CEN/TS 13130-16:2005

Materials and articles in contact with foodstuffs - Plastics substances subject to limitation - Part 16: Determination of caprolactam and caprolactam salt in food simulants

This document, part of EN 13130, specifies an analytical procedure for the determination of caprolactam in the food simulants distilled water, 3 % w/v aqueous acetic acid,
15 % v/v aqueous ethanol and rectified olive oil. The level of caprolactam monomer determined is expressed as mg caprolactam/kg of food or food simulant. The method is appropriate for the quantitative determination of caprolactam in an approximate analyte concentration range of 1,5mg/kg to 30 mg per kilogram of food simulant.
This method is also applicable to the determination of the specific migration of caprolactam sodium salt, PM/Ref No 14230, as caprolactam sodium salt instantaneously hydrolyzes to caprolactam when in contact with aqueous media.
NOTE   The method should also be applicable to other aqueous food simulants as well as to other fatty food simulants e.g. sunflower oil, a mixture of synthetic triglycerides and volatile substitutes for fat simulants.

Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln - Substanzen in Kunststoffen, die Beschränkungen unterliegen - Teil 16: Bestimmung von Caprolactam und Caprolactamsalz in Prüflebensmitteln

Diese Technische Spezifikation, Teil der EN 13130, legt ein Analyseverfahren zur Bestimmung von Caprolactam in den Prüflebensmitteln destilliertes Wasser, 3%ige Essigsäure (m/V) in wässriger Lösung, 15%iges Ethanol (Volumenanteil) in wässriger Lösung und rektifiziertes Olivenöl fest. Der ermittelte Gehalt an monomerem Caprolactam wird in Milligramm Caprolactam je Kilogramm Lebensmittel oder Prüflebensmittel angegeben. Das Verfahren eignet sich zur quantitativen Bestimmung von Caprolactam im angenäherten Konzentrationsbereich des Analyten von 1,5 mg/kg bis 30 mg je Kilogramm Prüflebensmittel.
Das Verfahren ist auch für die Bestimmung der spezifischen Migration von Caprolactam-Natriumsalz, PM/Ref-Nr. 14230, geeignet, weil Caprolactam-Natriumsalz in Kontakt mit wässrigen Medien unverzüglich zu Caprolactam hydrolisiert.
ANMERKUNG   Das Verfahren sollte auch auf andere wässrige Prüflebensmittel sowie weitere fettige Prüflebensmittel, z. B. Sonnenblumenöl, eine Mischung synthetischer Triglyceride und leicht flüchtige Ersatzstoffe für Fettsimulantien, anwendbar sein.

Matériaux et objets en contact avec les denrées alimentaires - Substances dans les matiéres plastiques soumises à des limitations - Partie 16: Détermination du caprolactame et des sels de caprolactame dans les simulants d'aliments

Le présent document qui fait partie de l'EN 13130, spécifie un mode opératoire d'analyse pour la détermination du caprolactame dans les quatre simulants d'aliments suivants : eau distillée, solution aqueuse d'acide acétique à 3 % (m/v), solution aqueuse d'éthanol à 15 % (v/v) et huile d'olive rectifiée. La teneur en caprolactame déterminée est exprimée en mg de caprolactame par kg de denrée alimentaire. La présente méthode convient pour la détermination quantitative du caprolactame dans une gamme de concentrations d'analyte comprise approximativement entre 1,5 mg et 30 mg par kilogramme de simulant d'aliments.
La présente méthode est également applicable à la détermination de la migration spécifique du sodium de caprolactame, PM / Ref N° 14230, étant donné que le sodium de caprolactame s'hydrolyse instantanément en caprolactame lorsqu'il entre en contact avec les milieux aqueux.
NOTE   Il convient que la méthode puisse également être appliquée à d'autres simulants aqueux ainsi qu'à des simulants gras tels que l'huile de tournesol, un mélange de triglycérides synthétiques ou des succédanés volatiles des simulants gras.

Materiali in predmeti v stiku z živili - Snovi v polimernih materialih, katerih koncentracija je omejena - 16. del: Določevanje kaprolaktama in natrijeve soli kaprolaktama v modelnih raztopinah za živila

General Information

• Status: Published
• Publication Date: 22-Feb-2005
• ICS: 67.250 - Materials and articles in contact with foodstuffs
• Technical Committee: CEN/TC 194 - Utensils in contact with food
• Drafting Committee: CEN/TC 194/SC 1/WG 2 - Methods of test for monomers
• Current Stage: 6060 - Definitive text made available (DAV) - Publishing
• Start Date: 23-Feb-2005
• Completion Date: 23-Feb-2005
• Ref Project: SIST-TS CEN/TS 13130-16:2005 - Materials and articles in contact with foodstuffs - Plastics substances subject to limitation - Part 16: Determination of caprolactam and caprolactam salt in food simulants

Overview

CEN/TS 13130-16:2005 specifies a validated analytical procedure for the determination of caprolactam (and caprolactam sodium salt as caprolactam) migrating from plastics into food simulants. It is part of the EN 13130 series covering substances in plastics that are subject to limitation for food contact materials. The method quantifies caprolactam in distilled water, 3% w/v acetic acid, 15% v/v ethanol, and rectified olive oil, with an approximate working range of 1.5 mg/kg to 30 mg/kg (expressed as mg caprolactam/kg food or simulant). The method was pre‑validated by a five‑laboratory collaborative trial.

Key topics and technical requirements

• Analytes: Caprolactam (monomer) and caprolactam sodium salt (instantaneously hydrolyses to caprolactam in aqueous media).
• Principle: Quantification by gas chromatography (GC) using an internal standard (caprylolactam); oil simulants are extracted with ethanol/water prior to GC analysis.
• Calibration and quantification: Calibration is performed with standards containing known caprolactam and caprylolactam levels; results reported as mg/kg.
• Confirmation: Use of a second GC column of different polarity or GC/MS to confirm identity.
• Performance range: Suitable for approximate analyte concentrations from 1.5 mg/kg to 30 mg/kg.
• Apparatus & conditions: GC with flame ionization detector (FID) and appropriate column selection; example column types and GC parameters are provided to ensure separation of caprolactam and internal standard.
• Sample prep: Aqueous simulant samples are spiked with internal standard (procedure given); fatty simulants (olive oil) are extracted into a water/ethanol mixture before analysis.
• Quality & safety: Reagents of analytical grade, storage guidance for standards, and a general warning about chemical hazards.

Practical applications

• Routine migration testing for plastics and food contact materials to verify compliance with regulatory limits for caprolactam.
• Analytical laboratories performing specific migration and monomer residual testing using standardized, interlaboratory‑validated methods.
• Industry quality control for manufacturers of polyamide (nylon) articles and other plastics where caprolactam may be present.
• Regulatory bodies and conformity assessment laboratories assessing compliance with EU food contact legislation.

Who should use this standard

• Accredited testing laboratories (food contact testing)
• Plastics manufacturers and quality assurance teams
• Regulators and enforcement laboratories monitoring specific migration from food contact materials

Related standards

• EN 13130-1: Guide to test methods and selection of food simulants (read in conjunction with Part 16).
• Other parts of the EN 13130 series (related monomer/migration test methods) and relevant EU Directives related to plastics in contact with food.

Keywords: CEN/TS 13130-16:2005, caprolactam, food simulants, migration testing, food contact materials, gas chromatography, caprolactam sodium salt, EN 13130.

Standards Content (Sample)

SLOVENSKI STANDARD
01-april-2005
0DWHULDOLLQSUHGPHWLYVWLNX]åLYLOL6QRYLYSROLPHUQLKPDWHULDOLKNDWHULK
NRQFHQWUDFLMDMHRPHMHQDGHO'RORþHYDQMHNDSURODNWDPDLQQDWULMHYHVROL
NDSURODNWDPDYPRGHOQLKUD]WRSLQDK]DåLYLOD
Materials and articles in contact with foodstuffs - Plastics substances subject to limitation
- Part 16: Determination of caprolactam and caprolactam salt in food simulants
Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln - Substanzen in Kunststoffen,
die Beschränkungen unterliegen - Teil 16: Bestimmung von Caprolactam und
Caprolactamsalz in Prüflebensmitteln
Matériaux et objets en contact avec les denrées alimentaires - Substances dans les
matiéres plastiques soumises a des limitations - Partie 16: Détermination du
caprolactame et des sels de caprolactame dans les simulants d'aliments
Ta slovenski standard je istoveten z: CEN/TS 13130-16:2005
ICS:
67.250 Materiali in predmeti v stiku z Materials and articles in
živili contact with foodstuffs
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

TECHNICAL SPECIFICATION
CEN/TS 13130-16
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
February 2005
ICS 67.250
English version
Materials and articles in contact with foodstuffs - Plastics
substances subject to limitation - Part 16: Determination of
caprolactam and caprolactam salt in food simulants
Matériaux et objets en contact avec les denrées Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln
alimentaires - Substances dans les matiéres plastiques - Substanzen in Kunststoffen, die Beschränkungen
soumises à des limitations - Partie 16: Détermination du unterliegen - Teil 16: Bestimmung von Caprolactam und
caprolactame et des sels de caprolactame dans les Caprolactamsalz 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 13130-16:2005: E
worldwide for CEN national Members.

Contents
page
Foreword. 3
Introduction . 5
1 Scope. 6
2 Normative references . 6
3 Principle . 6
4 Reagents . 6
5 Apparatus . 8
6 Samples . 9
7 Procedure . 10
8 Precision . 12
9 Confirmation. 13
10 Test report . 14
Bibliography . 16

Foreword
This document (CEN/TS 13130-16:2005) 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
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.
Introduction
Caprolactam, C H NO, PM/Ref. No. 14200, is a monomer used in the manufacture of certain plastics
6 11
materials and articles intended to come into contact with foodstuffs. After the manufacture residual
caprolactam can remain in the finished product and may migrate into foodstuffs coming into contact
with that product.
Caprolactam sodium salt, C H NO Na, PM/Ref. No 14230, is a monomer used as a catalyst in the
6 10
anionic polymerisation of caprolactam. After the manufacture residual caprolactam sodium salt can
remain in the finished product and may migrate into foodstuffs coming into contact with that product.
Caprolactam sodium salt hydrolyzes instantly when in contact with aqueous media.
The method has been pre-validated by a collaborative trial with five laboratories.
1 Scope
This document, part of EN 13130, specifies an analytical procedure for the determination of
caprolactam in the food simulants distilled water, 3 % w/v aqueous acetic acid,
15 % v/v aqueous ethanol and rectified olive oil. The level of caprolactam monomer determined is
expressed as mg caprolactam/kg of food or food simulant. The method is appropriate for the
quantitative determination of caprolactam in an approximate analyte concentration range of 1,5mg/kg
to 30 mg per kilogram of food simulant.
This method is also applicable to the determination of the specific migration of caprolactam sodium
salt, PM/Ref No 14230, as caprolactam sodium salt instantaneously hydrolyzes to caprolactam when
in contact with aqueous media.
NOTE The method should also be applicable to other aqueous food simulants as well as to other fatty food
simulants e.g. sunflower oil, a mixture of synthetic triglycerides and volatile substitutes for fat simulants.
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.
3 Principle
The level of caprolactam in aqueous food simulants is determined by gas chromatography. Olive oil
test samples are extracted with a mixture of water/ethanol and the resultant solutions analyzed by gas
chromatography. Quantification is achieved using an internal standard, caprylolactam. Calibration is
achieved by analysis of relevant simulants containing known amounts of caprolactam and
caprylolactam.
Confirmation of caprolactam levels is established by gas chromatography using a column of different
polarity. Alternatively, confirmation can also be carried out by combined gas chromatography/ mass
spectrometry (GC/MS).
4 Reagents
NOTE All reagents should be of recognized analytical quality unless otherwise stated.
4.1 Analytes
4.1.1 Caprolactam, (6-Caprolactam; e-Caprolactam; Aza-2-cycloheptanone), C H NO
6 11
molecular weight: 113,16, purity > 98 % (GC).
4.1.2 Aza-2-cyclononanone, (8-aminooctanoic acid lactam; 8-Caprylolactam), C H NO
8 15
molecular weight 141,2, purity 99 %.
4.2 Chemicals
4.2.1 Ethanol, absolute
4.2.2 n-Heptane
4.2.3 Methanol
4.2.4 Water, deionized
4.3 Solutions
4.3.1 Ethanol/water = 1:2
Measure 200 ml ethanol (4.2.1) and make up with water (4.2.4) to 600 ml.
4.3.2 Standard stock solution of caprolactam in methanol (0,5 mg/ml)
Weigh to the nearest 0,1 mg approximately 50 mg of caprolactam (4.1.1) into a 100 ml volumetric
flask. Dissolve the caprolactam in methanol and make up to the mark with methanol (4.2.3).
Calculate the exact concentration in milligrams of caprolactam per millilitre solution.
Repeat the procedure to obtain a second stock solution.
NOTE The solution can be stored in a well-closed container in the dark for a maximum period of 3 months at
any temperature between - 20 °C to + 20 °C.
4.3.3 Internal standard stock solution of caprylolactam in methanol (0,35 mg/ml)
Weigh to the nearest 0,1 mg approximately 70 mg of caprylolactam (4.1.2) into a 200 ml volumetric
flask. Dissolve the caprylolactam in methanol and make up to the mark with methanol (4.2.3).
Calculate the exact concentration in milligrams caprylolactam per millilitre of solution.
NOTE The solution can be stored in a well-closed container in the dark for a maximum period of 3 months at
any temperature between - 20 °C and + 20 °C.
4.3.4 Diluted internal standard solution of caprylolactam in methanol (0,07 mg/ml)
Transfer by pipette 10,0 ml of the internal standard stock solution (4.3.3) into a 50 ml volumetric flask
and make up to the mark with methanol (4.2.3).
Calculate the concentration in milligrams of caprylolactam per millilitre of solution.
4.3.5 Standard solutions
Add to a series of 25 ml volumetric flasks, 0 ml, 1 ml, 2 ml, 4 ml, 6 ml and 8 ml of the standard stock
solution of caprolactam (4.3.2). Add to each of the flasks 5,0 ml of the internal standard stock solution
of caprylolactam (4.3.3) and make up to the mark with methanol (4.2.3). The standards thus obtained
contain approximately 0 µg/ml, 20 µg/ml, 40 µg/ml, 80 µg/ml, 120 µg/ml and 160 µg/ml of caprolactam
and 70 µg of caprylolactam per millilitre of methanol.
Calculate the exact concentrations in micrograms per millilitre of methanol.
Repeat the procedure using the second standard stock solution to obtain a second series of standard
solutions.
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 and preferably with an
automatic injection sampler, capable of separa
...