Designation:F1313–90(Reapproved2011)
Standard Specification for
Volatile N-Nitrosamine Levels in Rubber Nipples on
Pacifiers1
This standard is issued under thefixed designation F1313;the number immediately following the designation indicates the year of original adoption or,in the case of revision,the year of last revision.A number in parentheses indicates the year of last reapproval.A superscript epsilon(´)indicates an editorial change since the last revision or reapproval.
1.Scope
1.1This specification applies to the nitrosamine content of rubber used in the manufacture of nipples for infant pacifiers.
1.2This specification does not apply to plastic nipples(on pacifiers).
1.3The purpose of this specification is to establish a maximum level of allowed nitrosamines in rubber nipples and to outline a uniform testing method to determine such level.
1.4The values stated in SI units are to be regarded as standard.The values given in parentheses are for information only.
1.5The following precautionary statement pertains only to the test method portions,Sections5,and Appendix X4of this specification.This standard does not purport to address all of the safety concerns,if any,associated with its use.It is the responsibility 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 are given in Appendix X
2.
2.Terminology
2.1Definitions:
2.1.1lot—normal production run or,in the case of imports,
a shipment of items produced in the same time frame.
2.1.2nitrosamines—chemically active compounds princi-pally formed by the reaction of amines with oxides of nitrogen present in the environment.
3.Significance and Use
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3.1This specification is intended for use in reducing the normal exposure to nitrosamines.
3.2This specification refers only by way of example to the eight volatile N-nitrosamines identified below:
3.2.1N-nitrosodimethylamine,
3.2.2N-nitrosodiethylamine,
3.2.3N-nitrosodibutylamine,
3.2.4N-nitrosomorpholine,
3.2.5N-nitrosopiperidine,
3.2.6N-nitrosopyrrolidine,
3.2.7N-ethylphenylnitrosamine.
4.Test Method
4.1Determine nitrosamine levels by using either the meth-ylene chloride extraction method described in the collaborative study conducted by the National Center for Toxicological Research2or the Food and Drug Administration method.2
5.Acceptable Level
1983年的武则天三级
5.1A test sample of nipples,drawn from a standard pro-duction lot,shall not contain more than10ppb(in each of3 aliquots)of any one nitrosamine.In addition,the total nitro-samines of the sample shall not exceed20ppb.
5.2Each manufacturer or distributor of the product shall test the product in such a manner and at such intervals to ensure compliance in accordance with the methodology prescribed by the test procedure utilized.Records of all testing shall be retained for a period of up to three years.
6.Report
6.1Report the following information:
6.1.1Lot number,
6.1.2Date samples,
6.1.3Date tested,
6.1.4Individual nitrosamine content,and
6.1.5Total nitrosamine content.
1This specification is under the jurisdiction of ASTM Committee F15on Consumer Products and is the direct responsibility of Subcommittee F15.22on Toy Safety.
Current edition approved Feb.1,2011.Published June2011.Originally approved in1990.Last previous edition approved in2005as F1313–90(2005).DOI: 10.1520/F1313-90R11.
2Available from U.S.Government Printing Office Superintendent of Documents, 732N.Capitol St.,NW,Mail Stop:SDE,Washington,DC20401, www.v.
Copyright©ASTM International,100Barr Harbor Dr.,PO box C-700West Conshohocken,Pennsylvania19428-2959,United States
APPENDIXES (Nonmandatory Information) X1.BACKGROUND
X1.1This specification provides the rationale for the drafting of a voluntary product standard establishing accept-able levels and testing procedures for nitrosamines contained in children’s rubber pacifiers.
X1.2Some nitrosamines are known to be potent animal carcinogens and are suspected human carcinogens.In1981,the West German Government enacted regulations limiting the amount of preformed nitrosamine in rubber pacifiers.Nitro-samines are formed from amines used as accelerators during vulcanization of the rubber or are unintentional trace sub-stances present in stabilizers used in the manufacturing pro-cess.
X1.3In1982,the Consumer Product Safety Commission (CPSC)began meeting with rubber pacifier manufacturers and importers(most are imported),drawing their attention to both the carcinogenic potential as measured by laboratory bioassays on rodents and the results of an audit of those pacifiers on the market.The audit revealed nitrosamine levels ranging from “non-detectable”to as much as hundreds of parts per billion (ppb).The Toy Manufacturers of America(TMA)undertook to coordinate a program to lower the levels of nitrosamines and validate a single test method that could be duplicated in laboratories worldwide.This effort was a joint,round-robin program with the CPSC,the National Center for Toxicological Research(NCTR)and pacifier manufacturers/importers.An-other method of testing has been detailed by the Food and Drug Administration in their program to reduce nitrosamine levels in nursing nipples.
X1.4This specification currently recognizes two test meth-ods,one developed by the National Center for Toxicological Research(NCTR)(see Appendix X3),and one which is known as the Food and Drug Administration(FDA)method(see Appendix X4).Both methods have been corroborated and adopted as an approved method by the Association of Official Analytical Chemists.The process by which these methods were corroborated and adopted ensures that the methods are reproducible both within and between laboratories and that the methods provide equivalent test results.Several govern
ment and independent laboratories participated in the corroborative study in which coded quadruplicate samples of three compos-ites were sent to each laboratory for analysis and tally,conclusively providing evidence of reproducibility among laboratories.
X1.5The Consumer Product Safety Commission uses the NCTR method in analyzing pacifiers for nitrosamine content under its enforcement policy.3The FDA utilizes the FDA method in its Compliance Policy Guide,7117.15.4The CPSC and NCTR staffs characterize the NCTR method as cheaper, faster,and more reproducible,although both the NCTR and FDA have affirmed that their two methods give essentially the same results in their laboratories.
X1.6The test methodologies contained in Appendix X3 and Appendix X4define sample sizes and contain the requisite and prescribed procedure for sampling from a lot to be tested. X1.7On December27,1983,the CPSC issued a statement of policy that rubber pacifiers are hazardous substances as defined in Section2(g)of the Federal Hazardous Substances Act and are banned if they contain more than60ppb of nitrosamines as measured by the NCTR methylene chloride extraction test,effective January1,1984.
X1.8A collaborative study between the NCTR, manufacturers/importers and leading testing laboratori
es was initiated to validate the test for consistent results between laboratories.Manufacturers and importers have continued to work with manufacturing processes and independent laborato-ries to reduce nitrosamine levels during this period.Significant progress has been made since the start of the program.
X1.9In June,1985,a group of manufacturers met with the Toy Manufacturers of America to draft a voluntary specifica-tion.That specification was presented to a task force of consumers and manufacturers on August14,1985at ASTM Headquarters.This specification is the result of the corrections and suggestions made at that meeting,as well as comments from formal ASTM balloting procedures.
3Federal Register48,No.249,pp.56988–56990,available from Superintendent of Documents,U.S.Government Printing Office,North Capitol and H Streets,NW, Washington,DC20401.
4Federal Register49,No.252,pp.50789–50790,available from Superintendent of Documents,U.S.Government Printing Office,North Capitol and H Streets,NW, Washington,DC
20401.
X2.HAZARD ANALYSIS
X2.1The scientific community in Europe,Canada and the United States has concluded that nitrosamines are suspected human carcinogens.However,the actual risk to infants who use rubber pacifiers is probably very small.In fact,a risk assessment study conducted by the Rubber Manufacturers Association involving infant feeding nipples concluded on a worst case basis that the lifetime risk to a user of infant nipples (having 60ppb nitrosamines)was one in 23million.However,the Toy Manufacturers Association has approached this prob-lem,accepting that high levels of nitrosamines are unaccept-able and that low levels of 20ppb,that generally represent unavoidable contamination,are achievable.
X3.PROCEDURE FOR ANALYSIS OF N -NITROSAMINES IN PACIFIERS—A COLLABORATIVE STUDY
X3.1Reagents,Apparatus,and Pacifiers —All solvents were distilled in glass and all other reagents were chemically pure grade.
X3.1.1N-Nitrosamine Standard Stock :
X3.1.1.1External Standard Stock —Ten µg/mL in ethanol of 7N -nitrosamine mixture.
X3.1.1.2Internal Standard Stock —A solution of NDPA (5µg/mL in ethanol).X3.1.2Pacifiers.
X3.1.3Mineral Oil —White,light weight Saybolt viscosity 125/135.
X3.1.4Nitrosation Inhibitor —Ten mg alpha-Tocopherol/mL mineral oil.X3.1.5Keeper Solution:
X3.1.5.1For K-D Evaporation —Eighty mg mineral oil/mL dichloromethane.
X3.1.5.2For N 2Blowdown —Twenty mg mineral oil/mL iso-octane.
X3.1.6ThermoSorb/N 7Cartridges —Used as received for quantitative trapping of volatile N -nitrosamines.
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X3.1.7Variable Temperature Oil Bath —Thermostatically controlled oil bath capable of operating at 1
5063°C and of moving vertically with aid of a lab jack.
X3.1.8Purge and Trap Apparatus —The apparatus shown in Fig.X3.1contains the following parts:
X3.1.8.1Argon (Ar)gas cylinder and gage;X3.1.8.2Metering valve;
X3.1.8.3Purge gas manifold 4-position;
X3.1.8.4Nalgene needle valve Type CPE (No.6400-0125);X3.1.8.5Ground glass outer joints with pinch clamps,18/7;X3.1.8.6Impingers,50mL graduated glass tubes with 24/40clear-seal grease free joints,18/7ground glass ball joints,and 1mm inside diameter nozzle approximately 5mm above the bottom of the impinger;and
X3.1.8.7Variable Scale Flow-Check —Calibrated for purge rate in mL/min,of argon.A bubble meter for measuring gas flow rates for a gas chromatograph may be substituted.
N OTE X3.1—Do not use any rubber tubing,gaskets,o-rings,or any other items made of rubber in any part of this method.
X3.2Description and Use of the Purge and Trap Apparatus —The apparatus shown in Fig.X3.1was designed for the high temperature purging and trapping of seven volatile nitrosamines from a concen
trated sample extract/mineral oil mixture on four samples simultaneously.A cylinder containing prepurified argon (Ar)gas equipped with a high pressure regulator was used to supply 20psig to a flow metering valve that regulates the final purge flow through the samples.The gas stream was diverted into a tubular stainless steel manifold 250by 20mm outside diameter containing four exit tubes spaced 50mm apart and measuring 40by 10mm outside diameter.Each of these tubes were coupled using 9.52mm (3⁄8in.)Tygon tubing to Nalgene needle valves that serve dual purposes:as a shut off valve when assaying less than four samples;and for making minor adjustments in purge rate due to slight differ-ences in flow characteristics of the impinger and ThermoSorb/N cartridges.An 18/7ground glass outer spheri-cal joint was attached to the Nalgene valve to permit a quick,gas tight connection to the 18/7ground glass ball joint on the impinger inlet using the appropriate pinch clamp.As shown in Fig.X3.2the impingers were assembled by inserting the glass nozzle (1mm inside diameter orifice)into the sample mixture and coupling the 24/40grease free male and female joints together forming a leak free seal.Once sealed,the Ar gas was allowed to purge through the sample mixture,through the outlet tube of the impinger (see Fig.X3.2).Tygon tubing was used to connect the impinger outlet tube to the inlet side (marked “AIR IN”)of the ThermoSorb/N cartridge,that is simply a standard male luer syringe connector.The purged volatile N -nitrosamines were then collected on the sorbent contained in the cartridge with Ar effluent exiting from the female luer connector.The flow rate of Ar was measured directly from the cartridge with a variable scale flow meter
that
FIG.X3.1Diagram of Purge and Trap Apparatus Equipped With二氧化氯
Four Impinger
Tubes
had beenpreviously calibrated for flow rate of Ar gas (mL/min).A bubble meter can be substituted for the variable scale flow meter.The temperature of the sample mixture during purge was controlled by immersing the impinger up to the sample volume mark (approx.the 25mL line)in a thermo-statically controlled oil bath capable of operation isothermally up to 150°C.The gas manifold,as well as each of the impingers,were secured by clamps to a support grid;therefore,the oil bath was moved vertically in and out of position for high temperature purge.
X3.3Procedure for Extraction and Clean-Up of Pacifier Samples:
X3.3.1Prepare a composite of pacifier rubber by cutting a sufficient number of individual nipples for your replicate requirements from a single lot into 1to 2mm chips using stainless steel scissors and tweezers.Homogenize the compos-ite by freezing in a stainless steel blender jar with liquid nitrogen,
decanting the liquid N 2,blending at high speed for 1to 2min.Immediately transfer the homogenized composite to a glass jar with an aluminum foil lined lid and allow to equilibrate to ambient temperature.
X3.3.2Accurately weigh 5g samples from the composite into a 250-mL round bottom flask and add 100mL dichlo-romethane.
X3.3.3Spike the contents of the flask with 2mL of the internal standard (50ng/mL NDPA).Seal the flask and soak the contents overnight (16to 21h)at ambient temperature.
X3.3.4Then transfer the extract and rubber pieces to a glass extraction thimble fitted with a coarse porosity glass frit in a Soxhlet extraction apparatus.
X3.3.5Rinse the 250mL round bottom flask with 25mL dichloromethane,that was also transferred to the Soxhlet apparatus.
钱复业X3.3.6Extract the rubber pieces for 1h in the apparatus at the rate of eight cycles per hour.
X3.3.7After cooling,transfer the dichloromethane extract to a 250-mL Kuderna Danish (K-D)evaporator.
X3.3.8Then rinse the Soxhlet extraction flask with two 10-mL portions of dichloromethane and combine with the 125-mL extract.
X3.3.9Add 1mm of keeper solution and a few boiling chips to the extract.
X3.3.10Evaporate the extract in the K-D unit using a 3-ball Snyder column on a 55°C water bath until the volume is reduced to 3to 4mL.
X3.3.11Cool the K-D unit to room temperature allowing excess solvent in the Snyder column to rinse down the walls of the unit into the 4-mL K-D tube (totaling 3to 4mL).
X3.3.12After removing the 250-mL reservoir and the 3-ball Snyder column,reduce the volume of the extract to 2mL in the same K-D tube under a gentle stream of nitrogen (about 50mL/min)and transfer the 2mL extract using a disposable Pasteur pipet with two 1-mL mineral oil rinses to a 50-mL purge and trap apparatus containing 20mL of mineral oil and 1mL of 10-mg/mL alpha-tocopherol in mineral oil as a nitrosation inhibitor.
X3.3.13Assemble the purge and trap apparatus with ThermoSorb/N cartridges connected to exit tubes with a Tygon connector.
X3.3.14Adjust the argon flow rate to 400mL/min through the ThermoSorb/N cartridge within 65%(that is 380to 420mL/min Ar).
N OTE X3.2—The flow rate should be checked intermittently during purging,especially within the first 15min because of the initial increase in temperature of the sample.
X3.3.15Then immerse the purge tubes up to the sample line,or about the 25-mL mark in a 15063°C oil bath for 1.5h.
X3.3.16Remove and tightly cap the cartridge.
N OTE X3.3—This step is a good stopping point because the cartridge can be eluted the following day if time is a factor.
X3.3.17Elute the cartridge using a 10or 20-mL glass Luer-lok syringe connected to the female Luer-lok adapter (air exit side)with 20mL of acetone:dichloromethane (1:1;v/v),that was collected in a 30-mL culture tube.
N OTE X3.4—The 30-mL tube(s)should be scored with a file or a piece of tape placed at the 5-mL volume mark.
X3.3.18Evaporate the extract to approximately 5mL and then transfer with three 1-mL rinses of dichloromethane to a 10-mL graduated tube.
N OTE X3.5—For NDBA,evaporate the sample to 1mL for detection levels less than 10ppb.
X3.3.19After addition of 0.5mL of keeper solution (see X3.1.1.2),evaporate the sample (volume =8.5mL)to 2mL under a gentle stream of nitrogen.
N OTE X3.6—If the 2mL sample cannot be analyzed the same day as evaporated,then it would be advantageous to refrigerate the sample at a larger volume (that is 4to 5mL)and evaporate the next day prior to analysis by gas chromatography-thermal energy analysis
(GC-TEA).
FIG.X3.2Diagram of Close-Up of Impinger Tube Fitted With a
ThermoSorb/N 7
Cartridge
X3.3.20The 2-mL sample was analyzed by injecting an 8µL aliquot into the GC-TEA.
X3.4Gas Chromatography-Thermal Energy Analysis (GC-TEA)—The gas chromatograph (GC)used was a Hewlett-Packard Model 5710A instrument 5equipped with a 6-ft glass column (4mm inside diameter)packed with 10%Carbowax 20M/2%KOH on 80/100mesh Chromosorb W AW.The glass col
umn conditioned at 215°C overnight prior to use,was operated in the temperature program mode from 150to 190°C at 4°C/min.The injection port temperature was 250°C.The carrier gas was prepurified Ar gas that flowed at a rate of 40mL/min.The GC column was interfaced to a thermal energy analyzer Model 502via an 3.17mm (1⁄8in.)outside diameter stainless steel tube connected by Swagelok fittings and oper-ated at 170°C.The TEA pyrolysis chamber was kept at 500°C in the GC mode.The oxygen flow to the ozonator was 10mL/min.The cold trap was kept at −150°C using a liquid nitrogen-2methylbutane slush bath.The pressure of the reaction chamber was approximately 0.9torr.The TEA detec-tor response was recorded on a Hewlett Packard 3380A integrator.All sample injections into the GC-TEA system were 8µL aliquots of the sample extracts.
X3.5Quantitation —Quantitation is based on the internal standard technique.
X3.5.1Dilute the external standard stock solution with dichloromethane to 50,100,and 200ng/mL to be used as working standards for analysis.Inject 8µL into the GC-TEA to determine responses (peak heights)of NDPA and the other nitrosamines for use in the internal standardization calculation.X3.5.2Inject 8µL of each 2-mL unknown sample extract into the GC-TEA.Determine responses (peak heights)of NDPA and any other nitrosamines detected for use in the internal standardization calculation.
X3.5.3The calculation of results is as follows:
amount of y ~ppb !5
(X3.1)
peak height y ~a !3ng y
peak height
y ~b !
peak height NDP A ~a !3ng NDP A
peak height
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NDP A ~b !
3
100ng
sample weight ~g !
where:
amount of y =ppb of nitrosamine y in sample,
peak height y (a )=peak height in mm of nitrosamine y in sample,
peak height NDPA (a )=peak height in mm of NDPA (internal stan-dard)in sample,
ng y
peak height y ~b !
=ng of nitrosamine y per millilitre in the ex-ternal standard di-vided by the peak height in millimetres of nitrosamine y in the external standard,ng NDP A
peak height NDP A ~b !
=ng of NDPA per mil-lilitre in the external standard divided by peak height in milli-metre of NDPA in the external standard,sample weight (g)=grams of rubber sample analyzed,and 100ng
=total ng of NDPA (in-ternal standard)added to the sample.
X3.6Sample Homogenization Procedure —From each pacifier lot,remove eight to 24units for analysis depending upon the number of pacifier nipples (0.5to 1.6g/nipple)needed to analyze duplicate 5g rubber samples.Excise the nipples,using dichloromethane rinsed stainless steel forceps and scissors,from the plastic or rubber base and cut into 1to 2-mm chips.Many of the samples exhibit a stickiness after being cut,making homogenization very difficult.In order to break up the large clumps of rubber,transfer the sample into a 70by 155-mm stainless steel Sorvall omni-mixer cup.Pour liquid nitrogen into the cup to cover up all of the rubber chips.Then discard the excess liquid nitrogen into a waste Dewar flask using insulated gloves to handle the extremely cold metal cup.Homogenize the frozen rubber chips by attaching the cup to the mixer housing and setting the speed to approximately 40%of the maximum for 1min.Remove the cup containing the homogenized rubber chips from the mixer.Pour the chips into a 100-mL volume tinted glass sample jar with an alumi-num foil lined screw cap.Then store composited sample in a freezer at −20°C until needed for extraction.
N OTE X3.7—Be careful to avoid addition of any small balls of powdered rubber that might be formed in the blending process.
5
The sole source of supply of the apparatus known to the committee at this time is Hewlett-Packard,Avondale,PA.If you are aware of alternative suppliers,please provide this information to ASTM International Headquarters.Your comments will receive careful consideration at a meeting of the responsible technical committee,1which you may
attend.
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