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SAFETY OF RECYCLED PAPERBOARD:MINERAL OIL CONTENT DETERMINATION,
MIGRATION TO FOOD,AND CLEAN-UP STRATEGIES
Ilaria Braschi1,5
R. Lorenzini2, M. Barbanera3, L. Marchese4,5
1 Department of Agricultural Science, Università di Bologna (Italy);2 Coop Italia s.c.ar.l. (Italy);3 Department of Science and Innovation Technology and 4 Interdisciplinary Nano-SiSTeMI Centre, Università del Piemonte Orientale A. Avogadro (Italy)
OUTLINES
• MINERAL OIL IN PAPER-BASED FOOD PACKAGING
• EXTRACTIVE AND ANALYTICAL ISSUES
• “SHOPPING TROLLEY” CONTAMINATION SURVEY: RESULTS
• MIGRATION KINETICS FROM PACKAGING TO FOOD: RESULTS
• CLEAN-UP STRATEGIES: PRELIMINARY RESULTS
MINERAL OIL SOURCES:
ENVIRONMENT & FOOD
• ENVIRONMENT:SMOG & INDUSTRIAL POLLUTIONTRAFFICPETROLEUM SPILLAGESPESTICIDE FORMULATIONSCOSMETICS
• FOOD:JUTE BAGS BATCHING OILBAKERY & SWEETS ANTISTICKINGDUST BINDINGFRUIT & DRIED FRUIT POLISHINGPAPER BASED FOOD PACKAGING
Hydrocarbons are the most abundant xenobiotics in our body (~ 1 g)(Concin et al., Mineral oil paraffins in human body fat and milk, 2007)
PAPER-BASED PACKAGING DESTINATION
carton board paperboard
Source: Istituto Italiano Imballaggio, report 2010 on 2009 data
FRESH
RECYCLED
non-food28.1%
food42.4%
drinks19.1%
cosmetics &pharmaceuticals
10.4%
non-food40.5%
food22.2%
drinks11.3%
forniture12.8%
fruit-veg13.2%
RECYCLED
THE ISSUE OF MINERAL OIL IN PAPER BASED PACKAGING FOR FOOD CONTACT
• LACK OF TOXICOLOGICAL DATA ON HYDROCARBONS
• LACK OF RELIABLE ANALITICAL TEST FOR MINERAL OIL CONTENT
• LACK OF REGULATORY INTERVENTION
NEED OF A DOMINO EFFECT!
Solvent: Ethanol ideal for low MW & to swell fibres, hexane ideal for medium-high MW
T & time: high T & prolonged contact time extract more hydrocarbons but also more undesired compounds
Ideal: Ethanol:hexane = 50:50, 2h at RT
PAPERBOARD EXTRACTION OPTIMIZATION:RESULTS
hexane
EtOH
MeOH
hexane
EtOH
MeOH
Other extracted:DIPN (“recycling
markers”)& phthalates
MOSH MOAH
FOOD EXTRACTION OPTIMIZATION:RESULTS
Deep contamination:
pre-packaging hexane inadequate
Superficial contamination:
from packaging hexane is IDEAL
To evaluate deep contamination preparation of spiked “handmade pasta”:
just grounded
suspended in hexane3 h at RT
suspended inpolar solvent
3 h at RT
INSTRUMENTAL ANALYSIS:on line coupled normal phase HPLC-GC/FID
• Applicable to high lipid content (up to 20%) samples
• Columns & precolumns (retention gap technique): home-made
• LC isolation of fractions of interest sent to GC
• FID ideal: high linearity range & same RF for all hydrocarbons
R. Lorenzini et al. (2010) Food Add Contam, 27(12)1765-1774.
MINERAL OIL MIGRATING FRACTIONnC24 nC24 nC24
0
500
1000
1500
2000
2500
3000
3500
4000
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35
MO
SH c
once
ntra
tion
(mg/
kg)
sorted samples
0
500
1000
1500
2000
2500
3000
3500
4000
1 6 11 16 21 26 31 36 41 46 51 56 61 66M
OSH
con
cent
ratio
n (m
g/kg
)
sorted samples
FRESH FIBRES RECYCLED FIBRES
MOSH < nC24 CONTAMINATION:RESULTS
OPTIONAL SAFETY LIMIT: 4 ppm IN BOARD < 0.6 ppm IN FOOD
MINERAL OIL MIGRATION KINETICS:RESULTS
CONTROLLED MIGRATION PLAN on
withoutinternal barrier
WAS INVESTIGATED AS A FUNCTION OF • storage conditions (T, time, position)
• presence of internal bag• presence of external carton board box
R. Lorenzini et al., (2013) Food Add Contam, 4:760-770.
withinternal barrier
IN BOXED PACKS, MIGRATION CONTINUES UP TO END OF SHELF LIFE (ca. 1 year) REACHING HIGH CONTAMINATION LEVELS
MINERAL OIL CONTENT IN MUESLI UNDER DIFFERENT STORAGE CONDITIONS
0
5
10
15
20
25
30
35
40
0 100 200 300 400
F R E E
S HE LF
BOXC E NTRE
BOXCORNE R
mg kg ‐1 MOS H
days
MOSH MIGRATE FROM PAPERBOARD (BLACK) TO PLASTIC (PINK) AND THEN TO MUESLI (BLUE) STORED AT 60°C: PLASTIC BETWEEN PAPERBOARD AND FOOD ACTS AS A STORAGE LAYER FOR CONTAMINANTS.
“SPONGE EFFECT” of POLYOLEPHINIC BARRIER
1 2
43
MINERAL OIL FRACTION SHIFTING UNDER ACCELERATED MIGRATION
•HIGHER MW HYDROCARBONS SIGNIFICANTLY MIGRATE ONLY AT HIGH TEMPERATURES •ACCELERATED MIGRATION OVERESTIMATES AND MISREPRESENTS THE REAL MIGRATION PATTERN
PULP CLEAN-UP STRATEGIES
WASHING FLOATING
REDUCTION OF THE MINERAL OIL CONTENT OF RECYCLED PAPER BY USING ADDITIVES WITH HIGH AFFINTIY TO HYDROCARBONS (& OTHER POLLUTANTS)
THE ADDITIVES ARE RECOVERABLE AND RECYCLEABLE