1、BRITISH STANDARD BS 6068-2.99:2006 Water quality Determination of selected polybrominated diphenyl ethers in sediment and sewage sludge Method using extraction and gas chromatography/mass spectrometry ICS 13.060.50 BS EN ISO 22032:2009 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 02/11/200
2、9 06:54, Uncontrolled Copy, (c) BSIThis British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 January 2007 BSI 2009 National foreword The UK participation in its preparation was entrusted by Technical Committee EH/3, Water quality, to Subcommittee EH
3、/3/2, Physical chemical and biochemical methods. A list of organizations represented on this subcommitee can be obtained on request to its secretary. This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance
4、 with a British Standard cannot confer immunity from legal obligations. BS EN ISO 22032:2009 This British Standard is the UK implementation of EN ISO 22032:2009. It is identical with ISO 22032:2006. It supersedes BS ISO 22032:2006 which is withdrawn. ISBN 978 0 580 60562 8 Date Comments This corrige
5、ndum renumbers BS ISO 22032:2006 as BS EN ISO 22032:2009 Amendments/corrigenda issued since publication 30 June 2009 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 02/11/2009 06:54, Uncontrolled Copy, (c) BSIEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 22032 February 2009 ICS 13.
6、060.50 English Version Water quality - Determination of selected polybrominated diphenyl ethers in sediment and sewage sludge - Method using extraction and gas chromatography/mass spectrometry (ISO 22032:2006) Qualit de leau - Dosage dune slection dthers diphnyliques polybroms dans des sdiments et d
7、es boues dpuration - Mthode par extraction et chromatographie en phase gazeuse/spectromtrie de masse (ISO 22032:2006) Wasserbeschaffenheit - Bestimmung ausgewhlter polybromierter Diphenylether in Sediment und Klrschlamm - Verfahren mittels Extraktion und Gaschromatographie/Massenspektrometrie (ISO 2
8、2032:2006) This European Standard was approved by CEN on 28 March 2008. 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 bibliograp
9、hical references concerning such national standards may be obtained on application to the CEN 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
10、CEN member into its own language and notified to the CEN Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland,
11、 Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B
12、-1000 Brussels 2009 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 22032:2009: E Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 02/11/2009 06:54, Uncontrolled Copy, (c) BSIForeword The text of ISO 22032:2006 has been p
13、repared by Technical Committee ISO/TC 147 “Water quality” of the International Organization for Standardization (ISO) and has been taken over as EN ISO 22032:2009 by Technical Committee CEN/TC 230 “Water analysis” the secretariat of which is held by DIN. This European Standard shall be given the sta
14、tus of a national standard, either by publication of an identical text or by endorsement, at the latest by August 2009, and conflicting national standards shall be withdrawn at the latest by August 2009. Attention is drawn to the possibility that some of the elements of this document may be the subj
15、ect 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 European Standard: Austria, Belgium, Bu
16、lgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The te
17、xt of ISO 22032:2006 has been approved by CEN as a EN ISO 22032:2009 without any modification. ii BS EN ISO 22032:2009E EN ISO 22032:2009 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 02/11/2009 06:54, Uncontrolled Copy, (c) BSIiii Contents Page Introduction v 1 Scope . 1 2 Normative refere
18、nces . 2 3 Principle. 2 4 Interferences . 2 5 Reagents and standards 3 6 Apparatus 4 7 Sampling and sample pre-treatment. 5 8 Procedure 5 9 Calibration . 8 10 Test report . 11 Annex A (informative) Clean-up procedures . 12 Annex B (informative) Examples for separation conditions in gas chromatograph
19、y and mass spectrometry . 16 Annex C (informative) Typical ions and time windows for electron impact ionization detection 19 Annex D (informative) Examples of chromatograms and spectra 20 Annex E (informative) Precision data. 25 Bibliography . 26 BS EN ISO 22032:2009E EN ISO 22032:2009 Licensed Copy
20、: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 02/11/2009 06:54, Uncontrolled Copy, (c) BSIblank Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 02/11/2009 06:54, Uncontrolled Copy, (c) BSIIntroduction The user should be aware that particular problems could require the specification of additional
21、marginal conditions. BS EN ISO 22032:2009 vE EN ISO 22032:2009 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 02/11/2009 06:54, Uncontrolled Copy, (c) BSIblank Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 02/11/2009 06:54, Uncontrolled Copy, (c) BSI1 Water quality Determination of
22、selected polybrominated diphenyl ethers in sediment and sewage sludge Method using extraction and gas chromatography/mass spectrometry WARNING Persons using this International Standard should be familiar with normal laboratory practice. This standard does not purport to address all of the safety pro
23、blems, 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 this standard be carried out by s
24、uitably trained staff. 1 Scope This International Standard specifies a method for the determination of selected polybrominated diphenyl ethers (PBDE) (see Figure 1 and Table 1) in sediment and sludge using gas chromatography/mass spectrometry (GC-MS) in the electron impact (EI) or negative ion chemi
25、cal ionization (NCI) mode. When using GC-EI-MS, the method is applicable to samples containing 0,05 g/kg to 25 g/kg of tetra- to octabromo congeners and 0,3 g/kg to 100 g/kg of decabromo diphenyl ether (BDE-209), respectively. Approximately ten times lower concentrations can be quantified when using
26、 GC-NCI-MS. The risk of misinterpretation of interfering substances is smaller with EI due to its higher specificity. It is also possible to analyse other brominated diphenyl ethers according to this International Standard, after verifying its applicability in each case. Figure 1 Chemical formula of
27、 polybrominated diphenyl ethers BS EN ISO 22032:2009E EN ISO 22032:2009 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 02/11/2009 06:54, Uncontrolled Copy, (c) BSI2 Table 1 PBDE congeners determined by this method No. Congener Formula Abbreviation a Molar mass g/mol 1 2,2,4,4-Tetrabromodiphe
28、nyl ether C 12 H 6 Br 4 O BDE-47 485,795 0 2 2,2,4,4,5-Pentabromodiphenyl ether C 12 H 5 Br 5 O BDE-99 564,691 1 3 2,2,4,4,6-Pentabromodiphenyl ether C 12 H 5 Br 5 O BDE-100 564,691 1 4 2,2,4,4,5,6-Hexabromodiphenyl ether C 12 H 4 Br 6 O BDE-154 643,587 2 5 2,2,4,4,5,5-Hexabromodiphenyl ether C 12 H
29、 4 Br 6 O BDE-153 643,587 2 6 2,2,3,4,4,5,6-Heptabromodiphenyl ether C 12 H 3 Br 7 O BDE-183 722,483 2 7 Decabromodiphenyl ether C 12 Br 10 O BDE-209 959,171 4 aNumbering analogous to IUPAC nomenclature for PCB. 2 Normative references The following referenced documents are indispensable for the appl
30、ication 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. ISO 5667-13, Water quality Sampling Part 13: Guidance on sampling of sludges from sewage and water-treatment works
31、 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 Extraction of brominated diphenyl ethers from the dried sample by an organic solvent. Clean-up of th
32、e extract by, e.g. preparative multi-layer silica gel column chromatography. After concentration, separation of the brominated diphenyl ethers by capillary gas chromatography and detection by either mass spectrometry in the selected ion monitoring mode using electron impact (EI), or negative ion che
33、mical ionization (NCI). For determination of the concentration in the sample, an internal standard calibration over the total procedure is used. 4 Interferences When applying GC-NCI-MS, 2,2,4,4,5,5-hexabromobiphenyl (BB-153) and tetrabromobisphenol A can co- elute with BDE-154 and BDE-153, respectiv
34、ely, when using non-polar capillary columns and hence, interfere with the determination of the corresponding BDE congeners when monitoring the bromide ions m/z = 79 and m/z = 81. Moreover, naturally produced brominated compounds, such as halogenated bipyrrols and brominated phenoxyanisols, can be co
35、nsidered as potential interferences. Sources of contamination are the following: brominated diphenyl ethers used as flame-retardants in organic polymers. Therefore, contact of the sample or the reagents with these organic polymers shall be avoided. Transportation paths include airborne dust, vial co
36、vers, pasteur pipette fillers and recycled paper. BS EN ISO 22032:2009E EN ISO 22032:2009 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 02/11/2009 06:54, Uncontrolled Copy, (c) BSI3 5 Reagents and standards Only use reagents with negligibly low concentrations of brominated diphenyl ethers c
37、ompared with the concentration to be determined and verify by blank determinations. To prevent degradation, store standards in the dark at temperatures recommended by the manufacturer (calibration solutions should preferably be stored at approximately 18 C). 5.1 Solvents for extraction, clean-up and
38、 preparation of stock solutions. A variety of solvents may be used depending on the particular sample matrix to be analysed and the availability of commercial standard solution, e.g. toluene (C 7 H 8 ), or acetone (propanone, C 3 H 6 O), or a mixture of acetone (propanone, C 3 H 6 O) and hexane (C 6
39、 H 14 ), or heptane (C 7 H 16 ), or iso-octane (2,2,4-trimethylpentane, C 8 H 18 ), or nonane (C 9 H 20 ), or dichloromethane (CH 2 Cl 2 ) for residual analysis. 5.2 Reference substances. See Table 1. Solutions of reference substances are commercially available. 5.3 Internal standard substances. Sol
40、utions of reference substances for use as internal standards for electron impact ionization (Table 2, substances 1 to 5) and for negative ion chemical ionization (Table 2, substances 6, 7 and 8) are commercially available. Table 2 Examples of internal standards No Name Formula Abbreviation Molar mas
41、s g/mol Internal standards for GCMS with electron impact ionization 1 2,2,4,4-Tetrabromo 13 C 12 diphenyl ether 13 C 12 H 6 Br 4 O 13 C-BDE-47 497,703 5 2 2,2,4,4,5-Pentabromo 13 C 12 diphenyl ether 13 C 12 H 5 Br 5 O 13 C-BDE-99 576,599 5 3 2,2,4,4,5,5-Hexabromo 13 C 12 diphenyl ether 13 C 12 H 4 B
42、r 6 O 13 C-BDE-153 655,495 5 4 2,2,3,4,4,5,6-Heptabromo 13 C 12 diphenyl ether 13 C 12 H 3 Br 7 O13 C-BDE-183 734,391 6 5 Decabromo 13 C 12 diphenyl ether 13 C 12 Br 10 O 13 C-BDE-209 971,079 7 Internal standards for GCMS with negative ion chemical ionization a6 3,3,4,4-Tetrabromodiphenyl ether C 12
43、 H 6 Br 4 OBDE-77 485,795 0 7 2,2,3,4,4,5,6-Heptabromodiphenyl ether C 12 H 3 Br 7 OBDE-181 722,483 2 8 Decabromo 13 C 12 diphenyl ether 13 C 12 Br 10 O 13 C-BDE-209 971,079 7 aCheck for interferences when non-labelled PBDE is used as an internal standard. Other BDE congeners are suitable as interna
44、l standards, e.g. BDE-140. 5.4 Sodium sulfate, anhydrous, Na 2 SO 4 , powdered. 5.5 Operating gases, for gas chromatography/mass spectrometry, of high purity and in accordance with manufacturers specifications. 5.6 Nitrogen, of high purity, at least 99,999 % by volume, for drying and for concentrati
45、on by evaporation. BS EN ISO 22032:2009E EN ISO 22032:2009 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 02/11/2009 06:54, Uncontrolled Copy, (c) BSI4 5.7 Solutions of the single reference substances / internal standards. Use commercially available solutions (may be in nonane, toluene or is
46、o-octane) or prepare stock solutions, e.g. by dissolving 10 mg of each of the reference substances (5.2, 5.3) in toluene (5.1) in an amber, 10-ml volumetric flask and bring to volume (concentration: 1 mg/ml). Store at approximately 18 C in the dark. 5.8 Multicomponent stock solution of reference sub
47、stances. Accurately transfer between 100 l to 500 l of each single standard solution (5.7) into an amber, 10-ml volumetric flask and bring to volume with the appropriate solvent, e.g. toluene, or nonane, or iso-octane (5.1). (Concentrations are between 10 g/ml and 50 g/ml per substance.) 5.9 Calibra
48、tion solutions for multicomponent-multilevel calibration. Prepare, e.g. seven calibration solutions with concentrations according to the detection capacity of the mass spectrometer. Combine the multicomponent stock solutions of reference substances (5.8), internal standards (5.10) and, if necessary,
49、 injection standard (5.12) to produce the solutions (e.g. shown in Table 5) by appropriate dilution with the appropriate solvent, e.g. toluene, or nonane, or iso-octane (5.1). In order to avoid potential photodegradation, store the solutions in the dark. Check the concentrations of calibration solutions before use. Use one of the calibration solutions to optimize the GC-MS system and to determine the retention times
