CROPACK 2010 • Migration Testing • Overall migration • SML tests • Screening methods DI Michael Pitzl
Organisation and Facts • Private Testing and Research Institute • Legal form: Association / Ltd. • ~ 130 employees(status: 12/2009) • ~ 7.000 m2 floor space at 2 locations • Business Year 2009:Annual turnover: 13,8 Mio. EuroR&D: ~ 26 %Share of export: ~ 24 %
Locations and Departments Location Arsenal1030 Vienna, Arsenal Objekt 213,Franz Grill-Straße 5 Location Brehmstraße1110 Vienna, Brehmstraße 14a Applied Polymer TechnologyVarnishes and AdhesivesConstruction Sports Technology PackagingMedical Products Eco Technology Food Analysis Administration
Packaging (incl. food commodities) 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 • ...
Migration Mech. Stress Light Hygiene H2O Gas Migration Product Flavour Scalping Active Packaging
Potential Migrants • Glas • Silicates, heavy metals • Plastics • Plasticizers, monomers, antistatics ... • Paper • Additives and fillers (chalk etc.) • Metal • Aluminium, tin for acid contents
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)
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. 1895 / 2005 Plasticizers in gaskets in lids: REG (EC) Nr. 372/2007
European Standards concerning plastics in contact with foodstuff CEN TC 194 ´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
Simulants • Aqueous foods pH > 4,5 Distilled water (A) • Acidic foods pH 4,53 % (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 if ethanol content > 10 %:adaptation to the actual content!
Selection of the right Simulant List of simulants: Regulation 85/572/EEC Example:
Standardized Testing Conditions according to European Regulations / Austrian Plastics Regulation 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 70-100 °C): 2 h / 70 °C(all simulants) Overall migration – bottom sediments
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)
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
Structure of the actual EU-Laws For materials and articles in contact with foodstuff Recycl.-REG (EC) Nr. 282/2008 GMP-REG (EC) Nr. 2023/2006 Main-REG (EC) Nr. 1935/2004 A&I-REG (EC) Nr. 450/2009 Specific Directives Ceramik84/500/EEC amanded2005/31/EC Plastic 2002/72/EC amanded VO Nr. 975/2009 Reg. Cellulose 2007/42/EC Vinyl chloride 78/142/EEC BADGE, BFDGE, NOGE VO (EG) Nr. 1895/2005 List of Simulants 85/572/EECamended 2007/19/EC Rules Migration 82/711/EEC amended 97/48/EEC Analysis of VC-content 80/766/EEC Analyses of VC 81/432/EEC
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).
SML / QM Test Methods: migration test medium + GC, HPLC Positive List (excerpt):
SML – Save Testing Costs Special Cases: • 100% migration < SML • Calculation model
Chromatographic Separation Separation of substances mixture due to different retention times of each single analyte during the transport through the chromatographic bed
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.
Thermodesorber: Gas Chromatography
Screening Methods • Migration or directly in food • Which peaks are explainable, which are not? Criticism: Analysis method? Comparability? Undetected substances?
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
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
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/foil a) roll b) pile - full-surface contact - flexible - 1kg/dm² Sample Name / Storage
PIM – what‘s next? • New simulants e. g. Tenax:
PIM – what‘s next? • Priority:1. Specific migration2. 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“)
Contacts DI Michael Pitzl (ext. 597, E-Mail: firstname.lastname@example.org) • Österreichisches Forschungsinstitutfür Chemie und Technik (ofi) • Brehmstraße 14A • 1110 Vienna • +43-(0)1-798 16 01 – ext. • +43-(0)1-798 16 01 - 480