1、BSI Standards PublicationPD ISO/TS 16780:2015Water quality Determinationof polychlorinatednaphthalenes (PCN) Methodusing gas chromatography (GC)and mass spectrometry (MS)PD ISO/TS 16780:2015 PUBLISHED DOCUMENTNational forewordThis Published Document is the UK implementation of ISO/TS16780:2015.The U
2、K 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 publication does not purport to include all the necessaryprovisions of a cont
3、ract. Users are responsible for its correctapplication. The British Standards Institution 2015. Published by BSI StandardsLimited 2015ISBN 978 0 580 89579 1ICS 13.060.50Compliance with a British Standard cannot confer immunity fromlegal obligations.This Published Document was published under the aut
4、hority of theStandards Policy and Strategy Committee on 31 August 2015.Amendments issued since publicationDate Text affectedPD ISO/TS 16780:2015 ISO 2015Water quality Determination of polychlorinated naphthalenes (PCN) Method using gas chromatography (GC) and mass spectrometry (MS)Qualit de leau Dte
5、rmination des naphtalnes polychlors (PCN) Mthode par chromatographie en phase gazeuse (CG) et spectromtrie de masse (SM)TECHNICAL SPECIFICATIONISO/TS16780Reference numberISO/TS 16780:2015(E)First edition2015-08-15PD ISO/TS 16780:2015ISO/TS 16780:2015(E)ii ISO 2015 All rights reservedCOPYRIGHT PROTEC
6、TED DOCUMENT ISO 2015, Published in SwitzerlandAll rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
7、written permission. Permission can be requested from either ISO at the address below or ISOs member body in the country of the requester.ISO copyright officeCh. de Blandonnet 8 CP 401CH-1214 Vernier, Geneva, SwitzerlandTel. +41 22 749 01 11Fax +41 22 749 09 47copyrightiso.orgwww.iso.orgPD ISO/TS 167
8、80:2015ISO/TS 16780:2015(E)Foreword v1 Scope . 12 Normative references 13 Terms, definitions, and abbreviated terms . 23.1 Terms and definitions . 23.2 Abbreviated terms . 64 Principle 64.1 Extraction 64.2 Clean-up 74.3 Identification and quantification . 74.4 Quality 85 Contamination and interferen
9、ces . 86 Reagents and standards .107 Apparatus and materials.168 Sample collection, preservation, storage and holding times 198.1 General 198.2 Storage times . 199 Quality assurance and quality control 209.1 General 209.2 Spiking . 209.3 Recovery of labelled compounds assessment .219.4 Method blanks
10、 219.5 QC check sample . 2110 Calibration .2110.1 Operating conditions 2110.2 Mass spectrometer resolution 2210.3 Ion abundance ratios, minimum levels, signal-to-noise ratios, and absolute retention times . 2210.4 Retention time 2210.5 Column resolution performance check . 2310.6 Calibration by isot
11、ope dilution . 2310.7 Calibration by internal standard 2310.8 Combined calibration . 2410.8.1 General. 2410.8.2 Data storage 2410.8.3 Data acquisition .2410.8.4 Response factors and multipoint calibrations .2411 Sample preparation 2511.1 General 2511.2 Determination of solid particulate material . 2
12、511.3 Preparation of aqueous samples containing 2 g/l of solid particulate material or less .2511.3.1 General. 2511.3.2 Preparation of sample and QC aliquots .2611.3.3 Filtration of particles .2612 Extraction 2612.1 Separating funnel extraction of filtrates and of aqueous samples that are visibly ab
13、sent of particles . 2612.2 Solid phase extraction (SPE) of samples containing less than 2 g/l suspended particlulate matter 2712.2.1 Disk/cartridge preparation . 27 ISO 2015 All rights reserved iiiContents PagePD ISO/TS 16780:2015ISO/TS 16780:2015(E)12.2.2 Sample extraction 2712.3 Soxhlet or PLE ext
14、raction of filters or disks 2812.4 Macro-concentration 2812.4.1 General. 2812.4.2 Rotary evaporation .2812.4.3 Heating mantle .2912.4.4 Kuderna-Danish (K-D) .2912.5 Micro-concentration and solvent exchange 3113 Extract clean-up3113.1 General 3113.2 Back-extraction with acid and base . 3213.3 Gel per
15、meation chromatography (GPC) . 3213.3.1 Column packing .3213.3.2 Column calibration 3213.3.3 Extract clean-up .3313.4 Silica clean-up . 3313.5 Carbon column . 3413.6 Florisil clean-up 3413.7 Silver nitratesilica column . 3414 HRGCHRMS analysis 3514.1 General 3514.2 MS resolution 3514.3 Calibration v
16、erification . 3514.4 GC resolution . 3514.5 Blank . 3515 Qualitative determination .3616 Quantitative determination .3616.1 Isotope dilution quantification 3616.2 Internal standard quantification 3716.3 Determination of labelled compound recovery . 3716.4 Concentration in sample 3816.4.1 General. 38
17、16.4.2 Treatment of samples exceeding calibration range 3816.5 Results and reporting . 3817 Test report 39Annex A (informative) Use of alternate mass spectrometry detectors (LRMS, MSMS) 40Annex B (informative) Quality control and initial precision and recovery .43Annex C (informative) Calculation of
18、 toxic equivalents .45Annex D (informative) Pollution prevention 46Annex E (informative) Waste management 47Bibliography .48iv ISO 2015 All rights reservedPD ISO/TS 16780:2015ISO/TS 16780:2015(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national st
19、andards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International o
20、rganizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.The procedures used to develop this document and those intended for i
21、ts further maintenance are described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the different types of ISO documents should be noted. This document was drafted in accordance with the editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/d
22、irectives). Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of any patent rights identified during the development of the document will be in
23、 the Introduction and/or on the ISO list of patent declarations received (see www.iso.org/patents). Any trade name used in this document is information given for the convenience of users and does not constitute an endorsement.For an explanation on the meaning of ISO specific terms and expressions re
24、lated to conformity assessment, as well as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary informationThe committee responsible for this document is ISO/TC 147, Water quality, Subcommittee SC 2, Physical,
25、 chemical and biochemical methods. ISO 2015 All rights reserved vPD ISO/TS 16780:2015PD ISO/TS 16780:2015Water quality Determination of polychlorinated naphthalenes (PCN) Method using gas chromatography (GC) and mass spectrometry (MS)WARNING Persons using this Technical Specification should be famil
26、iar with normal laboratory practice. This Technical Specification 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 c
27、onditions.Attention is drawn to any relevant national safety regulations. A number of PCN congeners have dioxin-like properties and are toxic chemicals. All work with PCNs requires the utmost care; the national safety measures which correspond to those for toxic substances shall be strictly followed
28、.IMPORTANT It is absolutely essential that tests conducted in accordance with this Technical Specification be carried out by suitably trained staff.1 ScopeThis Technical Specification specifies a method for the determination of polychlorinated naphthalenes (PCNs), where “poly” means “mono” to “octa”
29、, in waters and waste waters containing less than 2 g/l solid particulate material (SPM) using high resolution gas chromatographyhigh resolution mass spectrometry (HRGCHRMS).NOTE 1 The congeners analysed by this method are listed in Table 1.The working range of the method is 20 pg/l to 8 ng/l. The m
30、ethod is optimized for PCNs, but can be modified to include other coplanar compounds such as polychlorinated dioxins and furans (PCDDs/PCDFs) and dioxin-like tetra- to heptachlorinated biphenyls (dlPCBs). This method can be used to determine PCNs in other matrices (e.g. biota, sediments, air); howev
31、er, additional clean-up steps and techniques can be necessary for samples with high organic loadings. Low resolution mass spectrometry (LRMS) and mass spectrometrymass spectrometry (MSMS) can be used.NOTE 2 LRMS and MSMS conditions are summarized in Annex A.Both LRMS and MSMS can be less selective t
32、han HRMS and there is a possibility of bias due to interfering compounds if these techniques are used.The detection limits and quantification levels in this method are dependent on the level of interferences as well as instrumental limitations.NOTE 3 The minimum levels (ML) in Table 4 are the levels
33、 at which the PCNs can typically be determined with no interferences present.This method is performance based. The analyst is permitted to modify the method, e.g. to overcome interferences, provided that all performance criteria in this method are met.NOTE 4 The requirements for establishing method
34、validation or equivalency are given in Clause 9.2 Normative referencesThe 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
35、of the referenced document (including any amendments) applies.TECHNICAL SPECIFICATION ISO/TS 16780:2015(E) ISO 2015 All rights reserved 1PD ISO/TS 16780:2015ISO/TS 16780:2015(E)ISO 3696, Water for analytical laboratory use Specification and test methodsISO 5667-1, Water quality Sampling Part 1: Guid
36、ance on the design of sampling programmes and sampling techniquesISO 5667-3, Water quality Sampling Part 3: Preservation and handling of water samplesISO 8466 (all parts), Water Quality Calibration and evaluation of analytical methods and estimation of performance characteristics3 Terms, definitions
37、, and abbreviated termsFor the purposes of this document, the following terms, definitions, and abbreviated terms apply.3.1 Terms and definitions3.1.1analytesubstance to be determinedEXAMPLE A polychlorinated naphthalene (PCN) congener tested for by the method specified in this Technical Specificati
38、on.Table 1 PCNs determined by this methodPCN No. (Reference4) Chlorine substitution CAS Registry No.Total MonoCNs Mono congener total2 2-MonoCN 91587Tot al DiCNs Di congener total6 1,5-DiCN 1825305Tot al TriCNs Tri congener total13 1,2,3-TriCN 50402523Tot al TetraCNs Tetra congener total27 1,2,3,4-T
39、etraCN 2002002428 1,2,3,5-TetraCN 5355563836 1,2,5,6-TetraCN 6792222942 1,3,5,7-TetraCN 5355564946 1,4,5,8-TetraCN 343257348 2,3,6,7-TetraCN 34588404Total PentaCNs Penta congener total49 1,2,3,4,5-PentaCN 6792225250 1,2,3,4,6-PentaCN 6792226352/60 1,2,3,5,7-/ 53555650/1,2,4,6,7-PentaCN 15022417253 1
40、,2,3,5,8-PentaCN 15022424154 1,2,3,6,7-PentaCN 150224161Total HexaCNs Hexa congener total63 1,2,3,4,5,6-HexaCN 5887788664/68 1,2,3,4,5,7-/ 67922274/1,2,3,5,6,8-HexaCN 1034269552 ISO 2015 All rights reservedPD ISO/TS 16780:2015ISO/TS 16780:2015(E)PCN No. (Reference4) Chlorine substitution CAS Registr
41、y No.66/67 1,2,3,4,6,7-/ 1034269661,2,3,5,6,7-HexaCN 10342697769 1,2,3,5,7,8-HexaCN 10342694470 1, 2, 3,6,7, 8-Hex aCN 1706287271/72 1,2,4,5,6,8-/ 909482801,2,4,5,7,8-HexaCN 103426922Total HeptaCNs Hepta congener total73 1,2,3,4,5,6,7-HeptaCN 5886314274 1,2,3,4,5,6,8-HeptaCN 5886315375 (OctaCN) 1,2,
42、3,4,5,6,7,8-OctaCN 2234131Note: PCN numbering nomenclature is detailed in Reference4. The CAS Registry Number is a unique numeri-cal identifier assigned by Chemical Abstracts Service (CAS) to every chemical substance described in the open scientific literature.3.1.2calibration standardsolution prepa
43、red from a secondary standard or stock solutions and used to calibrate the response of the instrument with respect to analyte concentrationSOURCE: ISO 17858:2007, 3.1.2 modified3.1.3calibration verification standardVERmidpoint calibration standard that is used to verify calibrationSOURCE: ISO 17858:
44、2007, 3.1.33.1.4congenermember of the same kind, class or groupSOURCE: ISO 17858:2007, 3.1.5EXAMPLE Any one of the 75 individual PCNs.3.1.5critical pairpair of isomers that must be separated to a predefined degree (e.g. 50 % valley) to ensure chromatographic separation meets minimum quality criteria
45、SOURCE: ISO 17858:2007, 3.1.6, modified “50 %” replaces “25 %”.3.1.6dioxin-like isomerPCN for which a relative potency to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) has been calculated see Table 2Table 2 Examples of relative potencies16Compound REP1,3,5,7CN(42) 0,000 011,2,5,6CN(36) 0,000 01Table 1
46、(continued) ISO 2015 All rights reserved 3PD ISO/TS 16780:2015ISO/TS 16780:2015(E)Compound REP1,2,3,5CN(28) 0,000 0011,2,3,4CN(27) 0,000 012,3,6,7CN(48) 0,0011,4,5,8CN(46) 0,000 000 11,2,3,5,7CN/1,2,4,6,7CN(52/60) 0,000 11,2,3,4,6CN(50) 0,000 11,2,3,6,7CN(54) 0,000 11,2,3,5,8CN(53) 0,000 011,2,3,4,5
47、CN(49) 0,000 0011,2,3,4,6,7CN/1,2,3,5,6,7CN(66/67) 0,011,2,3,4,5,7CN/1,2,3,5,6,8CN(64/68) 0,0011,2,3,5,7,8CN(69) 0,0011,2,4,5,6,8CN/1,2,4,5,7,8CN(71/72) 0,0011,2,3,4,5,6CN(63) 0,0011,2,3,6,7,8CN(70) 0,011,2,3,4,5,6,7CN(73) 0,011,2,3,4,5,6,8CN(74) 0,011,2,3,4,5,6,7,8CN(75) 0,13.1.7homologue groupcomp
48、lete group of isomersEXAMPLE Tetrachloronaphthalenes.SOURCE: ISO 17858:2007, 3.1.8 modified3.1.8isotope dilutionmethod using labelled (usually 13C) internal standards to correct for losses during sample preparation and analysisSOURCE: ISO 17858:2007, 3.1.9, modified “13C” replaces “13C12”.3.1.9metho
49、d blankaliquot of reagent water free of analytes treated exactly as a sample through the complete analytical procedure including extraction, clean-up, identification and quantification including all relevant reagents and materialsSOURCE: ISO 17858:2007, 3.1.11, modified “free of analytes” replaces “that is”.3.1.10recovery standard13C10-labelled PCN added before injection into the GC, to monitor variability of instrument res
