Document qd9O9ov7DOdVm6K87mpzp53GG

ESCAMBIA PLANT ------------- ^ INTEROFFICE MEMORANDUM To: From: Re: Mr. Copies:--^A. K. McMillan r*-. B.K. Driver R.E. Jones J. D. Evers Trip Report-VCL Monitoring Seminar held in Houston, Texas April 25, 1974 E.A. Primeau R.R. Spiegelhaltefi. W. T. Johnson 1 have just received my copy of the minutes to the VCL meeting I attended back in April. The attendees numbered 4D-50 and represented NIOSH (Mr. Charles MeCammon), Honeywell Division of Process Analyzers who sponsered the meeting, Monsanto, B.F. Goodrich, Catalytic, Inc. , Conoco, G. E. , a report from Dow and others. I feel that the meeting was profitable to us and based on what I heard we are quite advanced in our permanent sensor monitoring program compared to the others. BFG has been active since about mid 1973. Our first on-line, 10-point monitor was started March 7, 6 weeks after the first phone call was made to locate the analyzer. One general statement could express the monitoring program results and I believe this would include all the vinyl manufactures. It is this: Companies were surprised at the high level of VCL that was present when they first monitored, and surprised at how low the level dropped when corrective steps were taken. BFG actually showed the first chart recording they made which had VCL in excess of 1, 000 ppm. Later they were able to reduce to less than 50 ppm. I am not going to write a complete letter of my notes since you will find attached the minutes of the meeting plus other information that should helpful to Spike, ________________________- A similar meeting is planned for June 13, prior to the time that the Permanent Federal Law will be published. I understand that someone AP00034912 Trip Report - Page Two Since the meeting I have talked with one of the Honeywell representatives who is in charge of setting up the June 13th meeting and indications are that the proposed zero VCL. detectable limit will be opposed and probably 5-25 ppm will be asked for. He also said OSHA is preparing to propose limits for T. D. I. which would probably be 50 PPB with excursions not to exceed 200 ppm. He further stated that there seems to be some people who are more immune to T. D. I. and way and means to select these people are being considered, possibly VCL exposure might be more harmful to some than to others. In the minutes under BFC monitoring experience there is a reference to 5-6 ppm of background measurement. In our PVC plant here in Pensacola we have found 3-4 ppm of Methane and it remains fairly constant. This could possibly explain BFG's background level. We also found the Methane in a certified VCL calibration cylinder that we had purchased {we didn't ask for the Methane). This next seminar should be very informative and I plan to tape the entire meeting. BKD:pr attch. AP00034913 . Honeywell May 14, 1974 Mr, B, K. Driver Air Products & Chemical, Inc. P. 0. Box 467 Pensacola, Fla. 32592 Dear Mr. Driver: Please find enclosed for your information, the minutes of the April 25, 1974 discussion on Vinyl Chloride Monitoring. The tape recording equipment was not operating at the beginning of the dis cussion, so we have the notes from Jerry Scates as a fill-in. The permanent proposed Federal Register is out as of Friday, May 10, 1974. It requires monitoring for one part per million levels. I assume you will have 45 dayB to respond to this requirement. We talked about another meeting to taka place after the Register was released, and prior to your having to respond. Honeywell.will still sponsor this meeting if you desire. Please let me know as soon as possible so plans can be made. Very truly yours, RPisk Enclosure Ralph Powell, Sales Manager Process Analyzer Center HONEYWELL INC . 662S McGREW. HOUSTON, TEXAS 77017. TELEPHONE 713/64S-491I. AP00034914 VINYL CHLORIDE MONITORING DISCUSSION APRIL 25, 1974 AT HOISTON, TEXAS Introduction Holland introduced the Honeywell people attending with other participants identifying themselves and company afffiliations. Powell discussed the purpose of the meeting and emphasized that maximum benefit could best be obtained if all attendees were willing to participate. The listed topics of discussion were presented with resulting requests for six additional topics to be -added. OSHA Requirements McCammon explained the role of NIOSH and OSHA arriving at standards such as the one relating to exposure to vinyl chloride. NIOSH makes recommendations to OSHA which may or may not be followed. He stated that his particular area of specialisation was in gas and vapor sampling. It was emphasized that the emergency temporary standard (Federal Register of April 5 1974) would be in effect a maximum of 6 months, or that another standard would be out no later than October 5. NIOSH has been and continues to work on the solid adsorption method of sample collection. The use of charcoal as the adsorbent has not been recommended at present, but probably is the preferred material of those'evaluated to date. The acceptable method of taking grab samples is presently to use a 250 cc. glass collecting tube with Teflon stopcocks, sampling for 15 minutes. Monsanto commented they are presently using the glass tube method but feel the sample time should be reduced from 15 minutes to about 2 minutes due to the changes in VC1 concentration in the air over the longer time period. Carbonized saran spheres were one of the recommended adsorption materials, but were not considered practical from an availability and cost standpoint. NIOSH is presently using coconut charcoal for adsorption studies. The break-through point for 100 mg. of the charcoal is 3000 cc of air sample (0.135 gm. VCl). AP00034915 A migration effect of the adsorbed VC1 within the charcoal tube was discussed. Refrigerated storage prevents the migration. The problem of calibration was discussed, with emphasis on. the need to check the desorption of the VC1 from the charcoal being used. A desorption coefficient must be included in the calculation method. In desorbing the VC1 from the charcoal into carbon di sulfide, or THF, better efficiency can be obtained by cooling the CS2. The efficiency can be increased from a 70 - 75% level to 90 - 95# by cooling to dry ice temperature. NIOSH had received a .request to check another method of sampling, but still lean toward the charcoal tube method due to its being a usable method for CSHA inspectors. The inspectors could perform the tube sampling and send the sealed samples to Salt Lake City for analysis* Others commented on using a variety of techniques for sampling, including charcoal tubes, air bags, NDIE's and Century total hydrocarbon analyzers. Summary of MCA Meeting in Philadelphia Walston reported that most of the monitoring discussion emphasized personnel rather than area monitoring. It was questioned as to how personnel monitoring accomplished the intent of the existing standard in regard to preventing em ployees from entering, or remaining in, concentrations over 50 ppm VC1, MeGammon commented that he, and others at NIOSH, felt that area monitoring was the more important but that OSHA doesn't always follow all of their recommenda tions. Monsanto commented that area monitoring was much more feasible in an enclosed area such as PVC plants, but was a real problem in outside areas where fairly high wind currents existed, such as VC1 monomer plants. McCammon commented that EPA has already been investigating the VC1 concentration in ambient air. and would undoubtedly increase that activity. Walston reported on MCA testing being conducted at BLotest labs in Chicago. Mice, rats and hamsters are being tested for exposure to various concentrations of VC1. Mice exposed to 50 ppm VC1 for 7 hours a day, 5 days a week for 3 months had developed tumors. No tumors had been noted at that time in rats or hamsters exposed in an identical manner. Discussion Topics Since personnel fromDowwere unable to att end this meeting, they permitted a reading of their procedure for air sampling, recovery of the VC1, and method of analysis. AP00034916 Anticipated Regulation Requlregents Holland read an Advance Copy of an OSHA paper entitled "Sampling for VCM", which according to an unofficial OSHA source, may be very similar to the procedure ultimately Incorporated In the regulation. The OSHA procedure Is as follows: "Personnel breathing zone samples should be collected from employees. When collected by the CSHO, a Model SP-I Slpln Personnel Sampling Pump shall be used to collect the sample on NIOSH approved charcoal tubes. The flow rate of the pump shall be no more than 50 milliliters per minute, and the total sample tizi approximately one liter and/or a sampling time of 20 minute's where a concentration of approximately 50 parts per million is suspected. Where concentrations greater than 50 ppm are likely (for example, 100 parts); the sampling time should be 10 minutes. All measurements should represent the time when exposures are more likely to be the greatest, rather than random exposures throughout the work day._ No more than eight tubes per worker, per day, may be submitted for analysis. ' One or two tubes will suffice, if they represent maximum exposures. A sufficient number of area samples should also be collected to pinpoint high exposure areas for Implementation of control measures." Holland interpreted the phrase "No more than eight tubes per worker, per.day, may be submitted ..." as ultimately requiring submission of samples to OSHA's lab in Salt Lake. He also questioned whether the statement "A sufficient number of area samples shall also be collected to pinpoint high exposure areas." did or did not tmply a requirement for area monitoring. He also pointed out that the Sipin pump was probably mentioned simply because It Is the pump OSHA is presently using, .and v/as not Intended to imply that the pump was the only acceptable pump for this procedure. McCammon commented that the OSHA paper sounded more like a recommended sampling procedure for OSHA Inspectors, rather than something which would be included In the regulation. He also pointed out that although NIOSH has not recommended char coal tube samp11ng, It Is possible that OSHA may be considering this technique. McCanuton noted that It is unlikely that the regulation will specify a particular pump. The Slpln purrp was developed under a contract from NIOSH, and just happens to be the one OSHA is currently using. Three other companies also have pumps which meet NIOSH specifications for NIOSH/0SHA use: NSA; SKC, Inc. of Pittsburg; AP00034917 the performance of the unit In the range of 0-100 ppm was questionable. It Is felt that the Instrument would be adequate for detecting "hot spots". As a result of these tests, BFG has generally gone to the Century as its portable survey Instrument. It Is Ideal for monitoring levels around valves, flanges, packing, etc., since Its response Is almost Instantaneous. On the subject of permanent area monitoring, BFG considered three equipment types: Infra-red, gas chromatograph, and total hydrocarbon analyzer. In a "poly" building where vinyl chloride Is being used, about 95% of the vapors will be vinyl chloride. Therefore, for ease of maintenance, the total hydro carbon analyzer was selected.. A system was Installed last August, and the read out results have been somewhat surprising. It has become apparent that It is going to take a special type of sampling system to get usable results. The total hydrocarbon analyzer has a sensitivity of 1 ppm, full scale. Total hydrocarbon was selected over the gas chromatograph due to the feeling at that time that plant personnel lacked the proficiency required for maintenance of the gas chromatograph. The greater cost of the gas chromatograph was also a con sideration. The Wilks Hi ran 11 Infra-red analyzer was tried, and It was found to be less stable than had been expected. In fact, at the BFG Louisville plant, where mixed monomers are present, the vinyl chloride results were almost worthless. Vinyl chloride discrimination is not good In applications where various other components are present. When the total hydrocarbon analyzer was first put Into operation analyzing a single stream, readings were frequently In the area of 1000 ppm. The average., person cannot smell vinyl chloride at concentrations of less than 4000 ppm. Maintenance steps were initiated immediately to correct the leaks, and as a result, present readings' rarely exceed 50 ppm. The current time weighted average Is about 15-20 ppm. It should be noted that these readings were taken In a PVC "poly" plant where mixed vapors are not present. The detector used was a hydrogen flame, and the "background' was suppressed so that the readings are based on the best available citan air vs. that In the "poly" building. When the total hydrocarbon analyzer was first put Into use In August, a 200-foot l/4-lnch stainless steel sample line was used. At successive ranges of up to AP00034918 1000 ppm. Initial analyses (at a sample rate of 1200 cc/mlnute) showed Instances of vinyl chloride concentrations which exceeded each respective full-scale range. It was found that vinyl chloride stratifies, and moves through the air In waves. With a fixed probe, these waves are detected by the total hydrocarbon analyzer, thus producing occasional full scale excursions. Further experiments shewed that Installation of about a 1000 cc surge tank just before the Instrument provides sufficient mixing of good and bad air to produce a reasonably good record. It appears that stratification of vinyl chloride eliminates grab sampling as a workable monitoring technique. Soon after the Initial total*hydrocarbon analyses, BFG Installed a six-stream sampling system, using MSA end-of-Mne filters and two 40-mlcron sintered steel filters. Good filtering is essential in order to attain optimum results. The present system includes a slx-polnt/recor3erWanSti:Bi^ six-stream sampling system, with rotameters on each stream. Flow in the analyzer line is maintained by the analyzer pump, and flow in the other five lines is maintained by a separate pump In the sampling system. The sampling system pump is a Metal Bellows, which pumps about 30,000 cc/minute. Sample lines are 3/8-Inch polypropylene, which has been found to work just as well as stainless steel. Polyethylene will not work due to adsorption. Lines vary in length from 125 to 200 feet, and could probably be longer if necessary. BFG has approximately 150 people working on the vinyl chloride problem. All technicians are working on a seven-day week and all scientists are working on a six-day week until the problem is solved. BFG currently has 42 Centurys In use, 14 permanent systems In operation, and has just ordered 42 pumps. In addition, a computer system for readout is planned to handle the resultant load of data. As the system is new configured, a data read out Is produced once every two minutes. Readout rates of less than one minute are impractical due to the fact that the system requires 30*40 seconds to stabilize ',>1 each point. The system includes en automatic alarm feature which Is activated if the vinyl chloride level exceeds 50 ppm. When an alarm occurs, a man is sent to the respec tive area with a Century to pinpoint the leak. At a recent BFG meeting, It was unofficially announced that the maximum vinyl AP00034919 chloride level In BFG facilities will be 25 ppm, and a time weighted average not to exceed 10 ppm. These are BFG inter-company requirements, and are not necessarily related to OSHA requirements. At present,..it Is doubtful that any "poly" plant in the country can meet these requirements. The reason BFG is reducing peak levels from 50 ppm to 25 ppm is because of the tumors found In mice exposed to vinyl chloride for seven hours per day at SO ppm. Salzer commented that the concept of personnel monitoring may not be as important as some people think. The weakness of the technique is that a worker could be in a 400 ppm area for one hour, and If he then moves Into an area where there is no vinyl chloride, his time weighted average for eight hours'will be 50 ppm. Therefore. In order to comply with the requirement that "concentrations above 50 ppm cannot be permitted to occur", some form of permanent monitoring system appears to be necessary. BFG has made smoke tests In their plants to determine air flow patterns. These tests reveal some surprisingly complex patterns. The pattern of. a smoke bomb held at waist level is often entirely different from that of a bomb held at shoulder level. Again on the subject of personnel monitoring, it appears that the portable Century unit may be usable for this purpos'e. The unit weighs 10 pounds, and Includes a small recorder which can provide a continuous record of exposure over a 10 minute period. This would provide a much more detailed indication of the 10-minute exposure than would a single accumulated sample. BFG has not abandoned their Investigation of charcoal sampling, however they have hopes that the Century approach will prove to be feasible. It should be mentioned that the Century unit now has a new feature, which consists of a small Porapaic chromatographic column which will separate vinyl from other components. Vinyl Chloride tn Pried Resin Another problem which must be considered Is that of unreacted vinyl chloride which i retained in granular resin. BFG Is now considering ways to reduce current levels of 10, 50, and 100 ppm down to 1-3 ppm. The Implications of retained vinyl chloride are that if a company is extruding water pipe, and if that pipe is being used for drinking water, it is conceivable that the claim may be made that small amounts of AP00034920 8 vinyl are being Ingested. It is unlikely that this type claim will occur, but it Is possible. Tenneco commented that their research to date indicates that removal of vinyl from resins does not appear to be an Impossible task. Their findings thus far are only tentative, but do shew promise. Total Hydrocarbon Analyzer vs. Gas Chromatograph Initial BFG considerations In selecting the total hydrocarbon analyzer were: 1. Lack of suitably skilled maintenance personnel in their "poly" plants'for optimum maintenance of gas chromatographs; and 2. Lower cost of total hydrocarbon analyzer. if the acceptable level of vinyl Is lowered to "very few parts", no choice really exists but to go to the gas chromatograph. Especially in view of the fact that the total hydrocarbon analyzer measures vinyl chloride, plus other components which may be present. Cost of present BFG sample system Is about $3000., and cost of total hydrocarbon analyzer is about $2000. Neither of these is explosion proof. It should be pointed out that the analyzer cell Is not standard, but Is specially designed to withstand the corrosive effects of vinyl. In either a total'hydro carbon analyzer or a gas chromatograph, the FID cell should employ a monel or Teflon-coated aluminum bonnet. The corrosive effects of vinyl are more acute In the total hydrocarbon analyzer due to the greater sample volumes used. In the system BFG put Into operation In August, the FID cell has been checked about once every 10 days, and has not falled to date. BFG Is using a computer to compile the data from Its six-point system* The computer provides a time weighted eight hour average for each of the six locations being measured. It also provides an hourly average, and the high readings (past 50 ppm) for each probe. tv\ cl plant utilizing four or five analyzers, the volume of data leaves little option but to lnc)udc a computer for data compilation. The utility of a computer Instal lation is further enhanced by the fact that the regulation may ultimately require data retention for up to five years. With a computer In the loop, a bulk storage medium such as magnetic tape can be readily utilized. AP00034921 Blood Teats ? At BFG, every man working in areas of possible vinyl chloride has had a blood test. It Is a test which Is Intended to detect liver damage. Medical opinions vary as to its effectiveness. So far, there have been no negative comments from workers about the requirement that they take the test. The only significant problem BFG has had with respect to the blood test Is that 50% of prospective new employees fail the test. Other attendees reported similar failure rates in their experience. Controls Imposed on BFG employees before testing included "no alcoholic beverages ji ' for 48 hours prior to test", and no breakfast that morning". McCammon commented that from a toxicologists viewpoint, it is unlikely that a single-point biochemical cast is a reliable means of determining the medical status of an individual. Due to the many variables which affect the test results, it seems that a more realistic approach must necessarily Include the compilation of a personal medical history on each Individual, including such information as "amount of alcohol normally consumed". This information, along with successive test results, would produce a more meaningful collection of data on which to base a conclusion as to that employee's vinyl exposure and its effects. Some companies have experienced employee reluctance to taking the test, and other companies have received full cooperation. It appears that the Implementation of these tests is best received when proceeded by a good employee information effort. This effort should include pointing out that the test{s) can also detect problems other than vinyl exposure, and that If such problems are detected the employee will be so advised. The recommended blood test actually Includes tests of 12 separate blood characte ristics. Urinalysis, pulmonary test, and chest X-rays have also been suggested. It should be pointed out that the blood test simply detects a possible liver mal function, which may or may not be the result of vinyl. There are, of course, many other possible causes. Differences 8etween Problems of Polymer Plants and Momomer Plants Shell is conducting eight hour average bag sampling In its monomer plant. Their checks have shown that EDC Is more of a problem than vinyl chloride. Vinyl Is present only In very small amounts, and Increases only when a vessel Is opened. AP00034922 10 GLC analyses have shown a complete spectrum of conponenents. Primary emphasis has been on Identifying "safe" and "hazardous" areas, and In re-evaluating procedures accordingly. At BFG's Calvert monomer plant, a gas chromatograph Is being used to sample 10*12 points. Cycle tlme/l^abSut^S-lfi minutes, which loses a good deal of valuable Information. This Is a problem which must ultimately be resolved, but for the present, major effort is being focused on the "poly" plant problems. Conoco is monitoring their Lake Charles and Oklahoma City plants with the Century, air bags, and carbon tubes. At the Aberdeen plant they ere using a portable trailer which Is equipped with a four-stream total hydrocarbon analyzer. This system is used to monitor levels around the plant on a routine basis. They are monitoring four points in 10 minutes, on a semf-eontlnuous basis. The objective of this program Is to determine the operating parameters for a permanent monitoring system. So far, some of their checks have shown the air inside the buildings to be better than the air outside. Safety Equipment and Procedures BFG issues coveralls and a charcoal mask to each worker in an area of potentially high vinyl. The mask Is worn around the neck continuously for use if an alarm Is sounded. V/hen the eight-hour shift is finished, each man from the "poly" area is required to shower. Employees have voiced some complaints about having to wear the mask around the neck continuously. Tests run by BFG on charcoal masks showed that the charcoal element is exhausted after about three liters of vinyl chloride at about 50 ppm. At this rate, maximum effective life of one element Is limited to about one hour. Therefore, BFG pro cedures call for a change of element after each 45 minutes of use when operating in areas of 50 ppm or greater* GE commented that the back-pack air mask system weighs about 35 pounds, and each bottle lasts about 30 minutes* in addition, there is a great deal of employee resistance to any more than emergency use of the device. The unit is both heavy and uncomfortable. As a result, it appears that good engineering controls, rather than personal protective devices, are the only way to keep people working on the job. Relief Devices - '.'hat to do with vented materials. In Catalytic's last continuous PVC project, the PVC reactor had a conventional AP00034923 relief system consisting of a rupture disc and a relief valve. Vented material was disseminated Into the atmosphere at about the 5th floor level. At that ttme the stringent OSHA requirements were not .In effect. In view of current knowledge, It Is apparent that some form of recovery system is going to be necessary. Condco commented that they have current plans for Installation of flare and recovery systems at their Lake Charles plant. GE commented that in their plant, all relief systems and bleed systems are routed to a vent gas burner on the roof. This Is a water-submerged burner, which presum ably solves the problem of combustion of organic materials, but leaves the problem of disposing of the resultant polluted water. Syroposis of Conclusions from Preceedlng Discussions 1. Area monitoring Is generally better than personnel monitoring. 2. A need exists for portable personnel monitoring equipment. 3. The regulation limit on vinyl will probably be 50 ppm, and may possibly be as low as 10-25 ppm. 4. October 5, 1974 Is anticipated date for the regulation to go Into effect. 5. A problem exists In correlating data from personnel monitoring with data from area monitoring systems. 6. Two portable Instruments were mentioned, the Century and the SIpIn. 7. Infra-red was mentioned for permanent monitoring applications. Comments were made as to Its questionable stability. 8. Portable gas chromatograph was mentioned with respect to its use for personnel monitoring. 9. Total hydrocarbon analyzers were discussed for levels above 50 ppm, gas chrom atographs were discussed for levels below 50 ppm. Higher cost was mentioned as a drawback to the.GC, 10. Recommended sampling systems mentioned were four-streams, six-streams, and 12streams. Ethyl has 12-stream Htran II (f/R) on order. Several attendees comnented their experience with this unit was less than satisfactory. Ethyl reported good experience with these units to date. It appears that the number of samples collected should be equally divisible into 60 minutes, so that averaging becomes automatic when data is logged. For example, 10 strearr, produces a stx-mlnute time averaging of the sample; 12 streams is a AP00034924 /* f flve-mlnute sample; !5 streams is a four-minute sample, etc. Thus, the sanple system configuration might best be a trade-roff between averaging and speed of analysis. Honeywell commented that time Involved with using the gas chromatograph is 30 seconds for vinyl chloride and 75-80 seconds for vinyl chloride and EDC. 11. Sample system costs can be reduced significantly by using polypropylene tubing rather than stainless steel. 12. There Is a need for some means of bulk data storage. Suggestions included computers, magnetic tape and microfilm. Paper tape was also mentioned as a possible medium for intermediate storage, followed by voice-line data transmission to a central computer. 13. Surge tanks appear necessary to avoid problems of stratification. The question was raised as to whether OSHA will accept the results of sample systems which Incorporate this type of "smoothing" feature. 14. Host employees express no reluctance to taking the blood tests, especially If the benefits are pointed out In a good employee Information program. 15. Blood tests are non-conclusIve, with respect to vinyl exposure, due primarily to the fact that the results merely Indicate the status of liver function. Pre test controls of employee activities (eating, drinking, etc.) are necessary In order to achieve meaningful results# 16. Potentially dangerous conponents detected to date include vinyl chloride, EDC, and vtnylldene chloride. OSHA's list Includes about 400 components. At DowFreeport plant, Oow Is analyzing for 10-12 different chlorinate hydrocarbons. Dow posts dally results for employee information purposes. This Is made possible by their use of a computer-based area monltortng system. 17. Equipment mentioned Included a trailer-mounted monitoring system, alarm systems, protective clothing, charcoal air masks, back-pack air systems, etc. 18. The "after-the-fact" nature of the personnel monitoring concept appears to negate its use In preventing employees from entering hazardous areas. 19. Honeywell presented chromatographic runs indicating: a. tf specificity of vinyl chloride Is desired, and a 90-second analysis cycle Is acceptable, the only valve required Is a sample valve, assuming that no cofrponents "heavier" than 1,2-Dlchloroethane (EDC) - b.p. of 63.5*C - are present In the air sample. AP00034925 b. If both specificity and rapid analysis cycles are desired, the addition of a backflush-to-vent valve allows analysis every 1(0 seconds, and is a safeguard against components "heavier" than EDC. Based on subsequent tests, Honeywell stated that these analysis times can be reduced to 75-80 seconds and 30 seconds, respectively. With the 90-second cycle, J60 analyses ean be run In a 24-hour day. With the 40-second cycle, 2160 analyses can be run In a 24-hour day. It was pointed out that the analysis can be pro grammed to run at a less frequent rate, and if an excursion is detected, the frequency can be automatically Increased to provide a better profile of critical levels. The objective of the chromatographic runs was to demonstrate the feasibility of making a very precise measurement within the limitations of a minute, if this capability becomes a requirement for area monitoring. Anticipated Future Action and Meeting Summary Honeywell will act as a distribution point for dissemination of`.the results of this meeting, and of any subsequent Information provided by attendees. Maximum follow-up information from each company will be necessary In order to make this effort worthwhile. Any information of this type should be forwarded to Honeywell by about Hay 24. Honeywell will plan to distribute any resultant Input to all attendees on or about June 1. in the interim, any Information of an urgent nature will be sent out In bulletin form. The objective of this effort is Information sharing between all concerned parties. It was agreed that additional meetings of this type be held on a regular basis until the immediate urgency of the vinyl problem is resolved. McCammon (NIOSH) suggested that NIOSH, OSHA, and EPA be represented at future meetings. Manno (Honeywell) suggested that the meetings might be most effective if kept at a workable size, rather than issuing a blanket invttation to all agencies concerned. Manno also suggested that Tt might be prudent to advise OSHA at this time, of the defrclences of personnel monltorfng which were noted at this meeting. It appears that the only effective long-range solution to the problem lies tn utilizing high quality, well calibrated permanent area monitoring systems, with personnel monitoring used on a supplemental basts for special cases. Personnel nientioned as being involved with various aspects of the vinyl problem were: AP00034926 If Dr. Don Lassiter; Washington, D.C.; Phone 202-961-3878; Department of Labor representative working with OSHA in writing standards and in getting them in print. Thomas Curry; Houston, Texas; Director of OSHA-Houston office. Bruce Simpson; Houston, Texas; Assigned by Curry to handle OSHA liaison with Houston area companies. Charles McCaimton, Mr. Cradle, Dr. Alex TeasS, Dr. George Carson, Dr. Harris; NIOSH-CIncinattI, Ohio: Mr. Crable is Administrator of the Physical and Chemical Analysis Branch In the Oivision of Laboratories and-Criteria Development. Hts group is responsible for development of analytical methodology. Dr. Teass, who works for Mr. Crable, is more directly Involved with the day-to-dey operations of the group. Mr, McCammon Is involved with generation of standards pertaining to sampling. He is responsible to Dr. Carson, whose particular area of specialization is "parti culate sampling". Dr. Carson (s not currently Involved dl reetly'with the vinyl problem. Dr. Harris is Director of the Division of Laboratories and Criteria Development. The division makes recommendations to OSHA, which OSHA may or may rot choose to follow. All final regulation requirements are determined exclusively by OSHA. Bob Stevens, Andy O'Keefe; Contacts at the Environmental Protection Agency; Research Triangle, N. C. AP00034927 Table of Sorbents for Contaminants Listed in ACGIH 1970 Threshold Limit Values 1 American Industrial Hygiene AucSat!n and the American Conference of Governmental Industrial Hygienists Joint CominiltM on Respirators Introductory Statement '"The aiha-accih respirator COMMITTEE has prepared this table of sorbents for airborne contaminants in re sponse to questions from users of respirators. There is an apparent mystery about what is in a gas mask or chemical cartridge respirator that magically purifies the inspired air. There fore. the primary purpose of this table is to serve ns an educational aid to respirator users by eliminating some of the mystery about res piratory protection. The table may also be used in the laboratory to aid in selecting sor bents for gases and vapors. This printing updates the first list of sor bents that appears on pages 56 to 58 in Ret/liratery Pmh'clivf Deviect Manual, published ny AlliA-ACGIH in 1963. The manual lists gnu'* and vapon for which ACGIH assigned Tf.V values in 1961. This new table includes nil contaminants in the 1970 TLV list. As rniphasirt'd in the Manual, the actual capac ity of a sorbent for any specific contaminant is dependent upon many factors. Any list of sorbents must therefore be interpreted only as a guide. Users should refer to respirator man ufacturers for information on specific respi rators for specific contaminants. Sorbent Code 1. Activated carbon 2. Soda lime 3. Combination of activated carbon and so da lime 4. Silica gel 5. 1 iopcalite (with drier) 6. Impregnated carbon; example, carbon treated with mctalic salt to absorb am monia 7. Special sorbent (manufacturers proprie tary mix) 8. Filter, for highly toxic dusts 9. Filter, for toxic dusts Nottt: (1) Where two or more sorbent code num bers are listed after a substance, the sor bents are in decreasing order of prefer ence. Where a plus (4*) sign is used, both are required. (2) Very strong oxidizing substances in low concentrations may be sorbed by acti vated or impregnated carbon; however, carbon should not be used because of a possible explosion hazard with these combinations. For respiratory protec tion against very strong oxidizers, a selfcontained breathing apparatus should be used. List of Contaminants with Sorbent Code Substance Abate Acetaldehyde Acetic acid Acetic anhydride Acetone Acetonitrile Acetylene dichloride, see 1,2- Dicloroethylene Acetylene tetrabromide Acrolein Acrylamide - Skin Acrylonitrile - Skin Aldrin - Skin Allyl alcohol-Skin Ally! chloride Allyl glycidyl ether (AGE) Allyl propyl disulfide Sorbent 9 8+1 1 1.3 1 3 404. i' i j i AP00034928 American Indutltial Hygiene Anocialion Jot ; 405 Substance Sorbent Substance ' Sorbent 2*Aininocthanoi, see Ethanolamine Carbon black ' . Q. 2-Aminopyridinc i,7: Carbon dioxide 2 Ammonia ;: \ 7,6,4- Carbon disulfide-Skin .. I Ammonium sulfamate (Ammate) . 9 Carbon monoxide 5 u-Atnyi acetate rAmyl acetate Aniline-Skin ; ". 1, Carbon tetrachloride-Skin \ CV 1 1,7. Chlordane -Skin `Chlorinated camphene-5kin 'Air'' -1 9+1 *1 Anisicline (o,pisomcrs) - Skin 9 + 1 Chlorinated ciiphenyLoxide ` "I Antimony & compounds (as Sb) t 9. Chlorine '3,6 ANTU (Alpha naphthyl thiourea) - . 9 +1 . Chlorine dioxide ' ' " ' 2,7 Arsenic & compounds (as As) 6+9 Chlorine trifluorido 2.7 Arsine `-1j. 6,7. Chloroacetaldehydo 1 Azinpiios-tncthyl - Skin :,V9+1. Chioracetophenone (phenacylchloride) i*l* Barium (soluble compounds) . ; ' 9+6 '.Chlorobenzene (monochlorobenzene) .V Benzene (benzol) --Skin I",'.'-' 1 ' 0*Chlorobenzylidene malononiirile Benzidine -- Skin ;:"./a+i. (OCBM) 3.1 /f-Henzoquinonc, see Quinone ,. v Chlorobroniomethane 1 Benzoyl peroxide ",i. 9+i- . 2-ChIoro-],3-butadiene, tee Chloreprene Benzyl chloride ; ' 1,3. Chlorodiphenyi (42% chlorine) - Skin V Beryllium '.; ( . Chlorodiphenyi (54% chlorine) - Skin Biplicnyi, see Diphenyl 1- Chioro-2,3-cpoxypropane, see Boron oxide ' ..V'' '- Boron tribromide . ' Boron Trifluoride Bromine "'ominc pentafluoride 1. omofomt - Skin Butadiene {1,3-butadicne) ` 91 Epichlorohydrin 1 ,''.5+3 2- Chloroethanol, see Ethylene chlorohydrin' ' 5+3 1 Chloroethylene, see Vinyl chloride . 3 2,7 1: ,1' Chloroform (trichloromethane) . l*Oiloro-l-mtropropn Chloropicrin Chloroprene (2-chIoro-l, 3-butadicne) ftutancthiol, see Butyl mercaptan -Skin 2-IUi tanonc 1 2-Buioxy ethanol (Butyl ccllosolve) -Skin 1 Chromic acid and chromates (as CrOi) 8+2 Chromium, soluble chromic or ehromous 'Butyl acetate (nButyl acetate) w-Butyl acetate ` -/ /cr-Butyi Acetate , 1 . ,1 ' '1 salts as Cr Metal & insol. salts Coal tar pitch volatiles (benzene soluble 9 9 irrf-lhityl acetate ' ' 1 fraction) anthracene, DaP, phenanthrene, Butyl alcohol ',; l. acridine, chrysene, pyridine) 9+1 .ref-Butyl nicohol r Cobalt, metai fume 4e dusc, 8 /fr<-J5iityl nicnhnl i Copper fume .8 Bu tylaminc -- Skin 7,6,4 Dusts and mitts '. '9 fcrJ-Butyl chromate (at CrO,)-Skin -8 Colton dust (raw) 9 zt-Butyl glycidyl ether (BGE) Butyl mercaptan , l - '1 Crag-herbicide , Crcsoi (all isomers) -- Skin . . 9+1 1 /Mer<-Butyiiolucne l Crotonaldcltyde . 1 Cumene --Skin 1 Cadmium (metal dust and soluble salts) 9,6 Cyanide (as CN) --Skin ... 9+2 Cadmium oxide fume . ... v ` 8 Cyanogen .. * . i. . . 3 Calcium arsenate Calcium oxide Camphor , '.'. ` 9 9 . Cyclohexane ;... /\ '..9+1 Cydohexanol V `r , ' _ : j-,- \ * ' 1 Carbaryl (Scvin) V 9+1 .Cyclohexanone '1 \ .f . '.. AP00034929 / 406 June, 1971 Substance Sorbent Substance Sorbent . Cyctohcxenc Cyclopcmadiene 1 Dimcthylfomiaptidc-Skjn ! 2,6-Dimethylhcptanone, see Diisobutyl 1' 2,4-D DDT-Skin DDVP --Skin Decarborane -- Skin ' 9+1 9+1 9+1 9+7 ketone l ,1-Dimethylhydrazire -- Skin Dimethylphthalate Dunethyhulfate -- Skin 7,6,4 1 ! ,3 Dcnicton - Skin 8 + 1 Dinitrobenzene (all isomers)-Skin Diaccton alcohol (4*methyU2*pentanone) 1 Dinitro-o-cresoi -- Skin 9+3 9+3 1.2-Diaminocthane (Diazomcthane), see Ethylcnediamine Dinitrotoluene-Skin 9+3 Dioxane (diethylene dioxide)-Skin 1 Diboranc 1.2-Dibromoethane (ethylene dibromide).-- Skin 7 Diphenyl 1 Diphenyl amine 9 + 1, 7 1 Diphenyimethane diisocyanate, see methylene Dibutyl phosphate Dibulylphthalale Dichloroacctylene 8+1 1 3,7 bispheny! isocyanate (MDI) Dipropylene glycol methylether-Skin Di-rrc-octyi phthalate (Di-2- I e-Dichlorobcnzene 1 ethylhexylphthalate) 1 +8,9 /i-Dichlorobenzene 1 Dichlorodiiliioroniethanc 1 l,3.Dichioro-5-dimethyl hydantoin 3 1,1 -Diclilorocthane 1 1.2-Dichloroethane 1 1-2-DicMorocthyIcne l Dichiorocthyl ether-Skin l ichinromethane, see Nfcthylene chloride Dichloromonofluoromc thane l 1.1-Dichloro-l-niirocthane 3 1.2-Dichloropropane, see Propylenedieh- loride Dirhlorotetrafiuoroethane 1 Dicldrin --Skin 9+1 Dicchylamine 7,6,4 Diethylninino ethanol - Skin 7 Dicthylene triamine --Skin 7,6,4 Dicthylether, see Ethyl ether DifUiindibroiiiomcthanc 1 Dijdyddyl ether (DGE) 1 Dilmhoxybcnzcne, see Hydroquinone Diisobutyl ketone 1 Dihopropylaminc - Skin 7,6,4 Dipluuiyl amine 9+7 Diinctliosyntcthonc, sec Methyial Dimethyl acetamide -Skin 1 Ditnctln Inmine 7.6,4 DiinriliDnmmobenzene, see Xyliricne Dinietliylanilinc (X-dimclhylaniline) --Skin 7 Endosulfan (Thiodan*) 8+1 Endrin-Skin 8+1 Epichlorohydrin - Skin 1 EPN-Skin 9+1 1.2- Expoxypropane, see Propylene:oxide 2.3- Epoxy-1 -propanol, see Glyeidol Ethanethio), see Ethylmercaptan Ethanolamine 7,614- 2-EthoxycthanoI-Skin 1 2-Ethoxyethylacetate (Cellosotve acetate) - Skin 1 Ethyl acetate Ethyl acrylate-Skin 1 l Ethyl alcohol (Ethanol) Ethylamine Ethyl rrc-amyl ketone (5-methyl-3- 1 7,6,4 heptanone) 1 Ethyl benzene Ethyl bromide Ethyl butyl ketone(3-Heptanone) Ethyl chloride 5 1 1 1 Ethyl ether Ethyl formate l 1 Ethyl mercaptan 1 Ethyl silicate 1 Ethylene chlorohydrin - Skin 1 Ethylenediamine 7,6,4 Ethylene dlbromide, see 1,2-Dibromoethane Dimethylbcnzenc, see Xylene 1 Ethylene dichloride, see l,2*Dich!oroethane Diincthy I- i ,2-d ib romo-2, 2-dichiorocthyl Ethylene glycol dinitrate and/or phosphate, (Dibrom) 9+1 Nitroglycerin - Skin 1 American Industrial Hygiene Association Jakrhat 407 Substance Sorbent Substance Sorbent Ethylene glycol monomethylether acetate, see Methyl cellosolve acetate Ethylene imine-Skin 7,6,4 Ethylene oxide _1 Ethylidinc chloride, see 1,1-Dichioroethano N-Ethylmorpholtne-Skin 1 Ferbam Fcrrovanndium dust 9+3 9 Fluoride (as F) 9+3 Fluorine 3,2 Fhiorotrichloromethane Formaldehyde 1 1 Formic add Furfural - Skin 1 1 Furfuryl alcohol Gasoline 1 1 Glycidol (2,3-Epoxy*l-propanol) 1 Glycol monoethylcther, see 2-Ethoxyethanol Guthion, see Arinphosmethyl Hafnium 9 Hcptachlor-Skin Heptn.no (n-heptane) Hcxachlorocthane -- Skin Hexachloronapthalene - Skin Hexane (nhexane) 9 l ---J 9+1 1 2-Hcxanone 1 Hexone 1 we-Hexy) acetate Hydrazine-- Skin 1 7,6,4 Hydrogen bromide 2,3 + 9 Hydrogen chloride 2,3+9 Hydrogen cyanide-Skin Hydrogen fluoride 2,7 2,3,7 Hydrogen peroxide, 90% Hydrogen sdenide 2,7 6 Hydrogen sulfide Hydroquinonc 3,6 9+1 Inelcnc 1 Indium and compounds, as In 6 Iodine Iron oxide fume 9+1 9 Iron salts, soluble, as Fe Isoamy) acetate 9 1 Isoamyl alcohol 1 IsoLutyl acetate 1 Isobutyl alcohol 1 Isophorone Isopropyl acetate 1 1 Isopropyl alcohol 1 Isopropylamine 7,6,4 Isopropylether Isopropyl glycidyl ether (ICE) Keiene ;1 '1 1 Lead Lead arsenate Lindane - Skin Lithium hydride L. P. G, (Liquifiedpetroleum gas) 9 8 , .9 8 1 Magnesium oxide fume 9 Malathion - Skin 9+1 Maleic anhydride 9+3 Manganese 9 Mercury-Skin 6,7 Mercury (organic compound*) - Skin 8+6,7 Mesityl oxide 1 Methancthiol, see Methyl mercaptan Methoxychlor 9+1 2-Methoxyethanol, see Methyl cellosolve Methyl acetate 1 Methyl acetylene (propyne) 1 Methyl acctylenepropadiene mixture (MAPP) 1 Mcthyi acryiate - Skin Methylal (dimethoxynicthane) 1 1 Methyl alcohol (methanol) 1 Methylaxnine 7,6,4 Methyl amyl alcohol, see Methyl isobutyl carbinol Methyl isoamyl ketone 1 Methyl n-amyl ketone (2*Heptanone) 1 Methyl bromide-Skin .1 Methyl butyl ketone, see 2*Hexanone Methyl cellosolve - Skin 1 Methyl cellosolve acetate-Skin 1 Methyl chloride 1 Methyl chloroform 1 Mcthylcyclohexane 1 Mcthyicyclohcxanoi 1 e-Metbylcydohcxanone - Skin '1 Methyl ethyl ketone (MEK), see 2-Dutanone Mcthyi formate 1. Methyl iodide-Skin 1 Methyl isobuty) carbinol-Skin 1 Methyl isobutyl ketone, see Hexone Methyl isocyanate -Skin 1 Methyl mercaptan 1 Methyl methacrylate 1 Methyl propyl ketone, see 2-Pentanone I Substance Sorbent Substance . Sorbent Methyl silirnte 1 Phenol - Sfcin Methyl styrene 1 //'Phcnylcnediamine -- Skin Methylene bisphcnyl isocyanate (MDI) 8+1 PhcnyJcther (vapor) Methylene chloride (Dichloromethane) Mnlyhdrniirn (soluble compounds) 1 Phenylcthcr-biphcnyl mixture (vapor) D Phcnylethylene, sec Styrene (insoluble compounds) 9 Phenyl glycidyl ether (PGE) Mnnnmethyl aniline -- Sitin Phenyihydrazine - Skin Moiiomethyi hydrazine - Skin 7,6,4 Phosdrin (Mevinphos) -Skin, Mcnphoiine - Skin 1 Phosgene (Carbonyl chloride) Naphtha (coal tar) 1 Phosphine Naphthalene /?-N.>|>iithylnininc Nickel rarhonyl .Virkcl. meiiil and soluble compounds \ iemine - Skin Nitric acid Nitric oxide /i-Xitroiinilinc -- Skin Xiuobcnrcnc-- Skin /'-.Vuio-rhlorobcnrcnc-- Skin Nilrorlhnnc Xitroitm dioxide Nitiouen uil'luoridc Nitroglycerin -- Skin Xitnuucthnoe I -Nitrnprfipnne 1 7,6,4' 3+5 9 I 2,3 3 1 ] 3 1 2,7 2,7 1 1 1 Phosphoric acid Phosphorus (yellow) Phosphorus pentachloride .. Phosphorus pentasuflde . Phosphorus trichloride Phthalic anhydride Picric acid - Skin Pival (2-Pivalyl-l,3*indandione) Platinum (soluble salts) Polytetrafiuoroethylene decomposition products Propane /NPropiolactone Propargyl alcohol-Skin n-Propyl acetate Propyl alcohol 2-Xiiiopropane X'Xiirnsoclimcihylaminc (Dimethyl* 1 ri-Propyl nitrate Propylene dichloride iiiuosojiinine) -- Skin 7,6,4 Nitrotoiucnc -- Skin 1 Nitrntrichloromethnne, sec Cliloropicrin (Viarbloronapluhalcne -- Skin C Vtane 1 j Oil mist (mineral) 9+1 Propylene imine-Skin Propylene oxide Propyne, see Methylacetylene Pyrethrum Pyridine Quinone Osmium tetroxide 8 RDX- Skirt Ox;,Hie acid Oxygen difluoride O/onc S'*" 3 Rhodium, metal fume and dusts, 3.6 Soluble salts 7 Ronnel I'.ir,u|uni -- Skin g + 7 Rotenone (commercial) I'u/ aiiiion - Skin 8+1 Selenium compounds (as Se) I'fj.t.ihornne 7,1 Selenium hexafluoride Pent ari i lomnaphthalene -- Skin iVmaciilnroplicnol - Skin I'rmanv 9+1 Silver, metal and soluble compounds 9+1 Sodium fluroacetatc (1080)-Skin l Sodium hydroxide U-lVntiinnne Pi icliiorofthylcnc . 1 Stibine i 1 Stoddard solvent iVreliloron. ethyl mercaptan 1 Strychnine fVichlorvI fluoride 2.7 Styrene monomer (Phenylcthylenc) Petroleum distillates (Naphtha) 1 Sulfur dioxide l 7 I I 3 7,6,4 8+-1 3,6 6 S+l 8+2 94-3 9+3 9+3 3 8+3 8 8 8+3 J l I 1 1 1,7 1 1 1 9 1 1 9+ 94* 8 1 2 C l SO O l CD U1 CD -- -- C l CD CD  American Jnduitrial Hygiene Astocialion Journal 409 Substance Sorbent Sdbstancc Sorbent Sulfur hexafluoride 3 Tributyl phosphate 9 +3 Sulfuric acid 2 1.1.1- Trichloroeihane, see Methyl chloroform Sulfur monochloride 94*3 l,l,2*Trichloroethanc-Skin 1 Sulfur pentafiuoride 3 Trichloroethylene 1 Sulfur)'! fluoride .*'7,3 Tnchlorotuethane, see Chloroform Systox, see Demeton Trichloronaphthalenc - Skin 9 +1 2,4,5-T 9' 1,2,3-Trichloropropane 1 Tantalum TE15P- Skin Teflon decomposition products Tellurium Tellurium hexafluoride TEPP-Skin 9 1.1.2- Tricliioro-l,2,2-trifluoroclhane 8+1 Triethylamine ' 8 + 3 Trifluoromonobromomethane \ 8 Triincthyl benzene 3. 2,4,6*Trinitrophenol, see picric acid 8 2,4,6-Trinitrophenylmethyinitramine, 1 7,6,4 1 1 Tcrphenyls l,l,l,2-Tctrachloro-2,2-difluoroethane 1, l,2,2-Tetrachloro>l ,2-difluoroethane I, l,2,2-Tctrachhroethtttv - Skin 1 sec Tctryl 1 Trinitrotoluene - Skin 1 Triorthocresyl phosphate 1 Triphcnyl phosphate 9 +1 8+3 9 +3 Tetrachlorocihylenc, see Perchloroethylene Tetraehloromechane.sce Carbon tetrachloride Tctraehloronaphthalene - Skin 9+1 Tungsten & compounds, as W Soluble Insoluble Turpentine 9 9 1 Tetraethyl lead {as Pb) -Skin 8+1 Uranium (natural) soluble & insoluble Tctrahydrofuran 1 compounds as U 6 Tctrauicihyl lead (TJwlL) (as Pb) -Skin Vanadium (V.O, dust) $+1 (V,0, fume) 8 8 Teiramcihyl succinonitrilc - Skin Tvlranitromethanc Tciryl (2,4,6-Trinicrophenyl. mcthylnitramine) - Skin Thallium (soluble compounds) - Skin Thiram Tin (inorganic compounds, except Soil* and SnOa) 1 3 9+3 8 9+1 9 Vinyl benzene, see Styrene Vinyl chloride Vinylcyanidc, see Acrylonitrile Vinyl toluene Warfarin Xylene (Xylol) XyJidine - Skin I 1 G 1 1 Tin (organic empds) 8+1 Yttrium 9 Titanium dioxide Toluene (toluol) Tolucne-2,4'diisocyanate (TDI) o-Toluidine - Skin 9 l 9+1 1 Zinc chloride fume Zinc oxide fume Zirconium compounds (as Zr) 9 9 9 Toxaphene, tee Chlorinated camphene Received February 15, 1971 | i i i I I / r AP00034933 A Convenient Optimized Method for the Analysis of Selected Solvent Vapors in the Industrial Atmosphere LOWELL D. WHITE, DAVID G. TAYLOR. PATRICIA A. MAUER, nd RICKARD E. K.UPE.L U. S. Department of Health. Education, and JVellare, Consumer Protection and Environmental Health Service, Environmental Control Administration, Bureau a/ Occupational Safety and Health, 1014 Broadway. Cincinnati, Ohio 45202 Industrial hygienists have gCD<r*liy sampled for Industrial vjhrnt 'opofs either by taking grab samples or by measuring the concentrations with bulky rquipnient such as the Devi* balids meter. A convenient method is described for the determina tion of solvent vapors in atmospheric samples. A glass tube packed wish activated charcoal is used to take an integrated sample. A standard volume of 10 liters is sampled, and the tube is capped and renirned to the lalrvratory for analysis. The activated charcoal is desorbed with carbon disulfide, and an aliuuui is introduced into a gas chromatograph equipped with a flamt ionization dvlrrtir. Oj.iii'iLm i-ptraiing conditions have been established on the gas chromatograph for cite separation and analysis of selected solvent vapors of occupational health Imcrrsi. Data are ptotmed on both the adsorption and the desorption efficiencies of select'd solvent vapors, de termined by this method. The solvent* were benarne, n-h*iiyl acetate. 2-buianvne, carhop cetraehloride, chloroform, p*diOKane. ethanol, cchvi ether. Iso-octant, peechloroethylcne, pyridine, toluene, trichloroethylene, and x.ieoe. Introduction Analysis of solvent vapors m the industrial atmosphere for the deter mination ol worker exposure levels hat been a difficult problem for industrial hygiene chem ists,1 In evaluating occupational hazards,*-* industrial hygienists have generally sampled for solvent vapors by taking grab samples or by measuring the concentrations with bulky equipment such as the Davis halide meter. The collection and concentration of atmos pheric samples for analysis have been the most troublesome aspects in the assessment of sol* vent vapor hazards. Several specialized col lection-concentration techniques have been reported. The usual methods involve absorp tion in solvent**'4 or adsorpUon on coated or noncoated solid adsorbents,1-'* with de sorption in the laboratory by heat'-14 or a suit* XCrutum t( woiamUl (Mcifm pRaJuuti d( cdu* mtutt cndotHatst by tht 0.3. Public Kulik Service. able solvent.-1,1* and subset|uent analyses <i the rcauliiritv samplrs by eat chrotnatn^raplm procedures.1 As predicted by Ru-.hir.i'* m 1958, t!i- CUS < hioma-.o-ri n|'.h h.is pmven lr> he a valuable i. tiiai in.uiiu'.-jnt lur malting qualitative a;.-i q..... a.'.%writ vapor measuremrntt. Tin- luc-titf'd f ' .'V.v: tun -mJ Huy." which indicated ti.-.t .iU.-r.pl:-:i ul uicatiic vu:..ii-s could be accomplished by using activated charcoal with d'-w-rptlon hv car1 '-p disullute. holds crea: i.-rnmiic for application in cr.Ji.cJtti^ arid dcsa:b!..q organic soivc-nt vapors- Liquid desorption is advantageous, lince mul tipit- unity,, at tlic same sample are possible. The collection .efficiency of activated charcoal is not affected by variations in iciaiive hu midity, since water is easily displaced by or ganic vapors.*'" Variations in the mesh sizes and type* of charcoal (assuming adequate charcoal section lengthl apparently exhibit no significant difference in the collection and de sorption efficiencies.1*-'* A vnnoling system AP00034934 having a pump capable of drawing a mea surable -mount of air through a charcoal tube la nee*. /. The charcoal tubes are easy to make, seal, handle, transport, and store. Op timum operating parameters on the gas chromatograph have normally been estab lished for each compound to be determined.4-1*-" Experimentation conducted in this labora tory during the past several years indicates that a solvent vapor is rarely found by itself in the industrial atmosphere. Therefore, an analysis is desired that requires a minimum of time and effort to simultaneously separate and ({iiantitatively measure all the compounds in a solvent vapor mixture. Optimum operat ing conditions on the gas chromatograph for tile separation and analysis of fourteen select ed solvent vapors of occupational health inter est are presented. Data are given on both the adsorption and desorption efficiencies of these compounds, singly and in matrix, as deter mined by the sampling procedure of Otterson and Guy.11 For purposes of this paper, the word matrix will be used to include the total solution environment. Experimental Apparatus and Reagents Perkin-Elmrr Model 900 gas chromato graph equipped with dual flame ioniza tion detectors. Patex DIR-! digital integrator (not re quired). Honeywell Electronic 194 dual-pen strip chart recorder. Column {20 ft '< l/& in.) with l0CTo FFAP stationary phase on B0/100-tncsh acidwashed DMCS Clirotnosorb W solid support. Bureau of Mines (hade A helium. Prrpurifled hydrogen. Filtered compre*wd air. Pyrrx gins* tubing. 6 mm O.IJ . 4 mm l.D. Activated charroal. 20/40 mesh. Spectmgrade. spectroquality, and leageni- gradc solvents. Glass-stoppcrcd inicrocentriftige tubes. Hamilton syringes. 10. 25. and 100 /*!. Test chamber. 11540 liteis. with 3540-lpni Rush system. Nominal l-lpin stainless-steel limiting or ifices. Five-port, valved manifold. Ga"' vacuum pump. As. ated laboratory hardware and sup plies. Preparation of Standard Curves The following equation1* relates the parts per million by volume to the number-of mil ligrams of compound present in that volume of air at 25aC. Parts per million = 24,450 X milligrams per liter molecular weight Because a standard air sample volume of 10 liters is to be taken, the amount of compound (in milligrams) necessary to make standards at values of Dne-half the current TLV, the TLV. twice the TLV, 20. 40, 60. 80, 100, and 200 ppm concentration are calculated by this formula for each solvent. The solvents were benzene, n-butyl acetate, 2-butanone, carbon tetrachloride, chloroform, p-dtoxane, ethanol, ethyl ether, isooctane, pcrchloroethylene, py ridine. toluene, trichloroethylene, and xylene. A microlitcr syringe is used to inject the cal culated amount of solvent into exactly l ml uf carbon disulfide in a glass-stoppered vol umetric flask. Ten times the calculated amount may be injected into 10 ml of carbon disulfide to minimize the error due to the volatility of the carbon disulfide. Caution: Carbon disulfide is toxic and should be handled in a hood. The standard solutions should be stored in a refrigerator! they are useful for 2 days only. Any standard contain ing ethanol should be utilized soon after prep aration. owing to the rapid loss of ethanol from the solution. A 5-/d aliquot is withdrawn from the flask with a microiiter syringe and introduced into the ktas chromatograph. To eliminate dif ficulties arising from blow-back or distillation within the needle of the injection syringe, the solvent flush injection technique is em ployed.1* The syringe is first flushed with solvent srvtjal times to wet the barrel and plunger: Time ritivroliters of solvent is drawn into the -.rnnci* u* increase the accuracy and lepindunbiliiv n( llir injected sample volume. The needle is icmmed fiom the solvent, and AP00034935 CHROMATOGRAM Figure 1. Chromatogram ffl to If) niiimtr*, programmed from tOO' la UO'Ct the plunger is pulled back about 0.5 jd to separate the solvent flush from the sample with a pocket of air. The needle is ihcn im mersed in the sample, and tlie 5-/U aliquot is withdrawn, taking into consideration the volume of the needle, since the sample in the needle will be completely injected. After the needle is removed from the sample and prior m injection, the plunger is pulled hack tn minimize evaporation of the sample from the tip of the needle. The standard curve* are established for these fourteen compounds by using the same operating conditions on the gas chromat ograph as are used for the unknown samples. Curves are established with a strip chart re corder by plotting concentration versus av erage peak area. Prak area is determined hy multiplying ihr height of the peak by the width at half-height. Triplicate injections are made, anil thr average peak area is calcu lated. When an electronic digital integrator is employed, concentration is plotted against i lie average number of counts. Figure l is a trpresemative chromatogram of a 100-ppm standard that contains all fourteen solvents and lias hern programmed from 100 to 14fl"C. Table 1 lists the retention data (when programmed from I0CP to I40C1 and boil ing points for the fourteen compounds. Experimental Procedure Sampling Tubt Prrparatian Fire-polished straight glass tubes 6 inches long, 4 mm I.D., were packed with two linch sections (180 mg each) of 20/40-meslt activated charcoal. The two sections were separated with a plug of fiberglass and re- AP00034936 nmnawmM 228 Marca-AprU, iy/(f T*ut I Retention Dirt ind Boiiine Point* ilrtrn prund Flh\1 ether r.X.Vnr -Nilmr IN ruUne (tKmdi) 1? tm tst 2H :n6 144 142 415 J6I Boilin cn 8 . (HI 6(1 67 61 131 III 127 tot in l V'llulDI (mil iU ICS J!1 t?s 372 sse 463 J S.'U 646 taincd with plugs of fiberglass at each end. Both ends were name-sealed in such a man ner that they could be easily hroken in the field. These tubes were used to take an inlegrated atmospheric sample. 7>1 Charnbrr Sampling Known concentrations were gorturaicd m a 3540-hti.r test chamber by evaporating a cal culated volume <>f solvent into the chamber. A fan was used to thoroughly mix the vapors in the chamber (Figure 2). Five tubes were positioned in different areas of the chamber; the. ere connected by rubber tubing to a five-port, valved manifold with five nominal Llpm limiting orifices (Figure 3). An elec trically powered Gasc vacuum pump presid ed a constant rate of flow through these orifices (Figure 4). Before each experiment the chamber walls were saturated with the solvent vapor or vapors at a given concentration. The test chamber was then flushed at a rate of 3540 Ipm for 5 minutes to remove the solvent. Test chamber concentrations at values of one- half tiie current TLV. the TLV, and twice the TLV were then generated, both singly and in matrix, to determine the adsorption coefficients. A standard volume of 10 liters was sampled, nnd the tubes wrrr scaled and returned to the laboratory for analysis. To assess the effect of sampling rate and volume on the adsorption coefficient. 25 liters of pe troleum ether and acetonitrile (concentration 100 ppml were sampled at rates of 0.5. 1. 1.5, and 2 1pm. Drsor//jn Tubs Prrfwatifm Artivated charcoal equivalent to one see. tinn in the sampling tube (180 nig j was meas ured into a 2-inch. 4 min 1.15. glass tube sealed at one end and capped with Parafilm. A known volume of solvent was injected dircctlv into the activated charcoal with a microlitor svringe. and the tube was capped off with more Parafilm. Volumes of all fourteen solvents equivalent to concentrations of onc-half TLV. TLV. 2 TLV. fiO ppm. IDO ppm, and 200 ppm in 10 liters of air were injected into the activated eharroal. To determine the effert of a matrix on the desorption coefficient, various matrixes of four, seven, and fourteen compounds were injected imo a number nf tithes. The tubes were allowed to stand for 1 dav to assure lotiipb-te adsorption f ibr snjsrntfs) by rite i liarmnl. The activated charcoal in the tie. sorption utltes u;ls drsorbed in exactly rim same manner a <-.i< h of the rh.ircoal sections it the saiupiinn tulm )i : ki . Iii! r liainii'i, j lO-lilcr < a;'ii r . Analytical Procedure Dr">.'i ]>'inn r.i i)u- rntiaiiii materials was ,u imnjilishi tl by mint: I ml of cat bon distil- AP00034937 V;**>? s;1 ''^'LZ^^-^y'-i \" 'r--': i fap#*Z&W2i American Industrial Hygiene Association Journal 220 fide per 1-inch section of activated charcoal Each section was analyzed separately; the one nearest the pump was designated as sec tion B,.and the other was marked section A. Each section of activated charcoal was placed in a glass-stoppered luicracentrifugu tube, One milliliter Df carhan disulfide was added to the charcoal. Experimentation has indicated that desorption is accomplished in 150 minuet" if tite sample is shaken repeatedly or otherwise agitated. The resulting carbon disulfide solution was analyzed by introducing a 3-/d aliquot min a gas chromatograph. Either dual-tohunii. dif ferential operation or the uiicnnipcnsnicd mode of iteration can he used in the analy sis. A Honeywell Electronic 104 dual-pen strip chart recorder was used m record the peaks. Although the Hate* 1)111*1 electronic digital integrator was used for a nusulser "f determinations, it is not required. The operating parameters fm tlu- Perkin* Elmer Model 900 gas chromatograph have been designed to be optimum for all four teen compounds. The concent?Mton ol anv or all of these solvents can be determined from the same chromatogram. Temperature pro gramming is not necessary for this procedure, but it can be utilized to shorten the time required for analysis of a sample that con tains xylene and pyridine. Operating conditions for the Perkin-Klmer gas chromatograph are: 1. R5 cc/inin (70 psig) helium vainer flow 2. 65 cc/min (24 psig) hydrogen gas flow to detector " 500 cc/min (50 psigi air flow to de tector 4. 200CC injector temperature 't. 200C. manifold temperature (dewe- torl Oven U'mjxTatiue it Isothermal 11 ioo c: h I'eiiipvratme pmttiam it HtO'O initial u-mpcijimc fm h n lirm tes ii< ill :C per minute program from 100 to 1-10'C <' .i. i .... ............ .. r Kicuxs J Air pump and liiuicinii .uinee* Triplicate injections were made, and tin* average peak ruca for swell compound wu*. calculated from die chromatograms. By re fining die uwrogv ared back to the standard curves, the concentration in pares per iiullior. .mil din inul weight of cat'll solvent wcie easily d. ti nuined. The percent desorption >s calculated by di\ idiug the solvent weight that wjw tU-n-nmivd experimentally in the dcsorptiun tulu* cUuuwal lv die solvent weight th.u was injected imo du* rh.nvnal. trmhipliecl bs I no. AP00034938 Tabli II Chamber Desorption Perce. ,e Compound TLV No. of ConBontAU! CMf.>thhhntfOoitMnreorJtflnohenrro PPetnMdMiro*roeihrlrn* TXyntceHviftrerettK*frric $ts10 ic44tjtooonT0ooo0oJ0 (**. rinse) 7 r*s-~ 91 W- 93 t9972i SMS-6-<91) v1S9---9S1OS (T. Lr*Vr*e) 7 4V964, 9t-iro MU91 9R4f1i 5466564---4--913776702 99T0 7-9-i9on (m2v.TnLnVfel 7 93 M-<4 99 8 94 Mb SI-61 4962--1W00 Discussion Several columns were compared experimen tally to determine which column would effect a complete yet rapid separation of the four teen compounds. The groups of compounds represented are alcohols, acetates, amines, aromatics, ketones, ethers, halogenatcd hydro carbons. hydrocarbons, and halngenated ole fins. A 20-ft X Va-in. stainicss-stecl FFAP column fulfilled these requirements. This column has 10% FFAP stationary phase on 80/100-mesh acid-washed DMCS chromosorb W solid support. Desorption percentages determined for the fourteen compounds at chamber concentra tions of one-half TLV, TLV, and 2 TLV are given in T.ihlo II. Table 111 shows the desorption percentages far GO. 100. and 200 ppm concentrations in different matrixes. The percentages represent the average value of three to twelve determinations, These solvents have desorption percentages of over 90%, with the exception of ethanol and pyridine. Matrixes of three different random sets of seven or all fourteen components apparently do not significantly affect the desorption ef ficiencies of any of these compounds. As was also noted by Otterson and Guy," larger sec tions of activated charcoal appear to cause a decrease in desorption efficiencies. Several desnrption tubes that contained all fnuttern solvents adsorbed at 100 ppm con- rcntralions on the activated charcoal were desorbed with carbon disulfide. These samples were not shaken, stirred, or agitated in any manner. Aliquots from these samples were injected into the gas chromatograph at 30min intervals. Maximum desorption percen tage* were reached 3 hours after desorption began. Table IV shows the desorption ef ficiency variations for each solvent under these conditions. Experimentation indicated that maximum desorption can be accotn- * a mpouna N, of Cnmonnrnu Brj\reiit . Butyl f thyl Hhf r IVrchh'roe1 h r>luer\<* ne Talf. m Standard Desorption Percentage* Sf> Pism Av. Kancf1 Am. Kns I 9* 95 W 72 44 84-OJ M-UO 94-97 <M-|M rxi-tnj 40-95 6S-71 80-94 7 J 44 90 51 4+ 86-49 p6-m 70 64-71 61 92 95-100 47 00 60-66 <*3 79-10] 9J 91-95 10> PP_ _ 4v. H.nse Av Kino 1 99 r,7 01 ioo 40 98 9o-|l S6-M 47-100 85-4* 64-B4 n;-105 ll-t* V? % 6*-fig 97-IU] 7 96 54. 95-97 98 96 S7-M13 to. 95 94 Al It < 'r2 lol Wfr-)nO r* *V 0? r.9 1.3-72 95 93-96 94 91-46 OR 97-IUfl ppm Av Av. Rnnsr 14 4 85-1CD 95 41-99 si-ha 86-94 S. W, 6t JI-6H 60 57-64 UW U-II1 4K 40 192 99-ion t<6 W-71 'H at-97 94 AP00034939 American Industrial Hygitner Association Journal 231 plished in 30 minutes if the sample is repeatedly shaken or otherwise agitated. Tails IV Desorption Percentage Variation with Time Test runs with petroleum ether and ace tonitrile (concentration 100 ppm) at sampling rates from 0.5 to 1 1pm indicate that these rates do not affect the adsorption efficiency Copuiut G*fbva lelncl>)oxid 30 (Blaultt U SI Sboun* 9+ ISO of the activated charcoal tube. Tubes with four 1-inch sections of acti vated charcoal were used to sample and rolled each of the solvent vapors at chamber concentrations of twice the current threshold limit value. All solvent vapors were adsorbed on the first two 1-inch sections of activated XyJcnft SI 34 S3 Hi ttt ttti 0Bilirrd, *aup pled fffulrly. 96 toMn 'h 38 on 96 `JB % charcoal, based on the recovery data obtained from lh chamber experiment* (Table III. the overall efficiency was found to be equiva lent to the efficiency of the desorption stan dard (Table 111); thus the sampling ad sorption efficiencies were determined to be lOOt/fe. These results indicate that a single tube (iwe I-inch sections oi activated charcoal i can be used to sample and efficiently collect each of the fourteen solvent vapors up to at concentrations of TLV and greater. Depending on the matrix, a 1-inch section of chaicoal has a saturation limit of 28 to -15 nig (I00Q to 1500 ppm) of toial solvents, The saturation limit of a single solvent on a I-inch section of activated charcoal is 28 to 30 mg (600 to 1500 ppml. Each charcoal section efficiently collects the solvent vapors passing through it until the saturation limit is reached. concentration* of at least twice the threshold Summary limit value. A small, portable Willson Casrila pump capable uf aspirating an accurately measur able amount of air through a single ilurcual lube lias been employed to take a large num ber ot samples in the field. Analysis of these tubes indicated that many of the fourteen solvents can be determined with the flame ionisation detector in the parts-pur-biilion concentration range by volume in the ait. It is not necessary u> alter the above-mentioned analytical procedure or any of the parameters for these determinations This method was inadequate for the analysis of acetone and methanol. Polai compounds tend to he displaced from the lirst onto the second I-inch section of the charcoal lube when sampled in the presence of high concentrations of nonpolar organic solvents. Approximately 25f,t> of the aceto nitrile was displaced onto the second section when an equal coixeimation (10(1 ppmj of Fourteen selected atmospheric solvent va pors can be collected efficiently on activated charcoal prior to simultaneous separation and analysis by using a gas chromatograph equipped with a flame ionization detector. A matrix of seven or fourteen components apparently does not significantly affect the desorption efficiencies of any of these com pounds. Recovery data showed that the overal efficiency was equivalent to the effici ency of the desorption standaidt for each solvent vapor; therefore the sampling ad sorption efficiency was determined to be ll)0(lb for these solvents, Sampling rale and volume appaieutly do not affect the adsorp tion efficiency. 'Hie study also indicates chat a single chatLoal tube can be used to sample and efficient ly collect each of the fourteen solvent \.spurs at a concentration twice the emu-tit TI-\' Acknowledgments petroleum ether was present, u-gaidlvs* uf the Wc wish to acknowledge tins excellent as difference in sampling rate [0.5 to 2 1pm). 2- sistance of Ceola Moore, who prepared the Buianonc, chloroform, and ethanol were af- charcoal lubes. The assistance of John V. feeled in a similar manner when tested in Crable and Cathryn Dawson is also appre three random matrixes of seven components ciated. r 1GS9G PROPOSED RULES fc) The Deputy Admlnistratm ct* have bceti occupationally related. An .. the level from a celling of 500 ppm to 59 eriufiry Services, upon request to him. result of Uiis notification. amt after uun- ppm ceiling. It wni expressly recognised may approve other identification *yiterns suitatlon with the National Institute for that Ihls standard limiting exposures to In specific eases and under such condi Occupational Safety and Health a 60 ppm level was intended to be n ten tions a:! he may presence If ho deter 'NlOSH). and ft joint Inspection of the tative. interim standard, to be in eltcet mines that such systems provide the plant by OSHA, NIOSK, and the Ken no touccr than six mouths during which nccoo*ary information to allow- for trnec- tucky Department of Labor, a fret-fiud- time the whole question of possible safe back of the swine to their herd of origin. in*r henrins on possible hazards involved exposure to VC would be reconsidered Any person who wishes to submit writ tvU.1i the manufacture and use of VC more Cully and Srv tlve light of more in- ten data, views or arguments concerning was announced on January 30, 1074 '29 funnatlon. especially results of experi the proposed amendment may do so by Fft 3874) and held on February IS. 1974. ments which were known to be under fllinc thorn with Deputy Administrator. 2. Carclnoaenlcitu ol VC. Information way at that time. Vcterinaiy Services, Animal and Plant produced at this hearing demonstrated 4. Additional information, on April 15. Health Inspection Service. LLS. Depart that exposure of laboratory animals 1974, information and data were pre ment of Acrtcultuie, Kyatt&villo. Mmy- (mostly Sprague-Dawley rat*) to VC by sented to representative* of OSHA, 3and 207(12 before Ausust 12. 1074. inhalation at and below the then current NTOSU and Ilia EPA by tho Industrial All written submissions made pursuant OSHA standard of 500 ppm Induced Bio-Test Laboratories. Northbrook, Illi to this notice will he made available for tumors, including angiosarcomas of the nois, concerning results of animal ex public Inspection at the Federal BuildIn*, 9505 Belcrest Road, Room 870, llyattsviile. Maryland 20732, dui-ing reg ular hours of business <8 a.m. to 4:30 p.m.. Monday to Friday, except holidays) liver, Professor Ccsare Maltonl. of tlve Instituto di Oncologist, Bologna. Italy, reported on ft series of experiments on the eilect of exposure of rats, mice, and hamsters to VC at concentrations of posure studies with VC, sponsored by the Manufacturing Chemists Association (MCA). Although only preliminary hi nature, these results revealed that 2 out of 200 mice exposed to VC concentrations in a manner convenient to the public 19.000: 6.000: 2.500; 500: 250: and 50 of 50 ppm for 7 hours a day. five days ft business (7 CFR 1.37<b> ). ppm for varying periods of time (TR- week, for approximately 7 month.*, de Comments submitted should bear a 43-63). Some of the experiments have veloped angiosarcomas of the liver. reference to the date and pace number been concluded, and others are still on Tho Industrial Bio-Test Lab data in of this issue in the Fceeiut, Hechter. going. The experimental result* reported dicate that exposure to VC fit SO ppm Done at Washington. D.C., this 7th day of May 1974. Pierre A, Chaloux. . Acting Deputy Administrator. Veterinary Anhnai and Plant Health Inspection Service. were that tumors have been observed in groups of unimul* exposed to VC at con centrations ax law as 250 ppm. No tumors were observed in tho group of animals exposed to VC at a concentration of 50 ppm. It also appears that the total num ber of tumor*, as well os the numbers Df angiosarcomas of the liver, decreased may well constitute u serious health haz ard to employees. Also, tho question of n safe level of exposure for humans can not he determined at this time, and may cuntimio as a matter for scientific de liberation for many years. We therefore. conclude, thafcjtjs no"K.neciWftry_tQj>rO" `liSic^n^Lit CT0 to oo low a level as can [FI* Doca+-i08S3 Filed 8-9-74;8;43 am] os the concentrations of VC were reduced to 256 ppm. Another experiment by Pro -boxletected U*intf MteEritkioioates outline?' DEPARTMENT OF LABOR Occupational Safety and Health fessor Maltonl was reported underway hrtl'JS iitopcftJll. Involving the exposure of 300 aninmlC ' f5) The proposed permanent standard. to VC at concuntralions of 50 ppm, in Tho requirements for a complete stand Administration order to fu^css in a move definitive way ard under section Gift) of the Occupa 29 CFR Part 1910 ] whether tlwt level of exposure produces tional Safety and Health Act of 1970 | Docket OSII-3H] tumor* in animals. Data rcixjrtcd by are much more comprehensive than the Torkolxon, Oyen and Rowe (Amnlcan provisions of the isru promulgated on VINYL CHLORIDE Industrial Hycleno Association J 22: -'51- April 3. The following proposals nvo re- Proposed standard DC1 (1961)) Indicate that exposure to tponslvo to the additional information VC at concwiLv.Uons of 50 ppm failed to on the earehiournictty ef VC, and the 1. Background. Vinyl chloride leliloroethene) Chemical Abstract* Service Itecistry No. 75015.1* a synthetic chemi cal made by oxycliloiiniition of elhyleno or by hydroehlorinnlion of acetylene. It 1* the parent compound of a scries of tiiemoplnstlu rceln jioJymrr* nud copolymcrs which are widely used for con tainers. wrapping film, electrical Insula tion. pipe, conduit, and n variety of other products. Vinyl chloride has been inode commercially In thi.i country since 1C39 and present prorit'cllmi Is in cxccs* of seven billion pound* per year. Vinyl chloride (VO is ft eas at am induce tumors In rats, hamsters, rabbits, and doss. The employee* of the n. F'. Goodrich Chemical Compfmy who died from angio sarcoma of (he liver had an nvernuft ex posin'# of approximately l years u> vinyl chloride, at unknown concentrations, nud variable exposures t0 other volatile chemical*. (Tit B3). Bonus employee* of CJulon carbide. Firestone Tiro and Rub lev, and Goodyear were also reported hi post-hearing comments to havo had ex posure to vinyl chloride and to have died from angiosarcoma of the liver. Finally, autopsies of four deceased employees re requirements of the Act. A. Level of exposure. Tha proposed Mlandard for employee exposuro is set aE Tvi delectable level, rs'determined by it sampling au<Tanalytical!hlttlvodiftpabln f dclucUtis vinyl chloride at eoncentra- thc (utine, (he mctluidoif'eicn.l sensitivity prope^cd appears to be the most feasible and uruernlly available. A method nf l ppm sensitivity ha* been recommended to OfjliA by NtOfifl. To minimize the nimibci' of persons at- risk, r require bient temperature and pressure and I* ft chlorinated hyclroenvboa which Has moderate itver toxicity. Tito previous standard set a csiltr.j value of 500 part* per million (ppm) (29 Cl-'ft 1910.93, Table G-K. On January 22, 1974. the Occupational Safety and Heallh Administration (OSII.Y) was informed by the National Institute for Occupational Safety and Health iNIOSH) that Hie B. F. Good- rich Chemical Comivmy venorted Hint deaths of several of its employees front a rare liver cancer (angiosarcoma) may vealed their liver angiosarcoma tuiuor* were histologically Indistinwiiixiiablo from the angiosarcoma lumow oils'orvod in Ti'clcMor MaUoui't experimental animnis. 3. The nii'.craeticy Temporal'" Stand' ard. On the basis of nil Information available at time tune, and the fact lint employees aero being exposed at levels around Uto exiMvimentally observed ef fect level of 250 ppm. an Emergency Temporary Standard tETSi was promul gated on April 5, 1974 (39 RR 12312) a* 29 CFH 1019.93(1. Tills standard reduced ment would be eslobllihcd for regulating areas whoro vinyl rlalovlcle is manufac tured. reacted. alutcd.jL'iml Ird, .released, i'cnr.i-knncd, or used, including opera tion;; with polyvinyl chloride containing drive table JuveLi nf vinvl chloride. Access to the area* would be limited to author ized employees. J*. ,'ionttorinff. A program of monitorfra would bo required to establish whether there nra detectable levels In requiated arcs* and to permit determina tion of employee exposures on an In dividual bests. Provision would also be fCOIRAL IEGISUK, VOU 39, NO. 97--fBIDAY, MAf 10. 1974 APOOO34941 PROPOSED RUIDS 16S97 mnrtc lor on opportunity to observe record to an employee's physician on the (5) "Decontamination" means reduc monitoring by einrl'b'ir* or their dohr;- employee's request. fbtabUshmeius con tion of vinyl chloride concentrations to nated representative*. as required by sec- ducting VC operations would be required lwn than delectable levels. t.tcm 8'c' <D 1 of tiro Act. to Identify themselves to OSHA, arid to Ifl) "Detectable mpnn !in pli-. C. Control yictliodi. Where detectable report incidents laceirtcriU' resulting in borne concentration of vinyl chloride levels of VC ftie monitored, two pro Uio release of vinyl chloride. measurable by q aampiuig.an'd analytical grams would be IrirrcrecI; an ensioevr- Accordingly. pursuant to icclions B(b). .method capable of mcasuilsgxoucanLu- ing and ivork practice program to reduce levels below detectability: and while 1 ills C'e*, and sic-i of the Occupational Sorely and Health Act of 1P70 <84 Stat. ' ppiniso percent. Is on-going, el respiratory protection pro 1593. 153G. 1509; 29 U.S.C. C5S. G57), Sec ' f7l 'Director" means the Director. Na gram for employee* In the rcgulnirdnron. retary of Labor's Order Ho. 13-71 (35 Fft tional institute for Occupational Safety EnjtinecilPB control* nml work prac 81541 and 29 CFR Part 1011. It is here ami Health, or any person directed by tices are favored methods of compliance by proposed to amend 29 CFFl Part 1D10 him or the Secretary of Health. Educa because they lend to avoid coutamlju- by revising { l9lO.D3q as set forth below. tion, and Welfare to act for Cite Director. tion of the ambient nil in the workplace. Written dnt.i, views, and arguments HSi "Emergency" means an unforyecn Accordingly, it is proponed to require li'c conccvnlivt I he proposals may be mailed circiunaumco or set of circumstances, re institution of enciuuerlng controls amt to the Doc-fcct Ollieer. Docket OSH-30. sulting hi the release of vinyl chloride of workpractlco methods as soon as feasi Room -30. 1726 M Blreet. N.W.. Occupa Into areas occupied by employees. ble, and to require the use of respirator* tional fjnfrty and Health Administra ID) "Exposure" mean* actual-contact pending the Institution of such controls, tion. Waxhlngton. D.C. 20210, ]St- with vinyl chloride when unprotected by to supplement such control* where they iiuu-k'd not later titan June 10. 1974. required personal protective equipment are insuUlrieut to reduce concentrations Fur.-.uaiit to 29 CFR tCUl.ll <b) and and. clothing. of vinyl chloride below the detectable fci, interested poisons may file objec U0> "Fabricated product" means a level. In specified work situation*, and tion* to (he proposals, jenncsllng an In- finished product or port of such product, In cases of emergency. The proposal lor fovmal hearing with respect thereto, in mads of polyvinyl chloride, entirely or in continuous flow and pressure demand accordance with the following eoiidl- part. Including semifinished products types of respirators Is based on the icc- lion.*; such as him. sheet, block, bar, or extru omnienclations of NIOSH, which lia* ob (1) The objection* nw.a include the sion stock. served leakage through chemical car name and address of the objector: (ID "OSHA Area Director" moans the tridge respirators at high concentrations <2> The objections must be poat- Director for tho Occupational Safety nnd of VC. mrukccJ oti or before Julie 10. 1074: Health Administration Area OfPce hav A requirement would also be estab lished for the provision and use of pro tective clothing for employees in the reg ulated areas. The protective clothing would minimise skin contact with VC vapor, and would provide sonus measure of protection from splash of liquid hi the event of a spill or rupture of equip ment. Food, beverages, and like products would be prohiblitd In the vcaulited area. Written operational Rnd emergency plans would bo required. ftlor.E with em ployee training In roul ine and emergency duties. Specific requirements would be established for emergency actions nnd for routine maintenance and doconlumiURtlon operations, including vessel entry, which are known to present particular hazards. The Purposes of operational and i-iner- coney plans and training ?rc to apprise employee* of the hazards to which llicy iSi The objections must specify the provisions of the proposed rulo to which objection is taken, and must state tho grounds therefor: 4' Each objection must be separately stated awl numbered: ruid (S> The objections mutt be accom panied by a summaiy of the evidence proposed to ba adduced at the requested hearing. As revised, { 19l0.93q would read ns follow*: y HMO.OSq Vin>l Chloride. ii scope aflit application. (!) Till* section applies to any a ita or operation In which vinyl chloride ichlorocthcnc'. Chemical Abstracts Service Registry No. 75Q15. is manufactured, reacted, re leased. repackaged, stored, or used, in cluding areas Rnd operations involving polyvinyl chloride where deteetablo levels ol vinyl clilorido are released. t2i This section docs not apply to Hie ing jurisdiction over the geographic area in which the establishment is located. < 12> "Polyvinyl chloride" means poly vinyl chloride homopolymer Or copol ymer before such Is converted to a fab ricated product. (13) "Protective clothing" mean* clothing protective against vinyl chlo ride. (14* "Vinyl chloride" mean* vinyl chloride monomer. ilOf "Waste resin'' means any resin or other reaction products removed In the cleaning of equipment, such as ves sel* and piping. <) Reference. College of American Prtlhoprrnstx, 2.7ft n. Michigan Ave.. Chi cago, Illinois 611601. (4i Tlr.qttlatP'l. areas. (1) A-regulated area shall be established where (h vinyl chloride Is manufactured, reacted, re leased. repackaged, stored, or used: or * in nolyvmvi rnioridn capable of reh*7.7in.7 (5ct.'tr!*l<* levels of vjyl chlo may be exposed, of the precautions they handling or use of rubricated products ride is manufactured, reacted, released, must tako to avoid such hazards, and to mado ontliely or hi part ol polyvinyl repackaged, stored, or used. rehearse employees til the procedures they must follow In cniergcneie*. 1>. Medical svri-elUuitcc. Comprehen sive requirements for employee medical examinations are proposed, including necessary tests. Sonic additional tiuidnnec It included for Lius convenience of physicians. The proposed requirements have been recommended to O^ffA by NIOSH b. rea.toiir.bly appropriate to de tect liver dysfunction which may he in dicative of, or piTrti.qiositic to, the de velopment of liver noKlosarcomns. E. flccord.i and reports, Records of monitoring, mcdtral examinations, and chloride. <2> Access to regulated areas shall be ib* Dc/tinfjnrc*. it) "Assistant Secre limited to authorized employees: tary" means the Assistant Secretary of (3) A daily roster of employees enter Labor Cur Occupational Safety and Health. US. Department of Labor or his dcslsutee, ing regulated areas shall be made nnd maintained. The rosters, or summaries thereof, sliall be .kept for at ioist-20 i2> "Authorized employee" means an years. employee whoso duties require him to be* in the te'iulnted area nnd who has been specifically assigned by t)>c employer: and any employee who enters such an area a-v a designated representative of employees to exercise an opportunity to obscivc monitoring and measuring of vinyl chloride. ' <e> urontfortwff. (1) Every regulated Rica shall be nionitoredlor detccfg|)l4_ .levels of vinyl eh torfdc- <2> The monitoring shall assure that any exposure may bo determined for each authorized employee with a confi dence level of 95 percent. entry to regulated area* ore proposed, <31 "Closed container" means any (3) Employee* or their designated rep with provision for access by appropriate container which prevents the release of resentatives shall be afforded an oppor OSHA and NIOSK official*. Specific pro tiny) chloride to the environment. tunity to observe monitoring and measur visions for employee access to monitoring <4* "Contaminated" means capable ing required by this paragraph. TCeords ate included, os well as the re of re'rnaingr a detectable level of vinyl 11) Whcro exercise ol an opportunity quirement to furnish a copy of n medical chloride. requires entry to an area where the uso Ho.fia--rt.i--(0 FEOUAl 1E6IJ1EX, VOL. 39. NO. 9?--FRIDAY, MAY 10. 1974 AP00034942 jtve PROPOSED RULES cf protective clothing, cnulcm fa cilities. or procedures Is required, such clothing, equipment, facilities, and pro* cedurcs shall bo provided to all persons entitled to eicrolsc the opportunity, at no coat to any of them. (ill Persons exercising the opportu nity shall bo Instructed regarding: <A> The toxicity end Arc hazard of vlnylchloridc; and <B) Tile protective step* end measures necessary for their protection. <1111 Observers shall be permitted, nlthoutinterfcrence to the persons per forming tile monitoring and measuring, to: (A) Observe all steps and procedures related to the collecting- processing, and' evaluation of particular monitoring and measurement samples: <B) Record quantities and results obtained: (C) Observe the condition, of monitor:, liter and measuring equipment: <D> Receive a demonstration, of. the .calibration and function. tests..of..the monitoring and measuring equipment performed on site; and (El .Examine .Instructions and docu- znent* related to the procedures^ and J.QB. (4) Accurato and complete records of all required monitoring shnli jjo made and maintained for not less than 20 years. Such a rceortTsliaU (i) state ffie date of such monitoring ' and Tlie"levels determined; and til) identify Hie Inatru- ments and methodgjiscd. ~ (f) engineering controls and icorfc- prantice methods. (U Where detectable levels of vinyl chloride are measured. Immediate protection shall bs provided rrcuinst exposure to vinyl chloride by the uso of engineering controls, workpraettee methods, and respirators as follows: <j> Feasible engineering controls nnd workpractice methods shall immediately bo used to reduce airborne concentra tions of vinyl chloride below th* detect able level: (II) Wherever feasible engineering controls and wovUpracLlce methods which can bo instituted Immediately avo not sufficient to rcUuco concentrations of vinyl chloride below tho detectable level, they shod nonetheless be used to reduce the concentrations to the lowest prac ticable level, and shall bo supplemented by mean* of respirator* in accordance with paracraph <g) of tills section: (III) Wherever no fcaalblo enr.lneeting control or workpractlco mctliod can bo Instituted Immediately, immediate res piratory protection shall be provided m accordance with paragraph (g) of this section; and (Jv> In any ease covered by paragraph (f)(1) (11) or (Hi) of this section, tho employer shall also undertake as soon as practicable a program to reduce nil borne concentrations of vinyl chloride below the detectable level, or to the greatest extent foasiblc, solely by means of encineering controls and wovkpractlce meth ods and as soon ns feasible. <2) There shall be tests made process or equipment leaks and for emis sion of vinyl chloride which may result from workpraetieen. Tho frequency ot those tests shall be such as to insure tho Integrity of equipment and adherence to proper worttprticUces. <C) Jlcspiratorp protection, in A res piratory protection procram In accord ance with i 1010.134'shuil be established and implemented where respirators are required to be used by this section. (2) Respirators shall bo used only In cases of emergency and where required by any other provision of this section. Respirator* may not be used in lieu of feasible engineering controls or wortpvactlc* methods, (3) Respirators or combinations of respirators for protection against vinyl chloride shall be selected from among the following: <i) A positive pressure full facepiece self-contained breathing apparatus; (U) A pressure-demand full facepiece self-contained breathing apparatus op erating In the pressure-demand mode; (iii) A combination type "C" pressuredemand lull facepiece respirator oper ating in tho pressure-demand mode and a pressure-demand self-contained bi'catiilm; apparatus operating In the pressure-demand mode; or (Iv) A combination type *'C*' continu ous flow respirator and n, pressuredemand self-contained breathing ap paratus operating in the pressure-de mand modo. (h) Protcctlre elothino. (f) Employees entering regulated areas shall be pro vided full-body protoctlvo clothing, foot wear or shoo covers, and gloves, at no cost to them, and rc.iuircd to wear It while in tcio regulated area. (2) Where polyvinyl chloride powder containing detectable levels of vinyl chloride Is handled, employees shall also be: (I) Provided and required to wear hwlcoverings: (ID Required to remove all protective clothing at each exit from the regulated area; and Oil> Required to sliowor after tn* last exit of the day. (3) Clean protective clothing shall be provided whenever contaminated or soiled, but not less frequently them weekly. Contaminated clothing shall be decontaminated boforo rouse by removal for laundering or disposal. (i) Ilx/aicne /acuities and practices. (I) Where employees arc required by tht section to wear protective clothing and equipment, chango rooms shall bo provided In accordance with I 1910.111(0. (2) Where employees are required by this section to shower, shower facilities shall be provided in Accordance with I 1910.1'lU<i>(3). (3) Storage or consumption of food or bevernees. storage or use of smoking or nou-fuod chewing products, and tha storage or application of cosmetics arc prohibited In regulated areas. <j) fimcTornrv situation*. tl) A writ ten operational plan for emergency situations shall bo developed for each regulated area, (21 In tho event of on emergency, ap propriate portions of the plan shall ba put Into operation. li) Hazardous conditions created by tho cincigency shall be eliminated and the affected area sliall be decontami nated prior to the resumption of normal operations. illi Special medical surveillance by a physician sliall be Instituted within 24hours lor employes* present la the af fected Bvea at die tlmo of the emergency. (ill) Where an employee has a known contact with liquid vinyl-chloride such employee shall be required to shower os soon as possible, unless contraindicated by physical injuries. (iv> An incident report on the emer gency slwdl ho reported as required in paragraph frj>(2> of tills section. (3) Each authorized employee shall be trained in n program relating to the luiaards of vinyl chloride and the pre cautions for safe use. >1) The precram shall Include: (A) The nature of tho lire hazard, and the necessary protective steps; fB) Tho nature of the toxic hazard, including local and systcmla effects, acute and chronic effects including specifically the carcinogenic hazard; <C) The specific nature of operations which could result In exposure to vinyl chloride, and necessary protective steps: (D) The purpose for and application ot the medical surveillance program; (E) The purpose for and application of decontamination practices; iF> The purpose for and significance of ocncrgency practices and procedures; (O' The employee's specific role under normal operating or emergency condi tions: - 'll) Specific information to aid the employee In recognition and evaluation ot conditions cud situations which may result in tho release of vinyl chloride; (1) Tho purpose for and application of specific first ntd procedures and prac tices: CJ) A review of this standard at the employee's first training and indoctri nation program and annually thereafter. (it) All materials rclatlmr to tho pro gram shall ba provided upon request to authorized icpmeutfiUvcs of the Assist ant Secretary and die Director, <k> Zlpns and labels. (1) Entrances to regulated areas shall be posted with signs bearing the legend; CANCGR-SfifiPCrr AOMtT AREA ABTHORIZEU P&neOKNKL ONLY (2) Arens containing operations cov ered la paragraph (k> (1X4) of this sec tion shall be posted with signs bearing tho legend: CANCFR-SUSPECT AGENT IN THfS AREA I'VLL IMPERVIOUS: AIR-SUPPUED EQUIP MENT REQUIRED AUTHORIZED PERSONNEL ONLT (3) Contolnors of waste or other nsateilnis contaminated with vinyl chloride shall be labeled: FEDERAL REGISTER, VOL. 39. NO. 92--FRIDAY, MAY 1 i, \-JT4 [ j I [ . I | | AP00034943 'RUKUiLU KUUS uovy VINYL CHLORIDE CONTAM)HATTTU CANC'KRM-WATUlStTrKUCATIj AGENT DtSPOSF Of OR DKCO>~TM-nt-\VlZ USING AUTJIOR12KD PnUCL'DUHi.5 (<) Containers of polyvinyl chloride onUtlniiig detectable level* of vinyl .hloride shall Irt labeled: rOLYVJNYlj CHLORrnK CONTAINS VJNYL CKLOIUDE VINYL CHLORIDE IS A CANCER-SUarECT AGENT nurmam HY BREATHING AND T11IXOUOI1 SKIN 81 Containers of vinyl chloride shall le leDeieo: IINYL OKLOR1U12 DANGER EXTREMELY FLAMMAhLE OA3 under pnessunp; MAY 1'OI.YMF.RTXB WITH EXPLOSIVE FORCE POISON CANCER SUSPECT AGENT AND ANESTHETIC ABSOIUJED BY BREATHINO AND THnOUOII SKIN (81 No statement snail appear on or tear any required ?ipn, label or instrue;ion, which contradicts or detracts front Jia effect of any required warning, JnormaUon or Instruction. (1> Ar<tiHleimec and drcontnntirailon. ill Emphasis shall he placed upon mmcdlatc clean up of spill*, periodic in spection. prompt repair of equipment and calls, and proper handliiif?, Horace and ilsposal or decontamination of material* ;o prevent airborne contamination and accidental skin contact with vinyl chlo ride. WnsLo materials, equipment, and ather sources of vinyl chloride In closed containers, may not be placed in arena of sxcessiva temperature or srmliclit since build-up of internal pressure may result In rupture of the container, fire or explosion. (2) Waste resins or other materials lontaralnnlcd with vinyl chloride shall be placed, in cloned containers pending dis posal or decontamination. (3) Appropriate procedures shall be lovelopccl and implemented for the de contamination or disposal of all such waste material. (4J In maintenance or repair opera tions on contaminated--systems or quipnient. Including vessel entry, em ployees encaged in such operations shall ae (1) provided with and j-cquired to wear and use a whole-body air-supplied suit impervious to vinyl chloride, and a respirator In accordance with paragraph lg> of this scetton: and <tii required to shower after removing protective equip- nent, <51 protective clothing and equipment shnll bo clean and dry for each use. (0) When vessels or piping system* n.vo ypened local exhaust ventilation shall ho provided to remove the escaping vapor rrom all occupied areas. (1) (1) Vessels to be entered shall first bo ventilated and monitored so that tha concentration of vinyl chloride is reduced to a level within the protection factor capability of the protective equipment. in wiicn vessel* nre lo rae entered, an ] iipmq to siren vessel Midi be: <A> Opened. Wanked uud loused; or mi Where welded pining is In use, not . ers than a valves in series, which Isolate lie vessel from any oilier connection to uch Hue. must be closed and secured. (ill) No employee s I mil enter a vessel, :xcept when another employee properly mined and equipped, for' entry Is pro mt and is observing the employee in the easel. The observer shall havo moans 'or signalling for help in the event tins Mtiployee experiences problems. Under iuch conditions, the observer shall sig nal for iidp. and shall not enter to assist ;he employeo until another person is zrcscut W> observe. <m> Transportation loading ontf oartlny, (l) Facilities for the loading md unloading or vinyl chloride to and rom containers shall have each transfer ine und vapor-equniixfmt line equipped villi vent connection*, and shall have m inert gas purging system. Vent and >urgo effluent shall be returned to ft proo fs stream or flared in a safe location. <21 Procedures shall be developed and tnplomeuted for Iho transfer of vinyl ihlorldc. Written copies of such proco lures shall be provided employees en raged in such operations, and such eniiloyros shall be fully trained and reloursed in all procedures. (a) employees engaged in wunsier opsratione shall bo provided with and eqnircd to wear respirators in aceorduice with paragraph ig) of this section. un rammer uanaiviff operation), u) Sontnlncra of polyvinyl chloride releasng detectable levels of vinyl chloride ihsill be opened and transferred only .nulcr local exhaust ventilation which educes the concentration of vinyl chlo ride below ihe detcctabio level. (2) Hot operations, such as bub not Imltcd lo milling, calendering and cx.niding, which rclea.se detectable levels >f vinyl chloride, shall be carried ou only under local exhaust ventilation which reduces the concentration of vinyl chlo ride below the detectable level. >o) Atcatcas surveillance, nos later .linn ------------------- 1074. a program >f medical surveillance shall be Insti tuted. and shall provide each authorized nnployeo with an opportunity for cxMolnatlon* in accordance with this para graph. All medical examinations and procedures shall be performed by or under tha supervision of a licensed Doctor of Medicine iMDl or Doctor of Osteopathy IDO). Ail meciJcni examina tions and tests shall be provided without :ost to the employee. (1) At tile time of Initlnl employment, or upon Institution of screening, a physi cal examination shall be perforated with specific attention to detecting enlarge ment of Uver or spleen by abdominal palpation. <2> At tne time ox initial employment jr upon institution of screening, and an nually thereafter, a medical history checklist shall be completed by the em ployee. This list shall include questions concerning: i> Aieonoi miaKo: Hi Fait history of hepatitis; liil Pa*t exposure to potential hepaotoxic agents, including drugs and licmicals: Uvt Past history of blood transfix ions; and i v) Past history of hospitalizations. (3) At the lime of initial employment, ir upon institution of screening, n scrum nedmen shall be obtained lor screening rtth respect to the following blo-chemi- al determinations of liver function; i> lavni bilirubin; 111 Alkaline phcspliatase: iti) Serum glutamic oxalacctic tr&nsiminnso iouuT); (iv> Soruin glutamic pyruvic trans- imfnnse (SCPT): and <v> Gamma glustamyl traiispeptldase GGTP). (ii Addliiouai issis time may opiion- illy be considered for uso in screening nciude: u Lactic dehydrogenase; li) Scrum protein determinations: 111) Scrum protein electrophoresis; md (lv) Platelet count. (5) Laboratory analyses for all blologlal specimons included In medical exam- nation* f.linll be performed In laboi'oorles accredited by the College of American PnUieioglstc or licensed under 13 CFR Part 74. <oi it tne results of screening required n parnernpli to) (3) of this section ara lormai, screening shall be repeated: fi) Every six months for employees who hare been employed in vinyl chlo'Ido related operations for 10 years or nore: and (lip Annuaiiy for aii oiher employees interiiig rceulatcd areas. (7) If one or more liver functlou tests icrfomicd arc abnormal, scrum testing ihall be repented as soon ns possible, preferably within two to four weeks, ir io abnormalities are present upon re- (creening, sertun testing shall be rojeated in three months. (8) If abnormalities persist upon re- tcrecning, the employee shell be with drawn from areas where contact with vinyl chloride Is possible, and an lndlvidjalizcd medical workshop shall bo in- itituled. Susucslcd os initial steps are a complete physical examination and vari ous social procedures such ns hepatitis 13 anliecn determination and liver scan ning. If liver function abnormalities nvo Jctermincd to bo unrelated to ilvcr dis ease. the employee may be permitted to return to vinyl chloride-minted employ ment. subject to Individual medical evaluation. (Vi a complete and accurate record of the results of medical examinations shall be made and maintained for the dura tion of employment plus live years, or for 20 years, whichever Is longer. (p) Accords. (1) Records of monitor ing and measuring, medical records, and regulated urea entry rosters and sum maries. shall bo made available for ex amination and copying uixm request to authorised representatives of the Assist ant Secretary and tho Director. FEDERAL REGISUC, VOl. J7, NV. Y2--TXIBAT, MAT ID, 1171 AP00034944 * .r 16900 PROPOSED RULES <2) In the event that the am,..jycr ceases to do business and there is no suc cessor to receive and retain hi* record* lor the prescribed period, these records shell be transmitted by registered mat! to the Director, and each employee Indi vidually notified In writing: of ' this transfer. (3) Employees and their designated representatives shall be provided access to examine and copy records of monitor- in? and measuring. '4) Former employees shall be pro vided acces to examine and copy record* reflecting their own exposures* (31 Upon written request of nny em ployee, a copy oi the mcdlcnl record of such employee shall bo furnished to a physician designated by the employee in such request. <q> Reports. (U Not later than______ the following information shall be reported to tire 03IIA Area Director. Any change in such information shall be reported to the OSHA Aren Director within IS days of such Change. (ll The address and location of each establishment which has one or more regulated areas; and (U> The number of employees lu each regulated area during normal operations, including maintenance. <21 Incidents which result In the re learns of vinyl, chloride into any area where employees may be exposed shall bo reported In accordance with this para graph. (i) A report of the occurrence of the Incident and the facts obtainable at that time including n report on any medical treatment of affected employees shall bo made within 24 hours to the OSIIA Area Director. til) A written report shall tic filed with the OSHA Area Director within IS calendar days thereafter and shall In clude: (A) A specification of tho amount of material released: (B) A description of the area Involved and the extent of known and potential employee exposure and area affected: cC> A report on any medical treat ment of allotted employees arid any medical surveillance pronram imple mented: and (D> An analysis of tho circumstance* of the incident, end measures taken or to be taken, with specific completion dates, lo avoid further similar release*. (3> Upon completion ot on? monitoring <Set. COO, (c>, MiC Sic). St Stnt. 1593. 1538, 1500 (30 If.B.C. CM. 8571: Secretary of Lslior's Order No, 13-71 (38 Fit S734) Ricned at Washington, D.C. this Qth day of May. 1014. John StCNDcn, Assistant Secretary of tabor. [Fit na.7t-10748 Filed S--0-7t;8;t3 nm| DEPARTMENT OF TRANSPORTATION Federal Aviation Administration [ 14CFR Part 25] [Docket No. 13098; Notice 74-10] TRANSPORT CATEGORY AIRPLANES Typo A Passenger Emergency Exit Capacity Tho faa Is considering rule making to revise tho passenger seating configura tion limit that in applicable to Type A exits on transport category airplanes. Sections 23.007fc) (2) and (3) of the Federal Aviation Regulations (FARs) currently provide that for each pair of Type A exit* (consisting of one on each stdo of the fuselage) the airplane may have a maximum passenger seating con figuration of 100. This advance notice of proposed rule making is being Issued In accordance with tfio FAA'* policy for early Institu tion of public proceedings In actions re lated to rule jnakinrf. An "advaneo" no tice U issued to Invite early public par ticipation in the identification and se lection of a course or alternate courses of action with respect to a particular rule making problem. Interested person* are Invited to par ticipate In the rule making by submitting such written data, views, or avrjumente at they may desire. Communications should Identify the regulatory docket or noLice number and be submitted In duplicate to: Federal Aviation Administration. Of fice of tho chief Counsel, Attention: Rules Docket. AGC-fM, 8Q0 Independence Avenuo, SW,, Washington, D.C. 20531. Cormniraicntions should be received du or before July 9. 1974. to assure proper confideraUoii. All comments submitted Mil be available, both boferc and after the rlcslug date for comments, for ex amination by interested persons. Ilia regulatory provisions relating: to Tvpc A exits that arc coulslncrt In \ 23,801 of the Federal Aviation Populations were adopted by Amendment 25-15. ef conservative limitation may no h be applicable, tho FAA has institu regulatory Study project lo reevo tho limitation. Tire study will indue! factors criminally considered in e fishing the limitation a* well a* any . factors found to be pertiuent. 1 factors originally conslderel include linent evacuation tests and demon tions. exterior slides, the number, tion. and size of aisles and passage- and evacuation system reliability. Data available to the FAA on In- ico evacuation*, slide deployments, evacuation demonstrations indicate more than iflo passengers have evacuated through a Typo A exit 90 seconds. Tho data fuillier ind that Type A exit systems may higher In-service reliability than wa. ticipatcd at the time the limitation established in the regulations. Hew the FAA bclieres it Is Important tview nil relevant data on safety and considerations that may ba applical my proposed change in the Typo a Passenger seating limitation. To this tho FAA solicits data, views, and r. ntent* from all Interested persons oj questions set forth below. Data suor Ing an answer should bo suDmlUe Identified sufficiently that the FAA obtain or develop It. 1. Do the data available on evacu: tests end In-eervlcc incidents that r to tho evacuation capacity of Tyj exit* under emergency conditions i cate that the 100 passenger uniltat may safely be increased? 2. What reliability has been den strafed far Typo A exit systems by . ice experience end tests? 3. What relationships may be es Halted between reliability and passe: emergency evacuation capability of j A exit*? 1. How would the emergency cvntion capability of Type A exits be reeled by specific increases lu passe: seating capacity find by specific p.i*. ffer seating configuration coniideraUi 5. If there are other (actors should !;c considered, how should tlio evant (fat* b* related to the emerge evacuation capability o( Type A e: S. If tho commentator rccommr specific passenger capacities for con eratlon, what economic and safety br fit* or penalties would be associatfcd \ them? and measuring which discloses that any fective October 21. 1D67. That amend Issued In Washington, D.C., on Ma employee lias actually been exposed to ment also establlrhecl the provision, lu 1074. detectable levels of vinyl chloride, each such employee shall be individually noti fied in writing. Tha notice shall: (i) Be delivered not later than 10 working day* after completion of tha ) 23.803(c). that manufacturers show by demonstration that the maximum seat ing capacity of an airplane having a ca pacity of more than 4* passengers can bo evacuated to thu ground within 00 seconds, under conditions proscribed in C. R. Mtr.vsiN, Jr.. Acting Director, Flight Standards Scrclc | Fit Doc.74-10707 Filed fl-8-74;8:4S p Dtonitorlnc and measuring; Die regulation. As discussed in the pre fit) State the actual exposure In terms amble to Amendment 35-10. the allow [ 14 CFK Port 33 ] of concentration and time: and able passenger seating limit of 100 that | Dockst No. 74-NW-4 A D J iill) State the Steps which have been taken, ate being taken, and will be taken, with specific completion dates, to termi was established for each pair of Type A extscs was less than the evacuation ca pacity that hu<i boon demonstrated by test. As a result of receiving data and AIRWORTHINESS DIRECTIVES Boeing Model 737-100/200 Series Airplane* nate the exposure and prevent a recur Information tending to Indicate that The Federal Avlallan ndministrat rence. tome of tho considerations leading to the I* considering amending Part 39 of i fSOIIAl RfCISTK, VOl. 31. NO. *3--ntfDAY. MAT 10, 1974 AP00034945 - iThe vinyl-chloride fight is on Chemical companies are filing objec tion* to the Occupational Safety and Health Administration's proposed per manent exposure standards for vinyl chloride (CW, May 15,p. 25). Bat despite the outlook for prolonged hearings and accumulated data from many studies, OSHA is still hoping to adopt the stan dards, which call for "no detectable level" of VCM, by October. Calling the proposed standards "im practical," "unachievable" and "a disas ter for the industry," producers of vinyl chjoride end polyvinyl chloride are bas ing objections on three main points. These are, they allege, the unavailability of manufacturing technology to eliminate VCM completely, the economic impact on the industry (they oomend that plants will be dosed, jobs and markets lost) and laek ofdata to support the new rules. But industry chances of changing the standards appear to be getting worse, if last week's New York Academy of Sci ences meeting on toxicity of VCM and PVC is any indication. Charges of blood, liver and respiratory abnormalities result ing from exposure to vinyl chloride were added to the known cases of angiosar coma. Standard Setting*. The new standards proposed by OSHA define "no detectable exposure level" as being determined by devices capable of detecting concentra tions of I ppm. with an accuracy of 1 ppm., plus or minus 50%. "That's going to be tough to achieve," says Daniel Boyd, director of the agency's standards devel opment office. But Boyd observes that a combination of engineering controls, work practice methods and respirators could be used in complying with the rules. The standards would put plants in three categories: those at which "feasible engineering con trols" would be used to reduce exposure below detectable levels, those at which respirators would supplement work prac tice and engineering changes, and those at which respirators alone would be used because "no feasible engineering control or work practice method can be instituted immediately." But industry is saying that these cate gories are not practical. Reason: there is no technology available to completely eliminate exposure, so there has to be re liance on respirator systems. And these, industry adds, are dangerous and won't work. "Maybe we can build a new plant to approach the proposed standards," says Harry Conners, general manager of Diamond Shamrock's plastics division, "but we can't adapt existing plants to it." More Studies: What choice is left to in dustry? The answer could come from a series of economic impact studies that are being undertaken. One will be done by OSHA, although a contractor to do the work has not yet been hired. The Society of the Plastics In dustry has hired Arthur D. Little to study the economic impact or the new regu lations. That study could be ready within two months. In formulating its VCM rules, OSHA relied heavily on evidence of develop ment of angiosarcoma in mice at 50-ppm. exposure' during tests sponsored by the Manufacturing Chemists Assn, at Indus trial Biotest Labs. And now those labs and those of Ccsare Maltoni, is Bologna, Italy, are going to rue Amber tests on mice at 25, 40 and S ppm. But the indus try contends that much of this data doesn't relate to human exposure. Con nors cites cases of 17 workers at Diamond Shamrock's Deer Park, Tex., plant who have had 20 yean' exposure, he says, without damage. Also under investigation is emissions of vinyl chloride from manufacturing plants. The Environmental Protection Agency maintains that there are 6% VCM losses from PVC plants and concentra tions of 1-2 ppm. in air outside plants. Several PVC makers have been installing ventilation systems as protection for workers. Closing this outlet for air pollu tion reasons will prove an added hardship for the already-hard-pressed makers of VCM and PVC. And if limits are put on the amount of unreacted VCM on PVC resins, as is being considered by EPA, the industry may find it hu "nowhere to go," u one company spokesman put it. Dart takes the plunge Improved market conditions have trig gered one polypropylene expansion, and more may be in the works. Dan Industries, which had been con sidering expansion for some time (CW, Apr. II, `7i, p. 15), said last week it will build a lSO-million-tbs./year polypropyl ene plant n.etr Houston in a joint venture with El Pasoi'Producis, a subsidiary of El Paso Natural Oat. Startup is expected in '76; cost was not disclosed. The partnership already operates a Top of the news 130-million-lbs./year polypropylene plant in Odessa, Tex. That unit will be debottlenecked to up capacity by 10 mil lion Ibs./year, according to Dart's chem ical group president, Ralph M. Knight. Knight said the decision to build a new plant was based on forecasts that U.S. polypropylene demand will double, to about 6 billion lbs./year, by '80. Recent increases in prices of the material, be adds, should offset higher costs. Site for the new plant will be 5S0 acres in Bayport, Tex., recently acquired by ibe partnership from Friendswood Develop ment Knight said the site was chosen be cause it is close to other petrochemical complexes and to shipping facilities. Polypropylene is tight although not as scarce as tome other resins. Prices are firm, and industry observers say addi tional capacity is needed, since only Her cules and Amoco Chemicals have major U.S. expansions now in the works. Shortages won't vanish Shortages of vital feedstocks will be a major and long-lasting problem for the plastics industry, Amoco Chemicals' en vironmental coordinator, Victor A. Denslow, said last week at the annual techni cal conference of the Society of Plastics Engineer* in San Francisco. The short ages, be predicted, will last at least three years, perhaps 10, Denkow maintains that new feedstock capacity has been discouraged by low rates of return on investment ("3-5% in recent yean, sometimes almost zero"). In addition, he says, environmental considerations have limited the avail ability of energy and feedstocks. He cites these examples: nuclear plants, which could free hydrocarbons for chemical use, have been held up; the Alaska pipe line has also been delayed; Santa Barbara channel oil has not been available; and sulfur and strip-mining restrictions have cut the availability ofcoal AJI these factors, Denslow notes, will result in reduced availability of plastics and higher prices. "We can't yet assess the effect of higher prices on demand for plastics," he adds, but he says that it will probably lead to a drop in demand. Conference leader John J. Haher, gen eral sales manager for Borg-Wamer Chemicals, emphasized that "the plastics industry most prove to the oil companies that plastics represent a favorable'return on investment to their refineries." To get a share of available crude oil, he added, plastic producers will have to pay much higher prices. May 22. 1974 CHEMICAL WEEK 19 Top of the news Taxesundermine mining Texasgulf last week dramatized the growing concern of chemical process companies about tax measures now being considered in Ontario and elsewhere in Canada. The company said it postponed indefinitely its planned S95-miilion mine expansion at Kidd Creek, Out., citing tax uncertainties. The mine expansion would up copper-silver-lead-zinc ore production to 5 million tons/yeai from 3.6 million. The Ontario proposals pending in the legislature could tax "new" mine produc tion by large firms, such as Texasgulf, at rates as high as 77%, according to mining sources. Texasgulf, however, has said that it believes the new proposals also will contain some offsetting incentives, espe cially regarding processing and explor ation. Meanwhile, federal tax proposals that would increase levies on mineral profits to 50% also are pending but their future may depend hugely on the out come of the new Canadian elections now set for July 8. The Ontario proposals followed disclo sures by both British Columbia . and Manitoba that they want a bigger tax bite. One mining company calculates that the combined effects of the British Co lumbia and federal taxes could be a 104% assessment against its income. Falconbridge Nickel Mines comments that it will be re-evaluating expansion plans in the Sudbury area. Hudson Bay Mining and Smelting President H.A. McKenzie says the company's Stikine copper project in northwestern British Columbia is "in jeopardy." But International Nickel Chairman L. Edward Grubb asserts: "We cannot help but believe that as the long-range impact of the various tax programs becomes clearer, modifications will be made." Chlorine demand shifts After *75, the inorganic chemical indus try will move up behind organics to be come the second-biggest consumer of chlorine. That was the prediction of Al lied Chemical's H.W. Schullze at the Chlorine Institute's bicentennial sym posium in San Francisco last week. Next year, said Schultze, total chlorine demand will reach about 12 million net tons. The breakdown by industry, he added, will be organic chemicals, 8.43 million tons; pulp and paper, 1.42 million tons; inorganic chemicals. 1.15 million tons; water treatment, $27,000 tons; mis cellaneous uses, 471,000 ions. Schultze asserted that the growth of 20 CHEMICAL WEEK May 22. 1974 chlorinated hydrocarbons (especially vi nyl chloride, ehloicmethanm and propy lene chlorohydrin intermediates) will have the biggest impact on the growth of chlorine demand. He cautioned, how ever, that feedstock shortages and envi ronmental problems in manufacture, use and disposal of chlorinated hydrocarbons could curtail that growth. in inorganics, said Schultze, the in crease in titanium dioxide production via the chloride route also should boost chlo rine demand. One industry that Schultze said would reduce its demand for chlorine is pulp and paper. Reason: recent success of the oxygen bleaching technique in paper pro duction could substantially cut back chlo rine use in bleaching. Schultze forecast a growth rate of 6% for chlorine in the U.S. and 7-8% world wide daring the next 10 years. The faster foreign rate, be said, is a result of more rapid gains abroad by organic chemicals, particularly plastics. Schultze stated that demand will not increase as fast for caustic soda, caustic potash, metallic sodium, potassium ni trate, magnesium and other by-products of chlorine manufacture as Tot chlorine. How now, biphenyl cow? About 1,000 Michigan dairy cows were quarantined last week after a 10-month investigation by. federal and state agencies tied a drop in milk production to feed tainted by a fire-retardant chemical. The investigation disclosed that the af fected cows, producing both consumerand industrial-grade milk, were given feed contaminated with brominated biphenyl, a fiameproofing material far roofing and textiles. The chemical was ac cidentally blended with magnesium ox ide, a milk production booster, in special feed mixes prepared by Michigan Farm Bureau Services (Lansing). The probe found diet the fire retardant and magnesium oxide were packaged in similar brown bags by the manufacturer, Michigan Chemical (St. Louis, Mich.). Michigan officials say the tainted milk may have been distributed, but add that there is little health threat to consumers because in the packaging process it was greatly diluted with milk from unaffected herds. Health authorities are uncertain of the effect of brominated biphenyl on hu mans, but sate officials say the level of the chemical in the milk was "considera bly" higher than is permitted under fed eral regulations. GCA'S COLE: Powder coating* sales will jump, but fall short of earlier forecasts. Coated with uncertainty Sales of powder coating materials and application equipment will pick up sig nificantly during the rest of the decade-- but perhaps not as quickly as had been expeeted. That was the forecast of GCA Associates President Gordon E. Cole, Jr., at a powder coatings conference spon sored by New York University in New York last week. Because of (he uncertainties about au tomotive and glass bottle developments. Cole said, GCA's earlier sales forecast of 250 million lbs. of powder coating mate rials in *80 probably will not be reached until '82 or '83. In *74, he predicted, sales of the material will amount to 40 million lbs. Large automatic coating installations will grow in popularity, Cole said, be cause they save on energy and raw mate rials. On the other hand, the use of pow der coating for automobile lops will be "deferred," he said, because manufac turers are busy converting to the produc tion of compact cars, lack the extra capi tal needed to develop new coating equipment for car tops. Cole also stated that' it is nob certain when there will be large-volume powder coating or glass bottles for carbonated beverages. He said much will depend on the actions of soft-drink producers and on consumer protection legislation. Tbe biggest *73 powder coatings mar kets, said Cole, included piping; electri cal, fire and marine equipment; appli ances and wire goods; metal furniture. Epoxy, vinyl and polyester coatings went into these applications. apooo: