Water quality - Determination of polychlorinated naphthalenes (PCN) - Method using gas chromatography (GC) and mass spectrometry (MS)

This Technical Specification specifies a method for the determination of polychlorinated naphthalenes
(PCNs), where “poly” means “mono” to “octa”, in waters and waste waters [containing less than 2 g/l
solid particulate material (SPM)] using high resolution gas chromatography–high resolution mass
spectrometry (HRGC–HRMS).
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 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. biota, 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 spectrometry–mass spectrometry (MS–MS) can be used.
NOTE 2 LRMS and MS–MS conditions are summarized in Annex A.
Both LRMS and MS–MS 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 (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 requirements for establishing method validation or equivalency are given in Clause 9.

Qualité de l'eau - Détermination des naphtalènes polychlorés (PCN) - Méthode par chromatographie en phase gazeuse (CG) et spectrométrie de masse (SM)

Kakovost vode - Določevanje polikloriranih naftalenov (PCN) - Metoda plinske kromatografije (GC) in masne spektrometrije (MS)

Ta tehnična specifikacija določa metodo za določevanje polikloriranih naftalenov (PCN), pri čemer beseda »poli« pomeni vse od »mono« do »okta«, v vodah in odpadnih vodah [z vsebnostjo manj kot 2 g/l trdnih snovi z delci (SPM)] z uporabo visokoločljivostne plinske kromatografije – visokoločljivostne masne spektrometrije (HRGC – HRMS).
OPOMBA 1: Analogi, analizirani s to metodo, so navedeni v Tabeli 1.
Delovni razpon metode je od 20 pg/l do 8 ng/l. Metoda je optimizirana za poliklorirane naftalene, vendar jo je mogoče prilagoditi tako, da vključuje še druge koplanarne spojine, kot so poliklorirani dioksini in furani (PCDD/PCDF) ter dioksinom podobni tetra- do heptaklorirani bifenili (dIPCB). To metodo je mogoče uporabiti za določevanje polikloriranih naftalenov v drugih matricah (npr. živih organizmih, usedlinah, zraku); vendar so za vzorce z visoko organsko sestavo morda potrebni dodatni koraki in tehnike čiščenja. Uporabiti je mogoče nizkoločljivostno masno spektrometrijo (LRMS) in masno spektrometrijo – masno spektrometrijo (MS – MS).
OPOMBA 2: Pogoji nizkoločljivostne masne spektrometrije in masne spektrometrije – masne spektrometrije so povzeti v Dodatku A.
Postopka nizkoločljivostne masne spektrometrije in masne spektrometrije – masne spektrometrije sta lahko manj selektivna od postopka visokoločljivostne masne spektrometrije ter pri uporabi teh tehnik obstaja možnost pristranskosti zaradi motilnih spojin.
Mejne vrednosti zaznavanja in stopnje kvantifikacije v tej metodi so odvisne tako od ravni motenj
kot od instrumentalnih omejitev.
OPOMBA 3: Minimalne ravni (ML) v Tabeli 4 so ravni, pri katerih je poliklorirane naftalene običajno mogoče določiti brez prisotnosti motenj.
Ta metoda temelji na učinkovitosti. Analitik lahko prilagodi metodo, npr. za premagovanje motenj, če so izpolnjeni vsi kriteriji učinkovitosti v tej metodi.
OPOMBA 4: Zahteve za vzpostavitev preverjanja metode ali enakovrednosti so podane v točki 9.

General Information

Status
Published
Public Enquiry End Date
02-Jul-2018
Publication Date
09-Jul-2018
Technical Committee
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
22-Jun-2018
Due Date
27-Aug-2018
Completion Date
10-Jul-2018

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TECHNICAL ISO/TS
SPECIFICATION 16780
First edition
2015-08-15
Water quality — Determination of
polychlorinated naphthalenes (PCN)
— Method using gas chromatography
(GC) and mass spectrometry (MS)
Qualité de l’eau — Détermination des naphtalènes polychlorés
(PCN) — Méthode par chromatographie en phase gazeuse (CG) et
spectrométrie de masse (SM)
Reference number
ISO/TS 16780:2015(E)
ISO 2015
---------------------- Page: 1 ----------------------
ISO/TS 16780:2015(E)
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 internet or an intranet, without prior

written permission. Permission can be requested from either ISO at the address below or ISO’s 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 47
copyright@iso.org
www.iso.org
ii © ISO 2015 – All rights reserved
---------------------- Page: 2 ----------------------
ISO/TS 16780:2015(E)
Contents Page

Foreword ..........................................................................................................................................................................................................................................v

1 Scope ................................................................................................................................................................................................................................. 1

2 Normative references ...................................................................................................................................................................................... 1

3 Terms, definitions, and abbreviated terms ............................................................................................................................... 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 quantification ............................................................................................................................................. 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

9.3 Recovery of labelled compounds assessment ...........................................................................................................21

9.4 Method blanks ......................................................................................................................................................................................21

9.5 QC check sample .................................................................................................................................................................................21

10 Calibration ...............................................................................................................................................................................................................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 ......................................................................................................................................................................................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 preparation ........................................................................................................................................................................................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 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
---------------------- Page: 3 ----------------------
ISO/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

13 Extract clean-up..................................................................................................................................................................................................31

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 nitrate–silica column .......................................................................................................................................................34

14 HRGC–HRMS 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 ..........................................................................................................................................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, MS–MS) ..............................40

Annex 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

Bibliography .............................................................................................................................................................................................................................48

iv © ISO 2015 – All rights reserved
---------------------- Page: 4 ----------------------
ISO/TS 16780:2015(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 for which a technical

committee has been established has the right to be represented on that committee. International

organizations, 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 its 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/directives).

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 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 related to conformity

assessment, as well as information about ISO’s adherence to the WTO principles in the Technical

Barriers to Trade (TBT) see the following URL: Foreword - Supplementary 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 v
---------------------- Page: 5 ----------------------
TECHNICAL SPECIFICATION ISO/TS 16780:2015(E)
Water quality — Determination of polychlorinated
naphthalenes (PCN) — Method using gas chromatography
(GC) and mass spectrometry (MS)

WARNING — Persons using this Technical Specification should be familiar 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

conditions.

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.

IMPORTANT — It is absolutely essential that tests conducted in accordance with this Technical

Specification be carried out by suitably trained staff.
1 Scope

This Technical Specification specifies a method for the determination of polychlorinated naphthalenes

(PCNs), where “poly” means “mono” to “octa”, in waters and waste waters [containing less than 2 g/l

solid particulate material (SPM)] using high resolution gas chromatography–high resolution mass

spectrometry (HRGC–HRMS).
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 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. biota, 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 spectrometry–mass spectrometry (MS–MS) can be used.
NOTE 2 LRMS and MS–MS conditions are summarized in Annex A.

Both LRMS and MS–MS 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 (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 requirements 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 undated

references, the latest edition of the referenced document (including any amendments) applies.

© ISO 2015 – All rights reserved 1
---------------------- Page: 6 ----------------------
ISO/TS 16780:2015(E)
ISO 3696, Water for analytical laboratory use — Specification and test methods

ISO 5667-1, 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

performance characteristics
3 Terms, definitions, and abbreviated terms

For the purposes of this document, the following terms, definitions, and abbreviated terms apply.

3.1 Terms and definitions
3.1.1
analyte
substance to be determined

EXAMPLE A polychlorinated naphthalene (PCN) congener tested for by the method specified in

this Technical Specification.
Table 1 — PCNs determined by this method
PCN No. (Reference[4]) Chlorine substitution CAS Registry No.
Total MonoCNs Mono congener total
2 2-MonoCN 91–58–7
Total DiCNs Di congener total
6 1,5-DiCN 1825–30–5
Total TriCNs Tri congener total
13 1,2,3-TriCN 50402–52–3
Total TetraCNs Tetra congener total
27 1,2,3,4-TetraCN 20020–02–4
28 1,2,3,5-TetraCN 53555–63–8
36 1,2,5,6-TetraCN 67922–22–9
42 1,3,5,7-TetraCN 53555–64–9
46 1,4,5,8-TetraCN 3432–57–3
48 2,3,6,7-TetraCN 34588–40–4
Total PentaCNs Penta congener total
49 1,2,3,4,5-PentaCN 67922–25–2
50 1,2,3,4,6-PentaCN 67922–26–3
52/60 1,2,3,5,7-/ 53555–65–0/
1,2,4,6,7-PentaCN 150224–17–2
53 1,2,3,5,8-PentaCN 150224–24–1
54 1,2,3,6,7-PentaCN 150224–16–1
Total HexaCNs Hexa congener total
63 1,2,3,4,5,6-HexaCN 58877–88–6
64/68 1,2,3,4,5,7-/ 67922–27–4/
1,2,3,5,6,8-HexaCN 103426–95–5
2 © ISO 2015 – All rights reserved
---------------------- Page: 7 ----------------------
ISO/TS 16780:2015(E)
Table 1 (continued)
PCN No. (Reference[4]) Chlorine substitution CAS Registry No.
66/67 1,2,3,4,6,7-/ 103426–96–6
1,2,3,5,6,7-HexaCN 103426–97–7
69 1,2,3,5,7,8-HexaCN 103426–94–4
70 1,2,3,6,7,8-HexaCN 17062–87–2
71/72 1,2,4,5,6,8-/ 90948–28–0
1,2,4,5,7,8-HexaCN 103426–92–2
Total HeptaCNs Hepta congener total
73 1,2,3,4,5,6,7-HeptaCN 58863–14–2
74 1,2,3,4,5,6,8-HeptaCN 58863–15–3
75 (OctaCN) 1,2,3,4,5,6,7,8-OctaCN 2234–13–1
[4]

Note: PCN numbering nomenclature is detailed in Reference . 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.
3.1.2
calibration standard

solution prepared from a secondary standard or stock solutions and used to calibrate the response of

the instrument with respect to analyte concentration
[SOURCE: ISO 17858:2007, 3.1.2 — modified]
3.1.3
calibration verification standard
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 or 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 %” 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
[16]
Table 2 — Examples of relative potencies
Compound REP
1,3,5,7CN(42) 0,000 01
1,2,5,6CN(36) 0,000 01
© ISO 2015 – All rights reserved 3
---------------------- Page: 8 ----------------------
ISO/TS 16780:2015(E)
Table 2 (continued)
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
1,2,4,5,6,8CN/1,2,4,5,7,8CN(71/72) 0,001
1,2,3,4,5,6CN(63) 0,001
1,2,3,6,7,8CN(70) 0,01
1,2,3,4,5,6,7CN(73) 0,01
1,2,3,4,5,6,8CN(74) 0,01
1,2,3,4,5,6,7,8CN(75) 0,1
3.1.7
homologue group
complete group of isomers
EXAMPLE Tetrachloronaphthalenes.
[SOURCE: ISO 17858:2007, 3.1.8 — modified]
3.1.8
isotope dilution

method using labelled (usually C) internal standards to correct for losses during sample preparation

and analysis
13 13
[SOURCE: ISO 17858:2007, 3.1.9, modified — “ C” replaces “ C ”.]
3.1.9
method blank

aliquot 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 materials

[SOURCE: ISO 17858:2007, 3.1.11, modified — “free of analytes” replaces “that is”.]

3.1.10
recovery standard

C -labelled PCN added before injection into the GC, to monitor variability of instrument response,

and determine recovery of surrogate/internal standards

Note 1 to entry: An alternate compound with similar properties can be used if a labelled PCN standard

is not available.
4 © ISO 2015 – All rights reserved
---------------------- Page: 9 ----------------------
ISO/TS 16780:2015(E)
3.1.11
solid particulate material
SPM
suspended solids
non dissolved particle matter present in the sample
3.1.12
toxic equivalent factor
TEF
relative toxicity to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
[SOURCE: ISO 17858:2007, definition 3.1.17]
3.1.13
toxic equivalent quantity
TEQ
sum of toxic equivalents of each individual congener
[SOURCE: ISO 17858:2007, 3.1.18]
3.1.14
surrogate standard

C -labelled PCN added to the sample prior to analysis and used to correct for losses of the PCN

analytes during sample extraction or clean-up

Note 1 to entry: Surrogate standards have the same chemical formula and structure as the analyte of interest.

3.1.15
internal standard

C -labelled PCN or analogue added to the sample prior to analysis and used to correct for losses of

the PCN analytes during sample extraction or clean-up

Note 1 to entry: Internal standards do not have the same structure as the analyte of interest but can or may not

have the same chemical formula.
© ISO 2015 – All rights reserved 5
---------------------- Page: 10 ----------------------
ISO/TS 16780:2015(E)
3.2 Abbreviated terms
AR analytical reagent
CRM certified reference material
...

SLOVENSKI STANDARD
SIST-TS ISO/TS 16780:2018
01-september-2018
.DNRYRVWYRGH'RORþHYDQMHSROLNORULUDQLKQDIWDOHQRY 3&1 0HWRGDSOLQVNH
NURPDWRJUDILMH *& LQPDVQHVSHNWURPHWULMH 06

Water quality - Determination of polychlorinated naphthalenes (PCN) - Method using gas

chromatography (GC) and mass spectrometry (MS)
Qualité de l'eau - Détermination des naphtalènes polychlorés (PCN) - Méthode par
chromatographie en phase gazeuse (CG) et spectrométrie de masse (SM)
Ta slovenski standard je istoveten z: ISO/TS 16780:2015
ICS:
13.060.50 3UHLVNDYDYRGHQDNHPLþQH Examination of water for
VQRYL chemical substances
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
SIST-TS ISO/TS 16780:2018 en

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
SIST-TS ISO/TS 16780:2018
---------------------- Page: 2 ----------------------
SIST-TS ISO/TS 16780:2018
TECHNICAL ISO/TS
SPECIFICATION 16780
First edition
2015-08-15
Water quality — Determination of
polychlorinated naphthalenes (PCN)
— Method using gas chromatography
(GC) and mass spectrometry (MS)
Qualité de l’eau — Détermination des naphtalènes polychlorés
(PCN) — Méthode par chromatographie en phase gazeuse (CG) et
spectrométrie de masse (SM)
Reference number
ISO/TS 16780:2015(E)
ISO 2015
---------------------- Page: 3 ----------------------
SIST-TS ISO/TS 16780:2018
ISO/TS 16780:2015(E)
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 internet or an intranet, without prior

written permission. Permission can be requested from either ISO at the address below or ISO’s 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 47
copyright@iso.org
www.iso.org
ii © ISO 2015 – All rights reserved
---------------------- Page: 4 ----------------------
SIST-TS ISO/TS 16780:2018
ISO/TS 16780:2015(E)
Contents Page

Foreword ..........................................................................................................................................................................................................................................v

1 Scope ................................................................................................................................................................................................................................. 1

2 Normative references ...................................................................................................................................................................................... 1

3 Terms, definitions, and abbreviated terms ............................................................................................................................... 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 quantification ............................................................................................................................................. 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

9.3 Recovery of labelled compounds assessment ...........................................................................................................21

9.4 Method blanks ......................................................................................................................................................................................21

9.5 QC check sample .................................................................................................................................................................................21

10 Calibration ...............................................................................................................................................................................................................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 ......................................................................................................................................................................................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 preparation ........................................................................................................................................................................................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 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

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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

13 Extract clean-up..................................................................................................................................................................................................31

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 nitrate–silica column .......................................................................................................................................................34

14 HRGC–HRMS 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 ..........................................................................................................................................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, MS–MS) ..............................40

Annex 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

Bibliography .............................................................................................................................................................................................................................48

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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 for which a technical

committee has been established has the right to be represented on that committee. International

organizations, 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 its 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/directives).

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 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 related to conformity

assessment, as well as information about ISO’s adherence to the WTO principles in the Technical

Barriers to Trade (TBT) see the following URL: Foreword - Supplementary information

The committee responsible for this document is ISO/TC 147, Water quality, Subcommittee SC 2, Physical,

chemical and biochemical methods.
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SIST-TS ISO/TS 16780:2018
TECHNICAL SPECIFICATION ISO/TS 16780:2015(E)
Water quality — Determination of polychlorinated
naphthalenes (PCN) — Method using gas chromatography
(GC) and mass spectrometry (MS)

WARNING — Persons using this Technical Specification should be familiar 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

conditions.

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.

IMPORTANT — It is absolutely essential that tests conducted in accordance with this Technical

Specification be carried out by suitably trained staff.
1 Scope

This Technical Specification specifies a method for the determination of polychlorinated naphthalenes

(PCNs), where “poly” means “mono” to “octa”, in waters and waste waters [containing less than 2 g/l

solid particulate material (SPM)] using high resolution gas chromatography–high resolution mass

spectrometry (HRGC–HRMS).
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 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. biota, 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 spectrometry–mass spectrometry (MS–MS) can be used.
NOTE 2 LRMS and MS–MS conditions are summarized in Annex A.

Both LRMS and MS–MS 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 (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 requirements 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 undated

references, the latest edition of the referenced document (including any amendments) applies.

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ISO 3696, Water for analytical laboratory use — Specification and test methods

ISO 5667-1, 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

performance characteristics
3 Terms, definitions, and abbreviated terms

For the purposes of this document, the following terms, definitions, and abbreviated terms apply.

3.1 Terms and definitions
3.1.1
analyte
substance to be determined

EXAMPLE A polychlorinated naphthalene (PCN) congener tested for by the method specified in

this Technical Specification.
Table 1 — PCNs determined by this method
PCN No. (Reference[4]) Chlorine substitution CAS Registry No.
Total MonoCNs Mono congener total
2 2-MonoCN 91–58–7
Total DiCNs Di congener total
6 1,5-DiCN 1825–30–5
Total TriCNs Tri congener total
13 1,2,3-TriCN 50402–52–3
Total TetraCNs Tetra congener total
27 1,2,3,4-TetraCN 20020–02–4
28 1,2,3,5-TetraCN 53555–63–8
36 1,2,5,6-TetraCN 67922–22–9
42 1,3,5,7-TetraCN 53555–64–9
46 1,4,5,8-TetraCN 3432–57–3
48 2,3,6,7-TetraCN 34588–40–4
Total PentaCNs Penta congener total
49 1,2,3,4,5-PentaCN 67922–25–2
50 1,2,3,4,6-PentaCN 67922–26–3
52/60 1,2,3,5,7-/ 53555–65–0/
1,2,4,6,7-PentaCN 150224–17–2
53 1,2,3,5,8-PentaCN 150224–24–1
54 1,2,3,6,7-PentaCN 150224–16–1
Total HexaCNs Hexa congener total
63 1,2,3,4,5,6-HexaCN 58877–88–6
64/68 1,2,3,4,5,7-/ 67922–27–4/
1,2,3,5,6,8-HexaCN 103426–95–5
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Table 1 (continued)
PCN No. (Reference[4]) Chlorine substitution CAS Registry No.
66/67 1,2,3,4,6,7-/ 103426–96–6
1,2,3,5,6,7-HexaCN 103426–97–7
69 1,2,3,5,7,8-HexaCN 103426–94–4
70 1,2,3,6,7,8-HexaCN 17062–87–2
71/72 1,2,4,5,6,8-/ 90948–28–0
1,2,4,5,7,8-HexaCN 103426–92–2
Total HeptaCNs Hepta congener total
73 1,2,3,4,5,6,7-HeptaCN 58863–14–2
74 1,2,3,4,5,6,8-HeptaCN 58863–15–3
75 (OctaCN) 1,2,3,4,5,6,7,8-OctaCN 2234–13–1
[4]

Note: PCN numbering nomenclature is detailed in Reference . 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.
3.1.2
calibration standard

solution prepared from a secondary standard or stock solutions and used to calibrate the response of

the instrument with respect to analyte concentration
[SOURCE: ISO 17858:2007, 3.1.2 — modified]
3.1.3
calibration verification standard
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 or 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 %” 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
[16]
Table 2 — Examples of relative potencies
Compound REP
1,3,5,7CN(42) 0,000 01
1,2,5,6CN(36) 0,000 01
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Table 2 (continued)
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
1,2,4,5,6,8CN/1,2,4,5,7,8CN(71/72) 0,001
1,2,3,4,5,6CN(63) 0,001
1,2,3,6,7,8CN(70) 0,01
1,2,3,4,5,6,7CN(73) 0,01
1,2,3,4,5,6,8CN(74) 0,01
1,2,3,4,5,6,7,8CN(75) 0,1
3.1.7
homologue group
complete group of isomers
EXAMPLE Tetrachloronaphthalenes.
[SOURCE: ISO 17858:2007, 3.1.8 — modified]
3.1.8
isotope dilution

method using labelled (usually C) internal standards to correct for losses during sample preparation

and analysis
13 13
[SOURCE: ISO 17858:2007, 3.1.9, modified — “ C” replaces “ C ”.]
3.1.9
method blank

aliquot 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 materials

[SOURCE: ISO 17858:2007, 3.1.11, modified — “free of analytes” replaces “that is”.]

3.1.10
recovery standard

C -labelled PCN added before injection into the GC, to monitor variability of instrument response,

and determine recovery of surrogate/internal standards

Note 1 to entry: An alternate compound with similar properties can be used if a labelled PCN sta

...

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