ASTM F1313-90(1999)

Standard Specification for Volatile N-Nitrosamine Levels in Rubber Nipples on Pacifiers

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 in parentheses are for information only.
1.5 The following precautionary statement pertains only to the test method portions, Sections 5, and Appendix X4 of this specification. This standard does not purport to address all of the safety problems 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 Appendix X2.

General Information

• Status: Historical
• Publication Date: 09-Sep-1999
• ICS: 67.250 - Materials and articles in contact with foodstuffs
• Technical Committee: F15 - Consumer Products
• Drafting Committee: F15.22 - Toy Safety

Relations

• Replaced By: ASTM F1313-90(2005) - Standard Specification for Volatile N-Nitrosamine Levels in Rubber Nipples on Pacifiers
• Effective Date: 01-Sep-2005
• Referred By: ASTM F963-17 - Standard Consumer Safety Specification for Toy Safety
• Effective Date: 10-Sep-1999

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: F 1313 – 90 (Reapproved 1999)
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 (e) 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—a normal production run or, in the case of
compliance in accordance with the methodology prescribed by
imports, 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
6.1.5 Total nitrosamine content.
This specification is under the jurisdiction of ASTM Committee F15 on
Consumer Products and is the direct responsibility of Subcommittee F15.22 onToy
Safety. Available from the Superintendent of Documents, U.S. Government Printing
Current edition approved Aug. 31, 1990. Published October 1990. Office, North Capitol and H Streets, NW, Washington, DC 20401.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
F 1313
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.
F 1313
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
were distilled in glass and all other reagents were chemically
pure grade.
X3.1.1 N-Nitrosamine Standard Stock:
X3.1.1.1 External Standard Stock—Tenµg/mLinethanolof
7 N-nitrosamine mixture.
X3.1.1.2 Internal Standard Stock—A solution of NDPA (5
µg/mL in ethanol).
X3.1.2 Pacifiers.
X3.1.3 Mineral Oil— White, light weight Saybolt viscosity
125/135.
X3.1.4 Nitrosation Inhibitor—Ten mg alpha-
Tocopherol/mL mineral oil.
X3.1.5 Keeper Solution:
FIG. X3.1 Diagram of Purge and Trap Apparatus Equipped With
X3.1.5.1 For K-D Evaporation—Eighty mg mineral oil/mL
Four Impinger Tubes
dichloromethane.
X3.1.5.2 For N Blowdown—Twenty mg mineral oil/mL
X3.1.8.5 Ground glass outer joints with pinch clamps,
iso-octane.
18/7;
X3.1.6 ThermoSorb/N Cartridges—Used as received for
X3.1.8.6 Impingers, 50 mL graduated glass tubes with
quantitative trapping of volatile N-nitrosamines.
24/40 clear-seal grease free joints, 18/7 ground glass ball
X3.1.7 Variable Temperature Oil Bath—Thermostatically
joints, and 1 mm inside diameter nozzle approximately 5 mm
controlled oil bath capable of operating at 150 6 3°C and of
above the bottom of the impinger; and
moving vertically with aid of a lab jack. 14
X3.1.8.7 Variable Scale Flow-Check —Calibrated for
X3.1.8 Purge and Trap Apparatus—The apparatus shown
purge rate in mL/min, of argon.Abubble meter for measuring
in Fig. X3.1 contains the following parts:
gas flow rates for a gas chromatograph may be substituted.
X3.1.8.1 Argon (Ar) gas cylinder and gage;
NOTE X3.1—Do not use any rubber tubing, gaskets, o-rings, or any
X3.1.8.2 Metering valve;
other items made of rubber in any part of this method.
X3.1.8.3 Purge gas manifold 4-position;
X3.2 Description and Use of the Purge and Trap
X3.1.8.4 Nalgene needle valve Type CPE (No. 6400-
0125); Apparatus—The apparatus shown in Fig. X3.1 was designed
forthehightemperaturepurgingandtrappingofsevenvolatile
nitrosamines from a concentrated sample extract/mineral oil
mixture on four samples simultaneously.Acylinder containing
Available from Burdick and Jackson, Muskegon, MI, or equivalent, has been
prepurified argon (Ar) gas equipped with a high pressure
found satisfactory for this purpose.
regulator was used to supply 20 psig to a flow metering valve
Available from Thermo Electron Corp.,Waltham, MA, or equivalent, has been
thatregulatesthefinalpurgeflowthroughthesamples.Thegas
found satisfactory for this purpose.
Available from Consumer Products Safety Commission, Bethesda, MD, or
stream was diverted into a tubular stainless steel manifold 250
equivalent, have been found satisfactory for this purpose.
Number 6358, available from Mallinckrodt, Paris, KY, or equivalent, has been
found satisfactory for this purpose.
9 12
AvailablefromTheLabApparatusCo.,Cleveland,OH,orequivalent,hasbeen Number 772398, available from Wheaton Scientific, Millville, NJ, or equiva-
found satisfactory for this purpose. lent, has been found suitable for this purpose.
10 13
Available from Air Products Specialty Gas, Tamaqua, PA, or equivalent, has Number 753463, available from Wheaton Scientific, Millville, NJ, or equiva-
been found suitable for this purpose. lent, has been found suitable for this purpose.
11 14
Available from Nalge Co., Rochester, NY, or equivalent has been found Number 7083, available fromAlltechAssociates, Houston,TX, or equivalent,
suitable for this purpose. has been found suitable for this purpose.
F 1313
by 20 mm outside diameter containing four exit tubes spaced X3.3 Procedure for Extraction and Clean-Up of Pacifier
50 mm apart and measuring 40 by 10 mm outside diameter. Samples:
Eachofthesetubeswerecoupledusing9.52mm( ⁄8in.)Tygon
X3.3.1 Prepare a composite of pacifier rubber by cutting a
tubing to Nalgene needle valves that serve dual purposes: as
sufficient number of individual nipples for your replicate
a shut off valve when assaying less than four samples; and for
requirements from a single lot into 1 to 2 mm chips using
making minor adjustments in purge rate due to slight differ-
stainless steel scissors and tweezers. Homogenize the compos-
ences in flow characteristics of the impinger and
ite by freezing in a stainless steel blender jar with liquid
ThermoSorb/N cartridges.An 18/7 ground glass outer spheri-
nitrogen, decanting the liquid N , blending at high speed for 1
caljointwasattachedtotheNalgene valvetopermitaquick,
to 2 min. Immediately transfer the homogenized composite to
gas tight connection to the 18/7 ground glass ball joint on the
a glass jar with an aluminum foil lined lid and allow to
impinger inlet using the appropriate pinch clamp.As shown in
equilibrate to ambient temperature.
Fig. X3.2 the impingers were assembled by inserting the glass
X3.3.2 Accurately weigh 5 g samples from the composite
nozzle (1 mm inside diameter orifice) into the sample mixture
into a 250-mL round bottom flask and add 100 mL dichlo-
and coupling the 24/40 grease free male and female joints
romethane.
together forming a leak free seal. Once sealed, theAr gas was
X3.3.3 Spike the contents of the flask with 2 mL of the
allowed to purge through the sample mixture, through the
internalstandard(50ng/mLNDPA).Sealtheflaskandsoakthe
outlet tube of the impinger (see Fig. X3.2). Tygon tubing was
contents overnight (16 to 21 h) at ambient temperature.
used to connect the impinger outlet tube to the inlet side
X3.3.4 Thentransfertheextractandrubberpiecestoaglass
(marked “AIR IN”) of the ThermoSorb/N cartridge, that is
extraction thimble fitted with a coarse porosity glass frit in a
simply a standard male luer syringe connector. The purged
Soxhlet extraction apparatus.
volatile N-nitrosamines were then collected on the sorbent
X3.3.5 Rinse the 250 mL round bottom flask with 25 mL
...