3rd International Workshop Anthropogenic Perfluorinated Compounds, 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
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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
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.
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
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.