Document nkNaZBwdMpx9rw1yodeaBdZ9G

> - JOSEPH E. ZELLER JEROME S. HZCSH.U* CHARLES M. MEEHAN WTT - :aM s. 30RGHESAMI. JR ROBERT R. TIERNaN WATNZ V. SLACK DaVTD L. HILL martin v- azacovxc: JOUR S. SLORED carolz c. Harris MICHAEL ?. MORRONE LaRRT S. SOLOMON JOHN 9- dobzcx CHRISTINE A. MEAGHER SKIRL2T 3. TOJTMOTO PETER '-3* La cars * LAWRENCE P. SAURIM DEBORAH shcr trinxzh C. DOUGLAS JAjtRETT EHWARO l. zorwee ROBERT L. PLESHMER JONATHAN P. LEVINE SHZIlA A. MILLAR *osxo sas over LAW OPTICES Kslles A-ND Hecxm-oj USO 17-* STREET, N. W, SUITE lOOO WASHINGTON, O. C. 20036 May 11, 1981 TELEPHONE 303ASTuoo CABLE ADDRESS "ZELMaN" WRITER'S DIRECT DIAL NUMBER 202/457-1116 Mr. John R. Lawrence The Society of the Plastics Industry, Inc. 355 Lexington Avenue New York, New York 10017 Re: Employee Training Cncer OSEA Vinyl Chloride Standard Dear John: The purpose of this letter is to inform you of the recent completion of a case involving the employee training provisions of the Occupational Safety and Health Administra tion (OSEA) vinyl chloride standard. As you may recall, in September, 1973, an OSEA inspector issued a citation to Hooker Chemical Corporation. The citation noted Hooker's alleged failure to provide training on vinyl chloride for employees who worked in the calendering, compounding and warehouse areas. Hooker contested the citation for its Burlington, New Jersey facility on the basis that employees working in these areas were not required to be trained on the hazards of vinyl chloride. Both Hooker and OSHA's monitoring of vinyl chloride in the calender and compound facilities indi cated concentrations significantly belcw the 0.5 parts per million, (com) action level. tc: C' (1500 Activity: Scope: ANALYSIS OF OSHA's DEVELOPMENT OF STANDARDS FROM 1974 TO THE PRESENT aMMHBsaaBsasBsaBsassssBSsaaessssBEBssaa To gather, review and analyze regulations promulgated by OSHA since the VCM regulation. Primary emphasis will be to determine the evolutionary changes in philosophy concerning the exclusion of materials from the provision of the standards in instances when they contain low levels of regulated substances. Responsibility: Safety, Product Responsibility S tatus: Promulgated regulations have been gathered. Initial analysis demonstrates that for most regulated carcinogenic substances, an exemption level exists which excludes the application of the standard to residual levels below that level. 207C0024 'T T IIT I EXHIBIT VIII BFG TECHNICAL DOCUMENT A PHYSICAL MODEL TOR THE DIFFUSION OF VINYL CHLORIDE MONOMER FROM PVC OHDEB VARIOUS CONDITIONS OF STORAGE by M. M. O'Mara L. B. Crider &. I*. Bowles C. J. Tananek B.F.Goodrich Chemical Company Avon Lake Technical Center P.O. Bo* 122 Avon Lake, Ohio 44012 August 25, 1975 Activity: Scope: Status: OPINIONS- OF INDUSTRY TRADE ASSOCIATION COUNSEL AND BFG LAW DIVISION To ascertain whether legal counsel can recommend or approve.o removal of the OSHA carcinogen label from PVC products and, if so, under what circumstances. We have received a written opinion from Keller and Heckman (Counsel for SPI) that under certain specified conditions, labeling would not be required. It also appears that the BFG Law Division concurs in that opinion. 207C002S Abstract An empirical model, based on large scale laboratory experimental data, has been developed to show the relationship between the amount of residual vinyl chloride monomer (HVCM) in PVC resin and the concentration of atmo spheric vinyl chloride monomer (ATOM) under various conditions of storage. The variables studies in the experimental work leading to the development of this model include temperature, time, ventilation rate, KVCM content of the resin, mass/volume ratio and resin type (varying in porosity). The results obtained from a statistically designed series of 24 exper iments show the interactions of all the variables and permit (1) the effects of the variables to be established and (2) the derivation of a model which permits the AVQi levels to be predicted for any combination of the variables. The developed model has been used to predict the AVCM level in BFG warehouses at Avon Lake, Louisville and Pedrlcktown. We have found excellent agreement between predicted and measured AVCM levels at these three locations- and under a variety of storage conditions. Additionally, the model has been used to show ehae--under- less-chan the most severe storage conditions, the OSHA action level will not be exceeded (500 ppb AVCM) when the KVCM content of the scored resin does not exceed 18 ppm. Even -under, the most extreme storage conditions the OSHA action level is not exceeded -when the KVCM .content .of^.th*'-t^"Srin^i^yr5,Tjpm or -lesa.-v*, no a i -j ' * Activity: Scope: Status: MODEL OF AVCM CONCENTRATION, PREDICTED FROM RVCM LEVELS IN PVC RESIN, IN TRANSPORTATION SBSsrBSSBSBSBeaBBasaBBaBBB^&aBamimaBi^BHBaaB To model the transport of_ PVC resin under conditions which would result in the greatest possible AVCM concentrations. To establish the RVCM concentration which will not result in the exposure of workers to VCM above the action level of 0.5 ppm averaged over an 8-hour workday. A significant amount of monitoring data sire available from our Transportation Department. The data need to be gathered, reviewed, 0 analyzed and supplemented, if necessary. A report needs to be generated, based on the data, to reflect maximum RVCM concentration in resin which would support removal of the OSHA carcinogen label. Primary responsibility for this activity should rest with R&D. 0 u 0028 Table of Contents I. Technical Objectives...................................................................... Page 1 II. Introduction...................................................................... III. Statistically Designed Study....................................................................;----------- 3 17. Experimental ............................................................................................................... 3 (A) Descriptionof Model......................................................................... (B) Analytical Methodology...................................................................... ~5~7I (C) Theoretical Dlffusion of VCH inPhysical Model . . . .' .------- 11 3 7. Diffusion of 7CM Prom PTC Resins inModel i . . .:. .___ L5_ VI. Results and Conclusions . ................................ .......... 18 VII. Acknowledgments............................................... . 26 Till. Bibliography.............................................................................. ; . IX. Appendix................................................................................................. 27 28 C Activity: Scope: Status. MODEL OF AVCM CONCENTRATION, PREDICTED FROM RVCM LEVELS IN PVC RESIN, IN THERMAL PROCESSING To model the thermal processing of PVC resin under conditions which would result in the greatest possible AVCM concentrations. To establish the RVCM concentration which will not result in the exposure of workers to VCM above the action level of 0.5 ppm averaged over an 8-hour workday. Although they will likely be of only marginal value, a significant amount of data are available concerning the monitoring of customer facilities during the period from 1974 to 1976. Furthermore, current BFG monitoring of process operations includes not only the AVCM contribution from the thermal process being monitored, but also background AVCM contributed by our polymerization operations. A report needs to be generated to reflect maximum RVCM concentration in resin which would support removal of the OSHA carcinogen label. List of Figures and Tables Figure 1 Figure 2*5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10* Figure .11Figure 12 Figure 13 Schematic of Experimental System......................................... 6 Photographs of Experimental System....................................8 < 9 Theoretical 7s. Experimental Build-up of VCM In 55-Gallon Drum . . ...................................................... 14 Theoretical 7s. Experimental Build-up of VCM in 55-Gallon Drum after Experimental Modifications.................................................................................16 AVCM 7s. R7CM and Temperature ..... ....................... T 5 Days Aging 20 AVCM 7s. R7CM and Ventilation ............................................. T 5 Days Aging 21 AVCM 7s. K7CM and Warehouse Loading T 5 Days Aging 22 AVCM 7s. K7CM and Ventilation.............................................. T 30 Days Aging 23 AVCM 7s. S7CM and Warehouse Loading................................ T * 30 Day Aging 24 Prediction of AVCM in Warehouse Samples....................... 25 Table I Table 11 Table 111 Table 17 Table V Table VI Modeling Experiments................................................................... Basic Description of Physical Model...................... Gas Chromatograph and Data Handling System used to Monitor AVCM Levels................................................. VCM Calibration of Gas Chromatograph................................ Summary of VCM Diffusion Data.............................................. Experimental (Time/Concentration) Data............................ 4 7 10 12 17 29 ( I I r-rr r T. Technical Objectives Our major objective in this work was to develop, a physical model for the diffusion of vinyl chloride monomer (VCM) from PVC resins and compounds under various conditions of exposure during storage'-aad shipment. The critical variables included in the modeling study are: (1) residence time (2) temperature (3) ventilation rate (4) resin aass/storage volume ratio (5) BVCM content of the resin or compound (6) resin or compound type (varying in porosity) The developed model should be based on a statistically significant number of large scale diffusion experiments so as to show the interaction of all Cheabove variables and to allow the prediction of AVCM levels for any combination of the variables. II. Introduction At temperatures above the glass transition (Tg) point of PVC the solu bility of vinyl chloride monomer (VCM) accurately fallows Henry's law behavior for VCM contents up to 4000 ppm. This observation^) has lead to a rapid, simple gas chromatographic method for the determination of VCM in PVC from an analysis of the vapor phase (head space) over PVC powders in a closed con no -i O tainer. The time required for equilibration between che vapor and PVC phases can be estimated based on recently reported diffusion data^). p; j -T ywj ( r-TT r -3- III. Statistically Designed Experiments Using CCED (a time-share Computer Optimized Experimental Design program), 24 experiments were selected (see Table I) to study the variables listed below in an efficient manner and at the same time to describe their effects and interactions on AVGM as accurately as possible. The variables and'tHe' ranges over which they were studied were: (1) Temperature - 74 - 115*7 (2) Ventilation Bate - 0.5 - 3.0 Turnovers/Hour (3) Loading (PVC Volume/Storage Voltme) - 11 - 34T (4) Resin K7CM - .01 - 123 ppm (5) Basin Type - 102ZP P-5; 1Q3EP 7-76; 103EP; 110X334 (6) Dispersant Type - old technology; new technology (7) Time - 1 - 170 Hours IV. Experimental (A) Description of Model In order to meet the demands of the statistically designed (COED) diffusion study, the experimental phase of this program had to be capable of controlling the following experimental parameters: (1) tempe ra Cure (2) ventilation rate (3) mass/volume ratio n * -A O The basic physical model that was chosen to meet these requirements was one based on sealed metal storage bins (55-gallon drums) housed in an environmental I I -5- chamber where the temperature could be varied and controlled. A schematic of the entire experiment is shown in Figure 1. The schematic is divided into four key areas (A - D) which reflect the methods of ventilation, the sampling system and the analytical methodology. These four areas are described in Table II. Basically, the system was constructed in the following manner. Clean, dry nitrogen (A) enters the environmental chamber (B) through a split manifold. The ten drums were piped into the two manifolds through ten flow regulators. In this way, ventilation rates could be independently set in__ each drum. The exhausted atmosphere from the drums was directed to a sampling system (C) chat provided a split stream; one for vent and one for sampling. The sampling stream was interfaced to a gas sampling value/gas chromatograph/ data handling system (D). Sequential sampling of each of the drums was possible with this system. The environmental chamber is a Conrad Model WD-624 Temperature Humidity Chamber with an internal volume of 938 cubic feet.* Temperature control inside the chamber was 2*C; a maximum exposure temperature of 100*C is possible within the chamber. Photographs of the entire experi mental system are shown in Figures 2-5. (B) Analytical Methodology In order to analyze atmospheric vinyl chloride monomer (AVCM), a flame ionization gas chromatograph was interfaced to the sampling system through a gas sampling valve. To avoid human error in data calculations, a dedicated data handling system was interfaced to the gas chromatograph. Experimental specifics relative to these two systems are contained in Table III. Conrad Inc.; 141 Jefferson Street; Holland, Michigan. CJ O i h* O **t r 1 t 3* q d") L Ob 3^ " _ IjiL/cJf-1 Section A Table 11 Basic Descrintion of Physical Model (Safer to Figure 1) Description inlet nitrogen purge gas; maximum flow ~ 20 liters/minute B environmental chamber containing ten air*tight 55-gallon metal drums C 55-gallon drum sampling system D flame* ionization gas chromatograph/data handling system GENERAL LABELING REQUIREMENTS & EXCEPTIONS Export shipments of PVC resins or compounds will not normally be made if the product contains more than 10 ppm Residual Vinyl Chloride Monomer (RVCM). Packaged Geon resins and compounds meeting the above requirements and prepared for export shipment shall not be labeled. Materials containing higher RVCM levels than stated above can be shipped export only on the approval of the Administrative Director, International Department, each container of these materials, although approved as stated above, must then be labeled with the required OSHA statement. Pallet loads, not requiring the OSHA labels, will be stenciled "For Export" on all four (4) sides of the top and - bottom corrugated trays. If an export overwrap (Package Code 7 and 14) is required, stencil the words "For Export" on all four sides of the overwrap in the upper righthand corner. When individual bags are shipped, stencil the words "For Export" on each bag. Do not label or tag "Export" shipments of Geon latex packaged in drums. Stencil the words "For Export" on the side- wall of the drum near the top. All products marked "For Export" shall be stored in segregated areas of warehouses. Appropriate signs must be placed in these areas indicating that the material has been prepared for export; the signs must also display the OSHA warning label. 7/15/77 -2 n n a ti o Q 'll l.. D Gas Chromatograph with Sampling System C: The following "exception" products should be labeled: 1. All dispersion resins above (1) ppm will be con sidered as in grade 6. Any of th se mat- ials over one (1) ppm shipped domestically from our pla. zs must have the normal Marketing and Distribution approvals for this grade prior to shipment. 2. Hycar Acrylic Latex 2600X189 & 2600X228 should be labeled according to procedure covering Geon latexes. These are the only Hycar latexes that will require the OSHA label. 3. The following products have been classified as Flexible Geon Compounds and should be labeled: 8880-021, 8880-288 and 8878-288. 7/15/77 -4 o;coo:3 - 11 Calibration of Che system was accomplished through Che use of comnercially__ available standards (Precision Gas Sampling Corporation) and dynamic dilution of those standards. A typical calibration (checked periodically) and a regression analysis of that data is sunanarized in Table IV. This analysis' indicates good linearity over the range from 128 - 2000 ppb of VCM in the atmosphere. The slope from the linear regression analysis was used as input to die Integra tor/calculator in order to calculate all data. It is important to note that as the sampling proceeded to a range outside of the calibration range shown in Table 17, new calibrations were carried out to reflect these different ranges. At no time was a calibration extrapolated beyond the exper imentally determined range and used as a basis for analysis. (C) Theoretical Diffusion of VCM in the Physical Model It was necessary to check out the performance of the system in terms of theoretical diffusion. The main reason for doing this was to provide a final and independent check of the model, the sampling system and the- analytical system interacting together. It was further felt that this approach would lead to a definition of any VCM system absorption (or leakage) problems. The ab initio derivation of the mathematical model which describes the build-up of a gas in a dynamic system is described below. if: CQ = concentration of incoming air stream Cg s concentration indrum at any time (t) V = volume of drum M = flow into and out ofdrum t s minutes o GEON LATEX TANK TRUCK All tank trucks containing Geon latexes shall be tagged with a single trip service tag (approximately 3" X 5") (BFG 16590A). These tags shall state: POLYVINYL CHLORIDE CONTAINS VINYL CHLORIDE VINYL CHLORIDE IS A CANCER-SUSPECT AGENT The required statement is in 3/8" high letters. The tags are off-white with black lettering. The OSHA statement shall be printed on both sides of the tag. Tags are supplied with eyelets and wire ties attached. One tag shall be tied to each loading hatch and to the end of each discharge outlet. Requirements for these tags (BFG 16590A) can be reordered by using a Forms Requisition. This requisition should be sent to the attention of the Cleveland Forms Group. 7/15/77 - 6 207C00-0 GEON RESINS AND COMPOUNDS IN BAGS It is necessary to label (or stamp) each bag, prior to filling or shipment (in the case of filled bags), containing designated products. The following label (or stamp) will be used on each bag: POLYVINYL CHLORIDE CONTAINS VINYL CHLORIDE VINYL CHLORIDE IS A CANCER-SUSPECT AGENT The OSHA statement is in 1/4" high letters. All label printing is in BFG rfed on kraft colored pressure sensitive label stock. Any packages shipped individually, as non-unitized loads, must have one of the above specified labels affixed to each individual container. Hamd stamps, containing the required OSHA statement in 1/4" high letters, have been supplied to the PVC producing plants by the Warehousing & Packaging group. Hamd stamping ink will be black. These hand stamps may be used as am alternate to labels. Stamping should be done, in a clear area, on the bottom end of each bag where the product and lot identification is located. Requirements of labels (BFG 16591A) cam be reordered by using a Forms Requisition. This requisition should be sent to the attention of the Cleveland Forms Group. 7/15/77 - ID - 207C002.1 0 H i; 1I a. wQ./^ XW x: > -- < ai 3 * pe4 eX 2 Si >0 0eft--n mu Li Q% era ^m 00 PM* fl'l pC* 0 0 44 s 6 l (4 0 a x LH C o 0 9 c--r >0 0 li n i 2 a o a. u x^ H H 0 a s e4 0 0 as 44 a^4 60 AKc -H 404 -^0ug>7 0 a x u u-l 9 m o C4 CO N o /I <o r% o4 S0 IO oo o N o 57 04 76 04 04 56 m in o% 0 *-4 O >0 1 1 * P . A CO a %lO V VV wt m cn p* ui <* p* <n n tn S' N 0700:113 mo f*% A PN m4 cx ^ ^ O00 n si <n o Oo * CO * <*> a ^7 <*/ <*1 <14 p* fx mNlfl o o pi o oa ao oooo ii <n <h o o* <n a a Oa w O40 Om r^l aOVOfl Sj-' W OiflOe*i irtO<*i * m* tn r* *4 O t/i 1 m i/i </l i/i Ol n et i/i m i/i * n o i/I ^ *tf Mr* <s Nmir<i*i t!o N v* m^^ ^ <Tl (*1 r r- 9i~ 0r 0r^. --i V O ooo <CS0<N8 ^^ o.*---4I oo* <o --cmi a^^ea o a m n <n sr un < a "bo^< -< <r <r ,, 0 w 3 44 0 O N 8 0i O o u 04 tM 0 a a ao o CN <o 0 L3i 0 W CM CO HHM 0 i 0 3> U0 3 44 0 M m vO r^ wH 0i 0 H *** << < 0C&4 \n m*4 0 *U w3 0 W m* --( CN 0 s 0 H GEON RESINS AND COMPOUNDS IN (CT-200) BULK BOXES One label (BFG 16591A) should be placed on each large side panel (2 labels/box) to the.left of the Geon Vinyls logo on specified Geon products. The following label is to be applied to these boxes: POLYVINYL CHLORIDE CONTAINS VINYL CHLORIDE VINYL CHLORIDE IS A CANCER-SUSPECT AGENT The OSHA statement is in 1/4" high letters. All printing is in BFG red on kraft colored, pressure sensitive label stock. Requirements for form BFG 16591A can be reordered by using a Forms Requisition. This requisition should be sent to the attention of the Cleveland Forms Group. 7/15/77 - 12 07G00-1S 19 (5) storage time increases (6) higher porosity resin is used. This latter effect is significant only at early aging times (1 - 24 hours). Using the relationships described in the model, maximum KVCM resin levels can be determined which will assure that AVCM levels will be less chan 500 ppb for a variety of storage conditions. (See Figures 8 - 12 which show the effects of temperature, time, ventilation rate, loading and KVCM on AVCM.) Assuming chat 99% of the storage conditions are better than the adverse conditions [Temperature * 86*?, Ventilation =0.6 turnovers/hour, X volume of VC1 containing material in the warehouse = 30X], the KVCM of PVC resin oust be no greater than 18 oom to assure chat the action level is not exceeded. If compound is scored rather than resin; Che KVCM of the resin going into the compound can safely be 50 ppm. This applies to the following com pounds: flexible, rigid cubes, and rigid powder. If Che 500 ppb AVCM action level oust be met even under Che most adverse storage conditions [Temperature = 105*7, Ventilation =0.6 turnovers/hour, 35X loading of a warehouse volume with VC1 containing macerial], Chen che resin KVCM muse be no higher than 8.5 oom. Resin going into compound can still be 50 ppm. Figure 13 shows how well Che model predicts Che warehouse samples . obtained in April, 1975 at Avon Lake, Louisville and Pedricktown. As Che wl MISCELLANEOUS PACKAGES & SAMPLES We occasionally package small volumes of Geon resins, or compounds in special bags, boxes, fibre drums, etc. These containers frequently contain no Company identification. Each of these packages must be labeled: POLYVINYL CHLORIDE CONTAINS VINYL CHLORIDE VINYL CHLORIDE IS A CANCER-SUSPECT AGENT The required OSHA statement is in 1/4" high letters. This pressure sensitive label will normally be in BFG red (BFG 16591A) on kraft colored label stock; a kraft colored label with BFG blue printing (BFG 16592A) may be used if the prime container Company identification is blue. A label shall be nearly applied to each container. These labels can be reordered by using a Forms Requisition. This requisition should be sent to the attention of the Cleveland Forms Group. PVC resins, compounds and latexes are frequently distributed in sample (less than standard package) quantities. The inside containers must also be marked to comply with OSHA regulations. If containers are large enough, labels as specified above, should be used. For small sample containers attach a tag (BFG 16590A) as specified under the "Geon Latex Tank Trucks," 7/15/77 - 14 - 0;v;ooi3 21 - r |"j Figure 9. n AVCM VS.RVCM ond VENTILATION I I ( ITT - 23 - Figure II. AVCM vs. RVCM and VENTILATION TIME*30 OAYS AGING 1000 PVC RESIN/WAREHOUSE VOL.* 30% \ \ OSH A TVRNOVERS/HR. AVCM(ppb) 100 u 1.5 2.5 n I ( ( I ( TT T BFG TECHNICAL DOCUMENT M.J.AHMED-H.S.HALLER .. I Q. 1 $ i t |> H * LOCATION ALTC LOC A TlON CLEVELAND Srat isi. Lc s arui C.ouipul cr o* ' * 4/12/83 PllO <tr NO 1 Ul. Min'" *' ' ' > GPO'I*' T'l 1 * ` `J ' << T i , .1 iO f( I ,I INTRODUCTION; Since vinyl chloride monomer (or VCM) was determined a carcinogen BFGoodrich has successfully reduced the residual vinyl chloride monomer (or RVCM) concent of its resins and compounds. Despice this dramatic decrease in RVCM, BFGoodrich has continued to put carcinogen labels on certain PVC products. However, better technical criteria need to be established for carcinogen labeling of PVC compounds and resins. To dev.elop such criteria requires the determination of a relationship between RVCM in the PVC and the ambient VCM (or AVCM) during warehousing, storage aiid thermal processing of PVC. This report presents the data and relationship between resin RVCM and AVCM during transportation of PVC. OBJECTIVES; 1. To collect relevant existing data on the transportation of PVC, 2. To simulate transportation of PVC under conditions which yield maximum AVCM concentrations, and, hence, 3. Establish RVCM content of resins which yield AVCM concentration of 4.5 ppm averaged over an 8-hour period. CONCLUSION: Using the herein derived minimum air turn-over race of 3 per hour it can be seen from-Fljg-v 1-Chat, providing resin RVCM is 4 10 ppm the AVCM action level concentration of. .5 ppm "w"ilt*'not be exceeded. J 'T 1 i 31:8302 REFERENCE FILE L,. Z-2. or Z-3 tor the material in Table Z-l- volved. 'll) To Illustrate the formula pre- mx./M* * ! ibed In subdivision (l) of this subpara- j C iph. note that isoamyl acetate has an 8-hour time weighted average limit of : i AAccerttta?ldehvde.............................................. Kcrtie anhydride....................... . 100 p.p.m. (table Z-l). Assume that an | A e-tnr.e.. .............................. i ployee is subject to the following Acetonitrile............................... Acrtylwflt* dtchloride. sec l. 2* i < aosure: Otchlocoethylene................... Two hour* exposure at ISO p.p-m. AArcerotvlteeinn.e..te..tr,ahro.m..i.d.e................... 200 1.00410003 l ai Two hours exposure at 75 p.p.m. * 'our hours exposure at SO p.p.m. 1 bsUtuting this information In the IwtTQUla, we have 2X 180+2x73+4X50 I =81.23 p.pjn. AAcldryhlnam--iodketi-iS. ki.n................................. AIM aie*itoi-$kin.................. Allyl chlnrnr. *........................ C Ailylflycidvi ether aC)AUytpropy( disulfide 1-Amiiioechaiioi. ire Ethanol* 2-Ammiinnoep..y.r.t..d..i.n..e........................................................ ............. toi o. 5 50 Ammonium sultanate< Am- ijince 81.25 p.pon. is less than 100 p.pon., the 8-hour time weighted average limit, mate)........................................................... ii-Amyl acetate............................. lJ0 sec-Amyl acetate.......................... 1-5 ! exposure is acceptable. , (2) li) In case of a mixture of air con1 < ainants an employer shall compute the Aniline-Skin............................... 5 Amsidtne o. p-ijmer--Skin................... Antimony and compounds ras Sbi......................................................... equivalent exposure as follows: ANTV i alpha naphthyl thiourea).................................... -........ ! c, c, c. *-=---1----h . . . -- < f*l * l- ` Worn: . la the squlvaleat sxpoaurs for the mrtura. 1 3 Is the aoaesntntioa of a particular coa- i mnant. (Orfamc) Arsenic compounds(ss As).. Arsine............................................ * Axinpnao-met hyl--Skm.............................. Barium (soluble compounds)........... ......... Benxonulnone, so* Qumone.................... Tlenxovt oerotWe... .................................. Bensyi cftlonrte............. .............. 1 Biphenyl, see Diphenyl............................... Boron oxide.................................................. 1. C Boron uifiuonde...................... t L is ths sxposurs Umlt for that contami Bromine........................................ 0.1 so22n50 2. 400 TO 14 0.25 0. 3 5Q.'.S 41352 35 525 S50 19 0.5 as 0.3 as a0.s2 ...a..s.. 5 tS 3 ar nant, from table Z-l. Z-l. or Z-3. Bromofnrm--Skin........................ ne value of E. shall not exceed unity Butadiene (t. 3-Outadtene)........ Butanethiol. ate Bum rner- ). i fit) To scribed In illustrate the formula subdivision (l) of this presub- \ 1 2-Butonene................................. 2-natocv .tnsnet (Batrl Cet- laaolT,*--Skin........................... naragraph. consider the following Baivt acetate (ikbatyl acetau). posures: MO-Bom OCKOU................ . 0.5 1.000 200 50 150 90S 5 2.200 590 240 no 950 ton-Satyl aeetala.............. 200 950 Material Actual con* can(ration of 8-hour irpnwre 5-hour time vetfhtod aeerwe exposure Umlt Bacvl alcohol................................ sae-Botrl alcnhot......................... tert-Butyi aicehol........................ C BatTlamino--Skin.................. C tart-Bum enromautaa 100 150 100 5 . Aaattne Table Z-l)____ soop.pjn.... 1,000 O-O-Ui. J-BounooeiTable Z.t). 45 p.pjn___ . 200 p.p.m. Tohseoe < T.'ihle Z.2i........ to pJOB___ . 200 p.p4n. n-Butvl ftycMyl achar (BOE),, Bocyt marcaocao ------------ -------- f-tart-BatTlioluana..................... latemm arsenate 50 10 10 300 450 30IS0 ai 270 35 00 ohstltuting in the formula. we have: 900 48 40 Zm=----------1-------- 1------- 1.000 200 200 X-m0.500-l-0.22S-f-0.200 E.=0.923 Since E. is less than unity (1), the expo*ve combination Is within acceptable nits. (e> To achieve compliance with para graph (a) through (d) of this section, administrative or engineering controls .ust first be determined and lmpleented whenever feasible. When such wootrols are not feasible to achieve full compliance, protective equipment or any ~*.her protective measures shall be used i keep the exposure of employees to air intamlnants within the limits pre scribed In this section. Any equipment and/or technical measures used for this urpose must be approved for each parcular use by a competent industrial -ygienist or other technically qualified person. Whenever respirators are used. *heir use shall comply with 1910.134. Caletum oxide............................................. Cimpnnr 1 - ***** Car*aryt (Berm <$)_............................... Carton Mar*................................... ;----- Carbon dtoitda....... .. >.000 Carbon monniid.--------------------- >0 Chloriono-- Skin....................................... . Ciilonaalad eampnana--Skin................. Cbloftnaud dipbanyl Olid*-----C Chlonne enftaonde................. C CMoroacecaidehyde........... .. l ai ai i -ChloroacetAOiMAone (phenarylchlortda)............ . 0.05 CttioroPensene (moftocfilorobentenet.................... .............. :s a*C hloroOenxyttdeita malonomtnle fOC9M)....... aos ChloroOmmomethone.......... 200 3-Chtorn-i.5-butadiene, see CMnrnorene.............................. Chlnendinnenvl .'4*2 percent Ohlonnek--Skin ..................... ChtanvliOhenyi (54 percent Chlorine)--5kin....................... i-ChUirn,2.3-oniyoroP*ne. see Emcniornydrin......................... S-Chloroetnanol. see Ethylene chlornhydrtn............................. Chloroethyiene. see Vinyl cfiUtnde ........................... . C CJiroroforra (tnehloro- methane)............................... I -CMnro*1 .nt troorooane.............. rhioroiMcnn........................ . 20 0.1 CMoroprene <2<ftloro*l.3* Uitadiene)--Skin..................... h 240 100 17 Table Z-l-Continued p.p.m.* mt.;Ms * "hromium. sol. chromic, enromnm salts as Cr.............................. Metal anrt in*ni. salts.................................... a5 1 -oai tar pitch rouuies (hen- tene soluble fraction* amnrs- cene. HP. phenanthrene. acridine, chrysene, pyrene...................... a2 ?onuti, metal (uine ami dust.............. ......... Copper fume...................... .............................. al Xl Dusts ami Mists................................ -.......... rounn dust tiwj................................ . ! I* 3raCvJ) herbicide ............................................. rresol (ail isomers) --3kin.......... 5 ^roionaldehyde........................... 2 Cumene--Skin.......................... SO Cyanide fas CN)--Skin............. ................. ^ycMteuine............................... 300 L5 22 6 245 5 U 050 "ydofieianol................................ 50 200 L'ynoftetAmHie............................. 50 290 "yeiohetme ^vctnfM-nuulieuc .......... 300 1.915 T5 2du *. 4-D... 10 DOT-Skin............ .......................................... DDVP-Skin....................................................... OeeahonMie--,kln....................... a 05 I a5 iVmetoittg Skin............................................. ai Oinoetoiie sknltoi (4-hydroxy4>methyi-2-pentanonr)............. 50 240 1,2-dtanmoetnaiw. see Ethylenediamin*.................................................... ............ Dtasomethane.............................. Diborane. 0.2 0.1 a4 XI Oibutyi pftpephue...................... i 5 I XlHitylphtliaiate............................................. S C >DtchlcroPensenc................... 50 300 p-D4chlorot>encnc....................... *5 450 Dlchlorodlfluoromethane........... 1.000 i.950 l^DIchioneO^-diniethyl hydantotn....................................................... X2 1.1-Dtehioroethane. - -.............. 100 too 1.2-Diehloroethylene................... 200 790 C Diehloroethyi ether--Skin. .. 15 90 Dletiicromethane. see Dichtoromonohuoromethfine... i.orw C l.M>4ctiloro-!-mtroethiae.... 10 l^-Dkhloropeopane. sea Prooyleneaichlortde.................. Dichlaroutrafluoroethaoe.......... uooo Dleidiin--Sktn....................... Dietnytanine..... ........................ Diethytamno ethanol--Skin... Dlethylether. see Ethyl ether.... Diftuerodiltroniometnane........... C Dlclycidyl ether iDOE)........ DihydroxyPentetM. see 23 10 100 X5 4.200 00 7.000 X 23 73 30 DHtoOucy! ketone........................ DUsopropylamine--Skin........... DlmetnoeymethaAe. see Mefhvhd ............... . ............... DbnMliyl Kefunlh#--Skin.----Dlmethylamine........... ............... Dimethyiomuodensene. see 50 5 10 10 290 20 33 U DimethytonUlneiN-dimethyl- A ntUnei--Skin................... . s Dimethyl l,,i-dlbfomoX2-dichiafoethyi phosphate. D1mtnyUannamMa--Skin.. 2.6-Dtmetliylhcotanone. see Diuooutyt ketone...................... 1.1-Dimethylhyrtraxwe--Skin... Dimethylpnihalate....................... Dimethytsultate-- Skin............... Dmitrooetuene (all isomers)-- Skin............................................. Dtmtro<resol--5k(n^............... Dimtrotoluene--Skin.................... Diotane tDiethylene dioxide)-- Skin.......................... ................ Dioftenrl...................................... Dipnenytmethane diisocyanate tee Methylene hisohenyt aoeyanate (MOD. Dipropylene clycoi methyl *uer-- Skin............................... Di-see. octyl phthaiate (Di-2* ethvlhexviphtnaioui................ 10 X5 100 X2 100 F.meh lortiydnn--Skin................ 5 l^ F.ooiypropane. see PTooyteneoxtde................................... 2.3- F.poxv-1propanol. see GlyoOol......... .............................. See footnotes at tad of tsOle. 3 30 l 5 5 ail-42 300 1 900 5 X1 19 as :07C0(k.3 Occupational Sotety A Health Reoorter [Sec. 1910.1000, Table 2-11 18 Simulation ol 4/7/83 ' Dago 7 AVCM Concent ral ion During Transportation of 1'VC 2. Analysis of Model Variables (Cont'd) 2.3 Truck Loading (L) Equation (T) shows that, as might be expected, increased truck loading produces higher concentrations of AVCM. In discussions with transporta tion experts the assumption was made that 80" loading is the maximum that r.mld be expected. In this study, therefore, the truck loading was set at 80%. 2.4 Ventilation rate (V) Ventilation rate as measured by air turn-over/hour cannot be readily ascertained for a truck since it is dependent on numerous factors e.g. truck's material of construction, designof truck, speed at which truck is traveling,and climatic conditions. However, an effective air turn-over rate can be calculated from Equation if actual AVCM data measured inside the truck were available. Kruszynski(2,3) and Smith^^ have reported the AVCM concentrations inside the nose of a trailer immediately upon opening the doors, as well as immediately after a trailer has been unloaded. As can be seen from Table 1 AVCM concentrations did not exceed the action level limit for those cases where the samples were taken upon opening the doors. However, data where bag was broken and resin exposed did exceed the limit. Since this is the highest AVCM concentration reported, it was used in calculating the effective air turn-over rate. As shown in Appendix 1 the minimum effective air turn-over rate is approximately 6/hour. However, to eo ore greater safety margin simulations were carried out using 3 air turnovers/houi. 3. Discussion of Results With the variables fixed at levels given in Section 2 , Equation i^l) can be solved to predict the resin residual VCM (RVCM) which would produce AVCM concentration below the action level limit of .5 ppm. However, one of the var iables, the transportation time, cannot be ascribed a definitive value, and a range of values (4-72 hours) were assumed. Fig. 1 shows the relationship between the resin RVCM and the AVCM concentration inside a truck at 4, 24 and 72 hours. As can be seen from Fig. 1 Che AVCM concentrations do not exceed the action Limit of .5 ppm provided the resin RVCM content is below 10 ppm. It should be emphasized that Fig. 1 has been predicted using conditions which deliberately maximize the AVCM concentrations inside a trailer transporting PVC resins. c 0) r*l l* u I I I 'I'T T S limitation of AVCM Concentrations Pur ins Transportation of PVC 477/83 Pap.e i FIG. 1: RELATIONSHIP BETWEEN RESIN RVCM AND THE AVCM CONCENTRATIONS INSIDE A TRUCK AS PREDICTED BY O'-MARA ET AL MODEL(1). u I I ! it r Simulation of AVCM Coneencrat ions During Transportation of PVC 4/7/83 Page 7 References (1) O'Mara, M. M. et al, Journal of Vinyl Tech. Vol. 1, 3, page 168 (1979). (2) Krusaynski, R. J., BFG IOC, Dept. 5401, 7/8/75. (3) Ibid, BFG Customer Service Report, Proj. No. 3689, 12/20/74. (4) Smith, T. H., BFG Customer Service Report, 1/3/75. (5) Ahmed, M. J., Haller, H. S., BFG Technical Document, 3/31/83. MJA:HSH:vmt Distribution; P. Dunnigan R. D. Hardesty R. M. Kreager (first page only) R. J. Kruczynski L. P. Tenney CTF M. J. Ahmed H. S. Haller ( I ( BFG TECHNICAL DOCUMENT SMtlKle. and Computer THE BF GOODRICH COMPANY CHEMICAL GROUP Applications REPORT A ,, r ., c M J S. .AHMED-H. .HALLER LOCATION ALTC DATE 3/31/83 LOG 800 F * E E c l HhOt'ESltO H > LOC A T ION PROJEC T NO. CBCur PiUt ACC NO CLEVELAND MODELING OF VCM CONCENTRATIONS DURING THERMAL PROCESSING OF PVC INTRODUCTION: Since vinyl chloride monomer (or VCM) was determined a carcinogen BFGoodrich has successfully reduced the residual vinyl chloride monomer (or RVCM) content of its resins and compounds. Despite this dramatic decrease in RVCM , BFGoodrich has continued to put carcinogen labels on certain PVC products. However, better technical criteria need to be established for carcinogen labeling of PVC compounds and resins. To develop such criteria requires the determination of a relationship between RVCM in the PVC and the ambient VCM (or AVCM) during warehousing, storage and thermal processing of PVC. This report presents the data and relationship between resin RVCM and AVCM during a thermal processing opera tion of PVC. OBJECTIVES: 1. To collect relevant existing data on the thermal processing of PVC, 2. To model a thermal processing operation under conditions which yield maximum AVCM concentrations, and, hence, 3. Establish RVCM content of resins which yield AVCM concentration of averaged over an 8-hour period. .5 ppm CONCLUSION: Using the herein derived minimum air turn-over rate of 5 per hour,it can be seen from Fig.^-^ that providing. resin RVCM is < 32 ppm, th& AVCM action- Levei. concen-* tracion-of:. .3.ppm. wJJJL&ot J>e exceeded. r. PRINTED G3 \ '1 T T 1 Modeling of VCM Concentration During Thermal Processing of PVC 3/31/83 Page 3 1. MODEL DEVELOPMENT (Cont'd) However, the density of VCM changes with the inside temp. T. Using the ideal gas law the VCM density is given by PVCM * TM/RT, ---------- where P is the pressure O 1 Atm), R is the gas constant (* .7302), T is R, M is the molecular weight of VCM ( = 62.5). Substituting equations 4,5 into gives the volume of VCM inside a building, i.e. VT = 8 (RVCM X 10_6)fWpvc X RT/M ---------- Let Va be the volume of the air inside the building. (* volume of building V) If the number of air tum-overs inside the building is N^/hour then the total volume of air over an 8 hour period is given by VaT - 8VNt Substituting (^ into^) L^>AVCM On ppm basis this becomes. -------- 8<RVCH X 10-6) fWpvc * RT 8NtV 62.5 AVCM (RvCMHwPVC)fRT/(NTV 62.5). ---------- To solve equation requires quantification of each of the variables. This is'discussed in the next section. 2. ANALYSIS OF MODEL VARIABLES 2.1 PVC Processing Rate (Wp^g) Li ! i Since PVC processing rate is related to the volume of building (Va) the two i * variables have to be quantified with respect to one another. In accordance , with the philosophy of ensuring highest levels of VCM in the air and, hence, O greater safety margin the approach taken in this study was to maximize PVC rate and minimize bu-ilding volume. After consulting with thermal processing experts (J. Summers and G. Small) the building dimensions were assumed to be 25X40X100 ft. and PVC processing rate of 2000 ///Hr. This is equivalent to con tinuous running of almost 3 extruders over an 8 hour period in a small building. 2.2 Ambient Temperature Inspection of Equation shows that to maximize AVCM concentrations inside the building the ambient temperature needs to be maximized. Although the am bient temperature will depnd on the geographical location, type of building etc., it is safe to assume that temperature will have to be tolerable. Allowing for each of these factors 90F was selected as rh am H-ion*- oil* -- - ------