Migration of Migration of PerfluorochemicalsPerfluorochemicals
From Food Contact MaterialsFrom Food Contact Materials
Tim Begley
Office of Regulatory ScienceCenter for Food Safety and Applied Nutrition
Food and Drug Administration
Why are we interested in Why are we interested in perfluoroperfluoro chemical chemical
migration?migration?
• Perfluoro chemicals found in human serum (Olsen et al. 1999) . Occupational exposure.
• May 2000, 3M Company announce phase out of perfluorooctyl chemistry.
• August 2002, marine mammals, fishes and birds (Kannan et al. Environ. Sci. Technol.)
• Elderly in Seatle WA are found to have perfluorochemicals in their serum (Olsen et al. 2003) .
Why are we interested in Why are we interested in perfluoroperfluoro
chemical migration?chemical migration?
• PFOA is biopersistent / bioaccumulative
• Half-life in human serum may be 4.4 years (Butenhoff et al. 2004).
• Potential concerns for carcinogenesis; developmental/reproductive and immunotoxic.
• Many fluorochemicals regulated for food-contact contain PFOA as an impurity and/or have chemical moieties similar to PFOA.
22--perfluorooctylethanol or (8:2 telomer alcohol) has perfluorooctylethanol or (8:2 telomer alcohol) has
been shown to biodegrade to PFOAbeen shown to biodegrade to PFOA
DinglasanDinglasan, M.J.A., et al., 2004, Environmental Science and Technology, 38, M.J.A., et al., 2004, Environmental Science and Technology, 38, 2857, 2857--2864.2864.
PerfluorooctanoicPerfluorooctanoic acid = PFOAacid = PFOA
Structures of Structures of perfluorochemicalsperfluorochemicals
found in human serumfound in human serum
O
HO
FF
FF
FF
FF
FF
FF
F
FF
C
FF
F F
F F
F F
F F
F F
FF
F
F
F
S
O
O
-O
••PerfluorooctanoicPerfluorooctanoic acid = PFOAacid = PFOA
••PerfluoroocatanesulfonatePerfluoroocatanesulfonate = PFOS= PFOS
Typical Commercial Products Potentially Made Typical Commercial Products Potentially Made
with with FluorochemicalsFluorochemicals
Food package types that contain Food package types that contain
fluorochemicalsfluorochemicals
PolymersPolymers
PaperPapermicrowave popcornmicrowave popcorn
muffin bagsmuffin bags
frenchfrench fry bagsfry bags
pizza linerspizza liners
sandwich wrapperssandwich wrappers
burger/pizza boxesburger/pizza boxes
cookwarecookware
tubingtubing
gasketsgaskets
Historical Regulation in the USAHistorical Regulation in the USA
•• 1962 1962 PTFE for cookwarePTFE for cookware
•• 19841984 perfluorochemicalperfluorochemical elastomerselastomers
•• 19581958 paper coatings (priorpaper coatings (prior--sanctioned)sanctioned)
•• 19621962 11stst paper coatings (petition)paper coatings (petition)
Where are Where are perfluorochemicalsperfluorochemicals for for
paper regulated?paper regulated?
•• In US approximately 15 materials are In US approximately 15 materials are regulatedregulated
•• BfR also has a number of BfR also has a number of perfluoroperfluorochemicals regulatedchemicals regulated
Types of Types of perfluorochemicalsperfluorochemicals
added to food contact paperadded to food contact paper
•• PerfluoroPerfluoro telomer type telomer type
CC66 CC88 CC1010 CC1212 CC1414 basedbased
•• Polymeric typePolymeric type
Typical structures of Typical structures of perfluoroperfluoro telomer based telomer based
paper coatingspaper coatings
NH4+
POO
O
-OS
O
O N
F
FF
F F
FF
F
F
F
F
F
F
FF
FF
SOO
N
F
F
F
F
F
F
F
F
F
F
F
F
F
FF
F F
S
S
F
FF
HF
FF
F
F
FF
FF
F
FF
F
FF
F
F
F
FF
F F
F
F
F
FF
FF
F
O
O
OO
P
NH4+
F
FF
F
FF
F
F
F
FF
F
F
F
F
F
F
FFF
F F
F
F
F
F
F
F
F
F
F
F
F F
O
P
O
O
O
H2N
OH
OH
m/zm/z = 889= 889
m/zm/z 12021202
m/zm/z =1021=1021
Analysis of PTFE Cookware for PFOAAnalysis of PTFE Cookware for PFOA
Summary of PFOA analysis of some Summary of PFOA analysis of some
polymerspolymers
NDNDFEP TubingFEP Tubing
18001800PTFE Sealant TapePTFE Sealant Tape
44Dental TapeDental Tape
33Dental FlossDental Floss
44--7575PTFE CookwarePTFE Cookware
Conc. PFOAConc. PFOA µµg/kgg/kgMaterialMaterial
Does PFOA migrate from PTFE Does PFOA migrate from PTFE
during cooking?during cooking?
•• Use PTFE sealant film for migration test.Use PTFE sealant film for migration test.
•• PTFE film has CPTFE film has Cp0p0 = 1.8 mg/kg= 1.8 mg/kg
•• Test for migration at 100Test for migration at 100°°C and 175C and 175°°C C
into water and oil.into water and oil.
Typical LCMS analysis for PFOA Typical LCMS analysis for PFOA
migrating from PTFE into Miglyol at migrating from PTFE into Miglyol at
100100°°CC
400
600
800
1000
1200
1400
0 2 4 6 8
Time (min)
Rela
tive S
IM Inte
nsity
PFOA
Migration of PFOA from PTFE sealant Migration of PFOA from PTFE sealant
film after 2hrs at cooking temperaturesfilm after 2hrs at cooking temperatures
Mt (PFOA)
100°C Water 150 ng/dm2 ( 1.6 ±±±± 0.4µg/kg)
Miglyol 120 ng/dm2 (1.3 ±±±±.07 µg/kg)
175°C Miglyol 710 ng/dm2 (7.7±±±± 0.1 µg/kg)
Fractional PFOA Migration from PTFEFractional PFOA Migration from PTFE
•• Fractional Migration Fractional Migration oiloil at 175at 175°°C MC Mtt/M/M∞∞= 17%= 17%
•• Fractional Migration Fractional Migration waterwater at 100at 100°°C MC Mtt/M/M∞∞= 4%= 4%
Simulated Loss of PFOA from Cookware based on
Fractional Migration, Potential Values
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0 10 20 30 40
Number of uses
ng
/cm
2 i
n p
oly
me
r
0
0.02
0.04
0.06
0.08
0.1
0.12
ng
/g i
nto
Fo
od
Water
Oil
CP0 = 75 ng/g
Simulated Loss of PFOA from Cookware based on
Fractional Migration, Potential Values
0
0.05
0.1
0.15
0.2
0.25
0.3
0 10 20 30 40
Number of uses
ng
/cm
2 in
po
lym
er
Sinclair et al., Environ. Sci. Tech. 2007
at 179° - 233°C
Does PTFE Degrade to PFOA at High Temperature?Does PTFE Degrade to PFOA at High Temperature?
•• FDA, No detectable increase in PFOA in PTFEFDA, No detectable increase in PFOA in PTFE
•• Sinclair et al., Environ. Sinclair et al., Environ. SciSci. Tech. 2007, No . Tech. 2007, No
PFOAPFOA
Temperature Respnse for Heating an Empty 28cm
PTFE Coated Pan with a Flame
0
50
100
150
200
250
300
350
0 50 100 150 200 250 300 350
Time (seconds)
Tem
pera
ture
°C
32
132
232
332
432
532
632
Tem
pera
ture
°F
Smoke point for oils
FluorochemicalsFluorochemicals for Food Contact Paperfor Food Contact Paper
Fluorochemical Paper coatingsFluorochemical Paper coatings
•• Fluorochemical paper concentrations can Fluorochemical paper concentrations can be up to 0.5% or 5000 mg/kg.be up to 0.5% or 5000 mg/kg.
•• Temperature range for paper applications Temperature range for paper applications --55°°C C –– 200+200+°°C. C.
•• Most Most perfluoroperfluoro telomertelomer based paper based paper treatments have treatments have molecular weights >1000molecular weights >1000but the but the molecular sizemolecular size is similar to much is similar to much smaller molecules.smaller molecules.
F versus H
MW = 1121 MW = 510
Migration of chemicals with MW > 1000 ?Migration of chemicals with MW > 1000 ?
MW = 1121
Molecular Area = 558Ǻ2
MW = 510
Molecular Area = 541Ǻ2
Molecular Volume = 609Ǻ3 Molecular Volume = 530Ǻ3
C71H141 MW = 997 Molecular Volume = 1225Ǻ3
FF HH
Is PFOA in Is PFOA in PerfluorochemicalPerfluorochemical Paper Paper
Coatings and treated Paper Products?Coatings and treated Paper Products?
Concentration of PFOA in Concentration of PFOA in PerfluoroPerfluoro Paper Paper
Coatings and Paper ProductsCoatings and Paper Products
88 88 -- 160160PerfluoroPerfluoro paper coating paper coating
(not applied)(not applied)
0.90.9Hash brown potato bagHash brown potato bag
0.5 0.5 –– 1.21.2Sub Sandwich wrapperSub Sandwich wrapper
0.50.5Muffin bagMuffin bag
0.30.3Popcorn bagsPopcorn bags
CCp0p0 PFOA (mg/kg)PFOA (mg/kg)MaterialMaterial
Migration of PFOA from microwave Migration of PFOA from microwave
popcorn bags?popcorn bags?
Temperature of oil from microwave susceptor
heating
0
50
100
150
200
250
0 0.5 1 1.5 2 2.5 3 3.5
Time (min)
Te
mp
era
ture
°C
Migration of PFOA from Migration of PFOA from
microwave popcorn bags?microwave popcorn bags?
NoneNone detected into oildetected into oil
T. H. Begley, et al., 2005, T. H. Begley, et al., 2005, PerfluorochemicalsPerfluorochemicals: Potential sources of : Potential sources of and migration from food packaging. and migration from food packaging. Food Food
Additives and Additives and ContaminatsContaminats, 22 (10) 1023, 22 (10) 1023--1031.1031.
Test for Test for perfluorochemicalperfluorochemical
migration from commercially migration from commercially
produced paperproduced paper
Typical structures of Typical structures of PerfluoroPerfluoro telomer based telomer based
paper coatingspaper coatings
NH4+
POO
O
-OS
O
O N
F
FF
F F
FF
F
F
F
F
F
F
FF
FF
SOO
N
F
F
F
F
F
F
F
F
F
F
F
F
F
FF
F F
S
S
F
FF
HF
FF
F
F
FF
FF
F
FF
F
FF
F
F
F
FF
F F
F
F
F
FF
FF
F
O
O
OO
P
NH4+
F
FF
F
FF
F
F
F
FF
F
F
F
F
F
F
FFF
F F
F
F
F
F
F
F
F
F
F
F
F F
O
P
O
O
O
H2N
OH
OH
AABB
CC
Test conditions for Test conditions for
perfluorochemicalperfluorochemical migrationmigration
•• Food simulating liquids/foods at 100Food simulating liquids/foods at 100°°CC
•• SingleSingle--sided contact with paper sided contact with paper
•• Contact time 15 minutes Contact time 15 minutes
•• LCMS analysis for LCMS analysis for perfluorochemicalperfluorochemical
Typical structures of Typical structures of PerfluoroPerfluoro telomer telomer
based paper coatingsbased paper coatings
NH4+
POO
O
-OS
O
O N
F
FF
F F
FF
F
F
F
F
F
F
FF
FF
SOO
N
F
F
F
F
F
F
F
F
F
F
F
F
F
FF
F F
S
S
F
FF
HF
FF
F
F
FF
FF
F
FF
F
FF
F
F
F
FF
F F
F
F
F
FF
FF
F
O
O
OO
P
NH4+
F
FF
F
FF
F
F
F
FF
F
F
F
F
F
F
FFF
F F
F
F
F
F
F
F
F
F
F
F
F F
O
P
O
O
O
H2N
OH
OH
AABB
CC
Migration results for incidental contact, Migration results for incidental contact,
Coating Coating AA
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
Re
lati
ve
Mig
rati
on
(m
g/k
g)
Wat
erVin
egar
10%
EtO
H20
% E
tOH
25%
EtO
H30
% E
tOH
Butte
r
Oil
Migration results for incidental contact, Migration results for incidental contact,
Coating Coating BB
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Re
lati
ve
mig
rati
on
(m
g/k
g)
Wate
rVin
egar10%
EtO
H20%
EtO
H25%
EtO
H30%
EtO
H
Butte
r
Oil
Migration results for incidental contact, Migration results for incidental contact,
Coating Coating CC, paper produce in 1987, paper produce in 1987
0.000
0.100
0.200
0.300
0.400
0.500
0.600
0.700
0.800R
ela
tiv
e M
igra
tio
n
(mg
/kg
)
Wate
r
Vinegar
10% E
tOH
25% E
tOH
Butt
er
Oil
Potential Problem for Potential Problem for
Exposure Estimates?Exposure Estimates?
Water and oil are not the extremes!Water and oil are not the extremes!
Typical Migration Results From a PolymerTypical Migration Results From a Polymer
Migration of Irganox 1076 from PP at 135Migration of Irganox 1076 from PP at 135°°CC
0
500
1000
1500
2000
2500
3000
3500
4000
4500
µg
/dm
2
Wat
er
Gra
vy (n
o fat)
Bak
e bea
n
Bab
y Food (b
anan
a)
Corn
ed B
eef H
ash
Gra
y (1
0%fa
t)
Chic
ken S
oup
Chic
ken B
roth
Bab
y Food (t
urkey
)B
eef S
tew
Corn
Oil
Migration into EmulsionsMigration into Emulsions
•• Butter = waterButter = water--inin--oil Emulsion (20% / 80%)oil Emulsion (20% / 80%)
•• NonNon--ionic surfactant (ionic surfactant (polyoxyethylenepolyoxyethylenesorbitansorbitan / oil / water)/ oil / water)
•• Ionic surfactant (lecithin / oil / water)Ionic surfactant (lecithin / oil / water)
Migration from paper, 40Migration from paper, 40°°C 1 dayC 1 day
0
0.2
0.4
0.6
0.8
1
1.2
Mig
rati
on
µg
/cm
2
Butter
Chocolate spread
Emulsion -nonionic
Emulsion -ionic
Oil
Oil + ionic (soy)
Oil + nonionic
Migration of Fluorochemical is Migration of Fluorochemical is
Kinetic to food at 40Kinetic to food at 40°°CC
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
Mig
rati
on
µg
/cm
2
Chocolate
1 day
Chocolate
10 day
Butter
40 day, 4°C
Do Do PerfluoroPerfluoro telomer Paper Coatings telomer Paper Coatings
Migrate Under Actual Conditions of Migrate Under Actual Conditions of
Use?Use?
Migration from microwave Migration from microwave
susceptorsusceptor into oilinto oil
Results for migration of fluorotelomer Results for migration of fluorotelomer
from popcorn bagsfrom popcorn bags
2.1 mg/kg 2.1 mg/kg
77µµg/ dmg/ dm22
Concentration in Concentration in
Miglyol Miglyol afterafter 2 min. 2 min.
microwave heating microwave heating
1.4 mg/kg 1.4 mg/kg
4 4 µµg/ dmg/ dm22
Concentration in Concentration in
Popcorn Oil Popcorn Oil beforebefore
HeatingHeating
LCMS analysis of LCMS analysis of PopcornPopcorn for the Migration of for the Migration of
Fluorotelomer from Popcorn bagFluorotelomer from Popcorn bag
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
0 1 2 3 4 5 6 7 8 9 10
Time (min)
LC
MS
Re
sp
on
se
Fat Free Popcorn Control Popcorn
m/z = 921 --
m/z = 1021 --
-- m/z = 1121
Migration of Migration of perfluorotelomerperfluorotelomer into into
microwave popcornmicrowave popcorn
mg/kgmg/kgBrandBrand
2.12.1EE
1.21.2DD
3.83.8CC
0.80.8BB
1.21.2AA
Conclusions of Migration TestsConclusions of Migration Tests
•• The food The food simulantssimulants waterwater and and oiloil are not are not the extremes for these the extremes for these fluorochemicalsfluorochemicals..
•• The soy emulsifier (lecithin, 0.05%) can The soy emulsifier (lecithin, 0.05%) can change oil into a potent solvent for change oil into a potent solvent for migration.migration.
•• Fluorotelomers do migrate to food in the Fluorotelomers do migrate to food in the mg/kg (mg/kg (ppmppm) range.) range.
S
S
F
FF
FF
FF
F
F
FF
FFF
F
FF
FF
F
FF
FF
FFF
FF
F
F F
F
F
O
O
OHO
P
Migration to oil = noneMigration to oil = none
Migration to oil + emulsifier = hugeMigration to oil + emulsifier = huge
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