ASTM F1313-90(2005)
(Specification)Standard Specification for Volatile N-Nitrosamine Levels in Rubber Nipples on Pacifiers
Standard Specification for Volatile N-Nitrosamine Levels in Rubber Nipples on Pacifiers
ABSTRACT
This specification applies to the nitrosamine content of rubber used in the manufacture of nipples for infant pacifiers. This specification is intended for use in reducing the normal exposure to nitrosamines. Methylene chloride extraction method shall be used to determine the nitrosamine levels.
SCOPE
1.1 This specification applies to the nitrosamine content of rubber used in the manufacture of nipples for infant pacifiers.
1.2 This specification does not apply to plastic nipples (on pacifiers).
1.3 The 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.
1.4 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.
The following precautionary statement pertains only to the test method portions, Sections , and of 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 appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific hazards are given in .
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Designation: F1313 – 90 (Reapproved 2005)
Standard Specification for
VolatileN-Nitrosamine Levels in Rubber Nipples on
Pacifiers
This standard is issued under the fixed 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.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 3.2 This specification refers only by way of example to the
eight volatile N-nitrosamines identified below:
1.1 This specification applies to the nitrosamine content of
3.2.1 N-nitrosodimethylamine,
rubber used in the manufacture of nipples for infant pacifiers.
3.2.2 N-nitrosodiethylamine,
1.2 This specification does not apply to plastic nipples (on
3.2.3 N-nitrosodibutylamine,
pacifiers).
3.2.4 N-nitrosomorpholine,
1.3 The purpose of this specification is to establish a
3.2.5 N-nitrosopiperidine,
maximum level of allowed nitrosamines in rubber nipples and
3.2.6 N-nitrosopyrrolidine,
to outline a uniform testing method to determine such level.
3.2.7 N-ethylphenylnitrosamine.
1.4 The values stated in SI units are to be regarded as
standard. The values given in parentheses are for information
4. Test Method
only.
4.1 Determine nitrosamine levels by using either the meth-
1.5 The following precautionary statement pertains only to
ylenechlorideextractionmethoddescribedinthecollaborative
the test method portions, Sections 5, andAppendix X4 of this
study conducted by the National Center for Toxicological
specification. This standard does not purport to address all of
2 2
Research or the Food and Drug Administration method.
the safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
5. Acceptable Level
priate safety and health practices and determine the applica-
5.1 A test sample of nipples, drawn from a standard pro-
bilityofregulatorylimitationspriortouse.Specifichazardsare
duction lot, shall not contain more than 10 ppb (in each of 3
given in Appendix X2.
aliquots) of any one nitrosamine. In addition, the total nitro-
samines of the sample shall not exceed 20 ppb.
2. Terminology
5.2 Eachmanufacturerordistributoroftheproductshalltest
2.1 Definitions:
the product in such a manner and at such intervals to ensure
2.1.1 lot—normal production run or, in the case of imports,
compliance in accordance with the methodology prescribed by
a shipment of items produced in the same time frame.
the test procedure utilized. Records of all testing shall be
2.1.2 nitrosamines—chemically active compounds princi-
retained for a period of up to three years.
pally formed by the reaction of amines with oxides of nitrogen
present in the environment.
6. Report
3. Significance and Use 6.1 Report the following information:
6.1.1 Lot number,
3.1 This specification is intended for use in reducing the
6.1.2 Date samples,
normal exposure to nitrosamines.
6.1.3 Date tested,
6.1.4 Individual nitrosamine content, and
This specification is under the jurisdiction of ASTM Committee F15 on
6.1.5 Total nitrosamine content.
Consumer Products and is the direct responsibility of Subcommittee F15.22 onToy
Safety.
Current edition approved Sept. 1, 2005. Published October 2005. Originally
approved in 1990. Last previous edition approved in 1999 as F1313–90 (1999). AvailablefromU.S.GovernmentPrintingOfficeSuperintendentofDocuments,
DOI: 10.1520/F1313-90R05. 732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
F1313 – 90 (2005)
APPENDIXES
(Nonmandatory Information)
X1. BACKGROUND
X1.1 This specification provides the rationale for the conclusively providing evidence of reproducibility among
drafting of a voluntary product standard establishing accept- laboratories.
ablelevelsandtestingproceduresfornitrosaminescontainedin
X1.5 The Consumer Product Safety Commission uses the
children’s rubber pacifiers.
NCTR method in analyzing pacifiers for nitrosamine content
X1.2 Some nitrosamines are known to be potent animal under its enforcement policy. The FDA utilizes the FDA
carcinogensandaresuspectedhumancarcinogens.In1981,the method in its Compliance Policy Guide, 7117.15. The CPSC
West German Government enacted regulations limiting the and NCTR staffs characterize the NCTR method as cheaper,
amount of preformed nitrosamine in rubber pacifiers. Nitro- faster, and more reproducible, although both the NCTR and
samines are formed from amines used as accelerators during FDAhave affirmed that their two methods give essentially the
vulcanization of the rubber or are unintentional trace sub- same results in their laboratories.
stances present in stabilizers used in the manufacturing pro-
X1.6 The test methodologies contained in Appendix X3
cess.
andAppendix X4 define sample sizes and contain the requisite
X1.3 In 1982, the Consumer Product Safety Commission and prescribed procedure for sampling from a lot to be tested.
(CPSC) began meeting with rubber pacifier manufacturers and
X1.7 On December 27, 1983, the CPSC issued a statement
importers (most are imported), drawing their attention to both
of policy that rubber pacifiers are hazardous substances as
thecarcinogenicpotentialasmeasuredbylaboratorybioassays
defined in Section 2(g) of the Federal Hazardous Substances
on rodents and the results of an audit of those pacifiers on the
Act and are banned if they contain more than 60 ppb of
market. The audit revealed nitrosamine levels ranging from
nitrosamines as measured by the NCTR methylene chloride
“non-detectable” to as much as hundreds of parts per billion
extraction test, effective January 1, 1984.
(ppb).TheToyManufacturersofAmerica(TMA)undertookto
coordinate a program to lower the levels of nitrosamines and
X1.8 A collaborative study between the NCTR,
validate a single test method that could be duplicated in
manufacturers/importers and leading testing laboratories was
laboratories worldwide. This effort was a joint, round-robin
initiated to validate the test for consistent results between
program with the CPSC, the National Center forToxicological
laboratories. Manufacturers and importers have continued to
Research (NCTR) and pacifier manufacturers/importers. An-
work with manufacturing processes and independent laborato-
othermethodoftestinghasbeendetailedbytheFoodandDrug
riestoreducenitrosaminelevelsduringthisperiod.Significant
Administrationintheirprogramtoreducenitrosaminelevelsin
progress has been made since the start of the program.
nursing nipples.
X1.9 In June, 1985, a group of manufacturers met with the
X1.4 This specification currently recognizes two test meth-
Toy Manufacturers of America to draft a voluntary specifica-
ods, one developed by the National Center for Toxicological
tion. That specification was presented to a task force of
Research(NCTR)(seeAppendixX3),andonewhichisknown
consumers and manufacturers on August 14, 1985 at ASTM
as the Food and Drug Administration (FDA) method (see
Headquarters.This specification is the result of the corrections
Appendix X4). Both methods have been corroborated and
and suggestions made at that meeting, as well as comments
adopted as an approved method by the Association of Official
from formal ASTM balloting procedures.
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
FederalRegister48,No.249,pp.56988–56990,availablefromSuperintendent
of Documents, U.S. Government Printing Office, North Capitol and H Streets, NW,
methods provide equivalent test results. Several government
Washington, DC 20401.
and independent laboratories participated in the corroborative
FederalRegister49,No.252,pp.50789–50790,availablefromSuperintendent
study in which coded quadruplicate samples of three compos-
of Documents, U.S. Government Printing Office, North Capitol and H Streets, NW,
ites were sent to each laboratory for analysis and tally, Washington, DC 20401.
F1313 – 90 (2005)
X2. HAZARD ANALYSIS
X2.1 The scientific community in Europe, Canada and the worstcasebasisthatthelifetimerisktoauserofinfantnipples
United States has concluded that nitrosamines are suspected (having 60 ppb nitrosamines) was one in 23 million. However,
human carcinogens. However, the actual risk to infants who the Toy Manufacturers Association has approached this prob-
use rubber pacifiers is probably very small. In fact, a risk lem, accepting that high levels of nitrosamines are unaccept-
assessment study conducted by the Rubber Manufacturers able and that low levels of 20 ppb, that generally represent
Association involving infant feeding nipples concluded on a unavoidable contamination, are achievable.
X3. PROCEDURE FOR ANALYSIS OFN -NITROSAMINES IN PACIFIERS—A COLLABORATIVE STUDY
X3.1 Reagents, Apparatus, and Pacifiers—All solvents X3.1.8.4 Nalgene needle valveType CPE (No. 6400-0125);
were distilled in glass and all other reagents were chemically
X3.1.8.5 Groundglassouterjointswithpinchclamps,18/7;
pure grade.
X3.1.8.6 Impingers, 50 mL graduated glass tubes with
24/40 clear-seal grease free joints, 18/7 ground glass ball
X3.1.1 N-Nitrosamine Standard Stock:
joints, and 1 mm inside diameter nozzle approximately 5 mm
X3.1.1.1 External Standard Stock—Tenµg/mLinethanolof
above the bottom of the impinger; and
7 N-nitrosamine mixture.
X3.1.1.2 Internal Standard Stock—A solution of NDPA (5 X3.1.8.7 Variable Scale Flow-Check—Calibrated for purge
rate in mL/min, of argon. A bubble meter for measuring gas
µg/mL in ethanol).
X3.1.2 Pacifiers. flow rates for a gas chromatograph may be substituted.
X3.1.3 Mineral Oil— White, light weight Saybolt viscosity
NOTE X3.1—Do not use any rubber tubing, gaskets, o-rings, or any
125/135.
other items made of rubber in any part of this method.
X3.1.4 Nitrosation Inhibitor—Ten mg alpha-
Tocopherol/mL mineral oil.
X3.2 Description and Use of the Purge and Trap
X3.1.5 Keeper Solution:
Apparatus—The apparatus shown in Fig. X3.1 was designed
X3.1.5.1 For K-D Evaporation—Eighty mg mineral oil/mL
forthehightemperaturepurgingandtrappingofsevenvolatile
dichloromethane.
nitrosamines from a concentrated sample extract/mineral oil
X3.1.5.2 For N Blowdown—Twenty mg mineral oil/mL
2 mixture on four samples simultaneously.Acylinder containing
iso-octane.
prepurified argon (Ar) gas equipped with a high pressure
X3.1.6 ThermoSorb/N Cartridges—Used as received for
regulator was used to supply 20 psig to a flow metering valve
quantitative trapping of volatile N-nitrosamines.
thatregulatesthefinalpurgeflowthroughthesamples.Thegas
X3.1.7 Variable Temperature Oil Bath—Thermostatically
stream was diverted into a tubular stainless steel manifold 250
controlled oil bath capable of operating at 150 6 3°C and of
by 20 mm outside diameter containing four exit tubes spaced
moving vertically with aid of a lab jack.
50 mm apart and measuring 40 by 10 mm outside diameter.
X3.1.8 Purge and Trap Apparatus—The apparatus shown
Eachofthesetubeswerecoupledusing9.52mm( ⁄8in.)Tygon
in Fig. X3.1 contains the following parts:
tubing to Nalgene needle valves that serve dual purposes: as a
X3.1.8.1 Argon (Ar) gas cylinder and gage;
shut off valve when assaying less than four samples; and for
X3.1.8.2 Metering valve;
making minor adjustments in purge rate due to slight differ-
X3.1.8.3 Purge gas manifold 4-position;
ences in flow characteristics of the impinger and
ThermoSorb/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 the
impinger inlet using the appropriate pinch clamp.As shown in
Fig. X3.2 the impingers were assembled by inserting the glass
nozzle (1 mm inside diameter orifice) into the sample mixture
and coupling the 24/40 grease free male and female joints
together forming a leak free seal. Once sealed, theAr 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
FIG. X3.1 Diagram of Purge and Trap Apparatus Equipped With
Four Impinger Tubes directlyfromthecartridgewithavariablescaleflowmeterthat
F1313 – 90 (2005)
X3.3.6 Extract the rubber pieces for1hinthe apparatus at
the rate of eight cycles per hour.
X3.3.7 After cooling, transfer the dichloromethane extract
to a 250-mL Kuderna Danish (K-D) evaporator.
X3.3.8 Then rinse the Soxhlet extraction flask with two
10-mL portions of dichloromethane and combine with the
125-mL extract.
X3.3.9 Add1mmofkeepersolutionandafewboilingchips
to the extract.
X3.3.10 EvaporatetheextractintheK-Dunitusinga3-ball
Snyder column on a 55°C water bath until the volume is
reduced to 3 to 4 mL.
X3.3.11 Cool the K-D unit to room temperature allowing
excesssolventintheSnydercolumntorinsedownthewallsof
the unit into the 4-mL K-D tube (totaling 3 to 4 mL).
X3.3.12 Afterremovingthe250-mLreservoirandthe3-ball
Snydercolumn,reducethevolumeoftheextractto2mLinthe
same K-D tube under a gentle stream of nitrogen (about 50
mL/min) and transfer the 2 mL extract using a disposable
Pasteur pipet with two 1-mL mineral oil rinses to a 50-mL
purge and trap apparatus containing 20 mL of mineral oil and
1 mL of 10-mg/mL alpha-tocopherol in mineral oil as a
nitrosation inhibitor.
FIG. X3.2 Diagram of Close-Up of Impinger Tube Fitted With a
ThermoSorb/N Cartridge X3.3.13 Assemble the purge and trap apparatus with
ThermoSorb/NcartridgesconnectedtoexittubeswithaTygon
had beenpreviously calibrated for flow rate of Ar gas (mL/ connector.
min). A bubble meter can be substituted for the variable scale
X3.3.14 Adjust the argon flow rate to 400 mL/min through
flow meter. The temperature of the sample mixture during the ThermoSorb/N cartridge within 65% (that is 380 to 420
purge was controlled by immersing the impinger up to the
mL/min Ar).
sample volume mark (approx. the 25 mL line) in a thermo-
NOTE X3.2—The flow rate should be checked intermittently during
statically controlled oil bath capable of operation isothermally
purging, especially within the first 15 min because of the initial increase
up to 150°C. The gas manifold, as wel
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