Document 72ppRnQQop3VRkynz4a8jN6o
Anna's New York Academy of Sciences
Cat.T.ie. W.
, Vol. 14: 306. Urban & Schwarzenberg. Miinchen, West
Germany.
Oster, R. H.,
a & J. C. Krantz. 1947. Anesthesia. XXVII. Narcosis
with vinyl ci
e. Anesthesiology 8: 359.
Ostermays
67. Vinylchlorid. In Ullmanns Encyklopadie der technischen
Chezaie. Foerst, Ed
Urban St Schwarzenberg. Miinchen, West
Gerai]
Otto,
Krause, H. G. Jester, F. W. Schmidt St K. H. Glatzel. 1972.
ache portale Hypertension. Med. Klin. (Munich) 67:447.
Parj^^Iami, L. St C. Sassi. 1955. Rischi e patologia professional nella pro
ne e nella lavorazione di alcune materie plastiche. Med. Lavoro 46: 14.
F. A., W. P. Yant & C. P. Waite. 1930. Acute response of guinea pigs to
r apors of some new commercial organic compounds. V. Vinyl chloride. Public
'Health Rep.
__
j3^t06. Patty, F. A., Ed. 1963. Industrial Hygiene and Toxicology. Vol. II. Toxicology.
D. W. Fassett St D. D. Irish, Eds. 2nd edit Interscience Publishers, New York,
N.Y.
^Polish, E., J. Christie, A. Cohen St B. Sullivan. 1962. Idiopathic presinusotdal portai hypertension (Band's syndrome). Ann. Internal Med. 56: 624. [pper, H., F. Paronetto, r. Schaffner & V. Perez. 1961. Studies on hepatic ibrosis. Lab. InvesL 10: 265.
er, H. 1968. Pathology of portal hypertension. In The Therapy of Portal :rtension. N. G. Markoff, Ed. Georg Thieme Veriag. Stuttgart, West Ger-
,H.4r. Hutterer. 1970. Hepatic fibrogenesis and disturbance of hepatic
gtion. Ann. N.Y. Acad. Sci. 170: 88.
i. St S. Udenfriend. 1970. Hepatic fibrosis. Correlation of biochemical
and hologic investigations. Am. J. Med. 49: 707.
1 J>3. PUSHING A. 1965. O porashenii pefeni i zelJnyikh putei u raboiikh' zan1 jatyikn roizwodstwe nekatoryikh widow plastmass. Sov. Med. 28: 132.
^114. PVC proi
see good business ahead. 1969. Chem. Eng. News August 4: 18..
. 115. Quooss.
~9. Gesundheitsgefahren in der Kunststoffindustrie. Johann Am-
brosius B * 'erlag. Leipzig, East Germany.
S/' 116. Ramalinoas
V., K. L. Wio St S. K. Sama. 1962. Cirrhosis of the liver in
1 s Northern In)
clinicopathological study. Arch. Internal Med. 110: 350.
Ramalincasw/
St N. C. Nayajc. 1970. Liver disease in India. In Progress in
OiiiSSh/ Liver Disease.'
W
New York, N.
opper St F. Schaffner, Eds. Vol. Ill: 222. Grune St Stratton.
\S\ 18. Rappaport, A. M ^ circulatory changl
joblauch, R. G. Black St S. Ohira. 1970. Hepatic microfiding to portal hypertension. Ann. N.Y. Acad. Sci. 170:
1^S119. Ravenna, P. 1940.
, classification and pat! Vt20. Remmer, H. 1970. The . W1 Qcvvnr r> T R Jb A
, syndrome (fibrocongestive splenomegaly). Definition,
nesis. Arch. Internal Med. 66: 879.
gf the liver in drug metabolism. Am. J. Med. 49: 617/
CD lOAf Uanattr
kv.
............. ............ ......... .............. ...
Thank you for choosing
Advanced Information Consultants Vondor
for your document delivery needs
MI Mail
Trano Typo
GEO02
$vWificaOon
SfepDoto
602468
W Tl O U> ON NO
r.
$Coot
5
$ $M CNrp
|
ii 6LZ
to
INDUSTRIAL HYGIENE
AND
TOXICOLOGY
Second Revised Edition
FRANK A
Editor
VOLUME II
TOXICOLOGY
David W. Fassett and Don D. Irish, Editors Index by Mbs. Kathleen Kumler
Authors
W. B. Deichmann D. W. Fassett H. W. Gerarde C. L. Hake D. O. Hamblin L. W. Hazleton
F. W. Hetroth C. H. Hine D. D. Irish R. A. Kehoe M. L. Keplinger F. A. Patty
V. K. Rowe H. E. Stoktnger W. L. Sutton J. F. Tbeon R. J. Weir M. A. Wolf
INTERSCIENCE PUBLISHERS
a division of John Wiley & Sons, Neu> York/London
0 t'E 6 I'Z
aliphatic halogenated hydrocarbons
1303
: Skin Irritation. Propylene dichloride on the open skin causes only mild irrij^gon. Single short contacts will probably be without any effects. The intensity of e reaction is greatly increased when bandaged on the skin or when held close to Ike skin, by clothing.
Eye Irritation. Propylene dichloride causes some pain and irritation when gashed into the eye. It would not be expected to cause serious or permanent jijury. n should be washed out immediately with water.
J gygienic Standards of Permissible Exposure
The threshold limit of propylene dichloride was established by the American Conference of Governmental Industrial Hygienists, in April, 1959, at 75 p.p.m. (350 mg./cu. meter.) 55? I' S, flammability
'`""'he flammable limits of propylene dichloride are 3.4 to 14.5 per cent in air. > ignition temperature is 557 to 570C.
, CHLORIDE, CH2=CHCI (Monochloroethene)
* Uses and Industrial Exposures
; Vinyl chloride is used as a chemical intermediate primarily as a monomer in SJIastie manufacture. The fire and explosion hazard is by far the dominant prob-
o in handling vinyl chloride.
' Physical and Chemical Properties
Physical state: gas Molecular weight: 62.5 Specific gravity: 0.9121 (20/4C.) Melting point: --153.71C. Boiling point: --13.8C. T Vapor density: 2.15 (air = 1) er Vapor pressure: 2580 mm. Hg (20C.) Solubility: slightly soluble in water; soluble in ethanol and ethyl ether aor Flash point: --78C. (open cup) 1 mg./liter o 391 p.p.m. and 1 p.p.m. o 2.56 mg./cu. meter at 25C., 760 Hg
Physiological Response
Vinyl chloride appears to be a material of relatively low toxicity. The principal ^response seems to be one of central nervous system depression, which may result in (Symptoms of dizziness and disorientation that are somewhat similar to the reijponse from ethyl chloride exposure. There is the possibility of some lung irrita tion occurring from chronic exposure as some edema is observed in acute vapor
bFG36495
1
1304
DON D. IRISH
ALEPHATl
exposure. Most investigators did not observe kidney or liver damage. One group Skin. The boiling point o:
of authors indicated some hyperemia of the liver and kidneys from acute ex fere spilled on the skin, there
posure. It is concluded that the material has essentially a narcotic effect, with some lite.
lung irritation and a possibility of organ injury. There has been quite extensive Absorption, Excretion, an>
use of this material in the chemical industry but no clinical reports of injury.
ism of this compound. It is ap
Acute Vapor Exposure. Patty et ai.100 reported the response of guinea pigs excreted by the lungs. The litt
to single exposures to varying concentrations. The maximum time-concentrations jlarge part is excreted by the 1
in air for a single exposure survived by guinea pigs were as follows: 5 to 7 per cent ^ Hygienic Standards of Permiss
for 1 hour and 21/2 per cent for 8 hours. The maximum time-concentration in air
for a single exposure without serious disturbance was 1V2 per cent for 1 hour and
The threshold limit of vii
0.5 per cent for 8 hours. It will be noted that it requires a high concentration td
cause death.
-||
jaence of Governmental (1300 mg./cu. meter).
Incl
The same authors report that a concentration of 2*/2 per cent of vinyl chloride Torkelson et al.102t- sugges
in the air for a period of 3 minutes will cause dizziness and disorientation in ex? S. Flammability** posed men. They also observed a faintly pleasant odor at this concentration The explosive limits of vii Animals that died from acute exposures showed edema of the lungs and hyperemia, a air). The autoignition temp of the kidneys and liver.
Men exposed to vinyl chloride detected a slight odor at 4100 p.p.m. Thill f, Odor and Warning Properties
the lowest concentration at which an odor was detected. At 6600 p.p.m. for 1 hour, they noticed dizziness, sleepiness, and distinct odor.
Vinyl chloride has been investigated as a possible material for anesthi
Vinyl chloride has a mild property for excessive exposur *.
purposes by Peoples and Leake101 and by Oster et al.102 It was concluded vinyl chloride was unsatisfactory for use as an anesthetic because of its circulatra and cardiac effects. These studies were at 10 to 20 vol. fo and are hardly signify for industrial exposure.
Chronic Vapor Exposure. Essentially no investigations have been publish
HNYIIDENE CHLORIDE, *v
t' Uses and Industrial Exposure I" Vinylidene chloride is v.
nonomer in the production of
on the response to chronic vapor exposure. Schaumann85 exposed mice and rats found that they tolerated a level sufficient for "light narcosis" for period3 `o] hours daily for 5 to 8 consecutive days or for 1 hour daily for 4 weeks wii showing kidney or liver injury.
Torkelson et ai.102* (to be published) report repeated exposures of animals] 7 hours/day, 5 days/week. At 500 p.p.m., rats showed increased liver weight micropathology. At 200 and 100 p.p.m., rats showed increased liver weight, b; changes could be observed in dogs or guinea pigs. All species tolerated 50 pi] for 6 months. Repeated exposures for 1 hour/day at 200 or 100 p.p.m. were w| ated without observable effect.
LJPhytical and Chemical Prope.
Physical state: clear col Molecular weight: 96.9c Specific gravity: 1.218 < Freezing point: --122.5 Boiling point: 31.7C. Vapor density: 3.34 (ai Vapor pressure: 591 mn Refractive index: 1.427 ;` Per cent in "saturated" a
* Chemical Safety Data Sheet SD-56. Manufacturing Chemists As30c., Washington,
1954. M,F. A. Patty, W. P. Yant, and C. P. Waite, Public Health Repls. V. S., Reprinjj
1405,45, No. 34 (Aug., 1S30). **S. A. Peoples and C.D.Leake, J.Pharmacol.ExptL Therap, 48,284 (1933). "R. H. Oster, C. J. Carr, J. C. Krantz, and M. J. Sauerwald, Anesthesiou)fiJf, 'i
Density of "saturated" a Solubility: insoluble in Flash point: --15C. (< 1 mg./liter C= 252 p.p.n |Hg
(1947).
7cTM
T. R. Turkelsou, P. Oyei
BbG3
6496
ALIPHATIC HALOGENATED HYDROCARBONS
1305
One groi Skin. The boiling point of vinyl chloride is so low that if the liquid material a acute ej ''ere spilled on the skin, there is a possibility of severe cooling and possibly frost
t, with son 'itete extensii Absorption, Excretion, and Metabolism. Very little is known of the metabo'jury. ism of this compound. It is apparently readily absorbed by the lungs and rapidly guinea pij xcreted by the lungs. The little information that is available would indicate that icentratioi large part is excreted by the lungs unchanged.
!
c , Hygienic Standards of Permissible Exposure
a1 hou1r at The threshold limit of vinyl chloride was established by the American Conentration erence of Governmental Industrial Hygienists, in April, 1959, at 500 p.p.m.
1300 mg./cu. meter). nyl chlorii Torkelson et af.102` suggest 100 p.p.m. ation in e Flammabilitym ncentratia The explosive limits of vinyl chloride are: lower, 4% and upper, 22% (by vol.
yperem Q The autoignition temperature is 472.22C.
>.m. This Odor and Warning Properties
D.m. for l. Vinyl chloride has a mild, sweetish odor. The odor is not an adequate warning
Property for excessive exposure. esthet
eluded th TNYLJDENE CHLORIDE, CH2=CCI2 (1,1-Dichloroethylene) circulate* f signifies tises and Industrial Exposures
Vinylidene chloride is used as a chemical intermediate, particularly as a n publish lonomer in the production of plastics.
,nd rats SI , ienods of eks with
j
animals
weight ight, but' td 50 p.] were t<
antfChemical Properties
Physical state: clear colorless liquid Molecular weight: 96.95 Specific gravity: 1.218 (20/4C.) Freezing point: --122.5C. Boiling point: 31.7C. Vapor density: 3.34 (air = 1) Vapor pressure: 591 mm. Hg (25C.) Refractive index: 1.427 (20C.) Per cent in "saturated" air: 78 Density of "saturated" air: 2.8 (air = 1) Solubility: insoluble in water; soluble in organic solvents Flash point: --15C. (open cup)
.. h fel
POTENTIAL EXPOSURES IN INDUSTRY
2251
cause characteristic, fj t-producing machines |
strong joinings with cases cause a charac- ler parts of the body |
ontrol methods (see
Cement and Concrete
Cement is made from cement rock or a mixture of finely ground limestone, or other form of calcium carbonate, with clay, shale, slate, or blast furnace slags, rarely sandstone, and certain accelerators or retarders. The mixed powders are heated in a kiln, usually rotary, to about 1300 to 1400C. The kilns are heated by fuel jets of powdered coal, gas, or oil. The cement rock rarely contains more than 6 or 8 per cent quartz; the finished product usually less than 1 per cent, though occasionally it may contain up to 6.5 per cent. The dusts are ordinarily classed as nuisance dusts but their concentration may exceed the most liberal ideas of permissible limits.
There are several dust-producing operations and they are amenable to control measures. Some of these sources are: stone quarrying, crushing, grinding, the rotary kiln, screens, bagging operations, and the loading and unloading of cars. Dust clouds, if uncontrolled, not only are conducive to undesirable working condi tions but also constitute an atmospheric pollution nuisance in the community. Electrostatic precipitation as well as centrifugal collectors have been used success fully to remove the dust from the effluent air from kilns and silos, and the amount recovered is said sometimes to exceed 5 per cent of total raw materials. A method that has been successfully applied to the rotary kiln elsewhere (see Sand Refining) is to exhaust the hot kiln gases through baffled water-spray chambers and conduct the water flowing from the sprays through a settling basin from which the sludge may be recovered. The important factors in evaluating exposures are the degree of dust control and the free silica content of dust particles less than 5 p. in diameter. Lung injury from exposure to cement dust, however, has not been demonstrated and the most frequent, harmful result of exposure is that of skin irritation from the alkaline action of cement. In the mixing and use of concrete, the irritant, alka line action of the wet mixture is similar to that of the cement dust, and both warrant suitable control to prevent prolonged contact with the skin.
Chlorinated Waxes and Oils
Synthetic Cfdorowaxes. The synthetic chlorowaxes comprise a number of chlorinated hydrocarbons that are derivatives of naphthalene or diphenyL Halo.ftwax is the trade name of one manufacturer for the chlorowaxes.
The damage that may occur from inhalation, ingestion, and skin absorption ..of the chlorowaxes will vary with the degree of chlorine saturation of the com( pounds. The amount of dermatitis and poisoning increases rapidly as the amount' |_of chlorine in the waxes increases. The commonly accepted maximum permissible 1| limit for atmospheric contamination with trichloronaphthalene is 5 mg. per cubic -meter of air. Pentachloronaphthalene, one of the chlorowaxes carrying a high ' percentage of chlorine is restricted to 0.5 mg. per cubic meter of air. i Systemic poisoning from the chlorowaxes is generally characterized by
damage to the liver. Serious exposure may produce acute yellow atrophy. The
2252
FRANK A. PATTY
skin effects are commonly in the form of acne, which is more widely distributed 4
on the body than common acne.
J|
Among the recommendations for the prevention of chlorowax poisoning are' ' (1) vapors and dust should be controlled by exhaust ventilation to prevent^
exposure to amounts of the compounds in excess of the safe limits mentioned 4 above; (2) foremen and workers should be told of the toxicity of the materials thatJ they are handling and instructed to keep skin contacts with the material to at
minimum; (3) preemployment and periodical physical examinations should bei given with special attention to the skin and to the liver, liver function tests being!
performed periodically; and (4) the best hygienic conditions should prevail,! including the provision of clean work clothing, protective gloves, and protective creams. Those manufacturers who have had the most favorable results in pre venting chlorowax poisoning have provided double locker rooms, one for street clothes and one for work clothes, with a shower room in between. The worke should be required to take a shower every day before leaving the factory; it is we to provide supervision to make certain that this practice is complied with.
Air analysis for the chlorowaxes is most commonly performed by passing thS air over heated platinum in an electrically heated quartz tube; the waxes decom pose and the effluent gas is scrubbed in a column of glass beads moistened witj sodium carbonate; the chlorine is converted to sodium chloride which is recover! by washing the beads, and is usually determined nephelometrically. The impmger using amyl acetate as the collecting medium, has also been employed for collects of samples; afterward the samples are burned, products of combustion collect and chlorides determined.
Chlorinated Oils. There are two general types of oils falling within this cla the first contains additive substances such as carbon tetrachloride to improv cutting properties; the second has chlorine combined in complex organic structur
The chlorine additive agents may be recovered by distillation and are releas' from the oils in accordance with vapor pressure laws. The use of oil plus chi rinated hydrocarbon may be hazardous unless exhaust ventilation is provid Nausea and malaise are common complaints of workers handling the The haphazard methods used in preparing the mixtures tend to increase the dang Commonly the chlorine compound is added in unknown proportion as an antid for cutting difficulties. In some instances the mixture has been found to contain
much as 40 per cent carbon tetrachloride.
__
The chlorine in the second type of oil is firmly bound at lower temperatr
upon heating, little decomposition occurs below 200C.; near and above 25
hydrogen chloride is evolved. It is known that temperatures in excess of 300 are produced locally from heavy cutting operations. This type of oil proba can be used safely for light precision machining.
Animal experimentation has shown that chlorine compounds in oils may
a/bsorbed through the intact skin to cause liver damage. Dermatitis fror
rinated oils also occurs.
-t >
x>d. During cooking, the digester or along s of "sulfate wood aldehydes, traces of lium sulfide, methyl e pulp and digestion ling, and some subaporators, salt cake very furnaces, where aving the alkali and combustion gases are sulfurous gases and rbonate, and sodium ;reeable. Although in ntrations, there are flammable gases or
ipe of odorous gases, hem through caustic, washing with water >recipitation has also
aor is an aqueous bisulfites. The sulfur burning of sulfur or.J ntains high amounts! .1 operation. This isj
se of chlorine, whicha m bleaching powdenj te vat and be carrie owever, the exposure^ neral ventilation, chines and the mate*! dyes, plastics, gumsa tposures arising front s resulting from the from the coating ana dissolved in organic ir-conditioned roomij t.
54,35 (1939)
POTENTIAL EXPOSURES IN INDUSTRY
2297
Photographic Industry
Dermatitis and skin sensitization are the hazards of the photographic in dustry. Nasal and bronchial irritation and asthma are also reported from contact with developers and other photographic chemicals. The aminophenols are among the most common sources of skin disease from developers. Other irritating chemi cals include caustics, iron salts, mercuric chloride, strong acids, bromides, iodides, pyrogallic acid, and silver nitrate. The last substance is reported to have caused argyria, a condition in which silver is deposited beneath the skin. It is difficult, if not impossible, to remove the deposits completely.
The prevention of dermatitis lies in reducing to a minimum the contact of the chemicals with the skin. Cleanliness, protective clothing, and protective creams are the triumvirate for controlling the hazard.
Plastics and Synthetic Resins
Synthetic resins that have undergone complete condensation cause little difficulty in the cold, but where heat is applied, or an imperfectly combined com ponent is present, skin irritation and sensitization may result. The phenolformaldehyde and urea-formaldehyde resins owe their irritant and sensitizing properties chiefly to formaldehyde,38 but phenol and furfural (phenol-furfural resins) may also have some irritant effect. It is advisable to provide process ventilation for any dust-producing or vapor-producing process involving the manufacture, fabrication, or use of plastics whereby formaldehyde is released into the workroom atmosphere. Hexamethylenetetramine, which has a bad repu tation as a sensitizer, is harmful because it releases formaldehyde.3* Cashew nutshell liquid-formaldehyde resin is particularly offensive if any uncombined cashew nutshell liquid remains in the resin. "Oil stop," a waterproof resin made by mixing cashew nutshell liquid to a paste with powdered paraform (a polymer of formaldehyde) and allowing it to "set" or condense, is popular with electricians. Both of the constituents are irritants and sensitizers and there is a high incidence of dermatitis among users who carelessly contaminate their hands and clothing with the mixture.
Plastic glues for the manufacture of plywood, laminated asbestos, fiberboard. glass fabric, and similar products may be made of incompletely condensed resins containing formaldehyde along with acids, alkalies, peroxides, and other irritants and sensitizers. The screening, scaling, and mixing of such powdered glues are productive of dust and "conducive to dermatitis.
Many plastics such as vinyl chloride, vinyl acetate, polyethylene, poly styrene, and methyl methacrylate have proved to be more or less inert physio logically. Antioxidants and stabilizers added to some plastics, however, may occasionally cause adverse physiological effects. The majority of the dermatitis
" A. G. Crunch, Ind. Mei, 15,168 (1946). ** L. Schwarts, J. Invest. Dermatol, 6,239 (1945).
m
BFG36500
2298
FRANK A. PATTY
cases arising from prolonged contact with plastics of this nature arc caused by plasticizers added to eliminate brittleness and to produce flexibility. Some of these plasticizers are susceptible to the effects of heat and moisture and may separate from plastics that are in prolonged contact with the skin and cause either primary irritation or, more likely, sensitization. This presents a use problem rather than a
production problem. These plasticizers3 include derivatives of glycol, glycolic acid, phthalic acid, phosphoric acid, ricinoleic acid, and sebacic acid.
In evaluating and controlling exposures arising from the manufacture, fabri cation, or use of plastics, dermatitis is the primary consideration, but eye irrita tion and even the possibility of lung irritation should be considered. Dusts, especially those involving incompletely reacted materials, and curing agents, especially organic amine vapors, should be controlled by engineering methods; excessively warm and humid atmospheres also should be controlled; and direct skin contact with suspected irritants or sensitizers should be avoided. A supervised program of personal cleanliness and frequent changes of clothing are the best personal control measures wherever dermatitis is involved.
Occasionally persons do not respond to "hardening" and the standard pre ventive and protective measures. In such cases of unusual susceptibility it is necessary to transfer the workers to other work.
Pottery Industry
Silicosis and lead poisoning are the traditional occupational diseases toil potters. Free silica is present as flint in the pottery slip in amounts that make dust 9 control of a high order imperative. Respirable sizes of dust commonly show 40 toi 50 per cent free silica in slip houses. The use of lead compounds in decorating ware| also necessitates a high degree of dust elimination.
Most of the dangerous silica operations are concentrated in a few departments^ The slip house normally has more than half of the total significantly exposed! workers. Lead exposure is confined to sprays and dust from ware prior to itsj being fired.
Jiggering and batting out normally do not involve harmful exposures! Stampers should be provided with exhaust ventilation, however, as should! finishers. Dish makers do not have significant dust exposures. This statement; also applies to casting shops. Bisque and glost kiln placing and drawing dust-free operations. Flatware brushing is one of the dustiest occupations outsid^ of the slip house and it requires control. The transfer of raw materials fro|
boxcars to storage bins may involve excessive dust exposures. It is poor hygienic practice to draw hot air directly from the fire chamber
of the kilns into the workrooms to heat them: a system of heat exchangers should be used.
remo in hr. lesser
1 fluori clothi
BFG36501