3rd International Workshop Anthropogenic PerfluorinatedCompounds, June 15.-17. 2011

Migration of poly- and perfluorinated compounds from food contact materials

into food – Part I

Ludwig Gruber, Martin Schlummer, Romy Fengler

Fraunhofer Institute for Process Engineering and Packaging IVV, Freising, Germany

PERFOOD Progress Meeting 4, June 14.-15., 2011

Part ILudwig Gruber (Fraunhofer IVV): Migration of poly- and perfluorinated compounds from food contact materials into food* Screening for fluorinated compounds* Migration at ambient temperature* Migration at elevated temperature* Formation of FTOH from precursors

Part IIJutta Tentschert (BfR):Actual situation: Poly- and perfluorinated compounds for food contact materials

F-Screening methods for FCM

Surface spectrometry• Sliding spark spectrometry• WDXRF (new)• neg: EDXRF and FTIR

Volatile fluorinated Compounds• HS-GC-(EI)-MS• P&T-GC-EPED

Screening samples (n=123)

0

10

20

30

40

50

60

70

Pizza

Fast fo

od (fr

ench

fries

, burg

er)

Baking

pape

r

sand

wich pa

per

chee

se/sa

usag

e wrap

butte

r wrap

Card b

oard

(folde

d box

)

greas

eproo

f pap

er

noFCFC

Results of F-Screening

See:Fiedler et al.: Poster A05

18 19

51

177 10 12

39

15150

13

21

311

6 4

6

1

23

1 3

020406080

100120140160180

beve

rage

s

butt

er w

raps

card

boar

d pa

ckag

ing

chee

se w

raps

egg

pack

ages

fast

foo

d

filte

r m

atrix

inte

nded

for

bak

ing

pape

r pa

ckag

ing

popc

orn

bags

sand

wic

h pa

pers

saus

age

wra

ps

take

aw

ay fo

odpa

ckag

ing

amo

un

t o

f sa

mp

les

positive samples

negative samples

55%

6%

5%

19%

13%2%

GermanyThe NetherlandsBelgiumItalyNorwayGreek

Per- and polyfluorinatedcompounds in food contact material

See:Trier X, Granby K and Christensen J: Polyfluorinated surfactants (PFS) in paper and board coatings for food packaging. Environmental Science and Pollution Research: 1-13, 2011.

PFAS levels in food contact material

Fluorine containing coatings• e.g. PAPS• 0,2 % F (surface)• ~100 µg/dm²

Precursors• FTOH dominate• up to 10 µg/dm²• 8:2 dominating congener

PFCA• nn - 900ng/g• broad spectrum• No fixed ratio ofΣFTOH/ΣPFCA

0

10

20

30

40

50

60

70

80

PF-0

141

PF-0

029

PF-0

117

PF-0

064B

PF-0

143

PF-0

126

PF-0

133

PF-0

060

PF-0

054

PF-0

036

Samples

µg/g

10:2FTOH

8:2FTOH

6:2FTOH

What is migration ?

Packaging Food

Diffusion Partition Diffusion

Migration Cfood,t? ?

???

?Cp,t=0

Development of migration methods

T

t

Food / simulant

Refrigerator (16 tests)

- Long-term storage 1 – 30 days

- Low temperature (5°C)

- 3 food items, 4 simulants

Ambient conditions (8 tests)

- Medium-term storage 1 – 10 d

- Ambient temperature (20-40°C)

- 3 food items, 1 simulant

Fast-Food Restaurant (8 tests)

- Short-term storage up to 30 min

- Elevated temperature (60-80°C)

- 1 food items, 1 simulant

real / worst caseconditions

Oven (11 tests)

- Short-term heating 10 – 120 min

- High temperatures (180-250°C)

- 3 food items, 1 simulant

FTOH-Analysis of migration samples

Muffins were homogenized and sub samples of about 3g were fortified with isotope-labelled standards and extracted with n-hexane by pressurized liquid extraction (ASE 200, Dionex, Germany), applying Teflon®-free equipment.

Butter and Tenax samples were extracted with n-hexane by vortexing and ultrasonic bath after fortification with labeled standards. Afterwards, the extracts were cleaned by solid phase extraction using silica as adsorbent (PhenomenexStrata Si 1). Reduced extracts were subjected to GC/CI-MS analysis (TSQ 7000, Thermo) using methane for chemical ionisation.

Quantification was carried out by an isotope dilution method. Using the same analytical approach Tenax, both types of muffin dough and butter were analysedfor FTOH blanks.

FTOH-Migration at ambient temperature

0,0000 200,0000 400,0000 600,0000 800,0000 1000,0000 1200,0000 1400,0000 1600,0000 1800,0000

butter, 20°, 10d

butter, 30°, 1d

butter, 40°, 1d

butter, blank

Tenax, 20°, 10d

Tenax, 40°, 1d

Tenax, 40°, 10d

Tenax, blank

sandwich paper

ng/dm²

10:2 8:2 6:2

Ambient TFTOHButter > FTOHTenax

PFCA-Analysis of migration samples

Muffins, Butter and Tenax samples were extracted with methanol by using an ultrasonic bath after fortification with labeled standards.

Extracts were cleaned by solid phase extraction using a weak ion exchanger as adsorbent (Phenomenex Strata XAW) and analyzed with HPLC-ESI-MS (Waters Quattro LC).

Quantification was carried out by an isotope dilution method. Using the same analytical approach Tenax, both types of muffin dough and butter were analysedfor blanks.

PFOA-Migration at ambient temperature

Mid term meeting PERFOOD, June 7, 2011

0,607

0,848

1,6871,581

0,2630,144

0,614

0,0000,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

1,8

20 °C 10 d 20 °C 15 d 40 °C 10 d 40 °C 15 d

migration ng/dm²

blanks

migration conditions

Migration of PFOA from butter wrap into food simulant Tenax

• PFOA migrates into Tenax• Migration depends on time and temperature

• Blank levels are an issue to be solved

Migration conditions at elevated TT [°C] time

[min]food item/ simulant T [°C] time

[min]food item/ simulant

120 15 butter 200 10 muffindough 2

150 5 butter 200 20 muffindough 1

150 10 butter 200 20 muffindough 2

150 15 butter 200 30 muffindough 2

180 30 muffindough 2 220 20 muffin

dough 2

180 40 muffindough 1 220 60 TENAX®

180 40 muffindough 2

FTOH-Migration at elevated T

ng/dm²

 

0

200

400

600

800

Concentrat ion [n g/d m²] 

2.000

4.000

6.000

6:2 FT O H 8 :2 FTOH 10 :2 F T OHSubstance [ ‐] 

i nitia l va lu e muffin paper

m uffin 2 1 80 °C 3 0 min

m uffin 1 180 °C 4 0 min

m uffin 2 180 °C 4 0 min

m uffin 2 200 °C 1 0 min

m uffin 1 200 °C 2 0 minm uffin 2 200 °C 2 0 min

m uffin 2 200 °C 3 0 min

m uffin 2 220 °C 2 0 min

FTOH-Migration at elevated T

0

5 .0 0 0

1 0 .0 0 0

1 5 .0 0 0

5 0 .0 0 0

1 0 0 .0 0 0

C o n c e n tra tio n [n g /d m ²]

6 :2 F T O H 8 :2 F T O H 1 0 :2 F T O H

S u b sta n ce [ -]

i n i t ia l v a lu e m u ff in p a p e r

b u t te r 1 2 0 ° C 1 5 m in

b u t te r 1 5 0 ° C 5 m in

b u t te r 1 5 0 ° C 1 0 m in

b u t te r 1 5 0 ° C 1 5 m in

T e n a x 2 2 0 ° C 6 0 m in

ng/dm²

Daily Intake ?Simplified calculation example:

A migration/formation of10.000 ng/dm² ΣFTOH

equates to a daily Intake of 1.000 ng ΣFTOH / kg b.w.

Assumptions (Conventional approach):•EU cube (6 dm², 1 kg food)•Consumption of 1 kg food•60 kg bodyweight

Formation of FTOH from precursors

See: D'eon JC and Mabury SA: EnvironmentalHealth Perspectives 119: 344-350, 2011.

Migration at elevated T• Precursor transfer upon baking

• FTOH-Formation from precursorsin the food

• ppm levels• most likely hydrolysis

• Found Precursors now identified asdiPAPs. Work is ongoing.

Results after another heating

Mid term meeting PERFOOD, June 7, 2011

(2)

0

200

400

600

0

200

400

600

Concentration [ng/g]

6:2 8:2 10:2Substance [-]

(1)

0

4.000

8.000

12.000

16.000

20.000

C o n c e n t r a t i o n [ n g / g ]

6 : 2 8 : 2 10:2Substance [-] (4)

0

2

4

6

8

10

0

2

4

6

8

10(3)

0

2

4

6

8

10

Muffin paper Butter exposed to 150°C

Butter exposed to wrap at 5°C

White before, black afteranother 15 min@150°C

• Pure muffin paper (1)• Butter previously

in contact with muffin paper at 120 °C for 15 min (2)

• Pure butter 1, contaminated frombutter wrapper (3)

• Pure butter 2, from diPAP-freebutter wrapper (4)

Precursor migration into food

• No change in FTOH levels for butter and paper, treated separately with temperatures of 150°C

• Butter previously exposed to muffin papers exhibits significantly higher levels following a second heat exposure.

→Precursor compounds have migrated into the butter during the first heating process and delivers further FTOH by degradation during the second heating phase.

Summary• Butter and Tenax are appropriate food simulants

at ambient temperatures.• Butter, Tenax and also some doughs are

appropriate food simulants for elevated temperature.

• Migration experiments at elevated temperatures show formation of FTOH from precursors (diPAPs) orders of magnitude higher then initial FTOH values.

Acknowledgements:

This study was part of the EU project PERFOOD (KBBE 227525) and the financial support of the European Union is gratefully acknowledged.

Thank You for your attention !