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INTEROFFICE MEMORANDUM KBceweo 0CT U ^77 1977 V>V/ O1 To T. L. Carey From J. T, Barr cc: R. Burnham D. Francke R. Gilbert C. A. Hefberger R. McGinnis J. Novak E. Primeau F. Riddle J. Russell R. Schenck ~T~T W. Silowka W. M. Smith W. Stuben L. Tepper 0. Ward (ut Date--------13. October 1977 ----- V-invl Chloride Safety Association Meetlng October fi. 1977. (Location. Organisation, or Ooparimant) (Location, Organisation, or Dapartmnni] The Vinyl Chloride Safety Association held its annual meeting at Valley Forge, Penna., on October 6-7, 1977. A total of 83 persons from 32 companies attended, with 13 of the companies being outside the U.S*. This was a record attendance In both categories. Attendees from Air Products were the writer and Dale Francke and 01m Russell. The officers elected for next year were: Chairman, Vice-Chairman, Secretary, Program Treasurer H. Waltanatq, Goodrich H. Lloyd, Georgia Pacific H. Olsen, Ethyl J. Flores, Gt. American R. Hager, Stauffer In a general discussion of the alms of the Association it was concluded that no major changes were needed. A copy of the by-laws will be circulated to all members for review. A copy of the agenda is attached, and a brief review of each subject Is given below. PHYSICOLOGICAL EFFECTS Dr. R. W. McBurney of Diamond-Shamrock discussed the hazards of vlnly chloride. He described it as a relatively non-toxic narcotic which could cause death from arythmia in high doses. It is detoxified In the liver by sulfhydryl-bearing enzymes, and the chief target of the metabolites is'trte lining of the small blood vessels. This leads to two types of disease. Scleroderma is a reversible result of small vessel (3201 AP00028832 TO: Mr. T. L. Carey -2- Vinyl Chloride Safety Assoc. Meeting, October 6, 1977 plugging which is seen more In Europe than In the U.S. In a few especially susceptible people it can cause sensitivity to cold (Reynaulds Phenomena) and if the bone tufts are starved, resorption of the bone, resulting in finger clubbing, called acroosteolysis. It can also cause liver fibrosis, or cirrhosis, and enlargement of the spleen from high portal vein pressure. The above symptons are relatively rare. Even rarer Is angiosarcoma, a cancer of the liver blood vessel lining. The body seems to detoxify low doses safely, but at higher dosages the primary metabolic pathway Is swamped and attack on the body occurs from secondary metabolites. This disease Is very rare, about 25 cases per year In the U. S. It is sometimes seen In Infants, and can also be caused by arsenic and thorium Chemotheraphy is not effective, and It usually occurs at multiple sites In the liver and Is not operable. It would be reasonable to expect sarcomas at other sites as well as the liver, If this mechanism Is correct. He expressed the opinion that the threshold for rats to develop cancer was about 35 ppm, and felt that anything below 15 ppm was safe for humans, thus most of the effort spent on OSHA and EPA compliance Is a waste. About one person in 3400 develops cancer at high exposures, and he postulated a genetic predisposition to the disease. He further said that no medical screening program can be really effective, because there are no early warning signs. The normal population has 15-20X "abnormal** blood tests. Diamond-Shamrock returns men to VC exposure with 2 abnormal results In the SMA - 12 blood test if their liver scan Is normal. They do not perform a biopsy on employees, but refer them to their own physicians. Medical Surveillance H. Lloyd, of Georgia-Pacific led a discussion of medical surveillance practices. All companies have similar preplacement medical exams, and generally use the same tests as In their annual re-exam. Many report problems with alcohol consumption before the tests. Treatment .after an "emergency" was not consistent between companies. Some give blood tests, although they are not sure why. Even the definition of an emergency was not uniform, although most held that exposure to greater than 100 ppm without breathing protection as a definition. The employment of women of child-bearing capacity Is still an unsettled topic. About two-thirds do not permit them In exposure areas. Most companies make the annual re-exam a condition of employment, but where this rule has been challenged by an employee, the company has lost. Many have consolidated the VC exam and their routine physicals, especially where the company examines all employees. The average cost per employee was about $100. Some have eliminated one of the x-ray tests for employees with two exams/yr. AP00028833 TO: T. L. Carey -3- Vinyl Chloride Safety Assoc. Meeting, October 6, 1977 Chromosome Studies Per Ranges,of Norsk Hydro, gave a report on a recheck of their chromosome breakage study of 3'years ago. In the original study, they found that heavily exposed workers had a breakage count of about 4%, compared to 1.8* for controls. They repeated the study this year, three years after heavy exposure ceased, and found that carefully matched controls had 1.2% breakage and workers had 1.6%. They assume from this that the damage is reversible. He was asked to transmit this to SPI and MCA as soon as the report Is formalized. OSHA ENFORCEMENT H. Waltemate of Goodrich reported on four OSHA inspections at their plants which all occurred in the first week of August of this year. The Calvert City plant had a general KOSHA Inspection and received 15 citations, all non-serious, with 2 penalties totalling $100. The Long Beach plant was inspected by CALOSHA, with sampling being done for VC, benzene, lead, noise, dust and ammonia. This was prompted by the "Gregario Amendment", a new law on carcinogens passed this summer. They expect to receive citations for a respirator on which they had changed the connector and thus nullified the NICJH certification* .in employee with a beard (whom they claimed could not get a good respirator fit), drinking coffee in a regulated area, and an Improper dust mask in the compound area, where dust levels were high. The Louisville plant had a 12 day inspection* prompted by an employee complaint. They expect no citations there. The problem was that their employees do not believe the published results of the monitoring program, and want an independent check on exposures. Hooker said they have the same problems, but most companies reported otherwise. Their Pedricktown plant reported two massive releases in three weeks just before the inspection. A four day visit Included sampling for VC, Cadmium, carbon bldck, and noise. They expect citations for dust and an improper respirator in the compound area. * Waltemate offered to act as a clearing house for citations and policy letters from OSHA. Those having information of general interest can send those items to him, and he will circulate them to the group. Pantasote was cited and fined for storage of tankcar outside their regulated area. They now have the City Police patrol a section of track for them. AP00028834 TO: T. 1. Carey -4- Vinyl Chloride Safety Assoc. Meeting, October 6, 1977 Tenneco has had 19 inspections In two years, 13 of which included monitoring tests. They have received two citations. Borden was cited when OSHA sampling showed exposures of men In masks to 1.5 and 3 ppm. They were also refused the OSHA data, and were told that the decision was made In Washington. Stauffer contested a citation for an exposure over 25 ppm. The alleged number was reduced, then the citation dropped. Several companies have been told that employee complaints account for 60 - 701 of all inspections, and have a very high priority. Most companies contest their citations routinely to reduce the probability of serious repeat violations. Four companies use only area monitoring to calculate employee exposure, and seven use a conblnation of area and personal monitoring. The average concentration of the reactor area was Indicated to be as follows: below 0.5 ppm 0.5 - 1.0 1.0 - 2.0 2.0 - 5.0 2 companies 6 companies 8 companies 8 companies No one admitted to an average over 5. Goodrich did not establish a regulated area around their hew large reactors at Louisville. They have been inspected twice, with no comnents. No one is using the LSU badge-type personal monitor at present, although ICI and DOW are testing it, and preliminary results are good. A show of hands indicated that essentially all plants experienced ten or more excursions per month over 5 ppm, and many go above 25 ppm on occasions. Pimps and compressors are still the major sources of leaks. Great American reports more than a year of satisfactory service on their sealed pump. More companies alarm at 5 ppm than any other value. Most also use the zone alarm method, as do we, and the majority use both lights aad audible alarms. EPA UPDATE D. Kuhn of Conoco reviewed the EPA situation. No new information was presented except that Region 6 has questionnaires out on fugatlve emissions and controls, and that EPA has a contractor Inplant at DOW working on the same problem. A Firestone reported that Maryland is setting a fence-line limit on emissions. Massachusetts has also done so In at least one case, and Texas is proposing a similar rule, along with emission limits below that of the Federal EPA. AP00028835 TO: T. L. Carey -5- Vinyl Chloride Safety Assoc. Meeting, October 6, 1977 EMISSION CONTROL METHODS The writer led a discussion of the methods of disposal of vinyl chloride. An outline is attached. Twenty seven companies are using incinerators, four carbon beds, and two use solvent extraction. In a discussion on frequency of opening large storage vessels, the minimum frequency seemed to be about three years, with many taking five to seven years, Of longer. Only British Plastics reported any evidence of any corrosion problems, and that after 5-15 years of service. VCSA HISTORY -------- G. Schaff of Goodrich reviewed the history of the group, and led a discussion of its future. Most seemed satisfied with the present arrangements. The question arose as to the time necessary to retain the tapes made of each meeting, and members were asked to get advice from their legal groups. TRANSPORTATION R. Wilson of Stauffer discussed the recent DOT rule HM144, published 15 Sept, and effective 19 October. It requires modification to existing or new uninsulated cars in the transport of hazardous liquids, including VC, EDC, ammonia, and similar products. Shelf couplers will be required by 1979 on existing, and after Jan 1st, on all new cars. Estimated cost is $1000/car. Head Shields are also required, at a cost of $3500, and weighing 1300 lbs. Insulation is required to protect against a pool fire to maintain the wall below 800F. after 100 minutes. Cost will be $5 - 10M, weight will be increased 1-8 tons, and cars will be out of service A5 - 60 days. Relief valve requirements have also been changed. The Compressed Gas Association has petitioned for a review of this requirement. Placards and shipping papers have new requirements. One change has eliminated the cancer warning from the placard, so it will now be stencilled on the car near the dome. Specific wording on the cancer hazard arrd handling methods are required on shipping papers. Midland ball float guages and Drexelbrook cpapcitance gauges have replaced the older slip gauges. P. Bogart of Tenneco urged that those who have not signed up for the mutual response group of Chentreck, do so (we have not.). He said that Congress seemed to be taking some action to consolidate the 200 - plus organizations now Involved in emergency responses. The DOT and EPA have not resolved their disagreement over shipping hazards. AP00028836 TO: T. L. CAREY -6- Vinyl Chloride Safety Assoc. Meeting, October 6, 1977. TRUE CONFESSIONS J. Alvarez of Primex described a fire in their Pueblo, Mexico plant which occurred in June. Monomer was stored in 7 bullet tanks, 5 x 90 and 2 x 60 M gals. each. On the date In question, about 2.9 MM lbs. was on hand. An experienced mechanic was removing the top works from a plug valve on the bottom of one tank, and removed the plug bonnet plate rather than the top works bracket. The plug blew out and the 3" valve vented liquid. A visible vapor cloud formed in an area about 1100 x 800 ft. by 500 ft. high, and Ignited at a neighboring plant. The liquid stream then became a torch playing on adjacent tanks which then ruptured one by one until all were destroyed. They used the ASME - UPV code for relief valve area calculations rather than the NFPA code, so had only 25* of the relief area that the latter would have furnished. They also had an Inadequate wafor supply. One man was killed and three other burned. Damage was over $3MM. The fireball of the initial Ignition destroyed the laboratory, library, and offices. Books were charred through, and bottles were melted from the heat of the fireball, but blast damage was minor. They have installed a 200 ton bullet tank and are installing a 2000 ton sphere as replacements for these tanks. To reduce hazards in the future, these tanks are insulated, and have relief valves according to the NFPA code. The pump line Is reduced to 2" size, with an excess flow valve. This reduced flow rate requires a day tank for charging. They have revised their safety program and emergency action instructions. By .a show of hands from the floor, it developed that most attendees ''d6 not know which code their plants used for reliefs. One company reported use of a special 4 way valve that allowed use of one or both attached reliefs, but would not permit both to be shut off at the same time. Ten companies use excess flow valves on storage vessels, and many commented on the unreliability of those in sizes over 4 inches. Twelve companies now have foam systems installed. Nineteen use remote pneumatic valves, and 10 have fire-safe valves in this servide. Bob Franz of Union Carbide described briefly an explosion of a bulk polymerizer in their Texas plant on Labor Day. The final investigation report has not been presented to management, and will be made available to us later. A 6000 gaT "non-solvent" reactor exploded with little or no apparent warning, burning two men who were about 75 ft. away, one of whom died later. There was severe damage in the Imnediate area, and the blast was heard 20 miles away. One large piece of the reactor was found 1600 ft. away. I was told by another Carbide employee a few days after the explosion that at that time they suspected an overcharge of Initiator. Esso of Canada reported on the corrosion failure of 304 vessels In PVC service which they told us about on our trip there earlier this year. They have seen severe corrosion adjacent to welds in their 11 yr. old clad 304 strippers. None was found in 316 equipment. Being clad, there was no vessel failure as Goodrich reported two years ago. They now make a dye penetration test every two months. Dow said that they had seen the same. AP00028837 TO: T. L. Carey -7- Vinyl Chloride Safety Assoc. Meeting, October 6, 1977 and at chloride concentrations of 10 - 40 ppm the worst rates were at pH of 3-5. They also have had ss bolts fail In the salt air in Texas. The vapor phase of their recovery system seemed to be the worst area. Dale Francke described the incident of last January in the Escambia plant. The only comment from the floor was from Goodrich, who disables automatic valves in a work area by disconnecting the air supply lines. Union Carbide reported that a reverse buckling rupture disk and knife assembly was reversed by hydraulic pressure without the knife cutting the disk, thus preventing the relieving of the disk in any future overpressure. They are going to a B S & B reverse buckling scored disk that does not require a knife. Borden said that they have three years successful experience with a scored Fike disk that does not require a knife, and have-operated within 20 pounds of the set pressure without premature failure. INJURY STATISTICS H. Waltemate of Goodrich reviewed their accident history for the past few years. He pointed out the problem with the change in the data base from ANSI to OSHA, and suggests that the VC-PVC Industry compile It? own statistics, as do other special groups. This would be done by abstracting; annually the OSHA log of injuries on the attached form, using data for the entire facility, not just PVC, and he will act as the clearing house for the data. I recommend that we cooperate in this. The Goodrich experience has been well below general industry rates, but the incidence Increased in 1974-5 as the result of discovering the angiosarcoma cases. Their a\pthe-j`bb rates are about one-fifth of injuries at home. EMERGENCY PLANNING J. Van Winkle of Diamond Shamrock described several incidents at their plants which pointed up the failures in their planning methods. By a show of hands only 10 companies had held drills in the past year. He suggested several common fallings in this area. 1. Too much reliance on supervisory personnel. Emergencies usually happen on off-shifts. 2. Too much Involvement by supervision and guards. They have better things to do in an emergency than lay hoses, and are exposed to too much danger. 3. Failure to allow for turnover of personnel. Inadequate training or assignments to keep the emergency group effective. AP00028838 TO: T. L. CAREY - 8- Vinyl Chloride Safety Assoc. Meeting, October 6, 1977 He discussed the strong effort to certify and unionize firemen in the Houston area. One result would be to shut down a plant in case of a strike. INITIATOR STORAGE A. Dixon of Goodyear discussed Initiator handling techniques. The favorite storage method still is a walk-in freezer house with dual mechanical coolers, emergency power, and high temperature alarms. Eighteen companies use this method, and 10 of these are sprinklered. Twelve companies use the freezer chest method that we have. His main points were as follows: . ___ __ 1) Follow IRI standard on storage quantltes and separation distances. 2) Never return material to primary stock or reuse containers. 3) Rotate stock. 4) Assure air space between individual containers. 5) Workers should use plastic or rubber protective clothing. 6) Protect all containers on the work floor from heat and sparks. Tenneco reported that they had a fire when a hydraulic shock in the fire header lifted the valve to the storage house sprinklers and filled the house with warm water. When this was discovered, the water was drained out and the cooling units restarted. A few hours later the whole lot of initiator fumed off. A few companies use nitrogen or carbon dioxide Instead of water. This does not seem useful, since there Is enough oxygen In the peroxides to make the fire self-supporting. There is a move in Europe to bulk transport and storage of a 25% solution of initiators, tucidol is considering a frozen 25% suspension in water for those who wish to use the Goodrich procedures. MISCELLANY Georgia-Pacific has selected Crawford and Russell for their present PVC expansion program. This will include 3 contact fluid beds and two flash fluid beds, all from Niro, to get their rates up to 450 MM lb/yr. They also plan continuous stripping and additional blow-down vessels. They have no construction permits on this project yet. The monomer project has not been approved by the Board, but the caustic-chlorine expansion is going ahead. AP00028839 TO: T. L. Carey -9- Vinyl _Chloride Safety Assoc. Meeting, October 6, 1977. KemaNord has hopes that the Denmark project can move ahead. Local opposition has reversed Itself and they are appealing the permit refusal. JTB:djm AP00028840 VI? CHLORIDE SAFETY ASSOCIATION M*- `'1NG THURSDAY, OCTOBER 6th - FRIDAY, OCTOBER 7th, 1977 STOUFFER'S VALLEY FORGE HOTEL, PHILADELPHIA, PENNSYLVANIA hursday - 10/6/77 800 - 0900.............. 900 - 0915.............. 315 - 1000.............. 000 - 1050.............. .030 - 1045......... .. 1045 - 1115.............. 1115 - 1200.............. 1200 - 1300.............. 1300 - 1345.......................... 1345 - 1430.............. 1430 - 1445.............. 1445 - ISIS.............. 1515 - 1600.............. 1600 - .............. Friday - 10/7/77 0800 - 0830.............. 0830 - 0900.............. 0900 - 0930.............. 0945 - 1015.............. Agenda Subject Discussion Leader Registration Business Meeting 6 Election of Officers for 1978...................... ..................... R. Henderson Diamond Shamrock Vinyl Chloride Physiological Effects..Dr. R. W. McBumey Diamond Shamrock Medical Surveillance Problems.H. Lloyd - ------ Georgia Pacific Coffee Break OSHA Enforcement Action............................... H. ^alternate B. F. Goodrich OSHA Compliance Practices Review............D. Rhodes Tenneco Lunch EPA Update............................................................D. Kuhn Conoco Chemicals Emission Control Methods Review--.'...J. Barr Air Products Coffee Break VCSA History........................................................G. Schaaf B. F. Goodrich Transportation. Update....................................R. Wi 1 son Stauffer Chemical Major Accidents, Near Misses.................... J. Alvarez Primex , Industry Injury Review/Survey......... . ...H. Waltemate B. F. Goodrich Planning for Disasters................................ J. Van lfinkle Diamond Shamrock Catalyst Handling.................. ..........................A. Dixon Goodyear Open Discussion Period AP00028841 METHODS OF EMISSIONS CONTROL I. CHEMICAL. A., Acid Permanganate Used In UEI tape monitor system, and disposable cartridge masks. Very expensive and United by solubility in water. B.. Hypochlorite Produces EDC. Less expensive, solubility limited. C. Ozonalysis Laboratory scale only. Patented. Very expensive*___ ozone disposal' problem, possible explosion hazard. D. Incineration Most popular method, capable of low exit concentrations. Requires scrubber in most states, some reliability problems. Some companies use steam boilers. E. Catalytic Destruction Apparently used by two or three companies. Operates at somewhat lower temperatures than incineration, little or no auxiliary fuel. II. PHYSICAL A. Absorption In Solvent Capable of good control, becomes progressively more expensive as exit limit is reduced. B. Adsorption Carbon only adsorbent used cormercially. Capable of very low exit concentrations if unit staged and properly regenerated. Problems with impurity recycle, may need small Incinerator in addition. C. Cryogenic Expensive. Also has Impurity build-up problem. coimercially. Not used -- AP00028842 TOIL CgmUlE 8AFETT ASSOCIATION Company 9* Location Date Hggpgr TO: ---------------- H. Kelteaete BRQoodrlch Cbedal Division 6l00 Oak Trae Boulevard Cleveland, Cfelo V131 TOTAL CASES DUTfla Total Loot Workday Cam TUB n. mCORMSUE CASES Vusber of eatrlea In Col. T of tbe log. (1) BNbw Of entries In Col. 8 of tbe log. (S) NOnber of cbacks In Col. 9 of tbe log. (3) LOSS HOCKSAX CASS Cases Involving Dar Away Ikon Wort Says Away Proa Work . Days of Restricted Vork Activity N0KPA9AL CASES vrsaow . LOST WORKDAYS BWSW* TIONS OR flSMAHENT TRANSFERS Buaber of entries In Col. 9A of the log. (4) Sun of eatrlea In COl. 9A of ' tbe Log. (5) Sun of entries In Col. 9B Of tbe log. (6) NtWbci1 of cheeks In Col. 10 Of tbe log. (T) Mtrtber of checks In Col. 11 of tbe log. (8) TOTAL CASES RECORDABLE INC. RATS 1 LOST vofMttr CASES OKIUSCE RATE H CASES avoLnwc DATS AWAY FROM WORK INC. RATE m DA18 AVAY FROM VORK <HHFf Cave Historlea: APOO *!Wo. In fll * goo.000 Boon Exposure ifa. In Coloan (3) a 200.000 Bo. Mui^BcMira Exposure Bo. To Coluan ftp x i sc. Man-Houra npofti; Q NOS: On U* reverie aide Include a brief description of accidents, Injuries, fires, etc., having experience value. lfo.H6In. cyitimn (Si x 200-000 BOX 938 ALLENTOWN, PA. 18106 PHONE: 215-396-8343 from tho dtsk of JOHN T. BARR t*s /3 ---- i i il i r"' ?ST AP00028844