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) m Our date 1975-10-14 Ynur data Our rot. Osten Levin/UT Your ref. CL. Mr A. Ross Adams Air Products and Chemicals, Inc. 5 Executive Hall Building 656 E. Swedesford Road WAYNE PA 19087 USA Dear Mr Adams, { 10 ^ cuM ~\o ItM * ^6 Jr l u^ Jl VINYL CHLORIDE As promised at our meeting in Stockholm I forward to you a copy of the report sent to the Commission on Food Contaminants. Presently, I am in access only of the names of the members of this committee, would it be possible for me to identify the U.S. delegate on it later on I will inform you. Yours sincerely, Osten Levin / f. SPI- 10227 ] OPapplied chemistry division Cr.; i on cn Foad Cont ..minants Project No. 1: Collection of information on Food Contaminants derived from Food Packaging Part 1: Vinyl Chloride in the Packaging Material 1) Introduction During 1973 increasing concern was expressed about possible carcinogenic and other effects of vinyl chloride (VC). The practical imnj. ir.ations include n) the health of industrial workers exposed to VC during manufacture and processing of PVC, b) the migration of VC, whose presence in PVC has been uriequivocally demonstrated, into the atmosphere during processing, c) the migration of VC into food and drink packaged in PVC containers. A careful literature search over the last years revealed that most interest has been given to occupational hazards (points a and b) whereas data onnon-occupational exposure (point c) are relatively scarce. According to the objective of the project this report deals exclusively with VC in packaging materials and its migration into the packed 'ocdsiuifs. / SPI- 10228 2 Most of the data given in this report emerged from investigations performed in the author's laboratory and have not been published up till now. To enable a reasonable interpretation of the data the methods for analysis are described in detail. 2) VC in the packaging material In a technical report of VHO (l) the content of VC in food packaging material was summarized as follows: a) bottles generally contain less than 100 ppm and a level below ppm is now more usually observed, b) rigid film generally contains less than 10 ppm and a level of less than 1 ppm is often observed, .c) flexible film generally contains less than 1 ppm and a level below 0,2 ppm is usually observed. According to our analyses we observed three periods depending on the effort the manufacturer have undertaken to decrease the VC content.. .1. PVC-films of forner production charges (l. period) In the investigation of 80 PVC-filr of former production charges (up till approx. June 1974) the fre uency distribution of the VCcontent was found to be as shown in the following table. As can be seen from this table, the VC-conte:.. mostly varied between 200 and ^ 400 ppm. These PVC-films were made o' raw materials with high VCconcentrations. Sometimes VC-concentrations of more than 1000 ppm were found in powdered PVC. SPI- 10229 / 1 2. i'l nx iional stage (2. period) Immediately after discussions about the possibility of monomeric VC being detrimental to health had started, considerable efforts were made on the part of the PVC-processing industry to reduce the VC-content of PVC-films drastically. In Fig. 1 the reduction of the VC-content during processing is illustrated, starting from powdered PVC with a VC-content of over 1100 ppm. By hot mixing at different temperatures (50, 75 or 100C), cold-mixing, extrusion and in the film-making process the VC-content of the final product can be reduced to 85, 30 and 15 Ppm respectively. This confirms the finding of the Verband Kuhststofforzeugendo Industrie e.V. (2) that increased processing temperatures reduce the VC-content of PVC. During the transitional stage FYC-films were made, containing generally less than 50 ppm VC am' >nly in exceptional cases up to 100 ppm VC. At. the same time successful attempts were made by the PVC-menufacturing industry to aCc'.re the VC-content in the PVC starting materials. As can be seen from the next table, it was row possible for the processing industry to use powdered PVC containing lesi than j>0 ppm VC. SPI- 10230 X I C V'('.ronlt of PVC-powdors VC-cnn tent [ppj Number of neasu rement 3 < 20 17 20-50 7 50-100 4 ;> 10O 1 PVC-films with a low VC-content (3 period) c After all the difficulties had been surmounted, it was now possible to make PVC-films with a low VC-content. Of the charges produced between December 197** and Hay 1975 a total number of 776 films were C analysed. With a few exceptions the VC-concentrations were less than 5 PP. VC-content of recently produced PVC-films VC-content [ppm] Number of films <0.1 380 0 rS 1 O 308 1.1-2.0 2.1-5.0 5.1-10 53 32 3 From these values it is obvious that the PVC manufacturing and processing industries have made great efforts to reduce the VCcontent ol" their products and that the production of PVC-films with VC-concentrations ^10 ppra is now technically feasible. 3 Migration of VC into simulants and packed goods 3.1. Simulants To investigate the relationship between the VC-concentration in the packaging material and the VC-cor. out in the packed product, a;r,r:.!.io tests were carried out -sing the synthetic fat simulant i!P 307 lift 307 is a mixture of ynthetic triglycerides. The SPI- 10231 /... ) V. in i and dof 3 n> cc.rjo In .m is delivered by: bosII;'! Jiir i:su. >- < ii.-.i: in i t \ 3 ch-techni sche Dienste n'.bii, Hit i-'imul f-ti ' h'B 3'.' -1 tthe dcternination of tho migration of (.nck.i.ji ny material componen t into Catty food under standard condition* and with a high degiev of accuracy, The technique apnli.-n, I,-.:' l-<'cn i -<>>( t i i m detail by K. Kigge and J. Kocli (3). The table below shows the VC migration values for a PVC-film wi th a VC-c.ontent of 60 ppm at different temperatures (20C and 40C) as a function of ticn?.- Kroir. thc-se values it can be seen that during storage at 20C the VC content in the simulant increased continously. At 40C, however, the migration reaches a maximum, after which the VC content sLowly decreases again. VC-mioration from a PVC-film containing 60 ppm VC into HB 307 Storage tempera ture LM 2 VC- migration yUfl/dm 10 20 40 80 dnys days days days after 160 days VC-content of the film after 160 days [ppraj 20 5 8 15 29 45 40 18 29 60 57 51 14 0.7 2 In the calculation of the migration values (^ug/dra ) the following factors were taken into account: contact surface between PVC and simulant, weight of simulant and VC-content in simulant after storage. In the conversion of the migration values into the VC-content in the packed pr.>di!ct, the PVC-contact surface must be taken into account. Applying the rule of thumb that 1 kg is packed in 6 2 dm , the VC- con t c n t in the packed product stored at 20C for 80 days works out at 0.l8 ppm. The .following table and Pig. 2 show migration values for PYC-films contains di <~f erent VC-concentrations ( 10 days, 40C and 20 uays, ii SPI- 10232 c. (> VC-ml y r t i o n into I1B 't07 at 40C VC-content of the PVC-film [ppm] VC-rni gration [jig/dm^J after 10 days 20 days 1093 833 799 571 438 60 340 300 230 170 130 18 520 420 390 280 240 29 Especially from Fig. 2 it can be seen that a linear relationship exists between the VC content of the packaging material and the VC content in the fat simulant. For a given VC-lirait for the packed product the maximum permissable VC-concentration in the packaging material can be calculated from this relationship. Putting the life of a PVC-packed product at 8 veeks plus a margin of 4 weeks, the value for 80 days/20C (s. table) can be taken as a basis. Assuming the maximum permissable VCconcontretion in the packed product to be 1 ppm, ns recommended by Kunst sto f I komtni ssi on des Bundesg osundhel t samtes in Berlin, it can bo calculated that the packaging material must not contain more than 300 ppm. Jf the VC-limit for the packed product is, for instance, 0.05 ppm, the maximum permissable VC concentration in the packaging materiel is 15 ppm. Naturally, these values are only approximate values, as other factors, c.g. the contents/surface ratio, the wall thickness and hence the absolute VC-content in the packaging material also play a role. The results reported in this chapter have been published by 1'. k , :.t' -* ( ) . SPI- 10233 3 Food stuffs Only few data are available on the content of VC in food. After up to three year's rtorage in miniature PVC bottles, {jin and whisky contained 0,57 and 0,62 ppm of VC respectively (l). This led US Food and Drug Administration to the proposal to ban the use of PVC bottles for alcoholic beverages. The concentration of VC in orange squash and cooking oil have been found to be in the range of 0,01 to 0,08 ppm and 0,01 to 0,04 ppm respectively. Th^nj^jrati^nof^C^from^^VC^bojttljes^^^Jdhyjendeivt on the VC content of thebottle, the temperature and the duration of storage (l). 3.3. Hair care products Ve examined various hair cosmetics and the corresponding PVC packaging materials! Produe t Storage period at room temperature VC-content (ppm) Container 1 Filled product Shampoo A Shampoo B Shampoo C Shampoo D 30 weeks 30 weeks 30 weeks 5 months 51 44 15 162* 0. l4 O.56 0.08 0.6 Setting lotion 100 cc Setting lotion 19 cc Setting lotion V Setting lotion Y Setting lotion S Fon lotion 30 weeks 30 weeks 30 weeks 15 weeks 3 months 3 months 156 32 <1 l4l* 26* 2.8 0.25 <. 0.05 1.0 1.2 0.2 Hair conditioner A Hair conditioner B 30 weeks 30 weeks 31 18 0.24 0.37 during filling operation SPI- 10234 / * The measured values show a clear relationship between high VCcontent of the packaging and high VC-content in the packed product. Alcohol-based products were observed to absorb particularly large quantities of VC. 3.4. Rinsing agents The VC-contonts of different packed products were between 0.3 and 2,5 ppm. It should be considered that rinsing agents are used in dilutions of 1 t 100 with water - corresponding to VC-values of max. O.03 ppm. Product Storage period (weeks) VC-content (ppm) Household cleaner Dish washing fluid A 750 ml Dish washing fluid B 750 ml Rinsing fluid for automatic machines 35 0.4 19 1.1 24 0.3 17 0.3 31 2.2 31 2.5 21 1.0 29 1.0 29 1.3 20 1.6 20 2.0 Here we could only examine PVC-bottles pf another delivery: Values between 60 and 465 ppm VC were observed. 4. Methods A highly-sensitive method was required for the identification of VC. We decided to use the headspace technique and developed the following procedure in close accordance with the methods published by H. Puschmann (5) 4.1. Principle of the method For the investigation of PVC-products 10% solutions are prepared in closed injection flnsks. The solvent used is NtN-dimethyl acetamide (DMA) to wliioh about 20 ppm of diethyl ether have been added SPI- 10235 tin intern.il standard. These solutions are therraoxtated at 50c to establish the equilibrium. The subsequent gas chromatographic analysis of the ga3 phase is carried out with the GLC-automat Multifrakt K 40 (Perkin-Elmer). Packed goods are investigated analogously, whereby the ratio test material to solvent must be adapted for each packed good. 4.2. Reagents N,N-dimethyl acetamide, a.g., Merck diethyl ether, a.g., Merck vinyl chloride, 99.9^, Baker Chemicals Standard solution: Weigh 70 g of dimethyl acetamide into a 100-ml injection flask and add 140 mg of diethyl ether. Weigh exactly to 0.1 mg. Dilute this solution with dimethyl acetamide until the standard solution contains a defined amount of 2^ig ether /ml. Calibration solutions: Starting from a 0,2% solution of diethyl ether in DMA, calibration solutions with defined amounts of VC and ether are prepared by introduction of VC and subsequent dilution with DMA. 4.3. Preparation of samples Weigh 200 mg of PVC exactly to 0.1 mg into a 23-l injection- flask (accessories to F 40) and provide with a magnetic rod. Add 2 ml of standard solution with pipette and close flask immediately. Dissolve sample on a heatable magnetic stirrer while stirring vigorously. Finally the injection flask may be placed in a water o bath at about 60-70 C. As soon as all polymer parts are dissolved, o equilibrate the flask for JO min at 50 C in the water bath of the F 40. For the investigation of simulants or packed goods weigh 2 g of sample into injection flask anc! add 0.5 ml of standard solution. SPI- 10236 -10 C Add magnetic rod and close taut tuhn immcditly, Dissolve or homogenize xAuipl* in tho wurmth on a magnetic utirrur. Trans for ftftniplit to thormofitato of the F 40. Aftar JO min tho analysis can bo perfuratd. 4. Gas chromatographic conditions The gas chromatographic analysis is carried out with the Multifrakt F 40. Up to 30 samples are placed in the sample changer thermostate at 50C. After the equilibration time of 30 min, the analysis cycle is started. Instrument conditions on F 40: vater thermostate dosing line dosing time time of analysis blowing time re-entrance time column column temperature carrier gas retention times 50C 150C 5s 8 min (VC in PVC) 0,5 min 0,5 min high-grade steel tube, 4 m in length, 2 mm int. diam., packed with 15% of Ucon LB 550-x on Chromosorb V-HP (100-120 mesh) 60C 20 ml N^/min 3.45 min for VC 5.20 for diethyl ether The chormatograms are evaluated quantitatively in a connected 3352-B data system (Hewlett-Packard). Under the conditions given the cycle time is 9 min. After 22 analyses, the automatic course of analysis must be interrupted and the column temperature increased to l80C to heat out the DMA. After this the oven temperature again is adjusted to 60C and the automatic course of analysis restarted for further samples. The time of interruption due to heating-out is approx. 45 min. This SPI- 10237 PVC. In the determination of VC in packed goods longer times of analysis (up to 20 min) must be taken into consideration since some of these products contain easily volatile components which may influence the course of analysis constderably. .5. Determination of the calibration factors * For the determination of the calibration factors volumes of 2 ml of the calibration solutions arc placed in injections flasks and closed. The flasks are equilibrated in the F 40 and analysed under the conditions described above. The calibration factor F is calculated according to F AST .. cvc ____________ CS__T . VC AST peak area ether =* peak area VC Q ST "concentration ether (internal standard) CVC " concentration VC The instrument-dependent calibration factor was determined to F " 0.85 By addition of 200 mg of VC-free PVC to the calibration solutions it was ascertained that dissolved PVC does not influence the factor. The calibration factor-only applies to the quantitative determination of VC in PVC. For the determination of VC in simulants or packed goods new calibration factors must be determined for each substrate because of the varying solubility of VC. Moreover, it has to be ascertained that the samples under investigation do not show peaks interfering with the evaluation. This can be done by the analysis of samples which have not been in contact with PVC. SPI- 10238 The calculation in carried out according to AVC . F * CST ppm VC _________________________ ast The concentration for the standard the amount of the sample weighed in* is given in ppm, based on 4.7 Reproducibility of the method In order to check the reproducibility of the method, two scries of measurements were carried out. In each case we analysed 12 PVCbottles of the same batch. 1st series of measurements (Batch l) single values: 7*0 7*0 6.6 6.8 7.0 7*3 6.9 7.3 7.0 7.1 7.2 6.6 ppm VC mean value: 7.0 ^ 0.23 PPm 2nd series of measurements (Batch 2) single values: 0.62 0.56 0.57 0.60 O.58 O.57 0.55 0.57 O.58 O.56 0.6l 0.60 ppm VC mean value: O.58 + 0.022 ppm VC 4.8. Reference analyses Basing on two examples it shall be shown, in how far the analytical results of different laboratories are in agreement. Example 1: From Van den, Bergh + Jurgens Ltd., Purfleet, Great Britain, we obtained PVC-bottles ex I.C.I. The results of analysis are I.C.I.: our laboratory : 1.5 ppm VC 1.4 ppm VC SPI- 10239 S Example 2: Two batches of PVC powder ex Cheraische Werke Hills, Germany (CVH) were analysed at CVH and in our laboratory. The following values were ob tainod: Batch 1 2 Content of VC (ppm) CV11 our laboratory 01 93 4l 37 Since VC is an easily volatile substance, these differences in case of PVC powders can be explained already by different periods of sample preparation. 4.9* Detection limits The detection limit of the method for VC in PVC-powders and PVCpackaging materials is o.l ppm. In simulants and packed goods the detection limits depend on the substrate. VC-contonts as low as 0.01 ppm con still be identified accurately in simulants. 5 Conclusions On 26 March 1974 a group of European toxicologists discussed the available toxicological and migration data on VC, with special reference to its carcinogenic potential. The meeting was held at the National Institute of Public Health, Bilthoven, The Netherlands. As far as the problem of VC in packaging material is concerned the following conclusions were reached and agreed unanimously: "At the present time there is io need to recommend that PVC should be banned as a food-wrapping material. The basis of this conclusion is that relatively high concentrations of VC (by inhalation) are 1needed to produce a carcinogenic effect. In comparison,the exposure of man from food intake is probably much lower. The further quantitation of this factor will be possible when oral studies on VC have been completed. Furthermore, it was noted that even Ipss / SPI- 10240 14 C~ toxicological data woreavailable on possible alternative plastics for food wrappings* It was thought desirable and possible that PVC used for food and drink packaging should contain less than 20 ppm VC monomer. In effect this represents the establishment of a food grade of PVC, to ensure very low levels of contamination." (6) In their 57th meeting the "Kunststoff-Kommission" of the"Bundesgesundheitfcarat" in Germany declared that there is no evidence of any health hazard after consumption of food stuffs packed in PVC containers. In September 1974 90 days feeding trials, undertaken by the Dutch Zentralinstitut fur Ernahrungsforschung (CIVO-TNO) have been finished, whereby considerably higher amounts of VC have been applied orally than ever can be expected in food stuffs having had a contact with PVC. No toxicity was observed. Therefore the oral uptake of traces of VC in food stuffs has to be considered in another way than uptake of VC via inhalation (2). The "Kunststoffkommission" has no objections if, as a precaution, the content of VC in food stuffs is limited to 1 ppm. The statement bases upon the feeding trials and the analytical results and may be changed after obtaining the results of long-term feeding experiments which have already been asked for (2). Hamburg, 29 July 1975 G Billek, V.R. Eckert u. C. Roloff Unilever Forschungsgesellschaft mbH Hamburg 50. Behringstrafle 154 SPI- 10241 t>. r-.T''nri.'.s 1. Internationa 1 Agency for Hesearch on Cancer, Internal Technical Report No. 74/005, "Report of Vorki ng >: >u;: on Vinyl Chloride", Lyon, June I 9'M 2. Verband Kunststofferzeugende Industrie e.V. " VC/PVC : MaAnahmen y um Gesundhe i tsschutz" , Krankfurt/M. , November 197/* (. 3. K. Figge and J. Koch, Fd. Cocmet. Toxicol. II.. 975 (1973). ( 4. W.R. Eckert, fettc, seifen. ans tri chtni t tel, in press. 5 H. Puschmann, "The analytical determination of the content of residual monomers in PVC and food simulants" lecture on the occasion of the PVC discussion meeting, Darmstadt, 26th/27th September, 197^* G. G.J. Esch and M.J. van Logten, Information Bulletin ll.I.B.Il.A. 246 (197^) . SPI- 10242 Fig 2 M i g ration of VC into fat si mu l a n t H B 3 i) 7 ( C dm 2 /) a c k a g in a a ro a / kg ) VC in simulant SPI- 10243 UJO ii )! I! 750- i 500- O'v . ! t a. Roc' U U I !' :/ of (he ,> / U lOjcC A A 75C L> ! * loo-i B c P'/f : inr; "H i co i r: f.lIXlPCj 3 (. >' 0 i Of) M SPI- 10244 ; - . ,i ffADLii V '- ` ^ Exporinante 11, B3f6 t Expocure by. in h a la tio n to VC in . a ir , a$ 3QiQ00; '10,000j 6,000} 2,500 500r 250, 50 ppm,, 4 ;h ro i: d a ily ^ J dayo^WQcicly, fp r. 5? wooko;! ` o r ^ t h e ^ e x p o r i m b n t o ) ^ ' ;` ' ` , nosulto p fto r 135 vrcokav(onA SPI- 10245 .*1) Host a ris in g from aobaceotio glands Kxporiment BT2. i Exnonuro by in h a la tio n to VO in a ir , a t 200, 150, 100 ppm,, 4 hours d a ily , 5 days weekly, f o r 52 weeks, n o ru ltB a f t e r -77 wooks, ' 07 rrl OO UO P 4^ "f", oc :* o Z P Cl U o to G ro r* po " o 5 ti < *> -:*4- - freo-4* *fc3H5 M * HX*oi3 1 acia'\ CO P Eo >--i g M Po. + a Z o z 1 ,.\v m i ;.r; .; i \ < tacl a d H6 OO C H> c o Z i aa hd N>>> c *. ** >i . . 9' a tr5C*3 \ . CO R--'O < Oi -ra? TJ Iu ChsO *S>H > Pi &p K a r-J 55 d <P 0*1 +cd .. o to fri - voD o OJ V t . , ' i. i < . . v* V* ;-V;- .. I :t V : V ' - -.r' ' 'V in . I co . A . 1. 1 * ' ' . . 1 *' * ' . # ' *\ r* * r * * "N . *w *" . - VO .VO seo**. VO t*- o t\ CoM .. . in CO T~ m in * m p o 5< ec-t ow + c a G5o p. p. P. p. p. M P, M M > Cl o M O MO H O o C\J LTV O P +> o > o > >O 3 -H O Exporiment Bt3 t Exposure by in h a la tio n to VC in > i r , a t 10,000; 6,000j 2,500j 500j Hom i 2/jO; lto a 50 fto r ppm., 103 4 hr wtoka s .( l )d.a i l y j 5 day? v/oekly, fo r 17 wooke A ",, t-" **. \\ SPI- 10247 1) Between brackota aro rooorded tho turaourn oboerved a f t e r 103 weeks anon^the Spra^uo-Dawloy ra ta , in tho experiment B it , in.w hioh tho animals woro tro a to d f o r 52 weeks, ' A; .. ,;:K' ,'rr-MW 'tw- Experiment DT7 't Expoouro by in h a la tio n to VO in a ir , a t 10,000 } 6,000} 2,500} 500} 250; 50 ppm,,1 4 hra, d a ily , 5 days weekly, f o r 52 weelca. ; D ra in neu 1 (2 ) 1 .(2 ) 1) Between brackoto aro recorded tho tumaura oboorved a fte r 77 weoka tuaonff a comparable croup o f male Spra'cue-Dawluy ra ta tro a to d in '*th o ecuno way ' l 0 + (Q d tfl --( ri x> u 0. u. ' O 1-4 T"J, }! tr\ 1 1 CM* ;*- a n- : cj rj tn n 33 0 0 o.a x+. ... # CM 9 ** H:H a 10 a O l P0 cl O i*4 --0 u 0 6- s > M < T+ . O '? * .. iS >? 55 no -T*+ : T" CM CM . CM > - 1 I " ; : * TTM __ r . r .- .'l . CM T" '. 4-. I .-; 1 "I ,' ,-vv " ;: 1 -1--u ITV CO c- CO tB d} . ' -* i. . s H -Q n H Om ^4 E < x; 0 ' p. +* ro * -* O CM j-* . *', T~ - *-jj* - * . 0a 55 CM i 1 f- . \ 1 '* - ' * tJ fj 20 1--4 c3 to a O CM CM a- -- -- ___ ir\ Hc 0 a H & 11 1 11 1 t1 a> 0 U 5* d NO .i.... . < : ua + 0 1u . . < . > a c O 4* 01 d 1-3 P - 0 3> CO -H > c- C*" O rn CM . nr* * b VO CM m CD -V . / <* 3 U a O C c 55 + # < 0* H r-4 +* 00O rn m r0n 0 m O rn 0O *rr C.' O Ci H * Eh to P-4 e O < E-t p: < Ow * e er~- E PP aZU E p. Pi E P P. a p +0+ 0 C OMO 0 O 0 ME c MO 1 O r> O ITN PH l:~> >--1 4^ m 0 M O /H pH UD > CM > > r; O O T-- VO c. O 0 CD O O >> >> O > ri - G +-> O EH gpi-10248 . , -v V^ ' *' !r"Vir"7*,?.rv: 7- yr.--*. 1 ': ` /_*: , * .* '' ;;r: : v v.v: , - i ~ /. > . .. ' a a iOt o O'8 *.. ... O o.. Vi IS . , ;;:V ... .. v.*V-:?.^-**"vs** . . y* - TADLB 5 u iH O -I;;. cc sd Cri ** C V.y o- oDU . > fc. p. - 4? 4o* Vi 4T O Q c - >.* oado rl + U o *d o fc cS r-* og *+*5 <r- w J= 5L CrO rr c rl Vi O O 4* O > + .Q X Vi ed c S^. CM Si P.r- C pU O 4s E i--I o00 3 a O (4 13 X ~ r4 a VO---' X m S 4 4S3 a rl a X M * 'v ' sVim-iiv.*-*. *. -4*.vryj. ' ' .'V/ > ,> . ' '*;A ' ' \Y 1 y' . ; ,./> - s' \* . ' .. V r'; .V . .-AA ' ' V ' '' . -.i ' ; *;;,;1 .> n d % CO E a 0 O .c + o 4* -H UO e a C3 in -*O-? c tl oc o< 5 Sr* % O > H 1 64 .d rH - '. : M 42 a Od CO |J <vrj M >4 6 0 pc.+a S O O SC '# O S5 < 0B^ a sE to O cH d ts 4: 1 d0 N O S % -l 5 d n CO 3 y<y O1 *5 a + 0d Mdu 20 S4 <A CO ra 1 >4 0 d> CO > t-* +d 0 H * 1H 00 wi^t &5 F r1H 0 C3 O < w1 V> 1H ' .. ' . . r. : / *'. '' 1 A?'''.. '>V.V \x 1 T*- * \ .s ... i - .: ; 1 : .t'UV-''v'. - 1 . . .... j : . , CM ' I S i.-.- I-,' ' : ` ' * ;- . 1 -V": iv 1 **. . r : ' - ' > 1 ' 1 /,,. i } * .- - . 1F" 1 CM r- . * . .. .. . ' l ' " 11 O CM nO O m in CM m m a6Ge A A A <0 A A O A O a t: c F-t; c O^ O0 n O T3 >0 OU !H O CJ H O T3 1u M O -rl i-t O 1. <~* O- n1'- O-H >1--1oO>AL.T O CJ T- U VO 0 u O Vi T- >1 VO vA a0 OO 00OO > > 3- > 1 1 r *, b VO ^r* rl d + 0 (H -y . -1 7. -~f. : SPI- 10249 TABLE 6 SPI- 10250 o o m Oa o m - CM o 8o u -o to Vi O^ *. o OO ** * * B " S' cj n 4X ; o3 > 3 O 4 ao C .t< o o X Jtf <H 4 ** O U jB f-l fl.ON jc Vi rc H - S : 0 > E + .C pP.. Vai oa in +* OO' P' S X If* o K, CM (X, E-l . 5 u o 1) o f which w ith squomoua mo.taplaoia SPI- 10251 2) Souo a r is in g from uobaocoun glandii. o irv OJ Oo wv o o ICY a. O. Oo a ': ** -sc VO O - O'.-' \ * " O O-A:' o *n cT ` *- o -- += Cj ' , ->^` I* H -r CJ O o C Q i4 n' M ft i i + in- C -O O >* H -r t4 O d d s. 3 V i H . JS C (4 a oo .c c o o 0a a rt d (3 E O 0*3 C -aH.rH-i CJ= C-H On-* O Si ft - Cl O ci O t-P. cs o 5 c-t o o ar H ft S5 hJ fit u XI ct s8 o . CJ1 o CM Ci o 44 ti rJ o P. > O . , CS C. a ,,C *1 d o o g -r> Z 3o >4 . w 3C (0 el u1- rt a r.d CJ b* no oc fc-H P o .i. in CM . f .... CM HI o 5E < H o a o 1a 2g O , a u E f* C C-H = CH -C*1+-w cC:J JS ft t3 00 jo c z fcl fcc.ct3 a >Ot3 in CM . . ' ir I .1 *1 . ; CM CM in CM II VO tn o CM CM SPI- 10252 10/14/75 fit!L W DRAFT NO. 2 TECHNICAL SUBCOMMITTEE TO SPI VC/PVC STEERING COMMITTEE WORKING OUTLINE ON VINYL CHLORIDE POLYMERS FOR FOOD PACKAGING 1. We start our work with the firm belief that vinyl chloride polymers^that contain less than one^ppm residual vinyl chloride present no health hazard when used in food pack aging. However, because of the Delaney Amendment, there are only two pertinent arguments to the proposed FDA regulation. 1.1 There is no reasonable expectation that VCM will be- come a component of food, i.e., that it is not a food additive. -t ^ or 1.2 That VCM has not been found to induce cancer in man or animals by tests appropriate for the evaluation of 0 cdJU^* ^ fcT ..... / ,food additives ll) I, ( Our .committee will not, therefore, work on subjects like ^ economic impact, improvements vis-a-vis earlier products, r-] etc. unless we get new inputs from the steering committee or someone else. 2. Industry should submit data to prove that food contact applications of vinyl chloride polymers (film, sheet, bottle/rigid, semi-rigid, flexible/plasticized, unplasti cized) do not present a reasonable expectation of vinyl chloride migration. SPI- 10253 2 2.1 The primary basis of this submission should be data on improved polymers, compounds or fabricated products which contain such small quantities of monomer that one can demonstrate by theoretical calculations, that 100 percent migration would result in only 20 ppb in food. Because the theoretical calculations are exag gerated, much lower levels would occur under actual conditions, to the point where there is no reasonable expectation of migration (see p. 4053 of Fed. Register, September 3, 1975). 2.2 Supplementing this primary basis would be. 2.21 Theoretical calculations correlating monomer concentrations in polymers, compounds or fab ricated products to maximum possible migration using conservative mass to mass assumptions. 2.22 Supplemental information demonstrating a multi plicity of reasons that the maximum theoretical migration will not ocour. 2.221 Migration into the air rather than into the food. 2.2211 Initial equilibrium between airpolymer-food . 2.2212 Ultimate relationship as level SPI- 10254 3t of monomer in polymer becomes lower than level of monomer in food - ultimate effect no mono mer in food or polymer. \ 2.222 Kinetics of migration vs. monomer con centration showing that rate of migration from low monomer in polymer concentra tions are so slow (months, years?) that concentration in food simulating solvents would not approach theoretical in any practical time. This could be supplemented if the rates of diffusion into air were not as monomer in polymer concentration dependent. 2.23 Demonstration of non-linear partitioning of VCM from polymer to food simulating solvents when initial concentrations of monomer are low (a la Gilbert). 2.24 Analytical studies which demonstrate that there is no detectable migration (at sensitivities of 20 and 2 ppb) of vinyl chloride into food simu lating solvents from improved polymers, com pounds or fabricated products. 2.241 Supplementing these data will be a re view of the safety factors built into SPI- 10255 C 4 the FDA testing procedures for possible migration (food simulating solvents, time, temperature, no air interface, etc.). 2.3 Corollary to this submission, industry should propose that FDA revise their proposed regulation to confirm the prior sanction status of vinyl chloride polymers, compounds and fabricated products that do not cause any detectable migration of monomer into food simu lating solvents by a test method sensitive to 20 ppb. This sensitivity is appropriate because: 2.31 VCM has not been shown to induce cancer when injested by man or animal (outside the laboratory) . 2.32 VCM has not been shown to induce cancer in man or animals by tests appropriate fpr the evalua tion of the safety of food additives. 2.321 Statistics of effect levels 2.322 Gavage technique. 2.323 Appropriateness of high dose levels. 2.324 Threshhold and secondary carcinogen postulate. 2.325 No effect dose levels. 2.326 Rat vs. man. SPI- 10256 a 5 2.327 Definition of cancer when Delaney was enacted (1958). 2.33 Even if, all food were packaged in PVC all PVC for food packaging contained 0.2 0.4 ppm (??) of VCM all the VCM went into the food all food contained 20 ppb of VCM there would still be a 10,000 fold safety factor over the no effect levels indicated by lifetime feeding studies and by preliminary metabolic studies. 2.34 Traditional safety factors used for known poi sons are 100 to 1000 when no effect levels are based on lifetime feeding studies. Thus, use of safety factors in excess of 10,000 would not be appropriate. 2,4 Further, the FDA should place no restriction on the technique by which this low capability to migrate is obtained. 2.41 The FDA should not specify monomer levels in polymers, compounds or fabricated products. SPI- 10257 6 2.411 SPI should not concede product standards setting authority to FDA. 2.412 Someone may discover a technique to prevent residual monomer from being extracted by foods or food simulating solvents. 2.42 The FDA should not specify techniques - like plasticizers, compounding, etc. Requisite results should be defined with industry given the freedon to effect the result by a variety of techniques. 2.421 Plasticizing is not necessary to get down to low monomer levels in certain copolymers of vinyl chloride. 2.422 New techniques may be discovered to achieve the same effect with homo polymers (or trace copolymers). 2.5 Arguments can be presented [a la the Barnes Aide Memoire - part l.(d)) that discusses a need for a detectable level (say 10 ppb) that could be used as a control while assuring that 20 ppb is never exceeded. SPI- 10258