Materials and articles in contact with foodstuffs - Plastics substances subject to limitation - Part 20: Determination of epichlorohydrin in plastics

This document, part of EN 13130, specifies an analytical procedure for the determination of residual epichlorohydrin in coatings.
The method is appropriate for the quantitative determination of epichlorohydrin in the analyte concentration range of 5 ng/ml to 80 ng/ml of extract.  In general this allows for the detection of epichlorohydrin at the level of 1 mg/kg of polymer or in the case of coatings, where the amount of polymer cannot be determined, detection of 1 µg epichlorohydrin per square decimetre of coating is feasible.
In order to obtain reliable and reproducible results, it is essential that the method described in this part of EN 13130 is followed as closely as possible.

Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln - Substanzen in Kunststoffen, die Beschränkungen unterliegen - Teil 20: Bestimmung von Epichlorhydrin in Kunststoffen

Dieses Dokument, Teil der EN 13130, legt ein Analyseverfahren zur Bestimmung des Restgehaltes an Epichlorhydrin in Beschichtungen fest.
Das Verfahren eignet sich zur quantitativen Bestimmung von Epichlorhydrin im Konzentrationsbereich des Analyten von 5 ng/ml bis 80 ng/ml Extrakt. Im Allgemeinen ermöglicht das Verfahren den Nachweis von Epichlorhydrin bei einer Konzentration von 1 mg/kg Polymer oder im Fall von Beschichtungen, bei denen die Polymermenge nicht bestimmt werden kann, ist der Nachweis von 1 µg Epichlorhydrin je Quadratdezimeter Beschichtung technisch durchführbar.
Um zuverlässige und reproduzierbare Ergebnisse zu erhalten, ist es wichtig, das in diesem Teil der EN 13130 beschriebene Verfahren möglichst genau einzuhalten

Matériaux et objets en contact avec les denrées alimentaires - Substances dans les matières plastiques soumises à des limitations - Partie 20 : Détermination de l'épichlorohydrine dans les matières plastiques

Le présent document qui fait partie de l'EN 13130, spécifie un mode opératoire d'analyse pour la détermination des résidus d'épichlorohydrine dans les revêtements.
Cette méthode convient pour la détermination quantitative de l'épichlorhydrine dans une gamme de concentrations en analyte comprise entre 5 ng/ml et 80 ng/ml d'extrait. En général, elle permet de détecter l'épichlorohydrine à 1 mg/kg de polymère. Dans le cas des revêtements pour lesquels il est impossible de déterminer la quantité de polymère, la détection de 1 µg d'épichlorohydrine par décimètre carré de revêtement est envisageable.
Pour obtenir des résultats fiables et reproductibles, il est fondamental d'être le plus fidèle possible à la méthode décrite dans la présente partie de l'EN 13130.

Materiali in predmeti v stiku z živili - Snovi v polimernih materialih, katerih koncentracija je omejena - 20. del: Določevanje epiklorohidrina v polimernih materialih

General Information

Status
Published
Publication Date
22-Feb-2005
Current Stage
6060 - Definitive text made available (DAV) - Publishing
Due Date
23-Feb-2005
Completion Date
23-Feb-2005

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SLOVENSKI STANDARD
SIST-TS CEN/TS 13130-20:2005
01-april-2005
0DWHULDOLLQSUHGPHWLYVWLNX]åLYLOL6QRYLYSROLPHUQLKPDWHULDOLKNDWHULK
NRQFHQWUDFLMDMHRPHMHQDGHO'RORþHYDQMHHSLNORURKLGULQDYSROLPHUQLK
PDWHULDOLK

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

- Part 20: Determination of epichlorohydrin in plastics

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

die Beschränkungen unterliegen - Teil 20: Bestimmung von Epichlorhydrin in
Kunststoffen

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

matieres plastiques soumises a des limitations - Partie 20 : Détermination de
l'épichlorohydrine dans les matieres plastiques
Ta slovenski standard je istoveten z: CEN/TS 13130-20:2005
ICS:
67.250 Materiali in predmeti v stiku z Materials and articles in
živili contact with foodstuffs
SIST-TS CEN/TS 13130-20:2005 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 13130-20:2005
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SIST-TS CEN/TS 13130-20:2005
TECHNICAL SPECIFICATION
CEN/TS 13130-20
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
February 2005
ICS 67.250
English version
Materials and articles in contact with foodstuffs - Plastics
substances subject to limitation - Part 20: Determination of
epichlorohydrin in plastics

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 20 : Détermination de unterliegen - Teil 20: Bestimmung von Epichlorhydrin in

l'épichlorohydrine dans les matières plastiques Kunststoffen

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 13130-20:2005: E

worldwide for CEN national Members.
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SIST-TS CEN/TS 13130-20:2005
CEN/TS 13130-20:2005 (E)
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 .............................................................................................................................................. 14

9 Confirmation........................................................................................................................................ 15

10 Test report ........................................................................................................................................... 16

Annex A (normative) Equipment for the micro-distillation of epichlorohydrin from

dioxane extract.................................................................................................................................... 17

Bibliography ..................................................................................................................................................... 18

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SIST-TS CEN/TS 13130-20:2005
CEN/TS 13130-20:2005 (E)
Foreword

This document (CEN/TS 13130-20:2005) 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
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SIST-TS CEN/TS 13130-20:2005
CEN/TS 13130-20:2005 (E)

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.
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SIST-TS CEN/TS 13130-20:2005
CEN/TS 13130-20:2005 (E)
Introduction

Epichlorohydrin, 1-chloro-2,3-epoxypropane, C H OCl, PM/Ref. No 16750, is a monomer used in the

3 5

manufacture of certain plastics materials and articles, but mainly coatings intended to come into

contact with foodstuffs.

After manufacture residual epichlorohydrin can remain in the finished product and may migrate into

foodstuffs coming into contact with that product.

This analytical method allows the determination of the residual content of epichlorohydrin in coatings.

The method has been pre-validated by collaborative trial with two laboratories.

NOTE A limit on the residual quantity of 1 mg/kg polymer in final product has been set. However,

epichlorohydrin is mainly used in coatings on non-plastics substrates. The amount of coating on a final article, e.g.

coated cans, cannot be determined with an acceptable accuracy. Therefore, the residual content of

epichlorohydrin in coatings cannot be determined. The area of a coating is easy to determine and so the amount

of residual epichlorohydrin content can be determined in milligrams per square decimetre.

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SIST-TS CEN/TS 13130-20:2005
CEN/TS 13130-20:2005 (E)
1 Scope

This document, part of EN 13130, specifies an analytical procedure for the determination of residual

epichlorohydrin in coatings.

The method is appropriate for the quantitative determination of epichlorohydrin in the analyte

concentration range of 5 ng/ml to 80 ng/ml of extract. In general this allows for the detection of

epichlorohydrin at the level of 1 mg/kg of polymer or in the case of coatings, where the amount of

polymer cannot be determined, detection of 1 µg epichlorohydrin per square decimetre of coating is

feasible.

In order to obtain reliable and reproducible results, it is essential that the method described in this part

of EN 13130 is followed as closely as possible.
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

To determine the residual amount of epichlorohydrin in a coating, the sample material is extracted

with dioxane for 6 h at room temperature. Subsequently, the extract is distilled by means of a micro-

distillation. The concentration of epichlorohydrin in the distilled fraction thus obtained is determined by

derivatization of the epoxide with an aromatic sulfonic acid, i.e. 9,10-dimethoxyanthracene-2-sulfonic

acid (DAS), followed by reversed phase high performance liquid chromatography (HPLC) with

fluorescence detection. Depending on the quality and type of the HPLC column, it is possible to

separate the two isomers that are formed in the derivatization reaction of epichlorohydrin with DAS.

Quantification is achieved by means of external standard calibration using dioxane solutions fortified

with known amounts of epichlorohydrin.

Confirmation of epichlorohydrin is carried out by normal phase HPLC with fluorescence detection.

4 Reagents

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

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SIST-TS CEN/TS 13130-20:2005
CEN/TS 13130-20:2005 (E)
4.1 Analyte
4.1.1 Epichlorohydrin (C H OCl), purity > 99 %.
3 5
4.2 Chemicals
4.2.1 Acetonitrile (HPLC grade).

4.2.2 9,10-Dimethoxyanthracene-2-sulfonic acid sodium salt, i.e. DAS-Na, C H NaO S.

16 13 5
4.2.3 Dioxane > 99,5 %, absolute; over molecular sieve (H O < 0,01 %).
4.2.4 Hexane

4.2.5 Cation exchange resin, strongly acid with sulfonic acids as functional groups, ion form

H .
4.2.6 Isopropanol
4.2.7 Methanol
4.2.8 Water, deionized (HPLC quality).
4.3 Preparation of the DAS reagent

Dissolve approximately 100 mg DAS-Na (4.2.2) in 20 ml methanol/water (80/20). Heat the solution

slightly to obtain a clear solution. In a glass beaker, wash an amount of the ion exchange resin (4.2.5)

with methanol/water (80/20) and subsequently pour the slurry into a glass column with a diameter of

1 cm, until the resin has reached a height of ± 20 cm. Elute the DAS solution through the ion

exchange resin and flush the column with a mixture of methanol/water (80/20). Start to collect the

eluate at the moment the eluate has decreased to a pH of approximately pH 1 to pH 2. Continue

collecting the eluate until the pH starts to increase. Evaporate the solution thus obtained to dryness by

means of a nitrogen stream.

NOTE The dry residue should be protected from light and is stable for at least 1 year.

WARNING Do not deviate from the prescribed ratio of DAS-Na versus ion exchange resin.

4.4 Solutions
4.4.1 Stock solution of epichlorohydrin in dioxane (1 mg/ml)

Weigh to the nearest 0,1 mg approximately 50 mg of epichlorohydrin (4.1.1) in a 50 ml volumetric

flask. Make up to the mark with dioxane (4.2.3) and mix thoroughly.

Calculate the exact concentration in milligrams of epichlorohydrin per millilitre of solution.

Repeat the procedure to obtain a second stock solution.

NOTE The solutions can be stored in closed containers in dark for a maximum period of 3 months at any

temperature between - 20 °C and + 20 °C.
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CEN/TS 13130-20:2005 (E)
4.4.2 Diluted stock solutions of epichlorohydrin in dioxane (0,04 mg/ml)

Pipette 2 ml of the stock solution (4.4.1) into a 50 ml volumetric flask. Make up to the mark with

dioxane and mix thoroughly.

Calculate the exact concentration in milligrams of epichlorohydrin per millilitre of solution.

Repeat the procedure using the second stock solution to obtain a second diluted stock solution.

4.4.3 Standard solutions of epichlorohydrin in dioxane

Pipette into a series of 25 ml volumetric flasks, 0 ml, 0,5 ml, 1 ml, 2 ml, 3 ml, 4 ml and 5 ml of the

diluted stock solution (4.4.2). Make up to the mark with dioxane and mix carefully.

The standard solutions thus obtained contain approximately 0 µg, 0,8 µg, 1,6 µg, 3,2 µg, 4,8 µg,

6,4 µg or 8,0 µg epichlorohydrin per millilitre.

Calculate the exact concentrations in micrograms of epichlorohydrin per millilitre of solution.

Repeat the procedure using the second diluted stock solution to obtain a second series of standard

solutions.
4.4.4 DAS solution in acetonitrile (5 mg/ml)

Prepare from the DAS reagent (4.3) a solution in acetonitrile which contains approximately 5 mg DAS-

reagent per millilitre of acetonitrile.

The DAS solution in acetonitrile shall be prepared freshly before use and protected against light. The

solution is only stable for one day at room temperature.
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.

5.1 High performance liquid chromatograph (HPLC)

NOTE A chromatograph with an automatic injector or 20 µl injection loop, and a fluorescence detector, set

to λ 262 nm and λ 490 nm, connected to a strip chart recorder or integrator is preferred.

excitation emission

5.2 HPLC column, capable of producing a symmetric peak for epichlorohydrin, and capable of

separating epichlorohydrin from peaks originating from solvents and excess of DAS.

Appropriate operating conditions have to be established for the specific equipment used for the

determination.

NOTE The column and parameters established for the column used in the development of the method are

given below.
Column: Stainless steel 250 mm x 4,6 mm, filled with C coated silica, particle
size 5 µm (load of 10 % carbon and end capped)
Column temperature: ambient
Eluent : acetonitrile (4.2.1)
water (4.2.8)
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SIST-TS CEN/TS 13130-20:2005
CEN/TS 13130-20:2005 (E)
Gradient time in min % acetonitrile % water
0 55 45
5 55 45
15 70 30
18 70 30
21 55 45
31 55 45
Flow rate: 2 ml/min
Injection volume: 20 µl
Detection: fluorescence
Wavelength: λ = 262 nm
excitation
λ = 490 nm
emission
5.3 Crimper, for sealing sample vials.

5.4 22 ml sample vials with polytetrafluoroethylene coated butyl rubber septa and aluminium crimp

caps.
5.5 De-capper, for de-capping sample vials closed with an aluminium crimp ca
...

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