1、BSI Standards PublicationBS EN 16377:2013Characterization of waste Determination of brominatedflame retardants (BFR) in solidwasteBS EN 16377:2013 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 16377:2013.The UK participation in its preparation was entrusted to
2、 TechnicalCommittee B/508/3, Characterization of waste.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The Britis
3、h Standards Institution 2013. Published by BSI StandardsLimited 2013ISBN 978 0 580 77217 7ICS 13.030.10Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 30 September
4、 2013.Amendments issued since publicationDate Text affectedBS EN 16377:2013EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16377 September 2013 ICS 13.030.10 English Version Characterization of waste - Determination of brominated flame retardants (BFR) in solid waste Caractrisation des dchets -
5、 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. CEN members are bound to comply with the CEN/CENELEC Internal Re
6、gulations 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 application to the CEN-CENELEC Management Centre or to any CEN me
7、mber. 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-CENELEC Management Centre has the same status as the official versions.
8、 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, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Polan
9、d, 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, B-1000 Brussels 2013 CEN All rights of exploitation in any form a
10、nd by any means reserved worldwide for CEN national Members. Ref. No. EN 16377:2013: EBS EN 16377:2013EN 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 standards .6 6 Equipment 7 7 Sample pretreatment .8 8 Pr
11、ocedure .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 . 16 A.3 Gel permeation chromatography (GPC) . 1
12、8 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 chromatograms 23 Annex E (informative) Precision data . 25 An
13、nex F (informative) Summary of general requirements and recommendations . 27 Bibliography . 28 BS EN 16377:2013EN 16377:2013 (E) 3 Foreword This document (EN 16377:2013) has been prepared by Technical Committee CEN/TC 292 “Characterization of waste”, the secretariat of which is held by NEN. This Eur
14、opean 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. Attention is drawn to the possibility that some of the elemen
15、ts 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 following countries are bound to implement this Euro
16、pean 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, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slo
17、venia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 16377:2013EN 16377:2013 (E) 4 Introduction WARNING Persons using this European Standard should be familiar with common laboratory practice. This standard does not purport to address all of the safety problems, if any, associated
18、 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 this standard be carried out by suitably trained staff. BS
19、 EN 16377:2013EN 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 gas chromatography/mass spectrometry (GC-MS) in the electron
20、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 Table 1). It is also possible to analyse other brominated fl
21、ame 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 2,2,4,4-Tetrabromodiphenylether C12H6Br4O BDE-47 485,795 0 2
22、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 BDE-153 643,587 2 6 2,2,3,4,4,5,6-Heptabromodiphenylether C12H3
23、Br7O 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 this document and are indispensable for its application. For d
24、ated 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 dry residue or water content EN 15002, Characterization of wast
25、e 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 function 3 Principle Brominated diphenylethers (BDE) are extract
26、ed 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 techniques are soxhlet, sonication or pressurised fluid extract
27、ion. 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 chromatography and detected by mass spectrometry in the selected
28、 ion monitoring mode using electron impact ionisation (EI). Quantification is carried out by the internal standard method. BS EN 16377:2013EN 16377:2013 (E) 6 4 Interference Naturally produced brominated compounds, such as halogenated bipyrrols or brominated phenoxyanisols can be considered as poten
29、tial 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. Contamination routes include airborne dust, vial covers, pasteur pipette
30、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 prevent degradation, store standards in the dark at temperatures recom
31、mended 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 concentration sample tube, add 0,5 ml of toluene and concentrate
32、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) filled with a suspension of 50 g of Bio-Beads1)S-X3 (A.3.5.5) in the e
33、luent (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 after column chromatography clean-up (A.1) to a final volume of 0,5
34、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 of approximately 5 ml/min. Discard: 100 ml Collect: 200 ml BS EN 1
35、6377:2013EN 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 volume: 1 l Transfer line temperature: 280 C Ion source: 250 C EI energy:
36、 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 mm Column material: e.g. DB5-MS2)(5 % Phenyl) 95 % Methylpolysiloxane)
37、 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 European Standard and does not constitute an endorsement by CEN of these pr
38、oducts. BS EN 16377:2013EN 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 temperature: 300 C Ion source: EI energy: Resolution: Acquisition mode: 28
39、0 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 % Methylpolysiloxane) Temperature programme: 80 C (1 min) 20 C/min to 340 C (5
40、 min) BS EN 16377:2013EN 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 with conditions according to Example 2 in Annex B: Table C.1 Typical ions and
41、 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 325,877 337,917 100 Pentabromodiphenylether M+-2Br+2 C12H5O79Br281Br 9,70 to 10,40 4
42、03,787 415,827 100 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 C12H3O79Br381Br211,60 to 12,00 561,606 573,646 100 M+-2Br+6 C12H3O79Br281Br356
43、3,604 575,644 98 BDE-209 M+-2Br+8 C12O79Br481Br415,50 to 16,50 799,334 811,374 100 M+-2Br+10 C12O79Br381Br5801,332 813,372 78 BS EN 16377:2013EN 16377:2013 (E) 23 Annex D (informative) Examples of chromatograms Key Y relative abundance t time in minutes 1 BDE/MBDE 47 5 BDE/MBDE 153 2 BDE/MBDE 100 6
44、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 decabromodiphenylethane BS EN 16377:2013EN 16377:2013 (E) 24 Key Y relative abundance t time
45、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 BS EN 1637
46、7:2013EN 16377:2013 (E) 25 Annex E (informative) Precision data Table E.1 Validation data Matrix Substance l n nAPxmg/kg sRmg/kg CVR% srmg/kg CVr% 1 Filter dust BDE-47 12 46 17,3 0,925 0,355 38,44 0,067 7,27 1 BDE-100 10 38 21,0 0,176 0,083 46,92 0,018 10,44 1 BDE-99 12 46 8,7 1,329 0,488 36,69 0,14
47、2 10,68 1 BDE-154 10 38 10,5 0,115 0,038 33,27 0,012 10,45 1 BDE-153 11 42 19,0 0,277 0,064 28,35 0,019 8,54 1 BDE-183 12 46 21,7 0,59 0,25 42,33 0,058 9,89 1 BDE-209 9 35 20,0 19,21 10,85 56,46 1,01 5,26 2 Shredder light fraction BDE-47 12 48 0 1,074 0,477 44,43 0,297 27,65 2 BDE-100 9 36 0 0,157 0
48、,078 49,58 0,029 18,8 2 BDE-99 12 48 0 1,572 0,726 46,16 0,444 28,26 2 BDE-154 11 44 18,2 0,124 0,042 33,74 0,032 25,97 2 BDE-153 11 44 9,1 0,401 0,160 39,89 0,111 27,66 2 BDE-183 12 48 16,7 1,173 0,627 53,49 0,51 43,51 2 BDE-209 9 36 22,2 13,37 8,40 62,82 3,81 28,47 3 Shredder light fraction BDE-47
49、 12 46 26,0 2,548 0,95 37,29 0,142 5,58 3 BDE-100 10 38 21,1 0,228 0,135 59,12 0,018 7,81 3 BDE-99 12 46 8,7 3,337 1,167 34,98 0,449 13,44 3 BDE-154 11 42 0 0,362 0,253 77,41 0,069 21,12 3 BDE-153 12 46 0 1,02 0,506 49,59 0,257 25,21 3 BDE-183 12 46 8,7 3,129 1,704 54,46 1,004 32,09 3 BDE-209 9 33 10,0 65,02 39,15 60,21 12,52 19,26 5 Electro waste BDE-47 12 45 8,9 4,032 2,053 50,93 0,84 20,82 5 BDE-100 10 37 21,6 0,413 0,214 51,85 0,038 9,22 5 BDE-99 12 45 17,8 5,441 2,
