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Origin of the PFOS isomers Objective

Structure characterisation of seven constitutional PFOS isomers by high


The commercial PFOS solution contains different isomers1 due to the performance liquid chromatography (HPLC) coupled with electrospray
route of synthesis. Electrochemical fluoration (ECF) is the mostly used ionisation in the negative mode (ESI(-)) and tandem MS.
process and yields the following composition2:

• Monoperfluoromethyl branched Investigated isomers


• Dimethylperfluoromethyl branched • linear PFOS (L-PFOS) • 3-perfluoromethyl (3m-PFOS)
• perfluoroisopropyl (iso-PFOS) • 2-perfluoromethyl (2m-PFOS)
• Linear PFOS (70 %) • 5-perfluoromethyl (5m-PFOS) • α-perfluoromethyl (α-PFOS)
• 4-perfluoromethyl (4m-PFOS)

Instrumentation
¾ PFOS isomer fractions were obtained after derivatisation,
crystallisation and preparative scale HPLC, carried out by Wellington ¾ MS: 1200L Triple Quadrupole (Varian, USA) with ESI(-), capillary voltage:
Laboratories Inc. -45 V, spray voltage: 4 kV, collision gas: Ar. Collision energy: -40 V applied
to the molecular ions (m/z 499).
¾ Separation: Fluophase (Thermo Electron, 150 mm * 2.1 mm, 5 µm)
or X-Terra C18 (Waters, 100 mm * 3.0 mm, 5 µm).

ESI(-)-TQ-MS/MS spectra
iso-PFOS 5m-PFOS
L-PFOS
100 169/330
100 169 230 CF3 100 130
[FSO3]-
99 430 FSO3- m/z 99
CF2 CF2 230
CF2 130 CF 430 CF
219 / 280 180
m/z 99 CF2 CF2 80

Relative abundance [%]


2
SO3 -
Relative abundance [%]

2
Relative abundance [%]

430
80 CF3 CF2 CF2 - 80 CF 280CF 180
CF2 80
SO3
- 80
180 CF2 80SO3
2
119/380 219/280 80 CF3 380 CF
230
CF2 130 CF2
[FSO3]- CF2
CF3169 / 330 230CF2 CF2
60 80 m/z 99 60 130 130 60
99 CF3
380 330
499 180 40
40 40 180
230 280
169 80 499
20 119 20 20 99
230 499
130 219 280 330 219 380
219 280 330 0
0 0
100 200 m/z 300 400 500 100 200 300 400 500 100 200 m/z 300 400 500
m/z
4m-PFOS
3m-PFOS 2m-PFOS
CF3
100 180 [FSO3]- 100 130 [FSO3]- 100 80 CF3 [FSO3]-
130 430
m/z 99
430 330 319 / 180
m/z 99 m/z 99
80 330 80
Relative abundance [%]
Relative abundance [%]

CF2 180 CF2


Relative abundance [%]

CF2 80 430
CF CF2 SO3
-
80 CF2 SO3
-
CF2 330
CF2 230
CF 80
80 80 SO3
-

CF3 CF2
380 CF2 269 / 230 CF2 CF3
380
CF2 280 CF CF2 99 CF3 380 CF2 280 CF2 CF2
130 130
60 60 60 369 / 130
280 CF3 180
230 130
40 230 40 80 40 230 280
219 499
20 99 499 20 280 20
180 499
119 269 330 99 169 319
0 0 0
100 200 m/z 300 400 500 100 200 m/z 300 400 500 100 200 m/z 300 400 500

α-PFOS
100 99 [FSO3]-
m/z 99 Mass Spectrometric Characterisation
Relative abundance [%]

230
80 430 CF2 330
CF2 CF2 419 / 80 -
SO 3 ¾ Determination of the CF3 position on the chain by the missing fragment in the 0-
CF3 380 CF2 280 CF2 180 CF series. An arrow marks the missing fragments in the spectra
60 130
CF3
¾ Formation of preferential 9-series fragments by cleavage in the α-position of the
40 119 CF3 branching. The preferential fragments are circled in the spectra
219 ¾ Formation of the 0-series suppressed due to CF3 in the α position (α-PFOS spectrum)
20 169 269 419 499
¾Two main product ions in the spectrum of L-PFOS: m/z 80 and m/z 99
0
100 200 300 400 500 ¾ 2m-PFOS is a minor isomer in the fraction resulting in a low signal abundance
m/z
¾ Reduced isomer detectability when usual mass transition m/z 499 → 99 is
monitored: only L-PFOS, iso-PFOS, 2m-PFOS and α-PFOS give this fragment with a
relative abundance >50%
m/z 499 as precursor ions in all the spectra

References Acknowlegments
1- Langlois I. and Oehme. M. (2004) We would like to thank the Swiss National Fundation (project N°200020-101473) and the Norwegian
Organohalog.Compd. 66: 3973-3978. National Fundation (project N°102154) for financial support. Wellington Laboratories Inc. are
2- Kestner T. (1997) U.S. Environmental Protection greatefully acknowledged for providing us the isomeric fractions.
Agency. Docket AR 226-0564.