1、July 2009DEUTSCHE NORM English price group 15No part of this standard 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 13.060.50!$XjC“1537132www
2、.din.deDDIN EN ISO 22032Water quality Determination of selected polybrominated diphenyl ethers in sedimentand sewage sludge Method using extraction and gas chromatography/mass spectrometry(ISO 22032:2006)English version of DIN EN ISO 22032:2009-07Wasserbeschaffenheit Bestimmung ausgewhlter polybromi
3、erter Diphenylether in Sediment und Klrschlamm Verfahren mittels Extraktion und Gaschromatographie/Massenspektrometrie(ISO 22032:2006)Englische Fassung DIN EN ISO 22032:2009-07www.beuth.deDocument comprises 34 pagesDIN EN ISO 22032:2009-07 2 This standard is part of the series Deutsche Einheitsverfa
4、hren zur Wasser-, Abwasser- und Schlammunter-suchung Gemeinsam erfassbare Stoffgruppen (Gruppe F) (German standard methods for the examination of water, waste water and sludge Substance group analysis (group F) and describes method F 28. National foreword This standard has been prepared by Technical
5、 Committee ISO/TC 147 “Water quality” in collaboration with Technical Committee CEN/TC 230 “Water analysis” (Secretariat: DIN, Germany). The responsible German body involved in its preparation was the Normenausschuss Wasserwesen (Water Practice Standards Committee), Technical Committees NA 119-01-03
6、-02-13 AK Polybromierte Diphenylether and NA 119-01-03 AA Wasseruntersuchung. Designation of method F 28 “Determination of selected polybrominated diphenyl ethers in sediment and sewage sludge Method using extraction and gas chromatography/mass spectrometry”: Method DIN EN ISO 22032 F 28 As a result
7、 of national implementation process in Germany an error in the ISO Standard has become evident, which is corrected here: In the ISO Standard, subclause A.3.5 (GPS clean-up conditions), the dump value is erroneously given as 100 ml (10 min). The correct value is 50 ml (10 min). Expert assistance and
8、specialized laboratories will be required to perform the analysis described in this standard. Existing safety regulations are to be taken into account. Depending on the objective of the analysis, a check shall be made on a case-by-case basis as to whether and to what extent additional conditions wil
9、l have to be specified. Standard methods published as DIN Standards are obtainable from Beuth Verlag GmbH, either individually or grouped in volumes. The standard methods included in the loose-leaf publication entitled Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung will co
10、ntinue to be published jointly by Wiley-VCH Verlag and Beuth Verlag GmbH. All standard methods relevant to the Abwasserverordnung (Waste Water Regulation) (AbwV) included in the new Regulation on Section 7a of the Gesetz zur Ordnung des Wasserhaushaltes (German Water Management Act) concerning Anfor
11、derungen an das Einleiten von Abwasser in Gewsser together with the Abwasserverordnung and the Gesetz zur Ordnung des Wasserhaushalts have been published by Beuth Verlag GmbH as a loose-leaf collection Analysenverfahren in der Abwasserverordnung Rechtsvorschriften Standards or draft standards bearin
12、g the group title “German standard methods for the examination of water, waste water and sludge” are classified under the following categories (main titles): General information (group A) (DIN 38402) Sensory analysis (group B) (DIN 38403) Physical and physicochemical parameters (group C) (DIN 38404)
13、 Anions (group D) (DIN 38405) Cations (group E) (DIN 38406) Substance group analysis (group F) (DIN 38407) Gaseous constituents (group G) (DIN 38408) Parameters characterizing effects and substances (group H) (DIN 38409) Biological-ecological methods of analysis (group M) (DIN 38410) und Normen (Sup
14、plements). DIN EN ISO 22032:2009-07 3 Microbiological methods (group K) (DIN 38411) Test methods using water organisms (group L) (DIN 38412) Individual constituents (group P) (DIN 38413) Sludge and sediments (group S) (DIN 38414) Bio-assays with microorganisms (group T) (DIN 38415) In addition to th
15、e methods described in the DIN 38402 to DIN 38415 series of standards, there are a number of European and International Standards available as DIN EN, DIN EN ISO and DIN ISO Standards, which also form part of the collection of German standard methods. Information on Parts of these series of standard
16、s that have already been published can be obtained from the offices of the Normenausschuss Wasserwesen, telephone +49 30 2601-2448, or from Beuth Verlag GmbH, Burggrafenstr. 6, 10787 Berlin. In this standard, the unit “psi” is used. It should, however, be noted that the Gesetz ber Einheiten im Messw
17、esen (German Law on units in metrology) prohibits the use of the unit “psi” for official and commercial purposes in Germany. The DIN Standards corresponding to the International Standards referred to in this document are as follows: ISO 3696 DIN ISO 3696 ISO 5667-13 DIN EN ISO 5667-13 ISO 8466-1 DIN
18、 38402-51 ISO/TR 13530 DIN V ENV ISO 13530 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, evaluation of analytical results and linear calibration
19、functions used to determine the performance characteristics of analytical methods (A 51) DIN EN ISO 5667-13, Water quality Sampling Part 13: Guidance on sampling of sludges from sewage and water treatment works DIN V ENV ISO 13530, Water quality Guide to analytical quality control for water analysis
20、 DIN ISO 3696, Water for analytical laboratory use Specification and test methods DIN EN ISO 22032:2009-07 4 This page is intentionally blank EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 22032 February 2009 ICS 13.060.50 English Version Water quality - Determination of selected polybromi
21、nated 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 des boues dpuration - Mthode par extraction et chromatographie en phase gaz
22、euse/spectromtrie de masse (ISO 22032:2006) Wasserbeschaffenheit - Bestimmung ausgewhlter polybromierter Diphenylether in Sediment und Klrschlamm - Verfahren mittels Extraktion und Gaschromatographie/Massenspektrometrie (ISO 22032:2006) This European Standard was approved by CEN on 28 March 2008. CE
23、N 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 app
24、lication 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 CEN member into its own language and notified to the CEN Management Centre
25、 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, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland,
26、 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-1000 Brussels 2009 CEN All rights of exploitation in any form and by any
27、means reserved worldwide for CEN national Members. Ref. No. EN ISO 22032:2009: E2 Contents Page Foreword .3 Introduction.4 1 Scope5 2 Normative references6 3 Principle .6 4 Interferences 6 5 Reagents and standards.7 6 Apparatus.8 7 Sampling and sample pre-treatment .9 8 Procedure.9 9 Calibration12 1
28、0 Test report15 Annex A (informative) Clean-up procedures16 Annex B (informative) Examples for separation conditions in gas chromatography and mass spectrometry20 Annex C (informative) Typical ions and time windows for electron impact ionization detection 23 Annex D (informative) Examples of chromat
29、ograms and spectra.24 Annex E (informative) Precision data .29 Bibliography30 DIN EN ISO 22032:2009-07 EN ISO 22032:2009 (E) Foreword 3 The text of ISO 22032:2006 has been prepared by Technical Committee ISO/TC 147 “Water quality” of the International Organization for Standardization (ISO) and has b
30、een 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 status of a national standard, either by publication of an identical text or by endorsement, at the latest by August 2009, and con
31、flicting 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 subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. According
32、 to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, L
33、ithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice DIN EN ISO 22032:2009-07 EN ISO 22032:2009 (E) The text of ISO 22032:2006 has been approved by CEN as EN ISO 22032:2009 without any m
34、odification. Introduction The user should be aware that particular problems could require the specification of additional marginal conditions. 4 DIN EN ISO 22032:2009-07 EN ISO 22032:2009 (E) WARNING Persons using this International Standard should be familiar with normal laboratory practice. This s
35、tandard 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. IMPORTANT It is absolutely essential that tests
36、 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 using gas chromatography/mass spectrometry
37、(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 ether (BDE-209), respectively. Approximately te
38、n 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 International Standard, after verifying its
39、 applicability in each case. Figure 1 Chemical formula of polybrominated diphenyl ethers 5 DIN EN ISO 22032:2009-07 EN ISO 22032:2009 (E) Table 1 PBDE congeners determined by this method No. Congener Formula Abbreviation aMolar mass g/mol 1 2,2,4,4-Tetrabromodiphenyl ether C12H6Br4O BDE-47 485,795 0
40、 2 2,2,4,4,5-Pentabromodiphenyl ether C12H5Br5O BDE-99 564,691 1 3 2,2,4,4,6-Pentabromodiphenyl ether C12H5Br5O BDE-100 564,691 1 4 2,2,4,4,5,6-Hexabromodiphenyl ether C12H4Br6O BDE-154 643,587 2 5 2,2,4,4,5,5-Hexabromodiphenyl ether C12H4Br6O BDE-153 643,587 2 6 2,2,3,4,4,5,6-Heptabromodiphenyl eth
41、er C12H3Br7O BDE-183 722,483 2 7 Decabromodiphenyl ether C12Br10O BDE-209 959,171 4 aNumbering analogous to IUPAC nomenclature for PCB. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited appli
42、es. 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 ISO 8466-1, Water quality Calibration and evaluation of analytical methods
43、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 the extract by, e.g. preparative multi-layer silica gel column chromatography.
44、 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 chemical ionization (NCI). For determination of the concentration in the sample
45、, 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, respectively, when using non-polar capillary columns and hence, interfere with the det
46、ermination 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 considered as potential interferences. Sources of contamination are the followi
47、ng: 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 covers, pasteur pipette fillers and recycled paper. 6 DIN EN ISO 22032:2009-07
48、EN ISO 22032:2009 (E) 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 degradation, store standards in the dark at temperatures recommended by th
49、e 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 sample matrix to be analysed and the availability of commercial standard solution, e.g. toluene (C7H8), or acetone (propanone, C3H6O), or a mixture of acetone (propanone, C3H6O) and hexane (C6H14), or heptane (C7H16), or iso-octane (2,2,4-trimethylpentane, C8H18), or
