ANALYSIS OF PERFLUOROALKYL ANION FRAGMENTATION PATHWAYS

FOR LINEAR AND BRANCHED PERFLUOROOCTANOIC ACIDS (PFOA)

DURING LC/ESI-MS/MS
Gilles Arsenaulta, Brock Chittima, Alan McAleesa, Robert McCrindleb and Nicole Riddella.
a Wellington Laboratories Inc., Research Division, Guelph, Ontario, N1G 3M5, Canada
b Chemistry Dept., University of Guelph, Guelph, Ontario, N1G 2W1, Canada

Introduction
¾ LC-electrospray ionization-MS (LC/ESI-MS) and LC/ESI-MS/MS can be considered as the current standard for analysis of anionic perfluorinated compounds.1
¾ The belief by many is that the perfluoroalkyl anion fragments by ‘unzipping’ to produce CnF2n species.2
¾ Initial analysis in our laboratory of the mass spectrum of MPFOA indicated that the fragmentation mechanism of a perfluoroalkyl anion is more complex than one
involving simple sequential loss of neutral CnF2n fragments.
¾ Indeed, recent work3 has shown that the fragmentation mechanism of linear perfluoroalkyl carboxylic acids involves, after initial decarboxylation, rapid fluorine shifts,
which generate a series of new anions prior to secondary and tertiary fragmentation.
Objective
¾ To develop a fundamental understanding of the fragmentation mechanism for the perfluoroalkyl anions generated from perfluoroalkyl carboxylates under LC/ESI-MS/MS
conditions.
¾ To extend the investigation of perfluoroalkyl fragmentation to branched PFOA isomers .

Experimental
Chemicals : The branched isomers of PFOA were obtained from Wellington Laboratories.
LCMS/MS: The analyses were conducted on a Waters Acquity Ultra Performance LC interfaced to a Micromass Quattro micro atmospheric pressure ionization (API) mass
spectrometer (MS) in negative-ion electrospray mode. Tune parameters were optimized to promote the in-source fragmentation of each individual isomer from [Rf–CO2]¯ to
[Rf]¯. Product ion experiments were then carried out on [Rf]¯ (argon collision gas ~ 3.5e-3 mbar; cone voltage: 15V – 30V; collision energies: 15eV – 25eV).

Results and Discussions

Fragmentation of LPFOA
¾ The study was performed on the various branched isomers of PFOA shown in Figure 1.
¾ As expected, based on results of the previous study, LPFOA produces secondary daughter ion fragments at m/z 119, m/z 169 and m/z 219 (see figure 2). Note that no
signals were detected at m/z 269 (from primary carbanions 1a and 1g, see Figure 3) nor at m/z 69 consistent with the lower stability of primary carbanions.
¾ The secondary daughter ion fragments produced for each PFOA isomer is shown in Figure 2.

a) LPFOA b) P3MHpA
CF3CF2CF2CF2CF2CF2CF2CO2H CF3CF2CF2CF2CF2CFCO2H CF3CF2CF2CF2CFCF2CO2H
LPFOA P2MHpA P3MHpA
CF3 CF3

CF3CF2CF2CFCF2CF2CO2H CF3CF2CFCF2CF2CF2CO2H CF3CFCF2CF2CF2CF2CO2H

c) P4MHpA d) P5MHpA
P4MHpA P5MHpA P6MHpA
CF3 CF3 CF3
CF3

(CF3)3CCF2CF2CF2CO2H CF3CF2CCF2CF2CO2H CF3CFCFCF2CF2CO2H e) P6MHpA

P55DMHxA f) P44DMHxA
P44DMHxA P45DMHxA
CF3 F3C CF3

CF3CFCF2CFCF2CO2H

CF3 P35DMHxA g) P55DMHxA h) P45DMHxA/

F3C P35DMHxA

Figure 1. Structures of the perfluorooctane carboxylic acids

F F F CF 3 F F
i) P2MHpA
C C C
F

F F
F
C C C CO 2
-
P2MHpA produces a very weak spectrum because
F F F
m /z 4 13
F F
only a small % of the in-source fragmentation of m/z
-C O 2 413 produces m/z 369 and subsequent secondary
m /z 3 69 fragmentation to the “9-series” anions (see Table 1).
F CF 3
F F F CF 3 F F

F C C - + C F 2 =CF 2 F C C C -
C C
C C C
F
F F
m /z 2 6 9
F
F
F F F F F 5a Figure 2. LC/ESI-MS/MS: Secondary daughter ion scan from m/z 369
F F
F F F CF 3 F F

F C + C F 3 CF=C F C F 3
C C
- F C C C
C C -C F
F
F F

m /z 1 6 9
F
F
F F F F
5b Results and Discussion (con’t)
-
C F3 + C F 3C F 2 C F 2 C F = C F C F 3 F
F

C
F F

C
CF 3 F

C
F
Fragmentation of branched PFOA isomers
m /z 6 9
F
C

F F
C

F
-C
F 5b
F

¾ As an example, the fragmentation of P4MHpA will be outlined:

F

C
-
F
F F F 3C F F
F
ƒ Primary fragmentation (decarboxylation) produces the fragment m/z 369.
-

ƒ Rapid fluorine migration produces various anions (see figure 3).

+ C F 2 =C(C F 3 )C F 2 C F 3 -C
F F C C C F 3 CF 2 C F 2 (C F 3 )C =C F 2 + CF 3
C
C C C F m /z 6 9
F F
F
m /z 11 9

ƒ It is known that order of stabilities of perfluoro carbanions is 3°>2°>1°.4 Therefore, fragment 5c containing
F F F F F 5c

- E
F F F CF 3 F F
G
F

-C
F

F
the 3° carbanion (figure 3, highlighted) is expected to contain the highest equilibrium population.
CF3 + C F 2 = C F C F ( C F 3 )C F 2 C F 3 C F 3 C F 2C F = C F C F 3 + C

m /z 6 9
F

F
C
C
-
C

F
C

F
C

F
C

5d
F F
m /z 1 1 9
F Consequently, upon secondary fragmentation, the strongest signal is m/z 119.
F

¾ The other branched PFOA isomers follow the same pattern of fragmentation through a tertiary carbanion,
F F F CF 3 F F

F
C
C
-
C
C
C
C
F
H
C F 3 CF 2 C F= C FCF 2C F 3 + C F3
-

m /z 69
except for P2MHpA.
¾ P2MHpA shows minimal signs (see Figure 2) of the typical fragments m/z 369/219/169/119/etc but instead
F
F F F F 5d

F F CF 3 F F
I
F CF 3 F F produces unique anions at m/z 85 [CF3O] and m/z 63 [FCO]. This crowded carboxylate anion prefers to attack
C C
F

F
C
C
- C
C
C
C
F
C F3CF =C F2 + -

F
C

F
F
the neighboring alpha-CF3 instead of decarboxylating.
F F F F F 5e
m /z 2 1 9
Relative response factors
F F F CF 3 F F
J
F CF 3 F F ¾ The SIR relative response factor for the individual PFOA isomers are shown in Table 1.
¾ Certain isomers showed significant reduction in their SIM response factors relative to LPFOA because of
C F 2 =CF 2 +
C C
F
- C C C -
C C C F C C F

F F F F F 5f F F F F
m /z 2 6 9
facile in-source fragmentation.
Figure 3. Fragmentation pathway for P4MHpA ¾ The spectrum of P2MHpA is extremely weak because of the lack of “9-series” fragments.

Table 1. SIM response factors for the various branched PFOA isomers relative to linear PFOA (LPFOA)
References
1. de Voogt, P., Sáez, M., 2006. Trends Anal. Chem. 25, 326-342. Isomer P2MHpA P3MHpA P4MHpA P5MHpA P6MHpA P55DMHxA P44DMHxA P45DMHxA P35DMHxA
2. Lyon PA, Tomer KB, Gross ML. 1985 Anal. Chem. 57, 2984-2989.
3. Arsenault et. al. 2007. Rapid Commun. Mass Spectrom. 21, 3803-3814. %Relative response factor
(m/z 413) 1 40 90 110 100 90 50 75 36
4. Kirsch, P. 2004. Modern Fluoroorganic Chemistry. Wiley-VCH, 103.

%Relative response factor

A manuscript of this work is in preparation. (multi-channel SIM: 1 107 100 104 86 109 98 103 78
413/369/269/219 )