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 This British Standard was published under the authority of the S
2、tandards 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/3/2, Physical chemical and biochemical methods. A list of organizations represented on this subcom
3、mitee 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 with a British Standard cannot confer immunity from legal obligations. BS EN ISO 22032:2009 This B
4、ritish 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 It supersedes BS ISO 22032:2006 which is withdrawn.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 corrigendum renumbers BS ISO 22032:2006 as BS EN ISO 22032:2009 Amendments/corrigenda issued since publica
5、tion 30 June 2009EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 22032 February 2009 ICS 13.060.50 English Version Water quality - Determination of selected polybrominated diphenyl ethers in sediment and sewage sludge - Method using extraction and gas chromatography/mass spectrometry (ISO 2
6、2032:2006) Qualit de leau - Dosage dune slection dthers diphnyliques polybroms dans des sdiments et des boues dpuration - Mthode par extraction et chromatographie en phase gazeuse/spectromtrie de masse (ISO 22032:2006) Wasserbeschaffenheit - Bestimmung ausgewhlter polybromierter Diphenylether in Sed
7、iment und Klrschlamm - Verfahren mittels Extraktion und Gaschromatographie/Massenspektrometrie (ISO 22032:2006) 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 Europe
8、an 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 Management Centre or to any CEN member. This European Standard exists in three official versions (English
9、, 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 Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, C
10、yprus, 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 United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION
11、 COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-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: EForeword The text of ISO 22032:2006 has been
12、prepared 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 st
13、atus 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 sub
14、ject 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, B
15、ulgaria, 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 t
16、ext 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 22032:2009iii Contents Page Introduction v 1 Scope . 1 2 Normative references . 2 3 Principle. 2 4 Interferences . 2 5 Reagents and standards 3 6 Apparatus 4 7 Sampling and
17、 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 chromatography and mass spectrometry . 16 Annex C (informative) Typical ions and time windows for electron impac
18、t 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 22032:2009blankIntroduction The user should be aware that particular problems could require the specification of additional
19、 marginal conditions. BS EN ISO 22032:2009 vE EN ISO 22032:2009blank1 Water quality Determination of 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 fami
20、liar with normal laboratory practice. This standard does not purport 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. IMP
21、ORTANT It is absolutely essential that tests conducted according to this standard be carried out by suitably 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
22、 using gas chromatography/mass spectrometry (GC-MS) in the electron impact (EI) or negative ion chemical 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 eth
23、er (BDE-209), respectively. Approximately ten times lower concentrations can be quantified when using 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
24、 International Standard, after verifying its applicability in each case. Figure 1 Chemical formula of polybrominated diphenyl ethers BS EN ISO 22032:2009E EN ISO 22032:20092 Table 1 PBDE congeners determined by this method No. Congener Formula Abbreviation a Molar mass g/mol 1 2,2,4,4-Tetrabromodiph
25、enyl 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
26、H 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 app
27、lication 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 work
28、s 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 t
29、he 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 ch
30、emical 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, respecti
31、vely, 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 c
32、onsidered 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 c
33、overs, pasteur pipette fillers and recycled paper. BS EN ISO 22032:2009E EN ISO 22032:20093 5 Reagents and standards Only use reagents with negligibly low concentrations of brominated diphenyl ethers compared with the concentration to be determined and verify by blank determinations. To prevent degr
34、adation, 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 preparation of stock solutions. A variety of solvents may be used depending on the particular samp
35、le 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 H 14 ), or heptane (C 7 H 16 ), or iso-octane (2,2,4-trimethylpentane, C 8 H 18 ), or nonane (C 9
36、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. Solutions of reference substances for use as internal standards for electron impact ionization (Table
37、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 mass g/mol Internal standards for GCMS with electron impact ionization 1 2,2,4,4-Tetrabromo 13 C 12 di
38、phenyl 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 Br 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
39、 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 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
40、 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 internal standards, e.g. BDE-140. 5.4 Sodium sulfate, anhydrous, Na 2 SO 4 , powdered. 5.5 Operating gases
41、, 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 concentration by evaporation. BS EN ISO 22032:2009E EN ISO 22032:20094 5.7 Solutions of the single reference s
42、ubstances / internal standards. Use commercially available solutions (may be in nonane, toluene or iso-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:
43、1 mg/ml). Store at approximately 18 C in the dark. 5.8 Multicomponent stock solution of reference substances. 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 non
44、ane, or iso-octane (5.1). (Concentrations are between 10 g/ml and 50 g/ml per substance.) 5.9 Calibration solutions for multicomponent-multilevel calibration. Prepare, e.g. seven calibration solutions with concentrations according to the detection capacity of the mass spectrometer. Combine the multi
45、component stock solutions of reference substances (5.8), internal standards (5.10) and, if necessary, 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 poten
46、tial 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. As an alternative, determine and use relative retention times. 5.10 Stock solu
47、tion of the internal standards. Prepare a stock solution of the internal standards at an appropriate concentration in, e.g. toluene or iso-octane (2,2,4-trimethylpentane). Dilute this stock solution. See Table 5 for suggested concentrations of calibration solutions and sample extracts. 5.11 Clean-up
48、 material. See Annex A. 5.12 Injection standard. Use an injection standard, e.g. dibromooctafluorobiphenyl (C 12 Br 2 F 8 ), to determine recovery rates for the internal standard in each sample. 5.13 Baked sand. Bake sand for at least 8 h at 400 C. 6 Apparatus Clean all glassware by rinsing with ace
49、tone (propanone) (5.1). Heating the glassware to 400 C will reduce blanks. Recalibrate volumetric apparatus prior to use if heated. 6.1 Wide-necked bottle, 1 000 ml up to 5 000 ml capacity, for wet sediment or sludge. 6.2 Freeze drying apparatus. 6.3 Deep freezer. 6.4 Mortar and pestle, or a grinding mill. BS EN ISO 22032:2009E EN ISO 22032:20095 6.5 Drying ovens, capable of maintaining temperatures in the ranges
