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Determination of Polyfluoroalkyl
Substances (PFAS) in Food Products
Agustin Pierri, PhD
ASMS 2017
Indianapolis, IN
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Background
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Aliphatic backbone—from C4 on up
Typically per-fluorinated
Acid functional group
Unique environmental chemistry
Persistent
Lipophilic
Bioaccumulative
Polyfluoroalkyl Substances Polyfluoroalkyl Substances (PFASs)
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Uses?
Repellents
Performance chemicals
Consumer and industrial goods
Polyfluoroalkyl Substances (PFASs)
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Routes of exposure
Direct contact with food products
Environmental exposure
Polyfluoroalkyl Substances (PFASs)
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Target compounds
• Carboxylic acids
• Sulfonic acids
• Sulfonamides
• Sulfonamido-ethanols
6:2 FTS 8:2 FTS EtFOSA MeFOSA FOSA
EtFOSE
MeFOSE
PFBA
PFBS
PFDA
PFDS
PFHpA
PFHpS
PFHxA
PFHxS
PFNA
PFOA
PFOS
PFPeA
PFDoA
PFTeDA
PFTrDA
PFUdA
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Sample prep
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Sample prep approach
SPE:
Only suitable for water samples
Weak anion exchange offline SPE
QuEChERS:
Suitable for non-liquid samples
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QuEChERS
Screening:
C18 d-SPE
C18 d-SPE + hexanes
PSA/GCB d-SPE
C18/GCB d-SPE
C18/GCB d-SPE + hexanes
EMR-L
👎
👌👏
👎
👎
👎
👎
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EMR-Lipids procedure
Weigh 2.0 grams homogenized sample into 50 mL tube
Add 2 g of EMR-L + 10 mL H2O
Vortex 1 minute, centrifuge 5 minutes
Transfer 5 mL aliquot to tube with 2.5 g NaCl/MgSO4
Transfer 200 µL to conical vial for analysis
Add 10 mL MeCN, vortex 3 minutes
Based on:
Anumol, T., Lehotay, S.J., Stevens, J. et al.
Anal Bioanal Chem (2017) 409: 2639
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Analysis: LC/MS
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PFAS by LC/MS
Unique analytical challenges
Low levels
Relative polarities
Isomers
Contamination
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Sensitivity
1290 LC, 6460 QQQ
Choosing the right mobile phase modifier
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Mobile phase modifiers for ESI
Negative mode
Ammonium salts
Ammonium acetate
Ammonium formate
Ammonium fluoride—the secret sauce (usually)
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Mobile phase vs PFBA
Ammonium acetate
Acetic acid
Ammonium formate
Ammonium fluoride
Most polar: 👍
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Chromatographic conditions
Column: Zorbax RRHD Eclipse Plus C18
50 x 2.1 1.8 μm
Injection volume: 2 μL
Mobile phase: A: Water with 0.05% acetic acid
B: Acetonitrile with 0.05% acetic acid
Flow rate: 0.700 mL/min Time %B
0.0 5
0.5 5
1.0 40
7.0 90
7.2 100
9.5 100
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Mid level chromatogram (1 ppb)
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Low level (0.1 ppb)
Low levels: 👍
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Solvent blank
Instrument contamination: 👍
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Branched vs. linear sulfonates
Isobars: 👍
PFOS PFHxS
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Dynamic range
Calibrates up to 0.1 ppb – 1000 ppb
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Method performance
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Extracts Egg Milk Fish Butter Blank
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Absolute recoveries, milk
0
20
40
60
80
100
120
140
160
PFB
A
PFP
eA
PFB
S
PFH
xA
PFH
pA
PFH
xS
6:2
FTS
PFO
A
PFH
pS
PFO
S
PFN
A
FOSA
Me-F
OSE
8:2
FTS
Me-F
OSA
PFD
A
Et-
FOSE
Et-
FOSA
PFD
S
PFU
dA
PFD
oA
PFT
rDA
PFT
eD
A
Milk, ESTD
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0
20
40
60
80
100
120
140
160
PFB
A
PFP
eA
PFB
S
PFH
xA
PFH
pA
PFH
xS
6:2
FTS
PFO
A
PFH
pS
PFO
S
PFN
A
FOSA
Me-F
OSE
8:2
FTS
Me-F
OSA
PFD
A
Et-
FOSE
Et-
FOSA
PFD
S
PFU
dA
PFD
oA
PFT
rDA
PFT
eD
A
Egg, ESTD
Absolute recoveries, egg
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Absolute recoveries, butter
0
20
40
60
80
100
120
140
160
PFB
A
PFP
eA
PFB
S
PFH
xA
PFH
pA
PFH
xS
6:2
FTS
PFO
A
PFH
pS
PFO
S
PFN
A
FOSA
Me-F
OSE
8:2
FTS
Me-F
OSA
PFD
A
Et-
FOSE
Et-
FOSA
PFD
S
PFU
dA
PFD
oA
PFT
rDA
PFT
eD
A
Butter, ESTD
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0
20
40
60
80
100
120
140
160
PFB
A
PFP
eA
PFB
S
PFH
xA
PFH
pA
PFH
xS
6:2
FTS
PFO
A
PFH
pS
PFO
S
PFN
A
FOSA
Me-F
OSE
8:2
FTS
Me-F
OSA
PFD
A
Et-
FOSE
Et-
FOSA
PFD
S
PFU
dA
PFD
oA
PFT
rDA
PFT
eD
A
Fish, ESTD
Absolute recoveries
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0
20
40
60
80
100
120
140
160
PFB
A
PFP
eA
PFB
S
PFH
xA
PFH
pA
PFH
xS
6:2
FTS
PFO
A
PFH
pS
PFO
S
PFN
A
FOSA
Me-F
OSE
8:2
FTS
Me-F
OSA
PFD
A
Et-
FOSE
Et-
FOSA
PFD
S
PFU
dA
PFD
oA
PFT
rDA
PFT
eD
A
Milk, ISTD
Isotopic dilution corrected recoveries, milk
0
20
40
60
80
100
120
140
160
PFB
A
PFP
eA
PFB
S
PFH
xA
PFH
pA
PFH
xS
6:2
FTS
PFO
A
PFH
pS
PFO
S
PFN
A
FOSA
Me-F
OSE
8:2
FTS
Me-F
OSA
PFD
A
Et-
FOSE
Et-
FOSA
PFD
S
PFU
dA
PFD
oA
PFT
rDA
PFT
eD
A
Milk, ESTD
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0
20
40
60
80
100
120
140
160
PFB
A
PFP
eA
PFB
S
PFH
xA
PFH
pA
PFH
xS
6:2
FTS
PFO
A
PFH
pS
PFO
S
PFN
A
FOSA
Me-F
OSE
8:2
FTS
Me-F
OSA
PFD
A
Et-
FOSE
Et-
FOSA
PFD
S
PFU
dA
PFD
oA
PFT
rDA
PFT
eD
A
Egg, ISTD
Isotopic dilution corrected recoveries, egg
0
20
40
60
80
100
120
140
160
PFB
A
PFP
eA
PFB
S
PFH
xA
PFH
pA
PFH
xS
6:2
FTS
PFO
A
PFH
pS
PFO
S
PFN
A
FOSA
Me-F
OSE
8:2
FTS
Me-F
OSA
PFD
A
Et-
FOSE
Et-
FOSA
PFD
S
PFU
dA
PFD
oA
PFT
rDA
PFT
eD
A
Egg, ESTD
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0
20
40
60
80
100
120
140
160
PFB
A
PFP
eA
PFB
S
PFH
xA
PFH
pA
PFH
xS
6:2
FTS
PFO
A
PFH
pS
PFO
S
PFN
A
FOSA
Me-F
OSE
8:2
FTS
Me-F
OSA
PFD
A
Et-
FOSE
Et-
FOSA
PFD
S
PFU
dA
PFD
oA
PFT
rDA
PFT
eD
A
Butter, ESTD
0
20
40
60
80
100
120
140
160
PFB
A
PFP
eA
PFB
S
PFH
xA
PFH
pA
PFH
xS
6:2
FTS
PFO
A
PFH
pS
PFO
S
PFN
A
FOSA
Me-F
OSE
8:2
FTS
Me-F
OSA
PFD
A
Et-
FOSE
Et-
FOSA
PFD
S
PFU
dA
PFD
oA
PFT
rDA
PFT
eD
A
Butter, ISTD
Isotopic dilution corrected recoveries
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0
20
40
60
80
100
120
140
160
PFB
A
PFP
eA
PFB
S
PFH
xA
PFH
pA
PFH
xS
6:2
FTS
PFO
A
PFH
pS
PFO
S
PFN
A
FOSA
Me-F
OSE
8:2
FTS
Me-F
OSA
PFD
A
Et-
FOSE
Et-
FOSA
PFD
S
PFU
dA
PFD
oA
PFT
rDA
PFT
eD
A
Fish, ISTD
Isotopic dilution corrected recoveries
0
20
40
60
80
100
120
140
160
PFB
A
PFP
eA
PFB
S
PFH
xA
PFH
pA
PFH
xS
6:2
FTS
PFO
A
PFH
pS
PFO
S
PFN
A
FOSA
Me-F
OSE
8:2
FTS
Me-F
OSA
PFD
A
Et-
FOSE
Et-
FOSA
PFD
S
PFU
dA
PFD
oA
PFT
rDA
PFT
eD
A
Fish, ESTD
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Robust and versatile method for PFAS in food
Challenges unique to PFAS
Trace levels—MRL at 0.5 ng/g
Instrument contamination
Resolution
Handle complicated matrix
0
20
40
60
80
100
120
140
160P
FBA
PFP
eA
PFB
S
PFH
xA
PFH
pA
PFH
xS
6:2
FTS
PFO
A
PFH
pS
PFO
S
PFN
A
FOSA
Me-F
OSE
8:2
FTS
Me-F
OSA
PFD
A
Et-
FOSE
Et-
FOSA
PFD
S
PFU
dA
PFD
oA
PFT
rDA
PFT
eD
A
Butter, ISTD