Chair of Food Science and Food Contact Materials
Hydrocarbons from FCM as food contaminants:
Focus on polyolefins and hot-melt adhesives
Martin Lommatzsch
Barcelona, 16.11.2016
Outline
Chair of Food Science and Food Contact Materials
1. Mineral oil hydrocarbons
2. Polyolefin oligomers
Reference: seilnacht.com
3. Hot-melt adhesives
Reference: badische-zeitung.de
Reference: reka-klebetechnik.de
2
Mineral oil hydrocarbons
Mineral oils
Polyolefins
MOSH: Mineral oil saturated hydrocarbons
 Accumulation in human tissue
(1-10 g per person)
Hot-melt adhesives
MOAH: Mineral oil aromatic hydrocarbons
 Partially genotoxic
• Source: mostly printing inks
(recycled newspaper; printing on boxes)
• Migration into food via gas phase (5 – 50 mg/kg)
• Solutions: Functional barriers or virgin board
3
Mineral oil hydrocarbons
Mineral oils
Polyolefins
Hot-melt adhesives
Sources of MOSH and MOAH
4
Analysis of mineral oil
hydrocarbons
Mineral oils
Polyolefins
Hot-melt adhesives
 HPLC-GC-FID method for mineral oils according to Grob & Biedermann (2012)
Recycled cardboard:
MOSH fraction (Saturates)
MOAH fraction (Aromatics)
Human tissue:
5
Polyolefins
Mineral oils
Polyolefins
Hot-melt adhesives
Types of polyolefins:
Polyethylene (PE)
Packaging:
Polypropylene (PP)
LDPE, PP
LLDPE
HDPE
- Bags and films
- Sealing layer
- Bottles and cups
Production: - Flexible tubes
- Sealings
- Other plastic components
6
Fingerprints of polyolefins
MOSH fraction
Mineral oils
Polyolefins
LDPE
LLDPE
HDPE
PP
Hot-melt adhesives
Human tissue:
 Migration into food can reach
10 ppm
 No sufficient toxicological data
about polyolefin oligomers
 Possible analogies to mineral
oil hydrocarbons?
7
Polyolefin oligomers
Mineral oils
Polyolefins
linear
Hot-melt adhesives
branched
POSH:
Polyolefin oligomeric
saturated hydrocarbons
POMH: Polyolefin oligomeric monounsaturated hydrocarbons
POSHOC: open-chain POSH
POSHCY: cyclic POSH
POSHOX: oxidized oligomers
MOSH fraction
Unique structures
POMH
 Distinctive feature
to MOSH
O
O
8
Sealing layer
Mineral oils
Polyolefins
Hot-melt adhesives
Comprehensive analysis of the sealing layer via GCxGC
C24
C16
IS
C35
POSHoc
IS
POMH
POSHcy
IS
IS
IS
1076
Cycy
Sq
POSHox
2
3
1
11
5
10
4
?
IS
7 8
6
IS
13
9
16
Erucamid
17
18
168
?
ox168
Oleamid
14
IS
Degradation products
of antioxidants
9
Sealing layer
Mineral oils
Polyolefins
Hot-melt adhesives
LC-GC analysis with double preseparation of the sealing layer
 MOSH fraction subdivided into saturates and monoenes (LC-LCAg+-GC)
Complete [mg/kg]
C16-24
C24-35
145
275
POSH
Branched POSHoc*
n-Alkanes*
C16-24
C24-35
C16-24
C24-35
40%
60%
54%
30%
POSHcy*
C16-24
C24-35
6%
10%
POMH [mg/kg]
POHox* [mg/kg]
C16-24
65
C16-24
15
C24-35
130
C24-35
35
* Concentrations obtained from GCxGC analysis
10
Comparison:
Sealing layer and cardboard
Mineral oils
Polyolefins
Sealing layer
Recycled cardboard
GCxGC
GCxGC
LC-LC-GC
LC-LC-GC
 No signals in MOAH fraction
Hot-melt adhesives
11
Migration: Simulation
Mineral oils
Polyolefins
Hot-melt adhesives
Parameters:
• 1 dm2 of the sealing layer (75 µm) in 10ml sunflower oil 60min, 95◦C (pasteurization)
POSH
POMH
C16-24
95 µg/dm2
100 %
25 µg/dm2
55 %
C24-35
185 µg/dm2
100 %
40 µg/dm2
45 %
 Roughly 0.4 mg/dm² (polyolefin oligomers, C16-35) migrate under these conditions
12
Migration: Food samples
Mineral oils
Polyolefins
Hot-melt adhesives
Sample
Tomato sauce
Carbonara sauce
Pesto
Fat content
1,2 %
9,4 %
46,0 %
Pasteurization
60 min, 95°C
60 min, 95°C
---
Storage
4-8°C
4-8°C
< -20°C
Packaging
1,5 kg in 12dm2
1,5 kg in 12dm2
1,5 kg in 12dm2
POSH C16-35
2,0 mg/kg (MOSH)
1,5 mg/kg
0,5 mg/kg
POMH C16-35
<0,1 mg/kg
0,35 mg/kg
0,1 mg/kg
P
O
S
H
 Transfer >50% from the sealing layer into pasteurized fatty food (carbonara sauce)
13
Hot-melt adhesives
Mineral oils
Polyolefins
Hot-melt adhesives
Hot-melt adhesives (HMA) mainly consist of various types of waxes, resins and
polymers. The main individual types were investigated:
Paraffinic waxes
Hydrocarbon resins
PE copolymers
Conc. of saturated
Hydrocarbons [g/kg]
<0.1 – 20
10 – 120
0.2 – 0.5
Conc. of aromatic
Hydrocarbons [g/kg]
<0.1
<0.1 – 60
<0.1
Amount in the HMA
formulation
20 – 30 %
30 – 50 %
20 – 50 %
Regulation 10/2011
FCM 93: 0.05 mg/kg FCM 97: no SML
FCM 94: no SML
FCM 95: no SML*
---
* White mineral oils (paraffinic)
Disclaimer: The origin and potential SMLs of hydrocarbon mixtures is not
displayed during analysis
14
Hot-melt adhesive
Mineral oils
Polyolefins
Hot-melt adhesives
Chromatograms of a hexane extract of a hot-melt adhesive from a
commercial rice (risotto) sample packed in virgin board folding box
MOSH fraction C16-24: 20 g/kg HMA
C11
MOAH fraction C16-24: 6 g/kg HMA
5B 1/2-MN
Cycy
Cho
TBB
Paraffinic
wax
C13
Per
C27
C18
C27
C18
C36
HC resin
C36
HC resin
C16-24
C16-24
 Migration via gaseous phase (C16-24)
15
Hydrocarbon resins
Mineral oils
Polyolefins
Fraction
Hot-melt adhesives
C5
C9
DCPD
(«Piperylenes»)
(«Aromatics»)
(Dicyclopentadienes)
Monomers
Oligomers
(saturated)
C16-24
GC
C16
C24
C35
C16
C24
C35
C16
C24
C35
 These products can be fully or partially hydrogenated after synthesis
16
Migration from HMA into rice
Mineral oils
Polyolefins
Hot-melt adhesives
 500g rice (risotto) packed in 7.5 dm2 virgin board and closed with 1 g hotmelt
 Hexane extract (24h, RT) of 1 cm rice bottom layer (25g)
5B
1/2-MN
Per
TBB
Cycy
Cardboard
Cardboard
C11
Cho
C16
C13
Risotto
Risotto bottom
Risotto bottom
Risotto
Risotto middle
Hotmelt
Risotto middle
C16
C24
C35
MOSH fraction: 2.7 mg/kg C16-24
17.12.2013
C24
Hotmelt
MOAH fraction: 0.7 mg/kg ≤C24
17
Estimation of migration
Mineral oils
Polyolefins
Hot-melt adhesives
Simulation (6 months at ambient temperature):
Test package with polenta (corn semolia) as food simulant and 1 g of HMA
 1 – 6 % of saturated hydrocarbons of sufficient volatility (C16-24) were
transferred from the HMA into the simulant
Storage test with real food (12 months at ambient temperature):
Roughly 800g of oat flakes were packed in folding boxes of virgin board
and closed with 0.5 g of HMA formulation
 Up to 10 % of saturated hydrocarbons of sufficient volatility (C16-24)
migrated from the HMA into the food
 Migration depends on the formulation, application and storage conditions
18
Migration from re-sealable
packaging
Mineral oils
Polyolefins
Hot-melt adhesives
Hot-melt pressure sensitive adhesives (HMPSA) can also release
hydrocarbons into food: Cheese in PE packaging (no migration barrier).
Four different HMPSA
samples for re-sealing
show similar peak patterns
in GC.

Top slice
23 mg/kg
9 mg/kg
2nd slice
5 mg/kg
5 mg/kg
 Migration into cheese was
observed for the top slice with
direct contact to the resealable layer. The 2nd slice was
not affected of substantial
migration, but shows natural
occurring terpenes.
19
Migration paths
Mineral oils
HMA in folding boxes
Cardboard
Polyolefins
Hot-melt adhesives
HMPSA in re-sealable
packaging
HMPSA in re-sealable
packaging
-no migration barrier-
-incorporated barrier-
Hotmelt
Food
?
≈ 1-10% Transfer of
HMA hydrocarbons
(C16-24) into food
Food
Food
??? % Transfer of
HMPSA hydrocarbons
(C16-35) into food
No substantial Transfer of
HMPSA hydrocarbons
(C16-35) into food
 Safety by Design 20
Summary
Chair of Food Science and Food Contact Materials
MOH
POH
(mineral oil hydrocarbons)
(polyolefin oligomeric
hydrocarbons)
HCROH
(hydrocarbon-resin
oligomeric hydrocarbons)
Aliphatic
hydrocarbons
(MOSH fraction)
Aromatic
hydrocarbons
-----
(MOAH fraction)
Exemplary
chromatograms
Recycled cardboard:
MOSH + MOAH
Polyolefin granulate (LDPE):
POSH + POMH
Hydrocarbon resin (C9):
HCROSH + HCROAH
(Section C16-35)
21
Summary
Chair of Food Science and Food Contact Materials
MOH
POH
(mineral oil hydrocarbons)
(polyolefin oligomeric
hydrocarbons)
(hydrocarbon-resin
oligomeric hydrocarbons)
Concentration 150-700 mg/kg (C16-24) in
of hydrocarbons analyzed recycled cardboard
in the respective
FCM
300-1400 mg/kg (C16-35)
in analyzed sealing
layers
Up to 60 g/kg (C16-24) in
HMA estimated from conc.
In analyzed tackifier resins
≤10 mg per kg foodb
≤5 mg per kg foodc
Migration into
food (worst case)
Regulations
a
≤100 mg per kg fooda
HCROH
Future German regulation on
According to Art. 3 of
According to Reg. (EU)
MOH from recycled cardboard Reg. (EC) 1935/2004, a
10/2011:
MOSH
risk assessment has to
No SML for petroleum
C10-16: 12 mg/kg
be performed for NIAS,
hydrocarbon resins,
C17-20: 4 mg/kg
such as POH.
hydrogenated (FCM 97)
C21-35: 2 mg/kg
MOAH
Common regulation for hydrocarbon
C10-35: 0.5 mg/kg
Vollmer et al. 2011, b BiedermannBrem et al. 2012, c Barp et al. 2015
contaminants in food?
22
Chair of Food Science and Food Contact Materials
THANK YOU
Dresden Old Town
for your attention
and especially to
Prof. Thomas Simat
Dr. Konrad Grob
Maurus Biedermann
…and industry partners
More Information on:
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