► Aim

► Compliance
Tools
Development, verification
and validation of migration
► Migration
Model model for foods.
► Fundamental
Constants
► Migration Closing Conference, Foodmigrosure Project,
translation tool 27-28 September 2006
R. Brandsch, FABES Forschungs-GmbH, Munich
► Validation
► Outlook
1
Aim

Work package 5

► to establish on the basis of the

experimental data set (from work
package 3) an advanced migration
model for the migration of low
molecular weight components from
plastic materials into foodstuff
→ by adapting the validated diffusion
model that exists for food simulants.

2
Compliance tools
FCM 1982 (82/711/EEC)
1985 (85/572/EEC)
► experimental testing under
conventional test conditions
(time/temperature & simulants)
1997 (97/48/EEC)
► substitute fat tests
(ethanol 95%, iso-octane & Tenax)
2001 (6. Amendment to 90/128/EC)
► migration modelling for plastics in
- overall migration contact with food simulants
- specific migration
(authorized substances (diffusion models based on scientific
from positive lists) evidence)
3
Compliance tools
FCM 2004 (EC 1935/2004)
► declaration of compliance (record-
keeping of supporting documents)
future (Active & Intelligent Packaging)
► authorisation granted to the applicant
(authorisation limited to application)
future (4. Amendment to 2002/72/EC)
- overall migration ► functional barrier concept
- specific migration
(authorized substances
(maximum migration level of 0.01
from positive lists) mg/kg food for "permitted substances")
(permitted substances
migration below
0.01 mg/kg food)

4
Compliance tools
FCM future (4. Amendment to 2002/72/EC)
► fat consumption reduction factor, FRF
(fatty foods and lipophilic substances)
future (4. Amendment to 2002/72/EC)
► ethanol 50% - new food simulant
(for milk and milk products)
future
► migration modeling for plastics in
- overall migration
- specific migration contact with food
(authorized substances
from positive lists) future
(permitted substances
migration below
► migration modeling for multilayer
0.01 mg/kg food) materials in contact with food
5
Compliance tools
FCM future
► estimation of consumer exposure
from food contact materials

⎡ kg ⎤ ⎡ mg ⎤
⎡ ⎤
∑ Food ⎢ day ⎥ ⋅ SM ⎢ kg ⎥
Exp ⎢
mg
= ⎣ ⎦ ⎣ ⎦
⎥
⎣ kg (bw) ⋅ day ⎦ body weight [kg ]

● specific migration (SM) is one of the

key inputs
⇒ to be estimated by modeling into
foods
6
Migration Model
Steps to carry out a simulation:
► Define your objective and measures
of performance
► Develop the conceptual model
► Create the mathematical model
► Quantify the input parameters
► Implement and solve the
mathematical model using a
computational tool
► Evaluate, explain and present the
results

7
Migration Model
Objective and
measures of
performance ● objective (question to be answered):
- estimation of specific migration from
plastic food contact materials into food.
● measure of performance
(model output):
- specific migration from plastic food
contact materials in food.

8
Migration Model
Develop the
conceptual model
● conceptual model (current
Migrant understanding of the system):
- representation of significant features,
DP DF events and processes.
⇒ - initial content of migrant
- volume and contact area
- time and temperature
KP,F
- diffusion process
- partitioning
- boundary conditions

plastic food

9
Migration Model
Create the
● mathematical model (represents the
mathematical
system quantitatively):
model
- set of input assumptions, equations
and algorithms describing the system.

Diffusion equation (Fick's 2nd law):

∂c ∂ c 2
=D
D⋅ 2
∂t ∂x c - concentration
t - time
x - space
D - diffusion coefficient

10
Migration Model
Create the Set of input assumptions:
mathematical
model
polymeric material
- homogenous on macroscopic scale
migrant
- homogenously distributed in polymer
interface
- no boundary resistance
interaction
- no swelling of polymer
reaction
- no loss of migrant
diffusion coefficient
- remains constant over time

11
Migration Model
Quantify the input
● input parameters
parameters
- to be quantified by specifying their
values.
Diffusion
coefficient, DP: − EA
DDP = D0 ⋅ e RT
D - diffusion coefficient [cm²/s]
Partition
D0 - pre-exponential factor coefficient, KP,F:
EA - activation energy [J] c P ,∞
P,F =
R - gas constant [8,314 J/molK]
T - temperature [K]
KP,F
c F ,∞
K - partition coefficient
c - concentration [mg/kg]

12
Migration Model
Implement & solve
● solve the mathematical model:
the mathematical
- use a computational tool capable of
model
solving the equations representing the
system.
Discretisation of space:

cin +1 − cin ⎡ cin−+11 − 2cin +1 + cin++11 cin−1 − 2cin + cin+1 ⎤

= D ⎢θ + (1 − θ ) ⎥
δt ⎣ (δx ) 2
(δx)2 ⎦
ci-1 ci ci+1

Numerical algorithm
xi-1 xi xi+1
layer
layer 1 layer 3
2
Discretisation of time:
∂ 2 ci ε ci −1 − (1 + ε )ci + ci +1
≈
∂x 2
(δ x2 )2

13
Migration Model
Evaluate, explain ● results:
and represent the - migration of substances from plastic
results food contact materials into food under
any conditions of use

14
Migration Model
Diffusion model
used for migration

D/K/.../D
modeling

D/K - polymer/simulant
D/K/D - polymer/food
D/K/D/K - polymer1/polymer2/simulant
D/K/D/K/D - polymer1/polymer2/food
D/D - polymer1/polymer1

15
Fundamental constants
Evaluation of ● fitting of experimental data points with
experimental data calculated migration curves under variation of
the partition coefficients between polyolefine
and food and diffusion coefficient in food.

time dependent kinetic

migration experiments

16
Fundamental constants
Evaluation of ● fitting of experimental data points with
experimental data calculated migration curves under variation of
the partition coefficients between polyolefine
and food and diffusion coefficient in food.

concentration profiles

17
Fundamental constants
Evaluation of
experimental data
(Gouda cheese)

Time dependent kinetic

migration experiments
Concentration profiles

18
Fundamental constants
Partition coefficients
(Gouda cheese)

c P ,∞
K P,F =
c F ,∞
19
Fundamental constants
Diffusion coefficients
(Gouda cheese)

− EA
D = D0 ⋅ e RT

20
Fundamental constants
Food groups ► food groups based on migrant uptake
properties (partitioning):
● Liquid foods
● Processed fruits and vegetables
● Dry foods
● Milk products
● Meat products
● Cheese products
● Margarine/Mayonnaise
● Chocolate products
● special cases (e.g. honey, etc.)
21
Fundamental constants
"Upper-level" ► "upper level" partition coefficients between
partition coefficients polyolefines and cheese products in
(cheese products) dependence of the octanol/water partition
coefficients log KO/W (polarity of migrants):

22
Fundamental constants
"Upper-level" ► "upper limit" diffusion coefficients DP* through
diffusion coefficients "upper limit" food specific constants, AF* in
(cheese products) cheese products:

− EA
D = D0 ⋅ e RT

D0 = e AF
— „Upper-Level“
EA Safety Limit:
Average EA =

AF = ln D + AF = -1,8 30 kJ/mol

RT
23
Migration translation tool
Migration translation tool:

DP/KP,F (simulants)
DP/KP,F/DF (food)
⇒ translation of migration data with
food simulants under conventional
test conditions, e.g. 10 days at 40°C
into food migration values under
real conditions of use, e.g. 180 days
at 5°C.

24
Migration translation tool

case A: Initial concentration of migrant in FCM cP,0 and diffusion coefficient of migrant
in FCM DP and partition coefficient between FCM and food simulant KP,S is
known
⇒ substitute KP,S with KP,F and calculate migration into food with MMF
case B: one of cP,0, DP, KP,S unknown
⇒ derive unknown value from migration data with food simulant by applying
MMS
⇒ substitute KP,S with KP,F and calculate migration into food with MMF
case C: two of cP,0, DP, KP,S unknown
⇒ make reasonable assumptions concerning one of the unknown values
⇒ derive second unknown value from migration data with food simulant by
applying MMS
⇒ substitute KP,S with KP,F and calculate migration into food by MMF

25
Migration translation tool - case A
Example
(PA6/Caprolactam) DP=7,075 e-10 (AP=8,2);
KP,S=45
2,5

2,0

migration [mg/dm²] 1,5

exp.
calc.
1,0

0,5

0,0
food simulant: 0 20 40 60 80 100 120
(well mixed liquid) time (hours)

water
26
Migration translation tool - case A
Example
(PA6/Caprolactam) DP=7,075 e-10 (AP=8,2); KP,F=160
DF=1,2 e-5
2,5

2,0

migration [mg/dm²] 1,5

exp.
calc.
1,0

0,5

0,0
food: 0 1 2 3 4 5
(semi-solid) time (d)

apple sauce
27
Migration translation tool - case A
Example
(PA6/Caprolactam) Comparison between well mixed and
semi-solid food (apple sauce)

2,5

2,0

migration [mg/dm²] 1,5

exp.
calc.N
1,0 calc.

0,5

0,0
0 1 2 3 4 5
food: time (d)

apple sauce
28
Migration translation tool - case C
Example
(LDPE/Triclosan)

29
Migration translation tool - case C
Example
(LDPE/Triclosan)

food simulant:
(well mixed liquid)
HB 307
30
Migration translation tool - case C
Example
(LDPE/Triclosan)
migration soluble in HB 307
KP,F = 1 - known
(reasonable assumption)

DP

food simulant:
(well mixed liquid)
HB 307
31
Migration translation tool - case C

Apply MMS:
initial concentration
1100 mg/kg
thickness
2400 µm
density (HDPE)
0,95 g/cm³
area
0,954 dm²
volume
100 ml
density (HAc 3%)
1 g/cm³ DP = 4,8 e-10 / K = 1
32
Migration translation tool - case C
HDPE AP‘-values from statistical evaluation
40
number of values: 134
35 mean value MWAP = 11,29 AP‘* = 14,5
standard deviation STABW = 1,76
30
confidence interval (95%) 7,85 - 14,74
25 ( = MW ± 1,96*STABW)

20

15

10

0
4 5 6 7 8 9 10 11 12 13 14 15 16

AP'-value
mean value
for exposure
assessment !
DP = 1,1 e-10
33
Migration translation tool - case C

Apply MMF:
DP = 1,8 e-8 / KP,F = 3,6
initial concentration
1100 mg/kg Calculation of Triclosan migration after
thickness 150 days at 5°C into gouda cheese by
2400 µm use of MMF:

density (HDPE) mF,t = 0,8 mg/dm²

0,95 g/cm³
area According to directive 85/572/EEC:
0,954 dm² Reduction factor for HP307 migration
at 40°C: X = 3
volume
100 ml
mF,t = 2,37 mg/dm² : 3 =
density (gouda cheese) 0,79 mg/dm²
1 g/cm³
34
Validation
"Upper-level"
diffusion- and Diffusion model for plastic materials
partition coefficients in contact with food:

DP*/KP,F*/DF*
⇒ overestimation of migration for
compliance purpose under real
conditions of use

35
Validation
Probability
distributions of Exposure estimation for plastic
diffusion- and materials in contact with food:
partition coefficients

DP/KP,F/DF
⇒ probabilistic estimation of
migration for exposure estimation
purpose

36
Conclusions & Outlook
40

35

30
AP‘* = 14,5
► Diffusion properties of plastics
(DP based on AP and molecular mass)
25

20

15

10

0
4 5 6 7 8 9 10 11 12 13 14 15 16
► Food groups according to partitioning
(KP,F based on log KO/W)
AP'-value

► Diffusion like behavior in food

(DF based on AF)
► Migration modeling in food
(upper limit values, DP*/KP,F*/DF*)
► Migration translation tool
(best values DP/KP,S + DP/KP,F/DF)
► Exposure Estimation
(probabilistic values - DP/KP,F/DF)

37