued
 publications,  such as results of scientific research studies, and pertinent
 state,  county or municipal reports,  etc.

        San Francisco, Los Angeles,  Cincinnati, Detroit,  Pittsburgh,  Harris-
 burg, Philadelphia and New York municipalities,  and of other cities have
 organizations and equipment for the  sanitary protection of atmospheric air
 which were in constant operation.  Special regional and municipal bureaus
 have been organized  whose functions were air pollution prevention through
 inspection and general watchfulness.  State  air pollution bureaus  usually had
 a staff  of approximately 20 to  24 employees, distributed as follows:  one
 bureau  chief,  6 engineers, 2 chemists, 10 inspectors,  laboratory techni-
 cian, and 4 laboratory helpers.  Much of the responsible personnel's time
 was given to the study of complaints, applications, suggestions and similar
 correspondence.  Non-compliance with the  regulations was usually noted by
 the inspectors who traveled through  regions assigned to them in automobiles
 equipped for field air analysis, making it possible to determine on the spot
 the type and extent of regulation violations,  which they reported to their
 chiefs.  Minor violations were reported immediately to the plant  manage-
 ment and nothing more was done about it if  the infraction was corrected; in
 more serious and stubborn cases'authorities could resort to financial or
 other type of penalties; financial penalties usually ranged between 25 and 500
 dollars, or jail confinement up to 2 months.

        While making  his, so-called, prophylactic observation  the sanitary in-
 spector had no authority to prevent industrial discharges into the atmospheric
 air; construction plans were examined in the blue print stage,  and, as a
 rule,  resulted in no changes.  Generally the sanitary authorities  did not
 participate in the planning or construction of industrial and community pro-
 jects.   The Division of Air Pollution of the  U.S.  Public Health Service
 offered  no suggestions for the  adoption of more  rational technological pro-
 duction  systems, or for the  replacement of highly toxic raw material by
 materials  of lower toxicity,  since  managements  of the industrial  enterprises
 were under no compulsion to accept  or follow such suggestions if they  should
 appear  unprofitable.

        Atmospheric air pollution investigations.  The type and intensity of  at-
 mospheric air pollutions  with industrial production and by-products dis-
 charges were investigated in stationary and mobile laboratories at desig-
 nated points.  Permanent or stationary laboratories at points of air  sample
 collection  and analysis were equipped with fully automatic or semi-auto-
 matic apparatuses.  Air samples were  examined simultaneously for NO,
 NO2 , CO,  CO2 ,  SO3 ,  H2S,  organic substances,  and hydrocarbons.  In the
State of New York air samples were  also analyzed for HF and O3 .  Air sam-
 ples were  collected and analyzed around-the-clock.  Results were fixed  on
 continuous recording paper or recording tape every 5 minutes, constituting
 a 24-hour  control of the state of atmospheric air pollution.  The fixed  rec-
                                   - 318 -
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ords were then sent to the Air Pollution Division Laboratory in Cincinnati,
Ohio, where the data were processed with the aid of electronic  computers,
written up, published in the form of reports and distributed among pertinent
scientists,  technicians, sanitarians, universities, research institutions ,
etc.  Fully automatically operating sample collecting, analyzing and record-
ing equipment was seen in centers located in New York,  San Francisco,
Washington, Harrisburg,  Detroit, Los Angeles, and other cities.  The num-
ber of air sample collecting points varied with the cities.  Thus,  New York
had 4 fixed points, San Francisco had 2 fully automatically operating sample
collecting points and 16 semi -automatically operating points.  Forty air
sample collecting points were seen in California, and 50 in Pennsylvania.
The USA  mobile laboratories  generally were assigned to vicinities surround-
ing known sources of atmospheric air pollution.   The mobile automobile lab-
oratories of Los Angeles collect and analyze up to 2,000 air samples annual-
       In 1960 the Air Pollution Laboratory of the Robert A. Taft Sanitary
Engineering Center of the Public Health Service assumed the task of col-
lecting and analyzing air samples at 50 stationary points equipped with
fully automatic sample collecting devices.  As was previously  indicated, the
Public Health Service,  and consequently the Robert A. Taft Sanitary Engi-
neering Center located in Cincinnati, are parts of the Department of Health,
Education,  and Welfare.   The Center has a personnel of 150, which includes
physicians, engineers, chemists, physicists, physiologists, biochemists,
chemical analysts, mathematicians, veterinarians, minerologists ,  sanitary
engineers,  etc.  The Center investigators visit cities in which they study the
sources, character and extent of atmospheric air pollution, and suggest suit-
able ways for the reduction of such pollution.  At the same time they instruct
local personnel in methods of air sample collection and analysis.   Up to the
time of the visit herein reported, the Cincinnati Center fully investigated
sources and extent of atmospheric air pollution in 11 states.  On the average
the Cincinnati Center conducts one extensive investigation per  year and
makes pertinent recommendations.  However,  as previously noted, com-
pliance with or action indicated by such  recommendations are in no way
obligatory.

       Training  of specialists.   Basic training of specialists and advanced
courses are conducted  at the Robert A.  Taft Sanitary Engineering Center in
Cincinnati,  Ohio.  The  study and instruction programs must be approved by
authorities  of the Public Health Service in Washington, i.e. , by pertinent
authorities  of the Department of Health,  Education, and Welfare.  Short
courses usually last from 1 to 3  days; longer courses may last up to one
year.  State and  municipal health departments send their  qualified  workers
to the Cincinnati Center to attend such courses  and pay all expenses.
Courses  offered  in 1962 -  1963 covered 75 different programs which in-
cluded the  following specialized  fields: air pollution, water  pollution,
radiology,  food hygiene and city planning.

                                    - 319 -
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       Scientific research and purification of industrial discharges.  No in-
ternal combustion engine had been designed at present which could eliminate,
neutralize or detoxify automobile exhaust gases by complete fuel combustion
or by other means.   For  this reason the atmospheric air of USA cities,
in particular, in the State of California, is intensely polluted;  according-
ly, a considerable volume of air pollution research is dtvoiad to the study
of automobile exhaust gases.  Thus,  in the. San Francisco laboratory lo-
cated near Berkeley, in Los Angeles, in San Bernardino,  Bartlesville,  Cin-
cinnati, Detroit, and in New York intensive studies are conducted to find
the factors and conditions which created smog,  and to determine the effect
which different exhaust gas components had on animals,  man,  vegetation,
etc.   Special experimental chambers had been constructed in which automo-
tive  exhaust gases are subjected to the action of artificial solar rays attempt-
ing to produce a laboratory photochemical smog.  Many  laboratories, espe-
cially in California, directed their fight against effects of automotive  exhaust
gases by experimenting with different designs of internal combustion engines
or by incorporating afterburners.  A mandatory law was  passed in California
in 1963 which required that all motor vehicles had to be equipped with special-
ly constructed afterburners for the purpose of lowering the concentrations of
toxic and harmful substances in exhaust gases.  The afterburners now in use
can reduce CO concentration to 1. 5%,  hydrocarbons to 275 parts per million;
some types of afterburners reduced the concentration of hydrocarbons to 20
parts per million and CO to 1.0%.  This law had not been faithfully complied
with, and specific means of enforcing it had not been adopted.

       The effect of smog on animals is being studied in special exposure
chambers equipped with automatically regulated devices for the determina-
tion  of the  chamber air composition.  Changes occurring in the experimental
animals' organisms  are also recorded automatically, and the results  of nu-
merous determinations and observations are processed by means of elec-
tronic computers.  In the Cincinnati Laboratory of Professor Kehoe investi-
gations were conducted on the effect of lead on man; the  experiments were
conducted in a special exposure chamber employing, as  it appeared to the
USSR observers, unusually high lead doses.  Members of the Epidemiological
Division of Cornell University in New York selected 1, 000 inhabitants in 9
city  blocks, the air pollution of which was approximately of the same  type
and intensity; selected persons belonged to different social groups  of differ-
ent financial levels.   Once a week all test persons  were  asked to fill out a
questionnaire of 150 questions related to their state of health, with special
emphasis on the condition of their respiratory organs.  This method of  mor-
bidity study seemed to lack scientific  objectivity; no provision was made for
a control group,  and no objective studies were made of the test subjects'
physiological systems and their functioning.

       Studies were conducted at the University of Southern California in
Riverside on air pollution effect on the general state of health of patients
suffering of emphysema under clinical conditions.  Two  wards of the
University's  clinic,  having only emphysematous patients,  have been devoted

                                    - 320  -
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exclusively to the study of this problem.  Patients of one ward inhaled natu-
ral outside air not previously purified; patients of the other ward inhaled air
freed from all harmful components.  It was hoped that a comparative  study
of the course followed by  the disease in' patients  of the two wards and of
their general state of health might lead to informative conclusions regarding
the effect of air pollution  on patients having emphysema.  The  study is still
in progress.

       Interesting studies were conducted on cancerogenic properties of some
chemical substances at the Bethesda Cancer Institute of the National Insti-
tutes of Health.  Similar studies were conducted at New York University.  At
the University of Southern California thorough and detailed animal experimen-
tal studies were conducted for the purpose of determining the effect of smog
on chemical changes of the blood,  tissues, physiology of the lungs, and  on
morphological tissue changes, paralleled by studies on the effect of smog on
the psychology of the experimental animals.   Problems related to the  theory
of smog  formation were being studied in the laboratory of Professor Haagen-
Smit at the University of California.  Problems related to the presence  of
lead in atmospheric air were  under  study at the same University.   The harm-
ful effect of air pollutants on vegetation was under study at the  University of
Southern California.  Studies were also conducted on the effects of ozone,
PAN, ethylene, sulfuric anhydride and of fluorine.  One of the  University's
air pollution laboratories  was located amid California's orange groves.  It
should be noted in this connection  that observations of smog effect on fruits
and vegetations were limited to  external damage and appearance without the
application of finer biochemical and  physiological methods  of investigation,
which lowered the usefulness and significance of the entire complex of stud-
ies and made the results  less  convincing.

       At the Department of Industrial Medicine of Michigan University, lo-
cated in Detroit,  studies  were conducted on the effect of atmospheric air
pollutants on respiration,  with special emphasis on the presence in the air
of cyanides and mercury  emitted by  plants of  the  rubber producing and pro-
cessing industry,  using duplicate groups of rats and rabbits. One group,
housed in three chambers, was  exposed to the inhalation of natural city  air;
animals  of the duplicate groups  inhaled purified air. Throughout the ani-
mals' survival period records were  kept of results of biochemical, physio-
logical and pathomorphological tests,  including enzyme tests.  Tests were
also conducted with the antibiotic tetracycline.  At the Yeshiva University
of New York studies were conducted to determine the causes of different
levels of seasonal  bronchial asthma morbidity in  some New York regions,
using hospital patient turnover data.  Investigators believed that seasonal
increase in bronchial asthma morbidity may be caused by the seasonal pres-
ence of microspores in the air,  but  this belief has not been decisively sub-
stantiated,  and studies and observations are  being continued.

       Interesting experiments  were also conducted in the  same laboratory
with mice and hamsters to establish the possible cancerogenic  effect of  th,e

                                    - 321  -
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inhalation of air polluted with SOS and simultaneously contaminated with
influenza virus.  At the  same institution studies were being conducted to
determine the cause of lung cancer in general, and with special reference
to cancerogenic substances, which included hydrocarbon fractions,  their
behavior in  the organism and elimination via the lungs.  At the time of  the
visit the investigators were studying substances resulting from the  oxidation
of hydrocarbons.  Synthetic cancerogens had been produced which,  accord-
ing to the  investigators,  elicited cancers in mice.  Professor Laskin devel-
oped a procedure for the production of cancer by introducing into the orga-
nism a thread saturated  with a cancerogenic substance,  which elicited
cancer development in 90% of the experiments.  Investigators did not deny
that cancer  can be produced by a variety of methods, but they apparently
concluded that cancer could not be produced in experimental animals by the
inhalation route alone.  Experiments were  being conducted with pure cancer-
ogens alone or in combination with other hydrocarbons.

       The  USA Bureau  of Mines cooperated in the development and study of
different problems  and phases of atmospheric air pollution.  Here attention
was concentrated on the  problem of  removing sulfur from crude oil. The
section of the Bureau which dealt with hard fuel, located in Pittsburgh,
analyzed the composition of flue  gases  resulting from combustion of hard
fuel, automotive exhaust gases,  and during the removal of sulfur  from hard
fuel.

       Investigations in  the USA in the field of sanitary atmospheric air pro-
tection were conducted along the following  channels:  designing and  building
equipment,  apparatuses  and devices for continuous automatic recording of
general atmospheric  pollution; designing and building improved devices  and
apparatuses for the detection  and determination of specific air pollutants,
such as cancerogens; studying the photochemical conversion processes  of
air pollutants under atmospheric conditions; experimental animal toxicolog-
ical studies, and determination of population morbidity related to atmospher-
ic air pollution; studying the effect of industrial air discharges on vegetable
life; studying meteorological aspects of air pollution; developing methods for
limiting or  reducing the volume  of industrial discharges into the atmospher-
ic air, including the discharge of automotive exhaust gases,  smoke  gases
emitted by domestic combustion  chambers, stoves  or furnaces, etc. The
procedures,  equipment and installations  recommended in all cases  were
much the same as those  recommended and  used in the USSR.

        The USSR visiting  delegation was presented with the opportunity to
examine purification installations in two electric heat and power stations,
one in Cincinnati,  Ohio,  and one in New York; in an asphalt-concrete plant
in Cincinnati, a typographical plant  in Philadelphia, and a crude oil process-
ing plant also in Philadelphia; other forms  of industrial purification equip-
ment and installations were shown on the screen by means of moving films.
On the basis of what the  delegation had the  opportunity to observe it can be
stated that the problem of  freeing flue and  smoke gases from sulfur was far

                                   - 322 -
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from having been solved in the USA; the most probable  means of combatting
SO3  discharged into the  atmospheric air was  limited to the  removal of sulfur
from the fuel.  Ash was  removed from the coke at electric  heat and power
stations by the two-stage methods, using multicydones and electrostatic
filters, the efficiency of which was 99%.  Smoke stacks were equipped with
teleinstallations  which controlled the smoke density.  Sleeve and bag filters,
made of glass wool or orlon, were widely used for the removal of dust.
Recovery installations and recovery systems were practically the same as
in the USSR.  The  observed asphalt-concrete plant was equipped with two
types of installations for gas afterburning,  and concrete mixers were
equipped with bag type filters for dust catching.

       Domestic trash burning in  smoke creating combustion chambers
seriously aggravated the air pollution problem  in the USA.  The recommend-
ed paper filters in this connection had not been widely  accepted.  About 60
private USA business  enterprises  were engaged in the  developement  of differ-
ent types  of wet or dry operating electrostatic and other dust catchers, and
gas afterburners,  as well as other types of purification installations.  Such
manufacturing organizations issued catalogues  widely used  by municipal
bureaus or divisions concerned with the practical control of atmospheric air
pollution.  Despite the fact that scientific studies in the field of atmospheric
air protection were conducted on a broad scale in the USA,  the attainment  of
practical  results was  not impressive.

       It  should  be noted that the work of Soviet hygienists  is widely know  in
the USA,  from translations  either in  the abstract form  or as full transla-
tions. The latter is particularly true of "sborniks" (collections) issued by
the USSR  Committee on Limits of Allowable Concentrations of Atmospheric
Air Pollutants.

                                   - 0 -
                                    -  323  -
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                     SUPPLEMENT
   A NEW TYPE  OF INTERNAL COMBUSTION  ENGINES




          (Precombustion Chamber Flame Ignition)
                       A. S. Sokolik
(Vestnik Akademii NaukSSSR,  Vol.  31, No. 10,  1961, pp 78-90)
                         - 324 -
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          A NEW TYPE OF  INTERNAL,  COMBUSTION ENGINES

                 (Precombustion Chamber Flame Ignition)


                              A. S. Sokolik

      (Vestnik Akademii Nauk SSSR, Vol.  31, No. 10, 1961,  pp 78-90)
       USSR electrification is a basic instrumentality in the building of
communism.  However, in the USSR, as in other industrial countries,
internal combustion engines (ICE) produced 90% of the country's energy
supply for the past decade or two.  This condition will  persist as  long as
studies fail to develop new ways of converting fuel into energy -which could
replace the use of internal combustion engines in transportation automo-
biles and  tractors.  Automotive  power generating engineers are now faced
with the problems of radically improving the ICE, especially with  respect
to a more  economic use of fuel.

       Two Types of Internal Combustion Engines:   All types  of modern
ICE used  in motor vehicles can be divided into two categories, based on
their methods of ignition,  of initiating the combustion process, and methods
of forming fuel-air mixtures:  a) engines with spark ignition and external
carburetion; and b) engines with compression ignition and internal car-
buretion by means of fuel injection into a cylinder,  where it becomes mixed
with compression heated air - the so-called "diesel" engines.

       The differences in  the ignition methods and  carburetion are inherent
in the fact that highest power concentration, i« e. ,  power per  liter of ef-
fective cylinder volume, can be  achieved in spark-ignited engines  with
relatively poor economy.  On the other hand,  a more effective  use is made
of fuel combustion heat in  diesels, but without full utilization of the effec-
tive cylinder volume.

       It became apparent at the time  of the First World War  that the
possibilities of improving  the operating economy in spark-ignited  engines
and the pressure feeding in diesels were rigidly limited by the  fact that
one would have to interfere with the normal course of combustion.  A de-
tonation "knock" appeared when  the thermodynamic efficiency  of the  operat-
ing cycle in a  spark-ignited  engine was increased by increasing the  degree
of compression.  The exhaust became  smoky  when excess air  in the air-
fuel mixture in diesel engines was lowered, so that the fuel-air ratio apr-
proximated a theoretical (stoichiometric) composition.   Combustion  became
explosive  ("diesel knock")  when  a rotational feeding apparatus was used,
and especially when the  ignitability of the fuel deteriorated.
                               - 325  -
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       Engine and Fuel.   Long before the complex physico-chemical na-
ture of these phenomena was understood, their relationship to the chemi-
cal structure  of hydrocarbons  was discovered, - on the one hand an in-
creased anti-knock  stability characterized hydrocarbons having a branch-
ed hydrocarbon  chain (isooctane being the highest standard), and, on the
other hand, an increased combustibility characterized hydrocarbons hav-
ing a straight hydrocarbon chain (cetane being the highest standard for
diesel fuels).  The opposite requirements for the chemical structure of
the fuels in both classes of engines arose from the  identical nature of de-
tonation ignition in the spark-ignited engine and the initial ignition in the
diesel.

       However, even fuels having a high cetane number failed to elimin-
ate smoke  formation.  Therefore,  increasing the cetane number of diesel
fuels played no decisive role in the technical progress of diesels as  in-
creasing the octane number of gasolines did in the development of carbure-
tor engines.  The 50-year history of spark-ignited engine  development
presents a continuous rivalry between petroleum industry achievements
in increasing  the octane number and the requirements of new  engines for
fuels having an increased antiknock stability.  This rivalry became  espe-
cially dramatic  during the development of the aircraft piston engine, in
which not only the permissible degree of compression and the improvement
of engine economy was dependent on the available octane number, but  also
the possibilities of supercharging the  engine and, thereby, the flight char-
acteristics  of the aircraft, - ceiling,  maximum  speed, take-off weight,
range. It was specifically the race for supremacy  in this basic World  War
II weapon that produced the most progress in increasing the octane number
of aviation gasolines, which was based on new petroleum manufacturing
processes  and on the synthesis of isooctanes and other hydrocarbons with
similar properties.

       At end of the Second World War the high-octane aviation gasoline
industry lost its chief consumer when first military and later civilian
aviation began the transition to jet engines, since the octane number re-
quired at that time for automobile  engines never  exceeded 80.  The  problem
of creating  a new mass market for the vast resources of high-octane avia  -
tion gasolines arose in the United States.  An intensive campaign was ex-
pressly developed during the  post-war years for a  sharp increase in the
compression ratio of automobile engines so that high-octane gasolines
could be used in them.  C. Kettering of General Motors Corporation stated
in his  report  "A More Effective Use of Fuel"1   (explanation of all foot-
notes will be at  the conclusion of this  paper) that increasing the compres-
sion ratio  in automobile engines from 6 to 12 would be a reality in the near
future.  D_ Caris and E. Nelson^ of the same firm discussed in their pa-
per the possible effect of increasing compression ratio to 20.   In this case
it was assumed  that the automobile engine would be converted in the near
future to 100-octane gasolines  and  that certain ethyl liquid additives  would

                                 - 326 -
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be used, which in themselves would create a number of additional problems,
both in a sanitary-hygienic sense and with respect to reducing the lifetime
of such vitally important parts of an ICE as spark plugs,  valves,  etc.

       It is still not clear to what degree the improved fuel economy of the
automobile attained by increasing the compression ratio justifies  making
the petroleum manufacturing process more complex, and especially the
overall reduction of motor fuel resources, which is associated with in-
creased antiknock stability of the gasolines.  In other words, to what ex-
tent did the economic  benefits  of the consumer coincide with the interests
of the  national economy.   There was also the additional problem in coun-
tries which had not developed a high-octane aviation gasoline industry as
to what extent were capital expenditures justified  in creating such an in-
dustry.

       In examining these problems it is  essential to know  whether in-
creasing the compression ratio was the only means of improving  the econ-
omic characteristics of an automobile engine, and whether modern science
could discover any other  way of achieving the  same aims,  but without in-
creasing the special requirements for a motor fuel or even by generally
eliminating any kind of requirements  for the chemical structure of the  fuel,
assuming,  of course,  that the  efficiency of the fuel would be maintained at
the level of modern gasolines.   It is  this problem in particular which is
the subject of this paper.

       How is the Economic Effect of the Compression Ratio Achieved?

       The most prevailing opinion, including the basic assumptions in
the previously mentioned Kettering paper, is that this effect was  complete-
ly due  to increase in the thermodynamic efficiency of converting heat into
energy and to increase the temperature differential  during expansion in
accordance with the formula Eff = 1 - 1/e   , where £ is the compression
ratio.  However,  engine economy increased in this way parallel with the
compression ratio only when other invariable  conditions were present.
The  economic effect actually achieved in increasing compression  ratio of
an automobile engine always significantly exceeded thermodynamic effi-
ciency.  Data of many researchers show that an increase in  automobile
engine efficiency caused by increasing compression ratio invariably con-
siderably exceeded increase in thermodynamic efficiency.  Thus, the
economy of an automobile engine increased by 90% while its  efficiency
increased only by 25% when the compression ratio was changed from 6. 25
to 12.   The research  workers of General Motors  Corporation have  also
come to a similar conclusion.*

       To understand  why the principle economic  effect depended on rais-
ing the compression ratio, the following must be remembered:  regulat-
ing the work an automobile engine accomplished in one cycle under a quick-
ly changing load (the so-called average indicated pressure which  deter-

                                -  327 -
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mined engine power at a given r. p. m.) by altering the air-fuel mixture in
the cylinder by throttling its flow, is a qualitative regulation of the load.
In this case a certain amount of excess fuel,  in contrast to the amount
which corresponded to complete combustion, must be added to obtain
completely stable engine operation under all  loaded conditions.  Thus, the
degree to which the mixture became enriched by unburned fuel increased
progressively as the load decreased.  In this way  an engine operated with
a known incomplete use of fuel efficiency during the most prolonged medium
and light loads,  or especially during city driving.

       Furthermore,  as follows from the theory of the working process,
it is most advantageous not to reduce the air-fuel  mixture when lessening
the load, but to gradually dilute it with air and thin out the mixture with
fuel.  In this case combustion temperature is reduced,  heat losses from
the burning gases to the cylinder walls are lessened,  and  index (k) ap-
proaches the adiabatic as the magnitude of thermodynamic efficiency in-
creased (cf. formula).  Therefore, despite the theory,  quantitative regu-
lation by throttle control, which requires reduced loads  of progressive mix-
ture enrichment and increasing unburned fuel losses, is being used in place
of the more economic  qualitative regulation by the mixture composition.

       Experience showed that the necessity of maintaining stable com-
bustion in an enriched mixture fell off with a sufficient  increase in the
compression ratio,  and that it also became possible to use some degree
of mixture impoverishment within a rather wide range.  American statis-
tical data show that the average enrichment of a mixture in automobile
engines noticeably decreased with increase in the  compression ratio."

       Therefore, it can be concluded that the greater part of the economic
effect attained by increasing compression ratio in an automobile engine was
an indirect effect of the enrichment reduction or complete enriched mixture
elimination and of the  use of lean mixtures during partial loads, i. e. , by
approximating an economic quantitative control of the mixture.,

       The problem presented earlier can be formulated now more speci-
fically as follows:   is increasing compression ratio    in an automobile
engine the only,  or most effective, way of eliminating unburned fuel losses
and of using qualitative control on partial engine loads ?  A definite answer
can be given now to this problem.  A physicochemical study of the combus-
tion process in an engine  yielded a more  rational and effective solution to
the problem of economic engine control than  increasing the compression
ratio. To understand  the essence of the new solution examine what factors
limit the steady  combustion of lean mixtures  in an engine, and why it is
necessary to introduce excess fuel.

       Spark Ignition and Combustion in an Engine.   In order to complete-
ly convert the heat of combustion into work the combustion process must

                                - 328 -
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begin during the terminal phase of the compression stroke to prevent piston
drag and end during the start of the expansion stroke to fully utilize the
power stroke.  Duration of the  combustion process does not exceed 1/10  of
a revolution within this  range,  which in a high-speed engine is  approximate-
ly 1/500 of a second.  Such a rapid combustion is made possible only by the
turbulent intermixing of the charge in the engine cylinder. The turbulent
pulsations in an engine cylinder are generated during the filling process
and increase in intensity with the number of revolutions, so that the factar
which accelerated combustion became automatically enhanced with a de-
crease  in combustion time.

        There are no generally  accepted viewpoints at present on the nature
of turbulent combustion. Studies made by this  author   and his associates
show that this type of combustion should be represented as an envelopment
of the fuel mixture by continuous combustion resulting  from the disorderly
intermixing of small fuel volumes and fresh gas.  The  following important
conclusion is drawn from these concepts which is confirmed by experi-
mental  data! turbulent combustion occurred  only in the presence of suffi-
ciently  developed flame  sources.  This fact is illustrated  in Figure 1 by
the two series  of motion picture frames showing the development of a flame
in a model engine combustion chamber, the first series shows  the flame
in a quiescent charge, while the second shows the same in an artificially
turbulent charge.   The  photographs show that continuous  ignition charac-
teristic for  turbulent combustion appears only after a certain critical vol-
ume of  approximately 2  cm in diameter was  attained.    Accordingly, it  is
possible to distinguish two  essentially different phases in an engine's  com-
bustion process:  1)  formation of a flame source open to the effect of tur-
bulence, and 2) turbulent combustion proper in which the basic charge mass
is combused.  In fact, it is the  first stage where only  about 1% of the
cylinder charge combusted, which actually determined the use  of economi-
cally  advantageous  poor mixtures.

        Fig. 1
                                            r |c j^'rlnir
                                            BKakiktefe/:


         Tuo »chl i«r«n-cin«««toar«phic velocity «xpo»ure ••neu of «()h«rie»l fl«n>« d«-
         velopment in (l) qui»sc«nt and (It) t>jrbul*nt 3*8, »t 1/3033 &ec. inttrvils
       The possibility of a flame arising from a spark was determined by
 a condition at which, the rate of reaction released within the volume of the

                             - 329 -
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primary nidus exceeded the rate at which heat was transmitted to a fresh
gas or to the spark plug electrodes.   Because  of this the charge agitation
necessary for the accomplishment of combustion in an engine within the
1/500 of a second inhibited the development of the initial stage of the pro-
cess.  The more intensive was the turbulent charge motion, the more diffi-
cult it was for the charge  to be ignited by a spark and to form the initial
flame  source.  On the other hand, this process  retarded the drop in the
rate of heat liberation when the fuel mixture was thinned either by excess
air or by inert combustion products.  Even with a slight degree  of leaning
(10-20% excess air) the formation of a flame source was delayed  to the
entry of the first portions  of a fresh mixture. This is how knocking appear-
ed in a carburetor, which  is the obvious  sign of delayed combustion in an
excessively leaned mixture.  It is specifically this condition which makes
it necessary to step up the fuel enrichment in proportion to throttling caus-
ing the appearance in the  residual gases of incomplete combustion products,
such as chemically  active CO and H2, which hasten flame formation.  En-
richment of the mixture and unburned fuel losses in modern automobile en-
gines at partial charge are not caused by faulty  design in the control system,
but by the necessity to insure flame  formation at partial  charge.

       The same reasons, which inhibit this process during throttling,
give rise to factors which  enhance it when the compression ratio is in-
creased.  The rate of volume heat liberation in  this case  increased  by
reduction in the concentration of residual gases  and by increase in the
charge density.  This explains the reason why increased compression
ratio gradually lowered the necessity of resorting to  mixture  enriching
at partial charge. In fact   there arises a slight fuel leaning. Increasing
the compression  ratio enhanced the partial elimination of disadvantages
inherent in a spark-ignition system at the expense of raising the require-
ments  for antiknock fuel stability.  In contrast to this, the system of pre-
combustion chamber-flame (PCF) ignition eliminates these disadvantages,
accompanied by a definite  reduction in the requirements for the antiknock
fuel stability.

       Precombustion Chamber-Flame Ignition  in Engines with External
Carburetion.   Two  main  principles form the basis of the PCF system.
Principle one can be  formulated as  follows:  To  insure optimal conditions
for the formation of an initial flame  source  in the cylinder of an engine
independently of the mixture composition in conformance  with  regulating
its charge the spark ignition has to be moved from the working cylinder
to a precombustion chamber, the capacity  of which is only 2-3% of the
capacity of the combustion chamber.  The precombustion chamber is con-
nected with the cylinder by one or more valves (Fig.  2) and is equipped
with a  spark plug and a valve which opens simultaneously with the main
intake  valve.  The precombustion chamber is filled with a mixture  from
the precombustion chamber carburetor simultaneously as  the cylinder is
filled with an air-fuel mixture from the main carburetor.  These two car-

                                - 330 -
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buretors are  in fact two sections  of a common carburetor and are regu-
lated so that the excess air in the  cylinder mixture accorded with the ex-
cess  fuel in the precombustion chamber.  The lean cylinder mixture enter-
ed through a valve in the precombustion chamber during the compression
stroke and mixed with the rich precombustion chamber mixture,  forming at
ignition moment  a mixture which easily ignited by a spark at any air-fuel
mixture in the cylinder.  Although control of the  precombustion chamber
mixture depended upon a specific ratio with the control of the  cylinder mix-
ture,  it will be shown later that the mechanism of the PCF-ignition system
itself makes  this dependence  very flexible.  In addition to the  mixture com-
position flame formation in the forechamber enhances the chamber purifi-
cation from residual gases,  lessened turbulence  as compared with a cylin-
der and promotes the formation of a flame in  the precombustion chamber.
Fig.  2
       The second basic principle of
the PCF system can be formulated as
follows:  turbulent combustion of the
main charge did not develop in the
course of the continually-increasing
turbulent motion effect of the charge
on the flame after spark ignition,
but developed as the result of the way
in which this charge ignited from the
hot gas  stream ejected at a high rate
through the precombustion chamber
nozzle or nozzles. The pressure dif-
ferential between the precombustion
chamber and  the cylinder required
to eject the stream can be determined
directly from pressure diagrams re-
corded simultaneously in the precom-
bustion  chamber and in the cylinder,
as shown in Fig0 3. This differential
is formed by the nozzle  pressure drop
against  the gas outflow from the pre-
combustiontion chamber, i. e.,  re-
sulting from the fact that  combus-
tion occurred here under conditions
of semi-enclosureo
       Some concept pertaining to the cylinder charge ignition mechanism
by the precombustion chamber stream can be illustrated by high-speed mo-
tion picture records of the precombustion stream development (Fig. 4) and
by ionization current records (Fig. 5) which can trace the development of
the chemical reaction itself at various distances from the nozzle.  It has
been established that this reaction was connected directly with the gas
ionization in the flames.  The motion picture records show that an igni-
    basic plan of fo^ocnaraber jet ignition
    F - forecharaberj C - mixture cylinder
                               - 331 -
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tion nucleus appeared in the stream at some distance from the mr/./.lr ami
then quickly enveloped the main charge.
Fig. 3                        An analysis of ionized oscillograms showed
                              that combustion in the precombustion  chamber
                              stream itself was pulsating at a frequency of
                              approximately  5000 cps, which is consider-
                              ably above the  normal pulsation frequency of
                              turbulent flame ignition. After  combustion
                              in the given zone is damped,  the same analy-
                              sis shows that  following some delay second-
                              ary ignition occurred at  normal frequency
                              of conventional turbulent flames of approxi-
   —:	   mately 1000 cps.
Pretcwre chtnjes durinj combustion in
(F) forecn»moer *nd  in (c) cylinder          On the basis of the described obser-
9°v::;rs::: :r;;;;;r^j-rr  vati°ns *can be  assumed that  at ^ stage
upper de*d pomtj i  - ismtij> noaentj  of the process  in the precombustion chamber
2 -ejection of hot  «treta fro* fore-
                              Stream the following occurred according to
laws governing a free stream: fresh gas was captured and underwent tur-
bulent intermixing with the hot gas; after the primary flame of high-fre-
quency pulsation is damped,  a genuine autoignition of the trapped gas oc-
curred which was identical with the pulsating ignition occurring during
the propagation process  of turbulent flames.
        Schlieren-cine«.toar.phic record. «* for«ch»»toer «tr««. ejection (3000/»ec.,.
        At exposure C-3 the nucleus of turculent ignition Begins t» «pf»««r.

                                - 332 -

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Fig. 5                                   Based on the identity of precom-
                                         bustion chamber ignition with the
                                         turbulent combustion mechanism
                                         it can be assumed that in such
                                         mixtures,  e.  g. , with  twice the
                                         excess air as against the theoreti-
                                         cal value of possible turbulent
                                         combustion,  rapid ignition from
                                         the precombustion chamber stream
                                         was possible.   Precisely this com-
                                         pletely removes the limitations of
                                         spark ignition in the basic  PCF-
                                         ignition mechanism  when diffi-
                                         cult to ignite or totally unignit-
   I _ Oscilloar.* of ioniz»tion flo.j  II -         .,,             , ,_
   fluctuations in the forech.wber f loaj  III - »-< the 1Dle mixtures with excess air
                 ignition nucleus                     ,
     « -section of c«iplete cowoustion extinction   are Used.

       Many technical details of the precombustion chamber system in-
cluding the choice of nozzle or nozzles, which insure smooth combustion
and provide sufficiently wide fuel leaning limits,  will be temporarily
disregarded and attention will be centered only on an important quality of
the PCF system to regulate itself,  or the extremely flexible control mani-
fested by the precombustion chamber  carburetor without loss of ignition
effectiveness.   This is a direct result of the PCF ignition mechanism it-
self,  and results specifically from following: •when the flame temperature
in a precombustion chamber drops with increase in the fuel excess  in the
precombustion chamber mixture, the  precombustion chamber stream com-
bustibility associated  with its heat  control, decreases accordingly,  even
though the factors facilitating ignition increased simultaneously.  The
chemical activity of burning gases  decreased as the combustion tempera-
ture in the precombustion chamber dropped, which is in accordance with
the lowered concentration of active centers, such as H, O,  OH in them.
However, the concentration of unburned combustion products, i» e. ,  H2
and CO,  which increased the ignitibility of fresh  gas, rose simultaneously;
pressure drop fell as  the combustion temperature in the precombustion
chamber decreased together with the velocity oi the precombustion  chamber
stream and the  volume of entrapped fresh gas.   The  precombustion chamber
stream insensitivity controlled by the  precombustion chamber mixture,
which has been  repeatedly checked by engine tests, considerably simpli-
fied the design ot an efficient precombustion chamber carburetor.

       The precombustion chamber ignition system can facilitate the
ignition of lean  mixtures down to idling; however such purely qualitative
control is not the most economical, only because the  mixture is being
thinned with air. When the excess  air is more  than 150% of the  theoretical
value, a progressive drop in the economy appears caused by a drop in the
rate of turbulent combustion with a drop in flame temperature.  Thermal

                                - 333  -
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 losses caused by retarded combustion  upon further leaning exceed the
 losses caused by flame temperature decreases.  Beginning with this maxi-
 mum leaning,  it becomes more advantageous  to reduce the power at a con-
 stant level of leaning,  i.e., at constant flame temperature, by throttling,
 that is by applying a qualitative-quantitative combination control.   Here,
 again, the profound difference between spark  and precombustion chamber
 ignition systems is obvious.  In the first system contamination of the air-
• fuel mixture by residual gases prevents the formation of a turbulent flame
 even with a slight degree  of air excess; in the second system throttling  has
 little effect on the initiating precombustion-chamber ignition stage  of the
 charge, and less  on the turbulent combustion propagation since both pro-
 cesses developed by intermixing fresh gas with combustion products.

       Duration of the combustion process active stage  in a maximum
 power course is reduced approximately 1 1/2 times in comparison with
 conventional spark ignition, since a turbulence created  by precombustion-
 chamber ignition  is superimposed on the natural turbulence  created by
 filling.  The significance of this  factor is   associated with the fact that,
 in accordance  with the currently  accepted theory of detonation "knock",
 it appeared primarily  during the complex multi-stage process of auto-
 ignition which  developed in the last portion of  the charge preceding a turbu-
 lent flame front.    Therefore,turbulent combustion acceleration can fore-
 stall detonation autoignition completion by creating,  for example,  the pos-
 sibility of increasing compression under  conditions of constant antidetona-
 tion fuel stability.

       The idea of precombustion chamber ignition originated in the In-
 stitute of Chemical Physics in 1935  in the  course of searching for a more
 effective method of preventing detonation ignition.  Numerous experiments
 showed that precombustion-chamber ignition presented the  possibility to
 increase compression  ratio by 1-11/2 units without changing the full proper-
 ties, or to decrease the required octane number by approximately  10 points
 at a given compression ratio.  Accordingly, an increase in thermodynamic
 efficiency brought about by raising compression ratio augments the basic
 economic effect of the  precombustion-chamber system which makes appli-
 cable the  use of lean mixtures at  partial charges.

       The PCF-ignition system  in a carburetor engine was subjected to
 a detailed study both in one-cylinder models7  and in true engines  .  A
 production model of a GAZ-52 automobile engine with a  precombustion-
 chamber ignition  system was built for a 3-ton truck jointly by the Gor'kii
 Automobile Plant and the Institute of Chemical  Physics of the USSR Academy
 of Sciences (L. A, Gussak).  The main characteristics of the engine are as
 follows:  number  of cylinders - 6; cylinder volume -  3.48 li; diameter - 82
 mm; stroke length - 114 mm; compression  ratio - 7.2; maximum power at
 3000 rpm - 86 h.p.

                               - 334 -
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        Precombustion chambers with a volume of 3% of the compression
chamber volume were  equipped with two 2.4 mm  diameter nozzles forming
a 60  angle between their axes and mounted in an overhead-valve type head.
The precombustion-chamber feed line was heated by exhaust gases to insure
fuel vaporization.  This engine did not differ outwardly or in control from
a conventional engine,  and did not create any additional manufacturing prob-
lems.   Comparison tests were conducted with one-cylinder model engines
having spark and precombustion-chamber ignition systems  using  55-octane
gasoline;  maximum compression ratios in terms  of detonation were 6.2 for
the spark type and 7.2 for the precombustion-chamber ignition type. Min-
imal specific  fuel consumption at 1200 rpm averaged 190 g/h. p0 hr.  for the
spark-ignition and 160  g/h. p.  hr for the precombustion-chamber ignition
type.  However,  in this case the fact should be taken into  consideration
that the minimum consumption recorded for the precombustion-chamber en-
gine was maintained through the entire range  of partial charge.  A corres-
ponding minimum consumption recorded for the spark-ignition type was
realized for a brief regime  close to a maximum charge and sharply in-
creased upon converting to  throttled regimes  and enriched mixtures.

       Even when lean mixtures were used with spark ignition the effect
was lowered to a considerable degree by the instability of the flame forma-
tion process.  The dispersity caused by  this in the record diagrams in
subsequent cycles shown in  Fig. 6 reflects  the incomplete utilization of a
nominal expansion degree.  In contrast,  the precombustion-chamber system
regularly repeated the combustion course from cycle to cycle.    An ex-
haust temperature  drop to 600° or below in the precombustion-chamber en-
gine coincided with the lower combustion temperature of lean mixtures be-
ginning with a load of 70% of the maximum.  The  exhaust temperature in an
engine with a spark-ignition system persisted  at 900  through the entire
charge range.

Precombustion Chamber-Flame Ignition in Engines with Internal Carbure-
tion.   This combination of precombustion-chamber ignition with the fuel
spray injected into the  cylinder presents the possibility of radically elim-
inating the principle disadvantages of the spark-and compression-ignited
engines.
       Fig. 6
                                                  UDP
                Diagram series of pressure in consecutive cycles of • motor
                • ith v«rk ignition and one «itf» forechanoer jet ijnttion
                   operating «ith a mixture containing 1201. «ir excess
-------
       Physico-chemical studies of the diesel combustion process found
that it consisted of two essentially different  autoignition stages and of the
turbulent combustion proper! it will be shown later that the two stages
were characterized by opposite requirements. Autoignition of a fuel stream
occurred in a succession  of "cold" flames, especially that type of chain
ignition  which liberated the fuel energy incompletely, and which was  com-
pleted by the formation of one or more flame  sources which enveloped the
entire fuel charge present during the process of turbulent combustion.9
The difference between these two stages is manifest primarily in the
opposite condition requirements for fuel vaporization and mixing  with  the
air.

       Calculations showed that only about 5% vaporization  of the injected
fuel was necessary for the  formation of the initial flame source.  Vaporiza-
tion of excess fuel and enhanced intermixing  with air reduced the autoigni-
tion zone temperature and  inhibited reaction development by prolonging the
interval  in autoignition period which increased the autoignition volume and
formed shock waves thereby turning diesel autoignition into one approximat-
ing the type of detonation ignition in a spark-ignited engine.   Vice versa,
the stage of turbulent  combustion depends upon the highest possible degree
of fuel-gas  intermixing.  In fact, even with an overall excess air present
there exist zones with a considerable lack of air when fuel droplets are
unevenly distributed within a volume.  The fuel does not burn in these zones,
but undergoes pyrolysis with subsequent liberation of free carbon.  In this
way factors which contribute to "knocking" elimination during autoignition
cause smokiness during the turbulent  combustion process and vice-versa.
An extremely high compression ratio  or a high-octane fuel must be used
in a diesel to prevent  "knocking"; a considerable amount of excess air must
be used to prevent smokinessj but this lowers the  maximum power develop-
ment.

       All attempts to overcome this internal diesel process contradiction
by changing ignition of the injected fuel from the  autoignition type to the
spark ignition type failed to yield the expected result. All proposed systems
were unsuccessful, including the widely advertised systems  of Hesselman en-
gine10 or the "Texaco process" design11; however, this was not due to faulty
design but resulted from the very conditions created by spark ignition of
a heterogeneous charge, and specifically from the fact that even very small
fuel drops entering an initial ignition  source sharply inhibited or made  im-
possible the development of an ignition reaction.    Calculations showed that
vaporization of a  fuel droplet 50-/LI in diameter and raising the fuel vapor
to the temperature of  reaction initiation consumed 0.20 microjoule, or  the
equivalent of the energy of  an igniting spark.

       It can be stated that spark ignition was least advantageous particu-
larly when a liquid fuel spray was present in the charge.  The following

                                - 336 -
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 precombustion chamber system advantages becomes especially obvious
 here:  the possible formation of a phase generating the flame source
 in a precombustion chamber filled with a completely vaporized fuel-air
 mixture coming from the precombustion-chamber carburetor accompanied
 by  the formation of an easily-ignited combination of mixture and air from
 the cylinder; the possibility of igniting air and fuel spray from  the precom-
 bustion chamber flow of hot gases, and of burning it in a turbulent flame.
 Turbulent ignition and propagation of a turbulent flame result from the in-
 termixing of a fresh charge with the combustion products at maximum flame
 temperature; for this reason the presence of a drop of unvaporized fuel
 will have a negligible effect on the thermal balance and speed of these pro-
 cesses.

       Accordingly, it is  only with the aid of a precombustion chamber
 system that ignition can be effected  before the beginning of any noticeable
 evaporation of fuel sprayed into the air immediately after being sprayed
 int© the cylinder,  thereby preventing the  appearance of the pre-flame re-
 actions of detonation ignition.   In addition, this system produces com-
 pletely smokeless combustion of the fuel-air mixture  without  excess air,
 leading to total cylinder  volume utilization.

       These possibilities of the precombustion chamber system  used .
 with internal carburetion have been fully  realized in 102 X 1141 ° [mm?]
 and 155 X 16013 [mm?]  one-cylinder models.

       Smokeless combustion down to the theoretical fuel-air ratio can
 be successfully obtained with precombustion-chamber ignition by uni-
 formly distributing  the forced fuel-spray through the entire combustion
 chamber volume by a centrally-mounted atmomizer (cf. Fig. 7).   The
 mean indicated pressure of 9. 5  kg/cm  obtained with a compression  ratio
 of 9 did not differ from the value obtained in the same cylinder operating
 on carbureted isooctane and spark ignition.  Qualitative-quantative con-
 trol yielded a minimum indicated specific fuel consumption of 140 g/h. p.
 hr, which approximated that of a diesel.   Accordingly,  judged by the
 maximal magnitude of indicated mean pressure and by the completeness
 of cylinder working volume the indexes here manifested were of a car-
 buretor operated engine  of spark ignition, but judged by fuel economy
 tke index  was  one of a diesel engine.  Detonation-free engine operation
 reduced to 25 is registered with octane number  (the octane number  re-
 quired at compression ratio of 9 is at least 100) when ignition moments
(ejecting the  ignited stream from the cylinder) are sufficiently close  and
 injection is completed.

       On the other hand,the ignitibility effect is lost when the  fuel is
 ignited from a precombustion chamber stream; the engine characteris-
 tics  remain unaffected when the cetane number is changed within the  (
 range  ©f 25 to 70; so does  volatiling when the temperature of 90% fuel
-------
 evaporation changes the range of 150 to 420 .   The possibility of doing
 away with the special requirements pertaining to the development of the
 "multifuel engine" realizable for the first time.  In addition to the purely
 operational  advantages of multifuel engines,  their use in an automobile
 or tractor motor pool should result in a considerable saving in motor fuel
 up to 30% according to American data.  The most important  result of re-
 placing existing engines with multifuel engines is probably the possibility
 of a more complete use  of petroleum as a chemical raw material and as
 a source of  motor fuel free from special requirements related to their
 chemical structure.
 Fig.  7
                                  The PCF ignition system transcends
                           the design perfection limits of existing spark
                           ignition and diesel engines  by their origin of
                           development and by their purpose  as scientific
                           analytical extrapolations from the  nature of
                           combustion processes and from methods de-
                           veloped for the control of the operating pro-
                           cess.   This class of engines is based on a
                           fundamentally new method of igniting homo-
                           geneous or heterogeneous  charges in a cylin-
                           der from a stream of hot gas.
                                   The industrial use of this class of car-
                            buretor engines, which is possible even  now,
                            will yield considerable savings in gasoline
                            consumption without requiring increased com-
                            pression ratio or the manufacture of high-oc-
                            tane fuel.  Engines of this type with internal
                            carburetion open possibilities of creating
                            multifuel engines which have  all the advantages
of spark-ignited and compression-ignited engines,  but without their  dis-
advantages .

       In conclusion it should be remembered that exhausts of engines
equipped with precombustion chamber flame ignition contained no products
of incomplete combustion and pyrolysis, such as  carbon monoxide,  car-
cinogens, smoke or other toxic  gases, which  is favorable from the view-
point of air protection  against pollution in cities saturated with automobile
traffic.
Schematic presentation of a
oith forecharaoer jet  ignition and
  internal  raiature formation
  I - atomiser; 2 - forechanber
1C.  Kettering,  "SAE Trans.11, 1947, No. 4, p. 669
2D.  Caris,  E. Nelson, ibid., 1959,  p.  112
3C.  McCuen, "SAE Trans. ",  1952,  No. 2,  p.  290
                                - 338 -
-------
4 J.  Campbell, D. Caris,  L-. Withrow, ibid., 1949,  No. 2,  p.  341
6 J.  Campbell, D. Caris,  L. Withrow, "SAE Trans.",  1949, No.  2,  p. 341
6A.  S. Sokolik, V. P. Karpov, Ye. S. Semenov, "Dokl. AN SSSR11 [Reports
  of  the USSR Academy of Sciences], 1959 v. 128, No.  6,  p.  1220
  V.  P. Karpov,  A.  S. Sokolik, ibid,  I960 v. 132,  No. 6, p.  1341
  V.  N. Voinov,  Using precombustion-chamber ignition in a  carburetor
  engine to control detonation and operation  on lean mixtures, Thesis,
  Leningrad, 1940; O.  S. Sergei1, Problems of Increasing the effective-
  ness of the combustion process in a carburetor engine,  Thesis,  Moscow,
  1951.
 Li.  A. Gussak, A Precombustion-chamber kerosene engine, Thesis,
  Kazan1,  1942; S. V. Rumyantsev, Study of a precombustion chamber
  ignition  system in  a M-105 engine, Thesis, Kazan', 1943.
9A.  S. Sokolik, V. Ya. Basevich,  "Journal of Physical Chemistry",  1954,
  v.  28, No.  11, p. 1935; V.  Ya.  Basevich,  A. S. Sokolik, ibid, 1956,  v.
  30, No.  4,  p.  729.
10S.  I. Akopyan, Electrically-ignited fuel-injection internal combustion
  engines, Moscow,  Mashgiz,  1945
1XE. Barber, B. Reynolds,  W. Tierney, "SAE Trans.", 1951, No. 1,
  p.  26
12A. S. Sokolik,  V.  P. Karpov,  in the collection "Combustion and carbure-
  tion in diesels", Moscow, Academy of Sciences Publishing House, I960.
13S. V. Rumyantsev,  M. D. Yermolayev, V. I. Domrachev, A. S.  Tikho-
  nov, A.  A. Bulavkin, A study of the flame system  of ignition as  applica-
  ble to aircraft engines, Moscow, Oborongiz, 1958.
                               - 339 -
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