1、Designation: F 1313 90 (Reapproved 2005)Standard Specification forVolatile N-Nitrosamine Levels in Rubber Nipples onPacifiers1This standard is issued under the fixed designation F 1313; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revisio
2、n, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This specification applies to the nitrosamine content ofrubber used in the manufacture of nipples for
3、infant pacifiers.1.2 This specification does not apply to plastic nipples (onpacifiers).1.3 The purpose of this specification is to establish amaximum level of allowed nitrosamines in rubber nipples andto outline a uniform testing method to determine such level.1.4 The values stated in SI units are
4、to be regarded asstandard. The values given in parentheses are for informationonly.1.5 The following precautionary statement pertains only tothe test method portions, Sections 5, and Appendix X4 of thisspecification. This standard does not purport to address all ofthe safety concerns, if any, associ
5、ated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. Specific hazards aregiven in Appendix X2.2. Terminology2.1 Definitions:2.1.1 lotnormal production run
6、 or, in the case of imports,a shipment of items produced in the same time frame.2.1.2 nitrosamineschemically active compounds princi-pally formed by the reaction of amines with oxides of nitrogenpresent in the environment.3. Significance and Use3.1 This specification is intended for use in reducing
7、thenormal exposure to nitrosamines.3.2 This specification refers only by way of example to theeight volatile N-nitrosamines identified below:3.2.1 N-nitrosodimethylamine,3.2.2 N-nitrosodiethylamine,3.2.3 N-nitrosodibutylamine,3.2.4 N-nitrosomorpholine,3.2.5 N-nitrosopiperidine,3.2.6 N-nitrosopyrroli
8、dine,3.2.7 N-ethylphenylnitrosamine.4. Test Method4.1 Determine nitrosamine levels by using either the meth-ylene chloride extraction method described in the collaborativestudy conducted by the National Center for ToxicologicalResearch2or the Food and Drug Administration method.25. Acceptable Level5
9、.1 A test sample of nipples, drawn from a standard pro-duction lot, shall not contain more than 10 ppb (in each of 3aliquots) of any one nitrosamine. In addition, the total nitro-samines of the sample shall not exceed 20 ppb.5.2 Each manufacturer or distributor of the product shall testthe product i
10、n such a manner and at such intervals to ensurecompliance in accordance with the methodology prescribed bythe test procedure utilized. Records of all testing shall beretained for a period of up to three years.6. Report6.1 Report the following information:6.1.1 Lot number,6.1.2 Date samples,6.1.3 Dat
11、e tested,6.1.4 Individual nitrosamine content, and6.1.5 Total nitrosamine content.1This specification is under the jurisdiction of ASTM Committee F15 onConsumer Products and is the direct responsibility of Subcommittee F15.22 on ToySafety.Current edition approved Sept. 1, 2005. Published October 200
12、5. Originallyapproved in 1990. Last previous edition approved in 1999 as F 1313 90 (1999).2Available from U.S. Government Printing Office Superintendent of Documents,732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West C
13、onshohocken, PA 19428-2959, United States.APPENDIXES(Nonmandatory Information)X1. BACKGROUNDX1.1 This specification provides the rationale for thedrafting of a voluntary product standard establishing accept-able levels and testing procedures for nitrosamines contained inchildrens rubber pacifiers.X1
14、.2 Some nitrosamines are known to be potent animalcarcinogens and are suspected human carcinogens. In 1981, theWest German Government enacted regulations limiting theamount of preformed nitrosamine in rubber pacifiers. Nitro-samines are formed from amines used as accelerators duringvulcanization of
15、the rubber or are unintentional trace sub-stances present in stabilizers used in the manufacturing pro-cess.X1.3 In 1982, the Consumer Product Safety Commission(CPSC) began meeting with rubber pacifier manufacturers andimporters (most are imported), drawing their attention to boththe carcinogenic po
16、tential as measured by laboratory bioassayson rodents and the results of an audit of those pacifiers on themarket. The audit revealed nitrosamine levels ranging from“non-detectable” to as much as hundreds of parts per billion(ppb). The Toy Manufacturers ofAmerica (TMA) undertook tocoordinate a progr
17、am to lower the levels of nitrosamines andvalidate a single test method that could be duplicated inlaboratories worldwide. This effort was a joint, round-robinprogram with the CPSC, the National Center for ToxicologicalResearch (NCTR) and pacifier manufacturers/importers. An-other method of testing
18、has been detailed by the Food and DrugAdministration in their program to reduce nitrosamine levels innursing nipples.X1.4 This specification currently recognizes two test meth-ods, one developed by the National Center for ToxicologicalResearch (NCTR) (seeAppendix X3), and one which is knownas the Fo
19、od and Drug Administration (FDA) method (seeAppendix X4). Both methods have been corroborated andadopted as an approved method by the Association of OfficialAnalytical Chemists. The process by which these methodswere corroborated and adopted ensures that the methods arereproducible both within and b
20、etween laboratories and that themethods provide equivalent test results. Several governmentand independent laboratories participated in the corroborativestudy in which coded quadruplicate samples of three compos-ites were sent to each laboratory for analysis and tally,conclusively providing evidence
21、 of reproducibility amonglaboratories.X1.5 The Consumer Product Safety Commission uses theNCTR method in analyzing pacifiers for nitrosamine contentunder its enforcement policy.3The FDA utilizes the FDAmethod in its Compliance Policy Guide, 7117.15.4The CPSCand NCTR staffs characterize the NCTR meth
22、od as cheaper,faster, and more reproducible, although both the NCTR andFDA have affirmed that their two methods give essentially thesame results in their laboratories.X1.6 The test methodologies contained in Appendix X3and Appendix X4 define sample sizes and contain the requisiteand prescribed proce
23、dure for sampling from a lot to be tested.X1.7 On December 27, 1983, the CPSC issued a statementof policy that rubber pacifiers are hazardous substances asdefined in Section 2(g) of the Federal Hazardous SubstancesAct and are banned if they contain more than 60 ppb ofnitrosamines as measured by the
24、NCTR methylene chlorideextraction test, effective January 1, 1984.X1.8 A collaborative study between the NCTR,manufacturers/importers and leading testing laboratories wasinitiated to validate the test for consistent results betweenlaboratories. Manufacturers and importers have continued towork with
25、manufacturing processes and independent laborato-ries to reduce nitrosamine levels during this period. Significantprogress has been made since the start of the program.X1.9 In June, 1985, a group of manufacturers met with theToy Manufacturers of America to draft a voluntary specifica-tion. That spec
26、ification was presented to a task force ofconsumers and manufacturers on August 14, 1985 at ASTMHeadquarters. This specification is the result of the correctionsand suggestions made at that meeting, as well as commentsfrom formal ASTM balloting procedures.3Federal Register 48, No. 249, pp. 569885699
27、0, available from Superintendentof Documents, U.S. Government Printing Office, North Capitol and H Streets, NW,Washington, DC 20401.4Federal Register 49, No. 252, pp. 5078950790, available from Superintendentof Documents, U.S. Government Printing Office, North Capitol and H Streets, NW,Washington, D
28、C 20401.F 1313 90 (2005)2X2. HAZARD ANALYSISX2.1 The scientific community in Europe, Canada and theUnited States has concluded that nitrosamines are suspectedhuman carcinogens. However, the actual risk to infants whouse rubber pacifiers is probably very small. In fact, a riskassessment study conduct
29、ed by the Rubber ManufacturersAssociation involving infant feeding nipples concluded on aworst case basis that the lifetime risk to a user of infant nipples(having 60 ppb nitrosamines) was one in 23 million. However,the Toy Manufacturers Association has approached this prob-lem, accepting that high
30、levels of nitrosamines are unaccept-able and that low levels of 20 ppb, that generally representunavoidable contamination, are achievable.X3. PROCEDURE FOR ANALYSIS OF N -NITROSAMINES IN PACIFIERSA COLLABORATIVE STUDYX3.1 Reagents, Apparatus, and PacifiersAll solventswere distilled in glass and all
31、other reagents were chemicallypure grade.X3.1.1 N-Nitrosamine Standard Stock:X3.1.1.1 External Standard StockTen g/mLin ethanol of7 N-nitrosamine mixture.X3.1.1.2 Internal Standard StockA solution of NDPA (5g/mL in ethanol).X3.1.2 Pacifiers.X3.1.3 Mineral Oil White, light weight Saybolt viscosity125
32、/135.X3.1.4 Nitrosation InhibitorTen mg alpha-Tocopherol/mL mineral oil.X3.1.5 Keeper Solution:X3.1.5.1 For K-D EvaporationEighty mg mineral oil/mLdichloromethane.X3.1.5.2 For N2BlowdownTwenty mg mineral oil/mLiso-octane.X3.1.6 ThermoSorb/N7CartridgesUsed as received forquantitative trapping of vola
33、tile N-nitrosamines.X3.1.7 Variable Temperature Oil BathThermostaticallycontrolled oil bath capable of operating at 150 6 3C and ofmoving vertically with aid of a lab jack.X3.1.8 Purge and Trap ApparatusThe apparatus shownin Fig. X3.1 contains the following parts:X3.1.8.1 Argon (Ar) gas cylinder and
34、 gage;X3.1.8.2 Metering valve;X3.1.8.3 Purge gas manifold 4-position;X3.1.8.4 Nalgene needle valve Type CPE (No. 6400-0125);X3.1.8.5 Ground glass outer joints with pinch clamps, 18/7;X3.1.8.6 Impingers, 50 mL graduated glass tubes with24/40 clear-seal grease free joints, 18/7 ground glass balljoints
35、, and 1 mm inside diameter nozzle approximately 5 mmabove the bottom of the impinger; andX3.1.8.7 Variable Scale Flow-CheckCalibrated for purgerate in mL/min, of argon. A bubble meter for measuring gasflow rates for a gas chromatograph may be substituted.NOTE X3.1Do not use any rubber tubing, gasket
36、s, o-rings, or anyother items made of rubber in any part of this method.X3.2 Description and Use of the Purge and TrapApparatusThe apparatus shown in Fig. X3.1 was designedfor the high temperature purging and trapping of seven volatilenitrosamines from a concentrated sample extract/mineral oilmixtur
37、e on four samples simultaneously. A cylinder containingprepurified argon (Ar) gas equipped with a high pressureregulator was used to supply 20 psig to a flow metering valvethat regulates the final purge flow through the samples. The gasstream was diverted into a tubular stainless steel manifold 250b
38、y 20 mm outside diameter containing four exit tubes spaced50 mm apart and measuring 40 by 10 mm outside diameter.Each of these tubes were coupled using 9.52 mm (38 in.) Tygontubing to Nalgene needle valves that serve dual purposes: as ashut off valve when assaying less than four samples; and formaki
39、ng minor adjustments in purge rate due to slight differ-ences in flow characteristics of the impinger andThermoSorb/N cartridges. An 18/7 ground glass outer spheri-cal joint was attached to the Nalgene valve to permit a quick,gas tight connection to the 18/7 ground glass ball joint on theimpinger in
40、let using the appropriate pinch clamp. As shown inFig. X3.2 the impingers were assembled by inserting the glassnozzle (1 mm inside diameter orifice) into the sample mixtureand coupling the 24/40 grease free male and female jointstogether forming a leak free seal. Once sealed, the Ar gas wasallowed t
41、o purge through the sample mixture, through theoutlet tube of the impinger (see Fig. X3.2). Tygon tubing wasused to connect the impinger outlet tube to the inlet side(marked “AIR IN”) of the ThermoSorb/N cartridge, that issimply a standard male luer syringe connector. The purgedvolatile N-nitrosamin
42、es were then collected on the sorbentcontained in the cartridge with Ar effluent exiting from thefemale luer connector. The flow rate of Ar was measureddirectly from the cartridge with a variable scale flow meter thatFIG. X3.1 Diagram of Purge and Trap Apparatus Equipped WithFour Impinger TubesF 131
43、3 90 (2005)3had beenpreviously calibrated for flow rate of Ar gas (mL/min). A bubble meter can be substituted for the variable scaleflow meter. The temperature of the sample mixture duringpurge was controlled by immersing the impinger up to thesample volume mark (approx. the 25 mL line) in a thermo-
44、statically controlled oil bath capable of operation isothermallyup to 150C. The gas manifold, as well as each of theimpingers, were secured by clamps to a support grid; therefore,the oil bath was moved vertically in and out of position for hightemperature purge.X3.3 Procedure for Extraction and Clea
45、n-Up of PacifierSamples:X3.3.1 Prepare a composite of pacifier rubber by cutting asufficient number of individual nipples for your replicaterequirements from a single lot into 1 to 2 mm chips usingstainless steel scissors and tweezers. Homogenize the compos-ite by freezing in a stainless steel blend
46、er jar with liquidnitrogen, decanting the liquid N2, blending at high speed for 1to 2 min. Immediately transfer the homogenized composite toa glass jar with an aluminum foil lined lid and allow toequilibrate to ambient temperature.X3.3.2 Accurately weigh 5 g samples from the compositeinto a 250-mL r
47、ound bottom flask and add 100 mL dichlo-romethane.X3.3.3 Spike the contents of the flask with 2 mL of theinternal standard (50 ng/mLNDPA). Seal the flask and soak thecontents overnight (16 to 21 h) at ambient temperature.X3.3.4 Then transfer the extract and rubber pieces to a glassextraction thimble
48、 fitted with a coarse porosity glass frit in aSoxhlet extraction apparatus.X3.3.5 Rinse the 250 mL round bottom flask with 25 mLdichloromethane, that was also transferred to the Soxhletapparatus.X3.3.6 Extract the rubber pieces for1hintheapparatus atthe rate of eight cycles per hour.X3.3.7 After coo
49、ling, transfer the dichloromethane extractto a 250-mL Kuderna Danish (K-D) evaporator.X3.3.8 Then rinse the Soxhlet extraction flask with two10-mL portions of dichloromethane and combine with the125-mL extract.X3.3.9 Add 1 mm of keeper solution and a few boiling chipsto the extract.X3.3.10 Evaporate the extract in the K-D unit using a 3-ballSnyder column on a 55C water bath until the volume isreduced to 3 to 4 mL.X3.3.11 Cool the K-D unit to room temperature allowingexcess solvent in the Snyder column to rinse down the walls ofthe unit into the 4-mL K-D tube
