CEN/TS 13130-9:2005

Materials and articles in contact with foodstuffs - Plastics substances subject to limitation - Part 9: Determination of acetic acid, vinyl ester in food simulants

This document, part of EN 13130, specifies an analytical procedure for the determination of vinyl acetate in the four conventional EU food simulants, water, 10 % (v/v) ethanol aqueous solution; 3 % (w/v) acetic acid aqueous solution and olive oil or an approved substitute. The level of vinyl acetate monomer determined is expressed as milligrams of vinyl acetate per kilogram of food simulant. The method is appropriate for the quantitative determination of vinyl acetate in approximate analyte concentration range of 1,2 mg/kg to 24 mg/kg food simulant.
NOTE 1   The method should also be applicable to other aqueous food simulants as well as to other fatty food simulants such as sunflower oil and a mixture of synthetic triglycerides.
NOTE 2   The suitability of the fat simulant should be assessed prior to setting up migration tests - it may be found necessary to use sunflower oil or a mixture of synthetic triglycerides if unacceptable interferences are found with olive oil.

Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln - Substanzen in Kunststoffen, die Beschränkungen unterliegen - Teil 9: Bestimmung von Essigsäurevinylester in Prüflebensmitteln

Dieses Dokument, Teil der EN 13130, legt ein Analyseverfahren zur Bestimmung von Vinylacetat in den vier
konventionellen EU-Prüflebensmitteln Wasser, 10 %iges Ethanol (Volumenanteil) in wässriger Lösung, 3 %ige
Essigsäure (m/V) in wässriger Lösung und Olivenöl oder ein zugelassenes Ersatzmittel, fest. Der ermittelte
Gehalt an monomerem Vinylacetat wird in Milligramm Vinylacetat je Kilogramm Prüflebensmittel angegeben.
Das Verfahren eignet sich zur quantitativen Bestimmung von Vinylacetat im angenäherten Konzentrations-
bereich des Analyten von 1,2 mg/kg bis 24 mg/kg Prüflebensmittel.
ANMERKUNG 1 Das Verfahren sollte auch auf andere wässrige Prüflebensmittel sowie weitere fettige Prüflebens-
mittel, wie z. B. Sonnenblumenöl und eine Mischung synthetischer Triglyceride, anwendbar sein.
ANMERKUNG 2 Die Eignung des fettigen Prüflebensmittels sollte vor Beginn der Migrationsprüfungen beurteilt
werden es kann sich als erforderlich herausstellen, Sonnenblumenöl oder eine Mischung synthetischer Triglyceride zu
verwenden, wenn bei der Verwendung von Olivenöl unannehmbare Störwirkungen auftreten.

Matériaux et objets en contact avec des denrées alimentaires - Substances dans les matières plastiques soumises à des limitations - Partie 9 : Détermination du vinyl ester d'acide acétique dans les simulants d'aliments

Le présent document, constituant une partie de l�EN 13130, spécifie un mode opératoire d�analyse pour la
détermination de l�acétate de vinyle dans les quatre simulants d�aliments conventionnels de l'UE : eau,
solution aqueuse d�éthanol à 10 % (v/v), solution aqueuse d�acide acétique à 3 % (m/v) et huile d�olive ou
substitut approuvé. La teneur en monomère d�acétate de vinyle déterminée est exprimée en milligrammes
d�acétate de vinyle par kilogramme de simulant d�aliment. Cette méthode convient pour la détermination
quantitative de l�acétate de vinyle dans une gamme de concentrations d�analyte comprise approximativement
entre 1,2 mg/kg et 24 mg/kg de simulant d�aliment.
NOTE 1 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 ou un mélange de triglycérides synthétiques.
NOTE 2 Il convient d�évaluer l�aptitude à l�emploi du simulant gras avant de conduire les essais de migration.
L�utilisation d�huile de tournesol ou d�un mélange de triglycérides synthétiques peut s�avérer nécessaire en cas
d�identification d�interférences inacceptables avec l�huile d�olive.

Materiali in predmeti v stiku z živili - Snovi v polimernih materialih, katerih koncentracija je omejena - 9. del: Določevanje vinilacetata v modelnih raztopinah za živila

General Information

• Status: Published
• Publication Date: 30-May-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 13130-9:2005 - Materials and articles in contact with foodstuffs - Plastics substances subject to limitation - Part 9: Determination of acetic acid, vinyl ester in food simulants

Standards Content (Sample)

SLOVENSKI STANDARD
SIST-TS CEN/TS 13130-9:2005
01-april-2005
0DWHULDOLLQSUHGPHWLYVWLNX]åLYLOL6QRYLYSROLPHUQLKPDWHULDOLKNDWHULK

NRQFHQWUDFLMDMHRPHMHQDGHO'RORþHYDQMHYLQLODFHWDWDYPRGHOQLKUD]WRSLQDK

]DåLYLOD

Materials and articles in contact with foodstuffs - Plastics substances subject to limitation

- Part 9: Determination of acetic acid, vinyl ester in food simulants

Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln - Substanzen in Kunststoffen,

die Beschränkungen unterliegen - Teil 9: Bestimmung von Essigsäurevinylester in
Prüflebensmitteln

Matériaux et objets en contact avec des denrées alimentaires - Substances dans les

matieres plastiques soumises a des limitations - Partie 9 : Détermination du vinyl ester

d'acide acétique dans les simulants d'aliments
Ta slovenski standard je istoveten z: CEN/TS 13130-9:2005
ICS:
67.250 Materiali in predmeti v stiku z Materials and articles in
živili contact with foodstuffs
SIST-TS CEN/TS 13130-9:2005 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 13130-9:2005
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SIST-TS CEN/TS 13130-9:2005
TECHNICAL SPECIFICATION
CEN/TS 13130-9
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
February 2005
ICS 67.250
English version
Materials and articles in contact with foodstuffs - Plastics
substances subject to limitation - Part 9: Determination of acetic
acid, vinyl ester in food simulants

Matériaux et objets en contact avec des denrées Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln

alimentaires - Substances dans les matières plastiques - Substanzen in Kunststoffen, die Beschränkungen

soumises à des limitations - Partie 9 : Détermination du unterliegen - Teil 9: Bestimmung von Essigsäurevinylester

vinyl ester d'acide acétique dans les simulants d'aliments in Prüflebensmitteln

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 13130-9:2005: 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 .................................................................................................................................................6

4 Reagents ................................................................................................................................................6

5 Apparatus...............................................................................................................................................7

6 Samples..................................................................................................................................................9

7 Procedure.............................................................................................................................................11

8 Expression of results..........................................................................................................................12

9 Confirmation ........................................................................................................................................13

10 Test report............................................................................................................................................14

Bibliography......................................................................................................................................................15

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Foreword

This document (CEN/TS 13130-9:2005) 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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SIST-TS CEN/TS 13130-9:2005
CEN/TS 13130-9:2005 (E)
Introduction

Acetic acid, vinyl ester (vinyl acetate) CH CO CH=CH PM/Ref. No 10120, is a monomer used in the

3 2 2,

manufacture of certain materials and articles intended to come into contact with foodstuffs. After manufacture,

residual vinyl acetate can remain in the polymer and may migrate into foodstuffs coming into contact with the

plastic material or product.

NOTE The following should be taken into account when carrying out a migration test. Vinyl acetate is known to

hydrolyze in aqueous media. In acetic acid solutions the hydrolysis is almost complete after 10 d at 40 °C. Vinyl acetate is

stable in olive oil.
The method has been validated by a collaborative trial with three laboratories.
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1 Scope

This document, part of EN 13130, specifies an analytical procedure for the determination of vinyl acetate in

the four conventional EU food simulants, water, 10 % (v/v) ethanol aqueous solution; 3 % (w/v) acetic acid

aqueous solution and olive oil or an approved substitute. The level of vinyl acetate monomer determined is

expressed as milligrams of vinyl acetate per kilogram of food simulant. The method is appropriate for the

quantitative determination of vinyl acetate in approximate analyte concentration range of 1,2 mg/kg to 24

mg/kg food simulant.

NOTE 1 The method should also be applicable to other aqueous food simulants as well as to other fatty food simulants

such as sunflower oil and a mixture of synthetic triglycerides.

NOTE 2 The suitability of the fat simulant should be assessed prior to setting up migration tests - it may be found

necessary to use sunflower oil or a mixture of synthetic triglycerides if unacceptable interferences are found with olive oil.

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 vinyl acetate in food simulants is determined by headspace capillary gas chromatography, using

flame ionization detection. Quantification is achieved using propionic acid, methyl ester (methyl propionate),

as an internal standard with calibration against relevant food simulants samples, fortified with known amounts

of vinyl acetate.

Confirmation of vinyl acetate levels is carried out by combined headspace gas chromatography/mass

spectrometry, or by repeating the analytical procedure using a gas chromatograph capillary column of different

polarity.

If automated headspace sampling cannot be performed, manual injection may be used ensuring that the gas

syringe and needle are preheated to the same temperature as the headspace vials before the headspace is

sampled.
4 Reagents

NOTE All reagents should be of recognized analytical quality unless otherwise stated.

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CEN/TS 13130-9:2005 (E)
4.1 Analytes
4.1.1 Vinyl acetate, CH CO CH=CH , purity greater than 99 %.
3 2 2

4.1.2 Methyl propionate, CH CH CO CH , purity greater than 99 %, which is free of interfering substances

3 2 2 3
which elute at the same retention time as vinyl acetate.
4.2 Chemicals
4.2.1 Water, HPLC grade.
4.2.2 N,N-dimethylacetamide (99,9 %)
4.3 Solutions
4.3.1 Stock solution of vinyl acetate in dimethylacetamide (6 mg/ml)

Weigh accurately approximately 0,15 g of the vinyl acetate into a tared stoppered 25 ml volumetric flask

containing about 10 ml of dimethylacetamide, and dilute to the mark with dimethylacetamide. Calculate the

exact concentration of vinyl acetate in milligrams per litre.
Repeat the procedure to provide a second standard stock solution.

NOTE The stock solutions can be stored in a well closed containers in the dark for a maximum period of three

months at any temperature between 5 °C and 20 °C.

4.3.2 Internal standard stock solution of propionic acid, methyl ester (methyl propionate) in

dimethylacetamide (6 mg/ml)

Weigh approximately 0,6 g of propionic acid methyl ester (methyl propionate), into a tared stoppered 100 ml

volumetric flask containing about 20 ml of dimethylacetamide, and dilute to the mark with dimethylacetamide.

NOTE The stock solutions can be stored in well closed containers in the dark for a maximum period of three months

at any temperature between 5 °C and 20 °C.
4.3.3 Standard solutions of vinyl acetate in dimethylacetamide

Into six 25 ml volumetric flasks, each containing approximately 5 ml of dimethylacetamide, add by pipette 0 ml,

0,5 ml, 1,0 ml, 2,0 ml, 3,0 ml and 5,0 ml of the stock solution (3.3.1). Pipette in 5,0 ml of internal standard

solution (4.3.2). Dilute to the mark with dimethylacetamide to give standard solutions containing a nominal

concentration of 0 mg/l, 120 mg/l, 240 mg/l, 480 mg/l, 720 mg/l and 1200 mg/l vinyl acetate. Shake thoroughly

to mix.

Calculate the exact concentrations of the standard solutions in milligrams per litre.

Repeat the procedure using the second stock solution prepared in 4.3.1 to give a second set of standard

solutions.

NOTE The standard solutions can be stored in well closed containers in the dark for a maximum period of three

months at any temperature between 5 °C and 20 °C.
5 Apparatus

NOTE An instrument or item of apparatus is listed only where it is special or made to a particular specification, the

usual laboratory glassware and equipment being assumed to be available.
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CEN/TS 13130-9:2005 (E)

5.1 Gas chromatograph, fitted with a capillary column capable of resolving vinyl acetate and the internal

standard from each other and other compounds present in the food simulants.

Appropriate operating conditions shall be established for the specific equipment used for the determination.

NOTE The following chromatographic column and conditions have been found to be satisfactory.

System 1

GC analytical column and temperature program for ethanol, water and olive oil food simulants.

Column: 25 m x 0,32 I.D dimethylsiloxane 5 µm film thickness
Temperature program: 50 °C held for 1 min, raised to 90 °C at 5 °C/min
raised at 30 °C/min to 120 °C, held for 5 min.
Carrier gas: Helium 2 ml/min.
Carrier gas split ratio 1 : 10
Run time: 20 min
Flame ionization detector 200 °C
Injector: 125 °C
System 2

GC analytical column and temperature program for 3 % w/v aqueous acetic acid food simulant.

Column: 25 m x 0,32 I.D polyethylene glycol 1 µm film thickness.
Temperature program: 54 °C held f
...