Störmer et al.
10.3389/fchem.2024.1397913
5.2.1 Migration into dry foods Migration into dry foods has been a topic for most of these scienti fi c publications because contact with dry foods represents a major application of paper in food contact. Urbelis and Cooper (2021) published a comprehensive summary review of 162 studies that examined migration into dry foods and its simulants, an important data source. The focus of this study was the extent of migration into dry foods and not speci fi cally from paper packaging but any type of food contact material. However, the largest part is paper relevant. This might correlate with the fact that most packaging for dry foods is paper. This review deals with the analysis of market food products, as well as of food products and food simulants in contact with food contact material, after experimental forti fi cation with known quantities of a migrant. The discussion on testing, information gaps, and remaining questions coincides with this review but is done from a different perspective. 5.2.2 MPPO as a simulant for dry food MPPO is the of fi cial EU food simulant (simulant E) for dry foods in the EU Plastics Regulation (EU, 2023). The development and use of MPPO as a simulant for dry foods go back to the 1990s. Piringer et al. (1993) published the method for the fi rst time as a convenient approach for determining the overall migration at high temperatures such as from non-stick coatings on frying pans and baking papers. The method was also applicable to the determination of speci fi c migration of organic substances from adhesives in paper food contact material (Gruner and Piringer, 1999). Since then, the so-called Tenax method has been increasingly used and has reached a Europe-wide of fi cial status with CEN EN 1186:2002-Part 13 (CEN, 2002a) for the overall migration testing of plastic food contact material at high temperature ( > 100 ° C) and the implementation of MPPO as food simulant E for dry foods in EU Regulation 10/2011 (EU, 2023). In parallel, the method was standardized for paper food contact material testing (CEN, 2003). The use and appropriateness of MPPO as a simulant for dry foods were reviewed by Van Den Houwe et al. (2018). The majority of collected data and cited references relate to paper materials. The performance of MPPO as a food simulant for dry foods is discussed based on comparisons with real foods and other food-simulating adsorbents. MPPO simulation compared with the real migration conditions into several foodstuffs (such as sugar, fl our, cake and certain pastries, semolina, instant baby formula, milk powder, rice, salt, cereals and even meat, chocolate, sweet matrices, fresh fruits, and vegetables) showed no underestimations of the real conditions. Van Den Houwe concluded that MPPO is suitable as a simulant for dry foodstuffs. Moreover, in their view, the only suitable simulant for the simulation of dry foodstuffs. 5.2.3 MPPO simulant versus dry foods: recycling components other than mineral oil In 1999 – 2002, an early and essential scienti fi c initiative was taken by EU Project FAIR CT 98 – 4318 “ Recyclability ” within its Section 2 “ Paper and Board ” (Raffael and Simoneau, 2002; Castle and Franz, 2003). Migration kinetics from 15 different paper sample types were comparatively investigated between dry foods (cookies, fl our, milk powder, noodles, salt, semolina, soup powder, sugar, and icing sugar) and MPPO at temperatures ranging from room
temperature up to 100 ° C. A selection of 12 surrogates [such as acetophenone, diphenylether, diisobutylphthalate (DiBP), and diisopropylnaphthalene (DIPN) isomers; Supplementary Table S1] of different chemical structures and volatilities was spiked into the paper samples before testing. Furthermore, partition coef fi cients between paper and food (simulant) as a crucial mass transfer parameter for migration modeling purposes were determined. Transfer from the paper rapidly reached its equilibrium, depending on substance and temperature, e.g., after 1 h at 100 ° C and 2 – 10 days at 23 ° C. Migration to MPPO was in almost all cases higher than into foods. The fi nal partition ining coef fi cient between paper and MPPO simulant was always at least one order of magnitude less than the one between paper and foodstuff. Thus, MPPO was found to be more severe than food concerning the adsorption/uptake of migrants from paper; therefore, it was considered to be a good simulant for dry foods. Diisopropylnaphthalene, intrinsically present in the recycled board, displayed a different kinetic behavior compared with the spiked-in experiments, which was explained by “ native ” DIPN being present in the encapsulated form (from the recycling of carbonless copy papers). This explanation is not necessarily correct because others found differences between “ native ” and forti fi ed substances also for other components like phthalates (Zülch and Piringer, 2010; Bradley et al., 2015). Aurela et al. (1999) compared the release of two phthalates (diisobutylphthalate and dibutylphthalate) from paper packages into (crystal) sugar with those into MPPO. The measured migration was similar in sugar stored for 4 months at room temperature and in MPPO stored for 10 days at 40 ° C or 2 h at 70 ° C. Alkylbenzenes (C10 – C13 alkyl chain) at 30 min at 70 ° C showed an overestimation factor of 3.8 in MPPO compared with hamburger rolls under the same condition (Aurela et al., 2002). Baele et al. (2020) observed a strong overestimation for volatile substances (1,3,5-tri-tert-butylbenzene, n-hexadecane, and n-heptadecane) by MPPO (indirect contact, 22 ° C, 16 weeks) in comparison to starchy, low-fat foods (noodles with and without eggs, wheat, and rice semolina) but similar migration as into chocolate. The difference decreased with decreasing volatility of the migrants. Summer fi eld and Cooper (2001) compared the migration of dibutylphthalate, diisobutylphthalate, and diisopropylnaphthalene from recycled board into various dry foods and MPPO. In identical conditions (10 days/40 ° C), migration into MPPO was similar or even lower than migration into rice but similar (diisobutylphthalate) or distinctly higher (diisopropylnaphthalene) when rice were stored for 6 months at 20 ° C. Diisopropylnaphthalene migrated in similar or even higher amounts in MPPO than in fl our and pastry at 40 ° C. Migration in fl our — stored for 6 months at 20 ° C — was similar to that after 10 days at 40 ° C. 5.2.4 Mineral oil components (MOSH and MOAH) in market samples A series of publications (2010 – 2016) dealt with the migration of mineral oil hydrocarbons (MOH, saturated: MOSH, aromatic hydrocarbons: MOAH) from paper food packaging into foods. The major focus was on dry foods and the underlying mechanisms. The authorship varied but centered around the Cantonal Food Control Lab of Zurich. The starting point was
Frontiers in Chemistry
06
frontiersin.org
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