Document v16Zn8K2pN3q8YzXVZQdZoMeR
OFFICE COPYBiochemical Research laboratory The Dow Chemical Company
Jfat-JE.E.D."7-
FEB 07 1958
EVALUATION Cfr 'CBEMZGftX -EXPOSURES
RECEIVED BY
' OP
COATINGS TECHNICAL SERVICE,
433 BUILDING
Signed Date IJ /-2<}/s-P
Tllet Tfi.l-l-S Chg.: 1219 Date: 1-22-38 By: J* E. Peterson
I ft/f- V | \ ' r
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CO
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PROBIEM
THIS REPORT IS THE PROPERTY OF
THE DOW CHEMICAL COMPANY
Recently,
has become 111* The Environmental Research
laboratory was requested to determine chemical exposures received
by him, and to assess these data.
- - CONCLUSIONS
I. .Exposures to airborne materials during the formulation,
mixing, sad calendering of .vinyl asbestos tile In 433 Building
Lfcemaluated. cm aa-23-54 and-on .1-13-36*.. Jtosults of. these
M+mmm
rfflelTtd by
during Tiljnrorfc with this material.
2. From December 1933 to December T1954V
worked
with vinyl asbestos tile formulations, and In the course
of that work was occasionally exposed to somewhat wxeesslve
' concentrations of airborne .asbestos*
DOU 01540 g
ST0030598
Biochemical Research laboratory T2.1-1-65 Page 2
During rthiM periodr timer^exposure to lead occurred,..tot ..his blood lead level on 3-7-55 was only 0*024 mg./lOO cc* blood, a . .normal figure* Exposures to cadmium during this period were to airborne concentrations of' V0.7 mg* .at intermittent. periods* No effect is expected as* a result of these exposures*
3. Prom the first part of 1955 to late 1956
worked -
mostly with latex in concrete, and exposures to vinyl-asbestos
tile ingredients were reduced accordingly*
4* From the last part of 1956 until the present he has been working with vinyl-asbestos tile formulations In a supervisory .capacity. During .this work he was probably exposed a maximum of 1-2 days per week to airborne-dost-concentrations of less than 3 mppcf cf. a. material .analyzing 20-3056 asbestos, less than556-SiOg* .an4d -About. C*02. cadmium. No effect can be -expectedfrom octnexpoaore.
5. "If
Hirttetilty is the result*of chemical exposure,
the cusitive agent is unknown at present. .Further air analyses
are to be made during a time when chlorinated polyethylene
is used as the resin binder in the tile formulations*
*/>. DOW 01541
ST0030599
Biochemical -Research laboratory T2.1-1-65 Page 3
-'`ragSCTTjreioirop data
has been ill with a lung difficulty, and overexposure '.to'chemicals '-encountered during'the :femulation, nixing, and calendering of vinyl-asbeatos tile formulations was suspected to
be the cause of his illness. The Environmental Research laboratory was requested to determine and evaluate his exposures.
On 12-23-34 an environmental survey.of. the vinyl^asbestos tile `
formulating operation was made by S. R. Johann; the results of
this work were reported on 5-5-55 (Pile Humber, T2.1-1-32). This
survey found that air concentrations of "inerts" (asbestos plus
calcium carbonate)* barium, and lead were too high for repeated
8-hour exposures., and even though exposures were not that prolonged,
reconraded the installation .of ..local exhaust:ventilation. Cadmium
was determined In the air, samples, but In all cases the amount
present was below the'limit of sensitivity of "the analytical
technique employed/leading-to sir concentration figures of
" less
tod * less'than" ~0*45
As a result of this investigation several changes were made*.
First, the use of lead and barium compounds In the formulation
was sharply curtailed. Second, operational techniques were
changed so that each-hatch was completely'fonwilsted before
mixing in the Banbury or Balcsr-Ferldns nchlnes, and mixing
these enclosed machines was always to be done prior to m 11 J:--.. .
W 03542
ST003 060p
Biochemical Research laboratory T2.I-I-65 Page 4
Third, cano^'hoote'Tferef,lnBterllS over the large 2-roll-mill and over the calender, but not over the small 2-roll mill usually used ...for preliminary.compounding .of .these.formulations*. .Finally, the 'Building Products group recently moved into new quarters where a bench-type hood is always available to control dust ;from dry ' mixing.
In connection with the environmental survey of December 1954,
.
* samples were taken for blood-lead determinations for the men
involved on this project.
_ blood lead concentration
was found to be 0.024 mg./lOO cc. of blood, a normal figure,
indicating insignificant exposure to lead. The other two men
Involved also ted normal blood lead values.
On I-15-58 a -second environmental survey of the vinyl-asbestos
tile operations was aede, partly bo assess the value of. indicated
- changes-In reducing exposares of 'personnelend -partly to gain
^more insight
ther*etemlca 1*acpcaur*s"fctet.
`may
have received recently.
The Ingredients used in vinyl-asbestos tile formulations have adhered quite well to the seme basic recipe for over a year.
DOW 01543
Biochemical Research laboratory T2.1-1-65 Page 5
STQ03060I
The recipe is as follows: Material
Weight Ratio
Resin -
..
May be chlorinated polyethylene
..
or resin 2716, the copolymer of
15# vinylldene chloride, 85#
vinyl chloride.
Dioctyl phthalate or tricresyl phosphate
17*5 2,25
Monoplex S-38 An epoxldized oil purchased from Rohm and Haas.
Metasap 624 Contains cadmium laurate
Aluminium stearate Paraffin wax leslmit -- Calcium- carbonate 'No. 18 graining sand -
A very fine sand Titancac RA50- 'Titanium dioxide Asbestos shorts, type 7M
. . 2.25
1.5 0.1 0.1 39*8 12.5
5.0 19.0
With: the mxceptlonfof 'dioctyl .phthalate and monoplex St38, which are liquidB, tll of theae materials are dry^powders, and normally are weighed into'a-stainless''-ateel^2Blxlx)g^>OMa,,in the open. Hils operation takes about 5 minutes. The mixing bowl is then placed under a mixer within a hood* mixed far a few mnutesv*and then:the two .liquids are added. -After.further mixing, the batch (which is still a .dry powder) la.poured into a paper bag held within the hood.
DOW 01544
STQ030602
Biochemical Research laboratory T2.1-1-65 Page 6
'-When -:lt*. Is dcfte , imighlBg. and blendlag * of 'the ingredients- takes place at a maximum frequency of about 3-half-days per week; an average frequency Is difficult to establish because two or three
* weeks'.may pass with no- activity in this area -at -all*. . normally would be involved in about 10^ of this work which 'Is usually done by a lab technician*
Dry powder from the paper bag is poured directly into the Baker- ^ Perkins or Banbury mixer - usually the Banbury*- `Here the:naterial is forced into a heated mixing chamber with an air-powered ram and Is mixed for about two minutes. The resulting mass Is semiplastic, and Is removed (sometimes with difficulty) from the mixer .and carried to the differential speed heated (200-300?.) 2-roll mill. On thiS 'miir it-is further blended and occasionally marbllizlng chips are added* Such "blending may take from 2 or 3 minutes to a half-hour depending upon the difficulties encountered*
- After.Jbeingj^thoroagh3y..i3d'Oiv-the ^2-roll mill .the.plastic mass Is-earrled'^bo*'the calender (basically a nooler heated..2-roll mill) a. few feet away* Here the material Is 'Squeezed -to a pre-determined thickness by a-pass'through' the .rtflls 5 * "the surfaoe ofthe -resultng strip is improved by a second pass through this machine* The strip of tile material is then cut into pieces of the* correct size for testing .with a shear.. .yrom. Banbury mixer to .finished .pieces of tile may take from 15 minutes to an hour or so for a single batch.
* X
DOW 01545
ST0030603
Biochemical Research laboratory T2.1-1-65 Page 7
The'TBftmiimna freqoeneyur-thlw Jofclw about -the^same as for weighing and blending, 3 half-days per week, and again, an average .frequency-la almost.Impossible to.establish* For.reasons of safety, two aen always rwork.togetber ln these:operations;
has been associated with about 8o of this work since the latter part of 1956*
On 1-15-38 several air analyses were made during vinyl-asbestos
.
tile manufacture* Air sampling equipment used was the Bausoh and Lomb dust counting microscope and the electrostatic precipitator. Results of these air analyses are presented In Table I. Samples 1-11 were taken with the B and L dust counting microscope and the concentrations are expressed in terms of millions of particles per cubic foot of air. (mppcf).. Samples 12-lA were taken with the electrostatic precipitator, and normally concentrations would be expressed-as milligrams of air contaminant per cubic eter 'of ,airr(mg.'^s^)VJ'wt "the"ssmples were unfortunately of ttoo^orfe*;iiBmtlaB:te'joibtat;weighable>qaantltde8 .af.dust.
t. DOW 01546
ST0030604
Biochemical .Research laboratory T2.1-1-65 Page 6
Sample No, 1
2 3
4 5 6 7 6 9 10
Table I .
Description ,
Dust Concentration, mppcf
An air sample taken directly over a paper bag of dry materials shaken to produce dust. This sample was mainly to establish the size range of the airborne particles, Breathing zone sample as a paper bag of formulation was dumped into the Banbury mixer, Sample of fume from the hot semiplastic mass as it was withdrawn from the mixer, not a breathing zone sample, Breathing zone of a man removing the semi-plastic mass from the Banbury mixer with steel picks, Breathing .zone while working the . material-on*the 2-roll mill, . ' Breathing wone while working the material on the 2-roll mill, ...Breathing zone of .man as he put ' 'the material' through the calender, ^'^Sreatdting^one while 'cutting the -tile to alee .on the -shear . Room air in the office, Breathing -zone 'of lab technician as he added dry asbestos fiber to the mixing container on a scale in the laboratory.
Moat 'particles ^ 5n In diameter, average about 2-3 A' 3.2
0.7
1.0
0.9
0.2
0.7 "0.5 0,2 ... .1.4.
s. DOW 01547
ST0030605
Biochemical Research laboratory T2.1-1-65 Pa*e 9
Sample No.
Description
'Dost Concentration, MPPCF
11 .
. .Jtanediately.outside of the bench ' hood where the dry.batchof. material ' was being mixed.
0.5
Length of Time of Sample
Dust Cone. mg./fa.3
12
Electrostatic precipitator 2 min.
Too little to weigh
sample in the breathing
zone while formulation
being mixed in the Banbury.
13 Breathing zone while work ing the formulation on the 2-roll mill.
Too little to measure
14
-Sample taken in bench hood
CaCOo - Main Constituent
over the container where the
Asbestos - 20-30$
dry -mixture -was being stirred. Si02
<5$
This .sample was.taken only to determine the relative propor
. Cd
0.02$
tions of the dust constituents
- in air.
.;*The resin-.'Bsed^fcr thertlle ^foimOatian,involved. An.the work described WTarble^l Hess- resin * 2716/ consist lng ,f the .polymer made from 13$ vinylldene.:chlorlde* ^3$ vinyl chloride.. Analysis of Sample 14 was *by x-ray diffraction and emission spectrograph; the organic materials ar. not "seen" by this method.
Vi.-
DOUI 01548
Biochemical Research laboratory T2.1-1-65 Page 10
ST0Q30606
S"
The dust* concentrations shown' In 'Table 2 nay he compared with the appropriate Industrial Hygiene Standards, listed in Table II. Industrial Hygiene-Standards are.concentrations which may be inhaled as-much as `8.`.hours per day,.5 days, per week. Indefinitely without ill effect.
Table II
Industrial Hygiene Standards
Material
Standard
Asbestos
5.0 mppcf
Silica (quartz)
5.0 mppcf
Cadmium
0.10 mg./r
Calcium Carbonate
15*0 mg./nr
Resin 2716
probably 15.0 mg./nr
An examination off Tables I and II readily shows 'that-at no time were the standards for asbestos or silica exceeded. Since -the.dust counting.microscope-determines the number, not the weight o particles*im*the.*ir. some-assumptions .aust. be made before the oadmium^exposure'oan -be'^eva-loatedi {1) assume that -the dost encountered near the Banbury mixer, 2-roll* mill .add callender had the same partible-size distribution as the"dost 'of"the dry mixture (confirmed by dark-field microscopic examination); (2) assume the dust particles were spherical with an average diameter of 2.5>i; (3) assume "the density of the particles was approximately 2*0 g./cc.
DOW 01549
S T 0030601
Biochemical Research-laboratory T2.1-1-65 Page 11
Using these assumptions, the weight concentration of dust corresponding to the highest observed particle concentration (3*2 mppcf) would be 1*85'~ Then, assuming that the particles were 0.0256* cadmium, the air concentration of cadmium was about 0.0004 mg./m.^, well below the 0.10 mg./nr Standard, especially considering that all of the assumptions made were conservative.
Thermal decomposition products of the resin and.plasticizers-use# could conceivably be the cause of trouble except that a great amount of experience at Dow and at other companies with these materials has shown that no adverse effects are to be expected even under.much worse, conditions than have been prevalent In 433 Building.
Remaining aa a possibility is the dust and/or thermal decomposition
products from chlorinated polyethylene, a new material. A survey
will be. made, when this material is again used In vinyl-asbestos
tile fcrMilations.ln'OTder to determine what .materials -are inhaled,
and in what concentrations. -Alec, -this dustj jil-ong with the dust
of ether materials*..-lS'-aoon -to be. investigated, by the Toxicology
Laboratory to determine the degree of Irritation caused by sub-
dermal injections. This investigation should help to decide
whether: or-not
lung injury .could.have been caused
by the resins used in vinyl-asbestos tile formulations.
DOW 01550
ST003060Q
Biochemical Research laboratory T2.1-1-65 Page 12 The'bench hood osed 'in 'the laboratory for dry mixing was evaluated by measuring air velocities at the face of the hood with an Anemotherm Air Meter. . The attached "Hood Survey Data Sheet" is self explanatory regarding findings and recommendations.
c.
DOW OiS51
HOOD SUftVIT DATA
aAm mc*cH
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DOW 01552
HOOD SUftVIY DATA
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DOW 01553
j 190G00IS
I m or evthor of ondhoee roodtfrisToporl comprising _- 13
pages with^__________
00901 of drawings, photographs, graphs, end
checked tho data herein agaiast tbo original aatrias vndar Biochemical v 'Laboratory fUo-Mwmbor _ 72,1-1,65_______________________________
I finishtd typing this report on.
1-29-58
comprising
13 pagos and placed therewith
.pages of
drawings, photographs, graphs from an original draft gives me by.
J. E. Petersonon 1-27-58
I have plaeod in tho plant moil5copies of this report for
transmittal to piease refer to the Distribution list of this report.
Omt,
?
itte-et eMrrsDSfUAA.
DOW 01554
ST0030612
Biochemical Research laboratory T2#1-1-65 Page 33
- -'.mrt IBK
Possible chemical exposures received by
of Coatings
Technical'Service-while working with vinyl-asbestos tile Semulations
are evaluated-as possible causes of his lung Injury.' No evidence
leading to the determination of a causltlve agent was found, but
plans were made for another survey to be performed when chlorinated
polyethylene is used as the resin In a tile formulation, and dust
of. this material .will also be investigated further, by the Toxicolfegy t
laboratory.
DISTRIBUTION
R. .B. Drubel, Coatings Technical Service, 433 Building N. R. Peterson, Coatings Technical Service, 433 Building
H, Gay., K.D., .Medical Department, 607 Building V. L. Tisdale, Safety Department, 401 Building : G ' E- v BoIstead,; Corapensat lor*: Department, 256 Building W. Snodgrass, Maint. Service Admin., 49 Building <7/9/71)
' .f
gck
DOW 01555
sjatung mitmoo
rucm<* p t
TRAPPING MI8HJM
ROTQMfTER sitting --
INDUSTRIAL HYGIENE SAMPLE RECORD
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DOW 01557
INDUSTRIAL HYGIENE SAMPLE RECORD
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DOW 01558
MOSLEM BATt
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CALCUCATIOHS HECORD
MATtKUL BIIWn/i-lM/I-Bjfat TO
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00UJ 01561
* -
eimncAi
IfY aASOWSTOSY
*-
-m., nnma-
t. .T. S. Peterson - Piochem Sm B B. s - THrm
u-hr Analysis of Dust Sasnle 60-2.
- .and- Spectroscopy. ..............
cutM m*. 1219-26
M
--*
1-16-58
. S-B*7 Diffract Ion Analysis:
'CmCDs -- . .chief constituent
Asbestos (serpentine variety) -- 20-30%
Quartz --
Trace (<5%)
There also appears to be a clay type
aterial present*
Jtalsslon Spectroscopy and X-gay fluorescence Analysis:
Cd -- .01-.02%
ST00306I9
J~21~56 S9R: vsr 2
rnmrn n *.%.%.
*r DOW 01562
ST0030620
--gage / of__/ -
Industrial.Hygiene Chemical Exposure Data Entry.Log Field Survey TWA -Exposure /pd Excursion Exposure Data
Report no. _ Q--\~\J 6>7Q
Jtete Q / 57
Building no 4/33
fndex no.
________
^ -'Units rof Data Y______ _ '....... y :*espiratr-#orn?
'
Master no.
Job Classification
Job Mo.
, v. ! Chemical Name '
DRf 3i70"7/ ^
:________ ______
DR#
TWA/Exc.
TKA/Exc.
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