CEN/TS 13130-28:2005

Materials and articles in contact with foodstuffs - Plastics substances subject to limitation - Part 28: Determination of 1,1,1-trimethylolpropane in food simulants

This document, part of EN 13130, specifies an analytical procedure for the determination of 1,1,1-trimethylolpropane in food simulants distilled water, 3 % (w/v) acetic acid aqueous solution, 15 % (v/v) ethanol aqueous solution and rectified olive oil. The method is appropriate for the quantitative determination of 1,1,1-trimethylolpropane in approximate analyte concentration range of 0,6 mg/kg to 12 mg/kg food simulant.
NOTE   The method should also be applicable to other aqueous food simulants as well as to the other fatty food simulants e.g. sunflower oil, corn oil or a mixture of synthetic triglycerides.

Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln - Substanzen in Kunststoffen, die Beschränkungen unterliegen - Teil 28: Bestimmung von 1,1,1-Trimethylolpropan in Prüflebensmitteln

Diese Technische Spezifikation, Teil der EN 13130, legt ein Analyseverfahren zur Bestimmung von 1,1,1 Trimethylolpropan in den Prüflebensmitteln destilliertes Wasser, 3%ige Essigsäure (m/V) in wässriger Lösung, 15%iges Ethanol (Volumenanteil) in wässriger Lösung und rektifiziertes Olivenöl fest. Das Verfahren eignet sich zur quantitativen Bestimmung von 1,1,1 Trimethylolpropan im angenäherten Konzentrationsbereich des Analyten von 0,6 mg/kg bis 12 mg/kg Prüflebensmittel.
ANMERKUNG   Das Verfahren sollte auch auf andere wässrige Prüflebensmittel sowie weitere fettige Prüflebensmittel, z. B. Sonnenblumenöl, Maiskeimöl oder eine Mischung synthetischer Triglyceride, anwendbar sein.

Matériaux et objets en contact avec les denrées alimentaires - Substances dans les matières plastiques soumises à des limitations - Partie 28 : Détermination du 1,1,1,-triméthylolpropane dans les simulants d'aliments

Cette Spécification technique, qui fait partie de l'EN 13130, spécifie un mode opératoire d'analyse pour la détermination du 1,1,1 triméthylolpropane 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. Cette méthode convient pour la détermination quantitative du 1,1,1-triméthylolpropane dans une gamme de concentrations d'analyte comprise approximativement entre 0,6 mg/kg et 12 mg/kg de simulant d'aliment.
NOTE    Il convient que la méthode puisse également être appliquée à d'autres simulants aqueux ainsi qu'à d'autres simulants gras, tels que l'huile de tournesol, l'huile de maïs ou un mélange de triglycérides synthétiques.

Materiali in predmeti v stiku z živili - Snovi v polimernih materialih, katerih koncentracija je omejena - 28. del: Določevanje 1,1,1-trimetilolpropana 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 13130-28:2005 - Materials and articles in contact with foodstuffs - Plastics substances subject to limitation - Part 28: Determination of 1,1,1-trimethylolpropane in food simulants

Standards Content (Sample)

SLOVENSKI STANDARD
SIST-TS CEN/TS 13130-28:2005
01-april-2005
0DWHULDOLLQSUHGPHWLYVWLNX]åLYLOL6QRYLYSROLPHUQLKPDWHULDOLKNDWHULK

NRQFHQWUDFLMDMHRPHMHQDGHO'RORþHYDQMHWULPHWLOROSURSDQDYPRGHOQLK

UD]WRSLQDK]DåLYLOD

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

- Part 28: Determination of 1,1,1-trimethylolpropane in food simulants

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

die Beschränkungen unterliegen - Teil 28: Bestimmung von 1,1,1-Trimethylolpropan in

Prüflebensmitteln

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

matieres plastiques soumises a des limitations - Partie 28 : Détermination du 1,1,1,-

triméthylolpropane dans les simulants d'aliments
Ta slovenski standard je istoveten z: CEN/TS 13130-28:2005
ICS:
67.250 Materiali in predmeti v stiku z Materials and articles in
živili contact with foodstuffs
SIST-TS CEN/TS 13130-28:2005 en,fr,de

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
SIST-TS CEN/TS 13130-28:2005
---------------------- Page: 2 ----------------------
SIST-TS CEN/TS 13130-28:2005
TECHNICAL SPECIFICATION
CEN/TS 13130-28
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
February 2005
ICS 67.250
English version
Materials and articles in contact with foodstuffs - Plastics
substances subject to limitation - Part 28: Determination of
1,1,1-trimethylolpropane 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 28 : Détermination du unterliegen - Teil 28: Bestimmung von 1,1,1-

1,1,1,-triméthylolpropane dans les simulants d'aliments Trimethylolpropan 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 13130-28:2005: E

worldwide for CEN national Members.
---------------------- Page: 3 ----------------------
SIST-TS CEN/TS 13130-28:2005
CEN/TS 13130-28:2005 (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 Expression of results.......................................................................................................................... 12

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

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

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

---------------------- Page: 4 ----------------------
SIST-TS CEN/TS 13130-28:2005
CEN/TS 13130-28:2005 (E)
Foreword

This document (CEN/TS 13130-28:2005) 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.

Informative Annex A details the relationship of this standard with the European Union Directives.

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 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].

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
---------------------- Page: 5 ----------------------
SIST-TS CEN/TS 13130-28:2005
CEN/TS 13130-28:2005 (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.
---------------------- Page: 6 ----------------------
SIST-TS CEN/TS 13130-28:2005
CEN/TS 13130-28:2005 (E)
Introduction

1,1,1-trimethylolpropane (TMP), C H O , PM/Ref. No 25600, is a monomer used in the manufacture

6 14 3

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

manufacture residual 1,1,1-trimethylolpropane can remain in the finished product and may migrate

into foodstuffs coming into contact with that product.

NOTE 1 The analytical method described in this part of EN 13130 is the result of a study on the determination

of the migration of 1,1,1-trimethylolpropane from plastics materials into food simulants. In the course of the study

several problems were encountered and solutions for these problems were incorporated in the final method. The

most suitable method is described in this part of EN 13130. The method was successfully pre-validated by the

developing laboratory tests, using the four official EU food simulants, to establish the precision data at the restriction

criterion. Also migration tests were performed with samples containing 1,1,1-trimethylolpropane as monomer in

contact for 10 d at 40 °C with 15 % v/v aqueous ethanol and olive oil.

NOTE 2 During the testing of the method by a second laboratory it appeared that the testing laboratory was

not able to reproduce the precision data as obtained by the developing laboratory. Based on the problems

encountered by the testing laboratory the method description was modified to make critical points more clear.

Within the scope of the project “Development of Methods of Analysis for Monomers” it was not possible to re-test

the method and therefore the method described should be considered as a useful analytical method, with limited

validation data. Further testing is required to demonstrate that the method can be applied with the required

accuracy.

The method has been pre-validated in a validation experiment only by one laboratory, the developing

laboratory.
---------------------- Page: 7 ----------------------
SIST-TS CEN/TS 13130-28:2005
CEN/TS 13130-28:2005 (E)
1 Scope

This document, part of EN 13130, specifies an analytical procedure for the determination of 1,1,1-

trimethylolpropane in food simulants distilled water, 3 % (w/v) acetic acid aqueous solution, 15 % (v/v)

ethanol aqueous solution and rectified olive oil. The method is appropriate for the quantitative

determination of 1,1,1-trimethylolpropane in approximate analyte concentration range of 0,6 mg/kg to

12 mg/kg food simulant.

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

food simulants e.g. sunflower oil, corn oil or 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.
3 Principle

Aqueous food simulants are saturated with potassium carbonate and extracted with ethanol/ethyl

acetate. After evaporation of the solvent, the extracted TMP is silylated with trimethylsilylimidazole in

pyridine. The amount of 1,1,1-trimethylolpropane silyl ethers are determined by gas chromatography

with flame ionization detection. 1,4-butanediol is used as an internal standard. Fat simulant is

extracted with water prior to derivatization.

Confirmation of the identity of 1,1,1-trimethylolpropane is established by combined gas

chromatography/mass spectrometry.
4 Reagents

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

---------------------- Page: 8 ----------------------
SIST-TS CEN/TS 13130-28:2005
CEN/TS 13130-28:2005 (E)
4.1 Analytes

4.1.1 1,1,1-trimethylolpropane (TMP), C H O or CH CH C(CH OH) , molecular weight 134,18;

6 14 3 3 2 2 3
boiling point: 297 °C; solubility: W, al; purity: > 97 % (GC).
4.1.2 Internal standard: 1,4-butandiol (BUG) or tetramethyleneglycol, C H O or
4 10 2

HOCH CH CH CH OH, molecular weight: 90,12; boiling point: 235,12 °C; density: 1,0171 g/ml;

2 2 2 2
solubility: W, al; purity: > 98 % (GC).
4.2 Chemicals
4.2.1 Water, deionized or HPLC grade.
4.2.2 Acetic acid, 100 %.
4.2.3 Ethanol, absolute.
4.2.4 n-Pentane, 95 %.
4.2.5 Ethyl acetate, 99,5 %.

4.2.6 Derivatizing reagent, trimethylsilylimidazole, TMSI in dry pyridine, in 1 ml ampoules.

4.2.7 Potassium carbonate, 99,9 %.

4.2.8 Cation exchange resin, strong acidic, sulfonated polystyrene resins with spherical

particles, capacity 1,7 meq/ml, size 50 mesh to 100 mesh).
The cation exchange resin shall be washed with methanol before use.
4.2.9 Sodium hydroxide, 99 %.
4.3 Solutions
4.3.1 Stock solution of 1,1,1-trimethylolpropane in ethanol (0,75 g/l)

Weigh to the nearest 0,2 mg approximately 75 mg TMP into a 100 ml volumetric flask and fill to the

mark with ethanol (4.2.3).

Calculate the actual concentration in milligrams of TMP per millilitre of solution.

Repeat the procedure to obtain a second standard stock solution.

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

three months at any temperature between - 20 °C and + 20 °C.

4.3.2 Internal standard stock solution of 1,4-butandiol (BUG) in ethanol (0,75 g/l)

Weigh to the nearest 0,2 mg approximately 75 mg BUG into a 100 ml volumetric flask and fill to the

mark with ethanol (4.2.3).

Calculate the actual concentration in milligrams of BUG per millilitre of solution.

---------------------- Page: 9 ----------------------
SIST-TS CEN/TS 13130-28:2005
CEN/TS 13130-28:2005 (E)

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

months at any temperature between - 20 °C and + 20 °C.
4.3.3 Intermediate standard solutions of TMP and BUG in ethanol

Pipette into a series of six 25 ml volumetric flasks 0 ml, 0,5 ml, 1 ml, 2,5 ml, 5,0 ml and 10,0 ml of the

TMP standard stock solution (4.3.1). Add 2,5 ml of the internal standard stock solution (4.3.2) and fill

to the mark with ethanol. The resulting intermediate standards contain approximately 0 µg/ml,

15 µg/ml, 30 µg/ml, 75 µg/ml, 150 µg/ml and 300 µg TMP per millilitre of ethanol and 75 µg BUG per

millilitre.

Calculate the actual concentrations of TMP and BUG in micrograms per millilitre of solution.

Repeat the procedure using the second standard stock solution prepared in 4.3.1 to provide a second

set of intermediate standards.

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

months at any temperature between - 20 °C and + 20 °C.
4.3.4 Diluted internal standard solution
Pipette 2,5 ml of the BUG internal standard
...