EN 15136:2006
(Main)Materials and articles in contact with foodstuffs - Certain epoxy derivatives subject to limitation - Determination of BADGE, BFDGE and their hydroxy and chlorinated derivatives in food simulants
Materials and articles in contact with foodstuffs - Certain epoxy derivatives subject to limitation - Determination of BADGE, BFDGE and their hydroxy and chlorinated derivatives in food simulants
This European standard describes a method for the determination of BADGE, BFDGE and their reaction products in food simulants: distilled water, 3 % w/v aqueous acetic acid, 10 % v/v aqueous ethanol solution and olive oil or sunflower oil.
A high performance liquid chromatography (HPLC) method is employed based on reversed phase HPLC and fluorescence detection.
The method is capable of determining BADGE and its derivatives at a minimum level of 0,05 µg/ml food simulant.
BFDGE and its derivatives can be determined at a minimum level of 0,1 µg/ml food simulant.
Direct HPLC analysis of the migration solutions may result in chromatograms difficult to interpret, due to interference from other components or the instability of the monomers resulting in a complex mixture of derivatives and/or reaction products. By forced hydrolysis of all epoxy groups and their reaction products, the quantification of the relevant substances is simplified and in addition the identities of the substances are indicatively confirmed.
NOTE In this European standard the term “BADGE, BFDGE and their derivatives” refers to the substances listed in Directive 2002/16/EC. These substances are listed in 4.1.
Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln - Bestimmte Epoxyderivate, die Beschränkungen unterliegen - Bestimmung von BADGE, BFDGE und deren Hydroxy- und Chlorderivaten in Prüflebensmitteln
Diese Europäische Norm beschreibt ein Verfahren zur Bestimmung von BADGE, BFDGE und deren Reaktionsprodukten in den Prüflebensmitteln destilliertes Wasser, 3%ige Essigsäure (m/V) in wässriger Lösung, 10%iges Ethanol (Volumenanteil) in wässriger Lösung und Olivenöl oder Sonnenblumenöl.
Angewendet wird ein Hochleistungs-Flüssigkeitschromatographie-Verfahren (HPLC), das auf Umkehrphasen-HPLC und Fluoreszenzdetektion beruht.
Das Verfahren ist für die Bestimmung von BADGE und dessen Derivaten bei einem Mindestgehalt von 0,05 mg/ml Prüflebensmittel geeignet.
BFDGE und seine Derivate können bei einem Mindestgehalt von 0,1 µg/ml Prüflebensmittel bestimmt werden.
Die direkte HPLC-Analyse der Migrationslösungen kann zu Chromatogrammen führen, die auf Grund von Störungen durch andere Komponenten oder der Instabilität der Monomere, die zu einer komplexen Mischung von Derivaten und/oder Reaktionsprodukten führt, schwer auszuwerten sind. Durch beschleunigte Hydrolyse aller Epoxygruppen und von deren Reaktionsprodukten wird die quantitative Bestimmung der betreffenden Substanzen vereinfacht und zusätzlich werden die Identitäten der Substanzen nachweislich bestätigt.
ANMERKUNG In diesem Dokument bezieht sich der Ausdruck "BADGE, BFDGE und deren Derivate" auf Substanzen, die in der Richtlinie 2002/16/EG aufgeführt sind. Diese Substanzen sind in 4.1 angegeben.
Matériaux et objets en contact avec les denrées alimentaires - Dérivés époxy soumis à des limitations - Détermination du BADGE, du BFDGE et de leurs dérivés hydroxylés et chlorés dans les simulants d'aliments
La présente Norme européenne décrit une méthode de détermination du BADGE, du BFDGE et de leurs
produits de réaction dans les simulants d'aliments : eau distillée, solution aqueuse d'acide acétique à
3 % (m/v), solution aqueuse d'éthanol à 10 % (v/v) et huile d'olive ou de tournesol.
La détermination est effectuée par chromatographie liquide haute performance (CLHP) en phase inverse et
détection par fluorescence.
Cette méthode permet de déterminer le BADGE ainsi que ses dérivés à une concentration minimale de
0,05 µg/ml de simulant d’aliments.
Le BFDGE ainsi que ses dérivés peuvent être déterminés à une concentration minimale de 0,1 µg/ml de
simulant d’aliments.
Une analyse CLHP directe des solutions de migration peut générer des chromatogrammes difficiles à
interpréter, en raison d'une interférence avec d'autres composants ou de l'instabilité des monomères
engendrant un mélange complexe de dérivés et/ou de produits de réaction. L'hydrolyse forcée de tous les
groupes époxy et de leurs produits de réaction permet de simplifier la quantification des substances
appropriées et de confirmer l'identité des substances.
NOTE Dans le présent document, l'expression « BADGE, BFDGE et leurs dérivés » se rapporte aux substances
citées dans la Directive 2002/16/CE [1] et son amendement, Directive 2004/13/CE [2]. Ces substances sont répertoriées
en 4.1.
Materiali in predmeti v stiku z živili – Nekateri epoksi derivati, katerih koncentracija je omejena – Določevanje BADGE, BFDGE in njihovih hidroksi in kloriranih derivatov v modelnih raztopinah za živila
General Information
Standards Content (Sample)
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Materials and articles in contact with foodstuffs - Certain epoxy derivatives subject to limitation - Determination of BADGE, BFDGE and their hydroxy and chlorinated derivatives in food simulantsULUDQLKMatériaux et objets en contact avec les denrées alimentaires - Dérivés époxy soumis a des limitations - Détermination du BADGE, du BFDGE et de leurs dérivés hydroxylés et chlorés dans les simulants d'alimentsWerkstoffe und Gegenstände in Kontakt mit Lebensmitteln - Bestimmte Epoxyderivate, die Beschränkungen unterliegen - Bestimmung von BADGE, BFDGE und deren Hydroxy- und Chlorderivaten in PrüflebensmittelnTa slovenski standard je istoveten z:EN 15136:2006SIST EN 15136:2006en,fr,de67.250ICS:SLOVENSKI
STANDARDSIST EN 15136:200601-september-2006
EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 15136March 2006ICS 67.250 English VersionMaterials and articles in contact with foodstuffs - Certain epoxyderivatives subject to limitation - Determination of BADGE,BFDGE and their hydroxy and chlorinated derivatives in foodsimulantsMatériaux et objets en contact avec les denréesalimentaires - Dérivés époxy soumis à des limitations -Détermination du BADGE, du BFDGE et de leurs dérivéshydroxylés et chlorés dans les simulants d'alimentsWerkstoffe und Gegenstände in Kontakt mit Lebensmitteln- Bestimmte Epoxyderivate, die Beschränkungenunterliegen - Bestimmung von BADGE, BFDGE und derenHydroxy- und Chlorderivaten in PrüflebensmittelnThis European Standard was approved by CEN on 23 January 2006.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the Central Secretariat or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the officialversions.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, Romania,Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2006 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15136:2006: E
Structures of the main compounds cited in this standard.20 Annex B (informative)
Principle of the determination of BADGE, BFDGE and their hydroxyl and chlorinated derivatives in food simulants.24 Annex C (informative)
Typical chromatograms of BADGE, BFDGE and some of their derivatives.25 Annex D (informative)
Determination of BADGE and its hydrolysis and hydroxychlorinated products in foodstuffs.29 Annex ZA (informative)
Relationship between this
European
Standard and the Essential Requirements
of EU Directives.30 Bibliography.31
All chemicals are hazardous to health to a greater or lesser extent.
It is beyond the scope of this European standard to give instructions for the safe handling of all chemicals, that meet, in full, the legal obligations in all countries in which this European standard may be followed.
Therefore, specific warnings are not given and users of this European standard 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 implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
The main application of these monomers is in epoxy coatings for cans and ends. The substances may also be used in organosol coatings. After the manufacture, residues of the substances or the reaction products can remain in the finished product and might migrate into foodstuffs coming into contact with that product.
The analytical method described allows for the determination of BADGE, BFDGE and their reaction products in aqueous and fatty food simulants.
1 Scope
This European standard describes a method for the determination of BADGE, BFDGE and their reaction products in food simulants: distilled water, 3 % w/v aqueous acetic acid, 10 % v/v aqueous ethanol solution and olive oil or sunflower oil. A high performance liquid chromatography (HPLC) method is employed based on reversed phase HPLC and fluorescence detection.
The method is capable of determining BADGE and its derivatives at a minimum level of 0,05 µg/ml food simulant.
BFDGE and its derivatives can be determined at a minimum level of 0,1 µg/ml food simulant. Direct HPLC analysis of the migration solutions may result in chromatograms difficult to interpret, due to interference from other components or the instability of the monomers resulting in a complex mixture of derivatives and/or reaction products. By forced hydrolysis of all epoxy groups and their reaction products, the quantification of the relevant substances is simplified and in addition the identities of the substances are indicatively confirmed.
NOTE In this European standard the term “BADGE, BFDGE and their derivatives” refers to the substances listed in Directive 2002/16/EC [1] and its amendment, Directive 2004/13/EC [2]. These substances are listed in 4.1. 2 Normative references The following referenced documents are indispensable for the application of this European standard. 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 the test methods for the specific migration of substances from plastics to food and food simulants and the determination of substances in plastics and the selection of conditions of exposure to food simulants ISO 648, Laboratory glassware – One-mark pipettes
3 Principle
3.1 Determination of BADGE, BFDGE and their derivatives in food simulants Proper quantification of the sum of BADGE, BFDGE and/or their derivatives is obtained by analysing the simulants twice: a first analysis of the simulant as obtained from the migration is performed and, if necessary, the substances are fully hydrolysed and the hydrolysed substances are determined in a second HPLC analysis.
This second analysis is used for confirmation and final quantification of the sum of BADGE or BFDGE and their derivatives as the bis(diol) derivatives. In the first instance, after the migration period, samples from aqueous food simulants are directly injected into a reverse phase HPLC column and the substances are separated using a gradient elution profile. For fatty food simulants, the substances are extracted with acetonitrile followed by HPLC
A flow chart showing the principle of the determination of BADGE, BFDGE and their derivatives in food simulants is given in Annex B. 4 Reagents
4.1 Analytes NOTE See Annex A for molecular structures. 4.1.1 BADGE
CAS no. 1675-54-3
4.1.2 BADGE.2HCl
CAS no. 4809-35-2
4.1.3 BADGE.2H2O
CAS no. 5581-32-8
4.1.4 BADGE.H2O
CAS no. 76002-91-0
4.1.5 BADGE.HCl
CAS no. 13836-48-1
4.1.6 BADGE.H2O.HCl
CAS no. 227947-06-0
4.1.7 BFDGE
CAS no. 2095-03-6
4.1.8 BFDGE.2HCl
4.1.9 BFDGE.2H2O
CAS no. 72406-26-9
4.1.10 BFDGE.HCl, prepared as follows: Dissolve approximately 50 mg BFDGE (4.1.7) in 25 ml dioxane, add 10 µl concentrated hydrochloric acid and reflux for 10 min.
Using a rotavapor evaporate the dioxane and dissolve the residue in 25 ml acetonitrile.
The mixture should contain the isomers of each of three substances BFDGE, BFDGE.HCl and BFDGE.2 HCl. This mixture is only used for reference purposes.
4.2 Reagents NOTE During the analysis, unless otherwise stated, only reagents of recognized analytical grade and distilled water of equivalent purity should be used.
4.2.1 Acetonitrile, HPLC grade
4.2.2 Boric acid 4.2.3 Ethanol 100 %, distilled 4.2.4 Methanol, HPLC grade 4.2.5 Sodium hydroxide 4.2.6 Water deionised, HPLC grade 4.3 Solutions 4.3.1 Borate buffer: 0,6 M
Dissolve 9,28 g of boric acid in 220 ml of water. Add 4,5 M sodium hydroxide solution to a pH of 8,5. Top up the volume to 250 ml with water. 4.3.2 Stock solutions of pure reference
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