Document 3QEB9bxDqgKgzmN5d8RZnz00y
REPORT no. 2970 TDfkL REPORT ON
AROCUtt IK OASES
Job No. 171-1089
File NO. 141
March IS, 1954 H. D. Richards, Jr.
RESEARCH DEPARTMENT Phosphate Division
Report No* 2870
FINAL REPORT OH AROCLOR IN GASES
Job No. 171-1089 File No. 141
' ropk Storied: *y ^I9p3
Prepered Bp: H. B. Richards. Jr.
' l Otk r.'jupi
October 16. 1953
leport Submitted: M&Tffh 1&> 1851
Chemists:
A. M. gtlanbury g. B-. Richards. Jr.
wore made of this report end distributed es follows:
File - St. Louis Library
A. X. Bllenburg
H. X. Nason
.
Duplicate File - St. Louie Library
Safe Deposit- or C. F. - St. Lottie
F. D. Zietrty
C. A. Rochwalt
N.m.T. Samaras Research Library File - A&niaton
P. O. BeaisBus - St. L
R. B. Nelly - St. L
H. L. Hubbard - St. L
T. 6. Allen *
Extra for XCL (England)
Extra for XCL (England)
Extra
Extra
Extra
.
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This Is Copy Mo. /JL
TtJa report and the information contained herein is the property of MONSANTO CHEMICAL COMPANY
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Thifl report ujd the infornation contained herein Is the property of Monsanto Chea4<oal Conpany, and should ha considered confidential* It should he re'tained by the recipient, and not copied or loaned to others.
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CONIBBS
I. Introduction
Pago 1
n. Sitanary
m. KtfmaoM .......................................................................... 2
IT. Experimental lfork .............. ..................................... 2
T. Discjussion ....................................................................... 9
n. Conclusions......... ................................. ..
11
THi Keccjaiondatioas ............................................................ 11
Operating Procedure for Villaon Products, Incorporated Chlorinated HydrocarbohSampling Apparatus ........................................ ... 13
l Data Sheet - Aroclor Vapor Detection................ 17
panplimg Positions ..................................................... 12
jDiagraamatio Sketch ......................... 18 (photograph of Saaples
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I. INTRODUCTION!
Dov Chemical Company la Interested in veins Aroclor as a plasticiser la manufacture of their Saran '(vixqrUdine chloride) plasties, hut is hesitant
for fear ^hat the Aroclor sapor might produce toxic affects upon the
personnel' In their plant.
.
At the re pest of the Sales Department this York urns undertaken to deter** mine the , Lroclor vapor concentration in the Anniston plant under usual
working c mdltlons. This data would then be used In ea attempt to con vince Dow that the use of Aroclor in their plant vould be safe.
An outgro]fth of the problem was the determination of the Aroclor vapor
itpresent ' a room which had boon painted with a styrene latex paint using
Aroclor a plasticizer. This work is of interest to the Plastics Division, and was undertaken with this project since the same apparatus and analyjt:leal procedures are used as in the Aroclor vapor tests in the plant.
H. SUMMARYi
An Interiji Report, No. 2892, covers tho work up to July, 1963. This report supplements tho Interim Report.
was continued in the plant under all normal operating condiohlorine concentration in the air varied greatly giving eallor concentrations ranging trm about 0.35 mg. per cu. meter 8 mg. per on. meter. The filtering and drawing operations most server# exposure to tho Aroclor vapors. Mo definite
exposure was determined.
A snail rjoom, 14* x 18* x 14*, was painted on four walls and on the ceiling
with Lust rex Latex Paint, Lot Mb. P-0938 containing Aroclor 1248. Tho
room has anly one door and a will 12" ventilating fan with no windows that
can be open. Most of the time the room was closed, especially, during tho
early tes|ting periods.
'
A hood, 2* x 8 1/2" x 7*, was also painted os three walls. Tho exhaust fan on the hood was not operated during the tost period. Two 1000 watt eleotrlc hot platei were turned on in tho hood to host tho air during the sampling operation.
Sampling cf the air la tho room revealed that tho Aroclor vapor concentration rapidly reached a maximum and then generally decreased to a relatively safe loN level after three days. In the heated laboratory hood the concentration remained on the 1.0 - 2.0 mg. per cu. meter range over a period of about one month. In a heated room it appears that the concentration of Aroolor
1248 vapors may remain high for a long period of tine.
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Bpport No. 2892, Interim Beport on Aroelor In Gases, Juno 17, 1953, H. B. Bichards, Jr.
IV. skpsBigMSNTAL WOEK:
The apparatus and operating procedure are described in the Appendix
tb Beport No. 2892. This description is supplemented in this
report by a photograph of the test apparatus, Willson Product's
Incorporated, Chlorinated Hydrocarbon Sampling Apparatus. The
sjuapling positions in the plant are the same as described in the
Interim Beport No. 2892.
'
Analytical Procedure: Anniston Test No. 20-25-41, Nephelometrio determination of Cl" ion.
Hfngei 5 - 120 micrograms in 20 ml. maximum volume.
Apparatus:
1. Fisher ELeetrophotooeter vith bins filter and 25 ml. sample tube.
2. 25 ml. glass stoppered volumetric flask or graduate.
( 3. 10 ml. measuring pipette and 10 ml. transfer pipette.
Solutions! 1. 3N Nitric Acid - 190 ml. CP cone. HNOg diluted to 1,000. 2. 0.8/S Silver Nitrate - 3 grams dissolved in 1,000 Ml. dis tilled mater. Store in dark bottle out of light.
3. 1% Thenolphthaloin. 1 gram solid in 100 ml. C? Hethanol.
Procedure: 1. Pipette required volume of eater solution into 25 ml.
volumetric graduate. Adjust sample site to obtain 10 120 micrograms of Cl In loss than 22 ml. For testing scrubber solutions of Aroelor vapor tests use 10 ml.
' 2. Add l'drop Pbenolphthalein and neutralise vith 3 N nitric acid (or dilute caustic if sample is acid).
3. Dilute to 22 ml. vith distilled voter.
4. Add 1 ml. HNO^ and 1 ml. AgNO, in this order.
5. Mix by inverting Only Pace and set In complete darkness
for 30 Min.
`"
6. Balance Electrophotometer vith distilled voter in both tubes, using blue filter and 25 ml. cylindrical sample
( tubes.
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- 37. Transfer saaple to the Eleotrophotooeter tuba quickly
with lialm exposure to light and road density or "A" scale. Send'quickly without prolonged exposure of seaple to the bean of blue light. 8. Coapere the scale reading with a calibration chart aade frost identical determinations of standard chloride solutions* 9. Hake a blank nut on all reagents and subtract fro* reading of step (8) or plot data of standard runs to include the chlorides of the blank, in which case the reading aajr be taken directly fro* the curve. However a new curve oust be Bade when reagents change. 10. To calculate parts per aillion (ppa.) of chlorides, divide answer in aiorograas by volume of saaple.
ppa. - KlcrograasCl Volume of Saaple
% Microeraas Cl Yoiune t 10,000
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Tost No.
10 29 80 81
45 46 47
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TABLE I ABOCLOB 1242 YAPPS COHCKWmTIOW IN THE PLANT
I ositioa No.
Concentration. Chlorino
nr/cu.a. Aroclor
Benarks
5 0.14 4 1.5 6 1.5 6-S 2.2
1 0.85 2 0.34
3 0.85
0.33 3.6 3.6 5.3
2.0 0.80 2.0
Still Tented on top. Still in operation
Press not operating and cold. 1242 in No. 2 B. T. at 110* C.
Both stills operating on 1242
Filter press replaced with Sparkler leaf filter which was cold
tiae of tost.
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lAHOCLOR 1254 TAPOa CCBCTOffRATION IM THE PLANT
Test Position Concentration, yr.cn. a.
Wo. ml___ Chlorine
Aroclor r
Remarks
24
25 27
32 33 34
35 36
37 38
39
40 7
42 64N
43 8 44 8
0.68
0.41 0.50
1.45 1.04 0,75
0.61 0.37
1.30 1.98
0.40
0.73
2.4
4.3
l.a
1.4
0.76 0.92
2.68 1.93 1.39
0.94 0.68
2.40 3.66
0.80
1.46
4.5
8.0 2.4
By steam reoorder_______ Still operating on 1254
Filtering 1254 at 110-115* C.
Pumping 1254 from receiver to B. T. By steam recorder
Filtering 1254 at 110.* C. Drumming 1254 at 150* C.`
KOIBt Tbo analytical procedure on samples 37-40 Inclusive mas carried 1/2 the normall sample site.
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9ABI* TTT
AROCLOR 1260 VAPOR C0WCBHmtl6K IW THE P1AKT
Test No.
1 osition No.
Concentration. ne/eu. n.
Chlorine
Aroolor
Renarks
11 5
0.32
0,53
Still la operation
13 4 14 5
0.55 0.52
0.92 0.87
Still open
15 6-S 1.5 2.5 16 6-N 1.2 2.0
Filtering 1260 at 125* C.
18 5
0.22
0.36
Still operating
(
18 4
0.91
1.5
Still open
*
20 4
0.75
1.2
Still charged and started
21 4
0.53
0.88
Still operating
28 8
2.8 4.6
Srunaing 1260 at 150* C.
22 7
1.1 2.2
By operator's desk, assuadag 50J5 Cl.
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-7TABLE IT AROCI 02 124B VAPOR FROM UTSTRBX LATEX PAINT. LOT P-OS38
Test Me.
Concentration. KZ./cu.
Chlorine
Aroclor
53 7/20
54 20
55 21 6$ 21 67 21 68 21 69 21 60 22 61 22 62 22 63 23 64 23 66 24 67 24 68 28 69 28
70 8/12 71 12 72 18 73 18
74 18 76 9/iO 78 10 79 10/5 80 S
0.32
1.28
0.93 0.92 0.63 0.96 0.52 0.57 0.30 0.65 0.12 0.14 0.11 4.9 i.14 2.5
0.34 0.21 1.3 0.62
0.57 0.23
0 0.18 0.43
0.67
2.68
1.93 1.93 1.11 2.0 1.1 1.2 0.62 1.1 0.25
.29 0.23 9.6 2.4 5.2
0.71 0.44 2.7 1.1
1.2 0.48
0 0.37 0.89
Remarks
Trap, At sample
Intake
Center, east. 30 sin. after painting
Center. 1 1/2 hrs. after painting
Center, sooth Center North east corner
In laboratory hood
Corner Center Corner Center Corner Center} Corner/ Anonolous deviation, Center) probably air contaa. ination. Corner Center In laboratory hood at 60* C. Corner .fan off 4 hrs. after
ventilating. Center Center Corner Center Comer
32* C.
32
31 31 32 46 45 50 S3 3? 40 33 33 84 33 34
38 35
37
41 37 85 35 34
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TABtt T
( BLANK AND HTSCE1UUB0P8 DETERMINATIONS
Teal No,
Total Cl ___
12 0.006 2$ 0.007 41 0 52 0.007 65 0 77 0.006
17 23
48 49 60 51
75 81
Concentration, ng./cu. m.
Chlorine
iroc'lor
0.21 0.32
0.32 0.89
0 0.64
0.10 0
0.42 0.64
- -- --
---- ----
Remarks
Reagent blanks. Total Cl in reagents to be subtrac ted from vapor determina tions.
atm. blanks on 5-19 and 5-20. on aroeler tank at North end of building. Assuming 5Q^ Cl.
Blanks on air in Instrument
room before painting. Tests
made on July 17.
.
Air blanks in instrument room. No heat on combustion tube. Tests made on 9-10. and 10-5. respectively.
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V. DISCTSSIONt
The conditions of the tests sad the limitations of the apparatus are such that absolute determinations of the chlorinated hydrocarbons are not possible. Comparative determinations of the total chlorine in the air during any specific test period can be made. The chlorine
dotpcted by this apparatus can be attributed to three sources!
1. Chlorinated hydrocarbons in the air (Aroclors, or any other chlorinated hydrocarbon).
2. Chlorine in the air as free Cl2 or as HC1.
3. Chlorine ion present in the absorption solution and wash
water.
.
Scojrc*
3 can be eliminated by use of Cl~ free reagents , or by
making blank determinations on the reagents used and subtracting the
Cl I from this source free the total. The latter method was used
throughout these tests.
The chlorine from source Mb. 2 listed above insofar as these tests axe! concerned is indistinguishable from the chlorine from the aroelors. Furthermore, the concentration of Cl2 and HC1 in the plant area varies so greatly and rapidly that the establishment of a satisfactory "blank" to {compensate for this source is impossible without a statistical evalu ation. It vas felt that the amount of work involved for such an evalu ation would sot be justified. For this reason the results from all the taper tests include chlorine from Souroos 1 and 2. Under normal plant conditions, however, chlorine from Source 2 should be relatively low and the results are therefore assumed as chlorine from Aroelor. In seme instances this assumption might produce gross error in the reported results, and must therefore be kept in mind in any discussion or evalu ation of the reported results.
Another assumption was made in the method of converting the ohlorine concentration in the air to Aroelor concentration. The Aroelor vapor was assumed to contain the same percent of chlorine as the aroelor from which it was vaporised. For example, Aroelor 1242 vapor vas assumed to contain 42$ chlorine. This assumption is probably not true sinjee the vapor would more likely he richer in the more volatile, lower
chlorinated material. Use of this assumption therefore minimizes the concentration of chlorinated hydrocarbon (Aroelor) calculated from any given chlorine concentration found in the air.
Tables I, XX, and XU are tabulations of all of the testa In the Aroelor plant. The calculated Aroelor vapor concentration was in the 0.6-1 mg. per eu. mater range during the still operation and with the sampling intake doss to the still except for the tests during Aroelor
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1242 operations vhich gars comparatively high results. The
average of the concentrations of Aroclor 1242 vapors tested by the
stills (Positions 1, 2, 4, fc 5) vas 2.1 ag. per cu.
vhioh la
abcat 2.3 tines as such as the average of 0.89 ag. per cu. a. for
the tests of Aroclor 1260 vapors in the saae positions. The most
severe concentrations were encountered Airing: filtering and
ag operations ranging from about 2 to 5 ag. per cu. aeter
r, with one test going up as high as 6 ag. per cu. aeter during
No Idoubt the droning operation results is the longest continuous exposure of an operator to high. Aroclor vapor concentration in the
at, but this exposure only takes place interaittantly usually with a fev days between the drunaing operation* The filter operation pro seats a severe exposure also, especially, If it is necessary to obaogo filter papers during filtration of an Aroclor batch. This operation requires 20-30 min. work in a heavy Aroclor vapor concen tration. Formerly, this operation was necessary an average of one to two tinea per shift if both stills vere producing liquid Jroelers. One of the filter presses was replaced by a Sparkler closed leaf filter about July 1, however, reducing the necessity of dressing a hot filter press to an average of probably less than once per shift.
An average daily exposure of the operator was not determined. As aay be peon in Tables I, H, fc HI the Aroclor vapor concentration varies quite widely* Several variable factors such as location, teaperature of proclor, operation being carried out, boiling point of the Aroclor under test, and direction and intensity of drafts through the still room all affect the aroclor vapor concentration. Furthermore, the tine spent by the operator in any one operation or location varies greatly from day to day. This situation makes establishment of an average daily exposure practically impossible'.' However, from general Observations in the plant it appears that the operator spends no acre
4 to 6 hours a day actually la the Aroclor still room, aad of time probably so more than half is spent in localities of savers Lor vapor concentration*
Table XT ia a complete tabulation of testa on the Lustrex Latex Paint, Lot! P-0938, froai Springfield* The saae limitations aad assumptions apply to thoso tests as to the plant tests. The Aroclor vapor concen tration ia the roam rose rapidly to a aardaua sad then decreased. This trend is best-presented graphiely ae in Fig. I. Two sampling positions warp employed in the room, one in the approximate center of the room, sad the ether vith the intake dose to the wall in the northeast corner of the room. These positions are noted in Table XT. The Aroclor con centration in the heated laboratory hood reaainod in the 1-2 ag. per cu.I meter at 45-80* 6. throughout the tost. Table T is a tabulation of the various blank determinations vhioh vere aade. The value used forj the reagent blank ia all of these tests vas 0.006 ag. Cl ,
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VI. CONCUJSIOMSt
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1 . M ibtdttt*
of Aroclor vapor concentration can
bo aads by tbo aethod used, due to presence of unknown quan
tities of Cl2 and BC1 in the air. The asstaqrtions aade pernit
siaplifiod evaluation of the data.
"
2* The apparent Aroclor ooncentratioa in the plant varies greatly from 0.5 to 1 ng. per eu. neter under nild conditions up to 5 to B ng. per cu. neter under the aost severe conditions.
3. The filtering and drugging operations present the aost severe exposure.
4. Xo average daily exposure aay be developed frca these data.
5. The Aroclor vapor concentration in the rooa painted with Lustrex Latex Faint was sufficiently high (greater than 1.0 ag. per eu.
aeter) to sake the rooa unusable for about 3 days. After this tbs odor and concentration of Aroclor 1248 dialwished to a safe Unit.
VH. BSCjOMHEMDATIOXSt
Any recoeoeadations on the lack of toxio effects of Aroclor la the
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"Sentrations found will have to ecae froa the Medical Deportaent, r, based on the present MAC of 1 ag./ cu. aster, it appears
Lsable to veer a soak or respirator if coaoontrations of Aroclor
high enough to be irritable to the nasal aaabrane.
se the rooa painted with lustrex latex Faint containing Aroclor __(8 definitely has an odor of drooler for several days after painting, caution should be exercised in reco--ending Aroclor for this use.
(Lid**/*-- H. I. UCBUmS
March 28, 1954
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SAMPUHB POSITIOKS
Position NUnbor I
Description
1* No. 1 still, sisolating position of operator's bead Suing
charring operations. 64" froa floor on vest side of still
. about 18" froa charging bole.
2 No. 1 receiver, at sight glass, siaulating position of
. operator's head. 04" free floor and 12" vest of sight glass.
8 No. 1 filter press] N- northside, 8- southside. 54" frea
floor and 15" frea edge of press vfaen on south side.or 8"
froa edge of .press vben on north side. Northside location
sisal ates operator's head position vben redressing tbs
filter press.
,
4. No. 2 still, ssae as position 1 above.
.6 No. 2 recsiver, saas as position 2 above.
6. No. 2 filter press, sane as position 3 above.
( 7. At operator's desk, 54" from floor and 8" beyond front edge
of desk to aisolate position of operator's bead vben writing at desk.
8# At soales for draining drooler. 54" frea floor and 14" froa Aroclor outlet. Opposite side of drua froa operator.
.8 Plank detendnatione ae described.
.10 Miscellaneous positions, as described.
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