Document npr02v8V59aRbV43nx6janyOm
Environment Canada
Environmental Protection Service
Environnement Canada
Service de la protection de I'environnement
March 1985
Canada
CMA 014362
ENVIRONMENTAL AND TECHNICAL INFORMATION FOR PROBLEM SPILLS MANUALS The Environmental and Technical Information for Problem Spills (EnviroTIPS)
manuals provide detailed information on chemical substances. This information is intended to assist the reader in designing countermeasures for spills and to assess their impact on the environment. The report has been reviewed by the Technical Services Branch, Environmental Protection Service, and approved for piftlication. Approval does not signify that the contents reflect the views and policies of the Environmental Protection Service. Mention of trade names or commercial products does not constitute endorsement for use.
EnviroTIPS manuals are available from: Piislications Section Environmental Protection Service Environment Canada Ottawa, Ontario CANADA K1A 1C8
CMA 014363
VINYL CHLORIDE ENVIRONMENTAL AND TECHNICAL INFORMATION FOR PROBLEM SPILLS
Technical Services Branch Environmental Protection Programs Directorate Environmental Protection Service Ottawa, Ontario
March 1985
CMA 014364
s Minister of Supply and Services Canada 1985 Cat. No. En 48-10 34-I985E ISBN 0-662-13983-6
BEAUREGARD PRESS LIMITED
FOREWORD
1
The Environmental and Technical Information for Problem Spills (EnviroTIPS) manuals were initiated in 19S1 to provide comprehensive information on chemicals that are spilled frequently in Canada. The manuals are intended to be used by spill specialists for designing countermeasures for spills and to assess their effects on the environment. The major focus of EnviroTIPS manuals is environmental. The manuals are not intended to be used by first-response personnel because of the length and technical content; a number of manuals intended for first-response use are available. The information presented in this manual was largely obtained from literature review. Efforts were made, both in compilation and in review, to ensure that the information is as correct as possible. Publication of these data does not signify that they are recommended by the Government of Canada, nor by any other group.
ACKNOWLEDGEMENTS
The final version of this manual was prepared by the staff of the Environmental Protection Service who wrote extensive revisions to the text, drafted illustrations and incorporated all comments and additions.
The level of detail present was made possible by the many individuals, organizations and associations who provided technical data and comments throughout the compilation and subsequent review of and input to this manual. The draft of this manual was prepared under contract to Environment Canada by M.M. Dillon Consulting Engineers and Planners, Concord Scientific Corporation and Waterloo Engineering Limited.
TABLE OF CONTENTS
iii
FOREWORD
ACKNOWLEDGEMENTS
LIST OF FIGURES
LIST OF TABLES
l SUMMARY
2 PHYSICAL AND CHEMICAL DATA
3 COMMERCE AND PRODUCTION
3.1 3.2 3.3 3.4 3.5 3.6 3.6.1 3.6.2 3.6.3 3.7 3.8
Grades, Purities Domestic Manufacturer Other Suppliers Major Transportation Routes Production Levels Manufacture of Vinyl Chloride General Raw Materials Manufacturing Process Major Uses in Canada Major Buyers in Canada
4 MATERIAL HANDLING AND COMPATIBILITY
4.1 4.1.1 4.1.2 4.1.3 4.1.4 4.1.5 4.2 4.2.1
4.2.2
4.2.3 4.3
Containers and Transportation Vessels General Cylinders Ton Container
Railway Tank Cars Tank Motor Vehicles Off-loading Off-loading Equipment and Procedures for Cylinders and Ton Containers Off-loading Equipment and Procedures for Railway Tank Cars and Tank Motor Vehicles Specifications and Materials for Off-loading Equipment Compatibility with Materials of Construction
5 CONTAMINANT TRANSPORT
5.1 5.2 5.2.1
General Summary Leak Nomograms Introduction
Page
i
i
vi
1
3
10
10 10 10 11 11 11 11 11 11 12 12
13
13 13 13 13 13 15 18
18
19 19 20
22
22 23 23
CMA 014366
IV
5.2.2 5.2.2.1 5.2.2.2 5.2.3 5.3 5.3.1 5.3.2 5.3.2.1
5.3.2.2 5.3.2.3 5.3.3 5.4 5.4.1 5.4.2 5.4.3 5.5 5.5.1 5.5.2 5.5.3 5.5.4 5.5.5 5.5.6
6
6.1 6.1.1 6.1.2 6.2 6.2.1 6.3 6.4
7
7.1 7.2 7.2.1 7.2.2 7.3 7.3.1 7.3.2 7.4 7.4.1 7.4.2 7.4.3 7.4.4 7.5 7.5.1 7.5.2
Nomograms Bottom puncture - liquid venting Top puncture - gas venting Sample Calculations Dispersion in the Air Introduction Vapour Dispersion Nomograms and Tables Figure 14: Normalized vapour concentration versus downwind distance Table 9: Maximum puff hazard half-widths Figure 17: Puff travel time versus travel distance Sample Calculation Behaviour in Water Introduction Nomogram for Spreading on Still Water Sample Calculation Subsurface Behaviour: Penetration into Soil Mechanisms Equations Describing Vinyl Chloride Movement into Soil Saturated Hydraulic Conductivity of Vinyl Chloride in Soil Soils Penetration Nomograms Sample Calculation
ENVIRONMENTAL DATA
Suggested or Regulated Limits Water Air Aquatic Toxicity Toxicity Ratings and Aquatic Effects Other Toxicity Degradation and Long-term Fate
HUMAN HEALTH
Recommended Exposure Limits Irritation Data Skin Contact Eye Contact Threshold Perception Properties Odour Taste Toxicity Studies Inhalation Ingestion Carcinogenicity Teratogenicity and Mutagenicity Symptoms of Exposure Inhalation Ingestion
Page
24 24 24 27 28 28 30
30 32 37 37 41 41 41 41 42 42 43 43 45 45 45
49
49 49 49 49 49 49 49
51
51 53 53 53 53 53 54 54 54 57 57 61 62 62 63
CMA 014367
V
7.5.3 7.5.4 7.6 7.6.1
8
8.1
9
9.1 9.1.1 9.1.2 9.1.3 9.1.4 9.1.4.1 9.1.4.2 9.1.4.3 9.1.5 9.1.5.1 9.1.5.2 9.1.6 9.1.7 9.1.8 9.2
10
10.1 10.2
11
11.1 11.1.1 11.2 11.3 11.3.1 11.4 11.5 11.5.1 11.6
12
12.1 12.2
Skin Contact Eye Contact Human Toxicity to Decay or CombustionProducts Carbon Dioxide and Hydrogen Chloride
CHEMICAL COMPATIBILITY
Compatibility of Vinyl Chloride with OtherChemicals and Chemical Groups
COUNTERMEASURES
Recommended Handling Procedures Fire Concerns Fire Extinguishing Agents Evacuation Spill Actions General Spills on land Spills on water Cleanup and Treatment Spills on water General Disposal Protective Measures Storage Precautions Specialized Countermeasures Equipment,Materials or Systems
PREVIOUS SPILL EXPERIENCE
General Train Derailment
ANALYTICAL METHODS
Quantitative Method for the Detection ofVinylChloride in Air Gas Chromatography Qualitative Method for the Detection ofVinylChloride in Air Quantitative Method for the Detection ofVinylChloride in Water Partition Infrared Qualitative Method for the Detection ofVinylChloridein Water Quantitative Method for the Detection ofVinylChloride in Soil Infrared Spectrophotometry Qualitative Method for the Detection ofVinylChloride in Soil
REFERENCES AND BIBLIOGRAPHY
References Bibliography
Page
63 53 63 64
65
65
67
67 67 67 67 67 67 68 68 68 68 68 69 69 69 70
71
71 71
73
73 73 74 74 74 74 75 75 75
76
76 83
CMA 014368
VI
LIST OF FIGURES
Figure
Page
1 VAPOUR PRESSURE
7
2 SOLUBILITY IN WATER
g
3 LIQUID DENSITY
g
4 LIQUID VISCOSITY
9
5 PHASE DIAGRAM
9
6 RAILWAY TANK CAR-CLASS 105A300W
16
7 TANK CAR WITH PUNCTURE HOLE IN BOTTOM OR TOP 8 PERCENT REMAINING vs TIME
24 25
9 DISCHARGE RATE vs PUNCTURE SIZE
25
10 PERCENT REMAINING vs TIME
26
11 DISCHARGE RATE vs PUNCTURE SIZE 12 SCHEMATIC OF CONTAMINANT PUFF
26 29
13 FLOWCHART TO DETERMINE VAPOUR HAZARD ZONE
31
14 NORMALIZED VAPOUR CONCENTRATION vs DOWNWIND DISTANCE 33
15 CONVERSION OF THRESHOLD LIMIT VALUE (TLV) UNITS (Volume % to g/m^)
34
16 CONVERSION OF LOWER FLAMMABILITY LIMIT (LFL) UNITS (Volume % to g/m^)
35
17 PUFF TRAVEL TIME vs TRAVEL DISTANCE
38
18 HAZARD AREA FOR STEADY WINDS, EXAMPLE PROBLEM
40
19 HAZARD AREA FOR UNSTEADY WINDS, EXAMPLE PROBLEM
40
20 MAXIMUM SPILL RADIUS vs SPILL SIZE
42
21 SCHEMATIC SOIL TRANSPORT 22 FLOWCHART FOR NOMOGRAM USE
44 46
23 PENETRATION IN COARSE SAND
47
CMA 014369
vii
LIST OF TABLES
Table 1
CONVERSION NOMOGRAMS
2 CYLINDER SPECIFICATIONS
3 RAILWAY TANK CAR SPECIFICATIONS
4 TYPICAL RAILWAY TANK CAR SPECIFICATIONS - CLASS105A300W 5 TANK MOTOR VEHICLE SPECIFICATIONS
6 COMPATIBILITY WITH MATERIALS OF CONSTRUCTION
7 MATERIALS OF CONSTRUCTION
8 WEATHER CONDITIONS
9 MAXIMUM PUFF HAZARD HALF-WIDTHS (FOR VINYL CHLORIDE)
Page 6 14 15 17 18 20 21 32 36
CMA 014370
1 SUMMARY
1
VINYL CHLORIDE (H2C=CHC1)
Colourless gas with a mild, sweet odour
SYNONYMS
VCM, VC, Chlorethene, Chloroethene, Chloroethylene, Vinyl Chloride Monomer, Vinyl C Monomer, Monochloro Ethylene, Monochloroethene, Ethylene Monochloride, Chlorure de Vinyle (Fr.)
IDENTIFICATION NUMBERS
UN No. 1086; CAS No. 75-01-1f; OHM-TADS No. 7216947; 5TCC No. 4905792
GRADES & PURITIES
Commercial or Technical grade, purity 99.9 percent
IMMEDIATE CONCERNS
Fire: Highly flammable. Flashback along vapour trail may occur Human Health: Human carcinogen; toxic by inhalation and skin contact Environmental: Harmful to aquatic life
PHYSICAL PROPERTY DATA
Shipping State: liquid (compressed gas) State (15C, 1 atm): gas Boiling Point: -13.4C Melting Point: -153.8*0 Flammability: flammable Flash Point: -78C (OC) Vapour Pressure: 336.5 kPa (20C) Density: 0.969 g/cm^ (liquid at -14C)
2.62 kg/m3 (gas at 25C) Solubility (in water): 0.11 g/100 g
H20 (25C)
Behaviour (in water): floats and boils; no reaction
Behaviour (in air): vapour is heavier than air
Odour Threshold Range: 1200 to 25 000 ppm
Polymerization: occurs if heated, in sunlight or presence of air; reaction is exothermic
ENVIRONMENTAL CONCERNS
In aquatic systems, vinyl chloride evaporates rapidly and degrades very slowly. Fish may bioconcentrate it by a factor of up to 1.9.
HUMAN HEALTH
TLV: 5 ppm (10 mg/m^) IDLH: not established
CMA 014371
2
Exposure Effects
Inhalation: Irritation to eyes, nose and throat. Causes dizziness, anesthesia, difficult breathing, lung irritation, headache and paralysis. Large concentrations may be fatal.
Contact: Irritation to skin and eyes. Contact with liquid causes frostbite and dry skin. Contact with eyes will cause inflammation of conjunctiva.
IMMEDIATE ACTION
Spill Control
Restrict access to spill site. Issue warning: "FLAMMABLE". Call fire department and notify manufacturer. Eliminate sources of ignition including traffic and equipment. Stop the flow and contain spill, if safe to do so. Avoid contact with liquid and inhalation of vapour; stay upwind of release. Keep contaminated water from entering sewers or watercourses.
Fire Control
Do not extinguish fire unless release can be stopped. Use foam, dry chemical, carbon dioxide, water spray or fog to extinguish. Cool fire-exposed containers with water. Containers may explode in heat of fire. Stay clear of tank ends.
COUNTERMEASURES
Emergency Control Procedures in/on
Soil: Construct barriers to contain spill. Remove contained liquid - if possible and using extreme caution - with pumps to vinyl chloride tanks. Otherwise, let evaporate.
Water: Contain contaminated water with dams or natural barriers. After VCM levels in water are low, release water.
Air: Use water spray to control flammable vapour. Control runoff to ensure it does not enter sewers or water courses until almost all VCM is evaporated.
NAS HAZARD RATING
Category
Fire..................................
Health Vapour Irritant............ Liquid or Solid Irritant, Poison...........................
Water Pollution Human Toxicity........... Aquatic Toxicity.......... Aesthetic Effect..........
Reactivity Other Chemicals.......... Water............................ Self-reaction................
Ratjn& 4
2 1 2
0 0 0
2 0 2
NFPA
HAZARD CLASSIFICATION
CMA 014372
3
2 PHYSICAL AND CHEMICAL DATA
Physical State Properties Appearance Usual shipping state Physical state at 15C, 1 atm Melting point Boiling point Vapour pressure
Densities Density
Specific gravity Vapour density
Fire Properties Flammability Autoignition temperature Burning rate Upper flammability limit
Lower flammability limit Heat of combustion Combustion products Flashback potential
Colourless gas or liquid under pressure (Dow MSDS 1980)
Liquid: liquefied compressed gas (HCG 1981) Gas -153.8C (HCG 1981; Kirk-Othmer 1983) -13.4C (HCG 1981; Kirk-Othmer 1983) 336.5 kPa (20C) (Dow MSDS 1980) 115 kPa (-10C) (Kirk-Othmer 1983)
0.969 g/cm3 (liquid at -14.2C) (Kirk-Othmer 1983) 0.908.4 g/cm3 (liquid at 21C) (HCG 1981) 2.62 kg/m3 (gas at 25C) (Matheson 1980) 0.9104 (liquid 20/20C) (Dow MSDS 1980) 2.15 (Dow MSDS 1980) 2.21 (25C) (Matheson 1980)
Highly flammable (NFPA 1978) -78C (Cleveland open cup) (DPIMR 1981) 472C (NFPA 1978) 4.3 mm/min (CHRIS 1978) 33.0 percent (v/v) (NFPA 1978) 22 percent (v/v) (Kirk-Othmer 1983; Matheson 1980) 3.6 percent (v/v) (NFPA 1978) 1134 kj/mole (20C) (CRC 1980) Carbon dioxide, water and hydrogen chloride (CRC 1980) May travel considerable distance to a source of ignition and flash back (NFPA 1978)
tma m a. 7
Explosiveness
Behaviour in a fire
Electrical ignition hazard
Other Properties Molecular weight of pure substance Constituent components of typical commercial grade Refractive index Viscosity
Liquid interfacial tension with air
Liquid interfacial tension with water (est.) Latent heat of fusion Latent heat of sublimation Latent heat of vaporization
Heat of polymerization
Polymerization expansion Heat of formation Ionization potential Heat capacity
constant pressure (Cp)
constant volume (Cv) Critical pressure Critical temperature Thermal conductivity
Saturation concentration
4
Forms explosive mixtures with air (NFPA 1978) At elevated temperatures, polymerization may take place with possible container rupture (NFPA 1978) May be ignited by static discharge (NFPA 1978)
62.499 (Kirk-Othmer 1983) 99.9 percent vinyl chloride (Dow MSDS 1980) 1.366 (liquid at 20C) (Ullmann 1975) Liquid: 0.273 mPa*s (-20C) (Kirk-Othmer 1983) Gas: 0.0107 mPa*s (20C) (Matheson 1980) 16.0 mN/rn (25C) (CHRIS 1978) 23.1 mN/m (-20C) (Matheson 1980) 30 mN/m (20C) (CHRIS 1978)
4.74 kJ/mole (at melting point) (HCG 1981) 25.65 kJ/mole (est.) 20.62 kJ/mole (at boiling point) (Kirk-Othmer 1983) 4.45 kJ/mole (-150C), 71.18 kJ/mole (156.6*0 (Ullmann 1975) About 35 percent (Ullmann 1975) 37.3 kJ/mole (25C) (Sussex 1977) 10.0 eV (Rosenstock 1977)
53.6 J/(mole*C) (25C) (HCG 1981) 84.5 3/(mole*C) (liquid at 20C) (Kirk-Othmer 1983) 50.6 3/(mole* *C) (25C) (HCG 1981) 5600 kPa (Kirk-Othmer 1983) 156.6C (Kirk-Othmer 1983) 7.95 x 10-3 W/(m-K) (25C, gas) (Matheson 1980) 8625 g/m3 (20C) (calc.)
CMA 014374
5
Dipole moment Dielectric constant
1.499 D (Kirk-Othmer 1983) 6.26 (17.2C) (Ullmann 1975)
Solubility
In water In other common materials
Of water in vinyl chloride
0.11 g/100 g H20 (25C) (Kirk-Othmer 1983)
Very soluble in diethyl ether, soluble in ethanol (CRC 1980) Soluble in methanol (Ullmann 1983)
0.03 g/100 g vinyl chloride (-15C) (Kirk-Othmer 1983)
Vapour Weight to Volume Conversion Factor 1 ppm = 2.577 mg/m3 (20C) (Verschueren 1984)
CMA 014375
VINYL CHLORIDE
6
TABLE 1
CONVERSION N0M0GRAM||
c - 40 -30 -20 -10
Temperature
LI
1
| Tn--TH1
1 11
F -40
0
0 10 20 30 40
1 11
f1
1
V' -
1 1I
1 11
50 100
50
1 11
80 70 80 1 1 , 1i 1 | M1 1
150
90 100 11 1|1
200
Pressure
1 kPa = 1 000 Pa
kPa 0
10 20 30 40 50 60 70 80 90 100
L1 r1
1 1 1 I, 1 I, 1 11 1 1 1 1 1
1 1|
Atmospheraa 0
0.1 0.2 0.3 0.4 0.5 0.8 0.7 0.8 0.9 1.0
kPa 0
L
r
psi 0
10 1 11 12
20 1 1 3
30
l 1 46
40 1 1 6
50 60 J ,1 111 78 9
70 60 90 100 ,| L 1 1 I II 1 11 10 11 12 13 14 16
kPa mmHg(torr)
0
L
r
0
10 1
11 100
20 30 11 *1 200
40 1 1
300
60 | 1
400
60 70
1 '
1
11
600
80 90
11 111
600
700
100 1
1
800
Viscosity
Dynamic Kinematic
1 Pa*a = 1 000 cantlpolae (cP) 1 m2/a - 1 000 000 cantlstokea (cSt)
Concentration (in water)
1 ppm ar 1 mg/L
Energy (heat)
kj kcal
0 1 1
0
kJ BTU
0 1 1
0
1 kJ s 1 000 J
10 20 30 |1 1 1' 5
40
1 11
10
60
| 1
60 1 1 16
70 |
11
80 90
. J-- 111
.1 1 .1
20
100
, 1, 1 11
25
10 20 30 40 50 60 70 80 90 100
1 1 1 1 | 1 | 1 __ L. 1 1 1 1 1 1 1 1 -i
r
10 20 30 40 60 60 70 60 90 100
o
N*
O
kg/m3 D nsity
lb/ft3
0 j 0
10 20 30 40 60
111 1--
1 ,| 1
1 23
i 1 4
i
80 90 100
1 1 , 1____ r1 56
CMA 014376
VINYL CHLORIDE
7 FIGURE 1
VAPOUR PRESSURE
Reference: PPH 1974
Temperature, (C)
CMA 014377
Solubility, (g/100 ml)
8
FIGURE 2
CHLORIDE
Temperature, (C)
__________________________________________________ FIGURE]^
LIQUID DENSITY
Density, (g/mL) z
CMA 014378
VINYL CHLORIDE
9 FIGURE 4
LIQUID VISCOSITY
1U _________ __________ ____________________ I________________________________________ __________ _____________________________
-60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60
Temperature, (C)
VINYL CHLORIDE
FIGURE 5
PHASE DIAGRAM
CMA 014379
10
3 COMMERCE AND PRODUCTION
3.1 Grades, Purities (Dow MSDS 1980; MCA 1972; Kirk-Othmer 1983) Vinyl chloride monomer is commonly sold as a liquefied gas, in a commercial
or technical grade with a purity of 99.9 percent. The following are the maximum levels of impurities found in vinyl chloride:
Impurity
Acetylene Acidity, as HC1 by wt. Acetaldehyde Alkalinity, as NaOH by wt. Butadiene 1-Butene 2-Butene Ethylene Ethylene dichloride (EDC) Nonvolatiles Propylene Water Iron, by wt.
Maximum level, ppm
2.0 0.5 0.0 0.3 6.0 3.0 0.5 4.0 10.0 150.0 8.0 200.0 0.25
3.2 Domestic Manufacturer (Corpus 1983; Scott 1979)
Dow Chemical Canada Inc. Box 1012, Modeland Road, Sarnia, Ontario N7T 7K7 (519)339-3131
3.3 Other Suppliers (CGB 1980)
Henley Chemicals Ltd. 1735 Bayly Street Pickering, Ontario L1W 3G7 (416) 831-3341
Kingsley and Keith (Canada) Ltd. 310 Victoria Avenue Montreal, Quebec H3Z 2M8 (514) 487-1550
St. Lawrence Chemical Co. (Sales) Ltd. 5405 Pare Street Montreal, Quebec H4P 1P7 (514) 731-3628
CMA 014380
11
3.4 Major Transportation Routes Current Canadian production of vinyl chloride is located in Sarnia, Ontario,
and Fort Saskatchewan, Alberta. The market area is in Ontario, Quebec and Alberta. The product is most commonly shipped in railway tank cars. 3.5 Production Levels (Corpus 1983)
Company, Plant Location
Nameplate Capacity kilotonnes/yr (1982)
Dow Chemical Canada, Sarnia, Ont. Dow Chemical Canada, Fort Saskatchewan, Alta.
TOTAL
Domestic Production (1982) Imports (1982)
TOTAL SUPPLY
100 320 420 231
-
231
3.6 Manufacture of Vinyl Chloride (Kirk-Othmer 1983; FKC 1975; EPA 1978)
3.6.1
General. Vinyl chloride is most commonly made by the "balanced process" in
which ethylene is reacted to produce ethylene dichloride which in turn is
dehydrochlorinated to produce vinyl chloride.
3.6.2
Raw Materials. The raw materials used in the manufacture of vinyl chloride
are ethylene and hydrogen chloride.
3.6.3
Manufacturing Process. Ethylene is reacted with hydrogen chloride and
oxygen (sometimes from air; however, pure oxygen is now preferred because of the lower
emissions) to produce ethylene dichloride. The reaction is usually carried out in the
vapour phase over catalysts containing copper chloride as the active catalyst. The overall
reaction is as follows:
CH2=CH2 + 2HC1 + 1/2 02-* C1CH2CH2C1 + H20
The ethylene dichloride is purified to remove any FeCl3 (which poisons catalysts in the next phase) and is reacted at 2500-3000 kPa at temperatures of 425-550C to yield vinyl chloride and hydrogen chloride. The hydrogen chloride is recycled to the first step (thus the name "balanced process" for this entire procedure).
CMA 0143 SI
12
The pyrolysis step results in a conversion of 50-60 percent per pass, with a residence time of 2-30 seconds. The following is the pyrolysis reaction:
ClCH2CH2Cl CH2=CHC1 + HC1 The resulting vinyl chloride is purified by distillation to remove the by products (unreacted material, chlorinated hydrocarbons, hydrocarbons). 3.7 Major Uses in Canada (Corpus 1983) Vinyl chloride is used in the production of polyvinyl chloride and 1,1,1-trichloroethane. In 1982, 86 percent of domestic production was used for polyvinyl chloride manufacture, 4 percent was used for 1,1,1-trichloroethane manufacture, and 10 percent was exported. 3.8 Major Buyers in Canada (Corpus 1983) Esso Chemical Canada, Sarnia, Ont. BF Goodrich Canada, Niagara Falls, Ont.; Shawinigan, Que. Novacor/DSAG, Ft. Saskatchewan, Alta.
CMA 014382
13 4 MATERIAL HANDLING AND COMPATIBILITY
4.1 Containers and Transportation Vessels
4.1.1 General. Liquid vinyl chloride is transported in steel containers and vessels equipped with safety devices and pressure tested at regular intervals. The sole Canadian manufacturer distributes vinyl chloride only by railway tank car; however, as cylinders or tank motor vehicles are occasionally used by distributors, these will also be covered (CCPA 1983).
4X2
Cylinders. Vinyl chloride cylinders are of steel construction with net mass
usually from 0.45 to 68.2 kg (1 to 150 lb.). A 68.2 kg (150 lb.) cylinder has a tare weight
of 63.6 kg (1401b.), a diameter of 260 mm (10 in.) and a length of 1400 mm (55 in.).
Cylinders must comply with specifications as described in Table 2 (RTDCR 1974; HMR
1978). Class 3A and 3AA cylinders having higher service pressures also may be used.
Laboratory cylinders are equipped with a CGA valve out connection No. 290 having a
thread size of 1.9 cm (0.745 in.) with left hand thread accepting a bullet-shaped nipple.
Lecture bottles have a special 0.8 cm (5/16 in.), 32 thread per inch, female outlet
(Matheson 1980).
4X3
Ton Container. The ton container is a welded steel tank (or cylinder) carrying
a net mass of 909 kg (2000 lb.). It must comply with specification 106A500X which states
that the container must have a fusion-welded longitudinal seam and a forge welded head
seam, pressure tested at 3450 kPa (500 psi) (TCM 1979). Dimensions of the ton container
are 207 cm (81-1/2 in.) long by 74.3 cm (29-1/4 in.) diameter. The heads are convex
inward. The sides are crimped inward to each end to form chimes which provide a
substantial grip for lifting beams. The container is equipped with two identical valves
near the centre of one end. The ton container valve differs from the cylinder valve only
in that it has no fusible metal plug and has a larger internal passage. Each valve connects
with an internal eduction pipe. The valves are protected by a removable steel valve
protection hood. All containers are equipped with fusible metal type safety relief
devices. Most have six fusible metal plugs, three in each end, spaced 120 apart. The
fusible metal is designed to melt between 70 and 73.9C.
4X4
Railway Tank Cars. Railway tank cars must comply with specifications as
described in Table 3 (RTDCR 1974). A typical 105A300W railway tank car is illustrated in
Figure 6; Table 4 indicates railway tank car details associated with this drawing.
CMA 014383
TABLE 2
14 CYLINDER SPECIFICATIONS
CTC/DOT* Specification Number
Description
3A150 3AA150
3E1800
4B150 4BA225 4BW225
Seamless steel cylinder. Maximum service pressure 1035 kPa (150 psi).
Seamless steel cylinder. Maximum service pressure 1035 kPa (150 psi). Steels definitely prescribed. Maximum carbon content 0.28%.
Seamless steel cylinder. Maximum service pressure 12 400 kPa (1800 psi) Maximum diameter: 50 mm (2 in.). Maximum length: 610 mm (24 in.).
Welded steel cylinder. Maximum service pressure 1035 kPa (150 psi).
Welded steel cylinder. Steels definitely prescribed. Maximum service pressure 1550 kPa (225 psi).
Welded steel cylinder. Steels definitely prescribed. Electric-arc welded longitudinal seam. Maximum service pressure 1550 kPa (225 psi).
* Canadian Transport Commission and Department of Transportation (U.S.)
The only opening permitted in the tank is a single manway located in the centre at the top. Four valves are momted inside the dome cover similar in arrangement to ammonia tank car unloading arrangement. Three of these are angle valves; the fourth, mounted in the centre, is a safety relief valve. The two liquid angle valves are mounted on the centre line of the tank, while the single gas angle valve and a gauging device assembly are mounted on the transverse centre line (TCM 1979; PPH 1974). Occasionally, the positions of the relief valve and gauging devices are interchanged.
Under each liquid valve is an eduction pipe fastened to the manway cover and extending to the bottom of the tank. At the top of each eduction pipe, immediately below the manway cover, is a rising-ball, excess-flow valve designed to close when the rate of flow of liquid exceeds about 3180 kg/h (7000 lb./h). This is a protective device designed to close automatically against the flow of liquid if the angle valve is broken off or, under
CMA 014384
TABLE 3
15 RAILWAY TANK CAR SPECIFICATIONS
CTC/DOT* Specification Number
Description
105A200W
105A300W I12A340W**
U4A340W**
Steel fusion-welded tank with manway nozzle. Insulated. Top unloading arrangement required. Test pressure 1380 kPa (200 psi). Bottom outlet or washout prohibited.
As above except test pressure 2070 kPa (300 psi).
Steel fusion-welded tank with manway nozzle. Uninsulated. Upper 2/3 must be painted. Top unloading arrangement required. Test pressure 2340 kPa (340 psi). Bottom outlet or washout prohibited. Maximum one opening for purging tank interior.
Same as 1I2A340W but manway may be located other than at top of tank. Valves and fittings need not be mounted on manway cover.
* Canadian Transport Commission and Department of Transportation (U.S.)
** Note: Both 112A340W and 114A340W have been retrofitted with head shields and insulation and are now designated 112J340W, 112T340W or 112S340W (CCPA 1983).
certain conditions, if the unloading line is severed. The safety relief valve is of the spring-loaded type. A 19 mm (3/4 in.) thermometer well and a gauging device (magnetic, manual or electronic) are also required (TCM 1979; RTDCR 1974).
4.1.5
Tank Motor Vehicles. Vinyl chloride tank motor vehicles consist of a cargo
tank pulled by a tractor. The maximum tank capacity is restricted by highway load limits.
They must comply with Transport Canada Specification TC331 (DOT MC331) as outlined in
Table 5 (MCA 1972). Most tanks have a capacity varying from 13.6 to 18.1 tonnes (15 to
20 tons). The minimum design pressure of these tanks is 1030 kPa (150 psi) (HCG 1981).
All tanks are provided with at least 13 mm (1/2 in.) of insulation protected by a
steel jacket. The only tank opening permitted is a manway located at the top. The valve
arrangement is the same as that on tank cars except that excess-flow valves are also
required under the gas valves. The operating angle valves are the same as those on tank
cars. Immediately below each liquid angle valve are an excess-flow valve and an
CMA 014385
VINYL CHLORIDE
16 FIGURE
RAILWAY TANK CAR CLASS - CLASS 105A it
Reference: TCM 1979; RTDCR 1974
Detail of top unloading arrangement
Detail of loading platform
CMA 014386
TABLE it
TYPICAL RAILWAY TANK CAR SPECIFICATIONS - CLASS 105A300W (TCM 1979; RTDCR 1974)
Description
Overall
Nominal capacity Car weight - empty Car weight - max.
Tank
Material Thickness Inside diameter Test pressure Burst pressure Valve release pressure
Approximate Dimensions
Coupled length Length over strikers Length of truck centres Height to top of grating Overall height Overall width Length of grating Width of grating
Loading/Unloading Fixtures
Unloading connections/ Valving
Safety Devices
Insulation
Tank Car Size (Imp. Gal.) 9000
21 000
28 000
41 000 L 30 300 kg 80 300 kg
(9000 gal.) (66 800 lb.) (177 000 lb.)
95 000 L
40 800 kg 83 500 kg
(21 000 gal.)
(90 000 lb.) (184 000 lb.)
127 000 L (28 000 gal.) 50 800 kg (112 000 lb.) 119 000 kg (263 000 lb.)
Steel
17.5 mm (11/16 in.) 2.2 m (88 in.) 2070 kPa (300 psi) 51 700 kPa (750 psi) 1550 kPa (225 psi)
Steel
17.5 mm (11/16 in.) 2.4 m (95 in.) 2070 kPa (300 psi) 51 700 kPa (750 psi) 1550 kPa (225 psi)
Steel 17.5 mm 3.0 m 2070 kPa 51 700 kPa 1550 kPa
(11/16 in.) (120 in.) (300 psi) (750 psi) (225 psi)
13 m 12 m 9m 4m 5m 3.2 m 2-3 m 1.5-2 m
(42 ft.)
(40 ft.) (29 ft.) (12 ft.) (15 ft.) (127 in.)
(7-10 ft.) (5-6 ft.)
20 m 19 m 16 m 4m 5m 3.2 m 2-3 m 1.5-2 m
(65 ft.) (63 ft.) (52 ft.) (12 ft.) (15 ft.) (127 in.) (7-10 ft.) (5-6 ft.)
20 m
20 m 16 m 4m 5m 3.2 m 2-3 m 1.5-2 m
(67 ft.)
(64 ft.) (53 ft.) (12 ft.) (15 ft.) (127 in.) (7-10 ft.) (5-6 ft.)
Two 76 mm (3 in.) valves to liquid, via check valve; one 51 mm (2 in.) valve to vapour space via check valve
Safety relief valve set at 1550 kPa (225 psi)
102 mm (4 in.) foam or cork insulation
TABLE 5
18 TANK MOTOR VEHICLE SPECIFICATIONS
TC* Specification Number TC331 (or MC331)
* Transport Canada
Description
Seamless or welded steel tank. Design and construct in accordance with ASME Code. One opening with protective housing and manway cover. Maximum design pressure 3450 kPa (500 psi). Insulated. Postweld heat treatment as per ASME Code. Gauging device prohibited. Minimum design pressure 1030 kPa (150 psi).
eduction pipe the same as those on tank cars. In addition, under each gas valve there is an excess-flow valve of different design, to prevent outward flow of gas if the angle valve is broken off. The safety relief valve is of the spring-loaded type.
4.2 Off-loading
4.2J
Off-loading Equipment and Procedures for Cylinders and Ton Containers. Both
cylinders and ton containers are handled and stored in the same manner. The following
points should be observed when handling and storing containers (MCA 1972):
Valve protection hoods should be in place. Containers should not be stored near ventilating systems. Store to minimize external corrosion. Store cylinders upright, ton containers on their sides. Store full and empty containers separately.
Cylinders deliver vinyl chloride gas when in an upright position and liquid when in an inverted position. Ton containers, when in a horizontal position and with the valves in a vertical line, deliver gas from the upper valve and liquid from the lower valve.
A check valve should be installed in feed lines when using cylinders or ton containers, to prevent the reactants from entering the container (MCA 1972).
CMA 014388
19
4.2.2
Off-loading Equipment and Procedures for Railway Tank Cars and Tank Motor
Vehicles. Railway tank cars and tank motor vehicles are basically off-loaded in the same
manner but only after the following precautionary items have been undertaken (MCA 1972;
VCM 1982):
Unloading operations to be performed only by properly instructed personnel.
Rail cars, tracks, loading platforms, etc., are grounded and piping is bonded and grounded.
Dead-end siding used only for vinyl chloride rail cars to be provided.
Brakes must be set, wheels chocked, proper derails employed, and caution placards displayed.
Suitable operating platform to be provided at unloading point.
The railway tank car or highway vehicle may be unloaded by pumping or by inert gas (MCA 1972). When using the pumping method, liquid is pumped from one of the two liquid angle valves. When gas is required, discharge vinyl chloride gas from the gas angle valve.
When using the inert gas method, dry inert gas (usually nitrogen) is used to increase car pressure. Larger unloading installations may have a suction line connected from the storage tank to a compressor which discharges compressed vinyl chloride gas to the tank car (MCA 1972; VCM 1982). The pressure on the car should never exceed the service pressure at which the safety valve is set to operate.
After unloading lines have been disconnected, valve outlet plugs should be immediately replaced to prevent thread corrosion. After unloading, leave at least 70 kPa (10 psi) vinyl chloride, to prevent the ingress of air, and mark the tank as "empty flammable gas" (VCM 1982).
4.2.3
Specifications and Materials for Off-loading Equipment. Under this section,
the components of a typical off-loading system handling dry vinyl chloride at commonly
employed temperatures and pressures will be discussed. These include pipes and fittings,
valves, gaskets, pumps and storage tanks.
Pipes and fittings should be of Schedule 80 seamless carbon steel designed to
have a working pressure of at least 690-1035 kPa (100-150 psi), with a safety factor
conforming to the ASME (MCA 1972). Pipeline joints should preferably be flanged or
welded. If threaded joints are necessary, extreme care must be taken to obtain clean,
sharp pipe threads, in order to ensure pressure-tight joints. These should be back welded
to ensure that there is no leakage and that there is good grounding (CCPA 1983).
CMA 014389
20
Steel plug valves are in common use (CCPA 1983). Cast steel diaphragm valves lined with chlorinated polyether resin will serve adequately (DPLV 1972). Valves and fittings should not be of cast iron as these can easily crack (VCM 1982). Viton may be used as a gasket material at normal operating temperatures.
A jacketed sealless magnetic drive centrifugal pump with "wet end" material of carbon steel gives good results. Chilled refrigerant should be fed to the jacketing to keep the pumpage below the boiling point and thus prevent vaporization. Leakage from this type of pump should be virtually eliminated. The pump must be provided with a drain so that repairs can be safely made.
Storage tanks should be of all-welded steel construction and grounded (MCA 1972).
4.3 Compatibility with Materials of Construction
The compatibility of vinyl chloride with materials of construction is indicated in Table 6. The unbracketed abbreviations are described in Table 7. The rating system for this report is briefly described below.
Recommended; Conditional;
Not Recommended:
This material will perform satisfactorily in the given application.
Material will show deterioration in the given application; however, it may be suitable for intermittent or short-term service.
Material will be severely affected in this application and should not be used.
TABLE 6
COMPATIBILITY WITH MATERIALS OF CONSTRUCTION
Application 1. Pipes and
Fittings
2. Valves
Temp. (C) 24
Most Normal
Material of Construction
Recommended
PVDF Chlorinated Polyether (DCRG 1978)
CS Cl (MCA 1972) SS (VCM 1982)
CS Cl (MCA 1972) SS (VCM 1982)
Conditional
Cl (VCM 1982) Cl (VCM 1982)
Not Recommended PVDC (DCRG 1978)
Copper (MCA 1972)
CMA 014390
TABLE 6
Application 3. Storage 4. Others
21
COMPATIBILITY WITH MATERIALS OF CONSTRUCTION (Cont'd)
Temp. (C) Normal 24-100
Material of Construction
Recommended Conditional CS Cl Cl (MCA 1972) (VCM 1982) Glass (CDS 1967)
Not Recommended
Aluminum (VCM 1982)
Copper Brass (VCM 1982)
TABLE 7
MATERIALS OF CONSTRUCTION
Abbreviation
Cl CS
PVDC PVDF SS
Material of Construction
Chlorinated Polyether Cast Iron, Austenitic Carbon Steel Fluorine Rubber (Viton) Glass Polyvinylidene Chloride Polyvinylidene Fluoride Stainless Steel
CMA 014391
22 5 CONTAMINANT TRANSPORT
5.1 General Summary
Vinyl chloride is commonly transported in tanks as a liquefied compressed gas. When spilled in the environment, it will form a liquid pool, spreading on the surface of a water body or on the ground as well as forming a visible vapour cloud. Vapour is released rapidly from the pool to the atmosphere by evaporation. The initial release will result in a large release of vapour (puff). As the vinyl chloride cools as a result of the evaporation, the vapour release will slow. If the ambient temperature is low, e.g., below the boiling point of -13.4C, little evaporation may occur.
When spilled on water, some of the material will dissolve, and the rest will evaporate to the atmosphere. The vapour cloud tends to hug the water and spread rather than lifting off the surface and dispersing.
Vinyl chloride spills on soil surfaces will partly vaporize, and partly adsorb onto the soil at a rate dependent on the soil type and its degree of saturation with water. Downward transport of the liquid toward the groundwater table may cause environmental concerns.
The following factors are considered for the transport of a vinyl chloride spill in the air, water and soil media:
|-- Leak from tank car
Rate of discharge L Percent remaining
Contaminant Transport
--Air -Water
--Vapour emission rate *--Hazard zone --Spread on water
'-Soil
Depth and time of penetration
It is important to note that, because of the approximate nature of the contaminant transport calculations, the approach adopted throughout has been to use conservative estimates of critical parameters so that predictions are approaching worst case scenarios for each medium. This may require that the assumptions made for each medium be quite different and to some extent inconsistent. As well as producing worst case scenarios, this approach allows comparison of the behaviours of different chemicals under consistent assumptions.
CMA 014392
23
5.2 Leak Nomograms
5.2.1
Introduction. Vinyl chloride is commonly transported as a liquefied
compressed gas at ambient temperature. While the capacities of the railway tank cars
vary widely, one size has been chosen throughout the EnviroTIPS series for development of the leak nomograms. It is approximately 2.75 m in diameter and 13.4 m long, with a carrying capacity of about 80 000 L.
If a tank car loaded with liquefied vinyl chloride is punctured on the bottom, all of the contents will drain out. The instantaneous discharge rate (q) is a function of the height of the fluid above the hole (H), the internal pressure of the tank (P), the hole size
(A) and shape, and a coefficient of discharge (C<j). For the purposes of nomogram preparation, a constant discharge coefficient of 0.8 has been assumed.
If the tank car is punctured in the top or at any point above the liquid level,
gas will be vented until all of the liquid has vaporized and the internal and external tank pressures have equalized. For the purposes of nomogram preparation, the liquid is
assumed to remain at a constant temperature (isothermal) equal to the ambient temperature (T). Consequently, the venting rate (q) is assumed to be constant until all of the liquid is vaporized. The venting rate is a function of the internal tank pressure (P),
which is equal to the saturated vapour pressure (Psat) * the liquid at temperature T. The assumed maximum tank ambient temperature is 40QC, yielding a saturated vapour
pressure (Psat)
kPa.
The assumption of isothermal conditions will maximize the gas release rate
from the tank and will be conservative for most cases. In reality, however, the boiling point of vinyl chloride is within Canadian environmental conditions (-13.4C) and thus the vapour emission from a puncture above the liquid level will be substantially less than predicted here. After the puncture, the vapour will be released rapidly; probably as a puff; evaporative cooling will substantially reduce subsequent emissions. It is estimated that the vapour emission rate would be about 1 order of magnitude lower than that predicted here if the car has lost some of its insulation and the ambient temperature is 10-30C. The rate predicted here will be true if the car has lost a substantial portion of its insulation and the ambient temperature is 40C or above. The vapour emission rate could be 3 or 4 orders of magnitude slower than predicted here if the ambient
temperature is near the boiling point. The aim of the nomograms is to provide a simple means to obtain the time
history of the venting process. This may include venting from a bottom puncture (liquid
CMA 014393
24
FIGURE 7
TANK CAR WITH PUNCTURE HOLE IN BOTTOM OR TOP
release) or from a puncture above the liquid level (gas venting). The details of the models used to calculate venting rates are described in the Introduction Manual.
5.2J2.
Nomograms.
5.2.2.1 Bottom pimcture - liquid venting.
Figure 8: Percent remaining versus time. Figure 8 provides a means of estimating the percent of vinyl chloride remaining in the standard tank car after the time of puncture for a number of different hole diameters. The hole diameter is actually an equivalent diameter and can be applied to a noncircular puncture.
The standard tank car is assumed to be initially full (at t-0) with a volume of about 80 000 L of vinyl chloride at 40C. The amount remaining at any time (t) is not only a function of the discharge rate over time, but also of the size and shape of the tank car.
Figure 9: Discharge rate versus puicture size. Figure 9 provides a means of estimating the maximum discharge rate (L/s) for a number of equivalent hole diameters. As the pressure force dominates the gravitational force, the discharge rate remains relatively constant as the tank empties.
5.2JZ.2 Top pwcture - gas venting.
Figure 10: Percent remaining versus time. Figure 10 provides a means of estimating the percent of vinyl chloride remaining in the standard tank car after the time of puncture for a number of different hole diameters. The hole diameter is actually an equivalent diameter and can be applied to a noncircular puncture. As isothermal conditions have been assumed, the internal pressure and venting rate are constant.
CMA 014394
VINYL CHLORIDE
25 FIGURE 8
PERCENT REMAINING vs TIME
1 \' \ IX
0.1
\
VINYL CHLORIDE
\___ ___
\
1
_______ _______ _____5___ ___ I I I I
10
Time of Puncture, t (min)
FIGURE 9
DISCHARGE RATE vs PUNCTURE SIZE
Equivalent Diameter of Puncture, d (mm)
CMA 014395
VINYL CHLORIDE
26
FIGURE 10
PERCENT REMAINING _______vs TIM^
VINYL CHLORIDE
Puncture in Top of Tank car
_________________ FIGUR^
DISCHARGE RATE vs PUNCTURE SIZE
CMA 014396
27
Figure 1 is Discharge rate versus puncture size. Figure 11 presents the relationship between discharge rate (kg/s) and the equivalent diameter of the hole for gas venting above the liquid level in the tank car. For any one hole size, the venting rate will be constant until all the liquid is vaporized. This is consistent with the assumption of isothermal conditions in the tank and results in a conservative estimate of the gas venting rate.
The values presented in Figure 11 are independent of the tank car size, but assume that the temperature of the liquid is 40C, yielding a saturated vapour pressure of 600 kPa.
5.2.3
Sample Calculations.
i) Problem A
The standard tank car filled with vinyl chloride 40C has been punctured on the bottom. The equivalent diameter of the hole is 150 mm. What percent of the initial SO 000 L remains after 1 minute and what is the instantaneous discharge rate from the tank? Solution to Problem A
Step 1: Calculate the amount remaining at t=l min
. Use Figure 8 . With t=l min and d=150 mm, the amount remaining is about
53 percent or 42 000 L
Step 2: Calculate the discharge rate
. Use Figure 9 . With d=150 mm, the instantaneous discharge rate (q) = 630 L/s
ii) Problem B
The standard tank car in Problem A has been punctured above the liquid level. The equivalent diameter of the orifice is estimated at 250 mm. How long will it take to empty the tank car and what is the release rate, assuming isothermal conditi ns? Solution to Problem B
Step 1: Calculate the time to empty . Use Figure 10
CMA 014397
28
. With d=250 mm, the tank empties (0 percent remaining) in approximately 17 min
Step 2: Calculate the discharge rate
. Use Figure 11 . With d=250 mm and assuming isothermal conditions, the venting rate
is constant at 80 kg/s. As noted above, this will be the most rapid discharge rate in normal circumstances; depending on ambient temperatures, insulation, etc., the rate could be up to 4 orders of magnitude slower.
5.3 Dispersion in the Air
5.3.1
Introduction. Since vinyl chloride under pressure is an extremely volatile
liquid, vapour released from a liquid pool spilled on a ground or water surface vaporizes
rapidly enough to consider the spill as producing instantaneous vapour in the form of a
puff. Only this type of vapour release is treated here. As noted above, the evaporation
rate after the puff is released would be slow and depends on ambient temperatures.
To estimate the vapour concentrations downwind of the accident site for the
determination of the flammability or toxicity hazard zone, the atmospheric transport and
dispersion of the contaminant vapour must be modelled. The models used here are based
on Gaussian formulations and are the ones most widely used in practice for contaminant
concentration predictions. The model details are contained in the Introduction Manual.
Figure 12 depicts schematically the contaminant puff configuration from a
surface release. The dispersion model represents the spill as an instantaneous point
source (with a total vapour release quantity, Qt) equal to the amount of contaminant
spilled.
Although no relevant spill information is available on the behaviour of a cloud
of vinyl chloride gas, it is expected that in the initial period immediately after the spill,
the cloud will behave as a denser-than-air gas. This is due primarily to the greater
density of vinyl chloride gas (2.2 times that of air at 20C) and due to the fact that the
vapour cloud arising from the cold bulk liquid will be cold itself. Ground hugging and gas
accumulation in low-lying areas may therefore be observed during the initial period.
Conventional Gaussian modelling will tend to depict heavier-than-air plumes (puffs) to be
narrower than observed.
Since the boiling point of liquid vinyl chloride is low for a liquefied gas (-14C
at 1 atm), spills on a ground surface at very low temperatures (-15C and less) will result
CMA 014398
VINYL CHLORIDE Wind Speed (U)
\
29
FIGURE 12
SCHEMATIC OF CONTAMINANT PUFF
CMA 0X4399
30
in considerable overestimation since the vapour emission rate would not approach that of a puff release situation and worst case values would be provided. Based on published information pertaining to spills of vinyl chloride at low air temperatures (-19C) onto snow-covered terrain (Fraser 1981), the use of the puff modelling method will greatly overestimate the hazard since only about 2.5 percent of instantaneously released vinyl chloride boiled off rapidly. For spills occurring at air temperatures of about 20C and greater, the puff modelling scenario will be more appropriate and more realistic results will be calculated. For these reasons it will be assumed that only 25 percent of the instantaneously spilled vinyl chloride will produce an instantaneous vapour puff. It is recognized that although 75 percent of the vinyl chloride remains and poses a potential source of hazard, the vapour emission rate will be small in comparison to the initial puff release. Also, the hazard zone determined for the initial puff release will provide conservative estimates.
5.3.2
Vapour Dispersion Nomograms and Tables. The aim of the air dispersion
nomograms is to define the hazard zone due to toxicity or flammability of a vapour cloud.
The following nomograms and data tables are contained in this section (to be used in the
order given):
Table 8: Figure 14: Table 9: Figure 17:
weather conditions normalized vapour concentration as a function of downwind distance maximum puff hazard half-widths puff travel time versus travel distance
The flowchart given in Figure 13 outlines the steps necessary to make vapour dispersion calculations and identifies the nomograms or tables to be used. This section deals only with the portion contained within the dashed box. Data on "total liquid discharged" is contained in Section 5.2. A description of each vapour dispersion nomogram and its use follows.
5.3.2.1 Figure 14: Normalized vapour concentration versus downwind distance. Figure 14 shows the relationship between the vapour concentration and the downwind distance for weather conditions D and F. The nomograms were developed using the dispersion models described in the Introduction Manual. The vapour concentration is represented by the normalized, ground-level concentration (C/Qt) at the centreline of the contaminant puff. Weather condition F is the poorest for dispersing a vapour cloud and
CMA 014400
VINYL CHLORIDE
31 FIGURE 13
FLOW CHART TO DETERMINE VAPOUR HAZARD ZONE
Step 1: Use Figure 8 Section 5.2
CMA 014401
32
condition D is the most common in most parts of Canada. Before using Figure 14, the weather condition must be determined from Table 8.
TABLE 8
WEATHER CONDITIONS
Weather Condition F
Wind speed < 11 km/h (=3 m/s) and one of the following:
overcast day night time severe temperature inversion
Weather Condition D Most other weather conditions
Use; The maximum hazard distance, X, downwind of the spill can be calculated from Figure 14 knowing:
Qt, the mass of vapour emitted (assumed equivalent to 25 percent of liquid spilled) . U, the wind speed (m/s) . the weather condition . the hazard concentration limit, C, which is the lower value of 10 times the
Threshold Limit Value (TLV, in g/m3), or the Lower Flammability Limit (LFL, in g/m^). Note: To convert the TLV, in ppm, and the LFL, in percent by volume, to concentrations in g/m3, use Figures 15 and 16
A hazard concentration limit of 10 times the TLV has been arbitrarily chosen as it represents a more realistic level at which there would be concern for human health on the short term (i.e., on the order of 30 minutes). The TLV is a workplace standard for long-term exposure and use of this value as the hazard limit would result in unrealistically large hazard zones.
5.3.2.2 Table 9: Maximum puff hazard half-widths. This table presents data on the maximum puff hazard half-width, (W/2)max fr a range of Qt values under weather conditions D and F. These data were computed using the dispersion modelling techniques given in the Introduction Manual for a value of 10 times the vinyl chloride Threshold Limit Value (TLV) of 0.013 g/m3, or 0.13 g/m3. The maximum puff hazard half-width represents the maximum half-width of the vinyl chloride vapour cloud, downwind of the spill site, corresponding to a hazard concentration limit of 10 x TLV. Table 9 is
CMA 014402
VINYL CHLORIDE
33 FIGURE 14
NORMALIZED VAPOUR CONCENTRATION VS DOWNWIND DISTANCE
Vapour Concentration, C/Q (m -3)
F CLASS D CLASS
Maximum Downwind Hazard Distance, X (km)
CMA 014403
VINYL CHLORIDE u (km/h) *
34
FIGURE 15
PUFF TRAVEL TIME _ VS TRAVEL DISTANCE
Time (seconds)
CMA 014404
VINYL CHLORIDE
35 FIGURE 16
CONVERSION OF THRESHOLD LIMIT VALUE _______________ (TLV) UNITS (ppm to g/nY*)
E
CL CL
$
oe
<cu: oooc
Molecular Weight Example: Vinyl Chloride, MW = 62.5, TLV= 5 ppm,
then TLV in g/m3 = 0.013
Note: data applicable at 25C and 760 mm Hg pressure
CMA 014405
TABLE 9
36 MAXIMUM PUFF HAZARD HALF-WIDTHS (FOR VINYL CHLORIDE)
Weather Condition D
Weather Condition F
q/t (tonnes)
4100 4000 3000 2000 1000
800 600 400 300 200 150 100
75 50 25 20 10
7.5 5 2.5 1 0.5 0.1 0.05 0.01
(W/2)max (m)
3995 3960 3550 3040 2330 2140 1920 1640 1470 1260 1130
970 865 740 580 535 415
370 320 250 175 135
75 60 35
(98.6 km)* Q/t = 5 tonnes -*
Q/t (tonnes)
190 175 150 125 100 75 50 40 30 25 20
10 7.5 5 2.5 1 0.5 0.1 0.05 0.01
(W/2)max (m)
1840 (98.2 km)* 1780 1665 1540 1400 1240 1040 945 835
775 705 525 460 395 - (W/2)max = 395 m 300 210 160
80 65 40
* Data are provided up to a maximum downwind hazard distance of 100 km.
Example: Note:
Under weather condition F and Q/j = 5 tonnes, the puff hazard half-width (W/2)max = 395 m
Above table is valid only for a vinyl chloride concentration of 10 x TLV , or 0.13 g/m3.
therefore only applicable for a vinyl chloride hazard concentration limit of 10 x TLV , or 0.13 g/m3. Also, data are provided up to a maximum hazard distance downwind of 100 km.
Under weather condition D, the wind speed (U) range applicable is 1 to 30 m/s. The range of instantaneous vapour emission rates (Q/j) used was 0*01 t0 4100 tonnes, respectively. If the entire contents of an 80 000 L (17 600 Imp. gal.) tank car spill, the mass spilled would be 77 500 kg or approximately 78 tonnes. Therefore, under class D of Table 9, data are provided for up to 52 times this amount.
CMA 014406
Under weather condition F, the wind speed (U) range applicable is 1 to 3 m/s. The range of instantaneous vapour emission rates (Q/j) used was 0.01 to 190 tonnes, respectively. Therefore, under class F of Table 9, data are provided for up to 2A times a standard rail car load.
Use: Knowing the weather condition and Qx, pick the closest value in the table and corresponding (W/2)max> maximum puff hazard half-width, in metres. (For an intermediate value, interpolate Qx and (W/2)max values.) Also refer to the example at the bottom of Table 9.
5.3-2.3 Figure 17: Puff travel time versus travel distance. Figure 17 presents plots of puff travel time (t) versus puff travel distance (Xt) as a function of different wind speeds (U). This is simply the graphical presentation of the relationship = Ut for a range of typical wind speeds.
Use: Knowing the time (t) since the spill occurred and the wind speed (U), the distance (Xt) can be determined which indicates how far downwind the puff has travelled.
5.3.3
Sample Calculation. The sample calculation given below is intended to outline
the steps required to estimate the downwind hazard zone which could result from a spill
of liquid vinyl chloride. The user is cautioned to take note of the limitations in the
calculation procedures described herein and in the Introduction Manual. The estimates
provided here apply only for conditions given. It is recommended that the user employ
known or observational estimates (i.e., of the spill quantity) in a particular spill situation
if possible.
Problem:
During the night, at about 2:00 a.m., 20 tonnes of liquid vinyl chloride were spilled on a flat ground surface. It is now 2:05 a.m. The temperature is 20#C and the wind is from the NW at 7.5 km/h. Determine the extent of the vapour hazard zone.
Solution:
Step 1:
Quantity spilled is given, Qx = 20 tonnes . Qx = 20 tonnes x 0.25 (assuming 25 percent instantaneous vapour) =
5 tonnes . Qx = 5 x 106 g
Step 2:
Determine the wind speed (U) and direction (D) . Use available weather information, preferably on-site observations
CMA 0X4407
VINYL CHLORIDE
38 FIGURE 17
CONVERSION OF LOWER FLAMMABILITY LIMIT (LFL) UNITS (volume % to g/m3)
40 30
20 15
10 8 6 5 4^3
2
1.5
1 0.8
0.6
0.5 0.4 0.3
0.2 0.15 0.1
Molecular Weight Example: Vinyl Chloride, MW = 62.5, LFL = 4%, then LFL in g/m3 = 100
Note: data applicable at 25C and 760 mm Hg pressure
CMA 014408
39
Given:
U = 7.5 km/h, then U = 7.5 * 3.6 = 2.1 m/s D = NW or 315 (D = Direction from which wind is blowing)
Step 3:
Determine the weather condition From Table 8, weather condition = F since U is less than 11 km/h and it is night
Step 4:
Determine the hazard concentration limit (C) . This is the lower of 10 times the TLV, or the LFL, so for vinyl chloride
C = 0.13 g/m3 (TLV = 0.013 g/m3; LFL = 100 g/m3)
Step 5:
Compute C/Qt
C/QT = ^-- = 2.6 x 10-8 m-3 5 x 1Q6
Step 6:
Calculate the hazard distance (X) from the instantaneous point source . From Figure 14, with C/Qy = 2.6 x 10"8 m-3 and weather condition F,
X = 16 km
Step 7:
Calculate the puff hazard half-width (W/2)max . Use Table 9 . With Qj = 5 tonnes . Then for weather condition F, (W/2)max = 395 m
Step 8: Step 9:
Determine the time since the spill . t = 5 min x 60 = 300 s Calculate the distance travelled (Xt) by the vapour puff since the time of the accident . Using Figure 17, with t = 300 s and U = 7.5 km/h, then Xt = 0.6 km (more
accurately from Xt = Ut = 2.1 m/s x 300 s = 630 m = 0.63 km)
Step 10:
Map the hazard zone . This is done by drawing a rectangular area with dimensions of twice the
maximum puff hazard half-width (395 m) by the maximum hazard distance downwind of the instantaneous point source (16 km) along the direction of the wind, as shown in Figure 18 . If the wind is reported to be fluctuating by 20 about 315 (or from 315 10*), the hazard zone is defined as shown in Figure 19
CMA 014409
VINYL CHLORIDE
40
Wind U = 7.5 km/h from 315 (NW)
FIGURE 18 HAZARD AREA FOR STEADY WINDS, EXAMPLE PROBLEM
VINYL CHLORIDE Wind U = 7.5 km/h from 315 110s
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ FIGURE 19 HAZARD AREA FOR UNSTEADY
WINDS , EXAMPLE PROBLEM
= X * 1000 x tan 10 + (W/2) max = -Jl..x . 1000 * tan 10 + 395 = - 3220 _ m = 3 2 km
CMA 014410
41
. Note that the puff has only travelled 0.63 km in the 5 minutes since the spill. At a wind speed of 7.5 km/h, there remain 123 minutes before the puff reaches the maximum downwind hazard distance of 16 km
5.4 Behaviour in Water
5.4.1
Introduction. When spilled on water, vinyl chloride will vaporize and at the
same time spread on the surface. Because it is only slightly soluble, a very small amount
will be dissolved in the water, the rest evaporating until it is removed.
For the purpose of nomogram preparation, the extent of spread on the surface
of the water has been estimated, assuming that none of the vinyl chloride is dissolved in
the water. However, the loss due to vaporization has been taken into account.
The rate of spreading on water is based on the balance of forces tending to
spread the liquid (gravity and surface tension) and those tending to resist spreading
(inertial and viscous forces). Since cryogenic liquids such as vinyl chloride are evaporated
quickly, only the initial gravity-inertia regime of spread is considered relevant (Raj 1974).
The maximum size of the spill pool depends to a large extent on the rate of vaporization.
The equations representing the spreading of the spill on water are presented in
the Introduction Manual. For the purposes of the nomogram presented, the water
temperature has been taken at 20C, representing a maximum for surface water bodies.
This condition maximizes the spill size.
5.4.2
Nomogram for Spreading on Still Water. Figure 20 is presented to simplify the
calculation of spreading on still water (without dissolution) and to estimate the time for
complete evaporation for a range of spill sizes. Assuming no dissolution in water. Figure
20 provides a simple means of estimating the maximum spill radius for vinyl chloride if
the spill size is known. The nomogram is based on data presented in the Hazard
Assessment Handbook (CHRIS 1974) and a computer model for simultaneous spreading and
evaporation of a cryogenic liquid spilled on water (Raj 1974). The bracketed figures on
the nomogram provide an estimate of time for complete evaporation of the spill. Because
of the short times involved, the complete time history of the spread of the spill has not
been considered. Similarly, the translation distance of the spill by wind or surface current
is not considered.
5.4.3
Sample Calculation. A 20 tonne spill of vinyl chloride has occurred on a large
lake. What is the maximum size of the spill (assuming no dissolution) and approximate
time for complete evaporation?
CMA 014411
VINYL CHLORIDE
42
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ FIGURE 20 MAXIMUM SPILL RADIUS
VS SPILL SIZE
Maximum Spill Radius, r,
Solution
. Use Figure 20 . With spill size = 20 tonnes, rmax = 25 m . Time for complete evaporation is about 5 min
5.5 Subsurface Behavimr: Penetration into Soil
5.5.1
Mechanisms. The principles of contaminant transport in soil and their
application to this work are presented in the Introduction Manual. Special considerations
related to the spill of vinyl chloride onto soil and its transport downward through the soil
are presented here.
Vinyl chloride is shipped as a liquefied compressed gas. It has a boiling point
of -13.4C at a pressure of 1 atmosphere. Consequently, when it is spilled onto soil,
extensive evaporation will occur. While most will be lost to evaporation, the balance will
infiltrate the soil. Evaporation will continue within the soil but at a reduced rate.
Vinyl chloride is only slightly soluble in water; thus, precipitation falling at the
time of the spill or water used to flush the site will not provide dilution of the chemical.
Traces may be carried in the aqueous phase into the soil but this is assumed to be
negligible.
CMA 014412
43
If the soil surface is saturated with moisture at the time of the spill, as might be the case after a rainfall, the spilled chemical will run off or pond and eventually evaporate.
For this work, the soils have been assumed to be at field capacity. This situation provides very little interstitial water to impede the contaminant's soil penetration and thus represents "worst case" analysis.
During downward movement, vinyl chloride may interact with the soil as well as evaporate. However, it is assumed that sufficient material will remain to allow movement toward the groundwater table.
Upon reaching the groundwater table, the contaminant will continue to move, now in the direction of flow within the capillary fringe. A "contaminated pancake" will be produced but will eventually dissipate through evaporation. This is shown schematically in Figure 21.
5.5.2
Equations Describing Vinyl Chloride Movement into Soil. The equations and
assumptions used to describe contaminant movement downward through the unsaturated
soil zone toward the groundwater table have been described in the Introduction Manual.
Transport velocities have been based on Darcy's Law assuming saturated piston flow.
5.5.3
Saturated Hydraulic Conductivity of Vinyl Chloride in Soil. The saturated
hydraulic conductivity (K0), in m/s, is given by:
where:
K0 = (pg)k u
k = intrinsic permeability of the soil (m2) p = mass density of the fluid (kg/m^) y = absolute viscosity of the fluid (Pa#s) g = acceleration due to gravity = 9.81 m/s2
The appropriate fluid properties are shown in the chart below. Data for 4C but not 20C were available.
Property
Mass density (p), kg/m^ Absolute viscosity (y), Pas Saturated hydraulic conductivity (K0), m/s
4C
939 0.24 x 10"3 (1.53 x 107)k
CMA 014413
VINYL CHLORIDE
44
FIGURE ?1
SCHEMATIC SOIL TRANSPORT
Evaporation
Possible Upflow Movement Due to Mounding
Soil: Coarse Sand -Porosity (n) = 0.35 -Intrinsic Permeability (k) = lO^m2 -Field Capacity (0jc) = 0.075
CMA 0144X4
5.5.4 Soils. The Introduction Manual describes the three soils selected for this work. Their relevant properties are:
Porosity (n), m3/m3 Intrinsic permeability(k), m2 Field capacity (0fc), m3/m3
Soil Type
Coarse Sand
0.35 10-9 0.075
Silty Sand
0.45 10-12 0.3
Clay Till
0.55 10-15 0.45
5.5.5
Penetration Nomograms. A nomogram for the penetration of vinyl chloride
into the unsaturated zone above the groundwater table was prepared for coarse sand only.
Penetration times for the denser soils, silty sand and clay till, would be several orders of
magnitude greater than for coarse sand. Evaporation during this period would leave little
or no contaminant for infiltration. Thus, spills on these denser soils should not result in
groundwater pollution problems.
The nomogram presents penetration time (tp) plotted against depth of
penetration (B). Because of the methods and assumptions used, the penetration depth
should be considered as a maximum depth in time tp. A flowchart for use of the
nomogram is presented in Figure 22. The nomogram is presented as Figure 23.
Since vinyl chloride is immiscible in water, some may remain within the soil
pores as a residual during transport. This has been neglected, however, since the material
will eventually evaporate.
5.5.6
Sample Calculation. A 20 tonne spill of vinyl chloride has occurred on coarse
sand. The temperature is 4C; the spill radius is approximately 8.6 m. Calculate the
depth of penetration 10 minutes after the spill and check the corresponding evaporation
loss.
Solution
Step 1:
Define parameters . Mass spilled = 20 000 kg (20 tonnes)
T = 4<>C
CMA 014415
vinyl CHLORIDE
46 FIGURE 22
FLOWCHART FOR NOMOGRAM USE
CMA 014416
VINYL CHLORIDE
7--------------
47 ___ FIGURE 23
PENETRATION IN COARSE SAND
Time of Penetration, tp (min)
\
0^/
4
i
/-___________ 02
4 68
Depth of Penetration, B (m)
1 0 12 CMA 014417
48
Step 2: Step 3:
r = 8.6 m . Soil = coarse sand . Groundwater table depth (d) = 13 m . Time since spill (tp) = 10 min
Calculate the area of the spill . A = nr2 = 232 m2
Estimate the depth of penetration (B) at time (tp) . For coarse sand, B = 22.5 m at tp = 10 min . Groundwater table has been reached in this time
CMA 014418
6 ENVIRONMENTAL DATA
6.1 Suggested or Regulated Limits
6.1.1
Water. The U.S. Environmental Protection Agency has recommended, for
maximum health protection, a concentration limit of 0 vinyl chloride in drinking water
(PTP 1980). Consideration was given to setting criteria of 0.517, 0.0517 or 0.00517 mg/L
for various risk levels (AWQC 1978).
6.1.2
Air. The U.S. Environmental Protection Agency proposed a stack emission
limit of 10 ppm in 1975, corresponding to emissions of about 10 kg/h per average-sized
plant (PTP 1980; EPA Std. 1975).
Canada has a limit for vinyl chloride content of exhaust gases of 10 ppm, or
2 kg/d, whichever is greater (Clean Air Act 1978). Ontario's limit is 560 yig/m^
emissions, at point of impingement, with a goal of 280 pg/m3 for ambient air (Ontario
Tentative Standards 1982). A guideline for ambient air is 0.2 ppm - 1/2 hour average
(APCD 1978).
6.2 Aquatic Toxicity
6.2.1
Toxicity Ratings and Aquatic Effects. Vinyl chloride has been assigned a
TLm96 of greater than 1000 ppm (RTECS 1979). Bacteria and fungi have been subjected
to 900 mg/L with no toxic effect noted (EPA 1976). The bioconcentration of vinyl
chloride in fish is estimated to bea factor of 1.9 (AWQC 1980).
6.3 Other Toxicity
For mammals, vinyl chloride has anesthetic properties above 500 ppm (OHMTADS 1981). It may act as an asphyxiant at high concentrations. Toxicity to plants varies from 10 to 10 000 ppm (in air) for a 7-day exposure period (EPA Assess. 1975).
6.4 Degradation and Long-termFate
In water, vinyl chloride does not appear to be sorbed, degraded or affected by microorganisms, as verified by experiments with 5 mixed bacterial cultures, 3 mixed fungal populations and 2 bacterial cultures (EPA Aqua 1976). The chemical degradation in water also does not appear to be significant. Vinyl chloride is rapidly lost to the atmosphere. Effluent water from a vinyl chloride plant may contain as high as 20 ppm but more typically 2-3 ppm (EPA 1974). The rate of exchange of gaseous vinyl chloride between water and air is about twice that of oxygen (EPA Aqua 1976). On this basis, the
50
half-life of 1 ppm VCM in water at a 1 m depth is estimated to be 26 min (Verschueren
1984).
In air, vinyl chloride photodegrades to hydrogen chloride or formyl chloride,
which in turn reacts rapidly to produce carbon monoxide and hydrogen chloride. The half-
life in air is estimated to be 2 days (CIC 1977).
CMA 014420
7 HUMAN HEALTH
Vinyl chloride is a colourless flammable gas at room temperature and pressure, with a pleasant, sweet odour at high concentrations. Human exposure to this synthetic compound is generally by inhalation and less frequently by skin absorption. Until very recently, its documented health effects were confined to Raynaud's syndrome-type symptoms (a syndrome characterized by deadening of sensations at the fingertips, whitening of fingers, and pain and sores on the hands), skin changes, bone lesions, acroosteolysis (deprivation or removal of calcium from bones in hands or feet), central nervous system depression, and disorders of the circulatory system (SOEHS 1975; EPA 1975; ICF 1974).
In 1971, a link was drawn between the inhalation of vinyl chloride monomer and malignant changes in rats. Later animal studies have further confirmed first reported cases. Subsequently, hepatic angiosarcoma (a rare form of liver cancer) cases among occupationally exposed workers were reported (SCC 1981; NTIS 1981).
In 1976, there were 48 known cases of vinyl chloride-related hepatic angiosarcomas in the world, 47 of which involved the handling of large quantities of liquefied vinyl chloride under pressure (SCC 1981). After detailed research and study, vinyl chloride is generally considered to be a confirmed human carcinogen (Doc. TLV 1981; USDHEW 1981; Doniger 1978; Senate 1974); as a result, its use has been restricted under environmental, drug, public health and regulatory laws.
Due to the tremendous usage of the chemical, its deleterious effects have been widely studied and documented. A number of agencies have reviewed vinyl chloride toxicology (VCT 1980; SCC 1976, 1981). Several reports have dealt with its carcinogenic, mutagenic and teratogenic effects. The compound is listed by the U.S. Environmental Protection Agency under the TSCA Inventory, Due to the large volume and repetitive conclusions of these tests, only the most recent or more significant of these have been documented.
The toxicological data summarized here have been extracted from reliable standard reference sources. It should be noted that some of the data are for chronic (long-term), low-level exposures and may not be directly applicable to spill situations.
7.1 Recommended Exposure Limits
The exposure standards for vinyl chloride are based upon its carcinogenic properties. Canadian provincial guidelines generally are similar to those of the USAACGIH unless indicated otherwise.
52
Guideline (Time) Origin
Time-weighted Averages (TWA)
TLV* (8 h)
USA-ACGIH
PEL (8 h)
USA-OSHA
Action Level
USA-OSHA
Recommended Exposure Level
USA-NIOSH
Time Weighted
Ontario
Average Exposure
Permissible Con B.C. centration (8 h)
Concentration moyenne (8 h)
Quebec
Carcinogenic Sub Saskatchewan stance (duration unspecified)
Short-term Exposure Limits (STEL)
Ceiling (15 min sample)
USA-OSHA
C iling (15 min sample)
USA-NIOSH
Concentration
Quebec
maxi male (15 min)
Maximum
Ontario
Other Human Toxicities
IDLH
TClo (intermittent)
Recommended Level
5 ppm (10 mg/m3) 1 ppm 0.5 ppm 1 ppm 2 ppm (5.2 mg/m3)
1 ppm, carcinogen 1 ppm, cancerigene None given, carcinogenic substance
5 ppm Minimum detectable 1 ppm 1 ppm, cancerigene 10 ppm (26 mg/m3)
No data 500 ppm
Reference
TLV 1983 NIOSH/OSHA 1981 GE 1978 NIOSH Standard 1974 Ont. Reg. 1982
B.C.1980
Quebec 1979
Saskatchewan 1981
NIOSH/OSHA 1981 NIOSH/OSHA 1981 Quebec 1979
Ont. Reg. 1982
RTECS 1979
Inhalation Toxicity Index
The Inhalation Toxicity Index (ITI) is a measure of the potential of a substance to cause injury by inhalation. It is calculated as follows:
ITI = 1315.12 (Vapour pressure, in mm Hg/TLV, in ppm) At 20"C, ITI = 1315.12 (2524 mm Hg/5 ppm)
= 6.6 x 105
CMA 014422
7.2 7.2.1
irritation Data Skin Contact.
53
Exposure Level (and Duration)
SPECIES: Human Unspecified
Unspecified Unspecified
Effects
Reference
Sclerotic changes of the skin and various lesions.
Allergic dermatitis.
Degenerative skin changes which histologically showed destruction of the elastic network of the connective tissue (hands, forearm, face).
TDB (on-line) 1981
TDB (on-line) 1981 SOEHS 1975
7.2.2
Eye Contact.
Exposure Level (and Duration)
SPECIES: Human Unspecified (liquid)
Unspecified (liquid)
Effects
Inflammation of conjunctivas and lesions in the cornea due to inflammation. Contact of eyes with escaping compressed vinyl chloride can produce frostbite.
Reference Lefevre 1980 Doc. TLV 1981
7.3 Threshold Perception Properties
7.3.1
Odour.
Characteristics: Mild, sweet, pleasant (Verschueren 1984) Odour Index: 100 (20C) (Verschueren 1984)
CMA 014423
54
Parameter Threshold Odour Concentration Detection Threshold
Media In air In air
Concentration
Reference
4000 to 25 000 ppm
''-rschueren 1984
1200 to 2000 ppm AWQC 1978
7.3.2 7.4 7.4.1
Taste. No data. Toxicity Studies bihalation.
Exposure Level (and Duration)
Effects
Reference
Acute Exposures
SPECIES: Human
25 000 ppm (3 min) 8000 to 12 000 ppm (5 min) 10 000 ppm 4000 ppm (5 min or more)
1000 ppm
500 ppm Unspecified
Unspecified
Dizziness and disorientation.
Intoxication signs are manifested.
Noticeable anesthetic effects.
Dizziness and confusion. Higher concentrations may lead to unconsciousness and death.
Slight anesthesia, drowsiness, slight visual disturbances, faltering gait, numbness and tingling of extremities.
tclo
After "massive" and apparently repeated exposures: euphoria followed by a state of inebriation similar to that of alcohol intoxication, epigastric pain and anorexia.
Two deaths reported from accidental acute VC poisoning. Cyanosis, local burns, congestion of lungs and kidneys, and failure of the blood to clot were noted.
TDB (on-line) 1981 ICF 1974 Patty 1981 SCC 1981
TDB (on-line) 1981
DPIMR 1981 TDB (on-line) 1981
SCC 1981
55
Exposure Level (and Duration) SPECIES: Dog 170 000 ppm (1 min) 100 000 ppm (4 h) SPECIES: Mice 86 000 to 123 000 ppm (1 min) SPECIES: Guinea Pig 200 000 ppm (18 min) 20 000 ppm (30 min) 5000 ppm (30-60 min)
SPECIES: Rat 6000 ppm (4 h) Chronic Exposures SPECIES: Human Unspecified
Unspecified
Unspecified
Effects
Narcosis Cardia arrhythmia
Narcosis
Reference
EPA Assess. 1975 EPA Assess. 1975
EPA Assess. 1975
Death
tclo
Pulmonary edema, hyperemia of kidneys and lungs.
INRS 1975 DPIMR 1981 INRS 1975
tclo
DPIMR 1981
In 168 workers, the incidence of Raynaud's syndrome was reported as 6 percent and the incidence of liver enlargement as 30 percent.
TDB (on-line) 1981
Several studies of workers exposed to VCM showed various degrees of liver damage (usually enlarged liver) and enlarged spleens.
EPA Assess. 1975
Clinical examination of exposed workers in Dundee Research Project - deficient circulation in the extremities (Raynaud's Phenomenon); osteolysis of terminal phalanges of the fingers and to a lesser extent of the toes; degenerative skin changes with destruction of the elastic network of the connective tissue;
SOEHS 1975
CMA 014425
Exposure Level (and Duration)
Unspecified Unspecified (mean 7 yr, 2 yr and 18 yr)
Unspecified
Unspecified
56
Effects
Reference
paresthesia of the fingers with thickening of the end segments; general symptoms of fatigue, breathlessness on exertion, dizzi ness, increased sweating, and pains in the upper epigastric region.
Three thousand workers employed in the PVC manufacturing industry were examined. Acroosteolysis with or without Raynaud's syndrome was found in 31 of these.
SOEHS 1975
Thirteen autoclave workers, mean SOEHS 1975 age 39, showed first symptoms from 1-1/2 to 3-1/2 years after exposure began. Found Raynaud's syndrome, clubbing and shortening of the fingers, skin changes resem bling scleroderma, with disorders of the circulatory system being the most common symptom. Labora tory tests showed reduced liver function in 11 of the workers.
Thirteen PVC workers showed similar symptoms to those listed above. Two of the men who had been removed from exposure, one for 6 months and one for 1-1/2 year, subsequently deve loped signs and symptoms of VCM disease in hands and feet.
SOEHS 1975
After repeated chronic exposures, the main neurological symptoms were headaches, irritability, dizziness, sleep disorders, diaphoresis, memory loss, general asthenia and paresthesia.
SCC 1981
7.4.2
Ingestion.
57
Exposure Level (and Duration)
SPECIES: Rat 500 mg/kg
Effects ld50
7.4.3
Carcinogenicity.
Reference RTECS 1979
Exposure Level (and Duration) SPECIES: Human 500 ppm (4 yr, intermittent) 200 ppm (15 yr, intermittent) Unspecified
Unspecified
Unspecified
Effects
Reference
TClo, carcinogen. \
RTECS 1979
Inhalation - equivocal tumorigenic agent.
RTECS 1979
Report of four deaths at B.F. Goodrich Chemical Company caused by the rare angiosarcoma of the liver. On investigation, NIOSH concluded vinyl chloride was a probable occupational carcinogen.
NIOSH Standard 1974
As of March 1976, there were 48 SCC 1981 known cases of vinyl chloride related liver angiosarcomas, 45 of which had resulted in death. All 9 of the Canadian cases worked in one plant in Shawinigan, Quebec, and 9 of the U.S. cases worked in one plant. These deaths had occurred over a period of 14 years, with the number per year showing an increase
with time.
A study of former Monsanto Company chemical plant employees has shown an increased incidence of cancer among workers
COHSN 1982
CMA 014427
58
Exposure Level (and Duration)
Unspecified Unspecified
1-10 ppm (long-term)
1 ppm (5 h/day, 5 d/wk, 35 yr) SPECIES: Rat 50 000 ppm-h
Effects
Reference
exposed to vinyl chloride; 34 of 110 deaths were from cancers: lung, mouth, digestive system and lymph glands. One .death was due to liver cancer. Only worksites where there had been exposure to vinyl chloride and polyvinyl chloride were examined.
In addition to liver angio sarcomas, lung cancer has been found in some epidemiological studies.
Lilis 1981; Apfeldorf 1981
A study of VCM and PVC process ing works revealed that in the VCM cohort there were signi ficantly elevated mortality rates due to malignancy of the lymphatic gland and hematopoietic tissues and the gastrointestinal tract, the latter primarily due to tumours of the liver.
Weber 1981
The long-term effects such as angiosarcoma, liver damage, Raynaud's syndrome may be due to levels as low as 1-10 ppm; onset of angiosarcoma is estimated to be 13-20 years; however, a few rare cases of shorter times (3-6 yr) were found.
EPA Assess. 1975
A study of epidemiological results and various statistical models places the risk of liver angio sarcoma at 1.5 x 10-* (5 out of a million) at this dosage.
Gehring 1979
Carcinogenic dose calculated from various concentrations and times including single doses.
Hehir 1981
CMA 014428
59
Exposure Level (and Duration) 6000 ppm (4 h/d 12 to 18 of pregnancy) 600 ppm (8 h/d, 5 d/wk)
250 ppm (39 wk) 250 ppm (35 wk) 50 ppm (30 wk) 34 g/kg (3 yr) 11 g/kg (3 yr) 250, 500, 2500, 6000, 10 000 ppm (127 wk)
SPECIES: Hamster 500 ppm (4 h/d for 30 wk) SPECIES: Mouse 5000 ppm-h
2500 ppm (5 h/d for 26 wk, intermittently)
Effects
TCL0, carcinogenic effect (inhalation).
Reference RTECS 1979
Angioscarcoma in 23 percent of animals; this was increased to 50 percent by administration of ethanol in water (5 percent by volume). It was concluded that ethanol is a co-carcinogen in relation to vinyl chloride.
Toxic dose, carcinogenic effect (inhalation).
Toxic concentration, carcinogenic effect (inhalation).
TClo, carcinogenic effect (inhalation).
Toxic concentration, carcinogenic effect (oral).
TDLp, carcinogenic effect (oral).
Induction of angiosarcoma in the liver and other organs, and other cancers. The percentage of animals having liver angio sarcomas varied but was around 10 percent; 50 ppm exposure resulted in no angiosarcomas.
Radike 1981
RTECS 1979 RTECS 1979 RTECS 1979 RTECS 1979 RTECS 1979 Maltoni 1974. IN NIOSH Standard 1974; ICF 1974
TClq, carcinogenic effects (inhalation).
RTECS 1979
Carcinogenic dose for mice determined by a variety of exposure periods and concen trations.
Toxic dose, neoplastic effects (inhalation).
Hehir 1981 RTECS 1979
CMA 014429
60
Exposure Level (and Duration)
Effects
Reference
250 ppm (35 wk, intermittently)
50 ppm (30 wk, intermittently)
50 ppm (6 h/d for 12 wk, intermittently)
Toxic concentration, carcinogenic effects (inhalation).
TC^q, carcinogenic effects (inhalation).
Toxic dose (inhalation),
RTECS 1979 RTECS 1979 RTECS 1979
SPECIES: Animal, unspecified
25 ppm (4 h/d for 1 yr)
5 liver angiosarcomas, 4 zymbal
Patty 1981
gland carcinomas and 1 nephroblas
toma in 120 test animals.
SPECIES: Rats, Mice, Hamsters
0-30 000 ppm (various exposures from single to 52 wk) (inhalation) 0.03 to 50 mg/kg (single dose to 5/wk for 52 wk) (ingestion or injection)
10 ppm (4 h/d for 1 yr)
1 mg/kg
A major study involving 7000 animals of various species, strains, and sexes was conducted. The results indicate that vinyl chloride is a multi-potential carcinogen affecting a variety of organs and tissues. Liver angiosarcoma was detected in all species; many types of tumours were found. Vinyl chloride shows carcinogenic effects whether it was administered by inhalation or ingestion and shows a clear dose-response relationship. Newborn animals are the most sensitive. Vinyl chloride shows carcinogenic effects even down to 50 ppm.
1 liver angiosarcoma, 2 extrahepatic angiosarcomas and 2 zymbal gland sarcomas in 120 test animals.
3 liver angiosarcomas, 1 extrahepatic angiosarcoma and 1 hepatoma in 150 animals.
Maltoni 1981
Patty 1981 Patty 1981
CMA 014430
7.4.4
61
Teratogenicity and Mutagenicity.
Exposure Level (and Duration)
Effects
SPECIES: Human Unspecified Unspecified Unspecified
Unspecified
Increased frequency of chromosomal aberrations in lymphocytes of exposed workers.
Increased fetal wastage among wives of male workers who have had occupational exposure to vinyl chloride.
An epidemiological study was made of an area where the general population was exposed to VCM. The population was shown to have an excess of birth defects compared to other communities; the fluctuation in defects corresponded with VCM fluctua tions in the environment.
An epidemiological study of workers in a plastic/rubber plant revealed a greater percentage of chromosomal breakage compared to workers in other industries; however, the breakage did not correlate to VCM exposure and thus another agent(s) is suspected.
SPECIES: Rat
1500 ppm (during the first, second or third trimester of pregnancy)
Increased fetal mortality and other fetotoxic effects when administered during the first trimester; no embryotoxicity was noted when vinyl chloride was administered during the second or third trimester.
SPECIES: Chinese Hamster
2500 or 5000 ppm (4 h/d for 5 d)
Chromosomal changes in bone marrow cells.
Reference NIOSH/OSHA Bulletin 197S NIOSH/OSHA Bulletin 1978; Hatch 1981 Laval 1981
Heath 1977
Patty 19S1
Patty 1981
CMA 014431
62
Exposure Level (and Duration)
Effects
SPECIES: Hamster
600 mg/kg 20 pph (5 h)
Cytogenic analysis assaying for chromosomal aberrations following administration of vinyl chloride (in vivo). No results reported.
Hamster lung cells were tested using microsomal mutagenic assay. No results reported.
SPECIES: Mouse
3000, 10 000 or 30 000 ppm for 5 d
No dominant lethal effects.
SPECIES: Drosophila melanogaster
1 pph
Sex chromosome loss and non disjunction tests have been performed (in vivo). Route of administration was by inhalation.
SPECIES: Salmonella typhimurium
11 percent (in air)
2 to 20 percent (in air)
Positive Ames test - concluded that vinyl chloride induced point mutagens but only after metabolic conversion.
Positive Ames test results by several investigators.
Reference RTECS 1979 RTECS 1979 Patty 1981 RTECS 1979
Senate 197^ Fabricant 1981
7.5 Symptoms of Exposure
General symptoms of exposure found in most information sources have not been specifically referenced. Only those of a more specified or unusual nature have their sources indicated.
7.5.1
Inhalation.
1. Irritation of nose and throat. 2. Headache.
CMA 014432
63
3. Overexcitement (TDB (on-line) 1981). 4. Anesthetic effects (Patty 1981). 5. Narcosis. 6. Numbness and tingling of extremities (TDB (on-line) 1981). 7. Visual disturbances (TDB (on-line) 1981). 8. Dizziness and disorientation. 9. Inebriation. 10. Faltering gait. 11. Euphoria. 12. Epigastric pain (TDB (on-line) 1981). 13. Anorexia. 14. State of shock (Lefevre 1980). 15. Loss of consciousness. 16. Coma. 17. Death as a result of cardiac or respiratory failure (Lefevre 1980).
7.5.2
Ingestion.
Ingestion is unlikely; however, if ingested, vinyl chloride would be toxic and cause tissue damage (AAR 1981).
7.5.3
Skin Contact.
1. Dry skin. 2. Allergic dermatitis (TDB (on-line) 1981). 3. Frostbite. 4. Irritation and burns from absorption of phenol stabilizer (GE 1978). 5. Various lesions.
7.5.4
Eye Contact.
1. Irritation. 2. Inflammation of conjunctiva. 3. Corneal lesions due to inflammation (Lefevre 1980).
7.6 Human Toxicity to Decay or Combustion Products
Polyvinyl chloride breaks down into hydrogen chloride and carbon dioxide when subjected to excessive heat or pressure. Extensive studies have shown that phosgene has not been detected under any practical circumstances (SCC 1976), although some sources
CMA 014433
64
report this product (GE 1979). Similar decomposition products might be expected when vinyl chloride burns.
7.6.1
Carbon Dioxide and Hydrogen Chloride. Carbon dioxide is a colourless,
odourless gas which in elevated concentrations may act to produce mild narcotic effects,
respiratory stimulation and asphyxiation. Its TLV* is 5000 ppm (8 h - TWA) and 15 000
ppm (STEL) (TLV 1983).
Hydrogen chloride may be present as a gas or a liquid. In contact with human
skin it causes irritation, inflammation, burns, blistering dermatitis and profound tissue
damage, depending upon concentration and length of contact. In contact with eyes it can
cause stinging, burning, opaqueness of the cornea and corneal necrosis. Inhalation causes
coughing, choking, ulceration of the mucosa, bronchitis, pneumonia and, in cases of
exposures to extremely high concentrations, pulmonary edema and death. The TLV* is
5 ppm (8 h - TWA) (TLV 1983).
CMA 014434
65 X CHEMICAL COMPATIBILITY 8.1 Compatibility of Vinyl Chloride with Other Chemicals and Chemical Groups
CMA 014435
66
8.1 Compatibility of Vinyl Chloride with Other Chemicals and Chemical Group (Cont'd)
CMA 014436
9 COUNTERMEASURES
9.1 Recommended Handling Procedures
The following procedures have been derived from a literature review. To avoid any deviation from the intended meaning, the wording of the original source has been presented essentially unchanged - in so doing, it is recognized that there may be discrepancies between different sources of information. It is recognized that countermeasures are dependent on the situation, and thus what may appear to be conflicting information may in fact be correct for different situations. The following procedures should not be considered as Environment Canada's recommendations.
9.1.1
Fire Concerns. Vinyl chloride is an extremely flammable gas. It readily forms
explosive mixtures in air (GE 1978). Its vapours may travel along surfaces to ignition
sources and flash back (NFPA 1978). It can undergo hazardous exothermic polymerization
if heated or if reaction is catalyzed (GE 1978).
9.1.2
Fire Extinguishing Agents. Stop leak before attempting to extinguish fire.
Use water spray at a safe distance to cool containers involved in a fire to prevent rupture
or explosion (ERG 1980).
Small fires: Dry chemical, or CO2. Large fires: Water spray, fog or foam.
Move containers from fire area if this can be done without risk. Stay away from tank ends. For massive fires, use unmanned hose holder or monitor nozzles (ERG 1980).
9.1.3
Evacuation. In the event of an explosion, the minimum safe distance from
flying fragments is 600 m in all directions. Keep internal combustion engines and other
sources of ignition at least 20 m from probable ignition area (EAG 1978).
9.1.4
Spill Actions.
9.1.4.1 General. Stop or reduce discharge of material if this can be done without risk. Eliminate all sources of ignition. Avoid skin contact and inhalation (Dow ERIS 1981). Controllable leaks of vinyl choride in containers can be plugged by driving wooden plugs in small holes and/or applying a neoprene patch for larger holes. The patch should be bonded or chained to the containers to make it secure (MCA 1972). Special kits for VCM tank car leak plugging are available (VCM 1982).
CMA 014437
68
For larger, uncontrollable leaks, control spread of vapours by water spray. Make provisions to minimize the mixing of air with VCM vapour in confined spaces and the burning containers. The use of water, N2 or any inert gas is recommended to prevent explosions (MCA 1972).
Application of a fluorocarbon water foam is recommended to diminish vapour and fire hazard (EPA 670/2-75-042). Tests of various foams revealed that most low expansion foams will reduce the vapour emission from a pool by a factor of about 2 (MSA 1982).
9.1.4.2 Spills on land. If liquid vinyl chloride is spilled on land, contain if possible by forming mechanical and/or chemical barriers to prevent spreading (EPA 670/2-75-042). If the ambient temperature is low (e.g., VCM does not evaporate rapidly), vinyl chloride can be pumped into appropriate containers for return to the manufacturer. This process must be conducted with extreme care, with correct equipment and trained individuals. Otherwise, the only safe countermeasure is to let the VCM evaporate.
9.1.4.3 Spills on water. Control, if possible, by using natural barriers or booms to limit spreading. Remove trapped material with suction hoses or pumps, using extreme caution (EPA 670/2-75-042). Otherwise, the only safe method is to let the material evaporate.
9.1.5
Cleanup and Treatment.
9.1.5.1
Spills on water. When vinyl chloride is spilled on water, activated carbon can
be applied at 10 percent the spill amount over the region occupied by 10 mg/L or greater
concentrations. Mechanical dredges or lifts can then be used to remove the carbon (EPA
670/2-75-042). Aeration of contaminated water will also substantially remove vinyl
chloride.
9.1.5.2 General. The following treatment processes have shown possible applicability for spill countermeasures:
Process Biological
Percent Removal (TSA 1980)
100
Process
Granular Activated Carbon Adsorption
Maximum Percent Removal (EPA 600/8-80-042E)
52
CMA 014438
69
9.1.6
Disposal. Waste vinyl chloride must never be discharged directly into sewers
or surface waters. Vinyl chloride monomer can be burned in a high-temperature
incinerator with a scrubber attached to remove any hydrochloric acid formed (GE 1978).
9.1.7
Protective Measures. For entry into a situation where the spilled material and
its characteristics are unknown, self-contained breathing apparatus and a totally
encapsulated chemical suit should be worn.
If the spilled material is known to be vinyl chloride:
Impervious clothing and seif-contained breathing apparatus should be worn (Dow ERIS 1981; GE 1978). The following clothing materials shows breakthrough times of approximately 1 hour: butyl rubber, polyurethane, styrene-butadiene rubber, and Viton (Little 1983). Any clothing which becomes contaminated with VCM should be removed immediately and thoroughly washed and dried before reuse (MCA 1972). Eye wash stations and chemical safety showers should be readily available in areas of use and spill situations (GE 1978).
The following is a list of the minimum respiratory protection recommended for personnel working in areas where vinyl chloride monomer is present (GE 1978). It should be noted that conventional activated charcoal respirators have a very low absorption capacity for vinyl chloride. In tests run at 50 ppm and 50 percent relative humidity, the breakthrough time is 40 minutes. At 100 ppm and the same relative humidity, the breakthrough time is 160 minutes. In high relative humidities, this time is lower (NIOSH 1974).
Condition
Vapour Concentration Up to 10 ppm Up to 25 ppm Above 25 ppm
Fire fighting
Respiratory Protection
Organic cartridge-type respirator. Canister-type gas mask, full facepiece. Air supplied or self-contained type respirators. Self-contained breathing equipment.
9.1.8
Storage Precautions. Store in a cool, well-ventilated place; an outside or
detached, noncombustible location is preferred. Keep away from oxidizing agents and
sources of heat or ignition. Protect cylinders against physical damage (GE 1978).
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70
9.2 Specialized Countermeasures Equipment, Materials or Systems
The following items are taken from a previous study (Dillon 1982) and should not be considered to be the only suitable specialized countermeasures equipment, materials or systems available. More details on the specifications, performance and availability of these items can be found in the referenced study.
Leak Plugging Chemical/Physical Modification
Emergency Safety Kit for VCM Tank Cars
Ultrox (UV-Ozone) Process
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71
10 PREVIOUS SPILL EXPERIENCE
10.1 General
This section contains information on previous spill experience which will be useful to readers in understanding spill response and countermeasures. Only those which meet the criteria are included, and thus, the number of experiences is not an indication of the problems or frequency of spillage. As technology in spill control advances, this section will be updated in future manual revisions to include the most useful information.
10.2 Train Derailment (MacGregor 1980)
A train derailment occurred in the early hours of the morning, in winter conditions, resulting in leaks in two tank cars carrying vinyl chloride. The leaks were found to be from a safety valve on one car and a hole, approximately 5x7 cm, in the other. The latter leak was not discovered until 4 days after the derailment.
The leak rate of vinyl chloride from the valve appeared to be low due to the ambient temperature being below the boiling point of vinyl chloride (-13.4C). Although the vinyl chloride concentration at snow level, 1 m from one of the leaking cars, was measured at over 200 ppm, levels at the normal human breathing zone were generally very low. Unexpectedly, some of the liquid vinyl chloride released penetrated the snow cover and became trapped between the earth and snow. This was indicated by anomalous crystalline patches observed in the snow. The remainder evaporated at varying rates depending on the temperature over the spill period. Little could be done to contain or recover the vinyl chloride under these circumstances.
On the third day of the spill, the leaking safety valve was capped and wreck clearing commenced. On the fourth day, the puncture in the second tank car was discovered, indicated by "a shimmering effect, like a gas main shimmering or a hot road shimmering in the summer time". An area of 6 x 9 m was roped off for a patching operation. After first cutting away the outer shell with hand shears to prevent explosion, a preliminary patch was made up using a metal portion of a shovel and a Teflon ironing board cover as a gasket. A permanent patch was later installed by driving a wooden plug into the puncture hole and covering it with Velodur "plastic metal" which was cured by warming overnight with an antifreeze-filled hot water bottle. The next morning, this plugging device was backed up with a 1.3 cm thick steel plate, curved to the contour of the inner shell of the car and pressed onto the shell by a bolt and metal lever. The vinyl chloride was then transferred from the damaged cars to new tank cars.
CMA 014441
72 An estimated 70 600 L of vinyl chloride monomer spilled from this mishap. Air monitoring was carried out both on and off site during cleanup. In general, breathing zone readings on-site were "nil" except in the immediate vicinity of the damaged cars, where levels occasionally exceeded 5 ppm (TLV#), restricting workers' access. No traces of vinyl chloride were detected in off-site air samples. In addition to air monitoring, on site and off-site sampling programs for soil, snowmelt water, drinking water and groundwater were carried out after the cleanup. No traces of vinyl chloride were found in the drinking water, although residual traces were detected in soil, snow and groundwater. Three months after the spill, the highest vinyl chloride concentration found at groundwater level (taken from the centre of the spill site) had declined to 0.05 mg/L.
CMA 014442
73 11 ANALYTICAL METHODS
follows.
The general approach adopted for each of the Priority Chemicals was as
Methods have been documented here for the analysis of samples from air, water and soil in a normally equipped chemical laboratory remote from the spill site.
Customary sources of standard or recommended analytical methods were consulted, and outlines are presented for each chemical. These sources included publications of the U.S. National Institute for Occupational Safety and Health (NIOSH), the U.S. Environmental Protection Agency (EPA), the American Water Works Association (AWWA), the American Society for Testing and Materials (ASTM), and the American National Standards Institute (ANSI).
If the standard or recommended methods were judged to be reliable and
specific enough for the analysis of environmental and materials samples from spill sites and if they do not require highly specialized laboratory equipment, no additional methods were sought.
If especially simple, reliable tests (e.g., commonly used industrial methods) were found, they have been presented as well.
11.1 Quantitative Method for the Detection of Vinyl Chloride in Air
11.1.1
Gas Chromatography (NIOSH 1977; CIAL 1977). A range of 0.008 to
5.2 mg/m^ (3.2 ppb to 2.01 ppm) of vinyl chloride in air may be determined by gas
chromatography using flame ionization detection.
A known volume of air is drawn through two 7 cm x 6 mm O.D. charcoal tubes
containing 2 sections of 20/W mesh activated charcoal separated by a 2 mm portion of
urethane foam. The first section contains 100 mg whereas the second, or back-up, section
contains 50 mg. A silanized glass wool plug is placed before the front absorbing section.
A sample size of 5 L is recommended. It is collected at a flow rate of 50 mL/min.
Both charcoal tube samples are scored before the first section of charcoal and
broken. The larger section of charcoal is transferred to a 2 mL stoppered sample
container containing 1.0 mL of carbon disulphide. The same operation is performed with
the back-up section. The samples should be allowed to desorb for 30 minutes. A 5 yL
aliquot of sample is injected into a gas chromatograph equipped with a flame ionization
detector.
CMA 014443
74
The vinyl chloride is determined using retention times and an electronic integrator which determines peak area, as well as a calibration curve. Typical gas chromatograph operating conditions are: helium carrier gas at 40 mL/min, hydrogen gas at 65 mL/min, air flow at 500 mL/min, injector temperature at 230C, detector temperature at 230C, and a column temperature of 60C. The column is 0.6 x 548.6 cm (0.25 x 216 in.) stainless steel packed with chromosorb W.
11.2 Qualitative Method for the Detection of Vinyl Chloride in Air
Vinyl chloride may be determined in air by the use of a Drager detector tube for vinyl chloride. A volume of air is drawn through a Drager detector tube for vinyl chloride using a multi-gas detector pump; a change in colour of the violet indicating layer to pale brown indicates vinyl chloride (Drager 1979).
11.3 Quantitative Method for the Detection of Vinyl Chloride in Water
11.3.1
Partition Infrared (AWWA 1981). A range of 40 to 400 ppm (40 to 400 pg/mL)
of vinyl chloride in water may be determined by partition infrared spectrophotometry. A
minimum of 1 L of representative sample is collected in an appropriate container.
The sample is acidified to pH 2 by the addition of approximately 5 mL of
50 percent hydrochloric acid. The sample is then transferred to a separatory funnel and
the sample container rinsed with 30 mL of Freon* 113 (l,l,2-trichloro-l,2,2-
trifluoroethane). The solvent rinse is added to the separatory funnel. The solvent layer is
drained into a 100 mL volumetric flask. The aqueous layer is extracted with two more
30 mL portions of solvent. The solvent extracts are combined in the volumetric flask and
the volume taken to mark with solvent.
The vinyl chloride is determined using 1 cm matched near infrared silica cells
and a double-beam recording I.R. spectrophotometer. The sample is scanned from 3200 to
2700 cm-1 with solvent in the reference beam. A standard curve is used to determine the
quantity of vinyl chloride in the sample.
11.4 Qualitative Method for the Detection of Vinyl Chloride in Water
Vinyl chloride may- be determined qualitatively in water by infrared spectroscopy. A sample is collected and extracted with Freon* 113 (1,1,2-trichloro-1,2,2trifluoroethane) as in Section 11.3.1. The sample is scanned from 3200 cm_l to 2700 cm'^ using a double-beam recording infrared spectrophotometer with Freon* in the reference cell. The presence of a characteristic absorbance pattern on the chromatogram indicates the presence of vinyl chloride (AWWA 1981).
CMA 014444
75
11.5 Quantitativ Method for the Detection of Vinyl Chloride in Soil
11.5.1
Infrared Spectrophotometry (AWWA 1981). A range of 40 to 400 ppm (40 to
440 pg/mL) vinyl chloride in soil may be determined using infrared spectrophotometry.
Approximately 20 g of soil, accurately weighed, are collected in a glass jar and
dried by the addition of magnesium sulphate. Freon 113 (l,l,2-trichloro-l,2,2-
trifluoroethane) is used to extract the vinyl chloride from the soil. Using 1 cm matched
quartz cells with Freon in the reference beam of a double-beam I.R. recording
spectrophotometer, the sample is scanned from 3200 to 2700 cm~l. The vinyl chloride is
determined using a calibration curve.
11.6 Qualitative Method for the Detection of Vinyl Chloride in Soil
Vinyl chloride may be determined qualitatively in soil by infrared spectroscopy. A sample is collected and extracted with Freon 113 (l,l,2-trichloro-l,2,2trifluoroethane) as in Section 11.5.1. The sample is scanned from 3200 to 2700 cm-1 using a double-beam recording spectrophotometer with Freon in the reference cell. The presence of a characteristic absorbance pattern on the chromatogram indicates the presence of vinyl chloride (AWWA 1981).
CMA 014445
76
12 REFERENCES AND BIBLIOGRAPHY
12.1 References
AAR 1981: BDM Corporation, The AAR Hazardous Materials Data Base, prepared for the Association of American Railroads, Parts I and II, McLean, VA (May, 1981).
APCD 1978: Air Pollution Control Directorate, Emissions of Vinyl Chloride to the Ambient Air Around Manufacturing Facilities in Ontario, Fisheries and Environment Canada, Ottawa, Ontario, EPS 5-AP-77-14 (1978).
Apfeldorf 1981: Apfeldorf, R. and P.F. Infante, "Review of Epidemiologic Study Results of Vinyl Chloride-Related Compounds", Environ. Health Perspect., Vol. 41, pp, 221-226 (1981).
AWQC 1978: Ambient Water Quality Criteria: Vinyl Chloride, U.S. Environmental Protection Agency, Washington, DC (1978).
AWQC 1980: Ambient Water Quality Criteria for Vinyl Chloride. U.S. Environmental Protection Agency, Washington, DC, PB 81-117889, EPA 440/5-80-078. (1980)
AWWA 1981: American Water Works Association, Standard Methods for the Examination of Water and Waste Water, 15th edition, American Public Health Association, Washington, DC., Method 503B (1981).
Bretherick 1979; Bretherick, L., Handbook of Reactive Chemical Hazards, second edition, Butterworths, London, England (1979).
B.C. 1980: Workers' Compensation Board of British Columbia, Industrial Health and Safety Regulations, Workers' Compensation Act, Vancouver, British Columbia (July, I980L
CBG 1980: Southam Business Publications Ltd., "1981 Chemical Buyers' Guide", Canadian Chemical Processing, Vol. 64, No. 9, Don Mills, Ontario (December, 1980).
CCP 1982: News/Update, Canadian Chemical Processing, Vol. 66, No. 1, p. 14 (19 February 1982).
CCPA 1983; The Canadian Chemical Producers' Association, List of Members Toronto, Ontario (1983).
CDS 1967: National Association of Corrosion Engineers, Corrosion Data Survey, Houston, TX (1967).
CG-D-38-76: Bauer, W.H. et al., Agents, Methods and Devices for Amelioration of Discharge of Hazardous Chemicals on Water, Rensselaer Polytechnic Institute for the U.S. Coast Guard, Washington, DC, CG-D-38-76 (August, 1975).
CHRIS 1974: U.S. Department of Transportation, CHRIS Hazard Assessment Handbook, U.S. Coast Guard, Washington, DC, CG-446-3 (April, 1974).
CMA 014446
77
CHRIS 1978: U.S. Department of Transportation, Coast Guard, Chemical Hazards
Response Information System (CHRIS), Washington, DC (1978).
'
CIAL 1977: Chemical Industries Association Ltd., The Determination of Vinyl Chloride: A Plant Manual, London (1977).
CIC 1977: "An Overview of the Vinyl Chloride Hazard in Canada", Chemistry in Canada, pp. 24-37 (Summer, 1977).
COH5N 1982: "Specific Monsanto Plant Worksites a Factor in Workers' Cancer Deaths?", Canadian Occupational Health and Safety News, Vol. 5, No. 6, p. 6 (February, 1981).
Corpus 1983; Corpus Information Services Ltd., "Vinyl Chloride", Chemical Product Profiles, Don Mills, Ontario (April, 1983),
CRC 1980: Weast, R.C. (ed.), CRC Handbook of Chemistry and Physics, 60th edition, Chemical Rubber Publishing Company, Cleveland, OH (1980).
DCRG 1978; Dow Chemical Company, Dow Chemical Resistance Guide for Dow Plastic Lined Piping Products, Midland, MI (1978^
Dillon 1982; M.M. Dillon, Survey of Countermeasures Systems for Hazardous Material Spills, Environment Canada, Ottawa, Canada (1982).
Doc. TLV 1981; American Conference of Governmental Industrial Hygienists (ACGIH), Documentation of Threshold Limit Values, fourth edition, Cincinnati, OH (1981).
Doniger 1978: Doniger, D.A., The Law and Policy of Toxic Substances Control, A Case Study of Vinyl Chloride, John Hopkins University Press, Baltimore, MD (1978).
Dow ERI5 1981: Dow Chemical Canada Inc., Emergency Response Information Sheet, Sarnia, Ontario (1981).
Dow MSDS 1980: Dow Chemical Canada Inc., Material Safety Data Sheet, Sarnia, Ontario (27 June, 1980).
DPIMR 1981: Dangerous Properties of Industrial Materials Report, "Vinyl Chloride", pp. 85-87 (January-February, 1981).
DPLV 1972: Dow Chemical Company, Dow Plastic Lined Valves, Midland, MI (1972).
Drager 1979: Leichnitz, K. (ed.), "Air Investigations and Technical Gas Analysis with Drager Tubes", Detector Tube Handbook, fourth edition, Lubeck, Germany, p. 156 (1979).
EAG 1978: U.S. Department of Transportation, Emergency Action Guide for Selected Hazardous Materials, Research and Special Programs Administration, Materials Transportation Bureau, Washington, DC (1978).
EPA 1974: Preliminary Assessment of the Environmental Problems Associated with Vinyl Chloride and Polyvinyl Chloride, U.S. Environmental Protection Agency, Washington, DC, PB-239-110 (1974).
CMA 014447
78
EPA 1975: The So-Called Vinyl Chloride Disease, U.S. Environmental Protection Agency. Washington, DC, PB-258-838-t (1975).
EPA 1976: Standard Support and Environmental Impact Statement, Volume 2: Promulgated Emission Standard for Vinyl Chloride, U.S. Environmental Protection Agency, Washington, DC, PB-258-827 (1976).
EPA 1978: National Emission Standards for Hazardous Air Pollutants. Inspection Manual for Vinyl Chloride, U.S. Environmental Protection Agency, Washington, DC, PB-289-778 (1978).
EPA Assess. 1975: Scientific and Technical Assessment Report on Vinyl Chloride and Polyvinyl Chloride, U.S. Environmental Protection Agency, Washington, DC, PB-249-461
EPA Aqua 1976: Dynamic Behaviour of Vinyl Chloride in Aquatic Ecosystems, U.S. Environmental Protection Agency, Washington, DC, EPA 600/3-76-001 (1976).
EPA Std. 1975: Standard Support and Environmental Impact Statement: Emission Standard for Vinyl Chloride, U.S. Environmental Protection Agency, Washington, DC. EPA 450/2-75-009 (1975).
EPA 600/2-80-076: Hatayama, H.K., J.J. Chen, E.R. deVera, R.D. Stephens, and D.L. Storm, A Method for Determining the Compatibility of Hazardous Wastes, Municipal Environmental Research Laboratory, Office of Research and Development, U.S. Environmental Protection Agency, Cincinnati, OH (April, 1980).
EPA 600/8-80-042E; Treatability Manual, Volume V, Summary, U.S. Environmental Protection Agency, Officio? Research and Development, Washington, DC, EPA 600/8-80042E (July, 1980).
EPA 670/2-75-042: Pilie, R.J. et al., Methods to Treat, Control and Monitor Spilled Hazardous Materials, U.S. Environmental Protection Agency, National Environmental Research Center, Cincinnati, OH, EPA 670/2-75-042 (June, 1975).
ERG 1980: U.S. Department of Transportation, Hazardous Materials, 1980 Emergency Response Guidebook, Research and Special Programs Administration, Materials Transportation Bureau, Washington, DC (1980).
Fabricant 1981; Fabricant, J.D. and M.S. Legator, "Mutagenicity Studies of Vinyl Chloride", Environ. Health Perspect., Vol. 41, pp. 189-193 (1981).
FKC 1975: Lowenheim, F.A. and M.K. Moran, M.K., Faith, Keye's and Clark's Industrial Chemicals, Wiley-Interscience, New York, NY. (1975)
GE 1978: General Electric Company, Material Safety Data Sheets, "Vinyl", Material Safety Information Services, Schenectady, NY (August, 1978).
Gehring 1979: Gehring, P.J., B.E. Watanebe, and C.N. Park, "Risk of Angiosarcoma in Workers Exposed to Vinyl Chloride as Predicted from Studies in Rats", Toxicol. Appl. Pharmacol., Vol. 49, pp. 15-21 (1979).
CMA 014448
79
Hatch 1981: Hatch, M., 3. Kline, and A. Stein, "Power Considerations in Studies of Reproductive Effects of Vinyl Chloride and Some Structural Analogs", Environ. Health Perspect., Vol. 41, pp. 195-201 (1981).
HCG 1981: Compressed Gas Association, Inc., Handbook of Compressed Gases, second edition, Van Nostrand Reinhold Company, New York, NY (1981).
Heath 1977: Heath, C.W., C.R. Dumont, 3. Gambler, and R.3. Waxweller, "Chromosomal Damage in Men Occupationally Exposed to Vinyl Chloride Monomer and Other Chemicals", Environ. Res., Vol. 14, pp. 68-72 (1977).
Hehir 1981; Hehir, R.M., B.P. McNamara, 3. 3r. McLaughlin, D.A. Willigan, G. Bierbower, 3.F. Hardisty, "Cancer Induction Following Single and Multiple Exposures to a Constant Amount of Vinyl Chloride Monomer", Environ. Health Perspect., Vol. 41, pp. 63-67 (1981).
HMR 1978: Association of American Railroads, Hazardous Materials Regulations of the Department of Transportation, Washington, DC (1978).
ICF 1974: ICF, Vinyl Chloride; A Case Study of the New Occupational Health Hazard, Geneva, Switzerland (1974).
INRS 1975: Truhaut, R. and 3. Berrod, "Les risques toxiques et cancerogenes du chlorure de vinyle", INRS, Cahiers de Notes Documentaires, No. 80, pp. 365-385 (1975).
Kirk-Othmer 1983; Kirk-Othmer Encyclopedia of Technology, 3rd edition, Vol. 23, 3ohn Wiley <Sc Sons, New York (1983).
Laval 1981; Association Between Birth Defects and Exposure to Ambient Vinyl Chloride, Laval University, for U.S. Environmental Protection Agency, Washington, DC, PB 81238883 (1981).
Lefevre 1980: Lefevre, M.3. and E.O. Becker, First Aid Manual for Chemical Accidents For Use with Nonpharmaceutical Chemicals, Dowden, Hutchinson, and Ross, Inc., Stroudsburg, PA (1980).
Lilis 1981: Llis, R., "Review of Pulmonary Effects of Poly(vinyl Chloride) and Vinyl Chloride Exposure", Environ. Health Perspect., Vol. 41, pp. 167-169 (1981).
Little 1983: Schwope, A.D., P.P. Costas, 3.P. 3ackson, and D.3. Weitzman, Guidelines for the Selection of Chemical Protective Clothing, A.D. Little Inc. for U.S. Environmental Protection Agency, Washington, DC (1983).
MacGregor 1980; Canadian Transport Commission, Railway Transport Committee, Western Division, Report on Inquiry into Derailment of CNR Train B806QM09 on 10 March 1980 at Deer, Manitoba, Otherwise Referred to as "The MacGregor Derailment", Saskatoon, Saskatchewan, Case No. WDR-8/80 (19 September 1980).
Maltoni 1981; Maltoni, C., G. Lefemine, A. Ciliberti, G. Cotti, and D. Carretti, "Carcinogenicity Bioassays of Vinyl Chloride Monomer: A Model of Risk Assessment on an Experimental Basis", Environ. Health Perspect., Vol. 41, pp. 3-29 (1981).
CMA 014449
80
Matheson 1974: Matheson Gas Products, The Matheson Unabridged Gas Data Book, Lyndhurst, NJ (1974).
Matheson 1980: Braker, W. and A.L. Mossman, Matheson Gas Data Book, Matheson Inc., Lyndhurst, NJ (1980).
MCA 1972; Manufacturing Chemists Association, Chemical Safety Data Sheet, Washington, DC (1972).
Merck 1976; Windholz, M., S. Budavari, L.Y. Stroumtsos, and M.N. Fertig, (eds), The Merck Index, ninth edition, Merck <Jc Co. Inc., Rahway, NJ (1976).
MSA 1982: MSA Corporation, Vinyl Chloride Monomer, Pittsburgh, PA (1982).
NFPA 1978; National Fire Protection Association, Fire Protection Guide on Hazardous Materials, seventh edition, Boston, MA (1978).
NIOSH 1974; National Institute for Occupational Safety and Health, An Evaluation of Organic Vapor Respirator Cartridges and Canisters Against Vinyl Chloride, Cincinnati, OH, PB 273881 (1974).
NIOSH 1977; National Institute for Occupational Safety and Health, Manual of Analytical Methods, second edition, Vol. 1, P&CAM 178, Cincinnati, OH (April, 1977).
NIOSH Standard 1974; U.S. Department of Health, Education and Welfare, NIOSH Recommended Standard for Occupational Exposure to Vinyl Chloride, National Institute for Occupational Safety and Health, Cincinnati70H( 1974).
NIOSH/OSHA Bulletin 1978; U.S. Department of Health, Education and Welfare, National Institute for Occupational Safety and Health, U.S. Department of Labour, Occupational Safety and Health Administration, Joint NIOSH/OSHA Current Intelligence Bulletin 28: Vinyl Halides - Carcinogenicity, NIOSH Publication No. 79-102, Cincinnati, OH (September, 1978).
NIOSH/OSHA 1981; U.S. Department of Health and Human Services, National Institute for Occupational Safety and Health (NIOSH), U.S. Department of Labor, Occupational Safety and Health Administration (OSHA), Occupational Health Guidelines for Chemical Hazards, NIOSH Publication No. 81-123 (198TL
NTIS 1981; National Technical Information Service, Toxicity of Vinyl Chloride, 1969 -May 1981 (Citations from the NTIS Data Base), Springfield, VAj PB 81-fc064d8 (1981).
OHM-TADS 1981; Oil and Hazardous Materials Technical Assistance Data System, U.S. Environmental. Protection Agency, Oil and Special Materials Control Division, Office of Water Program Operations, Washington, DC (1981).
Ontario Tentative Standards 1982: Ontario Ministry of the Environment, List of Tentative Standards, Guidelines and^rovlsional Guidelines for Air Contaminants as of January 1982, Air Resources Branch, Toronto, Ontario (19S2T,
CMA 014450
81
Ont. Reg. 1982; Ontario Ministry of Labour, Regulation Respecting Vinyl Chloride - Made Under the Occupational Health and Safety Act, Revised Statutes of Ontario, 1980, Chapter 321, Toronto, Ontario (July, 1982).
OSHA 1974: Occupational Safety and Health Administration, Proposed Regulation: Vinyl Chloride, Washington, DC, PB 297005 (1974).
Patty 1981: Clayton, G.D. and F.E. Clayton, (eds), Patty's Industrial Hygiene and Toxicology, Vols. 2A, 2B, Third Revised Edition, John Wiley and Sons Canada Limited, Toronto, Ontario (1981).
PPH 1974: Gallant, R.W., Physical Properties of Hydrocarbons, Gulf Publishing Company, Houston, TX (1974).
PTP 1980: Sittig, M. (ed.), Priority Toxic Pollutants, Health Impacts and Allowable Limits, Noyes Data Corp., NJ (1980).
Quebec 1979: Cabinet du Lieutenant-Gouverneur, Gazette officielle du Quebec; Partie 2, Lois et reglements, L^diteur Off iciel du Quebec (Novembre, 1979).
Radike 1981: Radike, M.J., L.K. Stemmer, and E. Bingham, "Effects of Ethanol on Vinyl Chloride Carcinogenesis", Environ. Health Perspect., Vol. 41, pp. 59-82 (1981).
Raj 1974: Raj, P.P.K. and A.S. Lakekar, Assessment Models in Support of Hazard Assessment Handbook, Prepared for the Department of Transportation, U.S. Coast Guard, Washington, DC, p. 238 (January, 1974).
Rosenstock 1977: Rosenstock, H.M., K. Draxl, B. Steiner and J.T. Herron, Energetics of Gaseous Ions, National Bureau of Standards, Washington, DC (1977).
RTDCR 1974: Canadian Transport Commission, Regulations for the Transport of
Dangerous Commodities by Rail, Published by Supply and Services Canada, Ottawa, Ontario (1974).
RTECS 1979: Lewis, R.J. and R.L. Tatken, Registry of Toxic Effects of Chemical Substances, 1979, Vols. 1 and 2, National Institute for Occupational Safety and Health (NIOSH), Cincinnati, OH (September, 1980).
Saskatchewan 1981: Saskatchewan Ministry of Labour, Occupational Health and General Regulations, Occupational Health and Safety Branch, Regina, Saskatchewan (May, 1981).
Sax 1979: Sax, N.I., Dangerous Properties of Industrial Materials, fifth edition, Van Nostrand Reinhold Company, New York, NY (1979).
5CC 1976: Arnold, E.J., Technical Aspects of Vinyl Chloride in the Environment, prepared for the Science Council of Canada (May, 1976).
5CC 1981: Phillips, M.J., Medical Aspects of Vinyl Chloride, prepared for the Science Council of Canada (June, 1981).
Scott 1979: Scott's Industrial Directory of Ontario Manufacturers, 12th edition, Penstock
Directories Limited, Oakville, Ontario (1979).
~~
CMA 014451
32
Senate 1974; Hearing Before the Subcommittee on Environment of the Committee on
Commerce, United States Senate, Ninety-third Congress, Second Session on Dangers of
Vinyl Chloride, U.5. Government Printing Office, Washington. DC (1974).
"
SOEHS 1975; Taylor, W., Technical Bulletin No. 7, Vinyl Chloride Monomer: A Review, Scottish Occupational and Environmental Health Service Ltd., Dundee, Scotland (April, 1975).
Sussex 1977: Pedley, J.B. and J. Rylance, Sussex-N.P.L. Computer Analysed
Thermochemical Data: Organic and Organometallic Compounds, University of Sussex, Sussex, Brighton, England (1977).
TCM 1979: General American Transportation Corporation, Tank Car Manual, Chicago. IL (May, 1979).
TDB (on-line) 1981: Toxicity Data Base, Toxicology Information On-Line, available from National Library of Medicine, Washington, DC (1981).
TDGC 1980; Transport Canada, Transportation of Dangerous Goods Code, Vol. 1 (Lists), Vol. 2, Ottawa, Canada (June, 1980^
TLV 1983: American Conference of Governmental Industrial Hygienists, TLV*s Threshold Limit Values for Chemical Substances and Physical Agents in the Workroom Environment with Intended Changes for 1983, Cincinnati, OH (1983).
TSA 1980: Shuckrow, A.J., A.P. Pajak, and J.W. Osheka, Concentration Technologies for Hazardous Aqueous Waste Treatment, Touhill, Shuckrow and Associates, Inc., Pittsburgh, PA (1980).
Ullmann 1975: Ullmanns Encyklopaedie der technischen Chemie, Verlag Chemie, Weinheim (1975).
USDOL MSDS 1978: U.S. Department of Labour, Material Safety Data Sheet, "Vinyl Chloride Monomer", PPG Industries Inc., Pittsburgh, PA (March, 1978).
USDHEW 1981: U.S. Department of Health and Human Services, Second Annual Report on Carcinogens, National Toxicology Program, U.S. Public Health Service, Washington, DC (1981).
VCM 1982: PPG Industries Inc., Vinyl Chloride Monomer: Handling and Properties, Natrium, WV (1982).
VCT 1980: U.S. Department of Health and Human Services, Vinyl Chloride Technology, Literature Search No. 80-8, National Library of Medicine, Washington, DC (1980).
Verschueren 1984: Verschueren, K., Handbook of Environmental Data on Organic
Chemicals, Van Nostrand Reinhold Company, New York, NY (1984).
TM"~
Weber 1981: Weber, H., W. Reini and E. Greiser, "German Investigations on Morbidity and Mortality of Workers Exposed to Vinyl Chloride", Environ. Health Perspect., Vol. 41, pp. 95-99 (1981).
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83
12.2 Bibliography
Air Pollution Control Directorate, Emissions of Vinyl Chloride to the Ambient Air Around Manufacturing Facilities in Ontario, Fisheries and Environment Canada, Ottawa, Canada, EPS 5-AP-77-14 (1978).
Ambient Water Quality Criteria: Vinyl Chloride, U.S. Environmental Protection Agency, Washington, DC (1978).
Ambient Water Quality Criteria for Vinyl Chloride, U.S. Environmental Protection Agency, Washington, DC, PB 81-117889, EPA 440/5-80-078.
American Conference of Governmental Industrial Hygienists (ACGIH), Documentation of Threshold Limit Values, fourth edition, Cincinnati, OH (1981).
American Conference of Governmental Industrial Hygienists, TLV*s Threshold Limit Values for Chemical Substances and Physical Agents in the Workroom Environment with Intended Changes for 1983,'Cincinnati, OH (1983).
American Water Works Association, Standard Methods for the Examination of Water and Waste Water, 15th Edition, American Public Health Association, Washington, DC., Method 503B (1981).
"An Overview of the Vinyl Chloride Hazard in Canada", Chemistry in Canada, pp. 24-37 (Summer, 1977).
Apfeldorf, R. and P.F. Infante, "Review of Epidemiologic Study Results of Vinyl ChlorideRelated Compounds", Environ. Health Perspect., Vol. 41, pp. 221-226 (1981).
Arnold, E.J., Technical Aspects of Vinyl Chloride in the Environment, prepared for the Science Council of Canada (May, 1976).
Association Between Birth Defects and Exposure to Ambient Vinyl Chloride, Laval University, for U.S. Environmental Protection Agency, Washington, DC, PB 81-238883 (1981).
Association of American Railroads, Hazardous Materials Regulations of the Department of Transportation, Washington, DC (1978).
Bauer, W.H. et al., Agents, Methods and Devices for Amelioration of Discharge of Hazardous Chemicals on Water, Rensselaer Polytechnic Institute for the U.S. Coast Guard, Washington, DC, CG-D-38-76 (August, 1975).
BDM Corporation, The AAR Hazardous Materials Data Base, prepared for the Association of American Railroads, Parts I and II, McLean, VA (May, 1981).
Braker, W. and A.L. Mossman, Matheson Gas Data Book, Matheson Inc., Lyndhurst, NJ (1980).
Bretherick, L., Handbook of Reactive Chemical Hazards, second edition, Butterworths, London, England (1979).
CMA 014453
84
Cabinet du Lieutenant-Gouverneur, Gazette officielle du Quebec; Partie 2, Lois et reglements, fEditeur Officiei du Quebec (Novembre, 1979).
The Canadian Chemical Producers' Association, List of Members, Toronto, Ontario (1983).
Canadian Transport Commission, Railway Transport Committee, Western Division, Report on Inquiry into Derailment of CNR Train B806QM09 on 10 March 1980 at Deer, Manitoba, Otherwise Referred to as "The MacGregor Derailment", Saskatoon, Saskatchewan, Case No. WDR-8/80 (September 19, 1980).
Canadian Transport Commission, Regulations for the Transport of Dangerous Commodities by Rail, Published by Supply and Services Canada, Ottawa, Ontario (1974).
Chemical Industries Association Limited, The Determination of Vinyl Chloride; A Plant Manual, London (1977).
Clayton, G.D. and F.E. Clayton, (eds.), Patty's Industrial Hygiene and Toxicology, Vols. 2A, 2B, Third Revised Edition, John Wiley and Sons Canada Limited, Toronto, Ontario (1981).
Compressed Gas Association, Inc., Handbook of Compressed Gases, second edition, Van Nostrand Reinhold Company, New York, NY (1981).
Corpus Information Services Ltd., "Vinyl Chloride", Chemical Product Profiles, Don Mills, Ontario (April, 1983).
Dangerous Properties of Industrial Materials Report, "Vinyl Chloride", pp. 85-87 (JanuaryFebruary, 1981).
M.M. Dillon, Survey of Countermeasures Systems for Hazardous Material Spills, Environment Canada,Ottawa,Canada(1982).
Doniger, D.A., The Law and Policy of Toxic Substances Control, A Case Study of Vinyl Chloride, John Hopkins University Press, Baltimore, MD (1978).
Dow Chemical Canada Inc., Emergency Response Information Sheet, Sarnia, Ontario (1981).
Dow Chemical Canada Inc., Material Safety Data Sheet, Sarnia, Ontario (27 June 1980).
Dow Chemical Company, Dow Chemical Resistance Guide for Dow Plastic Lined Piping Products, Midland, MI (1978).
Dow Chemical Company, Dow Plastic Lined Valves, Midland, MI (1972).
Dynamic Behaviour of Vinyl Chloride in Aquatic Ecosystems, U.S. Environmental Protection Agency, Washington, DC, EPA 600/3-76-001 (1976).
Fabricant, J.D. and M.S. Legator, "Mutagenicity Studies of Vinyl Chloride", Environ. Health Perspect., Vol. 41, pp. 189-193 (1981).
CMA 014454
85
Gallant, R.W., Physical Properties of Hydrocarbons, Gulf Publishing Company, Houston, TX (1974).
Gehring, P.3., B.E. Watanabe, and C.N. Park, "Risk of Angiosarcoma in Workers Exposed to Vinyl Chloride as Predicted from Studies in Rats", Toxicol. Appl. Pharmacol., Vol. 49, pp. 15-21 (1979).
General American Transportation Corporation, Tank Car Manual, Chicago, IL (May, 1979).
General Electric Company, Material Safety Data Sheets, "Vinyl", Material Safety Information Services, Schenectady, NY (August, 1978).
Hatayama, H.K., 3.3. Chen, E.R. deVera, R.D. Stephens, and D.L. Storm, A Method for Determining the Compatibility of Hazardous Wastes, Municipal Environmental Research Laboratory, Office of Research and Development, U.S. Environmental Protection Agency, Cincinnati, OH (April, 1980).
Hatch, M., 3. Kline, and A. Stein, "Power Considerations in Studies of Reproductive Effects of Vinyl Chloride and Some Structural Analogs", Environ. Health Perspect., Vol. 41, pp. 195-201 (1981).
Hearing Before the Subcommittee on Environment of the Committee on Commerce, United States Senate, Ninety-third Congress, Second Session on Dangers of Vinyl Chloride, U.S. Government Printing Office, Washington, D.C. (1974).
Heath, C.W., C.R. Dumont, 3. Gambler, and R.3. Waxweller, "Chromosomal Damage in
Men Occupationally Exposed to Vinyl Chloride Monomer and Other Chemicals", Environ. Res., Vol. 14, pp. 68-72 (1977).
Hehir, R.M., B.P. McNamara, 3. 3r. McLaughlin, D.A. Willigan, G. Bierbower, and 3.F. Hardisty, "Cancer Induction Following Single and Multiple Exposures to a Constant Amount of Vinyl Chloride Monomer", Environ. Health Perspect., Vol. 41, pp. 63-67 (1981).
ICF, Vinyl Chloride; A Case Study of the New Occupational Health Hazard, Geneva, Switzerland (1974).
Kirk-Othmer Encyclopedia of Technology, 3rd edition, Vol. 23, 3ohn Wiley Sc Sons, New
York ("983).--------
---------------------
Lefevre, M.3. and E.O. Becker, First Aid Manual for Chemical Accidents - For Use with Nonpharmaceutical Chemicals, Dowden, Hutchinson, and Ross, Inc., Stroudsburg, PA (1980).
Leichnitz, K. (ed.), "Air Investigations and Technical Gas Analysis with Drager Tubes", Detector Tube Handbook, fourth edition, Lubeck, Germany, p. 156 (1979).
Lewis, R.3. and R.L. Tatken, Registry of Toxic Effects of Chemical Substances, 1979, Vols. 1 and 2, National Institute for Occupational Safety and Health (NIOSH), Cincinnati, OH (September, 1980).
CMA 014455
86
Lilis, R., "Review of Pulmonary Effects of Poly(vinyl Chloride) and Vinyl Chloride Exposure", Environ. Health Perspect., Vol. 41, pp. 167-169 (1981).
Lowenheim, F.A. and M.K. Moran, Faith, Keye's and Clark's Industrial Chemicals, WileyInterscience, New York, NY (1975).
Maltoni, C., G. Lefemine, A. Ciliberti, G. Cotti, and D. Carretti, "Carcinogenicity Bioassays of Vinyl Chloride Monomer: A Model of Risk Assessment on an Experimental Basis", Environ. Health Perspect., Vol. 41, pp. 3-29 (1981).
Manufacturing Chemists Association, Chemical Safety Data Sheet, Washington, DC (1972).
Matheson Gas Products, The Matheson Unabridged Gas Data Book, Lyndhurst, NJ (1974).
MSA Corporation, Vinyl Chloride Monomer, Pittsburgh, PA (1982).
National Association of Corrosion Engineers, Corrosion Data Survey, Houston, TX (1967).
National Emission Standards for Hazardous Air Pollutants, Inspection Manual for Vinyl Chloride, U.S. Environmental Protection Agency, Washington, DC, PB-289-778 (1978).
National Fire Protection Association, Fire Protection Guide on Hazardous Materials, Seventh Edition, Boston, MA (1978).
National Institute for Occupational Safety and Health, Manual of Analytical Methods, Second Edition, Vol. 1, PicCAM 178, Cincinnati, OH (April, 1977).
National Institute for Occupational Safety and Health, An Evaluation of Organic Vapor Respirator Cartridges and Canisters Against Vinyl Chloride, Cincinnati, OH, PB 273881 (i"974y.
National Technical Information Service, Toxicity of Vinyl Chloride, 1969 - May 1981 (Citations from the NTIS Data Base), Springfield, VA, PB 81-806408 (1981).
News/Update, Canadian Chemical Processing, Vol. 66, No. 1, p. 14 (February 19, 1982).
Occupational Safety and Health Administration, Proposed Regulation: Vinyl Chloride, Washington, DC, PB 297005 (1974).
Oil and Hazardous Materials Technical Assistance Data System, U.S. Environmental Protection Agency, Oil and Special Materials Control Division, Office of Water Program Operations, Washington, DC (1981).
Ontario Ministry of Labour, Regulation Respecting Vinyl Chloride - Made Under the Occupational Health and Safety Act, Revised Statutes of Ontario, 1980, Chapter 321, Toronto, Ontario (July, 1982).
Ontario Ministry of the Environment, List of Tentative Standards, Guidelines and Provisional Guidelines for Air Contaminants as of January 1982, Air Resources Branch, Toronto, Ontario (1982).
CMA 014456
87
Pedley, J.B. and J. Rylance, Sussex-N.P.L. Computer Analysed Thermochemical Data: Organic and Organometallic Compounds, University of Sussex, Sussex. Brighton. England
(TO
Phillips, M.J., Medical Aspects of Vinyl Chloride, prepared for the Science Council of Canada (June, 1981).
Pilie, R.J. et al., Methods to Treat, Control and Monitor Spilled Hazardous Materials, U.S. Environmental Protection Agency, National Environmental Research Center, Cincinnati, OH, EPA 670/2-75-042 (June, 1975).
PPG Industries Inc., Vinyl Chloride Monomer: Handling and Properties. Natrium. WV
(1982).
----- -------------------------------------------------------------------- -------
Preliminary Assessment of the Environmental Problems Associated with Vinyl Chloride
and Polyvinyl Chloride, U.S. Environmental Protection Agency, Washington, DC, PB-239110 (1974).
Radike, M.J., K.L. Stemmer, and E. Bingham, ''Effects of Ethanol on Vinyl Chloride Carcinogenesis", Environ. Health Perspect., Vol. 41, pp. 59-82 (1981).
Raj, P.P.K. and A.S. Lakekar, Assessment Models in Support of Hazard Assessm nt Handbook, Prepared for the Department of Transportation, U.S. Coast Guard, Washington, DC, p. 238 (January, 1974).
Rosenstock, H.M., K. Draxl, B. Steiner, and J.T. Herron, Energetics of Gaseous Ions, National Bureau of Standards, Washington, DC (1977).
Saskatchewan Ministry of Labour, Occupational Health and General Regulations, Occupational Health and Safety Branch, Regina, Saskatchewan (May, 1981).
Sax, N.I., Dangerous Properties of Industrial Materials, fifth edition, Van Nostrand Reinhold Company, New York, NY (1979).
Scott's Industrial Directory of Ontario Manufacturers, 12th edition, Penstock Directories Limited, Oakville, Ontario (1979).
Schwope, A.D., P.P. Costas, J.P. Jackson, and D.J. Weitzman, Guidelines for the Selection of Chemical Protective Clothing, A.D. Little Inc. for U.S. Environmental Prot ction Agency, Washington, DC (1983).
Scientific and Technical Assessment Report on Vinyl Chloride and Polyvinyl Chloride, U.S. Environmental Protection Agency, Washington, DC, PB-249-461 (1975).
Shuckrow, A.J., A.P. Pajak, and J.W. Osheka, Concentration Technologies for Hazardous Aqueous Waste Treatment, Touhill, Shuckrow and Associates, Inc., Pittsburgh, PA (1980).
Sittig, M. (ed.), Priority Toxic Pollutants, Health Impacts and Allowable Limits, Noyes Data Corp., NJ (1980).
The So-Called Vinyl Chloride Disease, U.S. Environmental Protection Agency, Washington, DC, PB-258-838-t (1975).
CMA 0X4457
88
Southam Business Publications Ltd., "1981 Chemical Buyers' Guide", Canadian Chemical Processing, Vol. 64, No. 9, Don Mills, Ontario (December, 1980).
"Specific Monsanto Plant Worksites a Factor in Workers' Cancer Deaths?", Canadian Occupational Health and Safety News, Vol. 5, No. 6, p. 6 (February, 1981).
Standard Support and Environmental Impact Statement: Emission Standard for Vinyl Chloride, U.S. Environmental Protection Aeencv. Washington. DC. EPA 450/2-75-009 0975).
Standard Support and Environmental Impact Statement, Volume 2: Promulgated Emission Standard for Vinyl Chloride, U.S. Environmental Protection Agency, Washington, DC, PB258-827 (1976).
Taylor, W., Technical Bulletin No. 7, Vinyl Chloride Monomer; A Review. Scottish Occupational and Environmental Health Service Ltd., Dundee, Scotland (April, 1975).
Toxicity Data Base, Toxicology Information On-Line, Available from National Library of Medicine, Washington, DC (1981).
Transport Canada, Transportation of Dangerous Goods Code, Vol. 1 (Lists), Vol. 2, Ottawa, Canada (June, 1980)1
Treatability Manual, Volume V, Summary, U.S. Environmental Protection Agency, Office of Research and Development, Washington, DC, EPA 600/8-80-042E (July, 1980).
Truhaut, R., Berrod, J., "Les risques toxiques et cancerogenes du chlorure de vinyle", INRS, Cahiers de notes documentaires, No. 80, pp. 365-385 (1975).
Ullmanns Encyklopaedie der technischen Chemie, Verlag Chemie, Weinheim (1975).
U.S. Department of Health and Human Services, National Institute for Occupational Safety and Health (NIOSH), U.S. Department of Labor, Occupational Safety and Health Administration (OSHA), Occupational Health Guidelines for Chemical Hazards, NIOSH Publication No. 81-123 (1981).
U.S. Department of Health and Human Services, Second Annual Report on Carcinogens, National Toxicology Program, U.S. Public Health Service, Washington, DC (1981).
U.S. Department of Health, Education and Welfare, NIOSH Recommended Standard for Occupational Exposure to Vinyl Chloride, National Institute for Occupational Safety and Health, Cincinnati, OH (1974).
U.S. Department of Health, Education and Welfare, National Institute for Occupational Safety and Health, U.S. Department of Labour, Occupational Safety and Health Administration, Joint NIOSH/OSHA Current Intelligence Bulletin 28; Vinyl Halides Carcinogenicity, NIOSH Publication No. 79-102, Cincinnati, OH (September, 1978).
U.S. Department of Health and Human Services, Vinyl Chloride Technology, National Library of Medicine, Literature Search, No. 80-8, Washington, DC (1980).
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U.S. Department of Labour, Material Safety Data Sheet, "Vinyl Chloride Monomer", PPG Industries Inc., Pittsburgh, PA (March, 1978). U.S. Department of Transportation, CHRIS Hazard Assessment Handbook, U.S. Coast Guard, Washington, DC, CG-446-3 (April, 1974). U.S. Department of Transportation, Emergency Action Guide for Selected Hazardous Materials, Research and Special Programs Administration, Materials Transportation Bureau, Washington, DC (1978). U.S. Department of Transportation, Hazardous Materials, 1980 Emergency Response Guidebook, Research and Special Programs Administration, Materials Transportation Bureau, Washington, DC (1980). U.S. Department of Transportation, Coast Guard, Chemical Hazards Response Information System (CHRIS), Washington, DC (1978). Verschueren, K., Handbook of Environmental Data on Organic Chemicals, Van Nostrand Reinhold Company, New York, NY (1984). Weast, R.C. (ed.), CRC Handbook of Chemistry and Physics, 60th Edition, Chemical Rubber Publishing Company, Cleveland, OH (1980). Weber, H., W. Reini, and E. Greiser, "German Investigations on Morbidity and Mortality of Workers Exposed to Vinyl Chloride", Environ. Health Perspect., Vol, 41, pp. 95-99 (1981). Windholz, M., S. Budavari, L.Y. Stroumtsos, and M.N. Fertig, (eds.), The Merck Index, Ninth Edition, Merck <Sc Co. Inc., Rahway, NJ (1976). Workers' Compensation Board of British Columbia, Industrial Health and Safety Regulations, Workers' Compensation Act, Vancouver, British Columbia (July, 1980).
CMA 014459
BOD b.p. CC cm CMD COD cone c.t. eV
g ha Hg IDLH
Imp. gal. in. 3
kg kJ km kPa kt L lb.
LC50
lclo
LD50 LDLO LEL LFL m m M MAC
max mg MIC
min mm
Mg ym
EnviroTIPS Common Abbreviations
biological oxygen demand boiling point closed cup centimetre count median diameter chemical oxygen demand concentration critical temperature electron volt gram hectare mercury immediately dangerous to
life and health imperial gallon inch joule kilogram kilojoule kilometre kilopascal kilotonne litre pound lethal concentration fifty lethal concentration low lethal dose fifty lethal dose low lower explosive limit lower flammability limit metre meta molar
maximum acceptable con centration
maximum milligram maximum immission
concentration minute or minimum millimetre microgram micrometre
Be MMAD
MMD m.p. MW N NAS NFPA
NIOSH
nm 0 OC P
Pc
PEL PH
Ppb ppm
Ps
psi s STEL STIL
Tc
tclo
Td
tdlo
TLm TLV Ts TWA UEL UFL VMD v/v w/w
degrees Baume (density) mass median aerodynamic
diameter mass median diameter melting point molecular weight newton National Academy of Scien< National Fire Protection
Association National Institute for
Occupational Safety and Health nanometre ortho open cup para critical pressure permissible exposure level measure of acidity/ alkalinity parts per billion parts per million standard pressure pounds per square inch second short-term exposure limit short-term inhalation limit critical temperature toxic concentration low decomposition temperature toxic dose low median tolerance limit Threshold Limit Value standard temperature time weighted average upper explosive limit upper flammability limit volume mean diameter volume per volume weight per weight
CMA 014460