Document 2VNaq23kvg8dGz5DMrbL6zNa
o;ov DOW CHEMICAL U.S.A.'
February 20, 1974
A*STOW BUILDING 2030 DOW CENTER MIDLAND. MICHIGAN 840
Monsanto Company 800 N. Lindbergh Blvd. St. Louis, Missouri 63166
Attention: Mr. HT^Sv^/Frankel, Mgr, Raw Materials Purchasing
Gentlemen :
On February 15, 1974, Dr. V. K. Rowe, Research Scientist, Dow Chemical U.S.A. Health and Environmental Research Group, presented tcs'.Linrny to CSET. in rranhir.ctcn, D. C. concerning our toxicological data and industrial experience with vinyl chloride monomer ever the past several years.
Recognizing that some of our customers for VCW may not have attended the hearing, v/e are attaching a copy, of this testimony so that you will be familiar with the recommenda tions made by Low for Government-Industry action concerning this very serious problem.
We certainly urge you to call on us for any assistance needed regarding sampling procedures, testing, monitoring equipment., etc.; and we will do our utmost to help you in areas where we have experience.
Very truly yours,
3- $1 tttCti
T. R. Richardson Sales Manager Industrial Chlorc-Chcm
ro enc.
cc: T. Mann, Dow St. Louis Sales Office
. l*AO/,,,
AN OPWAT1NO UNIT OP THf DOW CHEMICAL COMPANY
RSV 0000219
TDXICDLDGICAL DATA A*ID IflDUSTRIAL EXPERIENCE WITH VIiJYL CHLORIDE
Testimony of
)r. V, K. Ron-/e
(esearch Scientist
USAtaw Chemical
li bland, Michigan
Public Hewing on Vinyl Chloride Occupational Safety and Health _ Administration Department of Labor
D. C.Washington,
February 15, 1974
rsv 0000220
TABLE OF (MBITS
INTRODUCTION
I. Scope of the Vinyl Chloride Industry
II. Toxicology of Vinyl Chloride
III.
Health Parameters Studied in Vinyl Chloride WORKERS
IV. Industrial Hygiene
V. Safety in the Vinyl Chloride Industry
VI.
Analytical Methodology
VII.
Recowendations fgr Goverwent-Industry Action
I.Appendix
Published References to the Biological Effects of vinyl Chloirde (Including CHEMI CAL ABSTRACTS lb52 - JANUARY 14, inTM mD Biological Abstracts 1552-
Appendix II.
Industrial Hygiene Surveys Involving Vinyl Chloride
(Each appendix to the tesiimony is a otflete volume IN A HARD-BACK BINDER. tACH IS SUBMITTED IN TRIPLICATE).
RSV 0000221
-It
itfrtmnioN
I V, K. U.S.A. Iam Rowe of Dow Chemical
Currently am a research
SCEINTIST CONCERNED WITH THE OVER-ALL BROAD ASPECTS OF Dow'S HEALTH
and Environmental Research. Prior to being naked to this post in late
1973,# I was Director of oik Toxicology Laboratory and Industrial
Hygiene research.
I shall summarize for the record the following: (1) scope of the VINYL CHLORIDE INDUSTRY; (2) THE BASIC TOXICOLOGICAL INFORMATION;
G) THE HEALTH PARAMETERS STUDIED IN VINYL CHLORIDE WORKERS; tt)
OUR INDUSTRIAL HYGIENE EXPERIENCE IN ALL OF OUR PLANTS; (53 ANALYTICAL AND MONITORING PROCEDURES; (6) ITEMS FOUND EFFECTIVE ITT MAINTAINING" SAFE OPERATING CONDITIONS; AND FINALLY (7) SOME SUGGESTIONS FOR THE FUTURE. I BELIEVE IT WILL BE APPARENT THAT THE INDUSTRY LEARNING
CURVE FOR VINYL CHLORIDE IS FAR ADVANCED.
RSV 0000222
1` ' **-
- ----------- --
-3-
U.S. PRODUCERS OF VINYL CHLORIDE
CO
rl o
0 H
e
Year
Total U.S. Production
Million Pounds *
*OH 4E) o6 o
J5 c CO
VO *o-l
*H fa <H 0)
<
O
fa OTOOO ct.
CQ
J<JQ
C
4C)
0
Q
oo)
c
oc 6*
Eo
Aoo
oc
o
CL,
E . On
cO o
uop.
u u T3
H > CoE
4) J5 <0
0 r1
CO [X]
o
H
JO fa CO
O
C
(4
E->
rH
0
O
*A
c 0c3 a;
O *cC
CO
rfHa
E
O
foa fa 3 co>d> *o0 CO a
1973* * 5,333
X XX XXX XXX X
1972* * 5,109
X XX XXX XXX X
1971
4,336
X XX XXX XXX X
1970
4,040
X XX XXX XX
XX
1969 1968 1967 1966
3,736 2,969 2,424 2,500
X XX XXX XX
X X X XXX XX
.X X X
XX XX
X XX
XX X
XX X XXX XXX XXX
XX XX XX
XX XX
1965
2,000
X XX
X
X
1964
1,615
X XX
X
X
XXX XXX
XX XX
XX XX
1963
1,435
X XX
X
X
XXX XX XX
1962
1,313
X XX
X
X
XXX XX XX
1961
1,044
X XX
X
XXX XX XXX
I960
1,037
X XX
X
' XXX XX XXX
1959
978
X
X
X
XXX X XX
1958 691 X X X
X X X XX
1957
627 X
X
X
X X XX
1956 597 X X X
XX X XX
1955
529
X X
XX X XX
1954
393
XX
XX X XX
1953
402
XX
XX X XX
1952
321
X *X
XX X XX
Source U.S. Tariff Commission Annual Reports (Reporting of quantity of vin'y
#1IU- -.S" .
T,-ricffhloccrimdeissbieo;-nan-
in 1952) Monthly
Reports
(s ubject
to
revision)
RSV 0000223
-*h
HoweveR/ the principal process/ used by Dow and most other producers
IN THE U*S j INVOLVES THE THERMAL DEHYDROHALQGENATION OF ETHYLENE
DICHLORIDE.
a^ic^ci- - - - - - - - - - *> ch^chci + hq ^
Vinyl chloride is one of the purest organic compounds produced commercially.
A TYPICAL ANALYSIS OF VINYL CHLORIDE PRODUCED BY DOW SHCMS LESS THAN 20 PPM
OF TOTAL ORGANIC IMPURITIES. THESE TRACE ORGANIC- IMPURITIES ARE ACETYLENE/ L3-BUTADIENE/ METHYL CHLORIDE/ AND VINYL ACETYLENE.
Nearly all vinyl chloride monomer shipped by Dow is uninhibited; however/ A SMALL AMOUNT IS INHIBITED WITH 25-75 PPM PHENOL. THE PHENOL IS SUB SEQUENTLY REMOVED BY USE OF A CAUSTIC WASH.
I WISH TO EMPHASIZE THE DIVERSITY OF PLANT AND PROCESS OPERATIONS IN PRODUCING AND USING VINYL CHLORIDE. COMMERCIAL PLANTS FOR PRODUCING VINYL CHLORIDE RANGE IN CAPACITY FROM MODEST SIZE LP TO SEVERAL HUNDRED MILLION POUNDS. SOME ARE NEW PLANTS/ SOME ARE 15 TO 20 YEARS OLD.
Three distinctly different polymerization processes have been com-iercialized TO PROVIDE THE WIDE VARIETY OF ESSENTIAL PLASTIC MATERIALS PRODUCED FROM
RSV 0000224
VINYL CHLORIDE (SUSPENSION, ENJLSION, AND BULK PROCESSES). POLYMERIZATION RECIPES AND SCHEDULES ARE OF NECESSITY QUITE VARIED. POLYMERIZATION PLANTS ARE BOTH OPEN-AIR AND ENCLOSED. I WILL CITE MANY OF OUR PLANT PRACTICES, BUT STRONGLY RECOMMENDED THAT OSHA RECOGNIZE THE DIVERSITY OF MONOMER MANUFACTURING AND POLYMERIZATION OPERATIONS IN CONSIDERING THE ESTABLISHMENT OF A WORKPLACE STANDARD OR STANDARDS, OTHER PRODUCERS AND PROCESSORS WILL HAVE DIFFERENT TYPES OF JOBS, DIFFERENT EQUIPf-ENT, AND DIFFERENT ENGINEERING, MONITORING, AND PROCEDURAL APPROACHES. DOW STRONGLY BELIEVES THAT A STANDARD SHOULD EMPHASIZE IN OBJECTIVE TERMS V.HAT IS TO BE ACCOMPLISHED SO THAT A NUMBER OF ENGINEERING AND PROCEDURAL APPROACHES MAY BE EMPLOYED UNDER THE STANDARD, DEPENDING ON THE PARTICULAR PLANT SITUATION.
RSV 0000225
6- -
II. TOXICOLOGY OF VIIIYL CHLORIDE
Earliest studies on vinyl chloride were limited to acltte exposures, as TYPICAL OF TOXICITY STUDIES OF THE DAY. THESE OBSERVATIONS LED TO ITS
CONSIDERATION AS A SURGICAL ANESTHETIC. GENERALLY,THESE STUDIES SHOWED
VINYL CHLORIDE TO BE LOW IN ACUTE TOXICITY, TO BE ANESTHETIC IN ACTION, AND
TO HAVE LITTLE CAPACITY TO CAUSE LIVER INJURY FROM EXPOSURES OF A FEW HOURS.
(1353)MaSTROM-ATEO EL AL. (1360) AND LESTER el AL.
REPORTED ON ACUTE
EXPOSURES OF ANIMALS AND HLMANS.
They reported very little effect until exposure concentrations approached
Mo10,000 ppm when hit-vans reported dizziness after 5 minutes exposure.
1/2 2 lG&OGODEATHS OCCURRED IN RATS EXPOSED FROM
TO HOURS' TO
PPM.
150,000 200,000 1/2 2toExposures to
ppm for
to hours caused anesthetic
DEATHS AS DID HIGHER CONCENTRATIONS FOR SHORTER PERIODS OF TIME.
RSV 0000226
-7-
ACUTE IflHALATIOiJ OF TOXICITY OF VINYL CHLORIDE
Species Rats, mice, and
guinea pigs
Guinea pigs Rats
Humans
CoticBfFfflicvi-^ppr^.
mooo
200,000 300,000
= QD%)
TO,000 100,000 150,000
None
- 4,000 8,000
12,000
16,000 20,000
Death or Other Effect
NO-DEATHS IN 0.5 HR ^
1/15 0/5 MICE) U/15 (5/5 RATS AND MICE
3/5 GUINEA PIGS)
2/5 (1 IMMEDIATELY, 1 IN 24 HRS)
NO DEATHS' IN 2 HRS 1 OF 2 DIED IN 2 W?S (2)
/o\
3/6 SLIGHT DIZZINESS IN 5 MIN ^
0/6
-3/6 SLIGHTLY UNSTEADY
Q2/6
SLIGHTLY LfiSTEADY,
1 reeling)
Intoxication of varying degree
Intoxication of varying degree.
MORE SEVERE
AIHA J.UJ
^ Masttomateo ex ALw
2L 334 (J9G0)
(2)
AIHA J.L ,ester Greenberg and Adams,
24, 265
(1963)
RSV 0000227
Some lung congestion and edema were present after 42 minutes exposure to 150,000 PPM, BUT LIVER AND KIDNEY INJURY WERE NOT APPARENT.
Since 1962, numerous non U.S. articles on vinyl chloride have appeared/ PARTICULARLY IN THE RUSSIAN LITERATURE. SEVERAL OF THESE STUDIES INVOLVED ACUTE EXPOSURES AND THE OBSERVED EFFECTS WERE GENERALLY SUBTLE REVERSIBLE CHANGES.
The CHRONIC TOXICITY OF VINYL CHLORIDE HAS BEEN STUDIED BY SEVERAL INVESTIGATORS. TORKELSON, OYEN, AND ROWE (1961) REPORTED THE FOLLOWING RESULTS.
Results of Repeated Seven-Hour Daily Exposures to Vinyl Chloride.
Exposure
PPM
MONTHS
500
4.5
200
6
Dogs
Guinea pigs
NOT EXPOSED NOT EXPOSED
NO EFFECT
NO EFFECT
Rats_____
Rarrtts
SLIGHT LIVER &
NOT EXPOSED
KIDNEY HISTOPATHOLOGY (central lobular granular ESGENSRATICN
AND INTERSTITIAL & TUBULAR CHANGES)
SLIGHT LIVER WEIGHT INCREASE
SLIGHT LIVER HISTOPATHOLOGY (CENTRAL L13ULAR
DEGENERATION t NECROSIS WITH
VACUALATICN AND SOME PERIPORTAL
CELLULAR INFIL TRATION)
1D0 50
6 6
NO EFFECT
NO EFFECT
NO EFFECT . NO EFFECT
SLIGHT LIVER WEIGHT INCREASE
NO EFFECT
NO EFFECT NO EFFECT
RSV 0000234
*i 9--
They concluded that workers exposure should be limited to less than 100
PPM WITH A TIME-WEIGHTED AVERAGE NOT TO EXCEED 50 PPM.
Lester. Greenberg, and Adams took exception to conclusions of Torkelson,
ET AL AND RECOMMENDED 500 PPM AS A TIME-WEIGHTED AVERAGE EXPOSURE.
RESULT OF REPEATED SBei-HOUR EXPOSURE OF r-'iALE CT fflSIE RATS TQ VlfTfL CHIQRIE
Exposure Conditions 50.000 ppm - 19 days
20.000 ppm - 90 lays
.Result.
Incoordination. Normal hematology. Increase LIVER WEIGHT, NORMAL GROSS PATHOLOGY. SLIGHT LIVER HISTOPATHOLOGY.
Normal hematology. Increased liver weight. Normal gross pathology. Slight liver HISTOPATHOLOGY. WHICH WAS CONSIDERED TO BE WITHIN NORMAL LIMITS.
RSV 0000229
ACGIHBecause of these conflicting reports,, the TLV Committee of the
in 1953 chose to change their TLV from 500 ppm as a maximum tii^-weighted AVERAGE FOR INDUSTRIAL EXPOSURE TO 500 PPM AS A CEILING VALUE. (AFRICAN Conference of Governmental Industrial Hygiene, 1953).
P. L.Because of the report of acroosteolysis in hlwans, Professor
Viola
of the Regina Eleva Institute for Cancer Research in Rome, Italy, attempted
TO PRODUCE THE DISEASE IN ANIMALS, HE EXPOSED RATS 4 HOURS PER DAY, 5 DAYS
PER WEEK TO 30,000 PPM (3%) VINYL CHLORIDE VAPOR. (VlOLA, MARCH 1970).
In his first report on the results of ]2 months exfosure, he described
PETAPLASTIC CHANGES IN THE BONES WHICH HE CONSIDERED SIMILAR TO THE HUMAN
HDISEASE ACROOSTEOLYSIS. e MADE NO MENTION OF HAVING OBSERVED CANCER IN
THESE ANIMALS UNTIL THE TENTH INTERNATIONAL CANCER CONGRESS IN MAY 1970.
In THE ABSTRACTS OF THIS f-EETING, (VlOUA, 1970), AND SUBSEQUENTLY IN
Nay 1971, Viola, Bigotti, and Caputo (1971) reported tu-iors of the skin,
LUNGS, AND BONES OCCURRING FIRST AFTER ID f'DNTHS EXPOSURE. THE AUTHORS
SUMMARIZED THIS WORK AS FOLLOWS:
RSV 0000230
(Ar/IRERats
Wistar strain) exposed for 12 months to vapors of vinyl
CHLORIDE DEVELOPED TUTORS OF THE SKIN, LUNGS, AND BONES. THE CUTANEOUS
TUMORS, WHICH ALWAYS APPEARED IN THE AREA IN WHICH SUBMAXILLARY AND PAROTID GLANDS ARE LOCATED, HAVE BEEN HISTOLOGICALLY RECOGNIZED AS EPIDERMOID CARCINOMAS, PAPILLOMAS, AND MUCOEPIDERMOID CARCINOMAS. THE
MORPHOLOGICAL CHARACTERISTICS OF LUNG RMORS, WHICH OCCURRED IN A LOWER
PERCENTAGE, WERE MAINLY OF THE ADENOCARCI NOTA TYPE, WITH THE EXCEPTION
OF A SINGLE EPIDERMOID TUMOR ORIGINATING FROM THE EPITHELIAL COVERING
ICELLS. n A MINOR NUMBER OF RATS, A LARGE PROLIFERATION OF CARTILAGINOUS
TISSUE DIAGNOSED AS OSTEOCHONDROfA DEVELOPED IN THE METACARPAL AND META
TARSAL REGIONS OF THE FOUR LIIBS."
N
This report by Viola et al. is apparently the earliest and only publication IN ALWHICH CARCINOGENIC ACTIVITY HAS BEEN ASCRIBED TO VINYL CHLORIDE.
THOUGH THERE ARE POSSIBLE DEFICIENCIES IN VlOLA'S STUDY, SUCH AS THE
QUALITY OF THE VINYL CHLORIDE SAMPLE USED IN THE STUDY, THE PRESENCE OF FOOD AND BEDDING IN THE EXPOSURE CHAMBER, AND THE EXCESSIVE EXPOSURE CONCENTRATION USED, THE REPORT NEVERTHELESS GAVE RISE TO SERIOUS CONCERN AND RESULTS) IN THE INITIATION OF ADDITIONAL ANIMAL STUDIES AND EPIDEMIOLOGICAL STUDIES WHICH ARE CURRENTLY UNDERWAY (KCA PRESS RELEASE).
RSV 0000231
41 m3*'
turn M *
1
StffWUZlNG, IT SHOULD BE EMPHASIZED:
A. Acute effects from short term exposure occur
ONLY AT HIGH ENVIRONMENTAL CONCENTRATIONS, B. Chronic or long-term effects occur at moderate
CONCENTRATIONS. The MOST SENSITIVE TOXICOLOGICAL RESPONSE OBSERVED TO DATE IS THE EFFECT ON THE LIVER, C. Tic central nervous system effect in human
BEINGS IS RELATED TO THE CONCENTRATION OF INHALED AIR.
Vfe ARE SUBMITTING TRIPLICATE COPIES OF THE TOXICOLOGICAL LITERATURE ON VINYL CHLORIDE FOR OSHA REFERENCE. THESE ARE APPENDIX I OF THIS TESTIMONY.
/
RSV 0000232
III. HEALTH PARArETERS STUDIED IN WORKERS
DOW IS COOPERATING WITH THE MANUFACTURING CHEMISTS ASSOCIATION WHICH HAS RETAINED TaBERSHAW-CoOPER TO CO AN INDUSTRY-WIDE STUDY OF THE HEALTH OF V.CRKERS EXPOSED TO VINYL CHLORIDE. CllRRENTYL, WE HAVE APPROX IMATELY 320 EMPLOYEES IN VINYL CHLORIDE OPERATIONS. Vfe HAVE SUBMITTED TO TABERSHAW-COOPER EMPLOYEE RECORDS COVERING 916' PERSONNEL WHO HAVE BEEN INVOLVED IN VINYL CHLORIDE OPERATIONS OVER THE YEARS. THIS STUDY IS INCOMPLETE AND WILL BE REPORTED AT AN APPROPRIATE DATE. HOWEVER, WE CAN MAKE THE FOLLOWING PRELIMINARY COMMENTS ON THE HEALTH PARAMETERS
DowOF VINYL CHLORIDE WORKERS.
PRELIMINARY DATA FROM Dow MANUFACTURING UNITS REVEAL NO DEATHS DUE TO CANCER OF THE LIVER.
Preliminary data likewise reveal no deaths due to cirrhosis of the UVER. Vfe HAVE NO CASES OF ACROOSTEOLYSIS.
At THE PRESENT TIME, WE ARE UNAWARE OF ANY LIVING EMPLOYEE WHO HAS BEEN`EXPOSED TO VINYL CHLORIDE SUFFERING FROM CANCER OF THE LIVER. Likewise, we know of no case of cirrhoiss of the liver in employees EXPOSED TO VINYL CHLORIDE. HOWEVER, THIS INFORMATION IS INCOMPLETE AND IS BEING SUBJECTED TO A CRITICAL SEARCH.
RSV 0000233
PRELIMINARY STUDIES IN TWO MAJOR MANUFACTURING LOCATIONS, WITH THE LONGEST HISTORY OF VINYL CHLORIDE PRODUCTION, REVEAL NO INCREASE IN ABNORMAL LIVER FUNCTION TESTS ABOVE THAT EXPECTED IN A SIMILAR UNEXPOSED POPULATION.
C. G. KRAMER, M.D. AND J. E. MUTCHLER PUBLISHED IN THE AMERICAN INDUSTRIAL HYGIENE ASSOCIATION JOURNAL IN 1972, A STUDY OF VINYL CHLORIDE WORKERS IN ONE LOCATION. FINDINGS SUGGEST THAT REPEATED EXPOSURE TO VINYL CHLORIDE AT TWA LEVELS OF 300 PPM OR ABOVE FOR A WORKING LIFETIME TOGETHER WITH A VERY LOW LEVEL OF VINYLIDENE CHLORIDE MAY RESULT IN SLIGHT CHANGES IN CERTAIN PHYSIOLOGICAL AND CLINICAL LABORATORY PARAMETERS. THE POSSIBILITY OF SOME IMPAIRMENT IN LIVER FUNCTION MUST BE CONSIDERED, EVEN THOUGH NO OVERT CLINICAL DISEASE WAS EVIDENT IN ANY OF THE INDIVIDUALS STUDIED. THIS STUDY SHOWED A DEFINITE DOSE-RESPONSE CORRELATION BETWEEN THE INTENSITY OF EXPOSURE AND THE DEVIATION FROM NORMAL VALUES.
WE WILL CONTINUE TO COOPERATE WITH THE MANUFACTURING CHEMISTS ASSOCIATION IN THE TABERSHAW-COOPER STUDIES. ADDITIONAL INDEPTH STUDIES WILL BE CONTINUED WITHIN THE VARIOUS MANUFACTURING UNITS OF THE COMPANY AND WILL BE REPORTED UPON WHEN COMPLETE.
RSV 0000234
fa
IV. INDUSTRIAL HYGIENE MEASUREMENTS OF VINYL CHLORIDE IN WORKPLACE A:
i
DOW HAS MONITORED THE WORKPLACE ENVIRONMENT BY A VARIETY OF TECHNIQUES, INCLUDING:
(A) CONTINUOUS MONITORING OF REPRESENTATIVE OR SELECTED WORKPLACE AREAS BY A COMBUSTION - CONDUCTIVITY ANALYZER.
(B> "GRAB" SAMPLES OF WORKPLACE AIR COLLECTED IN IMPERVIOUS PLASTIC BAGS OR ACTIVATED CARBON "SLUGS" (ABSORPTION). ANALYSIS OF SUCH SAMPLES IS NOW BY
--------- GAS CHROMATOGRAPHY, BUT YEARS AGO ANALYSIS WAS BY DETERMINATION OF TOTAL CHLORIDE OR BY INFRARED SPECTROSCOPY.
(C) PERSONNEL MONITORS BASED ON ABSORPTION ON ACTIVATED CARBON SLUGS, FOLLOWED BY GAS CHROMATOGRAPHIC ANALYSIS.
MONOMER PLANT #1 STARTED OPERATION IN 19*16. HISTORICALLY, SPOT .SAMPLING WAS CONDUCTED. LOADING OF TANK CARS, COLLECTION OF SAMPLES FOR PRODUCT ASSAY AND DISTILLATION OPERATIONS WERE THE ONLY TASKS WHICH NEEDED ATTENTION IN THE EARLY OPERATION OF THIS PLANT. IN 1972, AN EXTENSIVE INDUSTRIAL HYGIENE SURVEY WAS CONDUCTED. MULTIPLE GRAB SAMPLES WERE COLLECTED IN IMPERVIOUS PLASTIC BAGS AND ANALYZED BY GAS CHROMATOGRAPHY. THE FOUR CONTROL OPERATOR CLASSIFICATIONS HAD TWA VALUES BETWEEN 0.2 AND 1.3 PPM. MAINTENANCE EMPLOYEES HAD A TWA VALUE OF 1.7 PPM AND THE SUPERVISORY EMPLOYEES HAD A TWA OF 1.3 PPM. THE LOADING
RSV 0000235
45OPERATIONS HAD A TO VALUE OF
PPM AND THE LABORATORY EMPLOYEES
WHO COLLECT SAMPLES FROM STORAGE TANKS HAD A TO OF 14 PPM.
Personnel monitoring is presently being carried out on a systematic
I 1973,AND PERIODIC BASIS IN THIS PRODUCTION UNIT. n
ALL TO VALUES
10WERE BELOW
PPM EXCEPT FOR THE LABORATORY EMPLOYEES WHO HAD TO
30E)05OSURES OF UP TO
PPM, A LEVEL WELL BELOW OUR INDUSTRAIL HYGIENE
50GUIDELINE OF
PPM.
1958.Mdncfer Plant 82 started operation in
Limited surveys were
1955 TO's 9 60CONDUCTED IN
AND REVEALED
RANGING FROM TO
PPM.
An
1973, Au_IN-DEPTH SURVEY WAS CARRIED OUT IN
TO VALUES WERE BELOW
10 PPM EXCEPT FOR THE LABORATORY EMPLOYEES. ThEIR VALUES WERE BETWEEN
ID AND 15 PPM.
1959. I 1973 - 1974Monotcr Plant 85 began operation in
na
personnel
MONITORING STUDY, TO VALUES RANGED FROM LESS THAN 1 PPM TO 10 PPM.
OUR POLYMER PLANT #1 WAS OPERATED PROM 1946 TO 1972. BETWEEN 1950 AND 1959 SEVERAL INDUSTRIAL HYGIENE SURVEYS WERE CONDUCTED. A NIMBER OF JOB CLASSIFICATIONS (POLYMERIZER OPERATORS, DRIER OPERATORS, MONOMER STILL OPERATORS, AND MONOMER TRANSFER OPERATORS) HAD WORKPLACE ENVIRONMENTAL LEVELS RANGING FROM 50 TO 385 PPM VINYL CHLORIDE. AFTER INSTALLATION OF A CONTINUOUS ANALYZER
RSV 0000236
m ^ MjfiTiill--fi ! i ajtfftfiTTiTTi "rfnSffiP igfrigi Mi V
-
1959,FOR THE WORKPLACE AIR IN
IMPROVEMENTS WERE ACHIEVED# VlNYL CHLORIDE
TWA VALUES RANGED ROM 25 TO 85 PPM DURING THE PERIOD 1960-1967.
Our present polymerization plant, polymer plant number two, began operation
in 1953. of Tift.
Historically the TO values have been decreased over this period
I 105-240n the early history, TO values of
ppm were observed.
1973, 1 25During
TO values for vinyl chloride in the air were in the to
ppm
range.
life EMPHASIZE THAT THERE IS SOME VARIATION IN TO VALUES FROM DAY TO DAY FOR A GIVEN TYPE OF OPERATION, FOR EXAMPLE, OPERATORS INVOLVED IN PUMPING REACTORS SHOWED VALUES RANGING FROM 1 TO 34 PPM. SIMILARLY, THREE OPERATORS INVOLVED IN LOADING OPERATIONS HAD TO VALUES RANGING FROM 8 TO 31 PPM, He ENCOURAGE RECOGNITION THAT SUCH VARIATION will OCCUR IN NORMAL DAY TO DAY OPERATIONS INVOLVING TRANSFER OF MONOMER.
life ARE INCLUDING REPORTS ON A NUMBER OF OUR INDUSTRIAL HYGIENE MONITORING
STUDIES AS WRITTEN SUPPLEMENTS TO THIS STATEMENT. TpESE ARE LABELED
II.Appendix
_
-
In sugary, the INDUSTRIAL hygiene data show that levels of exposure below
50 PPM ARE ATTAINABLE IN BOTH PRODUCER AND USER PLANTS OF VINYL CHLORIDE.
RSV 0000237
It must be noted., however, that with older plants the achievement
OF SUCH GOALS WAV BE DIFFICULT, AND IN ALL PROBABILITY WILL REQUIRE MAJOR MODIFICATIONS THAT WILL TAKE TIME TO ACCOMPLISH,
RSV 0000238
' V. SAFETY IN THE VINYL CHUDRIDE IrlDUSTHY .
The operation of a safe plant involving the handling of toxic, hazardous MATERIALS REVOLVES AROUND:
1. Establishment of safe, practical allowable ENVIRONMENTAL LEVELS.
2. Implementing APPROPRIATE ENGINEERING and' OPERATING PROCEDURES TO ACHIEVE OR BETTER THESE LEVELS.
3. ftWIDING ANALYTICAL MONITORiNG CAPABILITY TO INSURE THE ENVIRONMENT IS MAINTAINED BELOW THE ESTABLISHED LEVELS AND TO DETECT EXCURSIONS ABOVE SUCH LEVELS.
*1. Initiating appropriate corrective action when BREAKDOWNS OCCUR AND GUIDELINES ENVIRONMENTAL LEVELS ARE EXCEEDED.
5. Developing and supporting an appropriate medical SURVEILLANCE PROGRAM.
Day HAS A SAFETY PHILOSOPHY THAT THE SAFETY OF OUR EMPLOYEES, OUR CUSTOMERS AND CUR NEIG-EORS IS OF PRIME AND OF UTMOST IMPORTANCE. THIS SAFETY PHILOSOPHY PERPEATES OUR OPERATIONS. To ACHIEVE OUR GENERAL SAFETY GOALS FOR VINYL CHLORIDE OPERATIONS AND TO ACHIEVE A GOAL THAT INDUSTRIAL EXPOSURE TO VINYL
rSV 0000239
f
CHLORIDE SHOULD BE KEPT BELOW 50 PPM ON A TIVE WEIGHTED AVERAGE.* WE HAVE ir'PLEI'ENTED THE FOLLOWING DESIGN AND ENGINEERING PRINCIPLES FOR VINYL CHLORIDE OPERATIONS:
1. Processing systems are closed with no open vessel OPERATION.
2. Current buildings where vinyl chloride is manufactured OR POLYMERIZED ARE OPEN TO THE ATMOSPHERE OR HAVE VENTILATION TO MINIMIZE CONCENTRATION BUIU>UPS.
3. Engineering design emphasizes reasonable process AUTOMATION AND REASONABLE REMOTE OPERATION IN ORDER TO MINIMIZE PERSONNEL EXPOSURE.
4. Vent exhaust systems are selectively located to MINIMIZE THE POSSIBILITY OF PERSONNEL EXPOSURE.
5. The nut-ber and quantity of samples for control ANALYSES ARE MINIMIZED.
Careful application of the above principles has led essentially to the ATTAINMENT OF OUR GOAL OF TVft VALUES OF LESS THAN 50 PPM IN OUR OPERATIONS.
We believe that good operating procedures must be tailored to each specific
PLANT/ THAT PLANT SIZE/ AND THE NATURE OF THE PROCESS AND PLANT LOCATION ALL WILL INFLUENCE THE EXACT PROCEDURES TO BE CARRIED OUT. I WILL MENTION
RSV 0000240
A FEW OF THE MORE IMPORTANT OPERATING PROCEDURES AND TECHNIQUES INVOLVED FOR ONE OF OUR MONOMER PRODUCTION PLANTS TO ILLUSTRATE THE COMPLEXITY OF GOOD PLANT OPERATION.
1. Employees are familiarized with emergency procedures and signals; for example, wind directional signals, HORN EMERGENCY CALLS, AND EVACUATION ROUTES.
2. Collection of analytical samples of vinyl chloride FROM STORAGE TANKS INVOLVES A CLOSED LOOP SAMPLING SYSTEM IN ORDER TO RETURN VINYL CHLORIDE TO THE PROCESS RATHER THAN VENTING VAPOR IN THE WORKPLACE ENVIRONMENT. LABORATORY SAMPLES OF VINYL CHLORIDE ARE HANDLED IN HOODS AND SAMPLE CYLINDERS ARE GROUNDED WHEN DISCHARGED. ON-LINE GAS CHROMATOGRAPHY IS BEING USED EXTENSIVELY TO MONITOR PRODUCT PURITY AND PROCESS OPERATION; THIS HAS REDUCED MARKEDLY THE NUMBER OF MANUAL SAMPLE COLLECTIONS REQUIRED.
3. Specially designed vapor equalizing lines CONNECTED BACK TO THE STORAGE TANK ARE EXPLOYED IN THE LOADING OF TANK CARS.
4. Environmental monitoring of air is being conducted BY A NUMBER OF TECHNIQUES. GAS DETECTOR ALARMS ARE LOCATED THROUGHOUT THE PLANT AT A NUMBER OF STRATEGIC
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LOCATIONS TO WARN OF ANY FLAWABLE CONCENTRATIONS. PORTABLE DETECTOR INSTRUMENTS ARE AVAILABLE FOR
CHECKING PLANT AREAS OR PROCESS EQUIPMENT PRIOR
AlRTO NCN~ROUTINE OPERATIONS AND PROCEDURES.
QUALITY SURVEYS WERE CONDUCTED IN MONOMER PLANT number 1 in 1971, During the first quarter of 1974, A CONTINUOUS ANALYZER SYSTEM FOR 12 STRATEGIC LOCATIONS IN THE PLANT WILL BE INSTALLED. THIS WILL PROVIDE CONTINUDUS BACKGROUND INFORMATION AND PROVIDE INSTANTANEOUS SIGNALS FOR ANY UN USUALLY HIGH CONCENTRATIONS THAT MIGHT OCCUR DUE TO LEAKS, SPILLS OR OTHER NON-ROUTINE SITUATIONS.
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In our polymerization operations, we have not had problems OF WORKER
ILLNESS FROM THE CLEANING OF POLYMERIZATION VESSELS. We UTILIZE HIGH
PRESSURE WATER JETS AFTER EACH POLYMERIZATION REACTION TO PREVENT POLYMER BUILD-UP. Our EMULSION POLYMERIZATION KETTLES REQUIRE MANUAL CLEAN-OUT EVERY TWO CR THREE MONTHS, AFTER WATER CLEANING OF THE VESSEL, ALL LINES
ARE BLANKED TO PREVENT ANY MATERIAL FRCM ENTERING THE VESSEL; THE ATMOSPHERE IS TESTED FOR OXYGEN SUPPLY, AND A CONTINUOUS VINYL CHLORIDE MONITORING PROBE IS PUT INTO THE VESSEL. CONCENTRATIONS MUST BE BELOW 50 PPM PRIOR TO VESSEL ENTRY. AlR PURGE IS MAINTAINED ON THE VESSEL DURING THE CLEANING
OPERATION.
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VI. ANALYTICAL rOHODOLDGY
Four remoDS are available for environmental monitoring of air for
TVE PRESENCE OF VINYL CHLORIDE:
1. CbraUSTION-CaNDUCTIVITY 2. Gas chromatography 3. Infrared sPEcraoPHoror-ETRY 4. Flame ionization spectrophotometry
Gas chromatography is very specific, but requires'about 10 minutes per sample, Flame ionization detectors have no specificity-responding
TO ALL CARBON-CARBON OR CARBON-HYDRO<2N BONDS, BUT ARE PORTABLE AND THE fEASUREMENT IS INSTANTANEOUS, THE COMBUSTION-CONDUCTIVITY METHOD RESPONDS TO ANY MATERIAL WHICH BURNS TO PRODUCE IONS, It RESPONDS RAPIDLY, INFRARED ANALYZERS ARE VERY SPECIFIC, RESPOND QUICKLY AND ARE PORTABLE, ALL OF THESE TECHNIQUES HAVE ADEQUATE SENSITIVITY, DETECTING CONCENTRATIONS OF 1 PPM,
FtRSONNEL MONITORING IS ACHIEVED THROUGH USE OF ABSORPTION TUBES FILLED WITH ACTIVATED CARBON, THE ABSORBED CHLORINATED HYDROCARBONS ARE DETERMINED BY GAS CHROMATOGRAPHY AFTER THERMAL RELEASE OR EXTRACTION BY CARSON DISULFIDE.
ftr Dow, most of our environmental monitoring has been with amisTiON-
VfeCONDUCTIVITY ANALYZERS.
HAVE USED THESE ANALYZERS FOR CONTINUOUS MONITORING
SINCE ]999 WITH EXCELLENT RESULTS.
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VII. RECaTHTOTia^S FOR GDOI-Eff-INDUSIFY ACTION
Dow QSKA1.
URGES
TO RECOGNIZE THE VOLUNTARY INDUSTRY
ACTION TO LOWER THE LEVELS OF EXPOSURE TO VINYL
CHLORIDE AND THE LEAD ROLE OF INDUSTRY IN OBTAINING
DATA ON THE VINYL CHLORIDE PROBLEM.
2. DOW BELIEVES THE INDUSTRY RECOGNIZES THE-NEED TO MAINTAIN ENVIRONMENTAL LEVELS BELOW THE OSHA STANDARD OF 500 PPM AND EVEN BELOW THE ACGIH RECOMMENDATION OF 200 ppm.
3. DOW BELIEVES THAT IT IS INDUSTRY'S AND GOVERNMENT'S RESPONSIBILITY TO INFORM ALL EMPLOYEES OR PERSONS WORKING WITH VINYL CHLORIDE ABOUT ITS HAZARDS AND TO DEVELOP AND IMPLEMENT TRAINING PROGRAMS TO HELP PREVENT OVER EXPOSURE AND INSURE PROPER REACTION IN EMERGENCY SITUATIONS. Me BELIEVE INFORMED EMPLOYEES WILL CO OPERATE IN ELIMINATING OVER- EXPOSURE AND SUGGEST KETVCDS FOR IMPROVEMENT.
-i 4# Based upon the medical and toxicological data available TO US AT THIS TIME, DOW BELIEVES THAT AN EIGHT-HOUR TWA OF 50 PPM IS A SATISFACTORY ENVIRCfIMENTAL STANDARD FOR VINYL
' CHLORIDE.
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ifc
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5. Daw IS SUPPORTING AND ACTIVELY COOPERATING IN LONG-TERM
INHALATION, METABOLISM AND EPIDEMIOLOGICAL STUDIES IN
ORDER TO OBTAIN THE MDST PRECISE DATA POSSIBLE RELATING
TO THE POTENTIAL FOR OCCUPATIONAL HEALTH ASSESSMENT.
V/EGO WILL STRONGLY SUPPORT INDUSTRY-GOVERNMENT
Cb)
EVALUATION OF THE DATA AS IT BECOMES AVAILABLE. Results of the epidemiological survey of vinyl
CHLORIDE WORKERS INITIATED ABOUT A YEAR AGO BY
MCA VIA CONTRACT WITH TABERSHAW-COOPER WILL BE '
AVAILABLE IN THE NEAR FUTURE. IT SEEMS REASONABLE
TO EXPECT THAT THESE RESULTS WILL PROVIDE ADDITIONAL AND SUBSTANTIVE BASIS FOR RULE-MAKING.
6. DOW BELIEVES RULE-MAKING SHOULD NOT BE BASED ON CONDITIONS
THAT EXISTED IN THE PAST BUT SHOULD BE BASED ON CONDITIONS
NIQSHAS THEY EXIST TODAY. BASED OtN
ACTIVITY AND ON WIDESPREAD
VOLUNTARY ACTIONS BY INDUSTRY, WE BELIEVE THERE IS NO NEED FOR A TEMPORARY EMERGENCY STANDARD. REALISTICALLY, WE
BELIEVE A TEMPORARY EMERGENCY STANDARD WOULD RESULT IN POLARIZATIONS RATHER THAN CONSTRUCTIVE DEFINITION OF AREAS OF CONCERN AND CONSTRUCTIVE PROBLEM SOLVING.
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We believe most producers/users of vinyl chloride have cr
VERY SOON WILL HAVE THE CAPABILITY TO MAINTAIN AN EIGHT-
CT.'ito 90HOUR TIME-WEIGHTED AVERAGE
OF PPM OR BELCW, THERE
FORE WE SUGGEST THAT STEPS BE TAKEN IN ORDER TO DEVELOP THE
STANDARD IN A REASONABLE WAY.
I(a) n order to assess THE STATE and MAGNITUDE of the
PROBLEM, WE SUGGEST THAT EACH PRODUCER/USER OF
. VINYL CHLORIDE COMPLETE AN INDUSTRIAL HYGIENE
SURVEY OF HIS OPERATIONS AND A MEDICAL SURVEY OF
VINYL CHLORIDE WORKERS WITHIN THREE MONTHS AND
REPORT THE RESULTS OF EACH SURVEY TO NIQSH/OSHA.
IF TWA's 50<B)
THE SURVEY REVEALS
IN EXCESS OF
PPM,
THE MANUFACTURER OR PROCESSOR SHOULD IMMEDIATELY TAKE STEPS TO REDUCE EXPOSURE BY OPERATIONAL AND/OR
ENGINEERING CHANGES AND REQUIRE THE USE OF APPROPRIATE RESPIRATORY PROTECTION BY HIS EMPLOYEES LIKELY TO BE EXPOSED TO SUCH LEVELS.
IF(c) THE MEDICAL SURVEILLANCE PROGRAM INDICATES
ABNORMALITIES THAT COULD BE ATTRIBUTED TO EXCESSIVE EXPOSURE TO VINYL CHLORIDE OR A CONDITION THAT COULD REASONABLY BE EXPECTED TO BE AGGRAVATED BY CONTINUED
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WORK WITH VINYL CHLORIDE/ THAT PERSON MIGHT WELL BE REMOVED TO ANOTHER JOB NOT INVOLVING SUCH EXPOSURE. W RECOWEND fllOSH ASSISTANCE IN DEFINING THE PRIORITY OF HEALTH PARAMETERS FOR STUDY.
Dew OSHA'SSUPPORTS
ESTABLISHMENT OF A PERMANENT HEALTH STANDARD
FOR VINYL CHLORIDE BY REGULAR RULEMAKING PROCEDURES,
We RECOMMEND THAT the STANDARD STATE what should be. accomplished,
LEAVING THE "HCW-TO-ACHIEVE COMPLIANCE" TO INDIVIDUAL PLANT IMPLEMENTATION.
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