SIST EN 1186-8:2002

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Materiali in predmeti v stiku z živili - Polimerni materiali - 8. del: Preskusne metode za celotno migracijo v olivno olje, s katerim je napolnjen predmetWerkstoffe und Gegenstände in Kontakt mit Lebensmitteln - Kunststoffe - Teil 8: Prüfverfahren für die Gesamtmigration in Olivenöl durch Füllen des GegenstandesMatériaux et objets en contact avec les denrées alimentaires - Matiere plastique - Partie 8: Méthodes d'essai pour la migration globale dans l'huile d'olive par remplissageMaterials and articles in contact with foodstuffs - Plastics - Part 8: Test methods for overall migration into olive oil by article filling67.250Materiali in predmeti v stiku z živiliMaterials and articles in contact with foodstuffsICS:Ta slovenski standard je istoveten z:EN 1186-8:2002SIST EN 1186-8:2002en01-september-2002SIST EN 1186-8:2002SLOVENSKI
STANDARDSIST ENV 1186-8:19971DGRPHãþD



SIST EN 1186-8:2002



EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 1186-8April 2002ICS 67.250Supersedes ENV 1186-8:1994English versionMaterials and articles in contact with foodstuffs - Plastics - Part8: Test methods for overall migration into olive oil by article fillingMatériaux et objets en contact avec les denréesalimentaires - Matière plastique - Partie 8: Méthodesd'essai pour la migration globale dans l'huile d'olive parremplissageWerkstoffe und Gegenstände in Kontakt mit Lebensmitteln- Kunststoffe - Teil 8: Prüfverfahren für dieGesamtmigration in Olivenöl durch Füllen desGegenstandesThis European Standard was approved by CEN on 4 January 2002.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 Management Centre 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 Management Centre has the same status as the officialversions.CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece,Iceland, Ireland, Italy, Luxembourg, Malta, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2002 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 1186-8:2002 ESIST EN 1186-8:2002



EN 1186-8:2002 (E)2ContentspageForeword.31Scope.52Normative references.53Principle.54Reagents.65Apparatus.76Preparation of test specimens.97Procedure.108Expression of results.169Test report.17Annex A (normative)
Determination of the suitability of olive oil as the fatty food simulant and oftriheptadecanoin as the internal standard.18Annex B (normative)
Determination of the need for sample conditioning.20Annex C (normative)
Determination of the need for sample conditioning and determination of themass of moisture sensitive test specimens, by vacuum drying.21Annex D (normative)
Determination of change in moisture content of test specimens by measurementof the transfer of water to, or from olive oil, by Karl Fischer titration.23Annex E (informative)
Typical chromatograms and calibration graph.25Annex F (informative)
Precision data.28Annex ZA (informative)
Relationship of this European Standard with Council Directive 89/109/EECand Commission Directive 90/128/EEC and associated Directives.29Bibliography.31SIST EN 1186-8:2002



EN 1186-8:2002 (E)3ForewordThis document EN 1186-8:2002 has been prepared by Technical Committee CEN/TC 194 “Utensils in contact withfood”, the secretariat of which is held by BSI.This European Standard shall be given the status of a national standard, either by publication of an identical text orby endorsement, at the latest by October 2002, and conflicting national standards shall be withdrawn at the latestby October 2002.This document supersedes ENV 1186-8:1994.This European Standard is one of a series of methods of test for plastics materials and articles in contact withfoodstuffs.This document has been prepared under a mandate given to CEN by the European Commission and the EuropeanFree Trade Association, and supports essential requirements of EC Directive(s).For relationship with EC Directive(s), see informative annex ZA, which is an integral part of this document.At the time of preparation and publication of this standard the European Union legislation relating to plasticsmaterials and articles intended to come into contact with foodstuffs is incomplete.
Further Directives andamendments to existing Directives are expected which could change the legislative requirements which thisstandard supports.
It is therefore strongly recommended that users of this standard refer to the latest relevantpublished Directive(s) before commencement of any of the test or tests described in this standard.EN 1186-8 should be read in conjunction with EN 1186-1.Their titles are as follows:EN 1186 Materials and articles in contact with foodstuffs – Plastics -Part 1Guide to the selection of conditions and test methods for overall migrationPart 2Test methods for overall migration into olive oil by total immersionPart 3Test methods for overall migration into aqueous food simulants by total immersionPart 4Test methods for overall migration into olive oil by cellPart 5Test methods for overall migration into aqueous food simulants by cellPart 6Test methods for overall migration into olive oil using a pouchPart 7Test methods for overall migration into aqueous food simulants using a pouchPart 9Test methods for overall migration into aqueous food simulants by article fillingPart 10Test methods for overall migration into olive oil (modified method for use in cases whereincomplete extraction of olive oil occurs)Part 11Test methods for overall migration into mixtures of
14C-labelled synthetic triglyceridePart 12Test methods for overall migration at low temperaturesPart 13Test methods for overall migration at high temperaturesSIST EN 1186-8:2002



EN 1186-8:2002 (E)4Part 14Test methods for 'substitute tests' for overall migration from plastics intended to come intocontact with fatty foodstuffs using test media iso-octane and 95 % ethanolPart 15Alternative test methods to migration into fatty food simulants by rapid extraction into iso-octane and/or 95 % ethanolThe annexes A to D are normative. The annexes E and F are informative.According to the CEN/CENELEC Internal Regulations, the national standards organizations of the followingcountries are bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark, Finland,France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Malta, Netherlands, Norway, Portugal, Spain,Sweden, Switzerland and the United Kingdom.SIST EN 1186-8:2002



EN 1186-8:2002 (E)51 ScopeThis Part of this European Standard specifies test methods for the determination of the overall migration into fattyfood simulants from plastics materials and articles, by filling of test specimens with a fatty food simulant attemperatures above 20 °C and up to, but not including, 100 °C for selected times.This method is most suitable for plastics in the form of containers and articles that can be filled.Testing samples by this method enables testing of non-homogenous articles provided they are not too large.NOTEThis test method has been written for use with the fatty food simulant, olive oil.
The test method can also be usedwith appropriate modifications with 'other fatty food simulants ' called simulant D - a synthetic mixture of triglycerides, sunfloweroil and corn oil.
These other fatty food simulants will produce different chromatograms for the simulant methyl esters to those ofthe methyl esters of olive oil.
Select suitable chromatogram peaks of the methyl esters of the other fatty food simulants for thequantitative determination of the simulant extracted from the test specimens.The test method described is applicable to most types of plastics, although there are some plastics for which it isknown not to be applicable.2 Normative referencesThis European Standard incorporates by dated and undated reference, provisions from other publications.
Thesenormative references are cited at the appropriate places in the text, and the publications are listed hereafter. Fordated references, subsequent amendments to and revisions of any of these publications apply to this EuropeanStandard only when incorporated in it by amendment or revision.
For undated references the latest edition of thepublication referred to applies (including amendments).EN 1186-1:2002, Materials and articles in contact with food – Plastics – Part 1: Guide to the selection of conditionsand test methods for overall migration.ISO 648, Laboratory glassware - One mark pipettes.ISO 4788, Laboratory glassware - Graduated measuring cylinders.3 PrincipleThe overall migration from a sample of the plastics is determined as the loss in mass per unit of surface areaintended to come into contact with foodstuffs.The selection of the conditions of test will be determined by the conditions of use, see clauses 4, 5 and 6 of EN1186-1:2002.Test specimens of known mass are filled with olive oil for the exposure time, at temperatures above 20 °C andbelow 100 °C, then emptied and blotted to remove oil adhering to the surface, and reweighed.The specimens will usually retain absorbed olive oil that is extracted and determined quantitatively by means of gaschromatography after conversion to methyl esters.
Methylation is carried out by reacting a borontrifluoride/methanol complex with fatty acids formed by hydrolysing the oil with potassium hydroxide.
An internalstandard, triheptadecanoin, is added prior to the extraction of the absorbed olive oil from the test specimens.
Thisensures that any active or extractable components of the plastics react with the internal standard, as well as withthe extracted olive oil. The internal standard is also subjected to the hydrolysis and methylation reactions, providingcompensation for any inefficiencies in the hydrolysis and methylation processes.SIST EN 1186-8:2002



EN 1186-8:2002 (E)6Migration into the olive oil is calculated by subtracting the mass of olive oil retained by the test specimen from themass of the test specimen after removing the olive oil, then subtracting this mass from the initial mass of thespecimen.The total loss in mass is expressed in milligrams per square decimetre of surface area of the specimen and theoverall migration is reported as the mean of a minimum of three determinations on separate test specimens.To allow for inaccuracies which may arise during the procedure and which may be difficult to detect, due forexample to contamination or loss of oil during the sample handling stages, four determinations are carried out onthe sample allowing for the result from one specimen to be discarded.This method includes variations which are applicable to certain plastics.NOTEBefore starting a migration exercise, the test sample should be examined for the presence of components interferingin the determination of the amount of olive oil extracted, see 7.1.
If an unacceptable amount of interference is present thensuitability of one of the 'other fatty food simulants' should be examined, see annex A and 9.3 and 9.5 of EN 1186-1:2002.
If aninterference is present which would interfere with the triheptadecanoin internal standard an alternative internal standard shouldbe used, see annex A, and 9.3 of EN 1186-1:2002.4 ReagentsNOTEAll reagents should be of recognized analytical quality, unless otherwise specified.4.1Olive oil, simulant D, as specified in 4.2 of EN 1186-1:2002.4.2Extraction solvent (see 9.1 of prEN 1186-1:2001).4.2.1For non-polar plastics, such as polyethylene and polypropylene:- Pentane 98 % boiling point 36 °C.For polar plastics, such as polyamide and polyacetal:- 95/5 by volume azeotropic mixture of pentane 98 % and ethanol 99 %.NOTE 1Pentane is a very volatile and highly flammable solvent.
Care should therefore be taken when handling this solventto prevent contact with sources of ignition.
Ethanol is also a flammable solvent.
It is not recommended that extractions witheither pentane or the pentane/ethanol mixture be left unattended, particularly overnight.NOTE 2Due to the low boiling points of
these solvents, cooled condenser water can be required to prevent undue loss ofthe solvent from the condenser.or4.2.2Other suitable solvent.NOTE 1In previous methods for determining overall migration into olive oil the extraction solvent used has been 1,1,2-trichloro-trifluoroethane. For environmental reasons the use of this solvent should be avoided where possible, see 9.1 ofEN 1186-1:2002.
Experience has shown that this solvent, although effective for most plastics requires longer periods ofextraction.NOTE 2Some solvents can contain non-volatile substances which, after hydrolysis and methylation processes, produce gaschromatography peaks with retention times similar to the retention times of olive oil methyl esters and methyl heptadecanoatefrom the internal standard. Solvents found to contain such substances should be redistilled before use.4.3Internal standard, triheptadecanoin (glyceryl trimargarate) CAS No. 2438-40-61) of a quality such that theproducts from hydrolysis and methylation processes do not contain substances giving detectable gas
1) The source of this is the Chemical Abstracts published by the American Chemical Society.SIST EN 1186-8:2002



EN 1186-8:2002 (E)7chromatography peaks (see 9.3 of EN 1186-1:2002) with similar retention times to the olive oil methyl ester peaks.Prepared as a solution containing 2,0 mg/ml in cyclohexane.4.4Potassium hydroxide solution, 11,0 g/l in methanol.4.5Boron trifluoride, methanol complex, approximately 150 g/l BF3.4.6n -Heptane.4.7Sodium sulfate.4.7.1Sodium sulfate, anhydrous, Na2SO4.4.7.2Sodium sulfate, saturated solution.4.8Diethyl ether.4.9Karl Fischer solvent, commercially prepared, methanol and chloroform based, water capacity of 5 mg/ml.4.10Karl Fischer titrant (for volumetric apparatus only), commercially prepared, water capacity of 2 mg/ml.5 Apparatus5.1Tweezers, stainless steel, blunt nosed.5.2Cutting implement, scalpel, scissors, sharp knife or other suitable device.5.3Rule, graduated in mm, and with an accuracy of 0,1 mm.5.4Analytical balance capable of determining a change in mass of 0,1 mg.5.5Conditioning containers, for conditioning test specimens at 50 % ± 5 % relative humidity and 80 % ± 5 %relative humidity at 20 °C ± 5 °C.NOTEFor 50 % relative humidity, 43 % w/v sulphuric acid solution in water is suitable and for 80 % relative humidity, 27 %w/v sulphuric acid solution is suitable. The solutions should be freshly prepared by adding a weighed amount of acid to asuitable volume of water, cooling to room temperature and making up to the required volume.It is recommended that relative humidity and temperature be maintained during the conditioning period.
Therefore thecontainers should be placed in a thermostatically controlled room or oven, at a temperature of approximately 20 °C, the settemperature should not vary by more than ± 1 °C.5.6Thermostatically controlled oven or incubator capable of maintaining the set temperature, within thetolerances specified in Table B.2 of EN 1186-1:2002.5.7Filter paper, lint-free.5.8Chromatography tank or any other airtight container for test sample storage.5.9Glass rods or metal gauze for use as spacers between test pieces during solvent extraction.5.10Antibumping beads.5.11Soxhlet type extractors, capable of holding test specimens on the supports, with 250 ml or 500 ml roundbottom flasks to fit.
SIST EN 1186-8:2002



EN 1186-8:2002 (E)8NOTEAlternative extractors capable of satisfactorily extracting absorbed olive oil from the test specimens can be used.5.12Water bath, capable of holding the flasks of soxhlet type extractors (5.11)5.13Rotary evaporator or distillation apparatus, for evaporation and collection of the extraction solvent.NOTEArtificially cooled water can be necessary for efficient condensation of a low boiling point solvent.5.14Steam bath or water bath.5.15Flasks, 50 ml, long neck with condensers to fit, for methyl ester preparations.5.16Measuring cylinders, complying with the minimum requirements of ISO 4788, 500 ml, 250 ml, 100 ml, 25 ml,and 10 ml.
A 10 ml graduated syringe may be used in place of the 10 ml measuring cylinder.5.17Pipettes, complying with the minimum requirements of ISO 648, 5 ml and 10 ml.5.18Lint-free cloth5.19Gas chromatograph, with flame ionisation detector equipped with an appropriate column.
When using apolar column, the major peaks of olive oil, such as C16:0, methyl hexadecanoate (methyl palmitate), C16:1, methyl9-hexadecenoate (methyl palmitoate), C18:0, methyl octadecanoate (methyl stearate), C18:1, methyl 9-octadecenoate (methyl oleate), C18:2, methyl 9,12-octadecadienoate (methyl linoleate) and the internal standardC17:0, methyl heptadecanoate (methyl margarate) shall demonstrate baseline separation. Optionally, a non-polarcolumn can be used which shall give baseline separation of the methyl esters with 16 and 18 carbon numbers andthe internal standard with 17 carbon number.NOTEThe following columns have been found to be suitable:- Column 1, polar column, WCOT fused silica column, length 50 m, internal diameter 0,25 mm, coated with a 0,21micrometre film of cyanopropyl silicone;- Column 2, non polar column, BP1, length 25 m, internal diameter 0,32 mm, with a 1 micron film thickness;- Column 3, polar column, stainless steel column 2 mm to 3 mm internal diameter and 2 m to 3 m length with a packingof 10 % to 20 % by mass of polyestersuccinate on a stationary phase of diatomaceous earth 80 mesh to100 mesh.5.20Glass tubes with ground glass necks and stoppers, of a volume of approximately 10 ml, for storing theheptane layer if necessary.5.21Vacuum oven or vacuum desiccator, capable of maintaining a temperature of 60 °C ± 2 °C.
The vacuumoven or vacuum desiccator shall be equipped with or connected to a vacuum pump capable of achieving a vacuumof 1,3 kPa or less.
The vacuum pump shall be provided with a time controller to switch on the vacuum pump everyhour for 15 min.NOTEIf a vacuum oven is not available, a vacuum desiccator placed in an oven at 60 °C can be used.5.22Desiccator containing self indicating silica gel or anhydrous calcium chloride.5.23Balance, capable of determining a change of mass of 10 mg.5.24Disposable plastic syringes with luer fitting. 1 ml or 10 ml size.5.25Wide gauge luer needles (80 mm ´ 1,2 mm).5.26Karl Fischer apparatus, either an automated volumetric titrator, or an automated coulometric titrator.
TheKarl Fischer titrator shall be capable of measuring the water content of the simulant with a precision (standarddeviation) of 10 mg/kg or less (equivalent to 1 mg/dm2 plastic).
An automated volumetric or coulometric instrumentshall be used.
Manual titration procedures do not give the required accuracy or precision.SIST EN 1186-8:2002



EN 1186-8:2002 (E)96 Preparation of test specimens6.1 GeneralIt is essential that test specimens are clean and free from surface contamination (many plastics can readily attractdust due to static charges). Before preparing test specimens, remove any surface contamination from the sampleby gently wiping it with a lint-free cloth, or by brushing with a soft brush.
Under no circumstances wash the samplewith water or solvent.
If it is specified in the instructions for use of the article that it should be washed or cleanedbefore use see 8.1 of EN 1186-1:2002.
Minimize handling of the samples and, where necessary, wear cottongloves.6.2 Number of test specimensNine test specimens are required for samples, in the form in which they are intended to be used.These test specimens are utilized as follows:a) four test specimens for the migration test;b) two test specimens to check for possible loss of volatiles;c) one test specimen to determine the suitability of olive oil as the fatty food simulant and triheptadecanoinas the internal standard (see annex A);d) two test specimens for determination of the surface area.If the conditioning test in annex C is used, one additional test specimen is required.NOTEThe two test specimens, b), are used to check whether the sample losses mass from the evaporation of volatiles,such as solvents, during the test period.
If the vacuum drying procedure in annex C is used these test specimens are notrequired as during the vacuum drying any volatiles will have been removed from the test specimens.If previous testing has established that interference in the gas chromatography procedure is unlikely and annex A isomitted, one fewer test specimen will be required.A minimum of three valid test results is required to calculate the mean.
Testing in triplicate is allowed but in thiscase if one test result is invalid repeat the entire procedure.6.3 Cutting test specimensIf the article is large, to avoid handling and weighing problems or using excessive amounts of olive oil it may bepreferable to cut it so that the surface of the test specimen in contact with the olive oil does not exceed 3 dm².If this is done, take care that olive oil does not come into contact with the cut edges of the test specimen.
It isimportant that the area in contact with the oil is determined as it will be incorporated into the calculation later.Scratch lightly an identification code on the external surface of each test specimen.NOTEIf only part of a specimen is tested, this part should be representative of the whole in terms of composition and wallor layer thickness.SIST EN 1186-8:2002



EN 1186-8:2002 (E)107 Procedure7.1 GeneralDetermine the applicability of the method by carrying out the procedure described in annex A.
If prior tests haveestablished that the method is applicable then annex A may be omitted.Before weighing, discharge any build up of static electricity with an antistatic gun or other suitable means.7.2 Initial weighing of test specimens7.2.1Determine the need for conditioning of the test specimens by carrying out the procedure described inannex B or in annex C.
If prior tests have established that sample conditioning is not required then annex B andannex C may be omitted.
If prior tests have established that the procedure described in annex D is applicable tothe sample, then annex B or annex C may be omitted.7.2.2If the tests described in annex B or annex C show that conditioning is not necessary, determine and recordthe mass of each test specimen.7.2.3If the tests described in annex B or annex C show that conditioning is necessary, follow the directions inthe relevant annex to determine the initial mass of the sample.7.2.4If the tests described in annex B show that conditioning is necessary, but constant mass cannot beachieved within five days then carry out the conditioning procedure described in C.3.1 or annex D.NOTE 1Long conditioning periods are not satisfactory due to oxidation of the olive oil which can occur upon prolongedconditioning.NOTE 2The conditioning procedures described in annex C and annex D can be used if it has been established that theseprocedures are more suited to the polymer type under test.7.3 Exposure to food simulantPlace a sufficient volume of olive oil in a beaker in the thermostatically controlled oven or incubator (5.6) which isset at the test temperature and leave until the test temperature has been attained.Place each test specimen on a clean, oil free surface and fill four specimens with olive oil to within 0.5 cm of thetop.
If the container has a specified nominal volume of contents, see 8.2 of EN 1186-1:2002.
Place into one of thefilled test specimens a thermometer or thermocouple.NOTE 1If the procedure described in annex D is used, it can be necessary to dry all of the olive oil used for the migrationtest, see D.3.2.NOTE 2Care should be taken not to spill any oil on the external surfaces.NOTE 3The two remaining test specimens are used to check whether the sample losses mass from the evaporation ofvolatiles, such as water, solvents and oligomers, during the test period.
If the vacuum drying procedure in annex C is applicablethese test specimens are not required as during the vacuum drying volatiles will have been removed from the test specimens.Place sufficient olive oil into a tube for use as reference standards in constructing the calibration graph (see7.6.2.2) and if the procedure in annex D is used, as a third blank sample for Karl Fischer titrations, stopper thetube.Place the four filled test specimens and the two empty test specimens and the reference oil in the tube in thethermostatically controlled oven or incubator set at the test temperature. This part of the operation should becarried out in the minimum time possible to prevent undue heat loss.SIST EN 1186-8:2002



EN 1186-8:2002 (E)11If the procedure in annex D is followed the test specimens filled with olive oil and the tube containing olive oil haveto be sealed.Observe the temperature of the thermostatically controlled oven or incubator or the olive oil (see NOTE 5) in thefilled article and leave the test specimens for the selected test period, taking into account the tolerances specified inTable B.1 of EN 1186-1:2002, after the olive oil in the test specimen has reached a temperature within thetolerance specified in Table B.2 of EN 1186-1:2002.NOTE 4Annex B of EN 1186-1:2002 includes tolerances on a wide range of contact times and contact temperatures.
All ofthese contact times and contact temperatures are not necessarily relevant to this Part of the standard.NOTE 5For exposure times of 24 h or more it is acceptable to monitor the temperature of the air bath of the thermostaticallycontrolled oven or incubator or refrigerator, instead of the temperature of the simulant.NOTE 6In this method the outer surfaces of the specimens in the thermostatically controlled oven or incubator are exposedto the oven temperature and hence can be effected by humidity changes in the thermostatically controlled oven or incubator.For some plastics materials these humidity changes can cause large mass variations that add to analysis time during sampleconditioning.
These variations can be reduced by putting all test specimens into an air tight container before placing in thethermostatically controlled oven or incubator.Remove the test specimens and the tube from the thermostatically controlled oven or incubator and immediatelyempty the test specimens that contained olive oil and allow the oil to drain.
Remove any adhering olive oil bygently pressing between filter papers (5.7).
Repeat the pressing procedure until the filter paper shows no spots ofolive oil.If the procedure in annex D is followed, transfer the olive from the test specimens into tubes and seal the tubes toprevent further change in the moisture content of the oil, seal the tube containing reference olive oil and carry outthe Karl Fischer determination of water content as soon as possible.7.4 Final weighing of test specimens7.4.1For those specimens which did not require conditioning to obtain their initial masses (see 7.2.2), weigh allsix test specimens i.e. the four that have been in olive oil and the two that were in the empty tubes and record themass of each test specimen.7.4.2If conditioning of the test specimens was carried out using the procedure in annex B (see 7.2.3) thenrepeat the procedure.7.4.3If conditioning was
...