SAFETY OF RECYCLED PAPERBOARD: MINERAL OIL CONTENT DETERMINATION, MIGRATION TO FOOD, AND CLEAN-UP STRATEGIES

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SAFETY OF RECYCLED PAPERBOARD: MINERAL OIL CONTENT DETERMINATION, MIGRATION TO FOOD, AND CLEAN-UP STRATEGIES Ilaria Braschi 1,5 R. Lorenzini 2, M. Barbanera 3, L. Marchese 4,5 ilaria.braschi@unibo.

1 SAFETY OF RECYCLED PAPERBOARD: MINERAL OIL CONTENT DETERMINATION, MIGRATION TO FOOD, AND CLEAN-UP STRATEGIES Ilaria Braschi 1,5 R. Lorenzini 2, M. Barbanera 3, L. Marchese 4,5 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)

2 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

3 MINERAL OIL SOURCES: ENVIRONMENT & FOOD ENVIRONMENT: SMOG & INDUSTRIAL POLLUTION TRAFFIC PETROLEUM SPILLAGES PESTICIDE FORMULATIONS COSMETICS FOOD: JUTE BAGS BATCHING OIL BAKERY & SWEETS ANTISTICKING DUST BINDING FRUIT & DRIED FRUIT POLISHING PAPER 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)

4% FRESH RECYCLED forniture 12.8% drinks 11.3% drinks 19.

4 PAPER-BASED PACKAGING DESTINATION non-food 40.5% food 22.2% non-food 28.1% food 42.4% RECYCLED fruit-veg 13.2% cosmetics & pharmaceuticals 10.4% FRESH RECYCLED forniture 12.8% drinks 11.3% drinks 19.1% carton board paperboard Source: Istituto Italiano Imballaggio, report 2010 on 2009 data

5 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!

6 PAPERBOARD EXTRACTION OPTIMIZATION: RESULTS MOSH MOAH hexane EtOH MeOH hexane EtOH MeOH 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 Other extracted: DIPN ( recycling markers ) & phthalates

7 FOOD EXTRACTION OPTIMIZATION: RESULTS Superficial contamination: from packaging hexane is IDEAL Deep contamination: pre-packaging hexane inadequate To evaluate deep contamination preparation of spiked handmade pasta : just grounded suspended in hexane 3 h at RT suspended in polar solvent 3 h at RT

$fractions of interest sent to GC FID ideal: high linearity range & same$

8 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

9 MINERAL OIL MIGRATING FRACTION nc24 nc24 nc24 R. Lorenzini et al. (2010) Food Add Contam, 27(12)

10 MOSH < nc24 CONTAMINATION: RESULTS FRESH FIBRES RECYCLED FIBRES MOSH concentration (mg/kg) MOSH concentration (mg/kg) sorted samples sorted samples OPTIONAL SAFETY LIMIT: 4 ppm IN BOARD < 0.6 ppm IN FOOD

MINERAL OIL MIGRATION KINETICS: RESULTS CONTROLLED MIGRATION PLAN on without internal barrier with internal barrier WAS INVESTIGATED AS A FUNCTION OF

11 MINERAL OIL MIGRATION KINETICS: RESULTS CONTROLLED MIGRATION PLAN on without internal barrier with internal 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:

12 MINERAL OIL CONTENT IN MUESLI UNDER DIFFERENT STORAGE CONDITIONS mg kg 1 MOS H days FREE SHELF BOX CENTRE BOX CORNER IN BOXED PACKS, MIGRATION CONTINUES UP TO END OF SHELF LIFE (ca. 1 year) REACHING HIGH CONTAMINATION LEVELS

SPONGE EFFECT of POLYOLEPHINIC BARRIER 1 2 3 4 MOSH

THEN TO MUESLI (BLUE) STORED AT 60 C: PLASTIC BETWEEN

13 SPONGE EFFECT of POLYOLEPHINIC BARRIER 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.

14 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

15 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

in cocoa and cocoa products and possible minimization strategies

Mineral oil hydrocarbons (MOSH/MOAH) in cocoa and cocoa products and possible minimization strategies International Symposium on Cocoa Research 13 17 November 2017 Lima/Peru Reinhard Matissek Food Chemistry