Document evQByn3RO1NXM0w6VGNX2kOKE
PLAINTIFF'S EXHIBIT
V
Biochemical Research laboratory
OFFICE COPY The Dow Chemical Company
u7
7
Noted E.E.D.
FEB 07 1958
EVALUATION OP - CHEMICAL EXPOSURES RECEIVED BY R. R. SPENCER OP COATINGS TECHNICAL SERVICE, 433 BUILDING
File:. T2.1-l-4 f)
Chg.: 1219 Date: 1-22-58 By: J. E. Peterson
LesoG ooJS
Signed Date
PROBLEM
THIS REPORT IS THE PROPERTY OF
THE DOW CHEMICAL COMPANY
Recently, R. R. Spencer has become ill. The Environmental Research Laboratory was requested to determine chemical exposures received by him, and to assess these data.
CONCLUSIONS
1. Exposures to airborne materials during the formulation, mixing, and calendering of vinyl asbestos tile in 433 Building were evaluated on 12-23-5*1 and on 1-15-58. -Results of these evaluations are .used -to assess exposures received by R. R. Spencer during his work With this material.
2. From December 1953 to December 1954, R. R. Spencer worked with vinyl asbestos tile formulations, and in the course of that work was occasionally exposed to somewhat excessive concentrations of airborne asbestos.
jfctftW*.
>--4
STQ030598
Biochemical Research laboratory T2.1-1-65 Page 2
During this period of tine exposure to lead occurredt but 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 Vo.7 mg./a^" at intermittent periods. No effect is expected as- a result of these exposures.
3. Prom the first part of 1955 to late 1956 Mr. Spencer worked mostly with latex in concrete, and exposures to vinyl-asbestos tile ingredients were reduced accordingly.
4. Prom 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 dust, concentrations of less than 3 mppcf of a material analyzing 20-30# asbestos, less than 5# Si0g And about 0.02# cadmium. No effect can be expected from such -exposure.
5. If Mr. Spencer's difficulty is the result of chemical exposure, the c^usitive agent xs unknown at present. Further air analyses are tc be made during a time when chlorinated polyethylene is used as the resin binder in the tile formulations.
ST0030599
Biochemical Research laboratory T2.1-1-65 Page 3
FRESERTATIOW OF DATA
R. R. Spencer has been ill with a lung difficulty, and overexposure to chemica 1b encountered during the formulation, mixing, and calendering of vinyl-asbestos tile formulations was BQBpected to be the cause of his illness. The Environmental Research Laboratory was requested to determine and evaluate his exposures.
On 12-23-54 an environmental survey of the vinyl-asbestos tile formulating operation wa3 made by S. R. Johann; the results of this work were reported on 5-5-55 (Pile Number, T2.1-1-32). This survey found that air concentrations of "inerts'1 (asbestos plus cuiciuin carbonate), barium, and lead were too high for repeated 8-hour exposures, and even though exposures were not that prolonged, recommended 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 air concentration figures of "less than" 0.66 mg./m^- and "less than" 0.45 mg./m^.
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 batch was completely formulated before mixing In the Banbury or Baker-Perkins machines, and mixing In these enclosed machines was always to be done prior to
n i -- * 11
ST0030600
Biochemical Research laboratory T2.1-1-65 Page 4
Third, canopy'hoodswere Installed over the large 2-roll mill ana 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. R. R. Spencer's 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 had normal blood lead values.
On 1-15-58 a second environmental survey of the vinyl-asbestos tile operations was made, partly to assess the value of. indicated changes in reducing exposures of personnel, and partly to gain more Insight into, the; chemical ^exposures 'that .R. R. Spencer may have received recently.
The ingredients used in vinyl-asbestos tile formulations have 'hh^red quit** we1! to the ssme basic recipe for over a year.
Biochemical Research laboratory
T2.1-1-65
Page 5
ST003060I
Urn..-
The recipe is as follows: Material
Weight Ratio
Resin May be chlorinated polyethylene or resin 2716, the copolymer of 15# vinylidene chloride, 85# vinyl chloride.
Dioctyl phthalate or tricresyl phosphate
17.5 2.25
Monoplex S-38 An epoxidized oil purchased from Rohm and Haas.
Metasap 624 Contains cadmium laurate
Aluminium stearate
Paraffin wax
Lesimit - Calcium carbonate
No. 18 graining sand A very fine sand
Titanox RA50- Titanium dioxide
Asbestos shorts, type 7M
2.25
1.5 0.1 0.1 39.8 12.3
5-0 19.0
With the exception of dioctyl phthalate and monoplex S-38, which are liquids, all of these materials are dry powders, and normally are weighed into a stainless steel mixing bowl in the open. This operation takes about 5 minutes. The mixing bowl is then placed under a mixer within a hood, mixed for a few minutes, and then the two liquids are added. After further mixing, the batch (which is still a dry powder) is poured into a paper bag held within the hood.
STQ030602
Biochemical Research laboratory T2.1-1-65 Page 6
When it-Is done, neighing and blending of the Ingredients takes place at a maximum frequency of about 3-ha If-days per week; cn average frequency is difficult to establish because two or three weeks may. pass with no activity in this area at all. Mr .'.Spencer 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 BajcerPerkins or Banbury mixer - usually the Banbury." Here the\material is forced into a heated mixing chamber with an air-powered ram and is mixed for about two minutes. The resulting mass is semi plastic, and is removed (sometimes with difficulty) from the mixer and carried to the differential speed heated (200-300P.) 2-roll mill. On this mill it is further blended and occasionally marbilizing chips are added. Such blending may take from 2 or 3 minutes to a half-hour depending upon the difficulties encountered.
.After being-thoroughly mixed on.the2-roll mill the .plastic mass is carried to the calender (basically a cooler heated 2-roll mill) a few feet away. Here the material is squeezed to a pre-determined thickness by a pass through the rolls; the surface of the resulting 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. Prom Banbury mixer to finished pieces of tile may take from 15 minutes to an hour or so for a single batch.
ST0030603
Biochemical Research laboratory T2.1-1-65 Page 7
The inaximam frequency or this Jab ia about the same as for weighing and blending, 3 half-days per week, and again, an average frequency is almost Impossible to.establish. For.reasons of safety, two men always work together in these operations; Mr. Spencer has been associated with about 80% of this work since the latter part of 1956.
On 1-15-58 several air analyses were made during vinyl-asbestos tile manufacture. Air sampling equipment used was the Bausch 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 12-14 were taken with the electrostatic precipitator, and normally concentrations would be expressed as milligrams of air contaminant per cubic meter -of air (mg. /rrr^), but the samples were unfortunately of too.short duration, to .obtain.weighable .quantities .of dust.
Sample No. 1
2
3
4
5 6 7 8 9 10
Biochemical Research laboratory
T2.1-1-65 Page 8
Table 1
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 zone while working the material on the 2-roll mill.
Breathing zone of man as he put "the material through the calender.
Brerathlng zone while cutting the tile to size 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.
Most particles - in diameter, average about 2-3 J' 3.2
0.7
1.0
0.9 0.2 0.7 0.5 0.2 .1.4
ST003060U
ST 0030605
Biochemical Research laboratory
T2.1-1-65 Page 9
Sample No. 11
12
13 14
Description
Dust Concentration, MPPCF
.Immediately outside of the bench hood where the dry.batch of material
was being mixed.
0.5
Length of Time of Sample
Electrostatic precipitator
sample in the breathing zone while formulation being mixed in the Banbury.
2 min.
Dust Cone. mg./m.3
Too little to weigh
Breathing zone while work ing the formulation cn the 2-roll mill.
Too little to measure.
Sample taken in bench hood over the container where the dry mixture was being stirred. This sample was taken only to determine the relative propor tions of the dust constituents in air.
CaCO^ - Main Constituent
Asbestos - 20-30#
S10,
<5#
Cd 0.02#
The.resin used for the tile formulation.Involved in the work described in Table I was resin 2716, consisting of the polymer made from 15# vinylidene chloride, 85# vinyl chloride. Analysis of Sample 14 was by x-ray diffraction and emission Bpectrograph *, the organic materials ar 'H *. ,:seen" by this method.
Biochemical Research Laboratory
T2,1-1-65 Page 10
ST0030606
The dust'concentrations shown In Table I may be 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
Asbestos
Silica (quartz)
Cadmium
Calcium Carbonate
Resin 2716
prooaoly
Standard 5.0 mppcf 5.0 mppcf 0.10 mg./m^ 15.0 mg./m^ 15.0 rag./m^
An examination of Tables 1 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 of particles, in the .air some assumptions must, be made before the cadmium exposure can be evaluated: (1) assume that the dust encountered near the Banbury mixer, 2-roll mill and Callender had the same particle-size distribution as the dust of the dry mixture (confirmed by dark-field microscopic examination); (2) assume the dust particles were spherical with an average diameter of 2.5(3) assume the density of the particles was approximately 2.0 g./cc.
ST0030601
Biochemical Rese-.rch laboratory T2.1-1-65 Page 11
Vsing these assumptions, the weight concentration of dust corresponding + c> the highest observed particle concentration (3.2 mppcf) would be i.85 mg./m.^. Then, assuming that the particles were 0.0256* cadmium, the air concentration of cadmium was about 0.0004 mg./m.^, well
3
below the 0.10 mg./rrr standard, especially considering that all of the assumptions made were conservative.
Thermal decomposition products of the resin and plasticizers used 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 as 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 formulations in order to determine what materials are inhaled, and in what concentrations. Also, this dust, along with the dust of other materials, is soon to be investigated by the Toxicology Laboratory to determine the degree of irritation caused by subdermal Injections. This investigation should help to decide whether or not Mr. Spencer's lung injury could have been caused by the resins used in vinyl-asbe3tos tile formulations.
Biochemical Research Laboratory T2.1-1-65 Page 12
The bench hood used 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.
S T 0030608
HOOD SURVEY DATA
rut huuiu---------
AJUTokc MuutiR
7aVb L.a/g-viIa-k3'tfZuaatiiw--------VJ D-
DATt tWW'kIHd l/jrlrA \e A b B/fcH
g\JiLOt*6r PRODUCTS JLA 8 . ?T3
INTERNAL RAFFLE?
EXTERNAL RAFFLE?
(CHEMICALS HANDLED IN THIS MOOO
PTdH WBCBrW|i?rt6 fB Th< WtULlii iVITBif ASBESTOS. PYC, PtAsrlerziKS. BTC
cMB*/ T Sot VFh/TS
S c VB V-S
lOUkiti at All NfWliwt IXTEWCTTB TgrWOB
jfH? DiFFil&Ea,.tUHT..AaQi QT-..&JElS&frL..LilI..Q. *La.Q.
>--am face velocity fob thshood_________________fQ
mMAUST BATE FORT--HOOD
// tfD
Cf.IL
F.P.M, BOOKOPeM.
-f
!-
T_ i
---ir~ --!'.................... ,
!
.
.
.. ;
ii
'
ii t
'i
ri i *o
<ts
xr
>r
f 2fh
:
!,
'
!1 !! ! ;1ii y
i ,'
' i 'i !
"" 47 1 ' 42
! [*Si1, ii . a1 ; !
,
+S
. ......
...i.. :.....................;
:..
*
4.T 30
J 1
t~ --------------
I___|_
J____L
HOOD CONDITIONS DURING THE SURVEY
ACTUAL FACE VELOCITIES
UW> S 5* f.pjl
FJ>JL
^ */ FPU
HOCO FACE AREA DURING SURVEY EXHAUST RATE DURING SURVEY
mwt ^?/v*
n- --m<
/2*l.7. SC. FT. t*ti CJJL A7 njmmmm abba
12,7
IMCD FOR A4R WLOCITY I _
AvtMCTiie** Am
ILLL >V?
hetc*.
S2S1
J.g.p.
CD O
CO
CD cr\
CD
CD
VARIANCE
.sa rr.
HOOD SURVEY DATA
C/3 --I CD CD CD CD OD
o
r
HOOD CONDITIONS DURING THE SURVEY
ACTUAL FACE VELOCITIES HOOD FACE AREA DURING SURVEY EXHAUST RATE DURING SURVEY
it_ FJPJL
$0. FT.
Ml cf,m. Z_
IRMRBfKEMEA.
/P.7
--TRIM--WT MEED ROR A-- VRLOCTTY MflW--NflfTli
0--ALNUMRC*
iORvrroR
ANfM&THZRM At* MSTTJt_________________ -XU?_____
MS* PI--fO ft rn D-D
VOIAMCE
sa FT. _
ST00306I I
I am an author of and have-read this report comprising --13----pages with^_pnges of drawings, photographs, graphs, and checked the data herein against the original entries under Biochemical Laboratory Fife-Heeler ^ ^-1-65
I finished typing this report on.
1-29-58
comprising. 13 pages and placed therewith.
.pages of
drawings, photographs, graphs from an original draft given me by.
J. E. Peterson
on 1-27-58
I have placed in the plont mail5copies of this report for
transmittal to p^ease refer to the Distribution list of this report.
Signature,
Date
ill*-4 PTUNTEO IN U.S.A.
ST00306I 2
Biochemical Research laboratory T2.1-1-65 Page 33
UNIT UHEX
Possible chemical exposures received by R. R. Spencer of Coatings Technical Service while working with vinyl-asbestos tile formulations are evaluated as possible causes of his lung injury. No evidence leading to the determination of a causitive 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 Toxicology Laboratory.
DISTRIBUTION
R. B. Drubel, Coatings Technical Service, 433 Building
N. R. Peterson, Coatings Technical Service, 433 Building
H. H. Gay, M.D., Medical Department, 607 Building
W. L. Tisdale, Safety Department, 401 Building
G. E. Bolstead, Compensation Department, 256 Building
W. Snodgrass, Maint. Service Admin., 49 Building (7/9/71)
` \~
t __ A '_ _ / r -
I,
gck
SAMPLING method
jl rulUe
MEDIUMTRAPPING
Pt
kotometer setting
VENTILATION:
INDUSTRIAL HYGIENE SAMPLE RECORD
SAMPLE RATE
PROELEM
AMETER TV.ROT
OR ORIFICE MO.
SLOG.
Y 3 2-
PROCESS
OATE
J hf /r? l) f HfC -/Hi 3fS TOS
OUTSIDE TEMP.
-- MADE TEMP_.
CT'PM/A5rTAEJR>IAPL>OV%7t- A/le*r*r*i,
SAMPLE St06I1PISLT i 11
1 L IZ.
description
5 >'
STAPT time STOP t**.*tr*/CcT/p ' f * ry;
/3:3 Y
3. Z
1 tl
iOSbt, /*VI H-S yy*fst E^T,
fiUM6 Xi -n*/ tff' .`X l/ViM/ . ujjh&+r< ytrbti-cn.
0
--C--O51 7 or
rCrDi
CO
Y to
B/tuJjLfMj J^rw -
'Ws t hi .
n:^t>
}.>
r <}
f*du r
/
tmp y*** hvJLslt- U)
flu /l**m
4*a//
EH his 3'ShrYh
/3: a i
0-*t
i?
SdW)4 Qaj
r
o.z
77
^iJW MJ Lj'/r
/3: Vt> fi.7
9U
1RWTD II 1.1.4.
S/hy.Tl ma tmwi. L4J L.. *
ty.it
D.f
SAMPLING METHOD TRAPPING MEDIUM
'
ROTOMETER SETTING
j VENTILATION:
INDUSTRIAL HYGIENE SAMPLE RECORD
SAMPLE RATE
PROBLEM
BLOC.
DATE
T3.hf-isr 3 x
V32.
i/'f/ro
ROTAMETER OR ORIFICE NO.
PROCEU (T
04cU^
toM____
_____________ _____"
OUTSIDE TEMP-
4M&0CTCMP.
MATERIAL
A<*SfJ70*j
J sample
i
<?
<ATLE
2
l? tnrrrt
description
( t/r^ .J/ )
TIME
START
STOP
CONCENTRATION
*P ttpi cJ________ g-3
(0 r Auj asiA-Cti*v /<)
A^Jlury <svt StLtdL
AV
uY
n
1+) &iS
"Wt* jt **JP
CP*t // S' /V<F
o.r
LT>
--1
CD CD CD CD cn
sr
J
no-am mrru > h.i.a.
SfArMfPcLIiNfGl*METHTOAD If* Pit C> Pj TA Tit ft
TRAPPING MEDIUM
ROTOMETER SETTING
INDUSTRIAL HYGIENE SAMPLE RECORD
SAtTLE RATE
PRORLEU
eldg.
DATE
3-o cfrx
TJ./'t-ite.-Z'' V33
ROTAMETER OR ORIFICE NO.
nprocess i//A/ A>Bsr*s
TUB
OUTSIDE TEMP.
MODE TEMP.
MATERIAL
VENTILATION:
I------------- --------------- - --------.........'........
' ........ ....................... ...........
"1 1
ej CD
O CT'I
cn
sample
-OOTTT.1 wot l.f, - 1
DESCRIPTION
& Am* JJkMLm
ai
Ah -'*>!*. * <n
TIME START STOP 2 vn11: sf
CONCENTRATION orr /ki *____ t A. *
1,0'2. /Vi Lo'Z,
to/iustu*y
tfu {& 9
tu>*/tA*rjr M'.Ob itw 7^-e. 3 '/iMA--jl] 2.3S\
StUn jAl "fhux* a*s\ LtnrtP a+4SL>
2-LmAm 7711 ^
HtCXAjr
J^hj J?. ^zttrb+0v\ /!/ i JtS
r
< 9./ /y.tStSa0.
mi.im RIITD II 1.1.4.
PROBLEM
TQA'l'b<
MOL. T.
ppm/m^'l
CALCULATIONS RECORD
RATE
S-JC.PH
MATERIAL
BUILDIMS
T*-
Y3J.
CONVERSION HALOGEN TO TOTAL
PROCESS
EXPLANATION OP CALCULATION*
DATE
SAMPLE
/z.
TIME
5. VOL. # -* L.o
ANALYSIS
S' **<*r.
*m/*p* CONC
& z>r wm
L. UaI ?&.
L6 mtf.
//$ /<rS-
9. Y
0
Y
rV1 tf-z-LMAW yT i J
JJL
tSZr W'
fL
am
^6^1
--H
q
CD r .1 CD CTk
JJL. C*%tAZ~liApi
cn
Cot^oif^ru
S (aJLsj*. *
uJL,.Ja
d
F S'ft O.0-&%
U*M WITD II I.LL
ST0030617
-dLjtoaaA&t. s. 0.
- 7. T~x & *tf*
fytsjfczii vdtortfiU *
j
_j- fy (if x/a~9) - S~Z.Jtt~ ^ 4rf *1^ 2
-<0^lco > 7 -d *l^/'Myh3____
1fvlljL ^JUmM? * ?' o X v . * /<T * = /C. W/<T* -*f
/(t`1/ ttcf** 2^. -X 3,0 ytO**
/-ftr* - SO -S'y/o"^ *y
?-.Tj( 1.0*3. x^T.^ * 1,&* 'n'z/m'*
D60* _*o_d._7j>
A'61`- 'V 'A
'Xl / 0 -
~ 1/
f
/7S
>* P
5'2?
?> * f . iur
2 Y
A^r
S la^wu^
OJ
prfh"^
4, /
...................list
S4/vd
J X* .
w
*d&iZir>
-^
7'tlinuH...A9-.
uA'r^ C*. <2>j
OflJtyC . ...Ja^
ST0030618
-i 'b 'bf-- /W ^
\ ?6 /;
^
t
t>-
ST003061 9
7 2./" t" ^
THS DOW CHEMICAL COMPANY 5PECTMOSCOPY LABOHATOHY
ioia7R
T.___J. E. Peterson - Biochen. Res. >-------Ha If. Riffl
...............
uhi^. Analysis of Dust Sample 60-2. X-Bav Diffraction, X-Ray Fluorescence
, And' Spectroscopy.
Char,* Ha. 1219--26 Siaaad
________________
n... g.fv
1-16-58Dan----------------------------------------------------------------------------------------------
X-Ray Diffraction Analysis;
CaCOs -- chief constituent
Asbestos (serpentine variety) -- 20-30%
Quartz
--
Trace 5%)
There also appears to be a clay type
material present.
Emission Spectroscopy and X-Ray Fluorescence Analysis;
Cd -- .01-.02%
1-21-58 HWR: vsr 2
tzs- v fnrti
ST0030620
Page
of
Industrial Hygiene Chemical Exposure Data Entry Log Field Survey TWA Exposure And Excursion Exposure Data
Report no. ^-|-|-3P-/ (nlO
Date Qj 5*7
Building no. ^/33______
Units of Data
Y_________
Master no.
Index no. Respirator Wom? ________ __
Chemical Name
b Classification
OQt 2-
Job No. DR# QSjQ 7/3> TWA/Exc.
336755 Q /3.7
DR# TWA/Ex c.
/
z
zzzzzz
*
z
zzz zz
i
f
f7