Document ZnzG3DyooXQqXzbdRJkkYxbVL

June 30, 19 9 3 TO : FROM PLANT MANAGERS HERM WALTEMATE CLEVELAND SUB PVC/VCM LABELING By now you should have implemented the labeling of PVC Resin with the OSHA Cancer Warning statement. Please advise me when you have started the labeling as instructed. Attached, for your information, is a copy of the letter sent to our customers advising them of this change. For your information the EHS Bulletin recently sent to you contains an error in that PVC Resin exports are not included with this change in labeling at this time. PVC Resin shipped to the U.S. and its territories will contain the OSHA Cancer Warning statement. PVC resin exported outside of the U.S. will be labeled according to the requirements of the country receiving the material and if the RVCM exceeds 8.5 ppm, the OSHA Cancer Warning label should be applied. PVCLABE.HW/JS Attachment: cc: W. Patient and Senior Staff R. Rosenau W. Ban L. Larson R. Grahek M. Hross D. Marshall R. Wronko H. Walte'mate 2szseooi BFG40091 %.jrg tf C4A64/24 /A/C. Dear Customer: Geon Canada Inc. Niagara Chemical Plant 6300 Iborold Town Une Rd.. P.O. Bo* 1026. Nlogara FaRi. Ontario L2E6V9 (316) 357-3131 June 25, 1993 Approximately ten years ago, BFG CANADA, INC. (the predecessor of GEON CANADA, INC.) discontinued the use of cancer warning labels on shipments of its vinyl resins. Prior to that time, resin shipments had been labelled to recognize that vinyl resins are produced from vinyl chloride monomer (VCM), which is a cancer suspect agent. Our early 1980's review of the health risks associated with our resins revealed that prime GEON resins are produced with such low levels of unreacted VCM that they will not produce a work place exposure exceeding the OSHA "action level" for VCM, and that they pose no health risk to customer personnel, our own personnel, or anyone else coming in contact with them. Prime GEON resins are shipped from our facilities containing only trace amounts of unreacted VCM (generally such traces amount to less than 3 parts per million, but on rare occasions can be as high as 8.5 ppm). Although GEON believes that such levels of unreacted monomer pose no health risks, those coming in contact with our resins may wish to know that a cancer suspect agent was used in .their production. We also wish to accommodate an emerging industry approach to labelling for such cancer suspect raw materials. Therefore, after a recent review, GEON CANADA, INC. decided to reinstitute a policy of labelling its resins. This labelling will take the form of tags placed on the top hatches of bulk railcars, the discharge valves of bulk trucks, and on air pallets. It will also be printed on bags used for GEON resin shipments. A copy of the label which will be used is attached for your review. IT SHOULD BE NOTED THAT THE REINSTITUTION OF LABELLING BY GEON CANADA, INC. DOES NOT REPRESENT ANY CHANGE IN THE WAY IN WHICH GEON RESINS ARE PRODUCED, OR THE RESIDUAL VCM SPECIFICATIONS TO WHICH THEY ARE PRODUCED. NOR DOES IT REPRESENT ANY CHANGE IN THE HEALTH RISKS ASSOCIATED WITH THE USE OF GEON RESINS. PLEASE NOTE THAT THE HMIS PORTION OF THE LABEL SHOWS THE HEALTH RISK ASSOCIATED WITH THESE PRODUCTS TO BE "INSIGNIFICANT," The use of these labels on bulk railcars, bulk trucks and air pallets will begin on July 1, 1993. The use of the labels on bags will be phased in over the balance of 1993. cy.iQiit-/ Servian * Innovation BFG40092 You may already consume materials in your operation which carry similar warning labels, and you and your work "force may be used to dealing with such warnings. However, we wanted you to be aware of this change, in the event that you or your personnel have not been used to receiving products carrying such labels. We at GEON are willing to answer any questions you may have with regard to this change in procedure, or work with you in answering questions posed by your employees. Please feel free to contact your GEON Account Manager should you require such assistance. As always, thank you for your business. Sincerely R. M. Rosenau Sales Director - Resins Attachment BFG40093 25286003 25286(504 KOOPQjq ) i Formats 3.0* x 4.25' PMS Black (Back) Formats 3.0" x 4.25" PMS Black (Front) PLANT MANAGERS DISTRIBUTION L. Maresca Avon Lake T. C. Patterson Niagara Falls, Canada C. Lee Avon Lake W. C. Fultz Pedricktown, New Jersey W. C. O'Brien Calvert City, Kentucky M. J. Breckenridge Plaquemine, Louisiana D. Laubacher Deer Park, Texas M. Guyer Henry, Illinois B. McWhirter LaPorte, Texas P. W. Shore Long Beach, California W. McDonald Scotford, Canada J. Canella Terre Haute, Indiana Mr. David Baker Altona (Australia) Mr. J. 0. Tyndall Mentone (Australia) H. Kletke Louisville, Kentucky BFG40095 PLATMGRS.DIS/JS 06-15-93 (WORDPERFECT-15) Cl <2 O o Cl FOR A GEON GOMRANY TECHNICAL DOCUMENT INTERNAL GEON USE ONLY IN AMBIENT VINYL CHLORIDE EXPOSURES EROM RESIDUAL VINYL CHLORIDE IN RVC RESINS AND COMROUNDS by Sara Butler Chuck Daniels Walt Edwards Jim Griffin Mike Mele Alan Olson Kirsten Reading Jim Summers June 3, 1993 DISTRIBUTION Lou Maresca Drucilla Knutsen Ashok Shah Mike Marshall Woody Ban Authors ALTC CTF-2 C/1 N GO con o BFG40096 C/I 05 05 O o TABLE OF CONTENTS AMBIENT VINYL CHLORIDE EXPOSURES PVC RESINS AND COMPOUNDS ABSTRACT FROM RESIDUAL VINYL CHLORIDE IN gaga 1 INTRODUCTION 9 EXPERIMENTAL 9 POWDER MIXING AND EXTRUSION IN THE ALTC LAB. 9 PLASTISOL MIXING AND FUSION IN THE ALTC LAB. 10 COMMERCIAL COMPOUNDING ON ALGC Z-LINE. 10 BULK RAIL MONITORING . . 11 COMMERCIAL WAREHOUSE MONITORING 11 ANALYTICAL METHODS 11 DISCUSSION 12 CONTROL OF AVCM EXPOSURE 12 MODELS FOR AVCM EXPOSURE 12 POWDER MIXING PROCESS EXTRUSION PROCESS 13 14 PLASTISOL FUSION IN THE LAB. 14 BULK CONTAINER OPENING AND SHORT TERM EXPOSURE 15 COMMERCIAL COMPOUNDING COMMERCIAL WAREHOUSE 16 19 MATERIAL BALANCE 19 MANUFACTURING CONCERNS 20 ANALYTICAL RELIABILITY 26 FALSE READINGS 27 LABELING PRACTICES IN THE U.S. 28 REFERENCES APPENDIX 29 30 C/1 05 05 o o ABSTRACT Previously, 8.5 ppm (weight basis) residual vinyl chloride (RVCM) in resins and compounds was set as the upper limit to assure that workers not contact more than 0.5 ppm 8 hour time weighted average (volume basis) ambient vinyl chloride (AVCM) in breathing air. The 8.5 ppm RVCM was based on models which assumed instant dispersion of VCM from the source into the whole room. One model assumed a material balance on measured RVCM would account for the VCM in the air. It is the conclusion of this study that the assumptions were in error. AVCM levels are not assured by RVCM alone, but are the joint responsibility of the supplier to control RVCM and the user to adequately ventilate. The previous practice of controlling RVCM to <8.5 ppm with a ventilation rate of 5 air turn-overs per hour, does result in an AVCM level <0.5 ppm. AVCM concentrations are higher in plumes than in the surrounding air. Thus the VCM is not uniformly distributed in the room. Material balances showed that AVCM levels should have been significantly higher than were detected in the sealed lab with controlled ventilation. More than 90% of the RVCM that was lost from the resin during powder compounding had disappeared. One explanation is that the VCM reacted with residual catalyst in the resin, or stabilizers, or air, or another ingredients in the compound, to form a chemical not detected as VCM in the compound or the air. Our new data indicate <0.5 AVCM is adequately met with existing commercial resins and compounds for processes including lab processing, commercial compounding, commercial processing, and warehousing. One exception was a warehouse situation where resins are normally stored at >8.5 ppm RVCM and action is required to reduce AVCM. Laboratory powder mixing and extrusion in a room where the air turn-over was turned down to l/hr, showed AVCM at 0.01 ppm. Monitoring the oven lab during the fusion of plastisols gave widely varying AVCM results. Most Reiszner badge results were at or below the detectable limit. However, duplicate badge samples on the lab operator were 0.24 ppm AVCM, higher than the material balance predicted values, indicating the operator had been in a plume. The AVCM level above a rail-car manway was tested just after opening and found to be non-detectable. The AVCM level inside the (1) BFG40098 25288003 car did exceed the 15 minute exposure ceiling level of 5 ppm. This indicates a need to warn about entering closed shipping containers before adequate ventilation. Commercial compounding process monitoring showed 38 samples <0.5 AVCM and 1 sample >0.5 AVCM. The high reading, 1.08 ppm AVCM, was on a packager operating a fork-lift and is suspected to be high because of hydrocarbon interference. Commercial warehouses in Henry, and ALGC showed <0.5 ppm AVCM, however Pedricktown, which ages dispersion resins containing above 8.5 ppm RVCM, showed readings >0.5 ppm AVCM, a situation being corrected. Air monitored by pumped charcoal tubes (OSHA acceptable) and by Reiszner badges was analyzed by headspace-gas chromatography. Residual vinyl chloride in resin, compound, and product was measured by direct injection- or headspace-gas chromatography. These methods have been shown to be accurate and precise under laboratory conditions. False negative readings for both air and PVC measurements would be unlikely. However, false positives could occur since other chemicals could elute with vinyl chloride in the gas chromatography analyses. Most competitors label their resins with a VCM warning. A summary of the experimental results is listed in the following tables. at <25 <35 (2) BFG40099 LABORATORY OPERATIONS S U D 3S 2: N BFG40100 (3) COMMERCIAL WAREHOUSES 90S623Z BFG40101 (4) COMMERCIAL BULK S H IP P IN G BFG40102 (5) 25288007 COMMERCIAL COMPOUNDING OPERATION BF0401o3 (6) 25288008 COMMERCIAL COMPOUNDING OPERATION O P E R A T IO N PVC com pounding: s to c k ctfange cleaner, c o n tro l room, s u p e rv is o r, rover, packager r i g i d PVC com pounding, powder m ixer, packager, o p e ra to r r i g i d PVC co m p o u n d in g , o p e ra to r AVCM , ppm 10 sam ples <0.05 to 0.28 3 samples 0.02 to 0.05 2 samples <0.01 to 0.14 0.16 0.03 0.38 S >a os a < B Z03 Cl] 55 2H OB OS H 1--i Q 2O wa -0 2c1 HM M TJ H C >a 3o h a se 00 J o BW w << BQ rn O' 2 O M BW C tt 3 5o a 43 CO a o B ftj M CL, z Xo B 32 c0 5. O z HQ JO a, x <w cn 2 u coM 0O)' M0) T<3d a: jo O' CM c o cO' w o c 3 g CUM S r-t Oo E-1 >.(4 M c0) XO X ft. ro O' \ H oo s c o cO' H XI c 3 0 cum o o -me ><4 c0U) ox X ft. VO m co CN c 0 cO' Vc 3 g CUM 0 0 Ms >cS cu r 0) o a ft. (4 X u c 0 C OI 2C O M*o .* c 03 MO L, CLh O -< Q) O *H a. o e CO m O' O' O' \ M rH H 00 00 03 .. - .; PVC com pounding, o p e ra to r, weighman, powder m ixer 10 sam ples <0.01 to 0.02 BFG40104 (7) 05 O OD COMMERCIAL VINYL PROCESSING SAMPLING METHOD NIOSH TYPE MONITOR personal DURATION hours o.s TEST DATE 1975 ENVIRONMENTAL CONDITIONS trailer just opened. --2 1975 1 to 4 1975 " " " " ' r 1 to 3 1975 " 1.5 1975 " 1.2 1975 just opening trailer. 1 to 2 1975 - - 0.25 '3 1975 1975 just opened trailer. 0.25 1 165 1975 1975 just opened railcar. - 1975 - "3 "1 1975 1975 " 0.5 to 4 1975 ' RVCM ppm <1.0 <1.0 <1.0 1.0 <1.0 35 <1.0 <1.0 <1.0 0.55 0.55 0.05 <1.0 <1.0 <1.0 OPERATION unloading flexible pellet compound from trailer flexible profile extrusion, operator, packager rigid cellular powder extrusion, operator, material handler, mixer flexible pellet extrusion, operator, lift driver flexible powder extrusion, mixer operator opening 6 samplinq truck . flexible powder extrusion, powder mixer, operator. rigid pellets, unloading rigid pallet extrusion, lift operator, operator opening resin railcar rigid powder extrusion, mixer operator rigid pellet extrusion, lift operator, operator flexible pellet extrusion, operator flexible pellet extrusion, operator, material handler flexible pellet extrusion, lift operator, operator AVCM, Ppm 2 samples <0.01 4 samples <0.01 3 samples <0.01 4 samples <0.01 2 samples <0.01 0.02 4 samples <0.02 to 0.40 <0.01 3 samples <0.01 0.46 2 samples <0.01 to 0.23 2 samples <0.01 2 samples <0.03 to <0.04 4 samples 0.06 to 0.31 3 samples 0.04 to 0.07 anm zsz BpG40l05 (8) INTRODUCTION A statistical model for ambient vinyl chloride monomer (AVCM) in warehouse situations correlates this AVCM to residual vinyl chloride monomer (RVCM) content of the stored suspension PVC resins <1*2). This model indicates that an RVCM less than 8.5 ppm is sufficient to assure an AVCM of less than 0.5 ppm (the OSHA action level for vinyl chloride). Critical assumptions are that the AVCM is uniformly and instantly distributed throughout the whole building and that the air turn-over is 0.6 times per hour. A physical model for AVCM in PVC processing buildings calculates that at an RVCM less than 15 ppm, the AVCM would be less than 0.5 ppm (S>. This model assumes that the AVCM is uniformly and instantly distributed throughout the whole building and calculates that the air turn-over is at least five times per hour. It also assumes all VCM lost from the resin goes to the room air. Neither of the above papers address dispersion resin storage nor processing. Investigation of the variations in AVCM within a building or room shows that VCM is highly variable and is concentrated in plumes coming from the point source <4>. Measurements of AVCM in various commercial processes were made in the mid-1970s, however, few measurements were made where both RVCM and AVCM were known. When RVCM was below 1 ppm, personal monitored AVCM was always below 0.5 ppm(S>. EXPERIMENTAL POWDER MIXING AND EXTRUSION IN THE ALTC LAB. Since the initial experiments run with plant resins yielded no detectable AVCM, a second trial was run with pilot plant produced resin with very high levels of RVCM. Suspension - Pilot plant resins typically have high porosities, which means that they strip easily and end up with low RVCM levels. Geon 110X334 is a low I.V., low porosity resin. The pilot plant recipe and stripping conditions weres adjusted to produce a resin with high RVCM. Results are listed below. fO CA LQX 193-637-088 193-637-090 193-637-092 193-637-128 Average RVCM fPPBD 163 30 7 208 103 weight 30 28 27 27 flbl o (9) BFG40106 A 6021 ft' room was ventilated at 1.0 air turn-over/hr. The exhaust was in the center of the room and the powder mixing in the corner. Geon 110X334 resin, specially made at 103 ppm RVCM and well above the normal production level, was Henshel mixed in a generic rigid PVC compound that contained 85% resin. The compound was mixed to 160F, the lid opened and filler added, then continued mixing to 180F. This compound was dropped to a cooler, cooled to 130F, then dropped to a drum. The rate was 55 lbs/hr. Monitoring was done with both Reiszner Badges and carbon tube and pumps. Placement of monitoring was in several positions in order to try to find the plumes. An 8928 ft3 room was ventilated at 1.0 air turn-over/hr. The exhaust was in the center of the room and the Brabender extrusion in the corner. The above generic compound at 45 ppm RVCM, was extruded at 2.9 lbs/hr at a melt temperature of 400F. Monitoring was done with both Reiszner Badges and carbon tube and pumps. Placement of monitoring was in several positions in order to try to find the plumes. PLASTISOL MIXING AND FUSION IN THE ALTC LAB. Plastisol #1 contained 67 PPM VCM. Plastisol #2 contained 137 PPM VCM. Plastisol Recipe - PHR Geon* 136, Lot P29N012 Geon* 217, Lot H2B0708 DOP ESO Synpron 940 11 57 3 2 12 9998 12 57 3 2 Fusion Conditions: Forced draft Blue-M oven 375 F for 5 minutes lOOg plastisol in 9"X13" aluminum cake pans 3 pans in oven at one time Fused samples cut from slab and placed hot in a 4 oz. jar then sealed with electricians tape. Testing was done 3 days later. The fusion lad) was exhausted at 1 air turn-over/hour. COMMERCIAL COMPOUNDING ON ALGC Z-LINE. The Geon Company commercial resin with the highest typical RVCM content is 110x377. This resin is currently produced at ALGCP. The polymerization is run at 82C, which is close to the glass transition temperature. The resin has very low porosity and is very difficult to strip. In addition, this resin is used frequently on Z-line. 25288012 (10) BFG40107 For the plant monitoring trial conducted in ALGCP, the resin plant made two lots of 110x377 with RVCM in the range of 7-10 ppm. The resin sat in a silo for several days before the monitoring test was run. RVCM data for the resin as used is listed below. Date Time RVCM (ppm) 1/26/93 18:00 4.75 24:00 3.87 1/27/93 08:00 2.36 BULK RAIL MONITORING Several rail-cars of resin were allowed to sit in the sun at Deer Park for several days. They were opened and immediately monitored with an h-nu meter for instantaneous levels of AVCM. The AVCM reading was taken in the center of the manway opening, just above the resin, and two feet above the manway. Weather conditions the day of the test were sunshine, 70F, slight breeze. Q aCIAL WAREHOUSE MONITORING Five Warehouses were selected for this study. Forty area and four personal monitorings were conducted, which was based on facility size and resin storage quantities. Warehouse storage included both suspensions and dispersion resins. ANALYTICAL METHODS Charcoal from badges and tubes was analyzed at Brecksville Research Center using a headspace-gas chromatography method (<>. This is the same method used for routine determination of AVCM in plants and warehouses. For residual vinyl chloride analysis, resin was taken at the start of the Henschel mixing or plastlsol preparation. Compound was taken as it came from the Henschel and, again, before extrusion; plastisol was sampled before curing. Sheet samples were taken at the exit of the extruder, and plastisol product was taken as it came from the oven. All samples were stored in completely filled and sealed glass jars. Most were analyzed within eight hours of being taken; if not, they were stored at 36C until analyzed. Analysis was by gas chromatography using either a direct injection method <7> at ALTC for RVCM levels above l mg/kg (ppm) or a headspace method (Standard Test Procedure 1005H) at ALGC for levels below 1 mg/kg* Results for samples analyzed by both methods were comparable. N) CA <35 a i- (id BfG40108 DISCUSSION CONTROL OF AVCM EXPOSURE There are many factors affecting AVCM exposure. 1) The amount of vcm supplied to the process or the RVCM of the resin or compound. 2) The general ventilation or air turn-overs per hour, which removes AVCM. 3) Local point source ventilation, which removes the VCM before it can come into the room. 4) The rate of resin or compound processed. 5) The percentage of VCM lost from the resin or compound during processing (Many previous measurements indicate that about 60% of the RVCM is lost during processing (3), however lost VCM could be lost to the air or could be chemically reacted to non-VCM products.) 6) Worker nearness to the VCM source or plume. 7) Air volume in a room for the dilution scenario where the room air is well mixed. Of the above factors, the RVCM is controlled by the Geon Company on resins and compound, but several other factors are controlled by the resin or compound processor. Thus it is a joint responsibility of The Geon Company and the user to control AVCM exposure. MnnBT.fi POP AVCM EXPOSURE There are models for calculating AVCM exposure. One model uses statistically fitted data for warehouse exposure <x>, however this model is only for suspension resins in a well mixed warehouse and is not applicable to melt processing. Uniformly mixed room models <3,*> were considered, however, most processes are not well mixed rooms and concentrated VCM in plumes often exist <4'. It was therefore decided to measure AVCM exposures under well controlled conditions to find the relationship of AVCM to RVCM in the resin or compound. Some of the assumptions in the new model are: 5AVCM (RVCM) (rate=lbs/hr) (ventilation turn-over/hour) These above assumptions are the same for the old <a> and new models. Other assumptions which differ from the old model are: s o M* (12) OLD vs NEW MODEL COMPARISONS SSCSSSSSSSSSSSSaBSSSS3BSSSaaSSSSanSSaBBPSSSSSSS3SSS= ;:n VENTILATION 1 air turn-over/hour AVCM as measured DILUTION find AVCM concentrations in a plume EXPOSURE highest measurement in a plume OLD MODEL* 5 air turn-overs/hour from a material balance instant distribution of AVCM into the whole room average calculated for the room Scale-up of AVCM to manufacturing scale involves RVCM in the resin or compound and the rate in lbs/hr. Worst case ventilation is assumed to be 1 air turn-over per hour. We find that air in a powder mixing operation or extrusion operation is quite stuffy at 1/hour, a plastisol fusion operation is quite smoggy, therefore 1/hour is expected to be the worst case acceptable. It is important to make several AVCM measurements so as to be able to find concentrations in plumes. POWDER MIXING PROCESS AVCM results are listed in Table 1 for a powder mixing operation. The highest readings are 0.01 ppm above the mixer and 3 feet from the mixer. Since we started with an uncontaminated room, these measurements may be 60% of equilibrium values and were corrected for scale-up (see Figure 1.) A summary of results and scale-up follows: I AIR turn-over/hour I RATE, lbs/hour RVCM, ppm MEASURED AVCM, ppm CALCULATED AVCM, ppm :S*B VALUES 1 55 103 0.01 SCALEifriCON^ 1 18,000 for a 1500 lb Henshel on a 5 minute cycle 1, 3, 8.5, 9 0.05, 0.2, 0.45, 0.5 This indicates that RVCM in resin could be as high as 9 ppm before the AVCM would be expected to reach 0.5 ppm in a commercial powder mixing process. (13) BFG40110 EXTRUSION PROCESS AVCM results are listed in Table 1 for a sheet extrusion process. The highest readings are 0.01 ppm on the personal monitor of Juan Rodriguez. Since we started with an uncontaminated room an equilibrium consideration was made as was made for powder mixing. A summary of results and scale-up follows: EXTRUSION AIR turn-over/hour RATE, lbs/hour Compound RVCM, ppm MEASURED AVCM, ppm CALCULATED AVCM, ppm LAB VALUES 1 2.9 45 0.01 SCALED COMMERCIAL 1 1500 for a siding extrusion 1, 2.6, 3, 8.5 | 0.2, 0.5, 0.6, 1,6 1 This indicates that RVCM in compound could be as high as about 3 ppm before the AVCM would be expected to reach 0.5 ppm in a commercial extrusion process. This also corresponds to a starting resin RVCM of 6 ppm. PLASTISOL FUSION IN THE LAB. Production samples of Geon 217 blending resin and Geon 136 dispersion were chosen to make the plastisol. In order to have sufficient quantities of VCM present in the plastisol to produce measurable AVCM levels, an artificially high RVCM Geon 217 sample was prepared. The 217 had 12,450 PPM of vinyl chloride monomer. Two plastisols were made, the first contained 67 PPM RVCM and the second 137 PPM RVCM. The plastisols were fused in aluminum cake pans at 375 F for 5 minutes in a standard Blue-M oven. Each pan contained 100g plastisol. 1900g of plastisol was fused each hour. One oven was used with about 3 pans being fused at a time. Plastisol #1 67 PPM RVCM was fused during the first hour and plastisol #2 137 PPM RVCM during the second hour. Duplicate Reiszner static badges were placed in locations near the oven door, in the oven exhaust hood, on the operator, on the floor and in the room corners. The exhaust hood was dampened such that there was only l air change per hour in the room. The lab had a volume of approximately 6300 cubic feet. (14) BFG40111 ..-5 The fused slabs from plastisol #1 were tested at 30 PPM RVCM and the #2 slabs at 79 PPM. The area was monitored during the 2 hours of actual fusing of plastisol, plus 30 minutes after fusion was completed. Based on air flow rates and plastisol RVCM vs slab RVCM, and assuming that all the VCM went into the room, then the average AVCM reading for the 2.5 hour period should have been 0.084 PPM on a volume basis by material balance. The duplicate lab operator samples measured 0.20 PPM. The monitor on the floor measured 0.04 PPM. All the other monitors tested at 0.01 PPM or less. The H-NU meter registered 0 to 5 PPM at various locations in the room. High readings were noted near the stack of fused slabs. This lab data was scaled to a rotocaster at 130 lbs/hr and is summarized in the following table. | PLASTISOL FUSION AIR turn-over/hour RATE, lbs/hour compound RVCM, ppm MEASURED AVCM, ppm CALCULATED AVCM, ppm LAB VALUES 1 2.6 102 0.24 SCALED COMMERCIAL 1 130 for a rotocaster 1, 2.6, 3, 0.2, 0.5, 0.6, { 8.5 1.6 BULK CONTAINER OPENING AND SHORT TERM EXPOSURE One area of concern for AVCM exposure was the opening of PVC rail-car manways. RVCM in the resin could be released as the rail-car sits in the sun, resulting in a "blast" of air high in AVCM reaching an operator as he opens a manway on the car. Several rail-cars of resin were allowed to sit in the sun at Deer Park for several days. They were opened and immediately monitored with an h-nu meter for instantaneous levels of AVCM. The AVCM reading was taken in the center of the manway opening, just above the resin, and two feet above the manway. Weather conditions the day of the test were sunshine, 70F, slight breeze. Readings at the manway level and just above the resin were the same. No RVCM was detected two feet above the manway. Results are listed on the next page. (15) BFG40112 Certificate <- of Analysis Lot# RVCM (ppm) BFGX1339 1.42 ACFX55986 1.81 BFGX1582 1.27 BFGX1385 3.13 BFGX1228 (X500) BFGX1018 0.03 3.01 RVCM reading,ppm Compartment at manway B 2.5 BC 1.5 B 1.5 BC 2.0 A 1.0 AC 3.5 A 4.0 AC 3.5 B0 BC 0 B9 BC 15 2' above 0 0 0 0 0 0 0 0 0 0 0 0 AVCM levels at any point above the manway opening on a railcar were consistently zero. As long as operators do not place their heads inside the manway, they should not be exposed to any measurable level of AVCM. If someone puts his head inside the rail-car, he could be exposed to an AVCM level above the 5ppm ceiling for 15 minute exposure. This would be a violation of the OSHA confined space entry rule, so this is not something that should ever occur. COMMERCIAL COMPOUNDING Building 441, ALGC Compound East was selected as the test location. This PVC compounding facility has two independent production lines consisting of a Farrel Continuous Mixing (FCM) operation and a Buss Extrusion line. The exposure area around the FCM was chosen for this study. The air exchange rate in B/441 was approximately l.3/hr. Major ventilation equipment included: mill hood exhaust, RS to GS screw, GS outlet, pelletizer and strip tank exhaust. The building size is approximately 38,000 FT* on floor level one. The sample duration selected for this study was 24 hours. During this time, 87241 Black and 87371 was produced using 110x377 resins stored in silo 202. Certificate of analysis RVCM was 8ppm for the PVC resin. An RVCM was also run on a silo sample prior to compounding. That result was 4ppm. (16) BFG40113 A test area audit was conducted prior to the study. Based on projected emissions source points, (16) area locations and (4) personnel monitorings were selected. The two sampling methods were as follows: 1) Area monitoring using a Dupont model 2500 pump with SKC 6x70 or 10x110 charcoal tubes. Established flow rates of 45cc/minutes for eight hour and 500 cc/minute for twentyfour hour monitorings. 2) Area and personnel monitoring using a Reiszner "MiniMonitor" passive docimeter badge. Device weight of 35 grams plus 1.35 g of unexposed activated charcoal granules. algc Plant___MonJ.-fcog-i.rxgi Buss LOCATION # OF SAMPLES RESULT (PPM) 1 H O V 1. Buss Line 1st Floor 9 0.006 2. Weighman 1 .04 3. Henschel Operator 1 .05 4. Line Operator 1 .04 5. Packager 1 1.08 6. Mill Area 3 .05 7. Z Line Henschel 1 <.01 8. Henschel Feed Hopper 1 .03 9. Pellet Cooling 1 .01 10. 4th Floor Resin Station 1 <.06 Also monitored was Louisville, Pedricktown mill line, and Henry mill line. These results are summarized in the following table. (17) BpG40ll4 C/T 03 03 CD COMMERCIAL COMPOUNDING OPERATION 0 Z0 3 8 & &FG40115 (18) ^3 Cj? COMMERCIAL WAREHOUSE Five Warehouses were selected for this study. Forty area and four personal monitorings were conducted, which was based on facility size and resin storage quantities. Warehouse storage included both suspensions and dispersion resins. Please note that 5 results at Pedricktown were above the section limit for Vinyl Chloride. Appropriate plant follow-up is in progress as of this writing. Warehouse Results LOCATION 1. Henry B/735 # OF SAMPLES 4 RESULTS (PPM) 0.11 - 0.14 2. Avon Lake B/438 6 <.02 - .11 3. Avon Lake B/452 4 <.02 - .11 4. Avon Lake B/421 15 <.25 5. Pedricktown Main Warehouse 15 <.036 - 1.0 5 results >.5 ppm* * Appropriate plant follow-up is in progress as of this writing. MATERIAL BALANCE A material balance was done for the low air exchange rate experiments run in ALTC using a CSTR (continuous stirred tank reactor) model. The model assumes instantaneous and complete mixing of any VCM released from the compounding process with the air in the room. The mathematical equations for powder compounding of the suspension resin and for curing of the plastisol are listed in the Appendix. For powder compounding, the material balance shows that there should have been a significant level of AVCM in the room. The average level throughout the room for the two hour test would have been about 1.7 ppm AVCM. Since we know that the well-mixed model does not accurately model compounding processes, we can apply the results of the calculations in a qualitative manner to the plume theory. Any badge near the Henschel mixer should have read an AVCM level significantly higher than 1.7 ppm AVCM. However, no reading near <7T 03 C3 h* (19) BpG40ll6 1 ppm was recorded. The RVCM that disappeared from the resin in the compounding process had to go somewhere. An explanation, based on the data we have, is that the RVCM reacts with residual resin catalyst, stabilizers or other ingredients to form something not detected as RVCM in the compound or AVCM in the air. The data seems to indicate that at least 90% of the RVCM simply reacts in this manner. The analysis of the material balance for dispersion Plastisol curing follows the same pattern. According to the well-mixed model, there should have been an average of about 0.16 ppm AVCM throughout the room over the course of the 2.5 hour experiment. The actual results included one reading of 0.24 ppm AVCM, which must have been in a plume. MANUFACTURING CONCERNS Tables 1 and 2 are a summary of the resin records used in the RVCM study to determine the effect that changes in RVCM specifications would have on current BFG production. The focus was on the poundage that would be effected by any specification changes. In some instances the actual poundage estimates for the given period analyzed were not available, however, the size of the sample for which poundage figures were available was large enough that is doubtful these missing poundage numbers would greatly influence the final estimates given below. Indeed, during the early phases of this analysis, with one quarter of the data presented in the final analysis available, the percentages that were being computed were quite close to the numbers shown below. The following tables can be summarized as follows: I. The current data analysis is based oh a TOTAL production of 1316 MM mass and suspension resin pounds. A. If the RVCM threshold limit is reduced to 5 ppm and manufacturing practices remain the same, the amount of product having levels above this value would increase by 3.5%. 1. Since bag-by-bag selection of material is not economical, any resin with production pounds in excess of 5 ppm would be affected. Thus the TOTAL poundage affected would represent 55.6% of the current poundage. In a similar fashion B. If the RVCM threshold limit is reduced to 3 ppm and manufacturing practices remain the same, the amount of product having levels above this value would increase by 7%. (20) BFG40lI7 C/t W & & 1. Since bag-by-bag selection of material is not economical, any resin with production pounds in excess of 3 ppm would be affected. Thus the TOTAL poundage affected would represent 64.5% of the current poundage. and C. If the RVCM threshold limit is reduced to 1 ppm and manufacturing practices remain the same, the amount of product having levels above this value would increase by 29%. 1. Since bag-by-bag selection of materials is not economical, any resin with production pounds in excess of 1 ppm would be affected. Thus the TOTAL poundage affected would represent 78% of the current poundage. (21) . 0 .0 0 0.00 fNoosr-ooooo*nooooooin ' <r o o ^HOsoooooooo9rooo'-*` o o o> oor-iwroooooooomoooO' i (fl n r> o i nt f-- n o O N o o o a'fiBfl'oiNoo^o. 0 0^*0000 lA^i/ir-o'ooo ooonooooo O O <v r-f o O O J> o N o I'M o O O o o <*i ^ o r' O o f* CM ^ OO ^O O >r o- H - O4oomooooooooo*ooono<yo<^ Hor***oooooor<*ooo-NO-Nf- O O --* N o < > o O O no o < O O fH o O ovfiornoorr^ooooooNovoNvflooo O^^^OO^^r>T*-0-HOOOO'OO^rO<tOOO 00000000'H-40'~*0000HOi IOOOO O O O' r* o m 0 0*0000 o O N O o O 1 . / .q O *H I NoB9ai^iflr'fl'ui3in'0(No('o(Na5 ^voin<Hor,,o^v(NrH`vtDtnr*r,'irtr*^>u^ i *o n e ro m h < T N M (V r* t/i O' nn h OOOOOOO^fOtO <00000000*00 ioottno'nr m +4 r* 0* e* + w* r+ tmi r* *p v o W --* U 3 a o Q <n -- NNN i/> i> ut <n ti> lA lA lA lA (A tf> iI ltltII1llIi I oooooooooooooo Ofn<HW>rf<oOir*or'*ooHN6< ora*MAoHH'AcM*rr*r>ino< oo>o<oo9'*tO(,>fno(*>*or,>vor<HNOfno*o<ro\iA<Ho^inf*<r,'*o^o< ^tr'*Aftnr>'p0'O^N'nr<^*^<^,von<finrs*c<^r>r"or<o<p-MO*oi HOe*eiA-<ooooHi i*-r*oo'ooroooHoo<ro OP'OO<0fnOt-irNr*-^ONrr*-^-r'i ft n ^-io*-*ooooOr-iOOwoooo*-<ooeoo'^oofloo/'n*(in<r'oor*ooooooo'Oooooo<^<s*^0'HOrH- Q oooooooooooooooooof*i^o^oooo9Nenooooo'voooooowoooooooooooo< oooooooo >00000000* OOOOOOOOOi OOOOOOOOO >ooooooooooooooo< 0(Nffin)HH4wviAiNO`oniA^iA^o'OHioeo'oini,nnBiAONiAr'rNon'iAO'ONOP*j<iAHnO'fl( NOiAllOOOOOOOf,'lAOOOOO*0^*ONlA(OinVO'Oir>lAO'OHrkOO<NOHWH/*VOOHO"400NVr'Ni O O O H O O ' OOOOOOOOOOO^OOf^OO' i O O 0> * w * * onoooo*HO*"*^< 100000^0001 Br'<flNl<>Wr4r'IAlOnr'l4<Or<>lrIHIA9BHB9liA(7lN'lA<,*BHr'HNO'*OBl*'Ha oonmoooooi*iooHOOo-(o<-iN'^''^o'ui'Nr^o>o'0*o*'riHooH>BO'BH ltAOHOr*'iOrtrniA' lOOOOOOOHiHOOOOOlAOHnOHOOMHHinOOOOOOHOHnoOOOOOOmOOO< 0 .4 6 0 .3 0 0.Q 1 iNAoaonAHO)<9"Ar40nHHa'O'o<H< W VO N f lANf KNnMA O SO r* J\ * *n O noA M H SO H H C4 Hn *H r,'or''OHH(NHp*n I^INO'INO'AArtVOP'AOTB 0 H n VO (N H H n O O h. AOr-B^MNO knr'0'Hfi<AO(*0 p* o eo o o ooQ o^os a 04SS'0<nQ >r*'f*ior**or<rN<i'\ O OvOtniAiAm^v^oOtJoiikSkilb -* XMXXXXXXX'W'WsooOO^OO-tX - -- *-4fNooooooo*,ifS#sirortr,r'00*,oOr^*Hrn9floc'0,oeooiv< c-r-r-oososost-* os *-* xxso'or-or-.JUXXXZZXXX < < X p**oor*r^<Nm<nr*ooooOOooo*-^*-*^ I I 1 I l fNOHHHMUHHH^fNfNIN <<<<<< uuuuuuuasKasasaSK UUUUyUUUUUflSaXSXflXSOXSXaXSXOXS>ONJ>cS*XPS>l'K>fiylil*BXa>itf-OXSXOXJXOXSXflSXaJiJKJfl"l3O*SJKJJJJXJJ<JJXJXyOXO<O5W25O5**5**5**5* OC?OaC5^0aOO<<<<<<<<*ZZZZZ*2i=ZZZZZZM^w*-MX<XXXXOOOOOOO JJJJJJJJJJ0.9.0.0'0.fl.0i0.UUUUUUWUUIilWUWUlil>>>>>>>MMMMMHHhi*PPlr,H ,<<^<<<<4<<<QaQQQQQO3:saB**SS**SS* = *'JjN3'J*JJJa5**ZSB2!0'0*0`0`0,a*0* pTOWM 121X10B 23 cfc (22) BFG40119 CO NT'RVCH SUMMARY FOR 5 AND 3 PPM RVCM J3 U <A r-4 c B 4oa on r- OfNMtf'PN(NO cn so oor-^orN-'Tsoo 4J -H O* O -t fO ri rN04p*M>040 H~ a n -- A J-- h C M <0 O 0 y 'H a Mnwo^rt^Mfirtno O 04 -4 O 0 0 < U A* 0 H -H 4^4 o * ha VO ................................................................... VO f>r***><nvA^r`i-40iH M -- om cu a* a <o -- mm ff o X ovooeovnoooror'r>r'<nv < oovr>noo40rtOtotH<n^ ................................................................................................. <oN*np'PtnNoNooN in m -4 h r n in h n in m r 04 <n <n 2 oooooooooooo^^r*uNo W OOOOOOOOOOOOOOO0404 ....................................................................................... ooooooooooooooooo 2 v'o'or'^n'oiNOOiHonninooo 4 4ooivomm4oo4oo0voo4oso O (NlNMVOfNrNHINMNOOrlN-4 bl 2 <ovMn9tminr>inHMin0r>iA*n K aCfNHOfnHf'/IN'IflVOV'ilA'd u ................................................................................................. )0tf^i0ino'0f4iNNvooin<A*4 TJ 04 04 04 04 o 04 0 tA 04 0 H 40 in o r* u m o 04 vo Ot m r- 40 o 04 04 o r r* o m* 04 p<4 44 04 04 H r-l u OS Oo Z ->4 in r* ro O* t-( < < < X X X < z Z O' r* <a M 0 m M3 r- 40 o o SO O o VO VO vO w 04 04 04 04 r-i o n 0 40 90 90 40 u u 04 0 Was W H -4 H w * X H r4 o (9 H "* o H ZzzzzZZzzzzZzZ z 33 3 33353 3 % 3333 H < o o o o o O o o o o o O o O o O o J f- H * H 6- H H H H H H H o U o a. CL, 04 a. A 0, 04 0# 04 04 04 04 a, 04 04 (A VA w (23) flFG^J20 s b L ) s jlp p m anl to ooo^oosnovooso rnOvfiP-OOOOOfN o^Of^ooolooaaooo'r- OOOOOINON >o o' r~- p o o r* *** rN o ^ w snr>roo-40sn p* o o o os o ooor'Po^o'flH H O H PM O <N O O o I o o OP-^VO l io iTl . (sBt E T o ta l Lbs (m illio n s ) % T o ta l R ecords > lp p Specs (ppm ) MAX M IN M EDIAN fMO>oa>wvinpfliin(7(n(ON(N(orNB) HnnnioninHr49)Nrt (N O O *4 <N P*' T V *4 H H r M PN r*i *4 o r* o *4 so --< mt VO N (*> (N r <n CM N VO OOOOOOOPNOSO aooocooooo^oo fNvooo*<noovmr* *4*4<Nm<N^-4<N*4 *\ r* r* os so *4 r- Vw o or-r-rMOoooso'Oo nvo^oooiO^or* sovovooooor-o'O^ 000\^0<NOm^ O0s^,O(N<Nr*i--irssr ofNrooovoo<no F-ir*^oon*ofNon* -4 *h o a o tnow* O'eo'o*oirtomr'<fi OU)tf'HmO0VNr>O ............................................. motnooooHOHO C-4 m VO *4 ^,<owoooo/>oos nn 9) n mry^0iooar>c n ^ r* h omor^'ooi'nooosso P *4 m VO in (N PO^VfiHOVAVAn ifl N 1-* T+ m (M PM N IO Ilf) OOOO in m in 0 a III 000 m *4 o II 00 <071\ I m..i.n..i.n..m...in... in m in in m n 00 000H II IIIII IIIII I OOOOOOO 000000 O M H irt N OP 000 o os m 0 o r* o 91 h 0 pm 0 o a o in 40 o os so m pipnofleM1 O PM H 10 14 o 0 H 4 0 0 (N 0 n P 0 O 0 ift 0 0 vn in os i/s p p 0i 9, H ID PM 0 H H 0 0 (4 H n 0 P* ev)woM(4nr'00O0 fM0NnPM9inPM9i(JMS r>NI-PMOOOHO0O00HOOOO>-(O0Hr>0O0Oi<S00HOO0OH0O(>*O9l0P4OH(SiriHO0nH0H m 0* r- m --* --1 *4 vo pm 0 h 0h m eoooooeoo*40*4100000*4 00-40000*40 aOQr'SOOeooiA rMinmoor^ooo 000000000 0<Sn4*HO<-40*4*4 000000000 000000000 m^omooooos 0000*40000 000000000 000000000 000000000 000000000 CMOOOOOOOO 000000000 000000000 oormooooo<N9im*4*4*4-^ 0PMO0I40PM0N 000*400000 P40OPM0P*PM dP400OS00OPN or*9ii/SHP4O0o mopnvooooo 000PN00P409I r,4inoip*4r0 PMO*4HHPM0Ort o*4Oo<*M0'<*siNm 000*400000 000000000 0>oon4oor4oo <n*4*4*400m00 00*40*4*4000 0000-40000 oop*>mooooonoo*40pi000HHn00P4r*0 0^(4400048)0(0^00 (4004(44rM9(00040 IMP40000000A0900 OOO4OH0TP49l04hOl OSOS90H40OH0O04 00CO4O0HOHCP400 mo*4<Nooooooo*4*4 ooooosno*4P,oo*4voo n*4*4fnoooooo*40 *4mooooooopnoooo in (4 PM0O0O>49(40H000n000(4 h00 en ^0N0nfMnr*0 o e0 *4 0 m *4 *4*40*4*4 <*4 4 0 0O44 r-- 4 os sj* in o --4 *4 P*S *4 <wr,4P*oo*4<,Af*in4r,*<NOMe4O!ininf*>sor*vAO0*(*i r*vor-o*4*4r4*4r-#nr*Mo^in^,4rP4r4r>-049spnoin<N *4 40 4P40 0PM44P4 O <3 u. 04fs04PM(MO O o oo Q O 0 o os Z 2 0 M O 09 h(4r>0Hn0ON Q X 03 0 0 o o v OS ^000 IN C4 M 0 OO 0Ot(4(4(40444Ofit <J o *. & e* t* *4 *4 *4<0>(4OOQaM*4l*SP*| 0 m m tr PMrt0r'poono4XfaIXXXXXXXU V0000*400<x iHPNOOOOOOOmni CQ OX xxsoor^or'mjuxx X Z Z X xx < <X X 4 0 009ioo*9'nh oor-cMPNpnfnr-ooo o o O 0 o O *4 *4 *4 *4 *4 00*4*4*4*4*4*4*4 } O 0000900NM1' p*r'r'r*r>9(09iff(H** m *4 ) | 1 t | N044 4 u u 4 4 4 N PM N N PM 444444444(34 XXXXXXX*4*4*- HH4HHH444P4N PM4h,000(3(j444 *4 <3 o *4 C,T JS3 03 00 <<<<<< P.i f.l M M PJ M 1.1 4 4 4 (M 4 >*>,>*XXXmJ.JJ*J*J*4J<.<<4<<<ZZZZZZZZ UUUUUUUUUUfXaCOCasaScCflSpXaiSQSiXaitfKaSa: aSXPSQSXflSJUJJJJiJOOOOOOZSSSaSSS 0<3U00O<300l3*<<<<<<<ZZZ Z Z Z Z Z Z ZZZZZZws-v4-ws-i-<<<<<<00000000 4JJJJ>JJJ4Ja.ba,ao.o,a.buuuuuuuuu <,<.,<.<<<<<,<aoaoaoaaxxxxxxxxx XXXXXXJJJJ*4JJZZZZZZO*o,a.a.a.o.a.fl. (24) BFG40121 MEAN R ecords R E S IN PLANT CONT'RVCM SUMMARY FOR 1 PPM RVCM 13 J in CS iqocu *j cu OH ~ aa uW vo voa\oiNHeuMNo o ^Hinooinoi'fl^ooo ........................................................................... Htnr*o~NO<*>0000 -4 --4 M-- XJ 4 C o 4 -N 4J -4 Eo- 8** V vo OlNHrlHHlrtlNfniO Nr*(nwinr,`HOH *4 n 4*0 8 4J u Ch o o Qt H u -* a * a; "'*^*r-Hvor>*orNOr"iOfNO-ir-c* <Nvom\omo>^^HO*no\^or**mr`r- .................................................. ................................................. mtn*o<s>.-<0'ooowoooov r* ifl io p* f* r* io m in in in U --8 a a. a V) mm II oo X ovootoo<nooo<Nor,`r>r>'<n'r < oovpmoov4o<*><fto^Hfnov JC ................................................................................................... 0NvnrkHnNovn(a4OO<iNin in m h a pi p oi m ^ 0 n in p* ^n n M Z 0000000 ooo<-4--fr-n H 0000000 oooooootNrn z 00000000000000000 Z ,'ovor-'omvors*oav-cnininooo anvonnMdoo^'^oooaio O P(VNinOfN(NHNfNOOHNH U Z <oiAAniAMnHPiflnaiiin fa<) 0....P...4..H...O...n..H...M....n..Y...i.O...0..O......H...9..l.i.O... ioni/ioiepiPtPi0<pooinpiH O NnniPioriMinN W IAOMO)IA(>0O uO H H M H IN M os in O (*> H (N o r* ^ p^HoH o O -N Z ft m mn M << < < XXX * Z Z P P* v> n v in io p* OOO^VOOOVOVOVO U <M r># n# m / 0Q000UUPIV0 OS -H H Z< J zSzSzSzZSzSzSzSzSz 000000000 z2to* zS z* z* 000 z2o oo H uO H uO a. o*cwo*a*o*o*aoQ* a. 0*0*0* o* w v to (25 r BFG40J22 fe $5 5 Pi ANALYTICAL RELIABILITY Vinyl chloride in the air is absorbed by charcoal in pumped tubes or in Reiszner badges; pumped tubes are approved by OSHA for air sampling. The charcoal is then removed and analyzed by headspace-gas chromatography. The precision and accuracy of the combination of air sampling and GC analysis has been studied earlier <9'10) "Recoveries of vinyl chloride by the Reiszner Badge compare favorably with results via carbon tube sampling. (Recovery=badge result/tube result expressed as per cent.) In addition, the precision of testing expressed by the coefficient of variation (standard deviation/average) looks good, relative to OSHA requirements." "OSHA requirements for combined precision and accuracy are easily met at all concentrations, despite the tendency for Reiszner results to be slightly higher at very low monomer levels. The following 95% confidence limits were determined for the Badge." i VCM: R&nge^ ppm ::: ::: Observed 95% l imits:::::: Allowed 95% limits less than 0.5 0.5 to 10 | greater than | 1.0 ppm 7.8% less than to 36.4% greater than the "true" value 1.9% less than to 17.5% greater than "true" value 7.7% less than to 10.3% greater than "true" value Plus or minus 50% of "true" value Plus or minus 35% of "true" value Plus or minus 25% of "true" value These results were based on tubes and badges prepared in the laboratory under controlled conditions. Extensive testing under actual plant conditions showed much poorer precision for both badges and tubes (see reference 9 for complete details). However, this probably indicated an actual variability of analyte concentration in the air. Similar variability was seen in a study done by the University of Utah Research Institute <1X>: "Comparative measurements of organic vapors with active (pumped charcoal adsorption tubes) and passive (diffusion) monitors showed good agreement in steady-state laboratory chamber tests but considerable discrepancies in field trails on painters, in which the monitors were worn on opposite labels under fluctuating conditions of vapor concentrations and air movement." "Continuous recordings by an I.R. gas analyzer of air samples drawn from the left and right lapels of a painter working under simulated field conditions showed large differences in (26) BFG40123 concentration corresponding to the differences found between monitors." It is important to note that this variability occurred with the pumped tubes, which are accepted by OSHA for air monitoring, as well as with the Reiszner badges. Area monitoring provided additional confirmation that variability of the personnel monitoring results was due to variability of the air and not to problems with the monitors. In these tests the monitors and air were stationary; for the personnel monitoring tests, they were in motion. Sixteen badges were attached to a rack and exposed in building 461 of the Avon Lake General Chemical Plant. This was done eleven times. The mean concentration ranged from 0.34 to 4.94 ppm and the coefficient of variation (relative standard deviation) ranged from 5.2 to 10.0%3 , which are similar to those for the laboratory tests. The relative standard deviation of Standard Test Procedure 1005H for residual vinyl chloride monomer in PVC is 2.63% at 2.09 ppm and 4.16% at 62.66 ppm<xa>. The precision of the direct injection analysis for vinyl chloride has not been determined but the relative standard deviation is expected to be less than 5% for levels above 10 ppm. FALSE READINGS There has been a concern about false positive and false negative results for both air and PVC testing. False positives are possible for both analyses since gas chromatography can not identify components. Therefore, if one or more other components elute with, or instead of, vinyl chloride, the peak area and concentration will be artificially high. False negatives are less likely for analysis of PVC and the charcoal in badges and tubes. However, the tubes and badges may not accurately sample the air to which they are exposed. Results, discussed above, show this to be unlikely. (27) BFG40i24 LABELING PRACTICES IN THE U.S. The following table summarizes the practices of Geon competitors. Many label all resins. Company Borden (BCP) Carbide GG Formosa Oxy Vista PVC LABELING IN U.S. Labeling Policy Comments All Blending & Susp. Resins are labeled. Signal label not used in Canada. Lawyers overruled rest of company. Even bottle resin is labeled. No warnings in MSOS or labels because RVC <lOppm. Policy partially based on BFG's 8.5ppm limit Emulsion & Disp. resins labeled per "OSHA Std" language. Susp. resin labeled on hopper cars on tag, so hatch is ventilated first. No labels on compounds. Revising policy and labels with help from industrial hygienist. May move to labeling disp. and susp. resin ( and maybe compound) in a very conservative fashion due to USEPA citations for VCM releases. Bottle resin not labeled ("mother's milk"). All other resins labeled. Compounds not labeled. "Dust & Fines & VCM can be hazardous at processing temperatures' Not haz. mtl. under Sara III. Warning label language is not OSHA language. Policy driven by lawyers. Monitoring 2 years ago showed 5 ppm RVCM in resin gives 99% confidence of being below OSHA limits. Can talk to Oxy's people & inspect their data. Oxy monitors customer plants on demand and always finds AVCM ND. Label-all resin and compound. Driven by responsible care anc^ liability issues. VCM Warning q OSHA Std. ft Q. GC (28) CO o BFG40125 REFERENCES 1. M.M. O'Mara, L.B. Crider, R.L. Bowles, C.J. Tomakek, " A Physical Model for the Diffusion of Vinyl Chloride Monomer from PVC under various Conditions of Storage", BFG Technical Document, August 25, 1975. 2. L.B. Crider, M.M. O'Mara, R.L. Bowles, Society of Plastics Engineers, "Safety and Health with Plastics", National Technical Conference, page 196, Denver, November 8-10, 1977. 3. M.J. Ahmed, H.S. Haller, "Modeling of VCM Concentrations During Thermal Processing of PVC", BFG Technical Document, March 31, 1983. 4. A. G. Andreopoulos, A. N. Karayannis, N. C. Markatos, Trans IChemE, 70 Part B. 75 (May 1992). 5. R. Kruszynski, "OSHA - NIOSH - APA, 2^ Quarter 1975 Update", Inter-Organization Correspondence, July 8, 1975. (Appendix). 6. Born, J.W.; "Method of Test for Vinyl Chloride Monomer in Air Using Activated Charcoal Monitors and Headspace-Gas Chromatographic Analysis"; BFGTD; January 30, 1986. 7. Samples were dissolved in tetrahydrofuran gram in lOmL); luL of the solution was injected into a Hewlett Packard 5890A GC equipped with a flame ionization detector and a 10 foot by \ inch (2mm ID) glass column packed with 1% SP1000 on Carbopack B. A response factor was determined by standard addition of VCM to the PVC solutions. 8. F.M. Galloway, "Diffusion Modeling of VCM Concentrations in Air",BFG Inter-Organization Correspondence, Jan. 15, 1993. (appendix). 9. Born, J.H.; "Evaluation of the Reiszner MiniMonitor Charcoal Badge as a VCM Monitor - Part II"; Status Report; August 12, 1985. 10. Fairlie, A.M.; "Evaluation of the Reiszner MiniMonitor Charcoal Badge as a VCM Monitor - Validation"; BFGTR; November 18, 1985. 11. Division, University of Utah Research Institute, December, 1981. 12. Environmental Reporter, PP 120:1088 through 120:1091, October 7, 1988, EPA Method 107. (29) BFG40126 APPENDIX (30) BFG40127 A) <> A) ilPGoodrich INTER-ORGANIZATION CORRESPONDENCE TO FIELD POINT OR OEPT & 81DG NO J. Summers_______________________________________________________ FROM FIELD POINT OR DEPT & BLDG NO ___F.M. Galloway_________________________at.tc psc-n SUBJECT DATE YOUR LETTER OATE THIS IfTTER i /ir/qi ~^ Diffusion Modeling of VCM Concentrations in Air This is to summarize my ideas concerning the possibilities of modeling the concentration of VCM in the air within compartments once it has been released from PVC during processing. SUMMARY The well-mixed model is a reasonable approach toward establishing general guidelines for VCM levels. Modeling of warm plumes containing higher VCM concentrations from some points of a process could be done, but would be rather specific from one example to the next. Handling these with local forced convection (e.g., suck up the plume into an exhaust) is an obvious answer anyway. Computational fluid dynamics would be appropriate only in an extreme case. If, in the process of data collection, some anomalies turn up, I would be happy to help try to interpret them in terms of some of these ideas, but I do not see any approach toward a general model, other than the well-mixed one, that would be of any value at this time. DISCUSSION The simplest approach is to assume that within a given compartment the concentration is uniform; i.e., the air is well mixed. I understand that your current approach is based on this assumption. There is a lot of justification for this assumption in most practical situations. I have reviewed the work of Gary Huvard, for example, (G.S.Huvard, "Tremco's Mono* Acrylic Sealant: Modeling the Release of Controlled Exposure Monomers and Solvent in Indoor Environments", Corporate Research Report, February 9, 1983), in which he modeled the air concentrations in rooms of solvents and monomers released from caulking material. He used the well-mixed assumption, citing several HVAC sources for support. He was primarily concerned with domestic environments where typically every effort is made to minimize air exchanges with the surroundings. In most manufacturing environments, effort is made to promote air exchange with the surrounding, thus leading to more forced convection currents and making the well-mixed assumption even more justifiable. The next level of complexity would be to define sub- ^ compartments, or zones, within a given total compartment, which are regions that are partially isolated from each other but still have some opportunity for air exchange. Examples of this are the so- & called "zone models" used in modeling transport of smoke from fires in multi-compartment buildings, where typically each compartment, or room, has two zones; an upper hot layer and a lower cool layer. The^' 8FG 49S6-NV 7/86 LITHO IN U S A. BFg40I2S well-mixed assumption is made for each layer, but mixing between the layers is assumed to be negligible (except for some well defined conditions). The volume of gas in each zone in a given compartment is computed from models for fire-driven (buoyant) flows. There is a slight analogy between the smoke transport models and the release of VCM from PVC during processing in that most of the VCM is probably released in areas of the process where the PVC is hot. Thus, a hot buoyant plume, transporting released VCM, would tend to form above the process. If this was relatively undisturbed, it would form a hot layer at the top of the compartment which would then contain most of the released VCM. However, it is likely that the temperature is not high enough to give enough energy to the plume to overcome the forced convection currents that exist in most manufacturing environments; thus, the plume would be dispersed before it could form a distinct "hot zone" at the top of the compartment. However, there could be local areas where this might be a consideration. For example, as we were touring the PVC compounding building at ALGC on 1/12/93, at one point we were on a mezzanine above a hot extruder machine. Molten PVC was exposed to the air as it went into the machine. There was also a partial ceiling above the mezzanine. It was distinctly warmer on the mezzanine than on the floor level where the machine was; you could feel a rather sharp thermal gradient as you came down the stairs. In a situation like that, if VCM is being released from the molten PVC it is likely that it would be concentrated in the hot air at the mezzanine level. Anyone in that area might be exposed to a concentration much higher than the average concentration in the whole room. In fact, warm zones like that above processing equipment are probably a pretty good tip-off to likely places to look for higher concentration levels as well, since the mechanisms for dispersion of temperature and concentration differences are similar. Local zones like this could probably be modeled to give at least a ball-park estimate of what the VCM concentration levels might be, but the correction for a situation like that is obvious; i.e., local forced convection near the extruder to break up that hot plume. The last level of modeling complexity would be to use computational fluid dynamics to compute in detail the velocity, temperature and concentration profiles existing in the room, or some part of the room. This would only be appropriate for looking at one specific case in which the results are deemed to be very important (e.g., a litigation case). It would not produce general results which could be used to establish guidelines. Distribution: RVCM Label Team F.M.Galloway & ft? AJ bFG40129 4 FIELO POINT OR OEPT. & SLOG.AfO. RICHARD J. KRUSZYNSKI CLEVELAND D/5401 (RdK-061-75) SUBJECT ' " OSHA - NIOSH - EPA 2nd Quarter, 1975 Update This report is presented as a quarterly effort to keep the plastics group informed of current activities in product-related environmental affairs. OSHA-NIOSH: Well, April 1st, 1975 came, April 1st 1975 saw and April 1st, 1975 finally conquered. The new OSHA guidelines have been set and it looks like they're here to stay. Within the past few weeks, the Supreme Court refused to hear an appeal from plastics industry representatives who attempted to have the Occupational Safety and Health Administration standards for employee exposure to vinyl chloride monomer eliminated. Many new inroads have taken place by the B.F.Goodrich Chemical Co. in regards to lowering residual vinyl chloride monomer levels of our resins. Although the levels have been reduced drastically in. most of the resins, these changes are being related to compound problems that are occurring in our customers' plants. These problems are being studied and, hopefully, a quick solution can be worked out. In my last quarterly report, I discussed our Bag Labeling Program and our objective to obtain "Real World Data.." The objective of the Bag Labeling Committee was to collect enough data from customers' plants and laboratory testing so as to obtain an exclusion from OSHA in regards to elimination of the PVC warning stickers from bags and boxes of compound and resin. Our program has just been completed. The results of our monitoring programs and lab testing are now being compiled. Jerry Cohan will write up the formal report and this will then be forwarded to OSHA for review. I have included a copy of a rough summary of sampling results. .The data that has been taken from our customers' operations shows that 49 out of 52 static or area samples showed levels that were either non-detectable or within the OSHA "action level" of 0.50 ppm. Our lower limit of detection at our Avon Lake Labs is 0.01 ppm. The remaining three area samples that showed higher levels of AVCM were taken in areas where direct workmen's breathing zones were not involved. Another plus factor is that all 42 personal samples taken f ellCwithin. the OSHA "action level" and in most cases, were less than our lower limit of detection of 0.01 ppm. j/m uitto u BFG40130 DISTRIBUTION PAGE 2 JULY 8, 1975 Envoronmental Protection Agency As was stated in my first quarter report, the primary concern of EPA is to develop an air emissions standard for vinyl chloride. It was originally reported that EPA intended to publish the proposed standard by June 20, 1975 in the Federal Register. However, as of this writing (July 8, 1975), the proposed standard has not been published. Perhaps the final standard will be pushed up a bit also. This is the only plastics related EPA information that I have to report at the present time. My next report in Fall of 1975, should contain the results of OSHA's actions regarding our Bag Labeling Program. Also, more definite state ments regarding EPA's actions should be available. RJK:cj s cc: JJS/GRT/DAP/WTR RJJ/DLA/RJA JDT/BFT/TAG File BFG40131 If -H .1 - ; TITLE I , .-- *... I I II. 1>. I-. vjO^JI.'mi.j l i.UiVil'Atn `III SKETCl-i S _ A M D COMPUTATIONS!U- Ii I` V, I!_ 'A ! .ion mo. -A--------------4--\J>\--^~da3t^7~ Tm-A in with |U .mnltr oJw.l, nml fslth nntnvA.. nnrn.,n. 'tin (ollCs.. o! ! . ^! I ^ ! o ; <V ....! Y V. 'I :X... M..... u 4- ^Q ^_ ..... or|" :i f- +*m--\-----<0 --- . I.. -i L it i it 11 ea !>) 10 li ZiZuL. ...! L- TITLE iI . _ _ i. SKETCHES AND COMPUTATIONS1 i i ........ ' i r" * " r' i - i - i i \ _SL T T -aL. 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J* !$ ' ! \i # '7 t~r-i-7'l''rs 4 1II ..-L.L'- ..!. !$ I. 3 ! 4-:.............L.pi\Z.i til 7: v w^ y mV ^ ^f*ii rI 5ai a! s ?? sq! Vj t: rf &$ ' d 5' V) A *!,! -1 N* ! * ' --4l \ V <0 -- .....;i" w^r --j-y*- -lit VVi '4 `... ' 5 ' : Ki i :I t .(<J V- I <5------X_ V I V 4 't\ ft- IS 1 \43l1u:j._.--_1--LLua {4--a-)X(-- t -V* ! r;n n.nJ' 3 -,-- L ._ i--i_j iI TXi J- 7^ 1% !| i JJ..u. -v x! !- !- ..V ;...... - - .....j"^{ - ') i '7) fXn.: %M* n vi;.... d) Xi \ ^ ' cd 'Tl oo-p* u> 4^ i\Cll TITLE Tl-ll: I). F. GOOlMvlCI I COA\l>ANY I SKETCHES AND COMPUTATIONS I T i H TTTT.fr~r .......... jT ..H_ 4 3'" n? ~>k^i fii Ti --L$L_l^l*LjvAMJV .LJ date, . T\in - l, oA,l, Vol., ,o I},..,. ^TaIoMow'. Jl . j \r ^\ j jv j$h Vi v \m !.....L.....I I. -I- I L I .1 b >>> < V..... t r~fc:-- i ii n1 fr \ -V s, 'f> n~ ,VH5. ---,-v----- I vc- MATERIAL balance APPENDIX-- SUSPENSION RESIN - POWDER COMOPNPTNG AIR \ ROOM VCM ' AIRN, VCM' ASSUMPTIONS 1. Complete mixing of VCM-Air in room. 2. 1# mol VCM = 359 cu. at room T, P. ft V dc_ = Q (cln - cout) ct cout = cln + (ct.0 - cln) exp (rQt) c,.0 = 0 (V) Cout^Ci. (1 - exp (rt)) ( V) B416/Lab 103 V = 6021 CU ft Q = 100 cfm, 1 volume change air per hour. Cin= 55t cmpd/ 0.85# resin / (103-45)1 VCM iMol 359scf Min Hr hr f cmpd 10`#resin 62.5IVCM / #Mol / lOOcf air / 60 Min 2.60 ppm 2.60 (1 - exp (-loot) (6021 ) t/min} 0 30 60 90 120 CoutlEEHLi 0 1.02 1.64 2.01 2.24 &FG40143 k] % o CO DISPERSION ~ PLASTISOL FUSION AIR __ N ROOM VCM ^ AIR> VCM V_dc_ = QiCi - Q0c0 = QfCi - c0) dt ASSUMPTIONS 1. 1# mol VCM cu ft @ room T,P. 2 . Complete mixing of air- VCM in room. cout = ctn + (ct.0 - cln) exp (-fit ) <=t-0 =0 (V ) Gout = cln(l - exp (-Qt ) (V ) B413/Lab 115 V = 4743 cu ft Q = 80 cfm, 1 volume change air per hour. RVCM = 38PPM, VCM released by plastisol during compounding 1ST HOUR 38# VCM 960*2 g Plastisol/ #Mol / 359scf/ Min Hr 10s# Plast-1 hr] 453.6g/ 62.5#/ #Mol /80cf air / 60 min = 0.192ppm VCM cout = 0.192 (l - exp r-80t1 ) [4743] t(min) 0 30 CputlPEffl) 0 0.076 60 0.122 2ND HOUR [ct.0 = -122] RVCM =67 cout = clB + [.12 2 - cin]exp(rM) (4743) c in 67 #VCM 960*2g plast/ # 10s# plast 453.6g #Mol 359scf / Min Hr 62.5# #Mol / 80 cfm 60 Min = 0.339 ppm VCM f.: a? C3 0 1A <0 BFG40144 Couc = 0.339 + [.122 - . 339)exp(-80t) (4743) = 0.339 - 0.217eXP f-80t) (4743) t (min) 0 30 g,,,. (ppm) .260 .157 3RD HOUR li/2 h9r). cout = clB + (ct.0 - cin) exp (z) cln= 0 (V) cout = 0.260exp (-80t) (4743) t (min). 0 30 CputfPPP) .260 .157 BFG40145 r,T K- G* cn t., o