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Per- and polyfluoroalkyl substances (PFAS) are used in the production of PTFE based coatings for cookware. In this study, emission of PFAS and further volatile organic compounds (VOC) from kitchenware articles were investigated. First, method development for thermal extraction of baking trays, frying pans and baking mats at 250 °C was done by testing three different extraction devices. A thermal desorption oven showed the best blank and highest recoveries of PFAS analytes (70–101% for 12 perfluorocarboxylic acids (PFCAs), 2 fluorotelomer alcohls (FTOHs), 3 per- and polyfluoroether carboxylic acids (PFECAs), 1 polyfluoroether (PFE)). Second, 18 cookware samples, a PTFE micro powder and 2 lab made coating strips have been investigated. No PFAS were detected in 12 samples (limits of detection: 1–13 ng/dm2). PFCAs (C5–C23) were detected in a baking tray in amounts up to 34 ng/dm2. A baking mat contained 3 ng/dm2 PFOA. FTOHs were not detected in the samples. A PFECA (bC7O2) and its hydride (bC6O2H PFE) were detected in one coating intended for use in frying pans. The hydrides of the PFECA mixture, b(C3O1)nC3 PFECA (Krytox 157FSH), were detected in five baking trays. The PFAS target analytes were not detectable in the five investigated frying pans. Analysing further VOC in the emissions of coatings, 175 compounds could be identified, including alkanes, alkenes, aromatic substances, esters, aldehydes, ketones, ethers, alcohols, carboxylic acids, siloxanes and sulphur, nitrogen, as well as chlorine containing compounds (< 10 µg/dm2). The identified substances cannot be connected to the basic coating polymer of the kitchenware articles, which were PTFE and PES. All samples have undergone a threefold thermal extraction. No substances could be detected in the second and third consecutive extraction, which means that a removal and no new formation of the investigated PFAS as well as the further VOC at 250 °C has occurred. [ABSTRACT FROM AUTHOR]

Per- and polyfluoroalkyl substances (PFAS) are used in food contact materials (FCMs), e.g. as production aids in the fabrication of PTFE based coatings for kitchenware or as additives in paper and board. Growing concerns about the environment and health related to PFAS have led to an increasing interest in monitoring PFAS levels in FCMs as well as their migration into food. In this study, method development for the analysis of PFAS by thermal desorption – gas chromatography – mass spectrometry (TD-GC-MS) was done. In addition to fluorotelomer alcohols (FTOHs), which are the only PFAS commonly analysed by GC-MS, it was proven that perfluorocarboxylic acids (PFCAs) and per- and polyfluoroether carboxylic acids (PFECAs) as well as their thermolysis products, perfluoroethers (PFEs) and perfluoroalkenes, can be analysed by GC-MS without prior derivatization. Screening for PFCAs and FTOHs was possible by electron impact ionization (EI) using group specific SIM fragments. Confirmation of identity has been done by EI scans as well as chemical ionization (CI) SIM measurements. LODs (limits of detection) of PFCAs, FTOHs and PFECAs in the TD-GC-MS instrument were in the low pg range. Thermal degradation of PFCAs and PFECAs during TD-GC-MS measurement was investigated. [ABSTRACT FROM AUTHOR]

Paper and board are used for packaging of moist as well as dry food. According to Regulation (EC) No. 1935/2004, food contact materials (FCM) must not bring about a deterioration in the organoleptic characteristics of foodstuffs. For testing the transfer of off-flavour (taint) from packaging to food via the gas phase (DIN EN 1230-2), relative humidity (rH) has to be adjusted. In contrast, rH is neither taken into account when testing the odour (DIN EN 1230-1), nor in chemical migration of volatile organic substances (VOC) onto the adsorbent Tenax® (DIN EN 14338). In this work, effect of different rHs on the desorption of VOC from paper and board was investigated by GC-MS analysis as well as by human sensory tests. Raising humidity led to an increase in VOC transfer, which was observed by increasing peak areas as well as the detection of more substances in GC-MS. Analytical results were in line with human sensory tests. The odour profile of the paper at 33 and 58% rH was described as cardboard-like, sweet and smoky. Impact substances for these olfactory impressions were (E)-2-nonenal, vanillin and 2-methoxyphenol as identified by GC with an olfactory detection port (GC-ODP). The increase to 75 and 100% rH resulted in the additional perception of cheesy/sweaty and fatty/rancid impressions, which were primarily caused by short-chain fatty acids and di-unsaturated aldehydes. [ABSTRACT FROM AUTHOR]

Tritan™ (a kind of glycol-modified polycyclohexylene dimethylene terephthalate) is a novel copolyester mainly in use for the production of sports bottles and food storage containers. Oligomers in three food-grade Tritan™ samples were identified after dissolution-precipitation by high performance liquid chromatography with diode array detection and mass spectrometry and quantified after alkaline hydrolysis to the monomers. The obtained overall oligomer content <1000 Da determined by hydrolysis ranged from 7.2 to 10.6 mg/g material. Three consecutive migration experiments were performed according to the Commission Regulation (EU) No 10/2011. Oligomer migration values decreased from first to third migration during all simulations. Less than 25 µg/kg (third migrate) were detected in bottle migrates when tested under room temperature storage conditions (40 °C, 24 h) with simulants 3% acetic acid, 20 and 50% ethanol and during hot-fill testing (70 °C, 2 h) with simulants 3% acetic acid and 20% ethanol, respectively, while 170 µg/kg were determined in 50% ethanol after migration at 70 °C for 2 h. Food storage containers that were labelled as microwave-suitable by the supplier were tested according to the Joint Research Centre recommendations for microwave dishware. A strong deformation of the containers as well as a loss of transparency were observed during the tests (100 °C, 2 h with 10% ethanol and 3% acetic acid in an autoclave, 121 °C, 30 min with sunflower oil), questioning the suitability of the material for microwave applications. Maximum oligomer migration was 379 µg/kg during the third migration (sunflower oil at 121 °C for 30 min). Based on the migration data and an in silico oligomer evaluation according to the threshold of toxicological concern concept, no exceedances of daily thresholds for oligomers are expected from a proper use of Tritan™ drinking bottles, even with hot drinks. [ABSTRACT FROM AUTHOR]

Styrene-acrylonitrile-copolymer (SAN) and acrylonitrile-butadiene-styrene-copolymer (ABS) are gaining in importance as food contact materials. Oligomers and other non-intentionally added substances can migrate into foodstuffs. Five SAN and four ABS samples from the German market and manufacturers were extracted and the extractable oligomers were characterised by high performance liquid chromatography-mass spectrometry/ultraviolet detection/chemiluminescence nitrogen detection/fluorescence detection and gas chromatography-mass spectrometry. Trimers, formed from acrylonitrile and styrene units, were determined to be the dominating group of extractable oligomers in SAN and ABS in concentrations of about 4900–15800 mg/kg material. Furthermore, styrene-acrylonitrile dimers, styrene oligomers, styrene monomer and ethylbenzene were identified in the sample extracts. Migration testing with three consecutive migrations for multiple use articles was performed for two SAN articles. Migration of trimers into water, 3% acetic acid, 10% and 20% ethanol under hot-fill conditions (70°C, 2 h) was not detectable above 9 µg/dm2, while 50% ethanol acting as a food simulant for milk (124 µg/dm2 trimers during the third migration) was shown to overestimate the actual migration into milk (< 11 µg/dm2 trimers at 70°C, 2 h). 2-Amino-3-methyl-1-naphthalenecarbonitrile (AMNC), an oligomer degradation product and a primary aromatic amine, was detected in all material sample extracts (0.3–17.1 mg/kg material) and was released into food simulants in low amounts (< 0.014 µg/dm2 during the third migration into 50% ethanol at 70°C, 2 h). [ABSTRACT FROM AUTHOR]

Polyesters are commonly used as food contact materials. During manufacture of polyesters different low molecular mass oligomers (<1000 Da) are formed in the polymer melt. These so-called non-intentionally added substances (NIAS) are potential migrants into foods. In this work, different polyester samples made of polyethylene terephthalate (PET), glycol-modified PET (PETG) and Tritan™ were investigated on their qualitative and quantitative oligomer composition. The analysis of acetonitrile extracts by HPLC-DAD/ESI-MS revealed the presence of about 100 linear (different combinations of hydroxyl-, carboxyl-, methyl ester end groups) and cyclic oligomers depending on the main and co-monomers. The identified oligomers were quantified in different extracts and after reprecipitation by HPLC-DAD using bis-hydroxyethylene terephthalate (BHET) as external standard. The amount of oligomers isolated by reprecipitation ranged between 0.80 and 3.4% in the respective polyester. Cyclic oligomers generally made up 90% or more of the isolated oligomers. Compared to the exhaustive extracts the leaching of oligomers into 20% ethanol (1 h, 60 °C) resulted in a considerable change of the oligomer distribution with a predominant detection of linear oligomers. This suggests linear oligomers to be relevant for migration into aqueous foods despite the dominant amount of extractable cyclic oligomers in polyesters. Analysis of the extractable oligomers of a PET preform and a PETG container and their corresponding raw material pellets revealed that the injection moulding process did not significantly change the amount of cyclic oligomers but did increase the amount of low molecular mass linear oligomers about twofold. [ABSTRACT FROM AUTHOR]

Coatings for cans or closures are essential to protect the metal from corrosion and the food from migration of hazardous metal ions. Since coatings are no inert materials, they can release substances of potential health concern into food. In the present study, a comprehensive analysis is presented for a complex two-layered polyester–phenol-coating commercially used for metal closures of complementary infant food in sterilised glass jars. Focussed on the identity and migration of cyclic polyester oligomers as a kind of predictable non-intentionally added substances, polyester resin raw materials (n = 3) as well as individual coating layers (n = 3) were characterised by several analytical strategies (size exclusion chromatography, high-performance liquid chromatography mass spectrometry, diode array detection, charged aerosol detection, monomer determination after alkaline hydrolysis, overall migrate). The main polyester monomers were terephthalic acid, isophthalic acid, trimellitic acid, ethylene glycol, diethylene glycol, neopentylglycol, 2-methyl-1,3-propanediol, 1,4-butanediol and tricyclodecanedimethanol. The coatings were extracted with solvents acetonitrile and ethanol (24 h, 60°C), food simulants 50% ethanol, 20% ethanol and water (1 h, 121°C) as well as homemade and commercial baby food (1 h, 121°C). The released total polyester content determined by alkaline hydrolysis ranged from 288 µg/dm2 (water, 1 h, 121°C) to 6154 µg/dm2 (acetonitrile, 24 h, 60°C). However, individual cyclic oligomers, mainly dimers, were released from the coating to up to about 140 µg/dm2. Migration into infant food was best represented by the food simulants water (up to 1% fat) and 20% ethanol (up to 5% fat). Cyclic polyester oligomers are classified as Cramer III substances by the threshold of toxicological concern concept associated to an exposure threshold of 1.5 µg/kg body weight per day. Exposure to cyclic polyester oligomers might be a potential concern for highly exposed infants. [ABSTRACT FROM AUTHOR]

Cyclic monomer and oligomers are the major migrating substances from polyamide (PA) food contact materials. An increase of caprolactam (+44%) and cyclic oligomer content (+27%, incl. caprolactam) in PA6 was observed by thermal treatment, here by extrusion of a PA6 film from a granulate. Migration experiments with a PA6 and a PA66 packaging film were carried out into food simulants according to directives 85/572/EEC and 82/711/EEC. Contact conditions (2 h/100°C) were chosen for a heat treatment of the food in the packaging, in this case production of scalded sausage. Aqueous and ethanolic food simulants clearly revealed to be the worst case for migration of cyclic PA6 and PA66 monomer and oligomers. Migration of cyclic oligomers into oil was one order of magnitude lower. No migration could be observed into isooctane (<8 µg dm−2). The substitutes for oil, 95% ethanol and isooctane, were inapplicable for simulating migration of cyclic oligomers into oil. Caprolactam showed different migration behaviour compared with cyclic oligomers, migrating into oil and water to the same extent depending on contact conditions. Fifty percent of the extractable caprolactam migrated from a PA6 sausage casing into scalded sausage (4.2 mg kg−1), residual 41% apparently were extracted by the boiling medium or during pretreatment (soaking) of the casing. Potential migration of caprolactam and cyclic oligomers from a PA6 tea bag was found to be 18% of the specific migration limit for caprolactam and 36% of the overall migration limit. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Paper and board are used for packaging of moist as well as dry food. According to Regulation (EC) No. 1935/2004, food contact materials (FCM) must not bring about a deterioration in the organoleptic characteristics of foodstuffs. For testing the transfer of off-flavour (taint) from packaging to food via the gas phase (DIN EN 1230-2), relative humidity (rH) has to be adjusted. In contrast, rH is neither taken into account when testing the odour (DIN EN 1230-1), nor in chemical migration of volatile organic substances (VOC) onto the adsorbent Tenax® (DIN EN 14338). In this work, effect of different rHs on the desorption of VOC from paper and board was investigated by GC-MS analysis as well as by human sensory tests. Raising humidity led to an increase in VOC transfer, which was observed by increasing peak areas as well as the detection of more substances in GC-MS. Analytical results were in line with human sensory tests. The odour profile of the paper at 33 and 58% rH was described as cardboard-like, sweet and smoky. Impact substances for these olfactory impressions were (E)-2-nonenal, vanillin and 2-methoxyphenol as identified by GC with an olfactory detection port (GC-ODP). The increase to 75 and 100% rH resulted in the additional perception of cheesy/sweaty and fatty/rancid impressions, which were primarily caused by short-chain fatty acids and di-unsaturated aldehydes. [ABSTRACT FROM AUTHOR]

A rapid, reproducible, and sensitive ion-exchange chromatography (IEC) method combined with graphite-furnace atomic absorption spectrometry (GF-AAS) was developed to separate and quantify basal amounts of both metallothionein (MT) isoforms in dab (Limanda limanda) liver samples. Dab liver homogenates were saturated with Cd, and obtained cytosols were purified by a two-step acetone precipitation prior to chromatographic analysis. Metallothionein isoforms were separated by IEC and were subsequently quantified indirectly by GF-AAS via their Cd contents. The amount of Cd needed for saturation was optimized. The efficiency of Cd saturation and acetone precipitation was proven by gel permeation chromatography (GPC) and metal distribution analysis. Based on the method of standard addition, a recovery for MT was 98% after acetone precipitation and 68% after IEC. The repeated determination ofMT isoforms in a dab liver homogenate resulted in coefficients of variation of approximately 12% for both isoforms. Based on the detection limit for GF-AAS, the calculated detection limit for MT isoforms is2 ng/mg protein. Therefore, this method is suitable for monitoring purposes. The implications of isoform-specific measurement for biomarker monitoring are discussed. [ABSTRACT FROM AUTHOR]