Österreichisches Forschungsinstitut für Chemie und Technik CROPACK 2010 Migration Testing Overall migration SML tests Screening methods DI Michael Pitzl

2  Private Testing and Research Institute  Legal form: Association / Ltd.  ~ 130 employees (status: 12/2009)  ~ m 2 floor space at 2 locations  Business Year 2009: Annual turnover: 13,8 Mio. Euro R&D: ~ 26 % Share of export: ~ 24 % Organisation and Facts

3 Location Arsenal 1030 Vienna, Arsenal Objekt 213, Franz Grill-Straße 5 Applied Polymer Technology Varnishes and Adhesives Construction Sports Technology Location Brehmstraße 1110 Vienna, Brehmstraße 14a Packaging Medical Products Eco Technology Food Analysis Administration Locations and Departments

4 Main Focus:  Certification / Consulting in case of Damage Claims  Testing & Quality Assurance  Assessment according to the European Food Legislation / LMSVG  Client‘s R&D-Projects  Branch-oriented R&D-Projects  Branch-oriented Training and Education ... Packaging (incl. food commodities)

5 Migration Scalping Migration Active Packaging H2OH2O Gas Flavour Product Light Mech. Stress Hygiene

6 Potential Migrants  Glas -Silicates, heavy metals  Plastics -Plasticizers, monomers, antistatics...  Paper -Additives and fillers (chalk etc.)  Metal -Aluminium, tin for acid contents

7 Migration How can be prevented that an illegitimate amount of contents of the packaging migrates into the product? Choosing the right packaging! Ensured by migration testing -Compliance with overall migration limit (OML) -Specific migration limits (SML) -Maximum legitimate residual content of the substance in the finished food contact material (QMA) !!! Consideration of actual applied conditions (time and temperature combinations)

8 Migration Testing Test conditions according to 2002/72/EC Basics for migration tests  82/711/EEC – Basic rules for testing migration  93/8/EEC – 1st amendment  97/48/EEC – 2nd amendment List of simulants: 85/572/EEC  2007/19/EEC – 1st amendment VC in PVC: 78/142/EEC (residual content and transfer to foodstuff) VC-analysis: 80/766/EEC, 81/432/EEC Certain epoxy derivatives: REG (EC) Nr / 2005 Plasticizers in gaskets in lids: REG (EC) Nr. 372/2007

9 CEN TC 194 CEN TC 194 ´Utensils in Contact with Food´ ´Utensils in Contact with Food´ SC 1: General chemical methods  Standard EN 1186: Test methods for overall migration  Standard EN or CEN/TS 13130: Standard methods for the specific migration (SML/QM) currently, 28 parts are published within this standard European Standards concerning plastics in contact with foodstuff

10  Aqueous foods pH > 4,5 Distilled water (A)  Acidic foods pH  4,5 3 % (w/v) Acetic acid (B)  Alcoholic foods: 10 % (v/v) Ethanol (C)  milk / milk products: 50 % (v/v) Ethanol  Fatty foods: Rectified olive oil (D)  Dry foods: none Simulants if ethanol content > 10 %: adaptation to the actual content!

11 Selection of the right Simulant List of simulants: Regulation 85/572/EEC Example:

12 Migration Testing:  Unknown contact time, application for ambient temperature or lower temperatures: 10 d / 40 °C (all simulants)  Unknown contact time & unknown application temperature: 4 h / 100 °C bzw. Reflux (simulant A, B, C) 2 h / 175 °C (simulant D)  Hot filling (< 15 min at °C): 2 h / 70 °C (all simulants) Standardized Testing Conditions according to European Regulations / Austrian Plastics Regulation Overall migration – bottom sediments

13 Migration Testing Substitute test for fatty foods  If the use of fatty food simulants is not feasible for technical reasons Substitution: defined test media and conditions, corresponding to the simulant D Iso-Octan Ethanol (95 %) Modified Polyphenylenoxid (Tenax)

14 Migration Testing  Consideration of the practical usage conditions of the packaging (e. g. for which foodstuff applied?)  Clarification of the usage conditions Selection of the simulant and test conditions (contact time and temperature)  Is overall migration limit complied (OML)?  Compliance with thresholds of the specific migration (SML) residual content in the commidity (QM)? Migration Tests for finished commodities

15 Structure of the actual EU-Laws For materials and articles in contact with foodstuff Main-REG (EC) Nr. 1935/2004 Specific Directives BADGE, BFDGE, NOGE VO (EG) Nr. 1895/2005 Vinyl chloride 78/142/EEC Reg. Cellulose 2007/42/EC Analyses of VC 81/432/EEC Analysis of VC-content 80/766/EEC Ceramik 84/500/EEC amanded2005/ 31/EC Plastic 2002/72/EC amanded VO Nr. 975/2009 Rules Migration 82/711/EEC amended 97/48/EEC List of Simulants 85/572/EEC amended 2007/19/EC GMP-REG (EC) Nr. 2023/2006 Recycl.-REG (EC) Nr. 282/2008 A&I-REG (EC) Nr. 450/2009

16 EU-Substances List / Synoptic Document  EU-Substances List -Based on: 2002/72/EG incl. supplements -Containing an authorised positive list of monomers and an incomplete list of additives  For certain substances thresholds are available which are expressed -either as maximum quantity in material or article (QM) -or as specific migration limit in food (SML).

17 SML / QM Test Methods: migration test medium + GC, HPLC Positive List (excerpt):

18 SML – Save Testing Costs Special Cases:  100% migration < SML  Calculation model

19 Gas Chromatography

20 Chromatographic Separation Separation of substances mixture due to different retention times of each single analyte during the transport through the chromatographic bed

21 Definitions  DECISION LIMIT : Threshold for the presence of an analyte (yes/no). If a sample possessed the exact content of the dicision limit, the analyte wouldn‘t be detected in 50 % of the measurements despite the presence of the analyte („false negative“).  DETECTION LIMIT : minimal concentration of an analyte, which is detected with a high likeliness (e. g. 95 %). The detection limit is usually twice the amount of the decision limit.  DETERMINATION LIMIT: lowest concentration of an analyte, which can be quantitatively detected with a determined accuracy. Quantitative analyse results are only declared above the determination limit. The determination limit equals approximately the triple amount of the decision limit.

22 Thermodesorber: Gas Chromatography

23 Screening Methods  Migration or directly in food  Which peaks are explainable, which are not? Criticism : Analysis method? Comparability? Undetected substances?

24 Special Regulation – Lid Gaskets Regulation 372/2007/EG  laying down transitional migration limits for plasticizers in gaskets in lids intended to come into contact with food SML for:  fatty food: 300mg/kg*  all others: 60 mg/kg*  baby / infant food: 30 mg/kg* (restriction for ESBO) * of food or food simulant

25 Example - ITX Isopropylthioxanthone (ITX)  Photointitiator in UV-curing printing inks  Application: outside of food packaging (compound for milk, cacao, juice)  Problems: -Set off–effect -Migration !!! Threshold 0,05 mg/kg ITX in food

26 How to test „Set off“? IVLV „cluster commodities“ Working group of German-speaking testing laboratories eurofins, Fresenius, GALAB, GfU, innoform, ISEGA, MUVA, Nehring, ofi, SQTS Agreement on common test conditions: Time / Temperature - at customer - at laboratory: a) guideline value 10 days at 40 °C b) alternatively according to actual application Pressure - three-dimensional - pile (according to customer) - flat/foila) roll b) pile - full-surface contact - flexible - 1kg/dm² Sample Name / Storage

27 PIM – what‘s next?  New simulants e. g. Tenax:

28 PIM – what‘s next?  Priority: 1. Specific migration 2. Overall migration  Overall migration: Test conditions OM1-9  Regulations for repeated contacts  Multi-layer materials and articles  Test at 10 d 60 °C for storage times > 30 d  Substitute simulants („scientific evidence“)

29 Österreichisches Forschungsinstitut für Chemie und Technik (ofi) Brehmstraße 14A 1110 Vienna  +43-(0) – ext.  +43-(0) DI Michael Pitzl (ext. 597, Contacts