Document b58oZeRqJ5dkn8YV2XeamNK73

SOUTH CHARLESTON PLANT UNION CARBIDE CORPORATION CHEMICALS AND PLASTICS P.O. 80* 8004, SOUTH CHARLESTON, W. VA. JS30I July 21, 1975 Mr. Grover C. Wrenn Chief, Division of Health Standards Development Occupational Safety and Health Administration U. S. Department of Labor Room N3663 200 Constitution Avenue, N. W. Washington, D. C. 20004 Subject! Interpretation of Occupational Safety & Health Administration Vinyl Chloride Standard Dear Grover Thank you very much for arranging the meeting on July 16, 1975 with Messrs. Edward Klein, Gene Regad, and yourself to discuss the problems involved in amending the Vinyl Chloride Standard and to dis cuss ways to provide the vinyl chloride resin industry with relief from burdensome and unnecessary parts of the Standard. The discussion did much to create an understanding of the problems of both parties. In reviewing my letter to you, dated May 2, 1975, on Classifica tion of Union Carbide Corporation Vinyl Resins, I believe it still clearly states the problem and a possible solution of the low residual monomer vinyl resin. Summarizing the letter it states! 1. The health hazard protected against by the Occupational Safety and Health Administration Vinyl Chloride Standard is the inhalation of vinyl chloride monomer. The objective of reducing the inhalation of vinyl chloride monomer should be achieved with a minimum of industrial disruption while perrfiitting OSHA to concentrate its enforcement effort in the most hazardous areas. 2. .Vinyl resins containing less than one part per million of vinyl chloride monomer are subjected to one or more additional processing steps; i. e., they are "fabricated" to contain extremely low residual monomer content. % Mr. Grover C. Wrenn -2 July 21, 1975 3. Data has been presented showing that when resins containing less than one part per million of residual monomer are processed, including so-called "mass melting", the amount of vinyl chloride released to the work space does not even approach the action level limit of 0, 5 ppm set by the OSHA Standard. Based on the objective of the Vinyl Chloride Standard and the data presented, the logical approach to effectively utilize limited OSHA enforcement personnel, to provide for worker safety, and to provide relief for those resin manufacturers who are producing these low monomer resins at extra cost is to classify these resins as "fabricated" products, thus limiting the application of the Standard to areas where excessive hazard exists. Union Carbide Corporation, a producer of many specialty vinyl chlorid resins, markets these products world-wide to many customers - large and small. Within the United States alone it has 1,483 individual customers for vinyl resins. Most of these customers are small manufacturing establishments that purchase less than truck-load quantities. These customers, in turn, produce semifinished goods such as lacquers, plastisols, and organosols which ar shipped to the ultimate user. These customers, as well as transportation companies, are withdrawing from handling and use of vinyl resins. The nature of this business is such that a clear statement of damage is not possible, but we can cite many cases of individual withdrawal as well as internal directives to not use vinyl resins in new applications. The loss of many small customers, as well as the loss of new applications, is tantamount to a slow termination of the business. We would appreciate your expediting the response to our request for an interpretation of the status of our products and thus clarify our situation. Very truly yours, R. N. Wheeler, Jr. CHEMICALS ; AND PLASTICS t ** MONITORINGTHE CONCENTRATION OF VINYL CHLORIDE IN THE WORK PLACE OR AMBIENT AIR Attachment 5 (p. 1 of 64) OUR APPRECIATIVE THANKS TO Cmury Systems Corporation ... Analytical Instrument Development, Inc..,, Mina Safety Appliance* Company ... for granting ut permission to reprint their publication* in thit booklet. NOTE: Union Carbide Corporation doe* not endorse the equipment item* or the method* Of analysis presented herein to the exclusion of all other vendors equipment or methods of analysis. Union Carbide Corporation does use these methods of analysis and tht equipment items in it* monitoring operations, and believes its monitoring procedures represent good practice. Union Carbide Corporation assumes no responsibility for the monitoring result* of others using the equipment or analytical methods listed In this booklet. IMPORTANT -- This information is offered solely for your consideration, investigation, and verification and is not to be construed as warranty or representation for which we assume legal responsibility. In using these meteriels, you must establish for yourself the most suitable formulations, production methods, and control tests to ensure the uniformity and quality Of your product. UNION CARBIDE is a registered trade muk of Union Carbide Corporation, U5A C1974 by Union Carbide Corporation. UNION CARBIDE CORPORATION e CHEMICALS AND PLASTICS * 270 PARK AVENUE. NEW YORK, N.Y. 10017 MONITORING THE CONCENTRATION OF VINYL CHLORIDE IN THE WORK PLACE OR AMBIENT AIR Monitoring the concentration of vinyl chloride in the work place air is currently required by the U.S. Department of Labor's Occupational Safety and Health Administration under the temporary standard for vinyl chloride, and will continue to be required under the permanent standard as promul gated in the Federal Register of October 4, 1974, and scheduled to become effective January 1, 1975. In addition, the Environmental Protection Administration will issue regulations requiring ambient air monitoring or setting specific limits on vinyl chloride emissions. The current and future OSHA regulations cover the vinyl chloride pro ducer, the resin manufacturer, and the resin pro cessor or fabricator who makes finished or semi finished products. OSHA regulations require monitoring of areas where employees may be exposed to vinyl chloride emissions or to polyvinyl chloride resins under a definite written program which includes the pos sibility of employee observers; the keeping of complete and accurate records for long periods of tua, stating dates, levels, and type of equipment iflp and with very high (95%) confidence levels for such monitoring procedures. . The method of analysis and the details of the program are at this time, within the above frame work, left up to the employer. Any monitoring system must take into consid eration the following factors: Potential for exposure to vinyl chloride is obviously higher for an employer manufac turing, using, or handling vinyl chloride mono mer. This potential for exposure is relatively lower for a polyvinyl chloride resin user. Response time is important for the employer vorking with vinyl chloride monomer. If an ver-limits emission occurs, he must take action nmediately to protect the employees. A resin >er is concerned only with the potential release ' the vinyl chloride monomer contained in the .in as a raw material. He is far less likely to /e an emergency which would expose emyees to high concentrations of vinyl chloride nomer. utiwatto low concentrations of vinyl chlorby^^ monitoring system is required in all .. Such sensitivity is 0.25 ppm. in air under ermanent standard. Flexibility of the monitoring system is of considerable importance, particularly, in a small business. With relatively few resources, such a company must be prepared to cope with regula tions from EPA, as well as OSHA, on vinyl chloride as well as other materials. Specificity of the monitoring system to vinyl chloride, such as a manufacturer of suspension vinyl chloride homopolymer, ie., PVC. Data from an organic vapor analyzer should be adequate. The vinyl chloride monomer pro ducer; the lacquer formulator; or any other manufacturer who works with other monomers or solvents needs to know the concentration of vinyl chloride and not the concentration of vinyl chloride plus naphtha or vinyl acetate. OSHA requirements also are a factor. The monitoring data should be acceptable to the compliance officer. The data should be com parable with the data from tests he performs. While not a part of the vinyl chloride standard, the employer should be able to monitor nui sance dusts as per OSHA requirement. Resin dust in the work space air may well be a factor in any OSHA inspection. Vinyl resin processors or users should consider their monitoring needs as they relate to the following categories: work space air vinyl chloride concentration, so that they can take appropriate action to protect their employees as well as meet the OSHA standard for monitoring. 2. When no measurable amounts of vinyl chloride monomer exist or are likely to exist in the work space air. Polyvinyl chloride resins produced by the dispersion or solution polymerization pro cess or vinyl resin compound that has already been hot processed generally contain 0 to 0.001 per cent free vinyl chloride monomer. Further hot processing, manufacture of organosols or plastisols, or the formulation of lacquers results in very little, if any, release of vinyl chloride monomer into the work space air. These resin users are concerned only with sufficient moni toring to meet OSHA requirements. They are not exempt from them even though the likeli hood of detecting vinyl chloride monomer in the work space air is remote. Resin users in this category might consider contracting out the monitoring work if commercial laboratory facilities are available, since needs are minimal. As with all simplifications, there is a large number of resin users who clearly fit neither category or who are not sure where they fit. These resin users or processors should query their resin or compound suppliers regarding the l chloride content of the resin or resins fg purchased. Since this content varies with type of resin and the vendor, it is wise to make such inquiries thoroughly and carefully. Resin users or processors in Category No. 1 ould consider a basic industrial hygiene labora ry consisting of the following items; \ chromatograph with a flame ionization detecor, such as Model 511 supplied by Analytical nstrument Development, Inc., Avondale, rnnsylvania 19311 for about $7,000 including cessory equipment. This instrument is sensitive to less than 0.1 m. vinyl chloride, and is generally useful for a Tty of other solvent monitoring operations. ;ral portable sampling pumps, such as the : Safety" Appliance "Monitaire" pump, e may be clipped to a worker's belt for nal sampling of vinyl chloride in air or dust . These pumps, including a battery charger, oproximately $280 each. ical balance sensitive to 0.01 milligram. ortnHfit of sample tubes, syringes, and as^P? for sample collection. The laboratory should be well ventilated with a hood for employee protection. Other facilities might include equipment for sample pump calibra tion and preparation of standard samples. This description is intended to portray only the broad outlines of such a laboratory. The actual outfitting of a laboratory is best left to a chemist or industrial hygienist. Analytical methods for determining vinyl chloride concentrations in air as ceiling values or time weighted averages as well as the concentration of vinyl chloride in resin are given in the Appendix. Vendor's descriptions of the specific equipmentitems are also included. Resin users or processors in Category No. 2 could use the same type laboratory facilities described for Category No. 1 users, or they could reduce the equipment cost by use of the following: A Century Systems Corporation Portable Or ganic Vapor Analyzer with Flame Ionization Detector, Model OVA-98. This analyzer has good sensitivity, good reproducibility, and is easy to operate. It costs approximately $3,000. The main disadvantage is that it is sensitive to all organic vapors, including vinyl chloride; thus, if other vapors are present, the reading translated to vinyl chloride concen tration will be higher than the actual concen tration. Century Systems Corporation is currently offering this instrument with chromatographic capability at a cost of approximately $3,500. The instrument with this option is specific for vinyl chloride or certain other solvents. This option, while relatively untested in the field, appears to be useful for the resin processor with limited laboratory facilities (see data sheet in Appendix.) One or more portable sample pumps with equipment for gravimetric sampling of air borne dusts, such as the Mine Safety Appliance Pump described previously. These cost approximately $200 each. Analytical balance sensitive to 0.01 milligram for dust monitoring weighings. These facilities would have to be supplemented with other laboratory equipment selected by the chemist or industrial hygienist. Methods of analysis and operating instructions for the equipment should be obtained from the vendor of the equipment purchased. The equip 'lent and analytical instruments list- J %4 062811 cd are precision measuring devices; therefore, they need to be operated and maintained by skilled, knowledgeable technicians. Again, like any other / precision measuring device, they should be cali brated and tested with standard samples either I prepared in the laboratory or purchased from a commercial supplier of such samples. This booklet attempts to review the factors involved in vinyl chloride monitoring and their application to a resin processor. It also suggests equipment and methods of analysis for considera tion. Its principal purpose is to stimulate thoughts and plans with regard to the problem of monitor ing vinyl chloride monomer concentrations. c APPENDIX 1. Department of Labor, Occupational Safety and Health Administration: Exposure to Vinyl Chloride, Federal Register, Volume 39, No. 194, pp. 35890-35898, Friday, October 4, 1974. 2. Vendors' Publications on Analytical Instru ments: Century Systems Corporation, Portable Or ganic Vapor Analyzer, Model OVA-98. Analytical Instrument Development, Inc., Portable Flame Photometric Gas Chromato graph, Model 511. Mine Safety Appliances Company, Model S Monitaire Sampler. 3. Methods of Analysis for Determining Vinyl Chloride in Air and in Resin: Vinyl Chloride, Determination in Air by Gas Chromatography. Vinyl Chloride, Determination in Air by Adsorption on Activated Charcoal and Analysis by Gas Chromatography. Determination of Residual Vinyl Chloride Monomer in Vinyl Resins. Dust, Determination of Total and Respirable Airborne Dust by Membrane Filter Sampling and Gravimetric Analysis. I ucc 062881 \ FRIDAY, OCTODER 4, 1574 WASHINGTON, D.C. Vofumo 39 o dumber 194 PART II CESi DEPARTMENT OF LABOR Occupational Safety And Health Administration EXPOSURE TO VINYL CHLORIDE Occupational Safety and Health Standards ucc Q62882 35890 RULES AND REGULATIONS , T7Ue 2?--Labor ployees from a rare liver canca (angio and abroad. OSHA proposed to revise Vhapter xvi~occupational safety AND HEALTH ADMINISTRATION, DE PARTMENT OF UBOR PART 1CJO--OCCUPATIONAL SAFETY AND HEALTH STANDARDS sarcoma) may have been occupationally related. As a result of this notification and alter consultation with NIOSH. and a joint Inspection of the B. F. Goodrich plant by OSHA, NIOSH and the Ken tucky Department of Labor, a fact-find 1910 93q and published a comprehensive proposal (39 FR 16E96i on May 10, 1974. Lo protect employees from hazards of exposure to VC. The proposal called for limitation of employee exposure to VC to "no dctecUNe level." as measured by a Standard for Exposers to Vinyl Chloride ing hearing was announced on Janu sampling and analytical method sensitive Pursuant to sections 8(b), 6(c), and ><c> ol the- Occupational Safety and Health Act of 1970 (St Slat. 1593, 1598. 1599; 29 U S C. 655. 6571 Secretary of Labor's Order No. 12-71 <36 FR B7S4> and 29 CFR Part 1911. I 1910 93 of Part 1910 of Title 29, Code of Federal Regu lations la hereby emended in the manner set fotth below. In order to provide an Occupational Safely and Health stand ard dealing with the exposure of em ployees to vinyl chloride. I. Bachorountl--<li Vinyl chloride. Vinyl chloride (chloroethene), Chemical Abstracts Service Registry No. 75014, Is a synthetic organic chemical made from ethylene or acetylene and chlorine by any of several processes. It Is the parent compound or a scries of thermoplastic resin polymers and copolymers which are widely used for containers, wrapping film, electrical insulation, pipe, conduit, and a variety of other industrial and consumer products. Vinyl chloride has been made commercially In this country since 1939, and present production is in excess of seven billion pounds per year. The vinyl chloride industry divides into three segments; monomer production, polymer production, and fabrication. Production of the monomer Is a largescale continuous process. Involving only .a few firms. There are comparatively few employees In this segment of the indus try, because the processes lend them selves to automation. Vinyl chloride (VC) Is used primarily In the production of polyvinyl chloride tpVC), s resin which is produced through batch processing The conversion of the VC monomer into a polymer or copolymer Is an incomplete process, 1 e.. not all of the monomer is reacted. PVC is fabricated by a variety of tech niques. including extrusion, injection molding and calendering, to form a fin ished product that needs' no further chemical handling. The vast majority of employees involved in the VC Industry ary 30, 1974 (30 FR 3874) and held on February J5.1974. Information obtained from this hear ing. particularly the preliminary reports of experiments conducted by Professor Cesaie Maltoni of the Instituto dl Oncologia, Bologna, Italy, demonstrated that vinyl chloride induced angiosarcoma In rats at levels as low as 250 ppm, and In other species at higher levels Experi ments performed at lower levels of ex posure were not completed at that time. Other testimony from medical witnesses and NIOSH. and the lesults of autopsies, led to the conclusion that the Goodrich workers had angiosarcoma of tlie liver and that VC probably was (he causal agent In the angicsarcomas observed. In post hearing comments, additional angiosarcoma deaths weie reported among workers who had been exposed to VC in plants operated by Union Carbide Corporation. Firestone Plastics Corpora tion and Goodyear Tire L Rubber Com pany. On the basts of all information avail able at that time, and the fact that em ployees were being exposed at levels around the experimentally observed ef fect level of 250 ppm. an emergency temporary standard <ETC> was promul gated on April 5. 1974 (39 FR 12341) pursuant to section 6(c) of the Act, as 29 CFR 1010 93q. This standard reduced the permissible exposure level from a celling of 500 ppm to a 50 ppm ceiling, and established other requirements, including, for example, monitoring and respiratory protection. It was expressly recognized that this standard limiting exposures to a 50 ppm ceiling was a tentative, interim standard, and that the whole question of exposure to VC would be considered more fully in the light of additional infoimation, especially the results of experiments which were known to be underway at that time. On April 15.1974. Information and data to 1 ppm. with an accuracy of I ppm 60 percent. The proposal also called tor the estshllshment of regulated areas and limited access to such areas to au thorized persona. A requirement lor monitoring of empioyee exposures was proposed, along with engineering and work practice controls to be implemented when exposures over the detectable limit were measured. Respiratory protection would have been required while engineering and work practice control* were being Implemented or where exposures exceeded the per missible limit even after feasible en gineering controls were Instituted. In addition, the proposed standard Included requirements for medical sur veillance. protective clothing, emergency procedures, training, specific protection during maintenance and decontamina tion operations, transportation loading and unloading operations and record keeping. (4) Hearing on the proposal. The pro posal, as published on May 10, 1974, allowed 30 days for Interested parties to submit written comments and to request an informal rulemaking hearing. In formal contacts with OSHA staff and early responses indicated that the sub ject was of great Interest and Importance to many persons. Because of the Umtted time available before expiration ef the six month period provided In section 8(c)(3) of the Act for promulcation of a final standard. It was decided to hold a hearing as soon as possible. Accord ingly. on May 24,1974. a notice of a hear ing was published (39 FR 18303), setting a hearing date of June 25, 1974. The hearing was conducted from June 25 through June 28, and again from July >. through July II, before Administrative Law Judge Oordon J. Myatt. All partici pants were given the opportunity to pre sent testimony and to cross-examine other witnesses. Persons participating In the hearing were given until August 23, are employed by fabrication Arms. Such firms range In size from those with few were presented to representatives of OSHA. NIOSH, and the Environmental 1974, to file additional posthearing com ments, including various Uems of Infor employees and simple equipment to large Protection Agency by the Industrial Bio- mation which were requested during the plants involving many employees and Test Laboratories. Northbrook, Illinois, examination of witnesses. considerable capital. concerning results of animal exposure (5) Economic and technical Impact Vinyl chloride <VC). a gaa at ambient temperature and pressure, fa a chlori nated hydrocarbon, which heretofore has been regarded as having moderate liver toxicity. The Initial standard, contained in Table-0-1 of 1910 93, established a ceiling votue of 800 parts of VC per mil lion parts of air. studies with VC. These studies were sponsored by the Manufacturing Chem ists Association. Although oniy pre liminary In nature at that time, these results revealed that 2 out of 200 mice exposed to VC concentrations of 50 ppm for 7 hours a day. five days a week, for approximately 7 months, had developed study. During the hearing, OSHA deter mined that additional facts would be needed to determine the practicality of certain aspects of the proposed stand ard. Accordingly, OSHA contacted on In dependent consultant, Foster D. Snell Corporation, to conduct studies of the feasibility of compliance at various ex 121 The emergency temporary stand angiosarcoma of the liver. posure levels. Including those proposed ard. On January 22. 1974, the Occupa (3) The proposed permanent stand* by OSHA and others advanced by in tional Safety and Health Administra ard Based on the demonstrated evidence dustry spoktwmfn. Snell was also com tion (OSHA) was Informed by the Na of VC's carcinogenicity In three animal missioned to collect Information regard tional Institute for Occupational Safety species (rats, mice and hamsters), and ing the economic costs of compliance. and Health tNIOSHt that the B. F. the substantial probability that VC had This action was announced at the cloee Goodrich Chemical Company had re been the causal agent In the eases of liver of the hearing, and Judge Myatt further ported that deaths of several of Its em angiosarcoma found In workers both here announced that the record would be kept FfDtlAL tieilTf*, VOL 3*. NO. Its--ISlOAT, OCTOUt 4. 1*74 RULES AND REGULATIONS 35891 open for a period of lime beyond August studies of MsJtonl and Bio-Test Lobora- may create a carcinogenic hazard, the 23. (-0 allow Interested persons to com- toiles Moreover. MaHoni's mvestlfatlons amount of exposure which la hazardous , merit In writing on the study. On August have demonstrated a dose-dependent re must be determined. The Burgeon Gen 10. 1974, OSHA announced that the pre lationship for induction of tumors fl e.. eral's Ad Hoc Committee referred to liminary study was available and that more tumors occur at higher exposure above concluded that cafe exposure levels comments were to be submitted no later levels), Including angiosarcoma of the for carcinogenic substance! cannot be than September fl. 1974 <36 FR 30814). liver. In rats. The Investigations of In- scientifically ditermtned. This position On September 13, 1674. OSHA Invited dusli ial Bio-Test Laboratories have dem Is supported by the testimony of NIOSH comments on both the preliminary and onstrated a similar relationship for at the hearing, Its recommendations for the final study, which was to be received both rats and mice These investigators b standard of no detectable level, and by on or before September 25, 1671 <39 FR have Induced angiosarcoma of the liver the testimony of expeit witnesses from 33009>. In rats and mire at exposure concentra the National Cancer Institute. 181 Environmental Impact statements, tions ol 60 ppm. and in hamsters at high Several witnesses and persons who sub A notice of Intent to file an environmen er concentrations of exposure. Additional mitted comments have taken a contrary tal Impact statement assessing the im tumors involving other organa, including view and have suggested that man Is less pact of a propore-d standard on occu the kidneys, lungs, and skin of exposed sensitive to biologic aberrations Induced pational exposuie to VC was published animals, were also observed in frequen by vinyl chloride exposure than experi In the Federal rtEcis-rra on April 24. cies much in excess of control animals. mental animals. Proponents of this posi 1974 <33 KR 14532). The notice Invited The incidence of tumors In mice In the tion have argued that if humans were as any person having Information or data Industrial Bio-Tex*. Laboratories Investi sensitive 'as rodents, an "epidemic" of on the environmental Impact to submit gations Is particularly pertinent. Of 200 cancer resulting from VC exposures It to OoHA by May 17. 1674 On June 12, mice <100 males, 100 females) exposed to should have already been discovered 1974, a draft environmental impact 60 ppm of vinyl cldoridc by Inhalation for among employees, They also argue that statement was prepared and circulated eleven montlis. 100 died Sixty-four ani the employees In w horn tumors have been to all Interested persons. Ten copies were mals died without gross postmortem observed are those who have considerable forwarded to the Council of Environ pathologic examination being performed. employment experience ax polymeriza mental Quality <CEQi, which published Of the 36 remaining animals for which tion reactor cleaner* Because It is gen a notice of Its filing and availability In the Fxderal Recistir on June 25, 1074 <39 FR 22975). A 45 day period was al lowed for the submission of comments on the draft statement- On September 5, 1674, the final environmental Impact a gross postmortem pathologic examina tion was performed, 13 <36 percent) were found with liver tumors (Including angiosarcomas), 21 <58 percent) with lung tumors. 9 <25 percent) with skin tumors, and one with a kidney tumor. erally agreed that reactor cleaning In volved high exposures to vinyl chloride In year* past, It Is argued that the lower levels currently found tn the workplace have not Induced cancer and are there fore safe. We reject this argument. statement was prepared and a copy of it and all substantive comments were sent to appropriate governmental agencies, private organizations, and other inter ested persons. CEQ published a notice of availability for the final statement on September 6. 1974 <39 FR 32350). The submission of comment was Invited un til September 26, 1974. The final state ment and all significant comments have been carefully considered in arriving at the final standard on occupational expo sure to VC. <7> The record. The record in thia proceeding is one of the most exhaustive ever relied upon by OSHA. It consists of pre and post-hearing comments and testimony received at both factfinding and rulemakJng hearings, the studies and Inspections conducted by OSHA person nel. the environmental Impact state ments, the economic and technical Impact studies, and all other relevant Information. In all. over 600 written com ments have been received, with more than 200 separate oral and written sub missions made with regard to the two hearings. The record Itself exceeds 4.000 pages. Employers, employees, labor unions, public health groups. Independ ent experts, physicians, research scien tists. and specialists in many fields have been Invited to submit Information and have made their views, knowledge and experience available to OSHA. The en tire record encompassing these submis sions waa thoroughly reviewed and evaluated in reaching the determina tionns. set forth Findings below. regarding carcinogenicity, Accoiding to the 1670 report by the Surgeon General's Ad-Hoc Committee on the Evaluation of Low Levels of En vironmental Chemical Carcinogens, the finding of cancer in two or more animal species may be extrapolated to indicate a carcinogenic hazard to humans Here, such a finding was made In three species that were exposed to VC by Inhalation-- a route comparable to employee ex posure. In addition, there were at least 13 confirmed cases of angiosarcoma of the liver among employees exposed to VC, a particularly significant number in view of the extreme rarity of this cancer in the U 8 adult male population (testi mony ol Dr. Marcus Key, Director ol NIOSH. at the rulemaking hearing). The findings of angiosarcoma of the liver in both experimental animals and exposed employees is compelling evidenre that exposure of humans to vinyl chloride induces this tumor. Industry spokesmen, at the hearing, conceded that VC Is carcinogenic for humans <e.g. testimony of Dr. McBurney, Rulemaking hearing, 1041), Accordingly, it is con cluded that VC must be regarded at a human carcinogen, and the probable causa] agent of angiosarcoma of the liver, and that exposure of employees to VC must be controlled. Additional evidence of tumor induction In a variety of other organs, Including lung, kidney, brain and skin, as well as non-malignant alterations, such as fi brosis and connective tissue deteriora tion. indicates additional oncogenic and toxicologic properties of vinyl chloride, which must be considered in establlsliing control regulations. (See testimony and The fact that approximately threequarters of those employees with the longest exposure to VC (greater than 20 years since Initial exposure) have not yet been located, makes it Impossible to determine the actual number of affected employee* The cases of liver turnon ob served to date have an average latency period, since Initial exposure, of approxi mately 20 years. If It Is assumed that In duction of angiosarcoma Is a dose-re lated phenomenon, and If employees en gaged In cleaning reactors did. In fact, receive larger doses of vinyl chloride, it would be expected that such tumors would be observed earlier for this em ployee population. For this reason, the significance of presumed tower doses cannot be accurately assessed until a longer period of time has passed, as a longer Induction period would be expected Initiation of expoeure to chemical carcinogens and induction of cancer are not necessarily synchronous events. Be cause of the physiologic complexities in volved with carcinogenesis. Induction of tumors does not occur in alt employee* with similar expoeure hlstoriee. For ex ample, Dr. Gchneiderman of the Na tional Cancer Institute emphasized dur ing his testimony that only about a filth of longer-term heavy smokers develop lung cancer. Accordingly, the Industry contention that exposure levels have been dramatically reduced since the 1940's (s not reliable evidence that cur rent levels of exposure ere safe. Some Industry spokesmen also sug gested that the apparent nonrandom exposure levels and feasibility--<l> Car results or studies by Bio-Test Labora distribution of observed cancer tn em cinogenicity of vinyl chloride. The car tories. Tnbcrxhaw-Cooper, Maltonl, ployees may indicate an exposure thres cinogenicity of vinyl chloride for three NIOSH. and Gelikoff.) hold for tumor Induction, based on varia animal species <r*t, mouse, hamster) has <2> Etpoture limiti. Upon finding that tions in the workplace design or prac been documented on the record by the exposure ol employee* to vinyl chloride tice and resultant employee exposures KOtkAt MOUTH, VOL 3*, NO. 1*4--HlDAT, CTOIII 4, ms t iJCC 062384 5892 RUUS AND BEGUlATtOttS (testimony fJ&d questiwting by Tenneeo i_VmJcal. Ic>. It hr.* siso been em phasized that in only 3 ol polymerlration plants where employees have been exposed to VC Tor more than 20 years have any employees developed angiosar c l , testimony of SeHkoff. Firestone, NCI, ondNIOSH.) In our new. the demonstration of can cer induction in humans at a particular level Is not a prerequisite to a determina tion that a suhsunce repretents a can confident that Industry will continue to do so. (4) CcmcJerfcnj. The conclusion* be low are based on a thorough review and evaluation of *11 the evidence submitted. Where dc-cfston* can be baaed on record coma ol the liver. This argument Is very cer hazard for humans at that level. It evidence, this has been done. Where, similar to that raised concerning vari would be Imprudent to assume man to however, factual ceitalntles are lacking ability of pest employee exposure. Al be less sensitive to VC exposure than ex or where the facts alone do not provide though geographic and workprectlce dif perimental animals la the absence of an answer, policy Judgments have been ferences may ultimately be demonstrated conclusive evidence. It would also be un made. to be factor* in distribution of angiosar founded to assume that animals will not There Is little dispute that VC Is car coma. sufficient information Is unavail develop tumors when exposed at concen cinogenic to man and we so conclude. able to exclude from consideration of trations of VC of less thin 50 ppm. However, the precise level of exposure risk thoee employees in workplaces for Should a sufficiently large number of ex which poses a hazard and the question which cases of cngloaazcoma have not perimental animals be exposed to VC at of whether a "safe" exposure level exists, bem observed. concentrations of less than 50 ppm, cannot be definitively answered on the It has also been ruxtested that the Schneidcrmxn said that It would be ex record. Nor Is it clear to what extent absence of cancer In a population ol 335 pected that some would develop VC In exposures can be* feasibly reduced. We Dow Chemical Company polymerization duced tumor*. cannot wait until Indisputable answer* mployces monitored over a period ol 7 (3) Feasibility- There 1* virtually no to these questions ere available, became years. Indicates that exposure to vinyl dispute that most. If not all. fabricators lives of employees are at stake. There chloride at concentrations ol less than are currently capable of reaching ex fore, we have bad to exercise our best 200 ppm Is safe (e study by Dr. Cook, posure levels of I ppm through engineer judgment on the basis of the best avail eubmltted at the hearing by Dow Chem ing controls. These employer* employ able evidence. These Judgments have re ical Company.) However, the group sur well over 95 percent of all employees ex quired a balancing process, in which the veyed did not Include all worker* who had been exposed, and the missing em ployees Included many who had the longer terra (over 20 years) exposures. posed to VC. Indeed, severe! fabricator* are already operating at this level (see SPI testimony). However, Industry spokesmen have universally claimed that overriding consideration has been the protection of employees, even thoee who may have regular exposures to VC throughout their working live*. Moreover, the statistically insignificant It Is Infeasible for the VC and the PVC Based on the available evidence and In size of the sample copulation decreases Industries to remain below 1 ppm con view of the above considerations, includ the possibility that tumor* would be sistently. using engineering controls. In ing feasibility, we believe that employee observed. addition, the Fnell study on technical exposures to VC must be reduced to * I Dow also presented preliminary data feasibility concluded Lh"t a 1 ppm ceil ppm time-weighted average (TWA). We In testimony at the hearing on the pos ing Is not feasible for the VC and PVC also believe that PVC and VC establish sible metabolic pathway* of VC. The Industries with prevent technology, but ments will, in time, be able to attain that hypothesis presented was that VC may that the VC Industry could currently at level through engineering controls, and exert Its carcinogenic effect by a metab tain lower exposure levels than the PVC that fabricator* can do so in the Im olite. and that the metabolite is pro Industry, tabor union spokesmen and the mediate future. duced only when VC U metabolised by a Health Research Oroup. Ine., however,' In addition to the TWA requirement, secondary metabolic pathway operating have suggested that such a level U at we have established a 5 ppm celling only when eniy me* regulating the prl- tainable. (averaged over a 15-mlnute period) In jlnary pathway are saturated, a* would Since there la no aetuil evidence that order to prevent exposure of employees be the result at higher exposures. The any of the VC or PVC manufacturer* to unacceptable high excursions. From preliminary data Indicated the possi have already attained * 1 ppm level or In *n operation standpoint, this celling bility of an additional pathway for fnet Instituted all available engineering level Is realistic because minor excur metabolism of VC in rat* exposed to con and work practice controls, any estimate sions up to the celling level ire likely to centrations of VC In excess of 220 ppm. as to the lowest feasible level attainable occur on a regular basis. However, the occurrence of angio must necessarily Involve subjective Judg III. The /Inalrfandard--fl) Scope end sarcoma in both rats and mice at VC ment Likewise, the projections of indus application. Bolt. the RTS *nd the pre exposure concentrations of 50 ppm in try, labor, and other* concerning feasi paid would apply the standard to tba dicate* that if a metabolite of VC is the bility are essentially conjectural. Indeed, entire VC Industry. Including manufac ultimate carcinogen, then It must be generated at lower exposure concentra tions to these species Although this re search raay be helpful to the thorough understanding of the carcinogenicity of VC, It appears that it does not yet offer evidenoe which can assist in determina tion of sate exposure concentrations for employee*, or even that such safe ex posures exist. A number of witnesses representing employers have stressed that there Is no evidence of cancer, either In employees or experimental animals, at exposure concentrations of VC less than SO ppm. (See t t, testimony of Firestone. Ten* neco Chemicals.) The conclusion of these witnesses was that no decision can be as Firestone has suggested. It is not pos sible to accurately predict the degree of Improvement to be obtained from en gineering changes until such changes are actually Implemented. We agree that the PVC and VC estab lishments win not be able to attain a 1 ppm TWA level for all Job classifications In the near future. We do believe, how ever, that they will. In time, be able to attain levels of 1 ppm TWA for most lob classifications most of the time. It Is ap parent that reaching such levels may re quire some new technology and work practice*. It may also be necessary to utilise technology presently used In other Industries. In any event, the VC and PVC Industries have already made great turer* of VC and PVC and fabricators, but excluding employer* handling or using fabricated product* made from VC. There le no dispute that a standard 1* required for the monomer and polymer Industries. However, the Society of Plas tics Industry <SPI) and various fabrica tor] (sec testimony of Goodyear, Gen eral Cable, etc.) recommended that fabricators be excluded from the standard. or that a separate requirement be established for them because many of them were already at or below the propot-d ceiling level. The record evidence establishe* that t least some employees in the fabricat ing industry are exposed in excess of the made concerning risk of exposure to VC strides in reducing exposure levels. (See permissible control limits (Bee NIOSH at concentrations less than 50 ppm. testimony Of Dow Chemical Co.. TR 913). testimony, TR log; Robintech TR 642), On the other hand, the testimony of For example, B. F. Goodrich testified In these circumstances, we believe that it most expert witnesses. Including some in dustry biomedical experts, stated that quantification of a safe exposure con centration is not possible with the pres ent state of scientific knowledge. (See ITR 1120) that It has reduced average exposure levels in several PVC plants from 35-40 ppm early this year to 12-13 ppm at the time of the hearing. We are Is imprudent to grant a blanket exemp tion for all fabricator*. Therefore, the final standard Is appllcsble to the fabri cation Industry, as well as the monomer reoMAi ttcimi, vol >y, no. t--rstOAv, groin 4, 1974 19 I |A'\ UOO 062885 RULES AND REGULATIONS 3589.1 and polymer Industrie*. Employer* who, temperature as PVC. for further pro below the action level, no further moni In fact, are substantially belocr the cessing, Indicates that a potential for re toring U required unless the employer posure Jir.dt wiu be subjected to only lease of the residue still exists. It ap has reason to suspect that any employee minimal burdens by virtue of the "action pears that the exemption of fabricated Is exposed In excess of the action level, *evel" to be discussed below. products should be limited to just those or unless changes have been made in Where employers In the fabricating Hems which will not undergo such mass production, process, control, type of resin, 1-duetry have exposures approaching the heating, Further, the opportunity to etc. permissible limit, they will appropriately demonstrate that exposures are below W'here the exposure level, without re be subject to the aUndard Employers the action level, and thus, discontinue gard to respirators, exceeds the permis handling or using fabricated products many duties of tho standard, provides a sible levels, monitoring must be conduc made of PVC were not included In the more positive control and an adequate ted at least monthly. Where exposures ETS or the proposal and are excluded relief. are less than the permissible levels, but from the final standard. This conclusion (2) Permissible exposure limit. The greater than the action level, monitoring Is based on the absence of ad^uate evl* standard sets an exposure limit of 1 ppm must occur at least quarterly. dence of exposure to VC In these opera averaged over any 8 hour period, and a (5) Methods of compliance. The stand tions The final standard clarifies the ex ceding ol S ppm averaged over any per ard, like the proposal, requires that em emption by defining a fabricated prod iod not exceeding IS minutes. ployers Immediately Institute feasible uct aa a product made wholly or partly As more fully discussed above, thU engineering and work practice controls from PVC which does not require further limit U based on an evaluation of the best to reduce exposures to at or below the processing at temperatures, and for available evidence and on a Judgment permissible exposure limit. times, sufficient to cause mass melting of that the health and safety of employees Where feasible engineering and work the PVC. 8PI and others (cf TO. 344) requested (hat PVC resins with less than 0.1 percent residual monomer be ex empted from the regulation now. and that the exemption level be reduced to 0 01 percent In three years SPI suggested that the exemption of materials with less than 0 1 percent of 14 carcinogens from 29 CFR 1910 P3p (39 ER 3756) was an appropriate precedent. The eases are not comparable, because no attempt had been made to set air concentration limits for the 14 carcinogens. The record did not Include Information that reliable moni toring and measuring techniques were available. Moreover, the exemption did not exempt airborne traces of carcino gens The administrative cutoff was pro vided to avoid regulation of materials about which there was no health haz ard Information, and which would have broadly extended the application of the regulation beyond the record- Herein, no Information was presented to show safe concentration results from the use of resins with specific levels Indeed, the proposal to change the level later, when Improved technology would permit such reduction, would seem to Indicate that must be protected to the fullest extent feasibte. In view of the fact that release ol VC in the VC and PVC manufacturing processes are variable, the 1 ppm celling level provided In the proposal would require maintenance of an average level significantly more difficult to attain through feasible engineering controls. Therefore, the exposure limit prescribed In the proposal has been rejected. (3) Action level. The final standard, unlike the ETS and the proposal, pro vides for an "action level" of 0 5 ppm TWA, one-half of the permissible ex posure limit. The purpose of the action level Is to minimize the Impact of the standard on the employers who have attained exposure levels well below the permissible limit. Thus, where the re sults of monitoring under paragraphs (dull or (d)(2> demonstrate that no employee Is exposed in excess of 0.5 ppm TWA, employers may. In effect, bo exempted from some provisions of the standard For example, fabricators who are below the action level are not re quired *o provide medical surveillance or to monitor again, unless the employer has reason to suspect that any employee practice controls will reduce exposures below the permissible levels, they must be Instituted. Where such controls will not reduce exposures below the permis sible level, they must nonetheless be im plemented to reduce exposures to the lowest practicable level, and be supple mented by the use of respirators to pro vide the necessary protection. There upon. a continuing program of engmeerlns and work practice controls must be Instituted to reduce exposures to the low est practicable level. When exposures are at or below the permissible exposure limits, the program may be discontinued. In addition, a plan for achieving con trol by engineering and work practice methods must be drawn up and be made available, upon request, to represent atives of OSHA and NJOSH. We recognize that many employers covered by the standard can not cur rently achieve compliance with the per missible exposure limit solely by the use of feasible engineering and work practice control*. The record also reflect* broad generic distinctions between the compli ance capabilities of the VC and PVC Industries. Some industry spokesmen. SPI has doubts about the safety of ft.i is exposed In excess of the action level. Including SPI (TO. 358-362), recom percent residue level Diamond Shamrock In our Judgment, exposures below the mended that a schedule of different per- (Exhibit 142) testified that there Is no action level do not present a sufficient missile exposure limit* and compliance direct relation. They Indicate that the hazard to warrant application of the en dates be established for the VC and PVC airborne concentration Is more related tire standard to the many employers who segment* of the Industry. to the physical form of the resin and are or will be below that level. This view assumes that the ability and the ventilation provided Also, monitor (4) Monitoring. The final standard, the time required to feasibly reach in ing data from Industry (cf. Exhibits 131. like the proposal, requires that Individual creasingly lower control levels is similar 166.1701 and OSHA (Exhibit 151) indi employee exposure levels be determined. wllhfn each Industry, but differs mark cate that levels In excess of I ppm may ThU may be accomplished by personal edly between Industries. While the record be found In fabrication operations. In or area monitoring. Some witnesses and does suggest that tuch differences do view of these facts and of the opportunity persons who submitted comments did exist between industries, as noted above. for employers to discontinue many duties not understand the meaning of the term It Is clear that Intra-industry differences upon a showing of no exposures above the "93 percent confidence level" In the also exist. Thus, the ability and time re action level, It does not appear that any proposal. Essentially It means that the quired by each employer to attain lower residue exemption Is either Justified or employer Is required to take a sufficient control levels may depend upon such necessary at this time. This course also number of measurements so that the re factors as the climate In which the plant agrees with a number of Industry pro sults obtained are statistically valid. We Is located, the age of equipment, the sue posals (cf. TO 660). have modified the proposal to establish of reactors, or the type of resin manu SPI (TO 3451. among others, asked that compounded PVC pellets be ex empted from the standard on the grounds that the pellets had too tow a residue to cause harmful or measurable emissions. While it appears that PVC pellets would accuracy range requirements for various measurement levels. These ranges are narrow enough to ensure that a deter mination of compliance can be made, and broad enough to allow the application of a variety of technologies factured or used. (Snell study, firestone testimony, etc.) Monitoring data also tends to support such Intra-Industry variation*. (See, c g Dow, Firestone, Tenneco.) As noted above, the standard requires have a lower residue level than virgin AH covered employers are required to all employers to Institute feasible engi PVC, the fact that the pellets must be conduct InltUl monitoring Where moni neering controls to the fullest extent and heated to a molten mass at the same toring and measuring results are at or to continue to Improve and apply engl- ivortAi aronra. vot. *, no. tea--stioar, ociosn a. wa 11 358M BUIES AND REGULATIONS necrlag caaLreJi until full compliance lx if the environmental level !e not con achieved. trolled to the permissible ezpoeure limit, We hav# sot established any deadlines then employees must be afforded respira for full compliance through engineering tory protection. controla because we are presently unable While exposures in excess of the per- to determine a ben it will be feasible for mlsrible level do constitute a hazard, we most establishments to reduce exposure believe that it is necessary to mitigate levels to Use permissible leveL tome of tlie problems associated with We also believe that the requirement Implementing a program of respiratory thet ezich employer reduce airborne con* protection while employees are being ctntraUona to the permissible level, or fitted and trained in respirator use. and to the lowest level feasible as soon as while other adjustments which may be practicable win provide for Lnter-indus- required are implemented. Therefore, try and Intra-Industry technological dif until January 1, 11378, where exposures ferences which da exist, aod will avoid are not in excess of a 25 ppm celling, the setting of separate Industry stand each employer must provide each em ards on the basis of tbe general situation ployee with an appropriate respirator. and conditions In each Industry. However, employees whose exposures do <$> Regulated areas. The proposed not exceed a 25 ppm celling, may decline standard would have required that regu to use the respirator. In which case the lated areas be established, that access be employer U not obligated to require Its limited to authorized employees, and use. During this adjustment period, em that dally rosters or summaries of those ployees will be trained In the uses, pur entering be kept for at least 20 years In poses and limitations of respirators, end objection to these requirements. It was the hazards of exposure to vinyl chloride. asserted that such control of access was Moreover, each employee will be notified not necessary from a health standpoint. In writing if he has been exposed In ex Secondly. It was claimed that these con cess of the permissible exposure limit. trols would Interfere with operations by Where exposures exceed a 25 ppm ceil preventing access of needed employees or ing, respiratory protection is mandatory non-employees, such as contractors, in light of our Judgment that much truck drivers, customers and consultants. greater risks are associated with such The purpose of establishing regulated exposures. areas In the proposal was to limit the The provisions In the final standard rfck of exposure to as few employees as regarding the selection and use of respi possible. This concern ts still paramount, ratory protective devices differ from and thus the limited access feature re those In the proposal. The descriptions of mains. The Anal standard amends the atmosphere-supplying respirators hove proposal slightly to allow "authorized been revised Vo indicate more clearly the persona" to enter regulated areas. This types of devices intended, and the maxi change, ft Is felt, will allow operations to mum permissible concentration level for continue without undue Interference. each device Moreover, the number of The final standard has also Increased the types of atmosphere-supplylnfi devices length of time dally rosters must be boa been increased. maintained from 20 to 30 years. This At the bearing Mr. Edwin C. Hyatt, an change was based largely on epidemio OSHA consultant, made suggestions re logical considerations. (See NIOSH testi garding the use of particular respiratory mony, tr. 119.) devices. We have concluded that his sug (7) Rtrptratarv protection. The final gestions arc meritorious. Therefore, the standard, like the proposal, requires the provisions for selection of atmosphere- use of respirators where employee expo supplying devices follow closely the rec sures exceed the permissible control level. ommendations contained In Ms testi Industry representatives made a number mony of 5PI and B. F. Goodrich) (TR of objections to proposed requirements with Hyatt's suggestions. (See e g. testi for respiratory protection. They stated mony of SPI and EL P. Goodrich) (TR thot the "no detectable level" would ef 85 it) We bad originally omitted alr- fectively require continuous wearing of punfylng respirators because none had respirators In PVC and VC plants, and been approved by NIOSH Tor use against that this is not feasible because respira VC, principally because they lacked In tors are cumbersome, present a safety dicators to signal the expiration of the hazard, and employees would not use service life Of the sorbent. Hyatt and them. other witnesses discussed In detail the We would agree thet respirators have desirability of being able to use canisters many drawbacks; the proposal did not or cartridge atr-purtfying respirators, contemplate them as a final solution. Tbe provided a sorbent could be shown to record shows that the PVC Industry par effectively absorb vinyl chloride with an ticularly may need several years before adequate service life. Recently, OSHA plant environmental levels can be re baa received respiratory, data from labo duced so that respirators are necessary ratories regarding the effectiveness of only occasionally. However, we cannot commercially available canisters and agree that respiratory protection should cartridges for vinyl chloride. These eval not be required simply because it is In uations were conducted separately by convenient, may require additional per NIOSH and by the B. F. Goodrich Com sonnel, Interferes with production, or pany and submitted to OSHA In poet- may require extensive retraining of em hearing comment*. The results Indicate ployees and restructuring of work prac that certain presently available canis tices. We have carefulfr considered all ters and cartridges effectively absorb the objections, and have concluded that vinyl chloride at relatively low concen trations. Za discussions of these findings with NIOSH. it he* Indicated that it Is willing to consider on an expedited basis the approve! of alr-purUylng respirators for use against VC. Consequently, we have Included three types of alr-purifyIng respirators Id the list of acceptable Units, subject to the approval of such units by NIOSH. The maximum concen tration for which each respirator may be used k based upon our evaluation of the data submitted by NIOSH and Goodrich. Because air-purifying respi rators do not Indicate sorbent exhaustion or breakthrough of VC, and because VC has no Inherent warning properties st levels for which these devices are used, strict administrative controls will be re quired for their uxe. Such controls In clude a program to assure timely re placement of canisters or cartridges and an alarm system to alert employees when vinyl chloride concentrations exceed the concentrations allowed for the particu lar type of respirator in use. <8> Noeordouj operationi. This Is a new section within the final standard. It encompasses essentially the proposal's requirements tor maintenance and de contamination but has restated them In terms of performance language to allow treater fiexJbillty for employers to deal with such operations. The Intent of the new section Is to protect employees en gaged In activities that present a risk of exposure to vinyl chloride In excess of the permissible levels. An example would be the cleaaing of a filter where resin con taining high residual monomer Is trapped. The proposal's requirement for fullbody, Impervious clothing has been re placed by tbe direction to use Impervious garments suited to tbe particular situa tion and probable extent of exposure. Thus, full-body clothing Is not always necessary, and Is therefore not required where less protection Is adequate. Since vessel entry falls within the definition of a hazardous operation, the vessel entry section of the proposal has been deleted from the final standard. (9) Emergency situations. Tbe defini tion of emergency has been recast tn terms of an unexpected massive release. The main objection to tbe aectlon on emergency situations In the proposal was that, as the term was defined, many ordinary leaks or operations resulting In a small release of vinyl chloride would be considered emergencies. This was not the intent of the proposal. Tbe final standard has been clarified to correct this ambiguity. It should be noted that the written operational plan required by the standard need not be developed for minor excursions above the permissible exposure limit, and that such excursions need not be reported. (10) Signs and labels. The thrust of the signs and labels section U to apprise employees of the cancer and fire haz ards. No objections have been raised with respect to Informing employees of the fire hazard. However, a number of ob jections were raised at the hearing and In written submissions to the require ment that the word "cancer" appear n all signs and labels. The principal argu- HDIKA1 UOISTH, VOi- av, NO. 1*4--fllDAT, OCTOSU 4. 1*74 11 ucc 062887 f\nu KtuuiAltQN) 35 -93 mtnt advanced Against Its use was that Indicated that the medical tests proposed posal It the requirement for maintenance the term "cancer" or "cancer-suspect are currently the only ones available of monitoring records and dally roster agent" scares employees and that In which are useful for medical surveillance sheets of authorized persons for 30 years. stead, fho met sage should contain In (TR 12J. Exh 05, TH 689-691). Conse Instead of 20 years. Additionally, the em structions on how to deal with the sub quently. the specific blood tests proposed ployer Is required to maintain medical stance <TR. 347). We believe that a have been retained as a minimum re records for the duration of an employee's diluted form of warning will not suffice. quirement to assist the examining physi employment plud 2Q years, or 30 years, V.'e appreciate the concern of employer* cian in determining fitness of potential whichever is longer. The original pro with the reaction of their employees But employees for assignment to workplace! posal called for only 20 years. we consider It Imperative that a worker involving VC exposure. In addition, al This change has been implemented be be fully fnformed, and that he realize the ternative medical examinations may be cause the latency period for induction of possible risks invoked In hts occupation. used where the examining physician de angiosarcoma ranges up to 30 years from Coupled with the training requirement termines that they are at least as good initial exposure. Therefore, as a mini In the standard, wt believe that the signs as those specified by the standard. mum. medical records must be main and labels required will adequately In The Tabershaw-Coopcr study and the tained for at least that long. It should be form employees of the hazard. In addi various animal experiments suggest that noted that spokesmen for both labor and tion, such signs will warn unauthoilzed VC may produce a wide spectrum of ma Industry recommended that this change personnel to keep out of regulated areas. lignant and non-mailgnant disorders. be made. Tlie proper application of most protec The general scope of the required medical The reporting Requirements are not tive measures requires an amount of examination has, therefore, been broad significantly different from those in the training and Indoctrination of employees ened to Include kidneys, skin, connective original proposal. However, Instead Of that cannot easily be conveyed on a sign tissue, spleen, and pulmonary system, as the requirement for reporting Incidents or label. Also, the variety of measures well as the liver. No additional specific which result In the release of VC Into that could be prescribed would result in procedures or tests are required, but rec areas where employees may be exposed, an unwleldiy or excessively detailed leg ommendations have been Included in the the final standard clarifies our original end Consequently, the required message Appendix to assist the examining physi Intent by stAting that only emergencies on signs and labels will not Include In cian. Because of the nonspecific nature must be reported. Also the requirement formation on precautions, relevant ol the required medical tests, it Is not for filing a detailed, written report symptoms, etc. The addition of suitable appropriate to prescribe timing, or type within IS days has been deleted. It has Information by the employer would be of followup tests, or to mandate with been concluded that submission, within permitted, providing it does not detract drawal from exposure based solely on re 24 hours, of as initial report that in In any way from the required statement. sults of the tests. Instead, the employer cludes facts immediately available, would The requirement In the proposal for Is required to obtain a statement from ordinarily be sufficient. However, U the labeling containers of vinyl chloride has the examining physician of the em OSHA Area Director requests further In been amended by deleting the reference ployee's suitability for continued expo- formation relevant to the emergency, the to the possible hazard of violent polym ture, when the examining physician ha* employer will be required to furnish such erization. Very little information was completed such tests as he considers ap information. developed on this hazard during the propriate. The employer is required to (14) Deleted portions of thi proposal. standard-setting procedure It does ap withdraw an employee only when this The proposal contained provisions re pear that this hazard Is essentially under statement Indicates that the employee quiring that shower facilities and change control and that the Are and carcino may be at added risk from continued VC rooms be provided, and that storage or genic hazards at present are the most exposure. consumption of food be prohibited in significant. Since labeling or placarding As with monitoring, there appear* to regulated areas. We have deleted these that is In compliance with the V 8 De be no basis for complete exemption of the provisions because It Is our conclusion partment of Transportation regulations fabrication industry from the require they are no longer necessary. Showering <19 OH Part 173, Subpart H) already ment for medical examination. The rec facilities are not required because pro warns of the Are hazard, only a state ment concerning the carcinogenic haz ard need be added to the Department of Transportation labels. ord does show fabricating establishments with concentrations of VC monitored considerably above the action level. In these Instances, medical surveillance of tective clothing, where required by the final standard, should protect employees from skin absorption by direct contact with VC and because there Is no reliable <ll) Afedieol surveillance. The princi affected employees wlU provide baseline evidence that VC vapor Is absorbed pal questions that have been raised re data for future evaluation of their health, through the skin. In addition, slnee we garding medical surveillance are the even If both monitoring and medical sur anticipate that most employees will not necessity and efficacy of requiring cer veillance are discontinued because im be wearing protective clothing and that tain spectfle serum enzyme determina proved controls reduce concentrations employees who wear protective clothing tions (SWA-13 senes) and the applica below the action level. Where exposures will change such clothing Infrequently, tion of medical examination require are below the action level, the medical we are not requiring that change rooms ments to the fabrication segments of the surveillance requirements do not general be provided. Industry where employees are exposed to ly apply. In addition, we feel that there Is in lower levels of VC. The objection has also <13) Training. A separate provision for adequate evidence showing that hazar been raised that the speclAcatton of tests employee training has been added to the dous amounts of VC can be absorbed and procedures Interferes with the ap Anal standard rather than Including it through Ingestion. For this reason, the plication of advances In medical knowl within the section on emergency situa requirement prohibiting the storage or edge. tions as in the proposal. The new para consumption of food in regulated areas A particular difficulty tn considering graph provides for training of employees has been deleted. medical surveillance Is that the moat concerning the carcinogenic hazard of The proposal also contained previsions commonly discussed lesion, angiosar VC. emergency procedures, the need for on malntentance and decontamination, coma-of the liver, currently cannot be monitoring and an annual review of the transportation loading and unloading, diagnosed until the victim Is terminal standard It also provides for training of and polymer handling operations. These and, usually, within months of death. employees concerning the purpose for, requirements are not mentioned In the Precursor physiologic alteraLions, which proper use of, and limitations connected final standard because attention to these might be reversible, have not yet been with respiratory protection. turns Is implicit in the requirement that directly associated with the lesion. Con US) Recarit and reports. The provi each employer reach the permlssable ex sequently. there are no speeiAe diagnos sions for recordkeeping contained in the posure limit or atutn the lowest feasible tic tests which can be prescribed which Anal standard require the preparation kveL will determine presence or absence of and maintenance of essentially the same (13> tffeettve date. In order to ensure this tumor at an early stage of develop information required by the proposal. that affected employers and employees ment. However, most medical witnesses The major change from the original pro will be Informed of the existence of these fgbttAt Bfditm, vol **, no. tee--nioar, ocrosti s, ieye IS S5S9S BUIES AND REGULATIONS provision* end that employer* affected ef the operation or because of an acci opportunity to observe the monitor era given an opportunity to familiarise dent in the operation, which would result ing and measuring required by thb themselves and their employee* with the in an employee exposure In excess of the paragraph. existence of the new requirements, the permissible exposure limit, (e> Regulated area. (1) A regulated elective date of the amendment to <81 "OGHA Aren Director" means the area shall be established where: | ISIO.SjQ will be January 1,1975. To pro Director for the Occupational Safety (1) Vinyl chloride or polyvinyl chloride vide continued protection for employees and Health Administration Aren Office l manufactured, reacted, repackaged, until that date, the provisions currently having Jurisdiction over tile geographic stored, handled or used; and cdntr.lncd In I I9l0.93q are hereby area In which the employer's establish (10 Vinyl chloride concentrations are promulgated, pursuant to aectlon 6<b>, ment b located. In excess of the permissible exposure S(c) and file) of the Occupational Safety 19) "Polyvinyl chloride" means poly limit. end Health Act. a* an occupational vinyl chloride homopoljmer or copoly (2) Access to regulated areas shall be safety and health standard effective mer before such Is converted to a fabri limited to authorized persons. A dally October 4, 1974, the amendment to cated product. roster shall be made of authorized per | 1010.93q set out below will supersede (10) "Vinyl chloride" means vinyl sons who enter. these provisions as of January 1. 1975. chloride monomer. </) Methods of compliance. Employee Accordingly, upon consideration of the (c) Permissible exposure limit. (1) No exposures to vinyl chloride shall be con whole record of this preceding. Part 1910 employee may be exposed to vinyl chlo trolled to at or below the permissible ex of Title 99, Code of Federal Regulations ride at concentrations greater than 1 ppm posure limit provided In paragraph <e) Is amended, effective January 1, 1975, by averaged over any 8-hour period, and of this section by engineering, work prac revision of 11910 93q to read ac follows: (2) No employee may be exposed to tice, and personal protective controb as 11910-9S* Vioyl chloride. (a) Scope and application. (I) Thta section Includes requirements for the control ot employee exposure to vinyl vinyl chloride at concentrations greater than 5 ppm averaged over any period not exceeding IS minutes. (3) No employee may f>c exposed to vinyl chloride by direct contact with follows: (1) Feasible engineering and work practice controls shall Immediately be used to reduce exposures to at or below the permissible exposure limit. chloride (chloroethtnel, Chemical Ab liquid vinyl chloride. (2) Wherever feasible engineering and stracts Service Registry No. 75015. (d) Monitoring. (1) A program of work practice controls which can be In (27 This section applies to the manu Initial monitoring and measurement stituted immediately are not sufficient to facture, reaction, packaging, repackag shall be undertaken in each establish reduce exposures to at or below the per ing, storage, handling or use of vinyl ment to determine if there la any em missible exposure limit, they shall none chloride or polyvinyl chloride, but does ployee exposed, without regard to the use theless be used to reduce exposures to not apply to the handling or use of fabri of respirator*, In excess ot the action the lowest practicable level, and shall be cated products made of polyvinyl chlo level. supplemented by respiratory protection ride. (3) Where a determination conducted In accordance with paragraph Ig) of thia (3> This section appUee to the trans under paragraph <d)ll) of this section section. A program shall be established portation of vinyl chloride or polyvinyl show* any employee exposures, without and Implemented to reduce exposures to chloride except to the extent that the regard to the use of respirators, tn ex at or below the permissible exposure Department of Transportation may cess of the action level, a program for de limit, or to the greatest extent feasible, regulate the hazards covered by this sec termining exposures for each such em solely by means of engineering and work tion. ployee shall be established. Such a pro practice controb. as soon as feasible. (b) Definitions. 1> "Action level" gram: (3) Written plans for such a program means a concentration of vinyl chloride (1) Shall be repeated at least monthly shall be developed and furnished upon of 0 S ppm averaged over an l-hour work where any employee b exposed, without request for examination and copying to day. regard to the use of respirators, In ex authorized representatives of the Assis a> "Assistant Secretary" means the cess of the permissible exposure limit. tant Secretary and the Director. Such Assistant Secretary ot Labor for Occupa (11) Shall be repeated not less than plans shall be updated at least every aix tional Safety and Health. US. Depart quarterly where any employee Is exposed, months, ment of Labor, or his designee. without regard to the use of respirators. (g) Respiratory protection. Wher* (31 "Aathorlred person" means any person specifically authorised by the em ployer whose dutlei require him to enter a regulated area or any person entering uch an are* as a designated representa tive of employee* for the purpose of ex ercising an opportunity to observe moni toring and measuring procedures. In excess of the action level. (Ill) Kay be discontinued for any em ployee only when at least two consecu tive monitoring determinations, made not lees than 5 working days apart, show ex posures for that employee at or below the action level. <3> Whenever there has been a pro respiratory protection is required under this section; (1) The employer shall provide a respirator which meets the requirement* of this paragraph and shall assure that the employee uses such respirator, except that until December 31, 1975, wearing of respirators shall be at the dberetion of (41 "Director" means the Director, duction, process or control change which each employee for exposures not tn ex National restitute for Occupational may result In an Increase in the release cess of 25 ppm, measured over any 15- Safety and Health. U & Department of of vinyl chloride, or the employer has mtnute period. Until December 31, 1975. Health. Education, and Welfare, or hia any other reason to suspect that any em each employee who chooses not to wear designee. ploye* may be exposed In excess of the an appropriate respirator shall be in (5) "Emergency" means any occur action level, a determination of employee formed at least quarterly of the hazards rence such as, but not limited to. equip exposure under paragraph <d> (1) of this of vinyl chloride and the purpose, proper ment failure, or operation of a relief de aectlon shall be performed. use, and limitations of respiratory vice which Is likely to, or doe*, result In <4> The method of monitoring and device*. masstve release of vinyl chloride. measurement shall have an accuracy (2) Respirators shall be selected from (97 "Fabricated product" means a (with a confidence level of 95 percent) Of among those jointly approved by the product made wholly or partly from not less than plus or minus 50 percent Mining Enforcement and Safety Admin polyvinyl chloride, and which does not from 0 25 through 0 S ppm, plus or minus istration, Department of the interior, require further processing at tempera 38 percent from over 0 5 ppm through and the National Institute for Occupa tures, and for times, sufficient to cause 1.0 ppm, and plus or minus 25 percent tional Safety and Health under the pro mass melting of the polyvinyl chloride over 1-0 ppm. (Methods meeting these resulting tn the release of vinyl chloride. accuracy requirements are available in (7) "Hazardous operation" means any operation, procedure, or activity where a the "NTOSH Methods"). Manual of Analytical release of either vinyl chloride liquid or (8) Employee* or their designated rep gas might be expected at a consequence resentatives shall be afforded reasonable visions ef 30 CFR Part II. (3> A respiratory protection program meeting the requirements of 11910.134 shall be established and maintained. (4> Selection ot respirators for vinyl chloride shall be as followa; HOftAl IICItTIA VOL JV. NO. 1*4--MIOAt, OCTOilJ 4. 1*74 14 EUIES AND REGULATIONS 35897 Atr*6*pKeric conctntrattcm */ wyl eMortS* JUqvittd apparatus (vl) The purpose for, and a descrip tion of, the medical surveillance (l) UniDown, or iv S.900 ppm-- Opan-elreult, *etf-eont*ln*4 breathing apparatus, praa- program; (U) Ko< crrrr t.CCO ppm (1U) ITot onr 100 (I) Pot otwM ppta... --------- cure damanA tjpfl. vtlb full furepleo*. (A) OomfctncttoQ typ* C auppUad air retp!rVor, pree- tun t3prairvj typa, with full or hall facepteea, tid nuiliUrf Kir-oooUIr.nJ air aupply; or (B) Typa C. *uppl(fd atr respirator continuous Cow typo, with foil or half ractplec*, and auxiliary e-If-coatAlorel air supply. w Combination typ C auppIiKj air raxpifalor de mand typ*. with full f*c*pi*c*, *nd utilUrp rlf'OOBt*tnc<l klr supply; or (B) Optn-ctreuK **lf-cont*lned breitblng app*r*tu* with full faceplcca. In drmind merit, or <0) Ttpt C supplied *lr rplrttor, demand typ*. with full ftcepleo*. (A) A peer ml atr-purlfying respirator with hood, helmet, full or half raceplec*. and * canister < vlli Emergency procedures; (vlli) Specific Information tp aid the employee tn recognition of conditions which may result in the release of vinyl chloride; and <ix> A review of this standard at the employee's first training and Indoctrina tion program, end annually thereafter. (3) All materials relating to the pro gram shall be provided upon request to the Assistant Secretary and the Director. <k> Medical turveWanct. A program of medical surveillance shah be Insti tuted for each employee exposed, with out regard to the use of respirators, to which provider acrvlc* Ilf* of *t Icrit * vinyl chloride to excess of the action hour* for cone*oration* of vinyl ehlorld* up level. The program shall provide each uo 3S ppm. or such employee with an opportunity for (B) Oa* m*k. front* or b*ek-tnousted canister which examinations and tests to accordance provider Mrvlc* Ilf* of *t Icvjrt 4 hour* for with this paragraph. Ail medical ex cooc*otrt|otit of vinyl chloride up to 3S ppm, aminations and procedures shall be per (t) Kot ov*r 10 ppm <A) Combination typ C ruppllcd-rlr respirator, detn*od typ*. with hrlf facaplecw, *nd auxiliary aclf-contalncd rlr supply; or (B) Tjrp* C *upplltd-*lr rrrpirktor, demand typ*, with half facepiece, or (C) Any chemie*] cartridge respirator With rn organic vapor cartridge which provider k kervlr* Ilf* of *t lent 1 hour for concentration* of vinyl ehlorld* up to 10 ppm. formed by or under the supervision of a licensed physician, and shall be provided without cost to the employee. <1) At the time of Initial assignment, or upon Institution of medical surveil lance; (1> A general physical examination shall be performed, with specific atten tion to detecting enlargement of liver, (5) (l) Entry Into uniown concentra tion* or concentration* greeter than 36,000 ppm (lower explosive limit) may be made only for purposes of life rescue; and (11) Entry Into concentration* of less then 36,000 ppm, but greater than 3,600 ppm may be made only for purposes of Ufa rescue, firefighting, or securing equipment so as to prevent a greater hazard from release of rlnyl chloride. (8) Where alr-purlfylng respirator* are used: (I) Alr-purlfylng cannUtere or car tridges ahall be replaced prior to tha expiration of their sendee life or tha end of the shift In which they are first used, whichever occur* first, and (II) A continuous monitoring and alarm system shall be provided where concentrations of vinyl chloride could reasonably exceed the allowable concen tration* for the devices In use. Such sys tem shall be used to alert employees when vinyl chloride concentrations exceed tha allowable concentration* for the device* In use. (7) Apparatus prescribed for higher concentration* may be used for any lower Concentration. <h) Hazardous oporations. (1) Em ployees engaged In hazardous operations. Including entry of vessel* to clean poly vinyl chloride residue from vessel walls, sh*B be provided and required to wear and use; (3) Protective garments shall be pro vided dean and dry for each use. (1) Emergency ntvations. A written operational plan for emergency situa tion* shall be developed for each facility storing, handling, or otherwise using vinyl chloride as a liquid or compressed gas. Appropriate portions of the plan shall be Implemented in the event of an emergency. The plan shall specifically provide that: (1) Employees engaged In hazardous operations or correcting situations of ex isting hazardous releases shall be equipped as required In paragraph (h) of this section; (2) Other employees not so equipped shall evacuate the area and not return until conditions are controlled by the methods required in paragraph (f) of this section and the emergency Is abated. (J) Training. Each employee engaged In vinyl chloride or polyvinyl chloride operations shall be provided training In a program relating to the hazards of vinyl chloride and precautions for Its safe use. (1) The program shall Include: (I) The nature of the health hazard from chronic exposure to vinyl chloride including specifically the carcinogenic hazard; (II) The specific nature of operations which could result In exposure to vinyl chloride In excess of the permissible limit and necessary protective steps; spleen or kidneys, or dysfunction to these organs, and for abnormalties to skin, connective tissues and the pulmonary system (See Appendix A). ill) A medical history shall be taken. Including the following topics: (A) Alcohol Intake: (B) Past history of hepatitis: (C> Work history and past exposure to potential hepatotoxlc agents. Includ ing drugs and chemicals; (D) Past history of blood transfu sions; and (E> Past history of hospitalizations. (Ill) A serum specimen shall be ob tained and determinations made of: (A) Total bilirubin; (B) Alkaline phosphatase: (C) Serum glutamic oxalacetlc trans aminase (SCOT): (D) Serum glutamic pyruvic transam inase (SGPT); and <E> Gamma glustamyl transpeptidase. (2) Examinations provided In accord ance with this paragraph ahall be per formed at least: (1) Every 6 mouths for each employee who has been employed to vinyl chlo ride or polyvinyl chloride manufacturing for 10 years or longer; and (U) Annually for all other employees. (3) Each employee exposed to an emergency shall be afforded appropriate medical surveillance. (4) A statement of each employee's suitability for continued exposure to vinyl chloride Including use of protec (I) Respiratory protection In accord (11) The purpose for. proper use, and tive equipment and respirators, shall be ance with paragraphs (c) and (g) of limitations of respiratory protective obtained from the examining physician this section; and devices; promptly after any examination. A copy (II) Protective garments to prevent skin contact with liquid vinyl chloride or with polyvinyl chloride residue from vessel waits. The protective garment* (Iv) The fire hazard and acute toxic ity of vinyl chloride, and the necessary protective step*; of the physician's ststement shall be pro vided each employee. (5) If any employee's health would b* ahaU be selected for the operation and (v> The purpose for and a description materially Impaired by continued ex IU possible exposure conditions. of the monitoring program; posure, such employee shall be with- RDttAl SKlIira, VOL It, ISO. 1*4--IDAT, OCIOBU 4, 1*24 35898 CW.2S ANO REGULATIONS drawn frc'ra possible oeatact with vinyl Jiloride. (6) Libor*lory analyses for all bio logical specimen* Included In medical eoaminadon* shall be performed In Laborttoriea licensed under 43 CFR Pert 74. <7J If tbs o* mi nine physician deter mines that alternative medical examina tions to those required by paragraph <k> < 1) of tldx section will provide at least equal assurance of detecting med ical conditions pertinent to the exposure to vinyl chloride, the employer may ac cept such alternative examinations as meeting the requirements of paragraph <k)(l) of thts section. If the employer obtains a statement from the examining physician setting forth the alternative examinations and the rationale for sub stitution. This statement shall be avail able upm request for examination and copying to authorized representatives of the Assistant Secretary and the Director. (!) Sicnu and labels. ill Entrances to regulated areas shall be posted with leg ible signs bearing the legend: Cshcra-Boarsc-T Aotm Am Aomoaizaa pnNNirrL OlCLT ' 13) Areas containing hazardous oper ations or where an emergency currently exists shall be posted with legible signs bearing the legend: CaMtia.-6awm Acxxe tit Twos Ami honenva KoeirweHT RxQurxra Atmtostcso ruMMis Owws (3) Containers of polyvinyl chloride resin a-aste from reactors or other waste contaminated with vinyl chloride ahull be legibly labeled: Contaminated with Vum CHtoamt Ciscn-Svinct Acme <4) Container* of polyvinyl chloride shall be legibly labeled: Polvumtl CMiosme (o> Tessa Nswa) Contains Ttvn Ciiuwsl ViHTt Cfeuina a a Ciscndcmn Axeirr (fi) Containers of vinyl chloride shall be legibly labeled either: tl Vu* TV. CxlNDt rimvKLT hiMMmi Oab Pssa Fmivii Cxvcxs-fiuvacT Acuvr or (111 Ih accordance with 49 CTR Fart 173. Bubpwrt H. with the additional legends: Cxncex-EusrecT Asm applied near the labor or placard. te> No statement shall appear on or near any required sign, label or instruc tion which contradicts or detracts from the efTeet of, any required warning. Information or luslrutklan. (m) Accords. <l> AH records main tained In accordance with this section shall Include the name and social secu rity number of each employes where relevant. (2) Records of required monitoring and measuring, medical records, and au thorized personnel rosters, shall be mode and shall be available upon request for examination and copying to authorized representatives of the Assistant Secre tary and the Director. (1) Monitoring and measuring records shall: (A) State the date of tuch monitor ing and measuring and the concentra tions determined and Identify the Instru ments and methods used: <B> Include any additional Informa tion necessary to determine Individual employee exposures where such expo sures are determined by meant other than Individual monitoring of employee*; and (C) Be maintained for not less than 30 years. <11) Authorized personnel rosters shall be maintained for not less than 30 years. till) Medical records shall be main tained for the duration of the employ ment of each employee plus 20 years, or 30 years, whichever u longer. (3) In the event that the employer ceases to do business and there Is no successor to receive and retain his rec ords for the prescribed period, these rec ords shall be transmitted by registered mail to the Director, and each employee Individually notified In writing of this transfer. (4) Employees or their designated representatives shall be provided access to examine and copy records of required monitoring and measuring. (5) Former employees shall be pro vided access to examine and copy re quired monitoring and measuring records reflecting their own exposures. <fl> Upon written request of any em ployee, a copy of the medical record of that employee shall be furnished to any physician designated by the employee. rn> Report*, (l) Not later than 1 month after the establishment of a reg ulated area, the following Information ahall be reported to the OSHA Area Di rector. Any changes to such Information ahall be reported within IS daya. (1) The address and location of each establishment which has one or more regulated areas; and <il> The mmbwr sd agirlsrsee tn etch regulated area during normal operations, including maintenance. <3> Emergencies, and the facts ob tainable at that time, shall be reported within 24 hours to the OSltA Area Di rector. Upon request of the Area Direc tor. the employer shall submit additional Information In writing relevant to the nature and extent of employee exposures and measure* taken to prevent future emergencies of similar nature. (3> Within IQ working days following any monitoring and measuring which discloses that any employee has been exposed, without regard to the use of respirators In excess of the permissible exposure limit, each such employee shall be notified In writing of the results of the exposure measurement and the steps being taken to reduce the exposure to within the permissible exposure limit. (o) Effective dates. <1) Until Janu ary 1, 1975. the provisions currently set forth In 1 16l0 83q of this Part shall apply. <21 Effective January 1, 1975, the pro visions set forth In I 1910.93q of this Fart shall apply. Arrtnotx A--EvmtMtHTUT Mutest, IwioxuxttoM When required text* under paragraph (k)(l) of this section show abnormalities, the lull should be repealed as soon le prae-' tlcablt. preferably wltbla 1 to 4 weeks. It tests remain abnormal, consideration should pa given to withdrawal of the employee from contact with vinyl chloride, while a more eomprehtoslve examination to made. Additional teste which may be uiefut: A. Far Metcry dysfunction: urine examina tion tor albumin, red blood eerie, and si follatlve abnormal cells. B. Pulmonary system: Forced vital capac ity, Forced nplratory volume at l second, and chest roentgenogram (posterior-anterior, 14 * 17 Inches). C. Additional serum teste: Lactic arid dabydrogennee, lactic acid dehydrogenase tooenzjms, protein determination, and protein electrophoresis. D. For a more comprehensive examlnarinn on repeated abnormal serum testa: Hepatitis B antigen, and liver scanning. (Secs 8 and I. 4 Slat. USB. 1891 (28 USC. 855. 857); Secretary of Labor's Order No. 12-71. M FS 1704) Signed at Washington, DC., this Ut day of October, 1974. John StCNout, Assistant Secretary of Labor. IPR Doe.74-22178 FUed 10-1-70.3:84 pm) KDfkAL IfCIITII, VOL If, NO. 1*4--UUDAY, OCTPIE1 4, 1*74 IN C VV O &GfijfCEy Adds Chromatographic Capability to their Portable and Fixed Organic Vapor Analyzers t rmMCOftDtft ji s*. Sw'v 41?"- CJ ( 4 *j7c^_' i l V'*| CENTURY MODEL OVA-98 PORTABLE INSTRUMENT WITH CHROMATOGRAPH ADAPTION & STRIP CHART RECORDER ADDED AS SHOWN. Now lor the first time a portable, continuous sampling Organic Vapor Analyzer which also has gas chromatographic capability is available in our OVA instrument series. And the most exciting (act of all is that this new analyzer, including the strip chan recorder, still maintains the lightweighl portability and reliability features which are characteristic of all OVA'S. This unique instrument permits not only the detection and quantitative analysis ol potentially hazardous vapors but also an "on-the-spot" qualitative analysis within minutes, depending upon the components under analysis. Elaborate and timeconsuming laboratory analysis is now significantly reduced because a compact, unique, gas chromatograph system is built right into the instrument. After location of potentially hazardous vapors, using the stan dard quantitative sample survey and analysis methods describ- d in the brochure "Century Portable Organic Vapor Analyzer", simply depressing the Column Valve will "switch" the chromatographic system into operation. This diverts a portion of the vapor sample through the column tor separation and subsequent readout on the strip chart recorder. At the same time, a charcoal finer is switched inio the sampling syslem to reduce the hydrocarbon background during analysis. When the Column Valve is depressed, an immediate negative reference indication is printed on the strip chart recorder which establishes a "starting time baseline" for the chromatographic analysis Subsequently, each component of the sample exits from the column into the detector chamber after its respective retention time. Each produces a peak on the logarithmic strip chart recorder and on ihe hand-held, logarithmically scaled meter Examples of typical analysis recordings of the linear time versus logarithmically scaled vapor level are shown in this brochure. Column selection for specific applications is facilitated by the availability of interchangeable columns, which can easily be changed by simply loosening two swagelok fittings. In addition 10 standard columns, which are designed for most standard in dustrial applications, special custom columns can be provided to cusiomer specifications or the customer can easily provide his own column. In summary, employers concerned with the safety of their employees can now rapidly determine the ppm composition of potentially hazardous gases within minutes after the "heart and extent of the problem" is determined. Give the OVA with column and recorder options a close look. It's at least one state of the art level`ahead of any instrument available for industrial hygiene or air quality control applications. 17 Of 1% 0.1% 1 00 ppm 1 0 ppm 1 ppm Vinyl Chloride I JS"- c > Gr O -- 68 sec. 3 ft. DNOP Column Note that tima basa la linear but hydrocarbon level Is log seated for measurement of low level trace elements. TYPICAL OVA PRINTOUTS SHOWING CLEAR COMPONENT SEPARATION ucc It 062893 B Si FEB Vsipop /Lrgs-Eyses* ucc 062894 .. GECvTUE^V FesrSsCsEe ^ FggarBB \5spop ^rasill^zer raroCe-csEs s?OLa sirad EE^a FBviFG'FBnriiCSinst INTRODUCTION A completely portable Or* ganic Vapor Analyzer (OVA) is now available to detect and measure hazardous gases found in almost all industries, including manufacturing, petro-chemical, and natural gas transmission and distri bution. The Century OVA is a highly sensitive instrument designed to measure trace quantities of organic mate rials in air. It incorporates a hydrogen flame ionization detection system which has similar analytical capabilities to those utilized in gas chroma tographs. The flame ioniza tion detector is an almost universal detector for organic compounds with the sensi tivity to analyze for them in the parts per million range (V/V) in air in the presence of moisture, nitrogen oxides, carbon monoxide and carbon dioxide. The instrument has broad application, since it has a continuous, chemically re sistant air sanfpling system and can be readily calibrated to measure almost all organic vapors. It has a single loga rithmically scaled readout from 1 ppm to 100.000 ppm or with lower maximum level, if desired. Designed for use as a portable survey instrument, it can also be readily adapted to fixed remote monitoring or mobile installations. It ii ideal for the determination of many organic air-pollu tants and in the monitoring of air in potentially con taminated areas. The unique feature of the instrument is its complete portability which enables an entire facility to be surveyed rapidly and thoroughly. When vapors are detected, the continuous sampling feature enables the origin of those vapors to be readily traced and corrective action initiated. In most cases a qualitative analysis is not justified until the presence of potentially hazardous vapors is detected and the source of the vapors is determined. If, after locating the source, the vapors or mixture of va pors cannot be readily identified, a sample can be taken and a qualitative anal ysis performed on standard laboratory equipment. How ever, location of the vapor source will many times reveal the type of vapor and the concentration level can then be read directly, by simply changing the instrument cali bration to the predetermined setting for that particular vapor. The OVA thus enables a comprehensive survey of an entire facility to be performed rapidly and economically in contrast to ineffective and costly spot sampling techniques. PRINCIPLE OF OPERATION The instrument includes a detector chamber where the organic vapor being analyzed is introduced into a small hy drogen flame. Air sample is drawn into the instrument at a constant rate of nominally two (2) liters per minute through a chemically resis tant line and pump. The oxy gen in the air sample is used to support the small hydro gen flame. Flames characteristically have electrical conductivity due to the presence bf electrons and ions generated from the burning fuel. When even trace amounts of organic material enter the hydrogen flame, car bon-containing ions are formed and the electrical con ductivity increases signifi cantly. This change in con ductivity is measured and the output is directly related to the concentration of organic materials. The exception to this phenomenon is carbon monoxide and carbon diox ide which evidently, due to their structure, do not pro duce appreciable ions in the detector flame. Thus, other organic materials may be analyzed in the presence of CO and C03. An electric field in the cham ber drives the ions to a col lecting electrode which causes a current to flow into a pre amplifier that is proportional to the ion collection rate. The rate of ion generation is a function of the quantity and Structure of the carbon com pound present in the sample. The ionization current is am plified in a logarithmic electro meter preamplifier, the out put of which varies as the logarithm of the input. This logarithmic feature enables measurement and readout of ionization rates over a range of up to five (5) decades (1 to 100,000) without range scaling. The output signal from the preamplifier is fed to the signal conditioning and con trol circuits for subsequent readout and alarm signalling. small hydrogen flame jet in the chamber. The instrument response is read on a hand held meter assembly or can be read out utilizing the exter nal monitor signal. An audible detection alarm is provided which can be pre-set to any desired level and which has a freauencv modulated tone which varies as a function of the signal level. The standard instrument includes an audi ble flame out alarm, battery test indicator and internal electronic calibration. The internal electronic calibration provides reference signals which are used in conjunction with a panel mounted gas selector adjustment to readily change the instrument calibra tion from one gas to another. Since the response of the in strument is dependent upon the chemical nature of the material being analyzed, it is necessary to calibrate the de vice with a standard sample of that particular organic vapor. However, the approxi mate response of the instru ment to hydro-carbons or compounds containing halo gens, oxygen, or nitrogen can be estimated from the structure of the compounds and utilization of empirical data. The internal electronic reference signals art provided so the operator can readily recheck the instrument re sponse from the point of ion collection to the readout meter. A fuel handling system in cluding storage tank, valves, regulators and gauges is in corporated to maintain the 0 Thii twitch H uud to introduce the HIGH oi LOW calibration aignal -irrenta. 'Hilt twitch turn* on power to the Internal pump. A low ptDurt gauge it utad to monl. tot the hydrogen prttjurt at the t lllary reitnctot. Thit valve h uted to tupply or elaet off the hydrogen fui to the dr zeetor chamber. Thit control it utad to ediutt tht iratrument ateetronic calibration. A hi^i pretaure gaugt mtaturet tht pretaurt in tht hydrogen tutl tank wdtich it an indication ol fuel tupply. Thit valvt it utad to tupply or etoaa off tht fuel tupply from tht hydrogen tank. Thii contractor it utad to connect tht battery pack to tht btrttry rachargtr aattmbly. Thii indicator uaad to monitor tha templt flow rata. Thit connaetor it uaad to connect tha Imtrument 0-5VDC output ognal to an aatamat monitor. Thit valvt k uaad to Opan ona and of tha inftrumant fual tank for refilling avith hydro^n. A tan-turn dial readout potantiemeear ft utad to aat t pradtttmtinad calibra tion raftranct t*vM for electronic calibration. Thii twitch b mod to Aim an alt by ttrumant electrical power aleapt pie emmp power and a<te to ditplay tha battery rfiargt condition. A potentiometer on back of malar b utad to tat tht vapor detection level at aOnch tha widtbff atarm b actuaod. >1 occ 062896 APPLICATIONS (1) Measurement of most toxic organic vapors present in industry for compliance with OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION (OSHA) requirement*. (2) Survey of gas distribution and transmission lines and equipment for compli ance with OFFICE OF PIPELINE SAFETY (OPS) requirements. (3) Various measurement and monitoring applications in the air pollution field. (4) Leak detection in gas handling equipment. (5) Detecting explosive-level gas conditions in indoor and outdoor locations. (6) Measurement of methane in underground mines. OTHER TYPICAL USES (1) Controlling and monitoring atmospheres in manufacturing and packaging operations. (2) Mudlogging, gas and mineral exploration. (3) Leak detection related to volatile fuel handling equipment. SPECIFICATIONS Sensitivity; 1 ppm (methane) Response time; Less than 2 seconds Readout 250 logarithmic scaled meter, various scales in the range of 1-100,000 ppm. External monitor connectbr. Sample flow rate: Nominally 2 liters per minute. Fuel supply: 75 cubic centimeter tank of pure hydrogen at max. pressure of 2300 PSIG, finable while in case. Primary electrical power. Rechargeable and replaceable battery pack, at 12 VDC. Service life: Hydrogen supply and battery power - 8 hours operating time minimum. Size: Side Pack Assembly 8% " wide x 11%*' long x 4'i" deep. Probe/Readout Assembly - variable Weight Side Pack Assembly -- less than 9 pounds. Probe/Readout Assembly - less than 2 Pounds. Operator requirements: One man, one hand operation. Detection alarm: Frequency modulated audible alarm. Can be pre-set to desired level. Flame-out indication: Battery test Pickup fixtures: Probe: Umbilical cord: Filtering: Side pack case; Standard accessories: Frequency varies as a function of detection level. Audible alarm plus visual meter indication. Battery charge condition indicated on readout meter or battery recharger. Variety of types for various applications. Telescoping adjustment over 8 inches or probe can be completely removed from Readout Assembly. Five (5) feet long with connectors for electrical cable and sample hose. In-line disposable and permanent particle filter* and optional activated charcoal filter. Molded high impact plastic case with carrying handle and shoulder strap. 1) Instrument carrying and storage case. 2) High pressure fuel filling hose assembly. 3) A.C. Battery charger. ucc 062897 MODEL 511 FLAME IONIZATION PORTABLE GAS CHROMATOGRAPH COMPLETELY PORTABLE RECHARGEABLE BATTERIES SELF-CONTAINED, REF1LLABLE GAS SUPPLY O ON-SITE ANALYSIS LOW POWER CONSUMPTION LOW WEIGHT --40 lbs. ISOTHERMAL OPERATION TO 175C ON-COLUMN INJECTION INTERCHANGEABLE FID-EC-TC DETECTORS USES GLASS OR METAL COLUMNS The Model 511 Portable Gas Chromatograph is a completely self-contained instrument. Con taining rechargeable Nickel-Cadmium batteries and a refillable gas supply this instrument may be carried fully operational to the sampling area and operated immediately upon arrival. The availability of three interchangeable detection systems allows the selection of the appro priate detector to perform virtually any isothermal gas chromatographic analysis. Accessability to the column and detector compartment is readily accomplished by the removal of the lid assembly from the instrument. Located on this lid assembly are the column, injector, detector, heaters and associated feed back circuits. For operator ease, all electrical connections are made through a mating plug. Incorporating state of the art electronic design, the Model 511 Portable Gas Chromatograph may be powered from a 110 volt source or from the self-contained Nickel-Cadmium batteries. The batteries are capable of powering the instrument for a minimum of 8 hours at oven tem peratures of up to 200C before they must be recharged. While th batteri s are being recharg d the instrument remains operational and may be used to perform additional analyses-. Where external gas supplies are available, they may be used with the instrument in order to conserve the gases located in the power pack. ucc SI 062898 APPLICATIONS Methane, Total and Non-Methane Hydrocarbons 45 ppm The use of valving systems allows the analysis of Total Hydrocarbons in one mode of oper ation and the separation of these materials in the other mode. Utilization of the back flush valve after the methane has been determined flushes all of the other compounds back into the detector where they can be measured if desired. Organic Solvent Vapors The .determination of the various individual compounds present in an air sample is an im portant analysis in the Environmental Health and Industrial Hygiene areas. Since the Model 511 separated the sample into its individual compounds it is possible to determine the con centration of each chemical. MMliftt*( HOW TO ORDER Model 511 Portable Flame Ionization Cas Chromatograph including rechargeable Nickel-Cad mium batteries, recharger and lecture bottles of all gases required for detector operation. Also includes a 6 ft. x V inch column packed with 10% DC-200 on Chromosorb W HP. Fittings provided on power pack for recharging lecture bottles to high pressure. Consult Price List for instrument and accessory prices. ANALYTICAL INSTRUMENT DEVELOPMENT, INC. RT. 41 S NEWARK RD., AVONDALE, PA. 19311 PHONE: (215)-26B-311 All Prices FOB Avondale, Pa. PB122 7/73 *4 'JCC 062899 Printed in USA Dala Sheet 08-01-01 Model S Monitaire Sampler Application The Model S MonitaireTM Sampler by MSA provides the necessary vacuum for sampling atmospheres which may contain certain toxic and combustible gases, vapors, dusts, fumes, and mists. Description The Model S Monitaire Sampler is a rechargeable-battery-operated dia phragm pump which supplies a vacuum source for many atmospheric testing devices including filter paper holders, charcoal tubes, impingers, and numer ous MSA portable gas detection instru ments. Flow rate is adjustable. Pump can be clipped to a worker's belt so that a continuous air sampling can be made over several working hours. The Model S pump features a dual valve assembly: a sample valve controls the sample flow directly, and a bypass valve controls bypass air which may enter through the center of the stem. The bypass valve permits the pump to operate efficiently by compensating for sample-flow restrictions. Low sampleflow requirements or highly restrictive sample devices introduce a pressure differential which must be reduced. The bypass valve introduces atmospheric air directly into the pump, reducing the pressure differential; the bypass may be partially or totally closed at higher sample rates. Proper bypass settings are specified in the instruction mate rials that are part of the Monitaire Sampler Kit. A tube fitting on the exhaust side of the pump permits use of the Monitaire Sampler for pressure operations. The battery charger has two charging rates to charge the Model S pump over night or Over weekends; fully charged battery will run the pump continuously for up to eight hours. ' The Model S Moni taire Sampler Kit includes: selfcontained batteryoperated pump, battery charger. Instruction man ual, pump mainte- ,. nance card, and attach^* type carrying case with room for accessories. Data Sheet 08-01*01 t Sampling method* Dust and mist collection. Filter paper holders adapt the Model S pump to the collection of dust, fiber, and particulate samples, plus detection of chromic acid mist and lead. This open-face-type Jj holder assembly is used for col- |--*>,, lecting samples {; ` for evaluating ~ asbestos, cotton, ! silica, lead, etc. Preweighed cassette o..i ,1 - & *]. Cyclone assembly Reusable tiller holder This respirable dust sampler uses a cyclone and preweighed filter cassette or filter holder to collect only the respirable fractions of a variety of dusts, such as coal and silica. This holder assembly adapts the Model S k pump to chem ically det ct chromic acid mist and lead dust and fumes. Collection data are given on chart at right ZyX v* , t _ * * - * *v V V * * * 7*. ['"svot*TM * '> v? t'. y Sampling data for chromic acid mist and lead dust and fumes Measured Component Threshold Limit Value for 1973 Calibration Range Sampling Time Chromic acid mist Lead dust and fumes 0.1 mg/M3 .15mg/M 0.1-2.1 mg/M3 .05-6.3 mg/M3 1 to 105 minutes 116 to 46 minutes Filler weighing balance Hazards of dust are often evaluated on a weight basis. A high degree of sensi tivity (.Of milligram) is required to relate collected samples 1o Threshold Limit Values. The Ainsworth Model 22MF Balance from MSA meets these requirements. I M pmm -c^fcmpting tubes. When used n^PRjel S Monitaire Sampler e MSA Tube Holder. MSA Char- impling Tubes provide for t collection of organic and ' vapors for subsequent analysis Moratory equipment. Each tube separate layers of charcoal: section and a reference ic vapor sampling tube will organic compound which is being collected, desorbed, d: such compounds include rbon tetrachloride, chloro* e, ethylene dichloride, trlie, and xylene. The mer; tube collects both elesmically bound mercury articulates containing ainfess-ste (tube tive, leak-free seal; -tip attaches to lapel 3 near wearer's fmplnger tests The Monitaire Sampler can be used with MSA Midget Impinger flask assemblies for dust, gas, and vapor sam pling, Total air borne particles are wetled down and collected in the impinger flask. Because of the pump design, a 0.1 cfm sampling rate at 12 in., H20 vacuum can be obtained. This rate can be maintained for up to eight hours with a fully charged battery. For sampling toluene diisocyanate (TDI). toluene diisocyanate urea, methylene di-para-phenylene isocya nate (MDI), and polymethylene polyphenyiisocyanate (PMPPI) vapors, en all-glass impinger flask is used with the Model S pump. irinnj wun ms a ponaoie gas detection Instruments. The Monitaire Sam pler will also provide a con tinuous vacuum for drawing gas samples through MSA portable detection equip ment fortesting periods up to eight hours. The test instruments can be placed up to 100 feet from the test location when sampling lines of V* -inch 10 tubing are used. MSA gas detection instruments that can be used with the Monitaire Sampler Include: Portable Gas Indicator Model 20 Portable Gas Indicator Model 21 Portable Gas Indicator Model 30 Portable Gas Indicator Model 40 Explosimeter* Model 2 Expfosimeler Model 2A Explosimeter Model 2B Explosimeter Model 3 Explosimeter Model 4 Explosimeter Model 5 Explosimeter Navy Type 8 Explosimeter Navy Type E Explosimeter AF Navy Type R-1 Gascope* Model 53 Portable Oxygen Indicator, 0-25% Range Portable Oxygen Indicator, 5-40% Approvals and standards Sampling pump has USBM Approval No. 2G-2239-2 as "permissible" for methane/air atmospheres. Factory Mutual approved as "intrinsically sate" for Class I, Division I, Groups C and D hazardous locations. Specifications Pump Type: diaphragm Dimensions: 2Vz in. x 5 in. x 5 in. Weight: 31 oz, including battery Battery and performance: 6-volt rechargeable battery, 8-hour continu ous operation on full battery charge Flow indication: 0 to 10 scale Maintenance: (1) valve stems should be cleaned periodically by removing valve and blowing with air; (2) flow-tube assembly is easily removed and replaced: (3) pump and charger should be stored in container when not in use Battery charger Dimensions: 2Vi in. x 3 in. x 4V4 in. Weight: 12Vi oz Power source: 16-hour rate for over night charging, 64-hour rate for week end charging Ordering information Catalog numbers 459660 4S8475 456059 996097 996338 459662 93385 459182 457629 Model S Monitaire Sampler Kit, complete with pump, charger, maintenance card, instruction manual, and carrying case Pump, Models Battery charger Maintenance card Instruction manual Carrying case Flow-tube assembly, 0 to 10 range Battery pack, replacement Calibration check unit for sampling pumps 92944 456243 456242 456228 456226 456246 625412 449347 459743 457392 Dust and mist collection accessories Holder assembly, filter disc Holder assembly, respirable dust, complete with cyclone and sampling line assemblies Holder assembly only, respirable dust Cyclone assembly only Sampling line assembly Kit, supplementary parts, including: 1 press/pry tool for 2- or 3piece aerosol filter holder (456223) 1 brush (625416) 1 tweezer (625417) 3 screens, stainless steel support (456224) Holder, aerosol filter, 2-piece: pkgof 12 Holder, aerosol filter, 3-piece: pkg of 10 Coupler, sampling line; pkg of 3 Coupler, stainless steel, for aerosol filter holder sampling with cyclone assembly 457391 39642 39G43 Coupler, plastic, for pre weighed cassette sampling with cyclone holder assembly Balance, filter weighing Carrying case for balance . 459003 459004 459054 Charcoal sampling tubes and accessories MSA Charcoal Sampling Tubes, mercury vapor, pkg of 12 MSA Charcoal Sampling Tubes, organic vapor, pkg of 12 MSA Tube Holder 93470 93495 Impinger test accessories Connector assembly for Midget Impinger flask Tubing for TDI or MDI flask i Note: This Data Sheet contain* only a general description ol the Model S Monitaire Sampler. While uses and performance capabilities are described, under no circumstances should this device be used until the instructions, labels, or other literature accompanying the product have been carefully read and the precau tions therein set forth followed. Only they contain the complete and detailed informa tion concerning this product MSA MINE SAFETY APPLIANCES COMPANY 400 PENN CENTER BlVD.. PITTSBURGH, PA. 15235 At your service: 76 branch offices in the United Stales: MSA CANADA. Downsview, Ontario (Metro Toronto), Halifax, Montreal, Winnipeg, Saskatoon. Edmonton. Calgary, Vancouver; representatives in principal cities of the world, cable address--"MINSAF" Pittsburgh beta Sheet 0S-01-O1 Primed in U SA 7** (L) VINYL CHLORIDE DETERMINATION IN AIR BY ADSORPTION ON ACTIVATED CHARCOAL AND ANALYSIS BY GAS CHROMATOGRAPHY 15-MINUTE SAMPLE PURPOSE AND LIMITATIONS This paper describes a procedure for measuring the exposure of personnel to vinyl chloride in the working environment. The method describes the preparation of standards which will determine vinyl chloride in the range of 9 to 90 parts per million by volume in air, based on a 15-min. sample at a flow rate of 100 ml per minute. Lower or higher ppm ranges can be determined by preparing additional standards to cover the range desired. (Vinyl chloride can be determined to at least 0.05 ppm by volume in air by this procedure, using more dilute standards.) PRINCIPLE The sample is collected by passing air through a glass tube containing activated charcoal which adsorbs any vinyl chloride vapors present. The vinyl chloride is then desorbed from the charcoal by carbon disulfide extrac tion and analyzed by gas chromatography. INSTRUMENT PARAMETERS Chromatograph C lumn ^Column temperature Injection temperature Detector Carrier Hydrogen flow rate Air flow rate Sampl size Ret ntion tine AID (Analytical Instrument Development, Inc.) Portable Chromatograph, Model 511, or equivalent chromatograph, with flame ionization detector. Six-foot x 1/8-inch stainless steel packed with 10% di(2-ethyIhexyl) sebacate on Chromasorb P, 80/100 mesh, NAW. 100*C isothermal 100C flame ionization detector helium or nitrogen 23 cc per minute 133 cc per minute 2 pi solvent flush technique 0.5 minute (adjust carrier flow until vinyl chloride elutes at this time) i *Notei If this column is used in a conventional chromatograph, '^ better separation of vinyl chloride from^other light . boiling impurities ViYl'*'be' obtained1by operation oi /rrT t he "column oven near ambient temper at ure-^O^C. The1 '"'AID portable chromatograph cannot be used at ambient ^temperature without modification since the h at from the flame ionization detector will"causV'the' temperature in thp column oven to rise to 60 to 70 C. < Alternate Column - Better Resolution Instrument Column Detector Column temperature Detector temperature Injector temperature Carrier gas Air flow Hydrogen flow Sample size Approximate elution time Hewlett-Packard 5750 gas chromato graph - dual column, or equivalent. 25-foot x 1/8 inch stainless steel packed with 25% by weight 75% C0880/25% Tergitol E-35 on 40/60 mesh rescreened Chromosorb P, flame ionization 40" to 100C at 4*0 pur minute 125C 125C helium, 30 ml per minute 350 ml per minute 30 ml per minute 10 pi 6.5 minutes 4 REAGENTS AND APPARATUS a) Personal sampling pump. MSA Model G or Bendix Micronair. Insert an in-line orifice made from a cut-off and restricted (pinched) hypodermic needle in the sampling line to the pump in order to obtain a 100cc per minute flow on these pumps. b) Hypo-vials, 15-ml size, Cat. No, 12911; Neoprene septa, Cat. No. 13233; alumina seals, Cat. No. 13214; and hand crimper. Cat. No. 13212, Pierce Chemical Company, Rockford, Illinois. c) Carbon disulfide, epectrophotometric grade d) Activated charcoal. Cat. No. 580-26, Barnebey-Cheney, Columbus, Ohio e) Soap film flow meter, 10-ml size f) Stop watch 5 PREPARATION OF THE ACTIVATED CARBON ADSORPTION TUBE a) Prepare the activated charcoal by placing the charcoal on a 40-mesh sieve and wash with demineralized water until no visible fines appear in the washings. b) Dry the carbon in a drying oven at 110*C until dry and free flowing (overnight). Store in a screw-top, glass bottle until needed. c) Cut 8-mm O.D. x 6-nun I.D. Pyrex glass tubing into 6-inch lengths and fire polish the ends. d) Insert a Pyrex glass wool plug two-thirds of the distance into the glass tubes. The longer section of tubing will be designated as the primary end, while the shorter side of the tubing is the back-up end. e) Pack the tubes with the activated carbon, using a length of 60 mm in the primary section and 35 mm in the back-up section. Retain the carbon with glass wool plugs. f) Seal the tubes with a red rubber septum or parafilm until ready for use. ucc 062905 X 6 SAMPLING PROCEDURE a) Remove the seals from the charcoal tube and attached the back-up section to a portable pump by means of a length of 1/4-inch Tygon tubing. b) Set the flow rate at 100 ml per minute through the tube with a calibrated rotameter. (NOTE: The 10-ml soap bubble flow meter can be used to obtain a more precise reading of the air flow through the tube if desired). c) Record the time the air sampling was started and the time when the sampling is completed. A 15-minute sample may be taken with this system. d) After sampling, recheck the flow rate and reseal the ends of the charcoal tube. Return the tube to the laboratory for analysis. e) Record the temperature and barometric pressure at the sampling site. 7 ANALYTICAL PROCEDURE a) Make a small hook at the end of a piece of wire and remove the glass wool plug from the primary end of the charcoal tube. Make sure that no charcoal particles adhere to the glass wool plug. b) Pour the charcoal into a 10-ml glass-stoppered volumetric flask and cool the flask and carbon in a wet-ire bath. . c) Pipet 3 ml of carbon disulfide (CS2) into the cooled flask and stopper securely. (CAUTION: Carbon disulfide is toxic and should be handled under a hood.) d) Agitate the flask periodically for at least 30 minutes. 9) Solvent Flush Injection Technique. This injection technique Is designed to eliminate difficulties arising from blowback or distillation with the needle of the microliter 6yrlnge. f) Flush a 10-/J1 syringe with CS2 several times to wet the barrel and plunger. g) Draw 2 jil of CS2 into the syringe and remove the tip of the needle from the solvent. Withdraw the plunger an additional 0.5 pi to separate the CS2 from the sample with a pocket of air. h) Dip the needle into the sample solution in the volumetric flask and withdraw the plunger until the air bubble between the solvent and the sample has passed the 2-jil mark on the syringe. 1) Remove the tip of the needle from the sample solution and adjust the volume In the syringe until the meniscus of the air bubble rests on the 2-yul mark. Remove the excess sample solution from the tip of the needle. j) Pull the plunger back an additional 0.5 jjI to prevent the sample solution from evaporating from the tip of the needle. k) Inject the entire contents of the syringe into the chromato graph. l) Measure the peak height and determine the vinyl chloride content from a previously prepared calibration ourve. 062^06 * 8 CALIBRATION CURVE a) Pipet 10 ml of carbon disulfide (CS2) into each of five 15-ml hypo-vials. Cap the vials with the Neoprene septa and aluminum seals, using the hand crimper. b) Place the hypo-vials in wet ice to reduce the vapor pressure of CS2. c) Cap one of the valves on a steel sample cylinder containing vinyl chloride with a 1/8-inch Swagelok tubing nut which has a chromatographic septum installed in the nut. d) Insert a hypodermic needle through the septum on the cylinder, open the valve and allow the vinyl chloride to vent through the needle for about 10 seconds to purge the air from the system. Remove the needle. ) Using the appropriate gas-tight syringe fitted with a number 27 gauge hypodermic needle, insert the needle through the septum on the cylinder and allow the pressure of the vinyl chloride to displace the volume of the syringe. Flush the syringe two times to remove any air which may have been trapped in the needle. f) Into the respective hypo-vials, Inject 0.2, 0.3, 0.5, 1.0, and 2.0 cc of vinyl chloride from the syringe. g) Shake the hypo-vials for one minute to put the vinyl chlorid in solution. These standards will contain 56, 82, 133, 260, 515 jigm of vinyl chloride per ml. (NOTE: These calcula tions are corrected for the dead space in the gas syringe needle. The cold CS2 solutions in the hypo-vials are under slight negative pressure. Measurements have shown that the dead space in the syringe needle amounts to 0.04 cc, and 0.02 cc of this volume is pulled into the hypo-vial by the negative pressure.) h) Allow the standards to warm up to room temperature, then inject these standards into the chromatograph using the procedure described in Section 7, paragraphs e through k. Shake the hypo-vials each time just prior to withdrawing a sample. i) Plot peak height versus micrograms of vinyl chloride per ml. 9 CALCULATION A x 3 x 24.5 L x 62.5 vinyl chloride, ppm by volume at 25*C and 760 mm A - pgro per ml of vinyl chloride read from calibration curve L - total liters of air sample (flow rate x time) S3 VINYL CHLORIDE DETERMINATION IN AIR BY ADSORPTION ON ACTIVATED CHARCOAL AND ANALYSIS BY GAS CHROMATOGRAPHY ` 4-HOUR SAMPLE 1 PURPOSE AND LIMITATIONS This paper describes a procedure for measuring the exposure of personnel to vinyl chloride in the working environment. The method describes the preparation of standards which will determine vinyl chloride in the range of 9 to 90 parts per million by volume in air, based on a 4-hour sample at a flow rate of 28 ml per minute. Lower or higher ppm ranges can be determined by preparing additional standards to cover the range desired. (Vinyl chloride can be determined to at least 0.05 ppm by volume in air by this procedure, using more dilute standards.) 2 PRINCIPLE The sample is collected by passing air through a glass tube containing activated charcoal which adsorbs any vinyl chloride vapors present. The vinyl chlorid is then desorbed from the charcoal by carbon disulfide extrac tion and analyzed by gas chromatography. 3 INSTRUMENT PARAMETERS Chromatograph Column - 'Column temperature Injection temperature Detector Carrier Hydrogen flow rate Air flow rate Sample else Retention time AID (Analytical Instrument Development, Inc.) Portable Chromatograph, Model 511, or equivalent chromatograph, with flame ionization detector. Six-foot x 1/8-inch stainless steel packed with 10% di (2-ethylhexyl) sebacate on Chromasorb P, 80/100 mesh, NAW. 100C isothermal 100 C ' flame ionization detector helium or nitrogen 23 cc per minute 133 cc per minute 2 pi solvent flush technique 0.5 minute (adjust carrier flow until vinyl chloride elutes at this time) jNotet If this column is used In a conventional chromatograph, r better separation of vinyl"chloride from other light J J boiling impurities will be obtained~'by operat ioh~oi , ,the column oven near ambient temperature -30*c. The I Deport able chromatograph cannot be used at ambient temperature without modification since the heat from Tthe flame 'ionization detector'will'cause"the temperature in the column oven to rise to 60 to 70 C, ucc a 062908 Alternate Column - Better Resolution Instrument Column Detector Column temperature Detector temperature Injector temperature Carrier gas Air flow Hydrogen flow Sample size Approximate elution time Hewlett-Packard 5750 gas chromato graph - dual column, or equivalent 25-foot x 1/8 inch stainless steel packed with 25% by weight 75% C0880/25% Tergitol E-35 on 40/60 mesh rescreened Chroraosorb P. flame ionization 40 to 100C at 4"C per minute 125 C 125C / helium, 30 ml per minute 350 ml per minute 30 ml per minute 10 pi 6.5 minutes 4 REAGENTS AND APPARATUS a) Personal sampling pump. MSA Model G or Bendix Micronair. Insert an in-line orifice made from a cut-off and restricted (pinched) hypodermic needle in the sampling line to the pump in order to obtain a 28 cc per minute flow on these pumps. b) Hypo-vials, 15-ml size, Cat. No. 12911; Neoprene septa, Cat, No. 13233; alumina seals, Cat. No. 13214; and hand crimper. Cat. No. 13212, Pierce Chemical Company, Rockford. Illinois. c) Carbon disulfide, spectrophotometric grade d) Activated charcoal, Cat. No. 580-26, Barnebey-Cheney, Columbus, Ohio e) Soap film flow meter, 10-ml size f) Stop watch 5 PREPARATION OF THE ACTIVATED CARBON ADSORPTION TUBE a) Prepare the activated charcoal by placing the charcoal on a 40-mesh sieve and wash with demineralized water until no visible fines appear in the washings. b) Dry the carbon in a drying oven at 110*C until dry and free flowing (overnight). Store in a screw-top, glass bottle until needed. c) Cut 8-mra O.D. x 6-mm I.D. Pyrex glass tubing into 6-inch lengths and fire polish the ends. d) Insert a Pyrex glass wool plug two-thirds of the distance into the glass tubes. The longer section of tubing will be designated as the primary end, while the shorter side of the tubing is the back-up end. e) Pack the tubes with the activated carbon, using a length of 60 mm in the primary section and 35 mm in the back-up section. Retain the carbon with glass wool plugs. f) Seal the tubes with a red rubber septum or parafilm until ready for use* M a SAILING procedure a) Remove the seals from the charcoal tube and attached the back-up section to a portable pump by means of a length of 1/4-inch Tygon tubing. b) Set the flow rate at 28 ml per minute through the tube with a calibrated rotameter. (NOTE: The 10-ml soap bubble flow meter can be used to obtain a more precise reading of the air flow through the tube if desired). c) Record the time the air sampling was started and the time when the sampling is completed. A four-hour sample may be taken with this system. d) After sampling, recheck the flow rate and reseal the ends of the charcoal tube. Return the tube to the laboratory for analysis. e) Record the temperature and barometric pressure at the sampling site. 7 ANALYTICAL PROCEDURE g) Make a small hook at the end of a piece of wire and remove the glass wool plug from the primary end of the charcoal tube. Make sure that no charcoal particles adhere to the glass wool plug. b) Pour the charcoal into a 10-ml glass-stoppered volumetric flask and cool the flask and carbon In a wet-ice bath. . c) Pipet 3 ml of carbon disulfide (CS2) into the cooled flask and stopper securely. (CAUTION: Carbon disulfide is toxic and should be handled under a hood.) d) Agitate the flask periodically for at least 30 minutes. e) Solvent Flush Injection Technique. This Injection technique is designed to eliminate difficulties arising from blowback or distillation with the needle of the mlcrollter syringe. f) Flush a 10-^1 syringe with CS2 several times to wet the barrel and plunger. g) Draw 2 jil of CS2 into the syringe and remove the tip of the needle from the solvent. Withdraw the plunger an additional 0,5 pi to separate the CS2 from the sample with a pocket of air. h) Dip the needle into the Sample solution in the volumetric flask and withdraw the plunger until the air bubble between the solvent and the sample has passed the 2-ul mark on the syringe. I) Remove the tip of the needle from the sample solution and ' adjust the volume in the syringe until the meniscus of the ait bubble rests on the 2-yul mark. Remove the excess sample solution from the tip of the needle. J) Pull the plunger back an additional 0.5 jjI to prevent the sample solution from evaporating from the tip of the needle k) Inject the entire contents of the syringe into the chromato graph. l) Measure the peak height and determine the vinyl chloride content from a previously prepared calibration curv UCC062910 3 CALIBRATION CURVE a) Pip t 10 ml of carbon disulfide (CS2) into each of fiv 15-ml hypo-vials. Cap the vials with the Neoprene septa and aluminum seals, using the hand crimper. b) Place the hypo-vials in wet ice to reduce the vapor pressur of CS2. c) Cap one of the valves on a steel sample cylinder containing vinyl chloride with a 1/8-inch Swagelok tubing nut which has a chromatographic septum installed in the nut. d) Insert a hypodermic needle through the septum on the cylinder, open the valve and allow the vinyl chloride to vent through the needle for about 10 seconds to purge the air from the system. Remove the needle. e) Using the appropriate gas-tight syringe fitted with a number 27 gauge hypodermic needle, insert the needle through the septum on the cylinder and allow the pressure of the vinyl chloride to displace the volume of the syringe. Flush the syringe two times to remove any air which may have been trapped in the needle. f) Into the respective hypo-vials, inject 0.2, 0.3, 0.5, 1.0, and 2.0 cc of vinyl chloride from the syringe. g) Shake the hypo-vials for one minute to put the vinyl chlorid in solution. These standards will contain 56, 82, 133, 260, 515 pgm of vinyl chloride per ml. (NOTE: These calcula tions are corrected for the dead space in the gas syringe needle. The cold CS2 solutions in the hypo-vials are under slight negative pressure. Measurements have shown that the dead space in the syringe needle amounts to 0.04 cc, and 0.02 cc of this volume is pulled into the hypo-vial by the negative pressure.) h) Allow the standards to warm up to room temperature, then inject these standards into the chromatograph using the procedure described in Section 7, paragraphs e through k. Shake the hypo-vials each time just prior to withdrawing a sample. i) Plot peak height versus micrograms of vinyl chloride per ml. 9 CALCULATION A x 3 x 24.5 L x 62.5 vinyl chloride, ppm by volume at 25*C and 760 mm A - pgm per ml of vinyl chloride read from calibration curve L - total liters of air sample (flow rate x time) ucc 062911 DETERMINATION OF RESIDUAL VINYL CHLORIDE MONOMER IN VINYL RESINS 1 PURPOSE A procedure for determining the amount of residual vinyl chloride present in vinyl rosins is described. The resin is dissolved in a solvent and tho vinyl chloride analysed using a gas chromato graphic technique. The method is applicable for use with poly(vinyl chloride), vinyl chloride-vinyl acetate copolymers and other vinyl resins in which there are no volatiles which interfere in the determination. 2 EQUIPMENT AND REAGENTS Gas Chromatograph, Hewlett-Packard (F and M) Model 5750 or equivalent, equipped with a hydrogen flame ionization detector. Tetrahydrofuran, reagent grade. Balance with accuracy to 0,10 gram. 2 SAMPLE PREPARATION Prepare the sample for chromatograph injection by dissolving the test resin in tetrahydrofuran (THF). Weigh 9 grams of THF into a suitable vial. Add 1 gram of the resin to be tested to the THF. Resin addition should be made as quickly as possible. Cap the bottle and place it on a can-roller to attain complete solution. When complete solution has occurred, the sample is ready for injection into the chromatograph. 4 INSTRUMENT PARAMETERS Instrument Hewlett-Packard (F and M) Model 5750 (or equivalent) equipped with hydrogen flame ionization detector. Column Six-feet by 1/8-inch stainless steel tubing packed with Chromosorb 102, 60/80 mesh. Temperatures: Column Injector Detector 100C for 4 minutes, manually increased to 250C 100*C (maximum) 300C (flame ionization) Sample Size 4 Microliters Flows: Helium Carrier Gas Hydrogen Compressed Air 25 cc/minute 20 psi at cylinder head* 40 psi at cylinder head. 4 (Continu d) Elution Times Vinyl Chloride Tetrahydrofuran 2.8 minutes 6.3 minutes 5 CALIBRATION Prepare solution mixtures of varying amounts of vinyl chloride in tetrahydrofuran to cover the expected range of concentration. Obtain from the chromatograph scan the area percent of vinyl chloride for each sample of known monomer content. Prepare a chart plotting the area percent vinyl chloride versus the known weight percent vinyl chloride to establish the relative detector response of the vinyl chloride with respect to tetrahydrofuran. 6 CALCULATION Determine the area percent vinyl chloride from the chromatograph scan for the resin solution to be characterized. Multiply this figure by 10, which converts the data to area percent vinyl chloride based on resin weight. Using the chart developed with the cali bration samples, read off the corresponding weight percent of vinyl chloride I P;^H~H ^^^^jgg^^ffitjessijifjl^uijaall5j yyiinnyyjjljy^JCt^fclo^^^^de^~K4i^on^on'err^a^^ nyl^Bes las ^^^rsl^^^^A^ea'-rP^ercentyC^Velr^ijPerd:entr --:-~Jt~rr-X^ii ;t:'IHt! Hiiv. 1-. 5v.r:F.n. ~'A vrr p-rp.-, ,r=H~ li?.;fc{-^rp ['"'Ev~ix^rr 3P3F7 rJMh rijvH fi-hrinr 'l'!:j3.-T C.iilrlr'r:J: V^:rsi |Vti` ^?.'-ra-WUi^_:1 r * "- i" '*"- srS:$ lui^l' m ]^ry-a: ^rr.<3Tl _ - ^ 'i'' -- f t~ Sh^iMrM O ___i -,^-;.j~i--J~-3~ o t ".==j;-5s~ --3= O rS^SS 4.v i rtrrira 'n.T rvr"t~t.U--~t. ^1 raa^arz-rr: ESfi--E; Bfease OP issaiseaMs* :-HHTl-:'i3 tjia ?Iriv (HHH^vpK-r EHb=!H! irrrt^nai ;i`|ir. ill! r'il".i(,!S.. yO * -:.*;i ""J m; H5THT i-it.f -1.`IfIiIs! -i,!:H, j:n..l1l*ijp' n ^iqfaplil iitr nlTi]i j! !!: "HT til: tt; -r. ill i:i!|j!i! mm. ijj iRURj ITUi t t ilil ,.i!.':i*;; n! ` I' I'. !:iiJi:!;|i:iii iE- sts? 0.0010 070020 0.0030 0.0040 Weight P rcent 0.0050 uco 0629H DUST DETERMINATION OF TOTAL AND RESPIRABLE AIRBORNE DUST BY MEMBRANE FILTER SAMPLING AND GRAVIMETRIC ANALYSIS 1 PURPOSE This procedure has been written to conform to recommended methods of sampling for dusts as published by the National Institute of Occupational Safety and Health CD and the American Industrial Hygiene Association. (2) 2 PRINCIPLE Total dust concentration is measured by drawing a known volume of air through a preweighed, 37-mm polyvinyl chloride membrane filter, sampling with the top cover of the filter holder removed (open faced). The filter is dried by means of vacuum and reweighed to give a measure of the dust concentration. Respirable dust is measured by using a 10-mm nylon cyclone ahead of the membrane filter to remove the larger or non-respirable dust particles before they reach the filter. The filter is treated the same as described for total dust. The table below gives the theoretical deposition of the dust particles. Aerodynamic diameter (pm), unit density sphere Percent passing cyclone 2 2.5 3.5 5.0 10.0 90 75 50 25 0 3 APPARATUS a) Personal sampling pump and charger, Model G, Part No. 456252, Mine Safety Appliance Co., Pittsburgh, Pa., or equivalent. (NOTE - Earlier models of the Model G pump were not equipped with a pulsation damper. If such a model is used, then the pulsation damper kit, MSA Part No. 449614 - should be ordered and installed before taking dust samples.) b) Cyclone and holder; Part No. 456243, MSA holder assembly complete with cyclone and sampling line assemblies. c) Filter holders for 37-mm filters; 2-section, Catalog No. MOOOD37PO, 3-section Catalog No. M000037AO, Millipore Corp., Bedford, Mass. d) Backup pad for 37-mm filter. Catalog No. AP1003700, Millipore Corp. e) Polyvinyl chloride membrane filters; 5.0 y pore diameter, Vinyl Metrlcel, VM-1, 37-mm diameter. Catalog No. 60714, Gelman Instrument Co., Ann Arbor, Mich. 41 1 f) Vacuum desiccator (use with a safety shield to contain glass fragments in the event of implosion if a glass desiccator is employed). g) Mercury manometer h) Analytical balance capable of weighing to the nearest 0.01 mg. i) Vacuum pump - capable of reducing pressure in the desiccator to 5 mm of Hg. j) Cellulose bands; 2-section holder part No. 625415, Mine Safety Appliances Co. 3-section holder - 41x25 mm, No. 28, Walter H. Jelly and Co., Franklin Park, Illinois. PREPARATION OF FILTER a) Place the VM-1 polyvinyl chloride filter into the vacuum desiccator and reduce the pressure to 5 mm Hg. b) After 15 minutes at the 5-mm pressure, allow the desiccator to return to atmospheric pressure. c) Make sure the balance is zeroed before weighing. Holding the filter by the edge with tweezers, place it on the balance pan and record the weight to the nearest 0.01 mg (WL). d) Insert a backup support pad into the bottom section of the filter holder. Carefully place the weighed filter on the support screen. e) For total dust sampling (3-section filter holder), place the middle and top sections on the bottom section. Press the sections together firmly until the outer edge of the filter is tightly held against the backup support pad. f) For respirable dust sampling (2-section filter holder) place the top section on the bottom section and press firmly. g> Insert the red and blue plugs into the inlets of the filter holders and slip a cellulose band from the storage solution over the outside of the holder. Allow the band to dry thoroughly before using. 5 RESPIRABLE DUST AIR SAMPLING PROCEDURE a) Remove the red and blue plugs from the 2-section filter holder, and insert the filter holder into the cyclone holder assembly, make sure the filter face is pointing downward toward the cyclone. b) Clamp the filter holder securely into the cyclone holder, so that the 0-rings are held tightly against the filter holder seats. c) Clip the cyclone holder assembly on the shirt collar of the employee. Attach the sampling lines from the cyclone to the inlet of the portable pump. d) Adjust the air flow through the cyclone by turning the adjusting screw on the pump until the flowmeter ball on the pump is centered on the red band on the flowmeter (1.8 liters per minute). If samples are to be taken for respirable coal dust, then the recommended flow rate through the cyclone and filter is 2.0 liters per.minute. This can be obtained by adjusting the flow on the pump until the flowm t r ball is center d under the orang band on the flowm ter. 41 A* ) Place the pump on a belt around the employee's waist. Record the time the pump was started. f) At the end of the working shift, stop the pump and record the time. Note: respirable dust samples need a minimum of 4-hours sampling time to provide enough sample to obtain an adequate amount of dust to weigh. g) Carefully remove the sampling assembly from the employee. Remove the filter and holder from the cyclone assembly and replace the red and blue plugs. Do not invert the cyclone assembly during this time as the larger particles of dust from the cyclone can fall onto the filter to give an erroneous weight gain. h) In the laboratory, split the cellulose band at the junction of the top and bottom section of the filter holder. Carefully pry off the top section. i) Place the bottom section containing the filter into the desiccator and reduce the pressure to 5 mm Hg for 15 minutes to dry the filter. j) After the desiccator returns to atmospheric pressure, gently lift the filter out of the bottom section of the filter holder by using a small rod through the hole in the bottom section. k) Check the zero setting on the balance to make sure it hasn't changed from previous weighing of the filter. Grasp the edge of the filter with the tweezers and reweigh the filter on the balance. Record the weight to the nearest 0.01 mg <W2). l) Clean the dust from the cyclone body before the next use. TOTAL DUST AIR SAMPLING PROCEDURE . a) Take a 3-section filter holder which has been prepared according to the directions in Section 4. Slice the cellulose band at the junction of the top section and center retaining ring. b) Remove the top section and the plug from the bottom section outlet. Attach a piece of tubing from the bottom outlet and connect the other end of the tubing to the Model G MSA pump. c) Adjust the air flow through the filter by turning the adjusting screw on the pump until the flowmeter ball on the pump is centered on the orange band (2.0 liters per minute). d) Place the pump on a belt around the employee's waist and clip the filter to the shirt collar of the employee with the face of the filter pointing down. ) Record the time the sampling pump was started. f) At the end of the working shift, stop the pump, and record the time. g) Carefully remove the filter from the employee. Replace the top cover and the plug in the bottom outlet. h) In the laboratory, split the cellulose band at the junction of the bottom section and the middle retaining ring. Care fully pry off the top and middle sections. 1) Place the bottom section containing the filter into th desiccator and reduc th pr ssure to 5 mm Hg for 15 minutes to dry th filter. 41 4 j) After the desiccator returns to atmospheric pressure, gently lift the filter out of the bottom section of the filter holder by using a small rod through the hole in the bottom section. k) Check the zero setting on the balance to make sure it hasn't changed from previous weighing of the filter. Grasp the edge of the filter with the tweezers and reweigh the filter on the balance. Record the weight to the nearest 0.1 (W^). CALIBRATION OF MSA SAMPLING PUMP a) Assemble the apparatus as shown in Figure 1. Tape the cap on the gallon bottle with vinyl electrical tape to insure a tight seal. b) Start the pump and adjust the flow until the ball in the flowmeter is centered on the red band (1.8 liters per minute). APPARATUS FOR CALIBRATION OF MSA PERSONAL SAMPLING PUMP 1000 ml Buret ~ Spray Trap S----Bulkhead p Fitting Q MSA Cyclone + Holder 1 Gallon wide mouth bottle MSA Pump Soap Solution Bottle Cap Figure 1 Drill 33/64 Me* for 1/4" bulkhead fitting* M 0 ucc 062919 r c) Moisten the interior surface of the buret with soap solution. d) Dip the end of the buret into the soap solution to start a bubble moving up the buret. e) T'ith a stopwatch, measure the time in seconds that it takes for the bubble to move from the zero graduation mark on the buret to the 1000-ral mark. f) Divide the time in seconds into 60 to obtain the flow rate in liters per minute. g) Repeat the determination, centering the flowmeter ball on the pump on the orange band (2.0 liters per minute). h) A wet test meter may be used in place of the soap-film buret if desired. 8 CALCULATIONS a) Respirable dust (W2-Wi) x 10 ------- p- ------- " respirable dust concentration in milligrams per cubic meter (mg/M3) F - Flow rate in liters per minute through the cyclone i and filter T - Total sampling time in minutes W, - Initial weight of the polyvinyl chloride filter in L grams Wg Final weight of the polyvinyl chloride filter in grams b) Total dust Use identical calculation except to report the value as total dust concentration in mg/M3. (F - flow rate in liters through the filter) ucc 062920 UNION CARBIDE CORPORATION CHEMICALS AND PLASTICS 270 .'ARK AVENUE, New York, N.Y. 10017 Sales Offices United Sfotta ATLANTA, GEORGIA 30329 ................................... 17 Executive Pirk Dr. .................. BALTIMORE (MOORESTOWN, N.J. SALES OFFICE)...... ................................................ BOSTON. MASSACHUSETTS 02194 ...................... 300 First Ave., Needham Hgts. ... BUFFALO (CLEVELAND. OHIO SALES OFFICE)............................................................... CHARLOTTE (ATLANTA. GA. SALES OFFICE).................................................................. CHICAGO. ILLINOIS 60606................................... 120 South Riverside Plata..... . CINCINNATI, OHIO 45227................................. ,,.3S14 West St............................... . CLEVELAND. OHIO 44114......................................1300 Lakeside Ave.. N.E.......... DALLAS. TEXAS 75207 ..........................................2710 Stemmon* Freeway ............ DETROIT (SOUTHFIELD. MICH. SALES OFFICE).... ......... ......................... ................... HOUSTON (DALLAS. TEXAS SALES OFFICE)............................................................... INDIANAPOLIS (CINCINNATI. OHIO SALES OFFICE)................................................... KANSAS CITY (CHICAGO. ILL SALES OFFICE).............................................................. LOS ANGELES. CALIFORNIA 90058...................... 2770 leonfs Blvd........................... MEMPHIS (ATLANTA. GA. SALES OFFICE)........................................ ,,.................. ...... METROPOLITAN AREA SALES OFFICE; HACKENSACK. N.J. 07601..............................One University Ptaze .................... MINNEAPOLIS (CHICAGO. ILL SALES OFFICE)............................................................. MOORESTOWN. NEW JERSEY 08057.....................Route 38 end Pleasant Velley Rd. NEW YORK (METROPOLITAN AREA SALES OFFICE; HACKENSACK. NJ.).................... PHILADELPHIA (MOORESTOWN, N.J. SALES OFFICE)................................................. PITTSBURGH (MOORESTOWN. N.J. SALES OFFICE).................................................. ST. LOUIS (CHICAGO. ILL SALES OFFICE).................................................................. SAN FRANCISCO (LOS ANGELES, CALIF. SALES OFFICE)_______ _____________ ___ FROM IDAHO, NEVADA. OREGON, UTAH, OR WASHINGTON............................... . SOUTHFIELD. MICHIGAN 48076........... ...............26500 Northwestern Hwey.......... ..404-633-6161 .301-944-8211 617-444-5400 ,716-837-6450 .704-364-1400 .312-822-7000 ..513-272-0206 .216621-4202 .-214-631-0010 .313-354-0800 .214-631-0010 .317-2563181 ..913-362-2200 .2165863061 .901-3965375 .201-6461111 .612-927-4221 ..609-2366200 .212-6965054 .2159263200 ..412-922-5700 ..314-7260324 ..416765-1000 .800-421-6050 316354-0800 Affiliates Pan AmmrlCM Eamtam Europ ARGENTINA ....__......__ --Union Carbide Argentine, S.A.I.C., Bueno* Aire* BRAZIL___________ ...___ Union Carbide do Brasil S. A., $ao Peulo, Rio d Janeiro CANADA...........Union Carbide Canada Ltd-. Amherst. Calgary, Fort Garry, Lechine, Lindsay, Surrey, Toronto. Vancouver CARIBBEAN ____ ____ -....Union Carbide Inter-America, Inc., San Juan, Puerto Rico COLOMBIA____...__ ....... Union Carbide Colombia, S. A., Bogota ECUADOR ....__ ______ ..... Union Carbide Ccuedor, CJL. Guayaquil MEXICO .............................Union Carbide Mexicana, S. A., Mexico. D. F. Guadalajara, Monterrey PERU .......................... .....Union Carbide Inter-America, Inc., Lima VENEZUELA ........'........ Union Carbide de Venezuela, C. A., Caracas WESTERN HEMISPHERE ....Union Carbidt Inter-Amenca, Inc. New York. N.Y. AUSTRALIA ___ __ ___ --.Union Carbide Auitralie Ltd.. Sydney, N, S. W. CEYLON ......... ............... Union Carbide Ceylon, Ltd., Colombo HONG KONG ........__ .Union Carbidt Asia Ltd.. Hong Kong INDIA_________ INDIA ............. .. -Union Carbidt India Ltd., Calcutta, Bombay, Madras, New Delhi INDONESIA P. T. Union Carbide Indonesia, OJakarta JAPAN ______ _ __.......--.Union Carbide Services Eastern Ltd., Tokyo MALAYSIA ........ NEW ZEALAND ...--_____ ...Union Carbide New Zealand Ltd., Auckland PAKISTAN ____ ..----National Carbon Co, (Pakistan) Ltd., Karachi PHILIPPINES ..... --. Union Carbide Philippines Inc. Manila SINGAPORE___ ----.Union Carbide Asia Ltd. TAIWAN ... ,, 'THAILAND .. ,, .--Union Carbide Thailand Limited, Bangkok AUSTRIA__________ -- Union Carbide Austria G.m.b.H. Vienna BELGIUM--------- -- ------Union Carbide Belgium, 6-1030 Brussels FRANCE ___________ --...Union Carbide France. F-94533 Rungtt (Peris) GERMANY__________ __ --Union Carbide Deutschland. G.m.b.H, DOsseldorT GREECE ....... . ITALY ......... .... . --Union Carbide Italia S.p-A. Milan NETHERLANDS ____ --Union Carbide Belgium, Amsterdam SCANDINAVIA_____ --Union Carbide Norden AB, Stockholm, SwsdMI SPAIN______________--Union Carbide Iberica, SA, Madrid SWITZERLAND .......... --.Union Carbide Europe, SA, Genovs UNITED KINGDOM Union Carbide U. K. Limited, London, Manchester. Rickmansworth: England . Y1774-4M AFRICA (CAST) ................. Union Carbide Africa Ltd-. Nairobi. Kenya AFRICA (SOUTH) ------....Union Carbide South Africa (FTy.) Ltd. Johannesburg Capetown. Durban; Republic of South Africa AFRICA (WEST). ............. Union Carbidt Africa Ud. Abidjan. Ivory CMt MIDDLE EAST AFRICA (NORTH)-------- - Union Carbide Middle Cast Ltd. Athens, Groses ucc 062921 Printed in UJ.A. BAKELITE VYHH is a medium molecular weight vinyl chloride-vinyl acetate copolymer resin* It dissolves readily in ketones, esters, chlorinated hydrocarbons, and combinations of these with aromatic hydrocarbons. APPLICATIONS BAKELITE VYHH is recommended for general coatings use. FOOD ADDITIVE STATUS BAKELITE VYHH is chemically identified in Food Additive Regulations $121.2514 for Resinous and Polymeric Coatings, and $121.2526 for components of Paper and Paperboard. Properties of BAKELITE Vinyl Resin Solution VYHH Propel1 ties Appearance Specific Gravity at 20/20C. Size, through a No. 20 USBS sieve. per cent by weight Apparent Density, lb. per ft.^ Heating Loss, 45 minutes at 105C., per cent by weight Poly(vinyl chloride), per cent by weight Lead, ppm. Test Methods Visual D 792 WC-7-F WC-2-B WC-160-H WC-294-B or D WC-20-D or K Required Values KTiite powder 1.36 t 0.005 98, minimum 30, approximate 3.0, maximum 85.0 - 86.5 5, maximum June, 1970 F-42808 (continued) BAKELITE and UNION CARBIDE are registered trade marks of Union Carbide Corporation, U.S.A. O Thit Information It not to bo tokon at warranty or roprotontotion for which wo otiumt local roaeoniibitity nor at pormlttlon or roeonw m*ndt*on Id predict *ny pttntti fiwtnlton without o it \% off*r*d tottfy for yttur coft*'dt'tion( iton ono UNION CARBIDE CORPORATION 270 PARK AVENUE. NEW YORK. N.Y. 10017 o 062922 < \ lution Properties 22 Per Cent Solution of Resin in 1:1 MIBK:Toluene Viscosity at 2SeC., cps. Color, per cent transmission Turbidity 10 Per Cent Solution of Resin in 1:1 MIBK:Toluene Insoluble Matter, per cent by volume Test Methods Required Values WC-31-W WC-S-K-2 WC-5-K-2 200 - 400 85, minimum 85, minimum WC-322-C 0.03, maximum TESTING METHODS Designated tests are made in accordance with current issues of ASTM or ONION CARBIDE (WC) Testing Methods. The former can be obtained from the American Society for Testing and Materials, Philadelphia, Pa., while the latter are available from Union Carbide Corporation upon request. E-42808 Printed in U.S.A. ---'' .'* :-*' '*-'- t-JMSM VINYL HESINS BAKELITE VINYL CHLORIDE-ACETATE RESIN VYNW-5 DESCRIPTION ... !2iaDj4s?.^iaaiiaaj^.v.T^^^^ . - _ ________ _ * * *, *.** ' *' M"* * BAKELITE VYNW-5 is a vinyl chloride - low vinyl acetate copolymer nonsolvent resin. APPLICATIONS BAKELITE Vinyl Chloride-Acetate Resin VYNW-5 is a blotter-type resin that is recommended for nonrigid applications, such as electrical insulation, film and sheeting, contour extrusion molding, injection and compression molding, and flooring. Properties of BAKELITE Vinyl Chloride-Acetate Resin VYNW-5 Properties Test Methods Size, per cent by weight through USBS sieve WC-7-F No. 40 No. 80 Heating Loss, per cent by weight. 45 minutes at 105C. WC-160-H Polyvinyl Chloride, per cent by weight WC-294-A Foreign Matter, slurry WC-15-P-1 Inherent Viscosity, 0.2 g. of resin/100 ml. of cyclohexanone at 30*C. D 2857 High Temperature Mill Stability: WC-163-B-3 Initial Color, per cent transmission Ultimate Stability, minutes Hard Resin Particles, per ft.2 WC-15-K-2 Plasticizer Absorption, per cent by weight D 1755 Apparent Density of Powdered Resin, WC-2-B lb./ft.3 D 1895 Typical Values 100 98 0.3 97.5 2 1.07 75 25 2 175 18.5 (continued) April, 1971 F-43380 11 on 062924 BAKELITE and UNION CARBIDE are registered trade" marks of Union Carbide Corporation, U.5.A. _____________________________________ __ _______ __ Thit information it not lo bt taken at a warranty or rtprtttntation for which w* ittumt lagti reipontibility no* at parmltiion or rttonv manoation to practice any patanttd invention without a litente. It it offered solely for your consideration, investigation and verification. UNION CARBIDE CORPORATION 270 PARK AVENUE. NEW YORK. N.Y. 10017 i `EST METHODS Designated tests are made in accordance with current issues of ASTM or UNION CARBIDE (WC) Testing Methods. The former may be obtained from the American Society for Testing and Materials, Philadelphia, Pa., while the latter are available from Union Carbide Corporation upon request. PACKAGING AND LABELING The standard package for BAKELITE Vinyl Chloride-Acetate Resin VYNW-5 is a four-ply multiwall Kraft paper bag containing 50 lb. net. desired, this resin can also be supplied in hopper cars containing approximately 75,000 lb. The package will be plainly marked with the product and lot numbers and the quantity. Shipments will be properly addressed to assure complete delivery to the purchaser. If PRECAUTIONARY LABELING On the basis of the toxicological, physical, and chemical properties of BAKELITE Vinyl Chloride-Acetate Resin VYNW-5. precautionary labeling used on the containers is as follows: FOR INDUSTRY USE ONLY r-43380 4/71-4M Printed in U.S.A. UCC 062925 DESCRIPTION An acid modified vinyl chloride-vinyl acetate copolymer resin of medium-molecular weight. Solubility characteristics are similar to those of BAKELITE VYHH resin. BAKELITE VMCH resin is recommended for general coatings use either alone or in combination with other vinyl resins to obtain good air dry adhesion to metal, paper, and other substrates. This resin is listed by chemical identity in the Resinous and Polymeric Coatings Food Additive Regulation 121.2514. Properties of BAKELITE Vinyl Solution Resin VMCH Property Testing Method Required Values Appearance Specific gravity Size, % by wt. through a No. 20 USBS Sieve Apparent Density, lb./eu.ft. approximate Heating Loss, 45 minutes at 105 C. , % by wt. Poly(Vinyl Chloride), % by wt. Maleic Acid, % by wt. Lead, ppm. Solution Properties, 22% solution of resin in 1:1 MIBK:Toluene Viscosity at 25eC. , cps. Colorrlight transmission at 475 m.f/600 m-f, per cent Turbidity:light transmission at 600 nvf Insoluble Matter, % by wet volume, 10% solution Visual ASTM D 792 WC-7-F WC-2-B WC-160-H WC-294-B or D WC-308-A WC-20-D or K WC-31-W WC-5-K-2 WC-5-K-2 WC-322-C White, powdered solid 1.35 0.005 98, minimum 30 3.0, maximum 85.0 - 88.0 0.8 - 1.2 5, maximum 200 - 400 85, minimum 80, minimum 0.03, maximum November, 1972 F-44259 BAKELITE and UNION CARBIDE are registered trade marks of Union Corporation, U.S.A. This information * not to bt taken at a warranty or ropretentation for which wt aitumt rcipontibility nor at prrmiation pt racom- mandation to practice any patented invention without a hcentt. It it offered toitiy for your tontideration, mvettifition and v*nt*ettipn. UNION CARBIDE CORPOxATlON 270 PARK AVENUE, N EW YO R K, N. Y. 10017 TESTING METHODS Designated tests are made in accordance with current issues of the ASTM or UNION CARBIDE (WC) testing methods designated. The former can be obtained from the American Society for Testing and Materials, Philadelphia, Pa., while the latter are available from Union Carbide Corporation upon request. PACKAGING AND LABELING The standard package for BAKELITE VMCH is a multi-wall paper bag containing SO pounds of product. The package will be plainly marked with the product and blend numbers and the quantity of material contained. BAKELITE VMCH is also available in bulk; by hopper car containing approximately 150,000 pounds;and in certain geographic areas, by hopper truck containing approximately 40,000 pounds. SHIPPING AND STORAGE BAKELITE Vinyl Solution Resin VMCH is a stable material when kept in closed containers stored in a cool dry place. PRECAUTIONARY LABELING On the basis of the toxicological, physical, and chemical properties of BAKELITE Vinyl Solution Resin VMCH, precautionary labeling used on the containers is as follows: FOR INDUSTRY USE ONLY TOXICOLOGICAL PROPERTIES BAKELITE Vinyl Solution Resin VMCH is a powdered resin which is essentially inert and non-toxic. Its dust is classed as a nuisance dust which is not known to cause lung disease. However, it is prudent not to exceed the recommended Threshold Limit Value for nuisance dust of 10 mg. per cubic meter of air or 30 million particles per cubic foot, whichever is the smaller r-44259 11/72-4M Printed in U.S.A. COATINGS AND n3. PLASTICS H-S MATERIALS BAKELITEVINYL RESIN SOLUTION VYHH FOR COATINGS DESCRIPTION BAKELITE VYHH is a medium-molecular weight vinyl chloride-vinyl acetate copolymer resin. It dissolves readily in ketones, esters, chlorinated hydrocarbons, and combinations of these with aromatic hydro carbons. APPLICATIONS BAKELITE VYHH is recommended for general coatings use. FOOD ADDITIVE STATUS BAKELITE VYHH is chemically identified in Food Additive Regulations ^121.2514 for Resinous and Polymeric Coatings and by reference in 9121.2526 for Components of Paper and Paperboard and in 5 121.2550 for Components of Closures. Properties of BAKELITE Vinyl Resin Solution VYHH Properties Appearance Size, per cent by weight. through a No. 20 USBS Sieve Heating Loss, 45 minutes at 105"C.t per cent by weight Poly(vinyl chloride), per cent by weight Test Methods Visual WC-7-F WC-160-H WC-294-B or D Required Values White powder 98, minimum 3.0, maximum 85.0 - 86.5 (continued) October, 1973 F-42808A BAKELITE and UNION CARBIDE are registered trade marks of Union Carbide Corporation, U.S.A. This Information It not to bt takan at a warranty or representation for which wa aiiumi left) ritpomibility nor at permission or rco<tv mandation to practice any patented invention without a license. It i offered solely for your consideration, investifttion and variiheation. UNION CARBIDE CORPORATION 270 PARK AVENUE. NEW YORK, N.Y. 10017 f. _ t 2- *f Solution Properties 22 Per Cent Solution of Resin in 1:1 MIBK:Toluene Viscosity at 25C., ops. Color, % transmission at 475 miv/600 im* Turbidity, light transmission at 600 mu 10 Per Cent Solution Resin 1:1 MIBK:Toluene Insoluble Matter, per cent by wet volume Test Methods WC-31-W WC-5-K-2 WC-5-K-2 WC-322-C Required Values 200 - 400 85, minimum 85, minimum 0.03, maximum TESTING METHODS Designated tests are made in accordance with current issues of ASTM or UNION CARBIDE (WC) Testing Methods. The former can be obtained from the American Society for Testing and Materials, Philadelphia, Pa., while the latter are available from Union Carbide Corporation upon request. All containers of BAKELITE Vinyl Resin Solution VYHH are plainly marked with the product nomenclature, blend number, and net weight. Shipments will be so addressed as to provide complete delivery to the purchaser. PRECAUTIONARY LABELING On the basis of the toxicological, physical, and chemical properties of BAKELITE Vinyl Solution Resin VYHH, precautionary labeling used on the con tainers is as follows: FOR INDUSTRY USE ONLY F-42808A 10/73-4M UCC 062929 Printed in U.S.A.