Water quality. Determination of selected per- and polyfluoroalkyl substances in drinking water. Method using liquid chromatography/tandem-mass spectrometry (LC-MS/MS)

Water quality. Determination of selected per- and polyfluoroalkyl substances in drinking water. Method using liquid chromatography/tandem-mass spectrometry (LC-MS/MS)

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1   Scope

This document specifies a method for the determination of the dissolved fraction of selected perfluoroalkyl and polyfluoroalkyl substances (PFAS) in non-filtrated drinking water using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The applicability of the method to other types of water like fresh waters (e.g. ground water, surface water) or treated wastewater can be validated separately for each individual case.
For each target compound both, eventually occurring branched isomers and the respective non-branched isomer, are quantified together. The selected set of substances determined by this method is representative for a wide variety of PFAS. This method has been validated for the analytes specified in Table 1. The list given in this table can be modified depending on the purpose and focus of the method. The lower application range of this method can vary depending on the sensitivity of the equipment used and the matrix of the samples. For many substances to which this document applies a limit of quantification (LOQ) of 1 ng/l can be achieved. Using high volume direct injection as described in part A or SPE as described in part B of the method allows lower LOQs. Analytical limitations can occur with short-chain PFAS or PFAS with more than ten carbon atoms in the carbon chain. Actual LOQs can depend on the blank values realized by individual laboratories as well.

NOTE This document enables the analysis of those 20 PFAS which are listed in point 3 of Part B of Annex III of the EU Drinking Water Directive, EU 2020/2184 [4], for the surveillance of the parametric limit value of 0,10 µg/l for the sum of PFAS.

Furthermore, alternatives and substitutes for these PFAS substances can be analysed using this document as well.
Table 1Analytes for which a determination was validated in accordance with this method
Analyte IUPAC name a ) Formula Abbreviation CAS-RN b )
Perfluoro-n-butanoic acid 2,2,3,3,4,4,4-Heptafluorobutanoic acid C4HF7O2 PFBA 375–22–4
Perfluoro-n-
pentanoic acid
2,2,3,3,4,4,5,5,5-Nonafluoropentanoic acid C5HF9O2 PFPeA 2706–90–3
Perfluoro-n-
hexanoic acid
2,2,3,3,4,4,5,5,6,6,6-Undecafluorohexanoic acid C6HF11O2 PFHxA 307–24–4
Perfluoro-n-
heptanoic acid
2,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoroheptanoic acid C7HF13O2 PFHpA 375–85–9
Perfluoro-n-
octanoic acid
2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-Pentadecafluorooctanoic acid C8HF15O2 PFOA 335–67–1
Perfluoro-n-
nonanoic acid
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-Heptadecafluorononanoic acid C9HF17O2 PFNA 375–95–1
Perfluoro-n-
decanoic acid
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,
10,10-Nonadecafluorodecanoic acid
C10HF19O2 PFDA 335–76–2
Perfluoro-n-
undecanoic acid
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,
10,11,11,11-Heneicosafluoroundecanoic acid
C11HF21O2 PFUnDA 2058–94–8
Perfluoro-n-
dodecanoic acid
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-Tricosafluorododecanoic acid C12HF23O2 PFDoDA 307–55–1
Perfluoro-n-
tridecanoic acid
2,2,3,3,4,4,5,5,6,6,7,7,8,8, 9,9,10,10,11,11,12,12, 13,13,13-Pentacosa-fluorotridecanoic acid C13HF25O2 PFTrDA 72629–94–8
Perfluoro-n-
butanesulfonic acid
1,1,2,2,3,3,4,4,4-Nonafluorobutane-1-sulfonic acid C4HF9O3S PFBS 375–73–5
Perfluoro-n-
pentanesulfonic acid
1,1,2,2,3,3,4,4,5,5,5-Undecafluoropentane-1-sulfonic acid C5HF11O3S PFPeS 2706–91–4
Perfluoro-n-
hexanesulfonic acid
1,1,2,2,3,3,4,4,5,5,6,6,6-Tridecafluorohexane-1-sulfonic acid C6HF13O3S PFHxS 355–46–4
Perfluoro-n-
heptanesulfonic acid
1,1,2,2,3,3,4,4,5,5,6,6,7,7,7-Pentadecafluoroheptane-1-sulfonic acid C7HF15O3S PFHpS 375–92–8
Perfluoro-n-
octanesulfonic acid
1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-Heptadecafluorooctane-1-sulfonic acid C8HF17O3S PFOS 1763–23–1
Perfluoro-n-
nonanesulfonic acid
1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-Nonaadecafluorononane-1-sulfonic acid C9HF19O3S PFNS 68259–12–1
Perfluoro-n-
decanesulfonic acid
1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heneicosafluorodecane-1-sulfonic acid C10HF21O3S PFDS 335–77–3
Perfluoro-n-undecanesulfonic acid 1,2,2,3,3,4,4,5,5,6,6,7,7,8,8, 9,9,10,10,11,11,11-Tricosafluoroundecane-1-sulfonic acid C11HF23O3S PFUnDS 749786-16-1
Perfluoro-n-dodecanesulfonic acid 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-Pentacosafluorododecane-1-sulfonic acid C12HF25O3S PFDoDS 79780-39-5
Perfluoro-n-tridecanesulfonic acid 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-Heptacosafluorotridecane-1-sulfonic acid C13HF27O3S PFTrDS 791563-89-8
4:2 Fluorotelomer sulfonic acid 3,3,4,4,5,5,6,6,6-Nonafluorohexane-1-sulfonic acid C6H5F9O3S 4:2 FTSA 757124–72–4
6:2 Fluorotelomer sulfonic acid 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctane-1-sulfonic acid C8H5F13O3S 6:2 FTSA 27619–97–2
8:2 Fluorotelomer sulfonic acid 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,
10-Heptadecafluorodecane-1-sulfonic acid
C10H5F17O3S 8:2 FTSA 39108–34–4
Perfluorooctanesulfonamide 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-Heptadecafluoro-1-octanesulfonamide C8H2F17NO2S FOSA 754–91–6
N-ethyl perfluorooctanesulfonamidoacetic acid 2-[Ethyl(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctylsulfonyl)
amino]acetic acid
C12H8F17NO4S EtFOSAA 2991–50–6
Hexafluoropropylene oxide dimer acid 2,3,3,3-Tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propanoic acid C6HF11O3 HFPO-DA 13252–13–6
4,8-Dioxa-3H-perfluorononanoic acid 2,2,3-Trifluoro-3-[1,1, 2,2,3,3-hexafluoro-3-(tri-fluoromethoxy)propoxy]
propanoic acid
C7H2F12O4 DONA 919005–14–4
Perfluoro-3-methoxypropanoic acid 2,2,3,3-Tetrafluoro-3-(trifluoromethoxy)pro-panoic acid C4HF7O3 PFMPA (PF4OPeA) 377–73–1
9-Chlorohexa-decafluoro-3-oxanonane-1-sulfonic acid 2-(6-Chloro-1,1,2,2, 3,3,4,4,5,5,6,6-dodeca-fluorohexoxy)-1,1,2,2-tetrafluoroethanesulfonic acid C8HClF16O4S 9Cl-PF3ONS 73606–19–6
a) IUPAC: International Union of Pure and Applied Chemistry
b) CAS-RN: Chemical Abstract Services Registry Number