SIST-TS CEN/TS 13130-21:2005

SLOVENSKI STANDARD
SIST-TS CEN/TS 13130-21:2005
01-april-2005
0DWHULDOLLQSUHGPHWLYVWLNX]åLYLOL6QRYLYSROLPHUQLKPDWHULDOLKNDWHULK
NRQFHQWUDFLMDMHRPHMHQDGHO'RORþHYDQMHHWLOHQGLDPLQDLQ
KHNVDPHWLOHQGLDPLQDYPRGHOQLKUD]WRSLQDK]DåLYLOD
Materials and articles in contact with foodstuffs - Plastics substances subject to limitation
- Part 21: Determination of ethylenediamine and hexamethylenediamine in food
simulants
Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln - Substanzen in Kunststoffen,
die Beschränkungen unterliegen - Teil 21: Bestimmung von Ethylendiamin und
Hexamethylendiamin in Prüflebensmitteln
Matériaux et objets en contact avec les denrées alimentaires - Substances dans les
matieres plastiques soumises a des limitations - Partie 21 : Détermination de
l'éthylenediamine et de l'hexaméthylenediamine dans les simulants d'aliments
Ta slovenski standard je istoveten z: CEN/TS 13130-21:2005
ICS:
67.250 Materiali in predmeti v stiku z Materials and articles in
živili contact with foodstuffs
SIST-TS CEN/TS 13130-21:2005 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST-TS CEN/TS 13130-21:2005

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SIST-TS CEN/TS 13130-21:2005
TECHNICAL SPECIFICATION
CEN/TS 13130-21
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
February 2005
ICS 67.250
English version
Materials and articles in contact with foodstuffs - Plastics
substances subject to limitation - Part 21: Determination of
ethylenediamine and hexamethylenediamine in food simulants
Matériaux et objets en contact avec les denrées Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln
alimentaires - Substances dans les matières plastiques - Substanzen in Kunststoffen, die Beschränkungen
soumises à des limitations - Partie 21 : Détermination de unterliegen - Teil 21: Bestimmung von Ethylendiamin und
l'éthylènediamine et de l'hexaméthylènediamine dans les Hexamethylendiamin in Prüflebensmitteln
simulants d'aliments
This Technical Specification (CEN/TS) was approved by CEN on 16 December 2004 for provisional application.
The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to submit their
comments, particularly on the question whether the CEN/TS can be converted into a European Standard.
CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available
promptly at national level in an appropriate form. It is permissible to keep conflicting national standards in force (in parallel to the CEN/TS)
until the final decision about the possible conversion of the CEN/TS into an EN is reached.
CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,
Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia,
Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36  B-1050 Brussels
© 2005 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TS 13130-21:2005: E
worldwide for CEN national Members.

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Contents
page
Foreword .3
Introduction.5
1 Scope.6
2 Normative references.6
3 Principle .7
4 Reagents .7
5 Apparatus.9
6 Samples.10
7 Procedure.11
8 Precision .14
9 Confirmation .15
10 Test report.15
Bibliography.17

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SIST-TS CEN/TS 13130-21:2005
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Foreword
This document (CEN/TS 13130-21:2005) has been prepared by Technical Committee CEN/TC 194 “Utensils
in contact with food”, the secretariat of which is held by BSI.
This part of EN 13130 has been prepared within the Standards, Measurement and Testing project,
MAT1-CT92-0006, “Development of Methods of Analysis for Monomers” and has been prepared by
Subcommittee (SC 1) of TC 194 "Utensils in contact with food" as one of a series of test methods for plastics
materials and articles in contact with foodstuffs.
This standard is intended to support Directives 2002/72/EC [1], 89/109/EEC [2], 82/711/EEC [3] and its
amendments 93/8/EEC [4] and 97/48/EC [5], and 85/572/EEC [6].
At the time of preparation and publication of this part of EN 13130 the European Union legislation relating to
plastics materials and articles intended to come into contact with foodstuffs is incomplete. Further Directives
and amendments to existing Directives are expected which could change the legislative requirements which
this standard supports. It is therefore strongly recommended that users of this standard refer to the latest
relevant published Directive(s) before commencement of a test or tests described in this standard.
This part of EN 13130 should be read in conjunction with EN 13130-1.
Further parts of EN 13130, under the general title Materials and articles in contact with foodstuffs - Plastics
substances subject to limitation, have been prepared, and others are in preparation, concerned with the
determination of specific migration from plastics materials into foodstuffs and food simulants and the
determination of specific monomers and additives in plastics. The parts of EN 13130 are as follows.
Part 1: Guide to test methods for the specific migration of substances from plastics to foods and food
simulants and the determination of substances in plastics and the selection of conditions of exposure to food
simulants
Part 2: Determination of terephthalic acid in food simulants
Part 3: Determination of acrylonitrile in food and food simulants
Part 4: Determination of 1,3-butadiene in plastics
Part 5: Determination of vinylidene chloride in food simulants
Part 6: Determination of vinylidene chloride in plastics
Part 7: Determination of monoethylene glycol and diethylene glycol in food simulants
Part 8: Determination of isocyanates in plastics
Part 9: Determination of acetic acid, vinyl ester in food simulants
Part 10: Determination of acrylamide in food simulants
Part 11: Determination of 11-aminoundecanoic acid in food simulants
Part 12: Determination of 1,3-benzenedimethanamine in food simulants
Part 13: Determination of 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A) in food simulants
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Part 14: Determination of 3,3-bis(3-methyl-4-hydroxyphenyl)-2-indoline in food simulants
Part 15: Determination of 1,3-butadiene in food simulants
Part 16: Determination of caprolactam and caprolactam salt in food simulants
Part 17: Determination of carbonyl chloride in plastics
Part 18: Determination of 1,2-dihydroxybenzene, 1,3-dihydroxybenzene,
1,4-dihydroxybenzene, 4,4’-dihydroxybenzophenone and 4,4’dihydroxybiphenyl in food simulants
Part 19: Determination of dimethylaminoethanol in food simulants
Part 20: Determination of epichlorohydrin in plastics
Part 21: Determination of ethylenediamine and hexamethylenediamine in food simulants
Part 22: Determination of ethylene oxide and propylene oxide in plastics
Part 23: Determination of formaldehyde and hexamethylenetetramine in food simulants
Part 24: Determination of maleic acid and maleic anhydride in food simulants
Part 25: Determination of 4-methyl-pentene in food simulants
Part 26: Determination of 1-octene and tetrahydrofuran in food simulants
Part 27: Determination of 2,4,6-triamino-1,3,5-triazine in food simulants
Part 28: Determination of 1,1,1-trimethylolpropane in food simulants
Parts 1 to 8 are European Standards. Parts 9 to 28 are Technical Specifications.
WARNING All chemicals are hazardous to health to a greater or lesser extent. It is beyond the
scope of this Technical Specification to give instructions for the safe handling of all chemicals, that
meet, in full, the legal obligations in all countries in which this Technical Specification may be
followed. Therefore, specific warnings are not given and users of this Technical Specification should
ensure that they meet all the necessary safety requirements in their own country.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to announce this CEN Technical Specification: Austria, Belgium, Cyprus, Czech Republic,
Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia, Slovenia, Spain, Sweden, Switzerland
and United Kingdom.
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CEN/TS 13130-21:2005 (E)
Introduction
Ethylenediamine (EDA), 1,2-Diaminoethane, C H N or H N-(CH ) -NH , PM/Ref. No 16960, and
2 8 2 2 2 2 2
hexamethylenediamine (HMDA), 1,6-Diaminohexane, C H N or H N-(CH ) -NH , PM/Ref. No 18460 are
6 16 2 2 2 6 2
monomers used in the manufacture of certain plastics materials and articles intended to come into contact
with foodstuffs. After manufacture, residual EDA monomer and HMDA monomer can remain in the polymer
and may migrate into foodstuffs coming into contact with that plastics article.
NOTE Stability tests in olive oil food simulant carried out under test conditions 10 d at 20 °C and 10 d at 40 °C
indicated that EDA and HMDA cannot be recovered, presumably due to chemical reaction with the olive oil. Therefore,
even though this analytical method works in principle with olive oil as a food simulant, the migration test using olive oil or
another fat simulant can provide false-negative results. Therefore, the method should only be applied in case of short
exposure periods with olive oil and if applied, a recovery check with spiked olive oil applying the same time/temperature
migration test conditions is recommended. Alternatively 95 % ethanol or iso-octane could be used as substitute fatty food
simulants.
The method has been pre-validated by a collaborative trial with two laboratories.
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1 Scope
This document, part of EN 13130, specifies an analytical procedure for the determination of EDA monomer and
HMDA monomer in the food simulants water, 3 % w/v aqueous acetic acid, 15 % v/v aqueous ethanol and
olive oil as well as in the substitute food simulants 95 % v/v ethanol and iso-octane. The level of EDA
monomer and HMDA monomer determined are expressed as milligram EDA per kilogram of food simulant and
as milligrams HMDA per kilogram of food simulant. The method is appropriate for the quantitative
determination of EDA at a minimum level of 1 mg per kilogram of food simulants and for the quantitative
determination of HMDA at a minimum level of 0,5 mg per kilogram of food simulants.
The method should also be applicable to other aqueous food simulants as well as to the other fatty food
simulants sunflower oil and a mixture of synthetic triglycerides.
2 Normative references
The following referenced documents are indispensable for the application of this document. For dated
references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.
EN 13130-1:2004, Materials and articles in contact with foodstuffs – Plastics substances subject to limitation –
Part 1: Guide to test methods for the specific migration of substances from plastics to foods and food
simulants and the determination of substances in plastics and the selection of conditions of exposure to food
simulants.
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3 Principle
The level of EDA or HMDA in a food simulant is determined by derivatization of the free diamine, using ethyl
chloroformate as derivatization agent followed by analysis of the resulting diurethane by gas chromatography
using automated sample injection and flame ionization detection (FID). Quantification is achieved using
propylenediamine (PDA) as an internal standard with calibration against relevant food simulants samples
fortified with known amounts of EDA or HMDA. Confirmation of EDA or HMDA levels is carried out by
combined gas chromatography/mass spectrometry (GC/MS) of the diurethane.
4 Reagents
NOTE All reagents should be of recognized analytical quality unless otherwise stated.
4.1 Analytes
4.1.1 EDA (1,2-diaminoethane), H N-(CH ) -NH , purity greater than 99 %.
2 2 2 2
4.1.2 HMDA (1,6-diaminohexane), H N-(CH ) -NH , purity greater than 97 %.
2 2 6 2
4.1.3 PDA (1,3-diaminopropane), H N-(CH ) -NH , purity greater than 99 %.
2 2 3 2
4.2 Chemicals
4.2.1 Ethyl chloroformate, Cl-C(O)-OC H , purity greater than 97 %.
2 5
4.2.2 Toluene
4.2.3 Diethyl ether
4.2.4 Distilled water
20
4.2.5 25 % (w/w) aqueous solution of ammonia, NH (d = 0,91kg/l).
3
Sodium sulfate, anhydrous.
4.2.6
4.2.7 Sodium hydroxide, NaOH, pellets 99 %.
4.2.8 Acetic acid, glacial 100 %.
4.2.9 Purified nitrogen, 99,999 %.
4.3 Solutions
4.3.1 Solution of NH in distilled water [approx. 3 % (w/w)]
3
Place 200 ml of distilled water (4.2.4) into a 250 ml Erlenmeyer flask, add 30 ml of 25 % aqueous NH solution
3
(4.2.5) and mix thoroughly.
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4.3.2 5 M solution of NaOH in distilled water
Weigh 50,0 g NaOH (4.2.7) with an accuracy of 0,1 g into a 250 ml volumetric flask and fill up to the mark with
distilled water (4.2.4) at room temperature.
4.3.3 3 % (w/v) acetic acid in distilled water
Weigh 15,0 g of acetic acid (4.2.8) with an accuracy of 0,1g into a 500 ml volumetric flask and make up to the
mark with distilled water (4.2.4).
4.3.4 Stock solutions of EDA and HMDA in water
4.3.4.1 Stock solutions of EDA in water with defined concentrations at approximately 1000 µg/ml
Weigh a defined mass at approximately 50 mg of EDA with an accuracy of 0,1 mg into a 50 ml volumetric flask.
Dissolve the EDA in water and fill up to the mark with water. Close and mix thoroughly.
Calculate the concentration in micrograms of EDA per millilitre of solution.
Repeat the procedure to provide a second stock solution.
4.3.4.2 Stock solutions of HMDA in water with defined concentration at approximately 500 µg/ml
Weigh a defined mass at approximately 25 mg of HMDA with an accuracy of 0,1 mg into a 50 ml volumetric
flask. Dissolve the HMDA in water and fill up to the mark with water. Close and mix thoroughly.
Calculate the concentration in micrograms of HMDA per millilitre of solution.
Repeat the procedure to provide a second stock solution.
4.3.5 Stock solutions of EDA and HMDA in toluene
4.3.5.1 Stock solutions of EDA in toluene with defined concentrations at approximately 1 000 µg/ml
Weigh a defined mass at approximately 50 mg of EDA with an accuracy of 0,1 mg into a 50 ml volumetric flask.
Dissolve the EDA in toluene and fill up to the mark with toluene. Close and mix thoroughly.
Calculate the concentration in micrograms of EDA per millilitre of solution.
Repeat the procedure to provide a second stock solution.
4.3.5.2 Stock solutions of HMDA in toluene with defined concentrations at approximately
500 µg/ml
Weigh a defined mass at approximately 25 mg of HMDA with an accuracy of 0,1 mg into a 50 ml volumetric
flask. Dissolve the HMDA in toluene and fill up to the mark with toluene. Close and mix thoroughly.
Calculate the concentration in micrograms of HMDA per millilitre of solution.
Repeat the procedure to provide a second stock solution.
4.3.6 Internal standard stock solution of PDA in water with a defined concentration at approximately
500 µg/ml
Weigh a defined mass at approximately 25 mg of PDA with an accuracy of 0,1 mg into a 50 ml volumetric flask.
Dissolve the PDA in water and fill up to the mark with water. Close and mix thoroughly.
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Calculate the concentration in micrograms of PDA per millilitre of solution.
4.3.7 Internal standard stock solution of PDA in toluene with a defined concentration at
approximately 500 µg/ml
Weigh a defined mass of approximately 25 mg of PDA with an accuracy of 0,1 mg into a 50 ml volumetric flask.
Dissolve the PDA in toluene and fill up to the mark with toluene. Close and mix thoroughly.
Calculate the concentration in micrograms of PDA per millilitre of solution.
NOTE The stock solutions can be stored at 5 °C to 20 °C for up to 3 months protected from light in septum capped
glass vials with minimum headspace.
When using toluene as a solvent, pay attention to possible precipitation of the solute at lower temperatures.
5 Apparatus
NOTE An instrument or item of apparatus is listed only where it is special, or made to a particular specification, usual
laboratory glassware and equipment being assumed to be available.
5.1 Gas chromatograph, equipped with a flame ionization detector (FID) and fitted with automatic sample
injection.
5.2 Gas chromatographic column, capable of the separation of EDA or HMDA and PDA diurethanes such
that the peaks of EDA or HMDA and PDA diurethanes do not overlap by more than 1 % peak area with other
compounds.
Appropriate operating conditions have to be established for the specific equipment used for the determination.
NOTE The following chromatographic column and conditions have been found to be satisfactory.
Column
30 m x 0,32 mm I.D. fused silica capillary column coated with 0,25 µm methylsilicone film
Injector: 280 °C
Oven program: 100 °C (3 min), 25 °C/min to 270 °C (2 min)
Detector (FID): 300 °C
Carrier gas: 2
Helium at inlet pressure 0,8 kp/cm
and linear velocity 25 cm/sec
Injection mode: split (ratio = 1:15)
Injection volume: 1 µl
FID gases: to be optimized according to the manufacturer's
specifications

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5.3 Glass sample vials, 2 ml, or of another size suitable for the par
...