1、BSI Standards PublicationBS EN 16694:2015Water quality Determinationof selected polybrominateddiphenly ether (PBDE) in wholewater samples Methodusing solid phase extraction(SPE) with SPE-disks combinedwith gas chromatography mass spectrometry (GC-MS)BS EN 16694:2015 BRITISH STANDARDNational foreword
2、This British Standard is the UK implementation of EN 16694:2015.The UK participation in its preparation was entrusted to TechnicalCommittee EH/3/2, Physical chemical and biochemical methods.A list of organizations represented on this committee can beobtained on request to its secretary.This publicat
3、ion does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2015. Published by BSI StandardsLimited 2015ISBN 978 0 580 84520 8ICS 13.060.50Compliance with a British Standard cannot confer immunity from
4、legal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 30 September 2015.Amendments issued since publicationDate Text affectedBS EN 16694:2015EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16694 September 2015 ICS 13.060.50 En
5、glish Version Water quality - Determination of selected polybrominated diphenly ether (PBDE) in whole water samples - Method using solid phase extraction (SPE) with SPE-disks combined with gas chromatography - mass spectrometry (GC-MS) Qualit de leau - Dosage du pentabromodiphnylther (PBDE) dans des
6、 chantillons deau totale - Mthode par extraction en phase solide (SPE) avec disques SPE, avec couplage chromatographie en phase gazeuse-spectromtrie de masse (CG-SM) Wasserbeschaffenheitt - Bestimmung von ausgewhlten polybromierten Diphenylethern (PBDE) in Gesamtwasserproben - Verfahren mittels Fest
7、phasenextraktion (SPE) mit SPE-Disks in Verbindung mit Gaschromatographie - Massenspektrometrie (GC-MS) This European Standard was approved by CEN on 27 June 2015. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standa
8、rd 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 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-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulg
10、aria, 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, Slovenia, Spain, Sweden, Switzerland, Tu
11、rkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2015 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members.
12、 Ref. No. EN 16694:2015 EBS EN 16694:2015EN 16694:2015 (E) 2 Contents Page European foreword . 4 Introduction 5 1 Scope 6 2 Normative references 6 3 Principle . 6 4 Interferences 7 4.1 Interferences with extraction and clean up 7 4.2 Interferences with GC-MS . 7 5 Reagents . 7 6 Apparatus 10 7 Sampl
13、ing 11 8 Procedure 11 8.1 Sample preparation . 11 8.2 Extraction by solid-phase extraction disks (SPE-disks) . 11 8.3 Solvent concentration. 12 8.4 Gas chromatrography and mass spectrometry . 12 8.5 Identification of individual compounds by means of GC-MS 12 8.6 Blank value measurements 14 9 Calibra
14、tion 15 9.1 Calibration with internal standards 15 9.2 Procedure 15 9.2.1 Evaluation of the range of linear relationship . 15 9.2.2 Two point calibration over the total linear range 15 9.2.3 Estimation of the accuracy of the calibration for the concentration of interest . 16 10 Quantification 17 10.
15、1 Determination of the BDE concentrations in whole water samples 17 10.2 Determination of the recoveries of the internal standards 18 11 Expression of results . 18 12 Test report 19 Annex A (informative) Suitable gas chromatographic conditions and example chromatograms . 20 A.1 GC-HRMS conditions fo
16、r the chromatograms in Figure A.1 20 A.2 GC-MS/MS conditions for the chromatograms in Figure A.2 23 A.3 GC-NCI-MS conditions for the chromatograms in Figure A.3 25 Annex B (informative) Repeatability and reproducibility data . 26 Annex C (informative) Examples of suitable solid phase extraction disk
17、s 29 Annex D (informative) Clean up procedure . 30 D.1 Reagents 30 BS EN 16694:2015EN 16694:2015 (E) 3 D.2 Procedure 30 Bibliography . 31 BS EN 16694:2015EN 16694:2015 (E) 4 European foreword This document (EN 16694:2015) has been prepared by Technical Committee CEN/TC 230 “Water analysis”, the secr
18、etariat 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 March 2016, and conflicting national standards shall be withdrawn at the latest by March 2016. This document has be
19、en prepared under a mandate given to CEN by the European Commission and the European Free Trade Association. 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 a
20、ll such patent rights. According to the CEN/CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of
21、 Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 16694:2015EN 16694:2015 (E) 5 Introduction WARNING Persons
22、 using this European Standard should be familiar with usual laboratory practice. This European 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 com
23、pliance with any national regulatory conditions. IMPORTANT It is absolutely essential that tests conducted according to this European Standard be carried out by suitably trained staff. Polybrominated diphenyl ethers (PBDE) are priority substances listed in Annex X of the EU Water Framework Directive
24、 (WFD, Directive 2000/60/EC) for which environmental quality standards (EQS) have been set at EU level for inland waters as well as other surface waters to protect the aquatic environment against chemical pollution (Directive 2008/105/EC). With the exception of metals, the EQS are expressed as total
25、 concentrations in the whole water sample. Furthermore, analytical methods used in WFD monitoring need to meet certain requirements as regards the minimum limit of quantification and the maximum tolerable measurement uncertainty (Directive 2009/90/EC). So far, there is no standardized method availab
26、le for the determination of PBDE in whole water samples fulfilling those requirements. Hence, the European Commission mandated CEN to develop or improve standards in support of the implementation of the monitoring requirements of WFD. Directive 2008/105/EC has been amended by Directive 2013/39/EU, h
27、owever this standard has been developed for the analysis of PBDE as listed in Annex A of Directive 2008/105/EC. The priority substances list in Annex X of the WFD includes technical pentabromodiphenyl ether, which is regarded as a mixture of the congeners BDE-28, BDE-47, BDE-99, BDE-100, BDE-153 and
28、 BDE-154. The annual average environmental quality standard (AA-EQS) for pentabromodiphenyl ether in inland surface waters is 0,5 ng/l and is defined for the whole water sample including suspended particulate matter (SPM) present in the sample. Compounds such as PBDE strongly adsorb to environmental
29、 solids resulting in a fraction bound to particles, which may be substantial. The aim of the method is to extract whole water samples in one single step to determine the dissolved as well as the particle bound PBDE fraction. Identification and quantification of BDE congeners at trace level concentra
30、tions require both highly sensitive chromatographic equipment and effective enrichment steps and awareness of the potential impact of blanks. BS EN 16694:2015EN 16694:2015 (E) 6 1 Scope This European Standard specifies a method for the determination of six selected polybrominated diphenyl ethers (PB
31、DE) listed in Table 1, representative for technical brominated diphenyl ethers (BDE) in water samples in mass concentrations 0,025 ng/l for each individual congener. The method uses solid-phase extraction with SPE-disks in combination with gas chromatography-mass spectrometry (GC-MS). It is applicab
32、le to the analysis of PBDE in surface water containing suspended particulate matter (SPM) up to 500 mg/l (whole water samples), drinking water and groundwater. The limit of quantification (LOQ) was determined according to ISO/TS 13530, on the basis of replicate determinations of the procedural blank
33、, carried out under reproducibility conditions. This method may be used for the analysis of other BDE congeners not listed in Table 1 or other types of water. However, it is important to verify its applicability before use. Table 1 Polybrominated diphenyl ethers (PBDE) determined by this method Cong
34、ener AbbreviationaFormula Molar mass CAS RNbg/mol 2,4,4-Tribromodiphenyl ether BDE-28 C12H7Br3O 406,8954 41318756 2,2,4,4-Tetrabromodiphenyl ether BDE-47 C12H6Br4O 485,7950 5436431 2,2,4,4,5-Pentabromodiphenyl ether BDE-99 C12H5Br5O 564,6911 60348609 2,2,4,4,6-Pentabromodiphenyl ether BDE-100 C12H5B
35、r5O 564,6911 189084648 2,2,4,4,5,6-Hexabromodiphenyl ether BDE-154 C12H4Br6O 643,5872 68631492 2,2,4,4,5,5-Hexabromodiphenyl ether BDE-153 C12H4Br6O 643,5872 207122154 NOTE EC numbers are not applicable for PBDE congeners. aNumbering analog to IUPAC nomenclature for PCB bCAS RN: Chemical Abstracts S
36、ervice Registry Number 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced docume
37、nt (including any amendments) applies. EN ISO 3696, Water for analytical laboratory use - Specification and test methods (ISO 3696) EN ISO 5667-1, Water quality - Sampling - Part 1: Guidance on the design of sampling programmes and sampling techniques (ISO 5667-1) EN ISO 5667-3, Water quality - Samp
38、ling - Part 3: Preservation and handling of water samples (ISO 5667-3) 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 A mixture of suitable internal
39、 standards (13C12-labelled BDE or fluorinated BDE) is added to a 1 l water sample, which is then extracted using a solid-phase extraction disk (SPE-disk). The disk is eluted with a BS EN 16694:2015EN 16694:2015 (E) 7 suitable solvent (5.4) or solvent mixture and the resulting extract is concentrated
40、 for analysis or further clean-up. Prior to injection, an injection standard is added to each extract, and an aliquot is injected into the gas chromatograph. The analytes are separated by capillary gas chromatography and detected and quantified by electron ionization high-resolution mass spectrometr
41、y (EI-HRMS) or alternatively, by low resolution negative chemical ionization mass spectrometry (NCI-MS) or low resolution tandem mass spectrometry (MS/MS). In the latter cases a clean-up step using e. g. a multilayer-silica column, and/or removal of sulfur, e. g. by gel permeation chromatography, ma
42、y be necessary. 4 Interferences 4.1 Interferences with extraction and clean up To avoid interference, collect samples as specified in Clause 7. Commercially available SPE-disks can differ frequently in quality. Variations in the selectivity of the materials can occur from batch to batch, and therefo
43、re might cause significant deviations in extraction yield. This does not basically impair their suitability, apart from a resulting higher detection limit of individual substances. To ensure that the analytical results have a high accuracy and precision, use materials from one batch for both measure
44、ment and calibration. Avoid major fluctuations in the extraction times and elution procedures within one sample sequence when analysing the samples. 4.2 Interferences with GC-MS Interferences may be caused, e. g. by the injection system used or by inadequate separation of the analytes. Experienced o
45、perators might be able to minimize this type of interference. Regular checking of the chromatographic and spectrometric system is required to maintain adequate performance. Required system stability should be checked regularly using a GC standard. 5 Reagents The reagents shall be free from impuritie
46、s possibly interfering with the GC-MS analysis. Use solvents and reagents of sufficient purity, i.e. with negligibly low impurities compared with the concentration of analytes to be determined. As reagents use, as far as available “residual grade” or better in order to obtain low blanks. Verify by b
47、lank determinations and, if necessary, apply additional cleaning steps. 5.1 Water, complying to grade 1 according to EN ISO 3696, or equivalent. 5.2 Operating gases for the gas chromatography mass spectrometry, of high purity and according to the manufacturers specifications. 5.3 Nitrogen of high pu
48、rity, i.e. minimum 99,996 % by volume, for concentration by evaporation. 5.4 Solvents for extraction, chromatography and preparation of reference solutions. A variety of solvents may be used depending on the procedural step and the availability of commercial stock solutions, e. g. toluene, C7H8(boil
49、ing point: 111 C), acetone, C3H6O (boiling point: 56 C), iso- or n-hexane, C6H14, (boiling point: 60 C), BS EN 16694:2015EN 16694:2015 (E) 8 iso-octane (2,2,4-trimethylpentane), C8H18(boiling point: 99 C), nonane, C9H20(boiling point: 151 C), dichloromethane, CH2Cl2, (boiling point: 39,7 C), ethyl acetate, C4H8O2(boiling point: 77 C), iso-propanol, C3H8O (boiling point: 82 C) for residual analysis. A suitable keeper is recommended (e. g. toluene), when reducing the volume of the extract to less than 0,5 ml.
