ZURICH, FRIBOURG, SHANGHAI, HONG KONG Food Contact Materials - a long Term Risk for Food Safety?...

ZURICH, FRIBOURG, SHANGHAI, HONG KONG

Food Contact Materials - a long Term Risk for Food Safety?

Pure and Applied Chemistry International Conference 2013

Bangsaen Beach, Chon Buri, Thailand

Dr. Thomas Gude

January,23rd 2013


Food Contact Materials - Definition

• Food contact materials are materials that are intended to be in contact with food. These can be things that are quite obvious like a glass, a can for soft drinks, but also machinery in a food factory or a coffee machine.

• Food contact materials can be constructed from a variety of materials like plastics, rubber, paper, coatings, metal etc. In many cases a combination is used; for example a carton box for juices can include (from the inside to the outside): plastic layer, aluminium, paper, printing and top coating.

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http://en.wikipedia.org/wiki/Food_contact_materials


Safety of Food Contact Materials

• Over the last 50 years the way we buy food has changed. In the past, some food items were usually sold ‘loose’ and taken home in a paper bag.

• Due to advances in technology, most food items are now sold pre-packed. We have a daily contact.

• During the contact of the food contact materials with the food, molecules can migrate from the food contact material to the food. Because of this, in many countries regulations are made to ensure food safety.

VERSUS

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Rapid alerts for foodstuffs imported into EU and failing food safety checks (2000-2011)

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The EC Law

Framework Regulation (EU) No 1935/2004

GMP-Regulation (EU) No 2023/2006

National Regulations Specific Measurements

Materials Substances Materials not regulated in Specific Measurements

- Ceramic Dir. 84/500/EC

- Celophane Dir 2007/42/EC

- Plastic Reg (EU) 10/2011 - Recycling- Plastic Reg (EU) 282/2008 - Active and intelligent

materials Reg (EU) 450/2009

- Nitrosamines Dir. 93/11/EC - BADGE, BFDGE &

NOGE Reg (EU) 1895/2005 - Bisphenol A Reg (EU) 321/2011 - Melamin und PAAs Reg (EU) 284/2011

a.o.: - Adhesives - Rubber - Glass - Metalls - Ion exchance resins - Paper a. Cardboard - Printing Inks - Wood - Textiles - Laquers a. Coatings - Waxes

Dir = Directive incl. Amendments Reg = Regulation incl.Amendments

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ZURICH, FRIBOURG, SHANGHAI, HONG KONG| Page 6

Regulation (EC) No 1935/2004October 2004

Materials and articles, including active and intelligent materials and articles, shall be

manufactured in compliance with good manufacturing practice so that, under normal or

foreseeable conditions of use, they do not transfer their constituents to food in quantities

which could,

• endanger human health, Risk Assessment, DoC, Supporting Documents,

Unknowns, NIAS

• bring about an unacceptable Migration, Overall - Specificchange in the composition of the food,

• bring about a deterioration in the Sensorial Testingorganoleptic characteristics thereof


Legislation versus Trust

http://jig.svi-verpackung.ch/

Appropriate documentation to demonstrate that the materials and articles, products from intermediate stages of their manufacturing as well as the substances intended for the manufacturing of those materials and articles comply with the requirements of this Regulation shall be made available by the business operator to the national competent authorities on request.Art. 16, Reg 10/2011 – supporting documents


GMP: Process-Safety

COMMISSION REGULATION (EC) No 2023/2006 of 22 December 2006on good manufacturing practice for materials and articles intended to come into contact with food

•Effective Quality Assurance System•Selection of Raw Materials according to predefined Specifications•Predefined Instructions and Processes•Migration or Invisible Set off of Printing Inks only in tolerated Amounts•No Direct Contact between Food and Printing Ink•Valid since 1.8.2008

•How we are able to check it?

•What will be accepted as GMP ?

•What is the proof of GMP?


Analysis of Food Contact Material

• 3 Level

• Mathematical Approach

• Modelling

• Migration Analysis

• Simulations

• Analysis in the Food

• What does fit best? What will be accepted by whom?

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PETPrintAdhesiveAluAdhesivePE


OrganolepticOdour

Taste

Odour – Taste: EN 1230-1, -2 50 or 75 % fry, 48 h and/or DIN 10955

DHS = Dynamic Headspace (Thermodesorption)HS-SPME = Headspace Solidphase MicroextractionHS = Headspace

ZURICH, FRIBOURG, SHANGHAI, HONG KONG | Page 11

Migration-Testing

• ..there is no packaging, which does not release any kind of substance – Zero is notpossible

• Migration is based on worst case simulations, but not any is an overestimation

• Proof of relevance of the results in food is missing (often)

• The unspecific overall migrate shows only that a material is inert, if it is below 10 mg/dm2 (for plastic only) – nothing else!!!!

• Specific Migration is key!


Specific Migration (in packaging/ in food)

• ~ 800 Plastic substances to be covered (it took 20 years to develop)

• But what’s about:

• ~ 2000 adhesives substances

• ~ 3000 ink substances

• ~ ??? Paper and paper board substances

• ~ ??? Rubber and Metal substances

• ...and others???

• Typically starting substances are known, but what else is present?

NIAS (Non Intentionally Added Substances)

IAS (Intentionally Added Substances)


Sources for Unknowns (in plastic)

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Starting Substances Food Contact Material

Monomers Polymer

Pre-Polymers Oligomers (POSH)

Additives Residual Monomers

Production Aids Additives and Reaction Products

Production Aids

NIAS NIAS

(Non Intentionally Added Substances)


Which risks are present for the combination packaging/food?

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Example: NIAS, Oligomers…………

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• Can be found in all plastics, lacquers…

• Monomers listed and assessed, Polymers uncritical, what's about Oligomers < 1000 Da

• Example Polyamide

• Actually no solution available

• Who performs Tox-Studies?


Example: Cyclo-di-BADGE (CdB)

Cyclo di Badge

Linear Epoxy Polymer

1618/04/23

• CdB is not detectable in liquid epoxy

resin

• CdB is only formed when BADGE and

BPA react to form a cyclic structure

in the polymerisation process used to

make solid epoxy resins

• CdB is not formed during curing of

coating

Identification:1 BADGE·2H2O 2 BADGE·H2O3 BADGE·H2O·BuEtOH 4 BADGE·H2O·Ph5 BADGE·H2O·BPA 6 BADGE·BuEtOH7 BADGE·Ph 8 cyclo-Di-BADGE9 BADGE·BPA 10 BADGE·BPA·BuEtOH11 BADGE (n=1)·BuEtOH 12 BADGE (n=1)·BPA13 BADGE (n=1)·BPA·BuEtOH 14 BADGE (n=2)

red:oxiran-containingChromatogram: Th. Siemat, TU Dresden


Example: NIAS in printed Cardboard (virgin fibre)

Routine Samples were analysed: printed cardboardTypical Approach:

Statement of Compliance for cardboard available

Tenax Migration: 10 d at 40° CGC/MS screening

? Photoinitiators ?Are they all assessed

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Top chromatogram: Bottom chromatogram:Laboratory blank Printed Cardboard MOSH = Mineral Oil Saturated Hydrocarbons

MOAH = Mineral Oil Aromatic HydrocarbonsPOSH = Polyolefin oligomeric saturated hydrocarbons


Example: MOSH/MOAH/POSH

mineral oil in food

1) Jute fibres2) Release agents (bakery ware,

raw material)3) Dust binder (grain, rice)4) Lubricating oil for machines5) Packaging material

• waxes as water repellent• printing inks• recycling

6) Contaminated animal feed 7) Environmental contamination8) …


Example: MOSH/MOAH

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Out of 4 drops of oil in the cardboard

3 drops of oil migrate into the food

1 drop of oil remains in the cardboard

Unprinted recycled cardboard

CardboardFor Rice

Rice

Migration in to Food

Rice in direct contact to recycled Cardboard

500g rice, 23 g Cardboard

Age: 8 months

Analysis with online LC/GC-FID

Ca. 80% of <C24 MOSH and MOAH in cardboard migrated

Chromatogram: K . Grob KL Zürich


Example: POSH• Oligomers from polyolefins

• Polyethylene, polypropylene, butylene plasticizers, resins for adhesives, poly alpha olefins (PAO)…

• in food contact used as

• plastic bags

• trays, bowls …

• heat-sealable layers on, e.g., aluminum foils or PET films

• adhesives: hot melts, plasticizers for polymeric resins

• lubricants, release agents

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Chromatogram: K . Grob KL Zürich


Example: POSH1. Polyolefins = the most important food packaging material

2. POSH often correspond to >90 % of the migrate from polyolefins (which tends to be substantial)

• POSH might be the quantitatively most important migrant of all

• Typical migration of critical C16-C35 POSH: - via gas phase (dry food): 1-5 mg/kg- via wetting contact: 10-20 mg/kg

3. Accumulation of various POSH?

4. Potential for reduction of low molecular mass oligomers?

5. POSH are known for very long, but neglected

6. What is the long term risk?| Page 21


Ways to deal with FCM

1. What do we know about the chemical behaviour of the intended materials from food contact side to outside

2. What do we know about the chemical behaviour of the food to be packed

3. What kind of barriers do we need – where and when?

BarrierCardboard

food food

MOSH/MOAHcontaminated

MOSH/MOAHcontaminated

Virgin Fiber

Animation by Dr. Hermann Seyffer, BASF SE 2011


Barriers– the future? Donor-Paper (Gravex & Sudan red)

spacer

barrier

Acceptor(PE-film)

Donor-Paper (Gravex & Sudan red)

spacer

barrier

Acceptor(TENAX)

Arrhenius equation


Ways to deal with FCM

4. What level of substances (negative/positive list) do we accept?

5. What means zero?

6. What documents should be checked in which intensity and how?

• All the data shall demonstrate, that a material is safe and suitable for use in contact with food!

• Documentation on several places needed

• Goal of process: Declaration of Conformity/Compliance

• However the term itself is quite critical


Checklist for Documents• Published on:

http://jig.svi-verpackung.ch/

• Close to Regulation 10/2011

• Should clarify the Business-to-Business information exchange

• It demands much more as the legislator is requesting

• Includes 7 pages explanations

• Formal Check of acceptance of DoCs – One Page

• 33 questions/checkpoints

• User can self- determine acceptance criteria


Material selection – the A and O for FCM

• The selection of the right material is based on the product (Food) specifications of the client (Processing; indented food contact etc.)

• Secondly a documentation check is mandatory:

• Technical Information for professional processing

• (eventually: Safety Data Sheet)

• Information to the Formulation (if access is possible)

• Declaration of Conformity

• Compliance work

• What was risk assessed?

• Chemical analysis reports

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The long term risk

• A risk assessment is key!

• Actually a strong focus is on known starting substances (EU approach)

• Are these the critical substances ?

• Lack of knowledge on IAS and NIAS

• Long term exposure to small amounts of substances may cause a food safety risk

• At the beginning we have to learn more about NIAS and IAS

• These substances may come back from a different source

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[T]here are known knowns

- there are things we know we know.

We also know there are known

unknowns

- that is to say we know there are

some things we do not know.

But there are also unknown

unknowns

– the ones we don't know we don't

know.


Example: A long term risk based on shelf life

Plastic is extremely slow to degrade in the

ocean. If it remains in the water long enough,

the sun and wave action break it into smaller

and smaller pieces that sink below the surface.

These pieces combine with the water to create

an “ocean soup.” The plastic extends as far as

100 meters below the surface and, in some

areas, is six times more plentiful by weight than

plankton. Broken-down plastic particles can

eventually be reduced to a size that can be

ingested by even tiny zooplankton. Every size

of organism, every creature in the food web in

the ocean, from the smallest filter feeders to the

largest whales, is consuming plastic.

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Charles Moore, Algalita Marine Research Foundation


The Target: Risk-Minimisation

Risk = Hazard x Exposure

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