Differentiating Resin Oligomers from MOSH/MOAH Hydrocarbon Resins, Rosin Resins and Pine Chemicals Annual Conference FEICA, Riga, 12-14 September 2018 Producers Association Representing European based producers of resins Members of the European Chemical Industry Council (Cefic). HARRPA exists since 1991 15 member companies in Europe for a total yearly production of more than 1 million tons and a total turnover around 1,5 billion euros >30 production sites in Europe / employing >3,000 people Henk-Jan de Jager Ruud van der Eerden Michaela Hofbauer
From-Farm-to-Fork Food safety Content • Introduction • What are Resins? • What are Mineral Oils? • What is the issue? • 2D vs 1D GC: C9 and DCPD Resins • Take-away messages Processing: Machine oils Packaging: Migration Food Harvesting & Plant growth Transport processing Retailer Consumer Storage & Packaging Crop protection Processing: Machine oils Environmental contamination: accidental
What are … Resins? Rosin and Terpene Resins are low molecular weight, high Tg polymers • Produced from feedstocks that originate from pine trees • The main building block used for rosin resins production is rosin (Colophonium) • Terpene resins are polymerized from terpenes • Rosin can be chemically modified through disproportionation, hydrogenation, dimerization and/or fortification with organic acids • Esterification of rosin with alcohols yields rosin esters Gum Rosin Tall Oil Rosin → Rosin and terpene resins are not mineral oils! Wood Rosin
What are … Resins? Hydrocarbon resins Hydrocarbons resins are obtained by polymerizing hydrocarbon monomers such as C5, C9 and DCPD. • Crude oil fractions (naphtha) are fed to steam-crackers to produce ethylene, propylene as well as other products • Monomers for hydrocarbon resins (olefins and di-olefins) are also created in the steam cracker process • Monomers are identified according to their chemical nature (e.g. C5, C9, ...) • Resins oligomers in hydrocarbon resins are formed as integral part of the resin polymerization process, DCPD C5 C9 → The monomers used to make hydrocarbon resins are not present in crude oil, Oligomers Mw but synthetically produced! Hydrocarbon resins are not mineral oils! Crude oil: “ …… cracking operations generate olefins (alkenes and cycloalkenes ), …. Olefins are not present in crude petroleum.” National Research Council. 1985. Oil in the Sea: Inputs, Fates, and Effects. Washington, DC: The National Academies Press, p.25.
What are … Mineral Oils? Definitions According to EFSA opinion (2012): “hydrocarbons containing 10 to about 50 carbon atoms, where the crude mineral oils remain by far the predominant source of the mineral oil hydrocarbons considered, but equivalent products can be synthesised from coal, natural gas or biomass.” Concawe (Mocrinis Workshop, 2017) Mineral oil is a generic term used to group several petroleum derived liquids, manufactured by atmospheric and vacuum distillation of crude oil followed by further refinement through extraction, dewaxing and hydrogenation or other treatment. • Significant difference between definitions • A clear mineral oil definition is missing Source: Concawe Mocrinis II Workshop (Brussels, 17-18 October 2017); https://www.concawe.eu/wp-content/uploads/2017/10/DEF_C_MM_digital.pdf
What is the issue? Contamination of mineral oils in food is a matter of food safety! Mineral oil expressed as MOSH (Mineral Oil Saturated Hydrocarbons) and MOAH (Mineral Oil Aromatic Hydrocarbons) Identified as a potential source of food contamination, primarily through recycling of paper Mineral oils sparked controversy about the health hazards of MOSH/MOAH species (bioaccumulation, carcinogenicity) Consumers groups (e.g. Food Watch) expressed their concerns Wish to monitor the situation and develop an inventory as a basis for possible regulatory action Regulations may be pursued that limit the MOSH/MOAH content of packaging materials Consequences for food producers, food packagers and their suppliers Action EC: Recommendation (EU) 2017/84: Monitoring of mineral oil hydrocarbons in food Generate reliable and comparable results Determine the possible source of mineral oil European Reference Laboratory (EU-RL) develops guidance for suitable test method
Implementing EU Recommendation Challenges due to selectivity of the test method Analytical technique: 1D GC Guidance stipulates the use of 1D GC analysis Test method suitable if you accept that all C10-C50 is MOSH/MOAH – even products of biological or vegetable origin Listed components in the Union list of the Plastics Regulation might contribute to MOSH/MOAH levels Demonstrated (*) that 1D GC does not sufficiently distinguish between mineral oils and other low molecular weight hydrocarbons If MOSH/MOAH levels are regulated, an improper analytical method could lead to the dismissal of evaluated and approved food contact materials (*) Lommatzsch, M., Biedermann, M., Grob, K., & Simat, T. (2016, October 17). Analysis of saturated and aromatic hydrocarbons migrating from polyolefin-based hot-melt adhesive into food. Food additives & contaminants, Part A, 33(3), 473-488
What is the issue? Analytical technique: 1D GC 1. Measures all hydrocarbons: Insufficient selectivity for mineral oil constituents and non-mineral oil constituents. Broad unresolved hump too complex for ID purposes: Too many peaks (=substances) 2. Severe overlap of peaks (resolution) Real world: recycled cardboard Ideal world: clean GC
What is the issue? Analytical technique: 2D GC Resin oligomers are not MOSH / MOAH! Need to develop an improved analytical technique that can distinguish between resin oligomers and MOSH/MOAH HARRPA • Initiative to develop a technique to distinguish between MOSH/MOAH and resins (Laboratory Lommatzsch & Säger) • Create awareness of the difference between MOSH/MOAH and resins among stakeholders. Resin families selected by HARRPA for 1D GC and 2D GC analyses Feedstock Tall Oil Rosin Rosin Terpene DCPD DCPD/C9 C9 C5 PMR Non-H2 α,β -Pinene AMS / Non-H2 Non-H2 Non-H2 Non-H2 Glycerol Ester mixture Styrene Modification Glycerol Rosin Partial H2 Phenol resin Partial H2 Partial H2 Partial H2 Aromatic Terpene / Ester Glycerol Ester Non-H2 Type Penta Rosin H2 H2 H2 Ester
2D vs 1D GC 1D GC: C9 resins Resin Saturated Hydrocarbons Resin Aromatic Hydrocarbons non H2 non H2 Recycled cardboard - Extract Partial H2 Partial H2 H2 H2 C10-C50 Overlap of MOSH/MOAH with resin oligomers could result in false positives!
2D vs 1D GC Analytical technique: 2D GC Hydrocarbon separation based on: Recycled cardboard – Extract • 1D GC Volatility • 2D GC Volatility and Polarity Food print of a mineral oil Orientation in 2D GC MOSH Main border cyclic MOSH Monoaromatics Di-aromatics Tri-aromatics Poly-aromatics Internal standards
2D vs 1D GC 2D GC: C9 resins Unsaturated hydrocarbons Mineral Oil footprint Non H2 Saturated hydrocarbons partial H2 H2 A. Dimers C B. Trimers C. Tetramers
2D vs 1D GC 2D GC: H2-DCPD resin Unsaturated hydrocarbons Saturated hydrocarbons A. Trimer B. Tetramer C. Pentamer D. Hexamer 13
2D vs 1D GC Conclusions • 1D GC is intended to determine (un)saturated hydrocarbons, but is limited for mixtures of hydrocarbons from different sources. • Concentrations of hydrocarbons in different fractions can be determined, but a qualitative evaluation is hardly feasible. • 2D GC identified and differentiated the vast majority of the resin oligomers from mineral oil hydrocarbons. EU Recommendation 2017/84 stipulates: • Generate reliable and comparable results of the monitoring • Determine the possible source of mineral oil This calls for a reliable and adequate (2D GC) analysis HARRPA strongly recommends that 2D GC is Correct Interpretation is key accepted and endorsed for MOSH/ MOAH Possibility to trace source of contamination analysis
Take-away messages 1. Resins are not minerals oils! The 1D (JRC method) is supposed to focus on finding MOSH and MOAH – false positives have been identified 2. 3. HARRPA with Lommatzsch lab evaluated 2D GC • Differentiation between resins and MOSH/MOAH • HARRPA encourages stakeholders to use 2D GC 4. 2D GC technology is more sophisticated and should be endorsed as a complimentary method 5. Our industry (HARRPA) is committed to continue working with all stakeholders on this to further develop a suitable method Acknowledgement to Laboratory Lommatzsch & Säger HARRPA Position paper on Resin and mineral oil analysis in food contact materials: http://www.harrpa.eu/images/Publications/HARRPA_MOSHMOAH_201712.pdf
Backup Slides 16
What are Mineral Oils? Concawe definition mineral oil 17 Source: Concawe Mocrinis II Workshop (Brussels, 17-18 October 2017); https://www.concawe.eu/wp-content/uploads/2017/10/DEF_C_MM_digital.pdf
What are MOSH / MOAH? Concawe definition MOSH & MOAH MOSH: Mineral Oil Saturated Hydrocarbons - chromatographic measure of alkane content of a mineral oil. MOAH: Mineral Oil Aromatic Hydrocarbons - chromatographic measure of aromatic content of a mineral oil. MOSH and MOAH are not substances, but constituents in mineral oil! 18
Who are the stakeholders? Overview situation HPLC-GCxGC- FID/MS (2D) HPLC-GC- FID (1D)
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