1、BSI Standards Publication PD ISO/TS 16780:2015 Water quality Determination of polychlorinated naphthalenes (PCN) Method using gas chromatography (GC) and mass spectrometry (MS)PD ISO/TS 16780:2015 PUBLISHED DOCUMENT National foreword This Published Document is the UK implementation of ISO/TS 16780:2
2、015. The UK participation in its preparation was entrusted to Technical Committee EH/3/2, Physical chemical and biochemical methods. A list of organizations represented on this committee can be obtained on request to its secretary. This publication does not purport to include all the necessary provi
3、sions of a contract. Users are responsible for its correct application. The British Standards Institution 2015. Published by BSI Standards Limited 2015 ISBN 978 0 580 89579 1 ICS 13.060.50 Compliance with a British Standard cannot confer immunity from legal obligations. This Published Document was p
4、ublished under the authority of the Standards Policy and Strategy Committee on 31 August 2015. Amendments issued since publication Date Text affectedPD ISO/TS 16780:2015 ISO 2015 Water quality Determination of polychlorinated naphthalenes (PCN) Method using gas chromatography (GC) and mass spectrome
5、try (MS) Qualit de leau Dtermination des naphtalnes polychlors (PCN) Mthode par chromatographie en phase gazeuse (CG) et spectromtrie de masse (SM) TECHNICAL SPECIFICATION ISO/TS 16780 Reference number ISO/TS 16780:2015(E) First edition 2015-08-15PD ISO/TS 16780:2015ISO/TS 16780:2015(E)ii ISO 2015 A
6、ll rights reserved COPYRIGHT PROTECTED DOCUMENT ISO 2015, Published in Switzerland All 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 int
7、ernet or an intranet, without prior 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 office Ch. de Blandonnet 8 CP 401 CH-1214 Vernier, Geneva, Switzerland Tel. +41 22 749 01 11 Fax +41 22 749 09 4
8、7 copyrightiso.org www.iso.orgPD ISO/TS 16780:2015ISO/TS 16780:2015(E)Foreword v 1 Scope . 1 2 Normative references 1 3 T erms, definitions, and abbr e viat ed t erms . 2 3.1 Terms and definitions . 2 3.2 Abbreviated terms . 6 4 Principle 6 4.1 Extraction 6 4.2 Clean-up 7 4.3 Identification and quan
9、tification . 7 4.4 Quality 8 5 Contamination and interferences . 8 6 Reagents and standards .10 7 Apparatus and materials.16 8 Sample collection, preservation, storage and holding times 19 8.1 General 19 8.2 Storage times .19 9 Quality assurance and quality control 20 9.1 General 20 9.2 Spiking .20
10、9.3 Recovery of labelled compounds assessment .21 9.4 Method blanks 21 9.5 QC check sample .21 10 Calibr ation .21 10.1 Operating conditions 21 10.2 Mass spectrometer resolution 22 10.3 Ion abundance ratios, minimum levels, signal-to-noise ratios, and absolute retention times .22 10.4 Retention time
11、 22 10.5 Column resolution performance check .23 10.6 Calibration by isotope dilution .23 10.7 Calibration by internal standard 23 10.8 Combined calibration .24 10.8.1 General.24 10.8.2 Data storage 24 10.8.3 Data acquisition .24 10.8.4 Response factors and multipoint calibrations .24 11 Sample prep
12、aration 25 11.1 General 25 11.2 Determination of solid particulate material .25 11.3 Preparation of aqueous samples containing 2 g/l of solid particulate material or less .25 11.3.1 General.25 11.3.2 Preparation of sample and QC aliquots .26 11.3.3 Filtration of particles . 26 12 Extraction 26 12.1
13、Separating funnel extraction of filtrates and of aqueous samples that are visibly absent of particles .26 12.2 Solid phase extraction (SPE) of samples containing less than 2 g/l suspended particlulate matter 27 12.2.1 Disk/cartridge preparation .27 ISO 2015 All rights reserved iii Contents PagePD IS
14、O/TS 16780:2015ISO/TS 16780:2015(E)12.2.2 Sample extraction 27 12.3 Soxhlet or PLE extraction of filters or disks 28 12.4 Macro-concentration 28 12.4.1 General.28 12.4.2 Rotary evaporation .28 12.4.3 Heating mantle .29 12.4.4 Kuderna-Danish (K-D) .29 12.5 Micro-concentration and solvent exchange 31
15、13 Extract clean-up31 13.1 General 31 13.2 Back-extraction with acid and base .32 13.3 Gel permeation chromatography (GPC) .32 13.3.1 Column packing .32 13.3.2 Column calibration 32 13.3.3 Extract clean-up .33 13.4 Silica clean-up .33 13.5 Carbon column .34 13.6 Florisil clean-up 34 13.7 Silver nitr
16、atesilica column .34 14 HRGCHRMS analysis 35 14.1 General 35 14.2 MS resolution 35 14.3 Calibration verification .35 14.4 GC resolution .35 14.5 Blank .35 15 Qualitative determination .36 16 Quantitative determination .36 16.1 Isotope dilution quantification 36 16.2 Internal standard quantification
17、37 16.3 Determination of labelled compound recovery .37 16.4 Concentration in sample 38 16.4.1 General.38 16.4.2 Treatment of samples exceeding calibration range 38 16.5 Results and reporting .38 17 Test report 39 Annex A (informative) Use of alternate mass spectrometry detectors (LRMS, MSMS) 40 Ann
18、ex B (informative) Quality control and initial precision and recovery .43 Annex C (informative) Calculation of toxic equivalents .45 Annex D (informative) Pollution prevention 46 Annex E (informative) Waste management 47 Bibliogr aph y .48 iv ISO 2015 All rights reservedPD ISO/TS 16780:2015ISO/TS 16
19、780:2015(E) Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards 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 f
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25、entary information The committee responsible for this document is ISO/TC 147, Water quality, Subcommittee SC 2, Physical, 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 u
26、sing gas chromatography (GC) and mass spectrometry (MS) W A R N I N G P e r s o n s u s i n g t h i s T e c h n i c a l S p e c i f i c a t i o n sh o u l d b e f a m i l i a r w i t h n o r m a l l a b o r a t o r y p r a c t i c e . T h i s T e c h n i c a l S p e c i f i c a t i o n d o e s n o t
27、 p u r p o r t t o a d d r e s s a l l o f t h e s a f e t y p r o b l e m s , i f a n y , a s s o c i a t e d w i t h i t s u s e . I t i s t h e r e s p o n s i b i l i t y o f t h e u s e r t o e s t a b l i sh appropriate safety and health practices and to ensure compliance with any national reg
28、ulatory c ond i t ion s . A t t e n t i o n i s d r a w n t o a n y r e l e v a n t n a t i o n a l s a f e t y r e g u l a t i o n s . A n u m b e r o f P C N c o n g e n e r s h a v e d i o x i n - l i k e p r o p e r t i e s a n d a r e t o x i c c h e m i c a l s . A l l w o rk w i t h P C N s r
29、 e q u i r e s t h e u t m o s t c a r e ; t h e n a t i o n a l s a f e t y m e a s u r e s w h i c h c o r r e s p o n d t o t h o s e f o r t o x i c s u b s t a n c e s sh a l l b e s t r i c t l y f ol lo we d . I M P O R T A N T I t i s a b s o l u t e l y e s s e n t i a l t h a t t e s t s c
30、 o n d u c t e d i n a c c o r d a n c e w i t h t h i s T e c h n i c a l S p e c i f i c a t i o n b e c a r r i e d o u t b y s u i t a b l y t r a i n e d s t a f f . 1 Scope This Technical Specification specifies a method for the determination of polychlorinated naphthalenes (PCNs), where “poly
31、” means “mono” to “octa”, 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 i
32、s 20 pg/l to 8 ng/l. The method 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. bio
33、ta, sediments, air); however, 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
34、MSMS can be less selective than 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
35、(ML) in Table 4 are the levels 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 requi
36、rements for establishing method validation or equivalency are given in Clause 9. 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 undat
37、ed references, the latest edition 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 methods ISO 5667-1
38、, Water quality Sampling Part 1: Guidance on the design of sampling programmes and sampling techniques ISO 5667-3, Water quality Sampling Part 3: Preservation and handling of water samples ISO 8466 (all parts), Water Quality Calibration and evaluation of analytical methods and estimation of performa
39、nce characteristics 3 T erms, d efinitions , and abbr e viat ed t erms For the purposes of this document, the following terms, definitions, and abbreviated terms apply. 3.1 T erms and definiti ons 3 .1 .1 analyte substance to be determined EXAMPLE A polychlorinated naphthalene (PCN) congener tested
40、for by the method specified in this Technical Specification. T a b l e 1 P C N s d e t e r m i n e d b y t h i s m e t h o d P C N N o . ( R e f e r e n c e4) C h lor i n e s u b s t i t u t ion CAS R e g i s t r y N o . Total MonoCNs Mono congener total 2 2-MonoCN 91587 Tot al DiCNs Di congener tot
41、al 6 1,5-DiCN 1825305 Tot al TriCNs Tri congener total 13 1,2,3-TriCN 50402523 Tot al TetraCNs Tetra congener total 27 1,2,3,4-TetraCN 20020024 28 1,2,3,5-TetraCN 53555638 36 1,2,5,6-TetraCN 67922229 42 1,3,5,7-TetraCN 53555649 46 1,4,5,8-TetraCN 3432573 48 2,3,6,7-TetraCN 34588404 Total PentaCNs Pe
42、nta congener total 49 1,2,3,4,5-PentaCN 67922252 50 1,2,3,4,6-PentaCN 67922263 52/60 1,2,3,5,7-/ 53555650/ 1,2,4,6,7-PentaCN 150224172 53 1,2,3,5,8-PentaCN 150224241 54 1,2,3,6,7-PentaCN 150224161 Total HexaCNs Hexa congener total 63 1,2,3,4,5,6-HexaCN 58877886 64/68 1,2,3,4,5,7-/ 67922274/ 1,2,3,5,
43、6,8-HexaCN 1034269552 ISO 2015 All rights reservedPD ISO/TS 16780:2015ISO/TS 16780:2015(E) P C N N o . ( R e f e r e n c e4) C h lor i n e s u b s t i t u t ion CAS R e g i s t r y N o . 66/67 1,2,3,4,6,7-/ 103426966 1,2,3,5,6,7-HexaCN 103426977 69 1,2,3,5,7,8-HexaCN 103426944 70 1, 2, 3,6,7, 8-Hex
44、aCN 17062872 71/72 1,2,4,5,6,8-/ 90948280 1,2,4,5,7,8-HexaCN 103426922 Total HeptaCNs Hepta congener total 73 1,2,3,4,5,6,7-HeptaCN 58863142 74 1,2,3,4,5,6,8-HeptaCN 58863153 75 (OctaCN) 1,2,3,4,5,6,7,8-OctaCN 2234131 Note: PCN numbering nomenclature is detailed in Reference 4 . The CAS Registry Num
45、ber is a unique numeri- cal identifier assigned by Chemical Abstracts Service (CAS) to every chemical substance described in the open scientific literature. 3 .1 . 2 c a l ibr at ion s t a nd a r d solution prepared from a secondary standard or stock solutions and used to calibrate the response of t
46、he instrument with respect to analyte concentration SOURCE: ISO 17858:2007, 3.1.2 modified 3 .1 . 3 c a l ibr at ion ve r i f ic at ion s t a nd a r d VER midpoint calibration standard that is used to verify calibration SOURCE: ISO 17858:2007, 3.1.3 3 .1 . 4 congener member of the same kind, class o
47、r group SOURCE: ISO 17858:2007, 3.1.5 EXAMPLE Any one of the 75 individual PCNs. 3 .1 . 5 critical pair pair of isomers that must be separated to a predefined degree (e.g. 50 % valley) to ensure chromatographic separation meets minimum quality criteria SOURCE: ISO 17858:2007, 3.1.6, modified “50 %”
48、replaces “25 %”. 3 .1 . 6 dioxin-like isomer PCN for which a relative potency to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) has been calculated see Table 2 T a b l e 2 E x a m p l e s o f r e l a t i v e p o t e n c i e s 16 Compound REP 1,3,5,7CN(42) 0,000 01 1,2,5,6CN(36) 0,000 01T a b l e 1 (cont
49、inued) ISO 2015 All rights reserved 3PD ISO/TS 16780:2015ISO/TS 16780:2015(E) Compound REP 1,2,3,5CN(28) 0,000 001 1,2,3,4CN(27) 0,000 01 2,3,6,7CN(48) 0,001 1,4,5,8CN(46) 0,000 000 1 1,2,3,5,7CN/1,2,4,6,7CN(52/60) 0,000 1 1,2,3,4,6CN(50) 0,000 1 1,2,3,6,7CN(54) 0,000 1 1,2,3,5,8CN(53) 0,000 01 1,2,3,4,5CN(49) 0,000 001 1,2,3,4,6,7CN/1,2,3,5,6,7CN(66/67) 0,01 1,2,3,4,5,7CN/1,2,3,5,6,8CN(64/68) 0,001 1,2,3,5,7,8CN(69) 0,001 1,2,4,5
