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)

ilaria.braschi@unibo.it

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