Document jBzgBdYk72y7nrg7bLEVwqzaQ

uc 1-J9-: Vc. - fOA INTERNAL CORRESPONDENCE RECEIVED NOV 7 1977 R, N, WHFFl FR; ^ CHEMICALS AND PLASTICS To (Nanel Division Location Dr. F. G. Willeboordse Chemicals & Plastics Bound Brook, N.J. cooyio Mr. R. W. Annonio - NY Dr. J. J. Brezinski - SC Dr. L. E. Brydia - BB Mr. A. E.Gabany - SC Ms. O. M. Garty - BB Dr. R.A. Gregory - BB Mr. R. W. Lasher - NY Mr. N. H. Re inking - BB Mr. W. I. Wertz - BB ^r. R. N. Wheeler - SC RIVER ROAD, BOUND BROOK, NEW JERSEY 08805 Originating Dept. November 2 , 1977 R &D Answering letter date su&>t Analysis of VCM in PVC Resins Attached is a copy of an analytical procedure for residual VCM in PVC resins sensitive to about 1 ppb which was developed by the FDA. It is quite possible that this may appear as a resin specification in the PVC regulation which is said to be coming out shortly (after two years incubation). We suggest that representative solvent vinyl resins and/or cured coatings be examined for residual VCM by this method so that we do not have any unpleasant surprises later. Very truly yours, WBA/bhm Att. /O $ W. B. Ackart TTpp 030798 JOSEPH E HELLER JEHOME fi HECENAN CHARLES K MEEHAN WILLIAM H BOBOHESANI, J*. EOBEHt B TIKHNAN WAYNE V BLACH DAVID L. HIUmartin W BEBCOVICI PETER M KEMKOV JOSEPH E HAD LET, JB CA BOLE C HaHEIS PETZH THOMAS SMITH MICHAEL T MOB BONE 1ABHT S SOLOMON JOHN B DUBECK CHRISTINE A MEAOHEB 5H!RLEv 5 *UJJM0T0 LAW OTT3CE5 Kei/leb and Heckman 1150 ir STREET, M. * SUITE IOOO Washington, d c. aooae October 24, 1977 TELEPHONE 803 4*7- llOO Cable address eelman' WRITERS DIRECT DIAL NUMBER 202/457-1110 No. 35 To: All members of SPI-VCM/PVC Mailing Lists Letter Highlights (1) The Food and Drug Administration has provided a preliminary, unofficial draft of an analytical procedure which it has developed for the determination of residual vinyl chloride (RVCM) in polyvinyl chloride (PVC) plastics. The analytical procedure has a claimed lower detection limit of * approximately one part per billion (ppb) in the plastic. Residual vinyl chloride levels ranging from fractional parts per billion (estimated) to the low ppb range were reported for a variety of plasticized PVC packaging materials. (2) FDA Commissioner Kennedy has stated that the Environmental Protection Agency (EPA) ought to exercise regulatory authority over public water systems and should exercise responsibility for the safety of tap water provided by public water systems. A formal agreement with EPA to this effect would place regulatory juris diction of PVC potable water pipe completely under EPA. zdies and Gentlemen: The purpose of this letter is to report on two matters relative to the Food and Drug Administration's (FDA) posture regarding polyvinyl chloride plastics. Activities of other agencies will be the subject of another report. ucc 030799 October 24, 1977 Page Two Analytical Procedure for Residual Vinyl Chloride We have previously informed you that PDA had been developing an analytical procedure for the determination of RVCM in polyvinyl chloride food-contact plastics with a claimed lower detection limit near 1 ppb. we have now obtained a preliminary draft version of this procedure and, despite its acknowledged preliminary and unofficial status, we are distributing copies with this letter because of the liklihood of widespread interest in the subject. In addition to a description of the methodology, the report includes the results of analyses conducted on a variety of PVC packag ing materials; RVCM levels ranging from fractional ppb (estimated) to low ppb concentrations were reported even for plasticized films. The report further indicates that the presence of vinyl chloride in these samples was con firmed by mass spectroscopy. Briefly, the new procedure involves the dissolution of the PVC sample in dimethylacetamide (DMAC), sparging the solution so obtained with a stream of helium to volatilize any vinyl chloride obtained in the sample, absorbing the volatilized vinyl chloride in ethanol at dry ice-acetone temperatures, and finally analyzing the ethanol containing the vinyl chloride by means of a headspace procedure utilizing a gas chromatograph with a flame ionization detector. Although we have not learned enough from our PDA contacts to draw any firm conclusions as to what FDA will do with regard to its final PVC Regulations in light of the development of this methodology, the possibility of strict application of the considerations set forth in the recent acrylonitrile beverage container decision when viewed in the context of the reported detection of vinyl chloride in all the samples listed in the FDA report indicates the need for close attention to this area of regulatory activity. PVC Potable Water Pipe Many of you will recall that FDA had proposed (Sep tember 19, 1975) that PVC water pipe be the subject of an Interim Food Additive Regulation until questions regarding the possible migration of vinyl chloride to potable water had been resolved. In Comments filed by The Society of October 24, 1977 Page Three the Plastics Industry, Inc., the argument was presented that responsibility for public water systems including the regulation of potable water pipe had been assigned by Congress to EPA and that, therefore, the proposed Interim Regulation was beyond the scope of FDA's authority. Shortly thereafter, an Inter-Agency Task Force was set up to resolve the jurisdictional question between FDA and EPA in this and a number of other areas of potential overlap of jurisdiction; however, no final memorandum of understanding has ever been issued despite reported staff agreement that the regulation of PVC potable water pipe should be an EPA responsibility. More recently, we reported that EPA Administrator Costle had asserted that this regulatory area was one assigned to EPA. Now we are enclosing (with the permission of the editor) reproductions of pages 18-20 from the October 17, 1977 issue of Food Chemical News which indicates that Commis sioner Kennedy is likewise in agreement that regulation to assure the safety of public water systems is an EPA responsibility. This report is particularly encouraging at this time since it is generally understood that the Bureau of Foods is making plans to reach some final decision on the long-pending proposed PVC rule making and will begin the preparation of a final Regulation in the "near future." We will continue to follow these and related develop ments and will report to you as fully and promptly as we can. In the meantime, if you have any questions, do not hesitate to contact us. ucc 030801 FOR REVIEW ONLY i So not clto or reprint. Beturn ms and revlw* within 21 days. TM- f.-termination enj Confirmation of > Polyvinyl Chloride Food Packaging pph Residual Vinyl Chloride In J. LA.ttEhCr OENMlSu-i, CHARLES V. BREDFR, T^XJTHY KtHEAL, ROGER C.jSNYDER, A. ROACH AND JAISS A. SPUON Division of Chemistry and Physics, Bureau of Foods, Food and Drug; Administration, Washington, 20204 ABSTRACT Tie uottr,-1 nation and conftnoatlon of rekldu&l vinyl chloride JVC) polyvinyl chloride (PVC) food packaging Mterials 1$ described PVC pacfcagir.j '.oterlals re dissolved In dliuethylacetaaide (OhACj. VC is sparged frou solution with helium gis ejnd collected In sealed vials of ethanol. Detection and quantitation of VC Isyperforned using a id space soling technique and standard gas chrooatography (6C) with t lame.ionlzatlor. detection. GC peak heights of about 51 full scale deflection (F53) are obtained for saoplesjof PVC containing 1 ppb VC. Polymer sarnies taken fro tubing, blood bags, food packaging files, bottles and unprocessed resin were analyzed. Residual VC levels ranged froa t/,3 to 91j ppb. Confirmation of VC v<*s done by GC/M3 using selected Ion recording of n/z C2 and 64 in conjunction with full mss sc^ns to laentlfy cor-ronents eluting near VC. ucc 030802 The ^election and quantitation of vinyl chloride (VC) In various Matrices have beer, continuing problems for the past several years. Since the Implication of VC es a cause of angiosarcoma of the liver (1) and several other diseases (?), there has existed a need for a highly sensitive and specific analytical method for tha determination and confirmation of residual VC In PVC food packaging materials. Previous ork In this laboratory (3) was Halted to quantitative determination of VC from PVC solutions at the 1 ?p& level by direct GC Injection. recent work has shown that headspace sampling techniques can 1crease sensitivities down to tha low ppb range (4,Sko,7). PVC materials or PVC solutions were held In sealed vials and heated for fast equilibration between liquid or solid and vapor phases. A large aliquot of the headspace was withdrawn for GC or GC/MS Injection. Further Increase in apparent sensitivity has been achieved by concentration of VC from the polymer solution Into another solvent using a sparging technique. This was suggested by fellar and Uchtenberg (d) and has beer, used by Japanese scientists (9) for several years. Js have modified the sparging and headspace sampling techniques to * ' obaai* tha Oescribau prucaduPee which peralt the determination and confirmation of 1 ppb VC In PVC material*. Polyser samples of tubing, bottles, fcloofl bays, food packaging film* and unprocessed PVC resins were analyzed using flare 1on1:atlon detection (FID) and confirmed by GC/MS. ucc 030803 -j- [t>utlon; Since vC Is a jas at roou leirperaturo and has been designated a carcinogen (1.10,11) by Inhalation, special handling pre cautions utust be taken to preserve the Integrity of the standard* as veil as to ensure the safely of the analyst. Only the septa-sealed vials describees under Apparatus were found satisfactory for handling VC. ^.rayefits y\) vii.yl u.lorUu. -- (1) Three lb cylinder (79/a pure), :;dthtfSOn, or equivalent. VC .as standard {1.00 ppus) containing ; ng VC/ .1 In nitrogen, i'C Scientific Cases, heamy, hj 07029 or equivalent. (t) Ethanol. -- Aisolute, Publicker Industries, Inc. or equivalent. Prior to use, Ust to show absence of co-eluting '-aterlals at the retention tlrue of VC unuer the conditions of analysis. (c) Of vthy 1 acetamide. -- 3 a*. Easta4n Practical Grade or equivalent. Pre-sparge the entire reagent bottle with helluu for 2-3 days before use. Prior to use. test to show absence of co eluting B4ter1a)s at the retention thue of VC under the condition* of analysis. Apparatus (a) Screw-Lipped tottles- -- <"'< o* narrow *>uih, 35+0.1 Hi, Are Scientific Supply Co., Vo. Vj-42b6, or equivalent. Stellar bottles with ? oi capacity. Caps with Teflon-lined septa (Alltech Associates, 'o. 9`>2C, or equivalent). ucc 030804 (L) Gat tyring*. -- Two, 6, and 1o -.1, Precision Sampling, Pressure-Lok, series A-i:, or equivalent. (c) Mul-Vlals. -- 5 nl, with caps end Teflon-lined septa. Alltech Associates :*o. 9506, or equlvalent. (q) Collection vials. -- P^rkln-Fluer f-42 headspace enalyzer vials with pray septa and aluminum seals. Capper (P-E ho. 10S-C106) and oecappcr (P-F ao. 105-0107) for vials, or equivalent. (c) Sparging apparatus. -- See descriptive drawings In Figs. 1 nJ l . (f) Forced draft oven. -- Precision Scientific Poppany, Thelco Model Id, or equivalent. (<) Gas chromatograph. -- I'twlett-Packard Model 76?0A. or equivalent, equipped with tecperature programmer and flame ionization Jetectors. C;*.rattng conditions: Temperature (C) -- Injection port 200, detector 260, coluon 110. After VC elution (% 7 min) program column to ldO at fastest rale and hold for 20 min; gas flows (rl/nln) -- carrier (He); 35 (0.7 rotaiaeter), makeup gas (He), 30, oxygen, 345, (3.36 roteaeter), hydrogen, 35, (0.75 rotameter), electrometer setting, kxlC`U fs ( ,) Chromatographic colucei. -- t' * 1/3 0.0. colled stainless steel (S5), filled with 80/100 mesh Porapak pretention time of VC approximately 7 win. IJCC 030805 -c- (1) Q-iS ciiru.-atQ iraph-'ass succtro, i-ttr. -- Finnlgan Ji'JOF cljctron 1,.ipect quaumpolr '-ass spscirowtcr equipped with Ftnnlgan J5`ju yas chromatograph anc Finnlgan ClOu cats system. fi.11 scans ana selected Ion recording of */i 62 and 64 were obtained under co-. pyter control, iterating conditions: Temperature -- Injector 170, column lbb, separator 216, transfer line 210; aftfer k'C eluted, cola* venteo and programmed to l.GwC to clear solvent from column; carrier gas hellu , /.6 aI/c.Im; sanple size 2.00 -*l headspace at !c0t column listed under (h). (j) Pli.t bottles. -- rilnt 1 lass !; oi narrow icuth, screw cap LottU-s, Flsiier Scientific (^.yiny t-atalo: unt-er /--,,3rP or .'Ivalent, wltti foil 11 m;l caps. c.'srotlon of Standards accurately wc-1 ,'n a i ot narrow Outr, bottle, ''Ini-Vial cap, and it.,1 tuu.. >'..d Sc' r;l absolute ethanol tu weighed bottle, fap and ^' rcwelgh. I.. a huod, prepare VC stock solution In this bottle by *ck1y uncapping bottle and adding u.6 " ~ 7 liquid VC from Inverted rceecr-coole-i cylinder of VC. Immediately cap bottle* tightly and U well by shaking. fewelgh and calculate VC concentration by weight l*w 1j,0O-4ij,iAjJ ppm). dilute this Stock solution by withdrawing aliquots through the septum with a syringe and Injecting Into a weighed, sealed container (l oi bottle) of ethanol. Acwelgh and calculate VC concen tration either In welght/weiyht ur In welght/volinse units (* SO pp*). is solution Is similarly diluted to yield a solution containing 1-6 pph,. "ait final dilutions Into 1u .1 of ethanol In a collection vial, paru working standards in the 1-60 ppb range. If refrigerated, is working standard 1$ stable for a period of up to one^week; multiple saptL-.. punctures shorten the working life of the standards. i. ucc 030806 -6- Determin$ the actual VC concentration in the headspace of the above working standard under conditions qt antlyiU By BlPiSt 8ffl-` parlson to the standard gas (1 ppm in N2) eenfcaiMRf ?. R0 Calculate an average partition coefficient using tfie fpllow^ equation: Equation #1: Partition Coefficient * -- CL rn~' * 0*29 .71/10 ml where Cv - Concentration in vapor (headspace) CL = Concentration in liquid .29 = 29% determined to be in headspace 14 ml = Volume of headspace (13 ml) plus volume of syringe (1 ml) .71 = 71% determined by difference to remain In liquid 10 ml * Volume of ethanol standard Preparation of Solvents and Samples Check the absolute ethanol to be used in the collection vials for materials co-eluting with VC by carefully pipetting 10.00 ml Into one of the vials and sealing the vial with a nand capper. Analyze as described under "Analysis." Drill two holes into the cap of the 3 kg reagent bottle of dimethyl acetamide (DMAC) and run a 1/16" Teflon or stainless steel tube to the bottom of the bottle through one of the holes. Sparge the DMAC using a slow flow of helium (5-15 ml/min) for several days at room temperature prior to use. After DMAC has been obtained which Is free of materials co-eluting at retention time for VC (determined by running a^reagent blank), add 200 ml to a 1 pint bottle along with a 2" Teflon coated magnetic stirring bar. ucc 030807 -7- Cut thick PVC sables such as tubing and bottles Into $cal1 pieces which will fit throvh the neck of the narrow youth pint bottles. Prepare f1 leu by rolling the sample Into a long narrow tuba which can be cut Into short sections to fit Into the bottle. Accurately weigh 20.00 y of PVC material and add to the bottle containing 200 at of 3HAC and the stirring bar. Tightly cap the bottle using cap h a foil liner* and stir contents until the PVC Is coepletely dissolved. Collett solution requires stirring fron two hours to overnight, depending ou the PVC forr-ulation Involved. Highly plasticized sables dissolve sore readily than do the uore rigid iiples. (Note - Opaque solutions art generally obtained when the PVC composition contains 1;*>act modifiers or pigments.) ;...alys1s "ter the PVC sawple Is dissolved In tl.e pre-sparged DHAC, add 10.00 1 - absolute ethanol to each of two collection vials. Interconnect the vlalswlth short lengths of 1/16" SS tubing u shown In Fig, 2, and cool in a thick Dry lea - ethanol slurry for 30 sin before use. Fit the bottle containing the PVC solution with * tight cap equlpptd with _ 1/16" SS sparse tube extending to the botton of the bottle. The apparatus Is shown 1 Mg. 1. Inverse the pint bottle containing the PVC solution In a stew bath and add hellun sparge gas via a needle valve through the 1/16 SS sparge tube at a rate of * 1/ In. Culckly leak check the apparatus by applying S;uv** to all Joints eed briefly plug the final outlet tube In order to build up pressure. After leak checking, allow tlt spar* gas to freely pass through the PVC solution, through c bulkhead fitting. Into the effluent tube and Into the collection vials Immersed In the Cry Ice - ethanol slurry. Sparging apparatus H shown in Fig. 2. ucc 030808 -6- After sparging for 2 to 2 1/2 hours, disconnect the collection , vials while still cold, decap using the deeapper r-88l y$118 8 fresh unpunctured septum. Analyze vials Immediately or yqgfir. refrigeration for no longer than 2 days. Fpr analysis, hspt vials to 90C In either a water bath or a forced graft pypp fthd allow to equilibrate at this temperature for a minimum of 1 hour. Heat a gas-tight syringe having an integral valve to 9QC in the forced-draft oven. Wear gloves to use the preheated gas-tight syringe and withdraw 1.00 ml of headspace. Close the lyringe valve and return syringe containing the sample to the oven for 5 min to vaporize any condensed solvent. Remove the hot syringe and Irmedlately Inject the sample into the gas chromatograph. Make standard VC gas injections (1.00 ml, 2.6 ng) both before and after each headspace sample ejection. Quantitate the unknown using the following equation (#2) Total ng VC in sample (ng/ml in HS)14 ml + (ng/ml In L1q)10 ml 20 g 20 g combined with equation #1 = 0.29 CL where 0.29 Equation # 2 giving Cv ppb VC in PVC * (Cv)14 ml * i|T).29TlO ml 20 g 20 g = 2.42 Cv The remainder of the sample in the collection vials after GC deter mination of residual VC is used to confirm the presence of VC by GC/MS. Equilibrate samples at 90C for 1 hour In a constant temperature "bath and withdraw a 2.CO ml aliquot of headspace with a preheated gas-tight syringe having an Integral valve. Inject the sample quickly Into the GC/MS to minimize cooling of the syringe and condensation of vapor. __ ucc 030809 * Calculate the response areas of V.' (>d anJ i4 using Flnninan Fevlsloti Ll software. Calculate the relative abundance of r.yz (*l and from the respond areal at th* retention Hue of vinyl chloride and compare to theoretical 3;1 ratio. f-.tsults and r1scustton Previous work In this laboratory Indicated that quantitative jeteralnations of VC In PVC at very lo*. levels would require a combination of headspace sailing and sparging. Headspace techniques nave the advantage Of allowing larger portions of the VC present in the sample to be injected Into the -3as chromatograph than could pc done by direct Injection of solutions. Undesirable coinponents can often be reduced or eliminated. Vnfortunately, the accurate determination of low ppb levels of VC in solid food packaging materials could not b* achieved using headspace sampling alone. This Is due to differing and unknown equilibration times froa. sample to sarnie, direct headspace sampling has teen shown to reliably jfctect low levels of VC In several food sl.Ailatlny solvents (I). If .`he polymer Is dissolved In a suitable solvent a favorable partition ing of VC Into the iteadspace may be obtained. f*ur desire to use a relatively dilute polyr.er solution to Insure rapid equilibration resulted In a low total VC concentration In the headspace for sanples containing VC at the ppb level. Therefore, an additional concentration step was needed. Sparging proylr.eJ a means of transferlng VC from a solution of low concentration to one of higher concentration. The combination of sparging and headspace s tip ling techniques produced the oeslred sensitivity. ucc 030810 -1.- i>:a; was chosen to -Mssolve the PVC because of Us excellent solvent properties and Its low volatility. >.bsclute ethanol was cAhosen u collection solvent because It mains a liquid at fry Ice teo^eraturet and Is an excellent solvent for vc. tiellu; was chosen as the sparge ;s because of Us low solubility In ethanol. The sparye train was designed to use readily available coipQnents, the pint bottle bein', chosen for Its convenience In folding 20 o of PVC It. CuC .1 of "'MA` without rntraliwent of the PSAC Into the gts sirta . C__z iraakaye of bottles occurred at the threads, possibly due to cvurtl ^.tcnlr.c, i.achlnlng nisc^tcl., or differences In co efficient of expansion between the glass and trass used In the cap 5*.ruction. /- ljr;er bottle (1 "t) eculd be used for the Jeter. Initton ' .c ot lower levels where u laryor saTple wojld be required. Figure 1 --i tne details of the cap and Figure shows the assembled sparging cratus. i?l .nalysls of the headspaces of several PVC sa.ples following :-.arg log utmost rated that VC could not be adequately resolved fro^ r coioponants using (irbowax 2o > or Mlar 10 C liquid phases In conventional packed columns. Chroitosorb 101, Chrowjsorb 103, Poraptk * Parapet fi. -wi*v1 Tenax r,r also provided Inadequate resolution. ChrojnosorL Ut was marginally useful but Is not recommended. The Porapal W colu mn was selected for Us excellent resolution of VC fro;, ill encountered Interferences except one component eluting ofter vr which sofetlues precluded baseline resolution. GC/t5 di.alysls showed that this co.nponent was IsoLutane. `..'hen using the porous polyvjr columns, fru. -tl r In to 1 hour was required before the t asu 11 ;:l was considered i'equate for the next analysis. ucc -li ne were unable to obtain syringes capable of sustained use at yuC. Syringe leakage* problems wre occasionally encountered due to sustained usea<je t 'iC0C. Syringes were tested by pulling bad the plunger, closing the Integral valve, end pushing on the plunger while Holding the syringe under water, A stream of bubbles Indicated leakage and the syringe was discarded. Pre-sparglng of the CMAC satisfactorily rewved possible Interferences contained therein, ho attempts to clean up the absolute ethanol were ?ade. If oaterlals co-eluting with VC were present in the chrcaatogreas of the blank ethanol, a new container was opened and checked. Tn general. Interferences were not a problem. Before attesting the analysis of unknown PVC taturlals, a coop let* analysis of a reagent blank should be obtained using the sparging apparatus described. A known amount of V't should then be sparged froo the apparatus to check for recovery, leakage, and the GC retention tlarti of VC under operating conditions. The detercinatlon of the partition coefficient (C.25) was cade by analyzing VC-ethanol solutions ranging In concentration fron 2.5 to 40 ppb. These solutions (10.00 ml) were prepared In collection vlalt and analyzed under the conditions of the analysis* An average of 37 determinations showed that 29% of the VC partitioned lute the headtptce. This was demonstrated by direct comparison to the standard gas <1 ppw In n,) which contained 2.6 ng VC/wal. Equation (1) was used for calculation of the partition coefficient. Standard deviation of ell determinations was 0.075. Spiking and recovery studies at levels of 7 to 26 ppb VC In DKAt and lJi PVC polyr-er solutions In DMAC were carried out for the entire procedure. The average recovery for 6 analysrs of TflAC containing no PVC was S3.. The average recovery for 21 polymer solutions was 93T. The PVC for the recovery studies was fret of residual VC. (^ote; PVC containing no VC was obtained by several precipitations froc ucc ;ctra,`iiyor&f.ir*n (THF) l.v.o . .cthdiiul. 'bout SO u of PVC fror. tubing or filr. was dissolve In a .ifnli-ur <u*iOunt of THF. This solution was * lowly pjureJ 1-*to a vigorously stirred leaker containing 'Ethanol. Ti e ratio of the T)'F solution to ^ti.anol was about 1 1C. The pre- itated PVC was filttreo onto a large Puchner funnel anJ air dried. , processing larjCr quantities of PVC. a large size blander was used the precipitation. Generally two to three precipitations provided PVC if the starting PVC contained no ore than about 1 ppm VC.) - variety of WC materials were analyzed using the '-tthod described ini are tabulated In Table 1. A typical FID chromatogram Is shown in 2 along with the chruuatuqra^ of the reagent blank. Thirteen samples were analys e -no found to contain VC at levels ranging from C.3 to 91? p;L In these PVC formulations. 5S s^vetro-otry was the confirmation step In the ;<ttbod. It provad *.*ijatle In the cevelopiaent of the wthod by Identifying cosaponents t; near the retention tice of vinyl chloride. This Insured In final pT-occdure that there were no corponents co-eluting with the chloride that would have Invallcated the GC quantitation, full CC/ S scans I ti lb-ih'b) cf U' of the simples chromatographed or. >ak *- were obtained to Identify the co^onents eluting near chloride. Figure ' Is the total Ion current profile of a typical u ole recorded frot; the elution of carbon dioxide until the elution uf ethanol. Th<. reagent blank, ana the samples were found to contain carbonyl sulfl is. propcnc-, water and acetaldehyde. Hilcrocethanp Hobutane and butu'it* were Identified in rrost of the sarnies. The retention tii;.es of the co.vponents Identified In each of the sarnies .;1ve to vinyl chlorite are listed In Table 2. Identification of ill co.vuunnts was based on spectral Interpretation and comparison reference cc.^Odods analyzed under the Identical FC/MS conditions. . ssimple represented by Fly 4 contained c ppb VC. At this level, a VC response was not t-vluent in tf* total Ion current profile but was r**.vM 1y u,M*arcnt In Fig ' which Is the selected Ion current profile of this s=pl.. ucc 030813 - 1J* Selected Id. r?corof ujz it? ano aas t:*cd to confirm the presence of VC. Tie characteristic J:1 ratio of these Ions at the retention ti-e of VC prodwceJ t-y the natural abundance of ^C1 and " In the molecular lor* of VC increased the specificity of the Tnls ratio was reproducible tc within 2t of the theoretical v<^(. when the level of residual fonoocr In the poly *r was 1 ppb. cnltorloj this n/z Sr and -* ratio insured that only compounds ror.lainlnj one chlorine atom anj thus the elemental coif'osltton of vinyl ci.lorlJe as a 'Olec-lar Ion or fra<>.er.t are possible Interferences lo the r.ass spr.ciroinctry cor.flr: atlon. fhlcrobutenes. eplchlorohydrin n.: dlchlorjethcm. Arc loe molecular weight torpo.rrvds that frocucs a frc j ?nt at -U i? containing one chlorine atom and are potential it^rfcrcr.cos to the ass spectro.netry confiroatlon. Analysis of es of epichlorohydrlr. and dlcMoroetbar.e U&tonstrated tint they miLr iftnr VC. The chlorobutenes t>e1nq heavier than butene would .ilso .:lute later than VC (1C). ' .c lack of co-elutlf.-, materials that would have Ir.terfcrred *Tth the FIr; results aade it unnecessary to quantitate the sa>ap!es by ~/`Z, ti-yod quantitation by SC/'*$ requires strict control of the analytical conditions and the construction of an analytical curvt frtw standards analyzed slr^ltaneously with the samples. Such an effort was considered redunoant In this case. HOC UjlJold  -.ferefrces {1} ''altonl, C., t trfeslne, (1974) fnvlron. '(%. 7, 327-400 {') Thoc.as. L.U., Popper, *)., rrrk. PC.. Sellkoff, I.. t Falk, . {1975) 'w r i.-j. .1. '-V-J.. 292(1). 17-22 (i) Lrtser, C.V., Oennlson, 3.I.. L Crown, (1975) 3A0AC 1214-1220 (-) r.jsea, -'-runa, 3. Parties, S.T.. Clacln, J.fc., !. Gilbert, 0.3. (1575) JAOAC 700-70? CO Van Merc;;, 3.5Lefl, U. (1376) J. Chro-j. 122, 1C3-137 {-.) flaehenko, jraJcr. ".V., Crown, M.F. L .enrlson, J.l. (1577) 3A0AC 00, VI^-jTj (7) SiClcf.t.i, :..l. (1070) ^r.al. rhe>-,. *.a, 139i-1402 ( ) tf;-lUr. T.A., Mchtenlwra. J.J. (l!*74) JAWHATfC., 7jf$-744 (9) A.ifl 1. -tthaJ attached to ' cc. 19, 1375 letter fro>z Suntto^ fcakelUe Ca^any, l td., 345 Park Avenae, *:ev York, HY 10027, to Hearln* Clerk, F0A. 5i*GC Fisher lane, 7ock<111a, ?3i 70352 (1;j) viola, P.L. (1970) Taitl. I.-.t. fencer Oanf., Houston, TX, Session 55, r. 74 2 (Abstract -.5) (11) Viola, P.L.. :i1<iOtt1, 7-.. ; Caputo, A. (1571) Cancer Ses. 31, 51C-52-' (12) W PjCkfcJ Calu.ui In Ods > Aranatography (1974) Suplna. 0*.A., SupelCO, Inc., P-plIefonte, PA ucc 030815 Table 1. PVC Sai.iplc Sundry `Acplfi 1 2 , '1t L 7 J ) K H 1? li 1-i Smple description Rigid calendared food grade sheet Thin plasticized food film Thin plasticized food flln Plasticized blood bag t>11 n plasticized copolyiaer food fils Thin plasticized food f11"> Plasticized foo.1 and . rilk tubing Plasticized beverage tubing Klgld vegetable oil bottle Rigid French tfitvr bottle French bottle molding coapound Thick plasticized canning sheet Hastlcized blood bag regent blank VC found* 1.2 2.5 2.1 1.2 2.1 0.6b 0.7b C.7b 120 913 0.6b C.4b 0.3b NDC a'>u*ni1taLed ;y tangent slicing VC peak and neasurlng peat height bstiu.ateJ value - belov netbod's quantitation Halt ' ' c: one detected ? 03081 Table 2 - Retention time of identified comp nents relative to VC r i Temp. Carbon- dioxide Carbonyl - sulfide Propene Propane Chioro- methane Water Vinyl Chioride I sobutane Butene Butane Sample No.* 1 2 3 4-tube 1 4-tube 2 5 6 6 7 8 11 12 13 13 2 ml Blank (spiked) 2 ml Blank (tube 2 155 155 155 155 155 155 155 120 155 155 155 155 155 120 155 155 .42 None .44 .50 .47 .55 .46 .55 .42 .44 .51 .44 .52 .32 .42 .44 .52 .44 .53 .43 .50 .46 .52 .31 .40 .43 .49 .43 oo1r IT? <uXj *sa>0zt .69 .71 1.00 1.07 1.20 1.22 .71 .72 1.00 1.19 .73 .74 1.00 1.17 1.17 .67 1.00 1.05 1.21 1.21 .72 1.21 .70 .70 1.00 1.20 1.20 .71 .72 1.00 1.20 1.26 .59 .65 1.00 1.20 1.22 .70 .72 1.00 1.20 1.22 .70 .72 1.00 1.06 l.lfi 1.17 .72 .70 1.00 1.20 1.20 .69 .69 1.00 1.20 1.21 .70 .70 1.00 1.07 1.20 1.20 .64 1.00 1.20 1.20 .70 .70 1.00 .70 1.23 1.17 1 tn1 0Oc4f r4O3o-1C> <COU' u r? r- T7 s1+0cn-z>rr_ 1.76 1.H6 2 ml Blank (spiked) no .10 .31 .42 .66 .66 1.00 Oi chioroethane 155 - elutes after ethanol 1,3-Butadiene 155 10 jjI Butane .51 1.1B 1.27 1ighter cls-2-Butene Acetaldehyde 120 155 155 .43 1.11 n.w 138 1.21 '-w >  t rt1nr>* r >9. 1 - Cn rift. ? - rffiufcut T*ib Fin. 3 - Cerent teor**s tf l.C *1 Hfirttptc* ftg, 4 - TotiT Icn cvrr*M nrofUe if sv^1 #3 Ce*tft1n1fte ?*1 0b >C Fla. * - SeWtto lea rocr.ivMiv' i>rof11*5 ot m/i fc? *n4 M of Edopt? *'i contain^1' ?.1 pi>t' VC 4 Inside bored to 1/4" Fig. #1 - CAP DETAILS A. For temporary use and preliminary tests a standard metal cap may be used by removing the liner, drilling a hole through the top, removing the surface paint with acetone, and soft soldering in a bulk head fitting with the sparge tube attached. The sparge tube is attached to the bulkhead fitting by drilling a hole slightly larger than 1/16 inch downward at an angle into the bore of the filling (See diagram). The flats of the nut portion and the upper major part of the threads should be avoided. After insertion of the sparge tube to the --cper length (enough to reach the bottom of the bottle), the tube Is silver soldered in place. A thick teflon or polyethylene gasket is then cut to fit the inside of the cap. The threads on standard metal caps are not sturdy enough for continual use and often strip off after a short time. Plastic caps were found to be unsatisfactory for even temporary usage. B. A more permanent cap for continual use has been designed. Machined from solid brass, the sparging cap consists of a hex-shaped cap (1 1/4 inch flats) threaded to the same configuration as the bottle and drilled and tapped in the top to accommodate a Swagelok 1/4 inch bulkhead fitting. /8" to 1/4* Reducing Union pig, #2 - Effluent Tube Details: Requires: (a) 7 inches of 1/8 Inch stainless steel tubing (b) 1/8 Inch to 1/4 inch reducing union (c) 5 feet of 1/4 inch 00 copper tubing A second collection vial Is required si'ice is ich as lOt -if the VC may pass through the first vial. At levels above If ppb a thiro vial i> rec nu; <'-d. ucc 030321 *3 O n o o CM ucc 030822 Itlilililiu u lilililtu lilih lih 1 001 UCC 030823 Page 18 October 17, 1977 FOOD CHEMICAL NEWS FDA has been compiling data on sodium Intake through Its marketbasket studies, Vanderveen said, forecasting an assessment of salt Intake. He predicted It will show that most people are consuming an adequate amount of salt, but that some consumers with unusual eating patterns may consume more than 20 grams a day. If so, Vanderveen continued, there may be a "great debate" on whether FDA should take any action. Noting that FDA's enrichment-restoratlon-fortLflcatlon regulations are on the "verge" of being finalized, Vanderveen said fortification "will become more and more impor tant." The new regulations, which he said spell out fortification practices, will take a balanced nutrient approach. Such an across-the-board policy is needed rather than consideration of fortification on an ltem-by-ltem basis, he said. The FDA-er predicted that new foods "will receive the brunt" of FDA's regulatory effort in the future, because it is an area in which "we can make changes." Amendment of Law Placed Emphasis on Nutrient Toxicity. FDA-er Savs A "big concern" of FDA will be nutrient toxlcltles, Vanderveen said, explaining that the amendment to FDA's law sponsored by Sen. Proxmire (D-Wls.), which limited FDA's authority to regulate vitamins and minerals, puts pressure on the agency to regulate on the basis of toxicity rather than need. The protein quality standard is a "matter of concern,* Vanderveen said, noting that FDA recognizes the weaknesses in use of the Protein Efficiency Ratio but has found no good alternative. He said the agency is also Interested In quality assessment of other nutrients. The FDA-er indicated that his agency is seeking new terms to use in place of the term "fiber," using this as an example of definition problems In nutrition. FDA's efforts in the field of nutrition were summarized by Vanderveen as dealing with: nutritional needs, especially regarding disease; application of dietary management of diseases; nutritional interactions between nutrients and other substances, such as food additives; nutritional toxicitles; bioavailability; and nutritional information and how to communicate it. University of Florida's Dr. Howard Appledorf, who presented nutrient data on various "fast foods, " attacked Assistant Agriculture Secretary Carol Tucker Foreman for stating that "fast foods are junk foods." He predicted a USDA "blitz" against fast foods, but predicted that fast foods will prevail. He stressed the possibilities of fast food items being used in school lunch programs to assure that students eat the food and receive the nutrition, and to reduce waste. FDA PREFERS REGULATING ONLY WATER USED AS A FOOD INGREDIENT uc c 030824 The Food and Drug Administration would prefer regulating water only as it is used as an ingredient in commercial food products. Food and Drugs Commissioner Dr. Donald Kennedy told the Environmental Protection Ag ncy recently (S e FOOD CHEMICAL NEWS, Sept. 5. Page 33). October 17, 1977 Page 19 FOOD CHEMICAL NEWS In an Oct. 4 letter to EPA Administrator Douglas M. Costle, the Commissioner said discussions between FDA and EPA seem to lead to a choice between two options: -- "FDA's role In regulating water could be limited to water used as an Ingredient In com mercial food products (e.g. In bread, canned punch, bottled water). EPA would assume plenary responsibility for safety of tap water provided by public water systems. This option would generally result In our agencies having mutually exclusive areas of respon sibility with respect to water. -- . LA could assume an active role In regulating water provided by public water systems in sd- 'tion to water used In commercial food products. This option might require FDA to :e food additive regulations for water treatment chemicals and would probably r = .= __ ... FDA establishment of poisonous or deleterious substance tolerance regulations for unavoidable contaminants In drinking water provided by public water systems. This cptirr would probably result in substantial overlap of our agencies' programs for regula tion of water." 2r. balance, the first option appears to FDA to be the preferable choice, Kennedy said, explaining that FDA believes Congress intended EPA to have full authority ever public water systems when it passed the Safe Drinking Water Act. .. recognition of the Congressional Intent, he continued, FDA would defer to EPA '^gulate drinking water, and would not regard water meeting EPA, State and local -dards as "actionable" when used as a food ingredient, poln:;ng out that FDA has red in the past to the drinking water program of the Public Health Service, cerns with this approach are, the Commissioner observed: "il; It is uncertain whether EPA has sufficient statutory authority to bring about adequate control; and (2) there may be a lack of resources to undertake all the evaluations that -ly would be required." Kennedy said he believed the new Toxic Substances Control Act (TSCA) would probably ci'-e EPA the necessary authority to "pre-clear" the application of new chemicals to production of water, but he added there would still be doubt as to the extent of EPA's authority to require submissions for evaluating substances that have been in use for some time. The Commissioner said he recognized that control of a new substance under TSCA - ' present some difficulties because of the need first to issue a regulation requiring .-at f'' "Ktance be tested. To regulate substances already in use, he continued, "EPA would need to conduct an inventory and itself undertake the burden of testing, ch leads to resource questions." He pointed out, however, that a need for addltlohal resources to carry out an ffectlve program of safety assurance for water treatment substances is a common problem under either option and probably should not be the primary factor in reaching a decision. He acknowledged that the second option offers greater ability under the Food, Drug and Cosmetic Act to exercise control over substances used In public water supplies, but he noted that FDA could only use the 406 approach for unavoidable contaminants. ucc Page 20 October 17, 1977 FOOD CHEMICAL NEWS "This approach would also carry with it a commitment to undertake a comprehensive review program In order to establish permanent tolerances for water treatment sub stances ," he wrote. Kennedy said the second option appears to prevent "a substantial prospect of waste ful duplication of effort by our agencies and of confusion arising out of overlapping regulation by two government agencies." If the first option is adopted, the Commissioner said steps would be needed to co ordinate responsibilities in an effort to avoid regulatory gaps, pointing out, for e- =~ple, food and food additives are exempt from TSCA. In cases of uncertainty as to which agency has responsibility, Kennedy advocated joint action, saying, however, it would be preferable to work under the Safe Drinking "Water Act. He added that a review of authority under this act would be helpful in determining a strategy that would minimize the workload of this option and Increase the likeli hood of its success. Meanwhile, Resources for the Future announced that It had begun planning a Safe T.-.nking Water Conference for Feb. 15-17 in Washington as proposed by Foremost foods (See FOOD CHEMICAL NEWS, Aug. 8, Page 53; and Aug. 22, Page 2). FDA TC PUBLISH TETRACYCLINE PROPOSAL OCT. 18 The Food and Drug Administration will publish its proposal to ban some feed uses rv tetracyclines in the Oct, 18 Federal Register, the agency Informed Congressional nmittees in an Oct. 3 letter. The House Appropriations Committee had directed FDA to Inform Interested groups o-> Capitol Hill at least 15 days in advance of proposals to ban uses of low-level antibiotics in feed (See FOOD CHEMICAL NEWS, Sept. 19, Page 7). In his letters to Appropriations subcommittee chairman Whitten (D-Mlss.) and other members of Congress, FDA Commissioner Donald Kennedy also revealed that a proposal on "distribution controls" for antibiotics "will be published shortly after tr.e tetracycline proposal." 'ri's Commissioner previewed the tetracycline proposal, as follows: "... The subtherapeutlc uses of tetracyclines Intended to be eliminated are those uses for which there are effec tive alternative drugs. Nontherapeutic uses of tetracy clines for which there are no alternative drugs available will be retained for use by the livestock industry. "Examples of effective altematlv drugs available for the uses of penicillin and the tetracyclln s Include bacitracin (zinc and methyl ne dlsalicylat ), erythromycin. uec 030826