Document OZNpMO30YERO899XDJ4124j1

t e- CONTINENTAL OIL COMPANY mttica ui iiTiiMitu urtiniiT ---- ANALYTICAL RESEARCH SECTION ! VI. jRESEARCH SERVICES 01VI SI ON technical service report NO. 407--74-GO February 11, 1974 aeeetll laowiCT f: R. E. Laramy to: Dr. Flync Kennedy luajtCT: TRIP TO ATTEND MEETINC OF THE VINYL CHLORIDE SAFETY ASSOCIATION A neetins `of che Vinyl Chloride Safety Association was held at the Sheracon-Hopkins Hocei in Cleveland, Ohio, on Friday, 3 February, 1974. I attended the meeting as a represencacive of Continental Oil Company. In. addition co myself, ocher CONOCO repre sentatives attending were Mr. George Tillson, plant manager, Oklahoma City PVC plant, Mr. Earl Cremillion, safety director. Lake Charles VCM plant and Mr. Jerry Powell, plant superintendent, Aberdeen, Mississippi PVC plant. This association is made up of VCM and PVC manufacturers for the purpose of sharing information with regard co plant safety. The meeting convened at 10 a.m. Friday, and although there was a tentative agenda, che meeting was very informal and varied from the agenda as co order; but the concent was covered sometime during che day..* Due co che informality of che meeting, noces were difficult co organize and names of individuals were almost impossible co coordinate with che companies they represented. No formal noces were taken by a secretary and no list of attendees was furnished. There were approximately o0 people in attendance and some of che companies represented CONOCO Dow General Tire ICI PPG Goodrich Hooker Air Products Diamond Firestone Tenneco Uniroyal The above list is not complete but covers chose companies I was able co determine. The meeting was called primarily because of che recent publicity given to the Coodrlch disclosure of possible relationship between VCM and liver cancer, particularly 7^ angiosarcoma. In view of this, che following agenda of topics was prepared for f*r. discussion: ( ' VVC 0000 740 * 4 BFG62268 Technical Service Report No. 407-74-GO Page 2 I. Monitoring VCL (vinyl chloride) contamination A. Equipment available S. Technique .-sed C. Current problems on obtaining reliable data II. Current Practices for Minimizing VCL Exposure A. Reactor purging (vacuum/displacing) B. Equipment bleeding C. Residual.VCL in slurry and effects in finishing area III.Future Actions A. In what manner can our industry best attach the problem I will attempt to relay the pertinent comments on each of the agenda items. The meeting was opened by Mr. Joe Mudd. of Ceneral Tire, who turned over the floor to Mr. Walt Iliff, of Uniroyal. Mr. Iliff gave a brief rundown of the MCA (Manufacturing Chemists Association) meeting held in Washington, 0. C., as a result'of the announce* . sent by B. F. Coodrich of the angiosarcoma diagnosis of personnel in their Louisville, Ky., PVC plant. As a resulc of the MCA meeting, various task forces have been estab lished, including a Work Practice Group and an Industrial Hygiene and Monitoring Group. The MCA adopted a policy of giving maximum cooperation to NIOSH (National Institute of Occupational Safety and Health) which is the organization, at least .for the present, chat will be investigating the VCM-liver cancer problem. It was also agreed chdc a meeting of the cask groups be held in Chicago on 20 February, 1974, to review their progress. A question from the floor was asked as to the conclusions from the Italian rac study (feeding rats with copious quantities, ^30,000 ppm, of VCM). To dace the results are inconclusive, but a final report will be presented at a cancer meeting co be held in Italy in the fall of 1974. With this introduction the first agenda item, i.e., the monitoring of vinyl chloride, was opened co the floor. Joe Mudd began the discussion by reviewing Ceneral Tire's efforts at their Ashtabula, Ohio, PVC plant. Presently they use only Drager cubes and sporadic air sampling. They have no idea of the TWA (time weighted average) amount of VCM in the air. A lively discussion followed as co whether PVC (polyvinyl chloride) dust was a major problem in the plants. Although nothing conclusive was stated, it was decided co cable the dust problem and pursue VCM monitoring. From this discussion it was made clear thae Coodrich is not seating and is not at all positive what chemical if any, is correlatable co the angiosarcoma. However, circumstantial evidence makes VCM a prime suspeet. Goodrich then gave a brief synopsis of their monitoring program which includes spot air sampling using che Century organic vapor analyzer (OVA), fixed sampling using a Bendix total hydrocarbon analyzer, and personnel monitors fashioned after chose used by Dow -Chemical. We have literature on all this so I will not elaborate further on che specifies. Pittsburgh Place Glass is also using che personnel monitors. Considerable concern was expressed by several individuals chat che total hydrocarbon analyzers, not being specific, could give erroneous results. In addition, the type and amounts of ocher hydrocarbons, including chlorinated and nonchlorinated, could be just as suspect as VCM. Dow Chemical proposed chat through their studies (which have been numerous and detailed) over che past 16 years, VCM was che chemical of importance and chat ocher compounds were present in concentrations so small as co ' be negligible. It was brought out, however, that Dow was concerned primarily with v-*! monomer plants and the same conclusions are probably not valid for resin plants. The Cm consensus of opinion appeared co be chat che Century OVA was indeed the instrument of C 3 choice for spot checks of the air throughout the plant and for use in finding VCM leakK',' w VVC 000000741 BFG62269 Technical Service Report No. 407-74-GO Page 3 The inclusion of a chromatographic column with this instrument would make it even more valuable. However, it was generally agreed that in addition to the OVA, fixed sampling and personnel monitoring were required. John Burr, of Air Products, has begun to install gas chromatographic analyzers with multiple'sampling stations. He is convincec we need eo know the type and amount of all Che organics in the air. These will require a capital outlay of approximately 515,000 each and he is proposing two to three such instruments in each of three plants. The Uilks Miran infrared detector was being used by Diamond-Alkali, but their complaints were much the same as those given by Goodrich, i.e., it weighs about SO pounds, which at best makes it only semiportable, and is rathe slow in response. However, it is sensitive and it is specific. The TVA catalytic combustion detector was discussed and again the complaints were much the same as chose given by Coodrich--it is not sensitive below SO ppm and is neither reliable nor stable at high sensitivity settings. Where to sample was the next question discussed. Other than using fixed and spot sampling, the question arose as to where the personnel monitors should be placed. Although placing tnem in close proximity to the breathing zone seemed the logical choic the problems of mounting and encumbering the personnel are obvious. Dow reported they mount theirs at the waist and have found excellent correlation of the results obtained there with the results obtained when the monitor is near the breathing zone. Ventilation patterns were discussed, and Goodrich volunteered that the VCM flows in waves, making discretion and careful examination of results mandatory. With our OVA analyzer at Aberdeen Dave Cox has found the same phenomenon, where orders-of-magnitude differences-in concentrations of VCM can be observed by standing in one spot and con-^ tlnuously monitoring. Goodrich reported that forced ventilation helped, requiring at i least 20 air changes per hour to make significant reductions of VCM in air when in S lfliLl.11'- concentrations ot approrimatej.y zuu ppm. With whatever type of monitoring finally used, the very valid point was made that accurate, thorough calibration had to be done if NIOSH was to be satisfied. Based on the visit to the Coodrich, Louisville, Ky., PVC plant, NIOSH submitted a list of precautionary monitoring and control procedures to the MCA (copy is attached). This list created great consternation among most of those present, eliciting such comments as, "This will shut down many PVC plants across the nation!". This list will be discussed at an open meeting to be held at the SheratonrHopkins Hotel (Pickwick Root beginning at 10 a.m., Tuesday, February 12. The general consensus of chose present was .chat several of the items needed clarification and modification. A representative from CONOCO should attend this meeting. Since Goodrich announced the liver problem, NIOSH has visited their Louisville plant and plans to visit a second plant during the week of 12 February. Hooker Chemical Company (New Jersey) has also been visited by NIOSH since the announcement. They had no details of what NIOSH found or will report. During the meeting, Tetmeco received word that NIOSH had contacted their plant requesting the age of the plant and number of employees, surely preparatory to a visit. In view of this, it was concluded by all chose present chat NIOSH will be visiting all plants in the very near future. It was also stated that the state of New Jersey is planning a meeting of.all PVC producers within the state sometime in the very near future. Diamond-Alkali gave a short presentation of their Immediate plans which can be sum marized as follows: VVC 000000742 c \r'fy BFG62270 1- - Technical Service Report No. 407-74-CO Page 4 1. Installing hydraulic cleaning sysceas in their reactors. 2. Use air purging sysceas. 3. Dally in-plant monitoring program--each individual will be personally monitored for one 8-hour shirc/week. 4. Continuous air eonitoring will begin as soon as equipment arrives. 5. SMA-12 blood tests for all personnel. 6. Annual physical exams for all personnel. 7. Possibly go to a liver profile test. Will wait on advice of medical people. In addition, B. F. Coodrich will probably disallow anyone with a liver disorder to work in VCM or PVC plants. Only two companies represented required a liver test in their pre-employment physicals; however, it was about unanimous that this will now be require by all companies. Practices to minimize VCL exposure were concentrated primarily in how to clean reactors without exposure to copious quantities of VCM. Harlan Jewett, of General Tire, gave a presentation on their system for accomplishing this. Since Ceorge Tillson, Jerry Powei and Earl Gremillion were present and are infinitely more knowledgable in this area char I, suffice it to say they are cognizant of the problem and are already working in this area. Future actions were reduced to waiting until the results of the HIOSH, MCA and OSHA meecings are known. It was decided that this association would meec again at the same place in approximately two to three months to discuss problems and progress. In susmiary, it was apparent to me chat the current problem is one of gigantic ramifi cations and needs rapid and serious consideration. Although VCM has not been proven to be the culprit, the companies have by design chosen to limit its presence in air and to closely monitor its concentration. As a goal, most of the companies present have chosen an upper limit of SO ppm VCM in air. This is a maximum and not a timeweighted average (TWA). The TWA should be considerably less. Steps to reduce VCM concentration in air have already been taken by some companies with the remaining companies at various stages of initiating or implementing programs. Monitoring che VCM levels is being attacked by all companies, some with programs already far advanced and some just beginning. The attitude was one of solving che problem, a positive approach, rather chan waiting to see if it goes away. It was not a question of whether to monitor but rather how much and how fast. Here again, che majority of companies are attacking the problem with considerable effort and hasce. The meeting was very informative to me and left no doubt in my mind of che seriousness of the problem and the immediate need for maximum effort and speed. APPROVED: 2-/ <4-7*/ Director Analytical Research Section BU Copies to: DBB-GP Separations Analysis Croup . VVC 00000074 3 BFG62271 M -jfr,- 'U+^J i . ,.JC.oPlB VCSA j c jjL-H<Li^^M~Gr:' I Mi >*** fet.7,n-u.f .,.r. ':. _ v:.-.v. !-*rc;t-iT " - - '*Enclosure 1 >*'>'>*=* r=5:rTtvq;r.'. . :. ' ; HIOSH Recoaended Precautionary Monitoring and Control Procedures for Polymerization Processes Involving Vinyl Chloride I. General Housekeeping Procedures n* ' X. The spillage of Vinyl Chloride and Polyvinyl Chloride in and around the production facilities should be controlled as follows: 1. Housekeeping procedures should be isplesented to assure ItssKdiece removal of VC and "PVC .jnacerial around polymerization operations including drying, packaging and loading operations. 2. Recovered PVC material which is to be packaged should be scored in closed containers. 3. Waste PVC material should be scored in closed containers and consideration should be given to the adequacy of its disposal and/or destruction. Care should be taken in the storage of closed containers to insure chat unsafe conditions do not result from an internal build-up of pressure in che container. Inventories of beginning and recovered quantities of VC and quantities of PVC produced, packaged and recovered should be made co determine losses and probable areas affecced. -- /rfrtu ? ? Slr^Jsz, iw-- C. PVC material should be removed from overhead structures and conduits where it tends co collect. D. Consumption of food should be permitted only in separate facilities provided for this purpose, and no food products should be permitted elsewhere in che polymerisation facility. IX. Protective Clothing A. K daily change of protective clothing including full coveralls, or the equilvalent, should be provided each employee in areas where possible exposure co VC PVC could occur. Clothing contaminated, by^ - accidental spills should be changed as, soon as feasible. Uvt-rt.Liyr(r&* jpy. U rJCrGtt , jTAs <C.. -------- -J1'------ B. Protective gloves and footwear, or fooceovers, should be worn as appropriate in those PVC operacions where exposure co PVC material is possible, (1*0 <Zre.%. C. Protective head covers should be worn during PVC operations as appropriate (e.g. hard hats in chose areas where physical protection of che head is necessary and hair coverings, or che equilvalenc, in VVC 00000074* * mV ' *ir * \ . *'* v :^- r 'j < . .T .o - r " BFG62272 operations such as cleaning of polymerization reactor tanka and packaging operations)- ol Where enployees are engaged in maintenance or cleaning operations of polymerization reactors tanks they should wear full impervious suits to guard against skin contact of FVC`material and VC vapors. Procedures for safe entry to confined spaces should be observed. HZ Showers ' . t "*: .V.--.'vT ' ____ i -r.'.i Showers at the termination of an eight-hour work shift should be mandatory for all workers wlth_oossible contact with VC-PVS^P^^ ( 17, Monitoring . Environmental Monitoring -- 1. In-plant environmental monitoring programs should be Implemented; and uhere workers are required to enter polymerization tanks, a survey of the VC. concentrations should be made in the reactors immediately after opening, immediately prior to entry of maintenance personnel and during the tank cleaning 'operation. 2. Data obtained from the environmental monitoring program should be used to indicate chose areas where efforts should be directed to reduce airborne levels of VC. 3. Positive programs to initially control VC levels well below - Che present Federal Standard of 500 ppm should be developed Csome companies are targeting at 50 ppm) and efforts to further reduce levels should be given consideration concomitantly with tbe > necessary nodificacions in engineering and design controls. ----- *7 J M*rtjL&IOJL'Ut+yX. ' 4. The* doncencracion of VC in exhaust ventilation should be determined to estimate the amount of VC lost during operations and che possible exposure of personnel immediately outside the facility. * 3. Monitoring. for PVC particulate material should be accomplished co estimate che degree of exposure to this substance throughout che facility. Personal Monitoring 1. Integrated, eight-hour personal monitoring samples should be obtained from chose employees considered co receive the greatest exposure co VC or PYC. vve 000000745 c. C: fl; h -2 )' v BFG62273 2. Breaching zone samples should be obtained Co complement environmental monitoring prograa for VC, and similar samples * should be obcaiaed for PVC. Respiratory Proeeccioa ... Because VC is a gas under ambient condidoas and PVC Is a solid under these conditions, it is reconeaded that respiratory protection for employees take these circumstances into consideration. A. Where employees are enganad" in cleaning aad maintenance operations iasidi* .polymerisettan reactors xhey should be equipped with an atcosphere-supplied respirator in order to protect against both VC vapor and PVC particulates. fonyrier& ZCZ . B. During housekeeping procedures and packaging operations where the possibility of PVC dust inhalation is a factor, it is reconended that an air-purifying respirator equipped with a mechanical filter designed to remove particulate material be worn. Respiratory protective devices which meet this requirssent, as veil as protect against VC vapors in concentrations less chan 0.1C have been approved by the NIOSH Testing and Certification Laboratory and bear the numbers: TC-23C-4Q, TC-23C-47, TC-23C-48: UUjLMSs*} C. Where employees are engaged Is transfer operations of VC from railway caakcars to storage facilities or at any similar transfer point which requires manual operations, they should wear a selfcontained breaching apparatus (BCBA) during such operations to guard against .unexpected release of VC during such, operations. ^ \ ( ,', f4mV D. Other operations involving possible exposure'to VC or Y7C should be evaluated as the individual situation exists and respiratory protection provided as appropriate. "--* WC 0000007*6 > ' . ... '- ---------- :-------------------- BFG62274 fO [< \ o w M CD