1、June 2014 Translation by DIN-Sprachendienst.English price group 10No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 8
2、5.060; 67.250!%2a:“2156223www.din.deDDIN EN 16453Pulp, paper and paperboard Determination of phthalates in extracts from paper and paperboard;English version EN 16453:2014,English translation of DIN EN 16453:2014-06Zellstoff, Papier und Karton Bestimmung von Phthalaten in Papier- und Kartonextrakten
3、;Englische Fassung EN 16453:2014,Englische bersetzung von DIN EN 16453:2014-06Ptes, papier et carton Dosage des phtalates dans des extraits de papier et carton;Version anglaise EN 16453:2014,Traduction anglaise de DIN EN 16453:2014-06See start of applicationwww.beuth.deDocument comprises 14 pagesIn
4、case of doubt, the German-language original shall be considered authoritative.05.14DIN EN 16453:2014-06 2 A comma is used as the decimal marker. National foreword This document (EN 16453:2014) has been prepared by Technical Committee CEN/TC 172 “Pulp, paper and board”, Secretariat: DIN, Germany), Wo
5、rking Committee WG 3 “Analytical methods for the assessment of paper and board in contact with foodstuffs” (Secretariat: ASI, Austria). The responsible German body involved in its preparation was the Normenausschuss Papier, Pappe und Faserstoff (Paper, Board and Pulps Standards Committee), Working C
6、ommittee NA 074-02-01 AA Chemisch-technische Prfverfahren fr Papier, Pappe, Faserstoff und Chemiezellstoff. The DIN Standard corresponding to the International Standard referred to in this document is as follows: ISO 7213 DIN EN 27213 National Annex NA (informative) Bibliography DIN EN 27213, Pulps
7、Sampling for testing EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16453 January 2014 ICS 67.250; 85.060 English Version Pulp, paper and paperboard - Determination of phthalates in extracts from paper and paperboard Ptes, papier et carton - Dosage des phtalates dans des extraits de papier et
8、carton Zellstoff, Papier und Karton - Bestimmung von Phthalaten in Papier- und Kartonextrakten This European Standard was approved by CEN on 9 November 2013. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the
9、 status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, Frenc
10、h, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria,
11、Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey a
12、nd United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2014 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref.
13、No. EN 16453:2014 EEN 16453:2014 (E) 2 Contents Page Foreword 3 1 Scope 4 2 Normative references 4 3 Principle 5 3.1 General 5 3.2 Interferences 5 4 Materials .5 4.1 General 5 4.2 Pasteur pipettes .6 4.3 Double mark glass pipette of 0,05 ml, 0,2 ml, 0,5 ml, 1 ml, 5 ml and 10 ml .6 4.4 Volumetric fla
14、sks of 5 ml, 10 ml, 50 ml and 100 ml 6 4.5 Screw-cap glass bottle PYREX of 250 ml with a Polytetrafluorethylene-septa cap .6 4.6 Graduated cylinder of 200 ml .6 4.7 Round flask of 50 ml and 250 ml 6 4.8 Glass funnel .6 4.9 Polytetrafluorethylene-screw-cap glass vial single use (capacity adapted to t
15、he volume of concentrate) .6 5 Apparatus .6 5.1 Balance: capable of accurately weighing 0,000 1 g .6 5.2 Round flask heater.6 5.3 Rotary vacuum evaporator .6 5.4 Gas chromatograph coupled to a mass spectrometer (GC-MS) .6 6 Reagents .6 6.1 General 6 6.2 Operating gases for gas chromatography/mass sp
16、ectrometry, of high purity and in accordance with manufacturers specifications.6 6.3 Ethyl acetate, C4H8O2, CAS N 141-78-6 6 6.4 Isooctane, C8H18,CAS N 540-84-1 .6 6.5 Internal standard stock solution: For example d4-ring-deuterated-dibutyl phthalate (D4-ring-DBP) at 10 g/l 6 6.6 Stock solutions of
17、individual phthalate at 1 000 mg/l in ethyl acetate .7 7 Sampling .7 8 Preparation of the test sample of water extract .8 9 Preparation of the test sample of the organic solvent extract 8 10 Preparation of the test sample of the MPPO Extract .8 11 Procedure .8 11.1 GC conditions 8 11.2 Calibration 9
18、 11.3 Analysis of test samples .9 12 Expression of results . 10 12.1 For organic solvent extract: Expression of results. 10 12.2 For MPPO extract: Expression of results . 10 13 Test report . 10 14 Precision data . 11 Annex A (informative) GC-MS total ion chromatogram of a standard calibration soluti
19、on of 2 mg/l of phthalates 12 DIN EN 16453:2014-06 EN 16453:2014 (E) 3 Foreword This document (EN 16453:2014) has been prepared by Technical Committee CEN/TC 172 “Pulp, paper and board”, the secretariat of which is held by DIN. This European Standard shall be given the status of a national standard,
20、 either by publication of an identical text or by endorsement, at the latest by July 2014, and conflicting national standards shall be withdrawn at the latest by July 2014. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/o
21、r CENELEC shall not be held responsible for identifying any or all such patent rights. According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech
22、Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom.
23、DIN EN 16453:2014-06 EN 16453:2014 (E) 4 1 Scope This European Standard specifies an analytical test method for the determination of phthalates in water, solvent and modified polyphenylene oxide (MPPO) extracts of paper and board materials and articles intended for food contact using gas chromatogra
24、phy coupled to mass spectrometry (GC-MS). This method is applicable to the determination of phthalates in concentration ranging from 0,025 mg/l to 0,5 mg/l for water and solvent extracts and 0,002 mg/dm2to 0,040 mg/dm2for MPPO migration depending on the individual substance, the specified volume use
25、d for analysis and the value of the blank. Table 1 Phthlates determined by this method Name Abbreviation Formula CAS N Structure Diisobutyl-phthalate DIBP C16H22O484695 Dibutyl-phthalate DBP C16H22O484742 Di-(-ethylhexyl)-phthalate DEHP C24H38O4117817 2 Normative references The following documents,
26、in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 645, Paper and board intended
27、 to come into contact with foodstuffs - Preparation of a cold water extract EN 647, Paper and board intended to come into contact with foodstuffs - Preparation of a hot water extract EN 14338, Paper and board intended to come into contact with foodstuffs - Conditions for determination of migration f
28、rom paper and board using modified polyphenylene oxide (MPPO) as a simulant EN 15519, Paper and board intended to come into contact with foodstuffs - Preparation of an organic solvent extract EN 27213, Pulps - Sampling for testing (ISO 7213) EN ISO 186, Paper and board - Sampling to determine averag
29、e quality (ISO 186) EN ISO 536, Paper and board - Determination of grammage (ISO 536) EN ISO 638, Paper, board and pulps - Determination of dry matter content - Oven-drying method (ISO 638) DIN EN 16453:2014-06 EN 16453:2014 (E) 5 EN ISO 18856, Water quality - Determination of selected phthalates us
30、ing gas chromatography/mass spectrometry (ISO 18856) 3 Principle 3.1 General Phthalates in the test extract from paper and board materials are determined by gas chromatography / mass spectrometry. The test extract is prepared from water, organic solvent and/or MPPO simulant according to respectively
31、: EN 645, EN 647, EN 15519, EN 14338. Other phthalates, as listed in Table 1, may also be analysed by this procedure but it is necessary to determine its applicability in each case. 3.2 Interferences Due to their use as plasticizer agents, phthalates are ubiquitous. Therefore, pay special attention
32、to avoid any contamination. In order to avoid interferences and cross contamination, do not use plastics materials (tubes etc.). Cross contamination is likely to occur with laboratory air. Therefore, remove as far as possible, plastic materials from the laboratory. Cleaning agents often contain phth
33、alates and may severely contaminate the laboratory air if in use regularly. Therefore, refrain from using these agents during application of this procedure. Phthalates may bleed from the septa of the injector port into the gas chromatograph, therefore use septa that are not likely to contaminate the
34、 system. Fittings of syringes or equipment and septa of the sampling bottles may as well contain phthalates. 4 Materials 4.1 General Common laboratory glassware, rinsed with ethyl acetate before use. After rinsing the glassware with solvent, let residual solvent evaporate under a fume hood. In case
35、of contamination, special attention should be paid to the volumetric flasks cleaning. For example the non-volumetric glassware could be cleaned in a furnace at 500C for at least 6 h. Glassware for volumetric purpose can change its properties due to the heating process and so should not be treated th
36、us. Phthalates are ubiquitous laboratory contaminants. Each lot of reagent used for this method should be checked for phthalates contamination. DIN EN 16453:2014-06 EN 16453:2014 (E) 6 4.2 Pasteur pipettes 4.3 Double mark glass pipette of 0,05 ml, 0,2 ml, 0,5 ml, 1 ml, 5 ml and 10 ml 4.4 Volumetric
37、flasks of 5 ml, 10 ml, 50 ml and 100 ml 4.5 Screw-cap glass bottle PYREX1)of 250 ml with a Polytetrafluorethylene-septa cap 4.6 Graduated cylinder of 200 ml 4.7 Round flask of 50 ml and 250 ml 4.8 Glass funnel 4.9 Polytetrafluorethylene-screw-cap glass vial single use (capacity adapted to the volume
38、 of concentrate) 5 Apparatus 5.1 Balance: capable of accurately weighing 0,000 1 g 5.2 Round flask heater 5.3 Rotary vacuum evaporator 5.4 Gas chromatograph coupled to a mass spectrometer (GC-MS) 6 Reagents 6.1 General Use as far as available reagents of analytical quality or better. Use only reagen
39、ts with negligibly low concentrations of phthalates and verify by blank determinations. 6.2 Operating gases for gas chromatography/mass spectrometry, of high purity and in accordance with manufacturers specifications 6.3 Ethyl acetate, C4H8O2, CAS N 141-78-6 6.4 Isooctane, C8H18,CAS N 540-84-1 Store
40、 the following solutions in glass bottles at 18 C, protected from light. 6.5 Internal standard stock solution: For example d4-ring-deuterated-dibutyl phthalate (D4-ring-DBP) at 10 g/l 6.5.1 General Weigh for example, approximately 0,1 g with an accuracy of 0,001 g of d4-DBP in a 10 ml volumetric fla
41、sk (4.4) and bring to volume with ethyl acetate (6.3). 1) PYREX is an example of a suitable product available commercially. This information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of this product. DIN EN 16453:2014-06 EN 16453:20
42、14 (E) 7 6.5.2 Solution A of internal standard at 100 mg/l in ethyl acetate Transfer 1 ml of the solution (6.5.1) into a 100 ml volumetric flask (4.4) and dilute to the mark with the ethyl acetate (6.3). 6.5.3 Solution B of internal standard at 10 mg/l in ethyl acetate Transfer 0,5 ml of the solutio
43、n A (6.5.2) into a 5 ml volumetric flask (4.4) and dilute to the mark with the ethyl acetate (6.3). 6.5.4 Solution C of internal standard at 0,5 mg/l in ethyl acetate Transfer 0,25 ml of the stock solution A (6.5.2) into a 50 ml volumetric flask (4.4) and dilute to the mark with the ethyl acetate (6
44、.3). 6.6 Stock solutions of individual phthalate at 1 000 mg/l in ethyl acetate 6.6.1 General In a 100 ml volumetric flask (4.4), weigh approximately 0,1 g with an accuracy of 0,001 g of each of the reference substances and bring to volume with ethyl acetate (6.3). 6.6.2 Intermediate solution of pht
45、halates at 50 mg/l in ethyl acetate Transfer 5 ml of each stock solution (6.6.1) into a 100 ml volumetric flask (4.4) and dilute to the mark with ethyl acetate (6.3). 6.6.3 Calibration standard solutions of phthalates in isooctane Five standard solutions are prepared by transferring respectively: 0,
46、05 ml, 0,1 ml, 0,2 ml, 0,5 ml and 1 ml of the Intermediate solution (6.6.2) in 10 ml volumetric flasks (4.4) and 0,5 ml of the solution B of internal standard (6.5.3) by adjusting the volume with the solvent used for the extract of paper and board, for the preparation of solution having respectively
47、 concentrations of about: 0,25 mg/l, 0,5 mg/l, 1 mg/l, 2,5 mg/l and 5 mg/l of phthalate, and 0,5 mg/l of Internal Standard stock solution in each calibration solution. 6.6.4 Individual solutions of phthalates in ethyl acetate 1 mg/l for determination of GC retention times Transfer 0,1 ml of stock so
48、lution (6.6.1) into a 100 ml volumetric flask (4.4) and dilute to the mark with ethyl acetate (6.3). 7 Sampling If the analysis is being made to evaluate a lot of paper, board or pulp, the sample shall be selected in accordance with EN ISO 186 or EN 27213, as relevant. If the analysis is made on ano
49、ther type of sample, report the source of the sample, and, if possible, the sampling procedure. Select the specimens so that they are representative of the sample received. If required, take a separate sample for the determination of the grammage in accordance with EN ISO 536 and/or for the determination of dry matter content with EN ISO 638. For any storage or transport between sampling and analysis, protect the sample from contamination by using for example aluminium foil to over-wrap DIN EN 16453:2014-06 EN 16453:2014 (E) 8 8 Preparation of the
