Wouter A. Gebbink*, Shahid Ullah, Oskar Sandblom, Urs Berger

Polyfluoroalkyl Phosphate Esters and Perfluoroalkyl Carboxylic Acids in Target Food Samples and Packaging – Method Development and Screening

Department of Applied Environmental Science (ITM), Stockholm University, SE-10691 Stockholm, Sweden

* Corresponding author: Phone: +46 8674 7519; Fax: +46 8674 7638; E-mail:

Supplementary Material

Table S1 List of identified mono-, di-, and triPAPs and their UPLC/MS/MS parameters

Table S2Matrix effects and recoveries of mono-and diPAPs spiked to a fish homogenate

Table S3Concentrations of 6:2/6:2 and 8:2/8:2 diPAPs and corresponding MLOQs in food samples

Table S4Recoveries (including matrix effects) of 13C-labeled mono- and diPAPs and M8PFOA in food analysis

Table S5Relative abundance of detectable mono, di, and triPAPs in food packaging materials (based on peak area compared to 6:2/6:2 diPAP)

Table S6Relative abundance of detectable diPAPs in food samples(based on peak area compared to 6:2/6:2 diPAP)

Table S7Detection of PFCAs in food packaging materials

Figure S1 Chemical structures of 6:2 monoPAP, 6:2/6:2 diPAP, and 6:2/6:2/6:2 triPAP

Figure S2 MRM chromatograms of multiple product ions for coeluting 10:2/10:2, 8:2/12:2, and 6:2/14:2 diPAPs in a Zonyl®-RP solution

Figure S3MRM chromatograms of detected diPAPs in ECO popcorn (food sample 1, prepared)

Figure S4Potential sources of PAPs and PFCAs in food samples

Table S1 List of identified mono-, di-, and triPAPs and their UPLC/MS/MS parameters

RRta / Precursor ion (m/z) / Product
ion 1 (m/z) / Product
ion 2 (m/z) / Cone voltage (V) / Collision energy (eV)
monoPAPs
6:2 / 0.36 / 443 / 97 / 10 / 18
8:2 / 0.58 / 543 / 97 / 10 / 24
10:2 / 0.76 / 643 / 97 / 14 / 20
12:2 / 0.91 / 743 / 97 / 10 / 20
diPAPs
6:2/6:2 / 1 / 789 / 97 / 443 / 50 / 34
6:2/8:2 / 1.18 / 889 / 97 / 443 / 50 / 34
8:2/8:2 / 1.39 / 989 / 97 / 543 / 50 / 36
6:2/10:2 / 1.41 / 989 / 97 / 443 / 50 / 36
8:2/10:2 / 1.62 / 1089 / 97 / 543 / 50 / 34
6:2/12:2 / 1.65 / 1089 / 97 / 443 / 50 / 34
10:2/10:2b / 1.79 / 1189 / 97 / 643 / 50 / 34
8:2/12:2b / 1189 / 97 / 543 / 50 / 34
6:2/14:2 / 1.80 / 1189 / 97 / 443 / 50 / 34
10:2/12:2c / 1.88 / 1289 / 97 / 643 / 50 / 34
8:2/14:2c / 1289 / 97 / 543 / 50 / 34
6:2/16:2 / 1.89 / 1289 / 97 / 443 / 50 / 34
12:2/12:2d / 1.98 / 1389 / 97 / 743 / 50 / 34
10:2/14:2d / 1389 / 97 / 643 / 50 / 34
8:2/16:2d / 1389 / 97 / 543 / 50 / 34
6:2/18:2d / 1389 / 97 / 443 / 50 / 34
triPAPs
6:2/6:2/6:2 / 1.91 / 789 / 97 / 443 / 50 / 34
6:2/6:2/8:2 / 1.97 / 789/889 / 97 / 443 / 50 / 34
6:2/8:2/8:2e / 2.02 / 889/989 / 97 / 443/543 / 50 / 34
6:2/6:2/10:2e / 789/989 / 97 / 443 / 50 / 34
8:2/8:2/8:2f / 2.06 / 989 / 97 / 543 / 50 / 34
6:2/8:2/10:2f / 889/989 / 97 / 443 / 50 / 34
6:2/6:2/12:2f / 789/1089 / 97 / 443 / 50 / 34

a Relative retention time (normalized to the retention time of 6:2/6:2 diPAP). Retention times of compounds highlighted in bold were confirmed with authentic standards, other compounds were identified in Zonyl®-RP

b,c,d,e,fCoeluting peaks

Table S2 Matrix effects and recoveries of mono-and diPAPs spiked to a fish homogenate

Compound / % Matrix effecta
(n=1) / % Recoveryb
(n=1)
monoPAPs
6:2 / 80 / 78
8:2 / 106 / 83
10:2 / 226 / 67
diPAPs
6:2/6:2 / 559 / 67
6:2/8:2 / 278 / 70
6:2/10:2 / 343 / 97
8:2/8:2 / 808 / 75
6:2/12:2 / 251 / 85
8:2/10:2 / 505 / 82
6:2/14:2 / 222 / 76
8:2/12:2 / 321 / 58
10:2/10:2 / 190 / 67
6:2/16:2 / 264 / 81
8:2/14:2 / 208 / 49
10:2/12:2 / 228 / 26
8:2/16:2 / 200 / 71

a %Matrix effect = (peak area spiked fish post-extraction) * 100/(peak area spiked solvent)

b %Recovery = (peak area spiked fish pre-extraction) * 100/(peak area spiked fish post-extraction)

Note: triPAPs were below detection limit in this experiment

Table S3 Concentrations of 6:2/6:2 and 8:2/8:2 diPAPs and corresponding MLOQs in food samples

Food sample / 6:2/6:2
(pg/g) / MLOQ
(S/N 10, pg/g) / 8:2/8:2
(pg/g) / MLOQ
(S/N 10, pg/g)
1 / Eco popcorn / Unprepared / 3.7 / 0.39
Prepared / 7.3 / 0.34 / 3.6 / 1.5
2 / Popcorn original / Unprepared / 1.4 / 0.24
Prepared / 13.0 / 0.22
3 / Popcorn extra butter / Unprepared / 2.1 / 0.62
Prepared / 5.3 / 0.08
4 / Thai food / Unprepared / 1.5 / 0.48
Prepared / 1.5 / 0.43
5 / Gorbys pirogue / Unprepared / 2.5 / 0.14
Prepared / 0.9 / 0.24
6 / Grandiosa pizza / Unprepared / 3.8 / 0.13 / 1.9 / 0.19
Prepared / 4.9 / 0.75
7 / Billy’s pan pizza / Unprepared / 3.6 / 0.28 / 2.2 / 0.53
Prepared / 1.9 / 0.29
8 / Apple pie / Unprepared / 1.8 / 0.18
Prepared / 3.0 / 0.28
9 / Oatmeal
10 / Potato chips / 6.4 / 0.18 / 3.6 / 0.59
11 / Muffin / 2.6 / 0.23
12 / QP burger / 2.1 / 0.14 / 1.0 / 0.23
13 / Cheese burger / 5.7 / 0.04 / 2.7 / 0.17
14 / Fries / 2.2 / 0.14

Table S4 Recoveries (including matrix effects)aof 13C-labeled mono- and diPAPs and M8PFOA in food analysis

Sample # / Food sample / % Recovery (n=1)
13C-6:2 / 13C-8:2 / 13C-6:2/6:2 / 13C-8:2/8:2 / M8PFOA
1 / Eco popcorn / Unprepared / 22 / 25 / 305 / 55 / 66
Prepared / 34 / 33 / 248 / 102 / 32
2 / Popcorn original / Unprepared / 0.8 / 0.8 / 133 / 16 / 67
Prepared / 1.7 / 1.6 / 199 / 22 / 53
3 / Popcorn extra butter / Unprepared / 0 / 0 / 79 / 14 / 61
Prepared / 0.3 / 0.5 / 204 / 19 / 91
4 / Thai food / Unprepared / 45 / 44 / 169 / 27 / 68
Prepared / 50 / 39 / 164 / 33 / 39
5 / Gorbys pirogue / Unprepared / 42 / 41 / 271 / 60 / 56
Prepared / 34 / 26 / 140 / 39 / 29
6 / Grandiosa pizza / Unprepared / 35 / 34 / 234 / 86 / 55
Prepared / 25 / 18 / 52 / 30 / 27
7 / Billy’s pan pizza / Unprepared / 41 / 35 / 263 / 54 / 80
Prepared / 23 / 12 / 72 / 35 / 10
8 / Apple pie / Unprepared / 41 / 39 / 140 / 32 / 66
Prepared / 30 / 19 / 39 / 28 / 55
9 / Oatmeal / 48 / 34 / 23 / 8 / 44
10 / Potato chips / 33 / 39 / 230 / 121 / 26
11 / Muffin / 12 / 9 / 143 / 26 / 39
12 / QP burger / 27 / 23 / 236 / 96 / 47
13 / Cheese burger / 22 / 14 / 175 / 87 / 73
14 / Fries / 23 / 15 / 151 / 32 / 28

a% Recovery = (peak area spiked pre-extraction) * 100/(peak area spiked solvent)

Table S5Relative abundance of detectable mono-, di-, and triPAPs in food packaging materials (based on peak area compared to 6:2/6:2 diPAP)a

Sample #b / monoPAP / diPAP / triPAP
6:2 / 8:2 / 10:2 / 6:2/6:2 / 6:2/8:2 / 8:2/8:2 / 6:2/10:2 / 8:2/10:2 / 6:2/12:2 / 10:2/10:2 / 6:2/14:2 / 10:2/12:2 / 6:2/6:2/6:2 / 6:2/6:2/8:2 / 6:2/8:2/8:2 / 8:2/8:2/8:2
8:2/12:2 / 8:2/14:2 / 6:2/6:2/10:2 / 6:2/8:2/10:2
6:2/6:2/12:2
Zonyl®-RP / 25 / 21 / 12 / 100 / 134 / 43 / 49 / 39 / 20 / 28 / 10 / 16 / 2 / 5 / 5 / 4
1 / 0.05 / 0.04 / 0.01 / 100 / 59 / 10 / 14 / 9 / 5 / 5 / 2 / 2 / 1 / 1 / 0.8 / 0.6
2 / 100 / 38 / 8 / 9 / 9
3 / 100 / 23 / 6 / 5 / 4 / 2
4 / 100 / 12 / 10 / 4 / 7 / 0.9 / 3 / 0.5 / 9
5 / 0.4 / 0.2 / 100 / 46 / 6 / 3 / 2 / 0.3
6 / 2 / 100 / 195 / 14 / 13 / 5 / 1
7 / 0.5 / 100 / 64 / 6 / 4 / 2
8 / 3 / 100 / 30 / 38 / 11 / 22 / 3 / 15 / 1
9 / 7 / 100 / 70 / 25 / 17 / 26 / 5 / 10
10 / 136 / 100 / 29
11 / 100 / 35 / 15 / 17 / 8 / 2 / 4
12 / 100 / 120 / 26 / 32 / 23 / 11 / 14 / 3 / 6
13 / 100 / 12 / 9
14 / 100 / 92 / 12 / 16 / 9 / 4 / 5 / 1 / 2 / 0.6 / 0.6

aNo matrix effect or recovery corrections were made

b See Table 1 for identification of food samples

Table S6Relative abundance of detectable diPAPs in food samples(based on peak area compared to 6:2/6:2 diPAP)a

Food sample / 6:2/6:2 / 6:2/8:2 / 8:2/8:2 / 6:2/10:2 / 8:2/10:2 / 6:2/12:2 / 10:2/10:2 / 6:2/14:2
8:2/12:2
1 / Eco popcorn / Unprepared / 100 / 18
Prepared / 100 / 103 / 12 / 18 / 21 / 5 / 11 / 3
2 / Popcorn original / Unprepared / 100 / 21
Prepared / 100 / 30
3 / Popcorn extra butter / Unprepared / 100 / 22
Prepared / 100 / 27
4 / Thai food / Unprepared / 100 / 29
Prepared / 100 / 28
5 / Gorbys pirogue / Unprepared / 100 / 69
Prepared / 100
6 / Grandiosa pizza / Unprepared / 100 / 94 / 11 / 16 / 17
Prepared / 100 / 99
7 / Billy’s pan pizza / Unprepared / 100 / 64 / 8 / 7
Prepared / 100 / 72
8 / Apple pie / Unprepared / 100 / 30
Prepared / 100 / 172
9 / Oatmealb
10 / Potato chips / 100 / 103 / 19 / 15 / 13 / 8 / 14 / 3
11 / Muffin / 100 / 22
12 / QP burger / 100 / 52 / 12 / 8
13 / Cheese burger / 100 / 50 / 15 / 7
14 / Fries / 100 / 42

aNo matrix effect or recovery corrections were made

b No PAPs were detected in the oatmeal food sample

Table S7Detection of PFCAs in food packaging materialsa

Sample #b / PFHxA / PFHpA / PFOA / PFNA / PFDA / PFUnDA / PFDoDA / PFTrDA / PFTeDA / PFPeDA
1 / X / X / X / X / X / X / X / X / X / X
2 / X / X / X / X / X / X / X / X / X
3 / X / X / X / X / X / X / X / X
4 / X / X
5
6 / X
7
8 / X
9 / X / X / X
10 / X
11 / X
12 / X / X / X / X / X
13 / X
14 / X / X / X / X

aPFBA andPFPeA were not detected in any sample

b See Table 1 foridentification of foodpackaging material

Figure S1 Chemical structures of 6:2 monoPAP, 6:2/6:2 diPAP, and 6:2/6:2/6:2 triPAP

Figure S2 MRM chromatograms of multiple product ions for coeluting 10:2/10:2, 8:2/12:2, and 6:2/14:2 diPAPs in a Zonyl®-RP solution

Figure S3MRM chromatograms of detected diPAPs in ECO popcorn (food sample 1, prepared)

Figure S4Potential sources of PAPs and PFCAs in food samples