1、December 2013 Translation by DIN-Sprachendienst.English price group 14No 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).I
2、CS 13.030.10!%*vI“2078338www.din.deDDIN EN 16377Characterization of waste Determination of brominated flame retardants (BFR) in solid waste;English version EN 16377:2013,English translation of DIN EN 16377:2013-12Charakterisierung von Abfllen Bestimmung bromierter Flammschutzmittel (BFR) in Feststof
3、fabfall;Englische Fassung EN 16377:2013,Englische bersetzung von DIN EN 16377:2013-12Caractrisation des dchets Dtermination des retardateurs de flamme broms (BFR) dans les dchets solides;Version anglaise EN 16377:2013,Traduction anglaise de DIN EN 16377:2013-12www.beuth.deIn case of doubt, the Germa
4、n-language original shall be considered authoritative.Document comprises 30 pages 11.13 DIN EN 16377:2013-12 2 A comma is used as the decimal marker. National foreword This document (EN 16377:2013) has been prepared by Technical Committee CEN/TC 292 “Characterization of waste” (Secretariat: NEN, Net
5、herlands). The responsible German body involved in its preparation was the Normenausschuss Wasserwesen (Water Practice Standards Committee), Working Group NA 119-01-02-02-05 AK Organische Analytik of Working Committee NA 119-01-02-AA Abfall- und Bodenuntersuchung. The DIN Standard corresponding to t
6、he International Standard referred to in this document is as follows: ISO 8466-1 DIN 38402-51 National Annex NA (informative) Bibliography DIN 38402-51, German standard methods for the examination of water, waste water and sludge General information (group A) Calibration of analytical methods, evalu
7、ation of analytical results and linear calibration functions used to determine the performance characteristics of analytical methods (A 51) EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16377 September 2013 ICS 13.030.10 English Version Characterization of waste - Determination of brominated
8、flame retardants (BFR) in solid waste Caractrisation des dchets - Dtermination des retardateurs de flamme broms (BFR) dans les dchets solides Charakterisierung von Abfllen - Bestimmung bromierter Flammschutzmittel (BFR) in Feststoffabfall This European Standard was approved by CEN on 10 August 2013.
9、 CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on
10、application to the CEN-CENELEC 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 translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELE
11、C Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy,
12、 Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17,
13、B-1000 Brussels 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16377:2013: EEN 16377:2013 (E) 2 Contents Page Foreword 3 Introduction .4 1 Scope 5 2 Normative references 5 3 Principle 5 4 Interference 6 5 Reagents and standar
14、ds .6 6 Equipment 7 7 Sample pretreatment .8 8 Procedure .9 9 Calibration . 11 10 Test report . 15 Annex A (normative) Clean-up procedures . 16 A.1 Multi-layer column chromatography I (Al2O3), column size: 22 mm 190 mm . 16 A.2 Multi-layer column chromatography II (Silica), column size: 22 mm 190 mm
15、 . 16 A.3 Gel permeation chromatography (GPC) . 18 Annex B (informative) Examples of separation conditions in gas chromatography and mass spectrometry . 20 Annex C (informative) Typical ions and time windows for electron impact ionisation detection . 22 Annex D (informative) Examples of chromatogram
16、s 23 Annex E (informative) Precision data . 25 Annex F (informative) Summary of general requirements and recommendations . 27 Bibliography . 28 DIN EN 16377:2013-12EN 16377:2013 (E) 3 Foreword This document (EN 16377:2013) has been prepared by Technical Committee CEN/TC 292 “Characterization of wast
17、e”, the secretariat of which is held by NEN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by March 2014, and conflicting national standards shall be withdrawn at the latest by March 2014. Attentio
18、n is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or 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
19、 following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherla
20、nds, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. DIN EN 16377:2013-12EN 16377:2013 (E) 4 Introduction WARNING Persons using this European Standard should be familiar with common laboratory practice. This standard does not purport
21、to address all of the safety problems, if any, associated with its use. It is the responsibility of the user to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions. IMPORTANT It is absolutely essential that tests conducted according to t
22、his standard be carried out by suitably trained staff. DIN EN 16377:2013-12EN 16377:2013 (E) 5 1 Scope This European Standard specifies a method for the determination of selected polybrominated flame retardants (BFR), chemically known as polybrominated diphenylethers (BDE), in waste materials using
23、gas chromatography/mass spectrometry (GC-MS) in the electron impact (EI) ionisation mode (GC-EI-MS). When applying GC-EI-MS, the method is applicable to samples containing 100 g/kg to 5 000 g/kg of tetra- to octabromodiphenylether congeners and 100 g/kg to 10 000 g/kg of decabromo diphenylether (see
24、 Table 1). It is also possible to analyse other brominated flame retardants applying the method described in this European Standard, provided the methods applicability has been proven. Table 1 Brominated flame retardants determined by this method No. Congener Formula AbbreviationaMolar mass g/mol 1
25、2,2,4,4-Tetrabromodiphenylether C12H6Br4O BDE-47 485,795 0 2 2,2,4,4,5-Pentabromodiphenylether C12H5Br5O BDE-99 564,691 1 3 2,2,4,4,6-Pentabromodiphenylether C12H5Br5O BDE-100 564,691 1 4 2,2,4,4,5,6-Hexabromodiphenylether C12H4Br6O BDE-154 643,587 2 5 2,2,4,4,5,5-Hexabromodiphenylether C12H4Br6O BD
26、E-153 643,587 2 6 2,2,3,4,4,5,6-Heptabromodiphenylether C12H3Br7O BDE-183 722,483 2 7 Decabromodiphenylether C12Br10O BDE-209 959,171 4 aNumbering for the BDE according to IUPAC nomenclature for PCB. 2 Normative references The following documents, in whole or in part, are normatively referenced in t
27、his 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 14346, Characterization of waste Calculation of dry matter by determination of dr
28、y residue or water content EN 15002, Characterization of waste Preparation of test portions from the laboratory sample ISO 8466-1, Water quality Calibration and evaluation of analytical methods and estimation of performance characteristics Part 1: Statistical evaluation of the linear calibration fun
29、ction 3 Principle Brominated diphenylethers (BDE) are extracted from the dried sample using an organic solvent. In case of high levels of plastic waste matrices, cryo-grinding is required in order to provide particle sizes that allow the complete extraction of the analytes. Appropriate extraction te
30、chniques are soxhlet, sonication or pressurised fluid extraction. The obtained extracts are concentrated and cleaned up by column chromatography and Gel Permeation Chromatography (GPC). Following the concentration and clean-up process, the brominated diphenylethers are separated by capillary gas chr
31、omatography and detected by mass spectrometry in the selected ion monitoring mode using electron impact ionisation (EI). Quantification is carried out by the internal standard method. DIN EN 16377:2013-12EN 16377:2013 (E) 6 4 Interference Naturally produced brominated compounds, such as halogenated
32、bipyrrols or brominated phenoxyanisols can be considered as potential sources of interference. Sources of contamination are brominated diphenylethers, used as flame-retardants in organic polymers. Therefore, contact of the sample or the reagents with these organic polymers shall be avoided. Contamin
33、ation routes include airborne dust, vial covers, pasteur pipette fillers and recycled paper. 5 Reagents and standards Only use reagents with negligibly low concentrations of brominated diphenylethers (BDE), compared with the concentration to be determined and verify by blank determinations. To preve
34、nt degradation, store standards in the dark at temperatures recommended by the manufacturer (4 C in the case of BDE). Temperatures 85 % and no interfering peak should appear in the gas chromatogram. If necessary, GPC conditions need to be modified to meet these requirements. Collect the eluate in a
35、concentration sample tube, add 0,5 ml of toluene and concentrate the extract to an approximate final volume of 0,5 ml. Proceed with further clean-up (e.g. A.2). A.3.7 Manual GPC clean-up Alternatively to automatic GPC (A.3.6), a manual GPC clean-up can be performed using a glass column (A.3.2) fille
36、d with a suspension of 50 g of Bio-Beads1)S-X3 (A.3.5.5) in the eluent (A.3.5.4). Cover the Bio-Beads1)material bubble-free with ethyl acetate:cyclohexane 1:1, allow settling of the material for 2 h and condition with 0,5 l of eluent (A.3.5.4) prior to first use. Concentrate the extract obtained aft
37、er column chromatography clean-up (A.1) to a final volume of 0,5 ml using the concentration device. Dissolve immediately in 2 ml of ethyl acetate:cyclohexane (1:1) and transfer onto the chromatography glass column. Then, 300 ml of the eluent (A.3.5.4) are put onto the column. Adjust an eluent flow o
38、f approximately 5 ml/min. Discard: 100 ml Collect: 200 ml DIN EN 16377:2013-12EN 16377:2013 (E) 20 Annex B (informative) Examples of separation conditions in gas chromatography and mass spectrometry Example 1: GC-EI-MS conditions Injection: on column 35 kPa Injector temperature: 110 C Injection volu
39、me: 1 l Transfer line temperature: 280 C Ion source: 250 C EI energy: 70 eV Resolution: low resolution, 1 mass unit Carrier gas: helium Guard column: length: 2 m inner diameter: 0,32 mm Column material: uncoated, deactivated Capillary column: length: 15 m film thickness: 0,1 m inner diameter: 0,25 m
40、m Column material: e.g. DB5-MS2)(5 % Phenyl) 95 % Methylpolysiloxane) Temperature programme: 110 C (0,2 min) 30 C/min to 200 C 20 C/min to 340 C (12,8 min) 2) DB-5 and ZB-5 are examples of suitable products available commercially. This information is given for the convenience of users of this Europe
41、an Standard and does not constitute an endorsement by CEN of these products. DIN EN 16377:2013-12EN 16377:2013 (E) 21 Example 2: GC-EI-MS conditions Injection: PTV, splitless, pressure-pulse injection Injector temperature: 90 C (0,1 min), 4 C/s to 360 C (15 min) Injection volume: 2 l Transfer line t
42、emperature: 300 C Ion source: EI energy: Resolution: Acquisition mode: 280 C 70 eV low, 1 mass unit SIM Quadrupol: 150 C Flow rate: 1,0 ml/min constant Carrier gas: helium Capillary column: length: 15 m inner diameter: 0,25 mm film thickness: 0,1 m Column material: e.g. ZB5-MS2)(5 % Phenyl) 95 % Met
43、hylpolysiloxane) Temperature programme: 80 C (1 min) 20 C/min to 340 C (5 min) DIN EN 16377:2013-12EN 16377:2013 (E) 22 Annex C (informative) Typical ions and time windows for electron impact ionisation detection Table C.1 gives typical ions and time windows for the compounds analysed with GC-EI-MS
44、with conditions according to Example 2 in Annex B: Table C.1 Typical ions and time windows for electron impact ionisation detection Compound Ion Formula Time window min 12Cm/z 13Cm/z Intensity % Tetrabromodiphenylether M+-2Br C12H6O79Br28,00 to 9,50 323,879 335,919 51 M+-2Br+2 C12H6O79Br81Br 325,877
45、 337,917 100 Pentabromodiphenylether M+-2Br+2 C12H5O79Br281Br 9,70 to 10,40 403,787 415,827 100 M+-2Br+4 C12H5O79Br81Br2405,785 417,825 98 Hexabromodiphenylether M+-2Br+2 C12H4O79Br381Br 10,60 to 11,50 481,698 493,738 68 M+-2Br+4 C12H4O79Br281Br2483,696 495,736 100 Heptabromodiphenylether M+-2Br+4 C
46、12H3O79Br381Br211,60 to 12,00 561,606 573,646 100 M+-2Br+6 C12H3O79Br281Br3563,604 575,644 98 BDE-209 M+-2Br+8 C12O79Br481Br415,50 to 16,50 799,334 811,374 100 M+-2Br+10 C12O79Br381Br5801,332 813,372 78 DIN EN 16377:2013-12EN 16377:2013 (E) 23 Annex D (informative) Examples of chromatograms Key Y re
47、lative abundance t time in minutes 1 BDE/MBDE 47 5 BDE/MBDE 153 2 BDE/MBDE 100 6 BDE/MBDE 183 3 BDE/MBDE 99 7 BDE/MBDE 209 4 BDE/MBDE 154 8 DBDPE/MDBDPE Figure D.1 GC-MS-Chromatogram of an electronic waste sample after clean-up (both columns and GPC), showing the BDE congeners and DBDPE decabromodip
48、henylethane DIN EN 16377:2013-12EN 16377:2013 (E) 24 Key Y relative abundance t time in min 1 BDE/MBDE 47 5 BDE/MBDE 153 2 BDE/MBDE 100 6 BDE/MBDE 183 3 BDE/MBDE 99 7 BDE/MBDE 209 4 BDE/MBDE 154 8 DBDPE/MDBDPE Figure D.2 GC-MS-Chromatogram of a shredder light fraction sample after clean-up (both columns and GPC), showing the BDE congeners and DBDPE decabromodiphenylethane DIN EN 16377:2013-12EN 16377:2013 (E) 25 Annex E (informative) Pre
