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

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ISO/TS 16780:2015(E)

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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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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
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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.
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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/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
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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
13
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 ”.]
12
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
13
C -labelled PCN added before injection into the GC, to monitor variability of instrument response,
10
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.
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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
13
C -labelled PCN added to the sample prior to analysis and used to correct for losses of the PCN
10
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
13
C -labelled PCN or analogue added to the sample prior to analysis and used to correct for losses of
10
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.
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3.2 Abbreviated terms
AR analytical reagent
CRM certified reference material
...