Characterisation of Elastomers as Food Contact Materials-Part 1: Quantification of Extractable Compounds, Swelling of Elastomers in Food Simulants and Release of Elements.

Elastomers are not a uniform class of materials but comprise a broad spectrum of chemically different polymers. Sealing gaskets, gloves, teats, conveyor belts and tubing are examples of elastomers being used as food contact materials (FCMs). Ten elastomer samples were evaluated with respect to the content of extractable compounds, migration of substances into ethanolic food simulants, swelling in food simulants and release of elements in different food simulants. The number of extractable substances <1000 Da was determined by comprehensive two-dimensional gas chromatography coupled with flame ionisation detection (GC × GC-FID) analysis of tetrahydrofuran (THF) extracts. The number of signals ranged from 61 (a thermoplastic elastomer (TPE)) to 690 (a natural rubber/styrene-butadiene-rubber blend (NR/SBR)). As for risk assessment, the decisive factor is which substances reach the food. The extent of substances that migrate into ethanolic food simulants was investigated. Elastomer FCMs can be the source of food contamination with heavy metals. Notably, contamination with lead was detected in some samples investigated in this study. It was shown that food simulants harbour the potential to morphologically alter or even disintegrate elastomeric materials. The results presented here highlight the importance to carefully choose the elastomer type for the intended use as FCMs as not every application may prove safe for consumers.

Release of Melamine and Formaldehyde from Melamine-Formaldehyde Plastic Kitchenware.

The release of melamine and formaldehyde from kitchenware made of melamine resins is still a matter of great concern. To investigate the migration and release behavior of the monomers from melamine-based food contact materials into food simulants and food stuffs, cooking spoons were tested under so-called hot plate conditions at 100 °C. Release conditions using the real hot plate conditions with 3% acetic acid were compared with conditions in a conventional migration oven and with a release to deionized water. Furthermore, the kinetics of the release were studied using Arrhenius plots giving an activation energy for the release of melamine of 120 kJ/mol. Finally, a correlation between quality of the resins, specifically the kind of bridges between the monomers, and the release of melamine, was confirmed by CP/MAS 13C-NMR measurements of the melamine kitchenware. Obviously, the ratio of methylene bridges and dimethylene ether bridges connecting the melamine monomers during the curing process can be directly correlated with the amount of the monomers released into food.

Aggregated aluminium exposure: risk assessment for the general population.

Aluminium is one of the most abundant elements in earth's crust and its manifold uses result in an exposure of the population from many sources. Developmental toxicity, effects on the urinary tract and neurotoxicity are known effects of aluminium and its compounds. Here, we assessed the health risks resulting from total consumer exposure towards aluminium and various aluminium compounds, including contributions from foodstuffs, food additives, food contact materials (FCM), and cosmetic products. For the estimation of aluminium contents in foodstuff, data from the German "Pilot-Total-Diet-Study" were used, which was conducted as part of the European TDS-Exposure project. These were combined with consumption data from the German National Consumption Survey II to yield aluminium exposure via food for adults. It was found that the average weekly aluminium exposure resulting from food intake amounts to approx. 50% of the tolerable weekly intake (TWI) of 1 mg/kg body weight (bw)/week, derived by the European Food Safety Authority (EFSA). For children, data from the French "Infant Total Diet Study" and the "Second French Total Diet Study" were used to estimate aluminium exposure via food. As a result, the TWI can be exhausted or slightly exceeded-particularly for infants who are not exclusively breastfed and young children relying on specially adapted diets (e.g. soy-based, lactose free, hypoallergenic). When taking into account the overall aluminium exposure from foods, cosmetic products (cosmetics), pharmaceuticals and FCM from uncoated aluminium, a significant exceedance of the EFSA-derived TWI and even the PTWI of 2 mg/kg bw/week, derived by the Joint FAO/WHO Expert Committee on Food Additives, may occur. Specifically, high exposure levels were found for adolescents aged 11-14 years. Although exposure data were collected with special regard to the German population, it is also representative for European and comparable to international consumers. From a toxicological point of view, regular exceedance of the lifetime tolerable aluminium intake (TWI/PTWI) is undesirable, since this results in an increased risk for health impairments. Consequently, recommendations on how to reduce overall aluminium exposure are given.

Element release from lead crystal ware and metallic hip flasks.

The release of 21 elemental ions from lead crystal ware and metallic hip flasks into different food simulants as well as alcoholic beverages was investigated in this study. For this purpose, an ICP-MS method including a sample pre-treatment based on microwave-assisted digestion was developed and validated. Elemental ion release from lead crystal glasses into artificial tap water, 0.5% citric acid solution and white wine, respectively, was only analysed for Pb. Within 24 h, Pb release from crystal glass was shown to increase with time. To account for repeated use, at least three consecutive release experiments were performed, which showed - with one remarkable exception - constant or decreasing levels of element ion release. However, after four months resting period, Pb release from crystal glass was higher than before. In contrast, all 21 elemental ions were detected to be released from the hip flasks into 0.5% citric acid solution, apple liqueur and herb liqueur, respectively. Release of Cd, Cr, Ni, As, TI, Sn and most prominently Pb from hip flasks was in the range of and above the respective release limit (SRL) as set by the Council of Europe (CoE). When focussing on the third repetition, only one out of six hip flasks met the suggested SRL for all determined elements in all test solutions. This demonstrates both, that the SRLs of the CoE can be met and that producers of hip flasks may have to review their manufacturing processes.

A multi-technique approach for the quantification of 60 plasticizers and selected additives using GC- and LC-MS/MS and its application for beverages in the BfR MEAL study.

The development of multi-analyte methods is always challenging, especially when the target compounds derive from many different substance classes. We present an approach to analyze up to 60 additives - mainly plasticizer - including 28 phthalates and 32 further compounds such as sebacates, adipates, citrates, fatty acid amides, among others. Our multi-analyte multi-technique approach combines a single sample preparation step with one GC-MS/MS and two LC-MS/MS quantification methods. We demonstrate the applicability for beverages by a full validation in tomato juice matrix and determining the recoveries in apple juice, mulled wine, and spirits. The approach features good reproducibilities and high precisions with limits of quantification in the low µg·kg-1 food range, enabling the method to be applied for enforcement and especially for exposure investigations. In course of the BfR MEAL study, 16 pooled beverage samples were examined and - if at all - analytes were found only in very low concentrations.

Impact of climate change on foodborne infections and intoxications.

Background: Temperature, precipitation, and humidity are important factors that can influence the spread, reproduction, and survival of pathogens. Climate change affects these factors, resulting in higher air and water temperatures, increased precipitation, or water scarcity. Climate change may thus have an increasing impact on many infectious diseases. Methods: The present review considers those foodborne pathogens and toxins in animal and plant foods that are most relevant in Germany, on the basis of a selective literature review: the bacterial pathogens of the genera Salmonella, Campylobacter and Vibrio, parasites of the genera Cryptosporidium and Giardia, and marine biotoxins. Results: As climate change continues to progress, all infections and intoxications discussed here can be expected to increase in Germany. Conclusions: The expected increase in foodborne infections and intoxications presents a growing public health risk in Germany.

Investigations on the Transfer of Quinolizidine Alkaloids from Lupinus angustifolius into the Milk of Dairy Cows.

Lupin varieties with a low content of quinolizidine alkaloids (QAs) like blue sweet lupin (BSL) have long been used as a protein source for dairy cows. A health concern for humans may arise from the transfer of acute toxic QAs from feed into cow's milk. This study is the first to quantify the transfer of QAs from BSL into cow's milk with experimental and modeling methods. Four lactating dairy cows were subjected to two 7 day feeding periods with 1 and 2 kg/d BSL, respectively, each followed by a depuration period. BSL contained 1774 mg/kg dry matter total QAs. Individual milk samples were taken twice daily and QA contents in feed and milk determined with liquid chromatography-tandem mass spectrometry. Transfer of QAs into the milk was already seen with the administration of 1 kg/d BSL, with differences in transfer rates (TRs) between individual QAs. A toxicokinetic model was derived to quantify and predict QA feed-to-food transfer. For the four most prominent QAs, our model shows an α-half-life of around 0.27 d. TRs were obtained for six QAs and were between 0.13 (sparteine) and 3.74% (multiflorine). A toxicological assessment of milk containing QAs as measured in this study indicated a potential health concern.

Development and validation of two analytical methods for urea determination in compound feed, including pet food, and yeast using high-performance liquid chromatography coupled with fluorescence detection and tandem mass spectrometry.

Urea is authorised in the European Union (EU) as feed additive for ruminants. Because of its high molecular nitrogen content, it is a substance for potential protein adulteration in non-ruminant feed. The EU defines a spectro-colorimetric method as an official control method for the determination of urea in feed, whereas the Association of Official Analytical Chemists (AOAC) in the United States recommends an enzymatic method. Discrepancies between results obtained by these different approaches have been reported, especially at low concentrations. Therefore, we developed and validated two methods for urea determination in compound feed, including pet food, and yeast (Saccharomyces cerevisiae) over a wide concentration range using high-performance liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) and fluorescence detection (HPLC-FLD) and compared performance with a commercial enzyme kit. Limit of detection (LOD) and limit of quantification (LOQ) were found to be 3 and 8 mg kg-1 for LC-MS/MS and 2 and 7 mg kg-1 for HPLC-FLD, respectively. For both methods, the variation coefficients ranged between 1.4% and 7.2% in ruminant feed used as reference material as well as spiked samples of complete feed for chicken, pet food for dogs and cats, as well as yeast. Recovery rates for spiked samples ranged from 86% to 105%. For real samples of complete feed for poultry, wet and dry pet food for cats and dogs and yeast amounts of urea between < LOD and 200 mg kg-1 relative to a feedingstuff with a moisture content of 12% were found. In comparison with the enzyme kit, the newly developed methods proved to be less time-consuming in sample preparation and more stable regarding matrix effects.

Transport of chlorinated paraffins (CPs) from baking oven doors into the food.

Chlorinated paraffins (CPs) have been repeatedly detected in the kitchen environment. Especially baking ovens were contaminated with high CP amounts on the insides of the doors. To investigate if CPs could be transferred into baked food, we spiked self-synthesized single chain C12-CP and C15-CP standards onto the inside door of an unused, CP-free baking oven. Experiments were performed under different conditions to assess possible CP transportation pathways. Coconut fat was used as food simulant, the exhaust air was monitored with cellulose filter paper and remaining CPs were collected via cotton wipes. In all experiments, both C12- and C15-CPs could be identified in both the food simulant and the cellulose samplers. Mean transfer rates into the food simulant amounted to 2.2% for C12-CPs and 5.8% for C15-CPs. Baking of food in CP-containing baking ovens may perceptibly increase the CP intake of consumers.

Ciguatera Mini Review: 21st Century Environmental Challenges and the Interdisciplinary Research Efforts Rising to Meet Them.

Globally, the livelihoods of over a billion people are affected by changes to marine ecosystems, both structurally and systematically. Resources and ecosystem services, provided by the marine environment, contribute nutrition, income, and health benefits for communities. One threat to these securities is ciguatera poisoning; worldwide, the most commonly reported non-bacterial seafood-related illness. Ciguatera is caused by the consumption of (primarily) finfish contaminated with ciguatoxins, potent neurotoxins produced by benthic single-cell microalgae. When consumed, ciguatoxins are biotransformed and can bioaccumulate throughout the food-web via complex pathways. Ciguatera-derived food insecurity is particularly extreme for small island-nations, where fear of intoxication can lead to fishing restrictions by region, species, or size. Exacerbating these complexities are anthropogenic or natural changes occurring in global marine habitats, e.g., climate change, greenhouse-gas induced physical oceanic changes, overfishing, invasive species, and even the international seafood trade. Here we provide an overview of the challenges and opportunities of the 21st century regarding the many facets of ciguatera, including the complex nature of this illness, the biological/environmental factors affecting the causative organisms, their toxins, vectors, detection methods, human-health oriented responses, and ultimately an outlook towards the future. Ciguatera research efforts face many social and environmental challenges this century. However, several future-oriented goals are within reach, including digital solutions for seafood supply chains, identifying novel compounds and methods with the potential for advanced diagnostics, treatments, and prediction capabilities. The advances described herein provide confidence that the tools are now available to answer many of the remaining questions surrounding ciguatera and therefore protection measures can become more accurate and routine.

Quantification of PET cyclic and linear oligomers in teabags by a validated LC-MS method - In silico toxicity assessment and consumer's exposure.

Determination of polyethylene terephthalate (PET) dimer up to heptamer 1st series cyclic oligomers, applying an LC-qTOF-MS method, has been developed and validated. Recoveries ranged between 80 and 112% with RSDs lower than 15%. An innovative semi-quantitative approach has been applied for 2nd and 3rd series cyclic oligomers, using the closest structural-similar 1st series cyclic oligomer standard as analytical reference. Oligomers from the three series were quantified in PET teabags after migration experiments with water and food simulants C (20% v/v ethanol in water) and D1 (50% v/v ethanol in water). No legal migration limits exist currently for these substances. In silico genotoxicity assessment of all identified oligomers has been performed and showed no genotoxicity alert for linear or cyclic molecules. Exposure assessment was performed using EFSA's approach on the total sum of migrating oligomers and on toxicological threshold-of-concern. Amounts found in water were in some cases significantly higher than the respective limits, especially in the worst-case scenario of multiple consumption.

Dietary exposure to elements from the German pilot total diet study (TDS).

Dietary exposure of the German adult population to the elements aluminium, copper, mercury (and as methylmercury), manganese and lead were assessed using data from the first total diet study (TDS) in Germany. In this pilot TDS, performed 2014-2015, 246 food samples were purchased in the Berlin area, prepared 'as consumed', and subsequently analysed. Dietary exposure for the German adult population between 14 and 80 years of age was estimated by combining TDS data with individual consumption data from the German National Consumption Survey II (NVS II). Estimated mean and high-level dietary exposure values showed that none of the elements analysed exceeded toxicological reference values; neither was there an undersupply of essential elements. Assessments for methylmercury and lead in women of child-bearing age, in particular, showed no considerable elevated intake levels.

Dietary Manganese Exposure in the Adult Population in Germany-What Does it Mean in Relation to Health Risks?

Manganese is both an essential nutrient and a potential neurotoxicant. Therefore, the question arises whether the dietary manganese intake in the German population is on the low or high side. Results from a pilot total diet study in Germany presented here reveal that the average dietary manganese intake in the general population in Germany aged 14-80 years is about 2.8 mg day-1 for a person of 70 kg body weight. This exposure level is within the intake range of 2-5 mg per person and day as recommended by the societies for nutrition in Germany, Austria, and Switzerland. No information on the dietary exposure of children in Germany can be provided so far. Although reliable information on health effects related to oral manganese exposure is limited, there is no indication from the literature that these dietary intake levels are associated with adverse health effects either by manganese deficiency or excess. However, there is limited evidence that manganese taken up as a highly bioavailable bolus, for example, uptake via drinking water or food supplements, could pose a potential risk to human health-particularly in certain subpopulations-when certain intake amounts, which are currently not well defined, are exceeded.

The analysis of saturated and aromatic mineral oil hydrocarbons in dry foods and from recycled paperboard packages by online HPLC-GC-FID.

The purpose of this study was to determine the concentrations of mineral oil hydrocarbons in dry foodstuffs packed in recycled paperboard, which were imported from different foreign countries to Germany. After collection, mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) in dry foodstuffs and recycled paperboard were analysed using online coupled high-performance liquid chromatography-gas chromatography-flame ionisation detection (online HPLC-GC-FID) far before the end of the shelf life of the samples. Our results showed that recycled paperboard has MOAH content higher than that of dry foodstuffs. The proportion of MOAH within total mineral oil hydrocarbons was determined to be 7-45% in dry foodstuffs and 4-48% in paperboard. In addition, 29% of the products were found to contain over 1.00 mg/kg MOAH, with a maximum of 2.72 mg/kg in oatmeal. White colour recycled paperboard contained lower amounts of MOSH and MOAH than that of brown and grey colour recycled paperboard. The MOSH concentration in dry foodstuffs ranged from 0.11 to 21.92 mg/kg (˂C25 hydrocarbons), which may be an indication of rapid migration. The lowest determined MOSH concentrations (˂C25 hydrocarbons) were found in sea salt and soda samples, even when their paperboard contained high mineral oil hydrocarbons. Our three samples in packages containing internal bags (for complete barriers) were found to have low mineral oil concentration due to reduced migration through plastic (acrylate-coated polypropylene). However, one sample, a 'crispy' product with an internal bag, contained the extreme amount of 21.92 mg/kg. Differences in contaminants observed in both dry foodstuffs and recycled paperboard may have been due to the different packaging and production techniques of the different countries. In addition, 8 of 24 dry foodstuff samples contained MOSH concentrations frequently exceeding the 2.0 mg/kg limit for MOSH C20-C35.

Validation and application of an LC-MS/MS method for the determination of cyclic oligomers originating from polyamide 6 and polyamide 66 in food simulant.

Polyamides (PAs) are used in the production of various food contact materials (FCMs) and articles such as kitchen utensils and packaging material. Cyclic oligomers have been identified as potential migrants from PA. This study describes the development, validation and application of a multi-oligomer analytical method based on LC-ESI-MS/MS for the identification and quantification of eight cyclic oligomers of PA 6 and four PA 66 migrating from FCMs into food simulant B (3% acetic acid) and beverages. It was proved that doubly charged precursor ions of the cyclic PA 6 and PA 66 oligomers above a mass of 500 Da are formed during the ionisation process of the electrospray technique used. Direct injection of a diluted food simulant into the LC-ESI-MS/MS system after migration makes the validated method a valuable tool for investigating migration of cyclic PA oligomers. The validation results demonstrate that the multi-oligomer method is applicable for the analysis of cyclic PA 6 and PA 66 oligomers in food simulant B. For all investigated cyclic PA oligomers, detection limits were in the range of 0.1-1.1 µg/l. Linearity (r2 ≥ 0.99), trueness values between 91% and 122%, and intra-day (RSDr < 10%) and inter-day precision (RSDR < 19%) were determined and satisfied validation criteria set out by the European Reference Laboratory for FCMs. The method was extended to tap water and tea. Finally, the multi-oligomer method was successfully applied to determine cyclic PA oligomers in migration solutions originating from different PA FCMs. In all migration solutions, concentrations of cyclic PA oligomers were determined above the LOQ. A preliminary risk assessment based on in silico tools was performed. The results demonstrate the urgent need for toxicological data that would facilitate the evaluation of the health risk of cyclic PA oligomers.

Transfer of primary aromatic amines from coloured paper napkins into four different food matrices and into cold water extracts.

The aim of this study was to compare the transfer of primary aromatic amines (PAAs) from napkins into cold water extract (CWE) with transfer into four different food matrices. An HPLC-MS/MS multi-analyte method for quantification of 26 PAAs in CWE was validated and applied. In addition, the method was validated for seven different PAAs in four different food matrices (cucumber, rice, pickled gherkin and butter cookie) representing wet, dry, acidic and fatty food. The CWEs of 12 coloured napkin samples were analysed, and 3 napkins released more than 0.01 mg kg-1 PAAs into the CWE. These three napkins were chosen for transfer testing with food samples. In total, seven different PAAs were quantified in the food samples. Results show that the transfer of the tested PAAs into the CWE is in most cases comparable to the transfer into the tested food samples. In some cases, the CWE overestimates transfer into food, except for the transfer of aniline into pickled gherkin, where the CWE underestimates transfer. Therefore, the CWE serves as an adequate and certainly not overestimating simulation of reality for the tested transfer of PAAs into the food samples.

Release of aluminium and thallium ions from uncoated food contact materials made of aluminium alloys into food and food simulant.

In order to investigate the release of aluminium ions from food contact materials, three different types of uncoated aluminium menu trays for single use were tested with the foodstuffs sauerkraut juice, apple sauce and tomato puree, as well as with the food simulants 5 g/L citric acid solution and artificial tap water. To mimic a consumer relevant exposure scenario, the aluminium trays were studied using time and temperature gradients according to the Cook & Chill method, also taking into account storage time at elevated temperatures during the delivery period. The release of aluminium was found to exceed the specific release limit (SRL) of 5 mg aluminium per kilogram of food specified by the Council of Europe by up to six times. Furthermore, a release of thallium was also detected unexpectedly. Kinetic studies showed a comparable behaviour in the release of aluminium, manganese and vanadium as components of the aluminium alloy itself. In contrast, thallium could be identified as a surface contaminant or impurity because of an entirely different kinetic curve. Kinetic studies also allowed activation energy calculations. Additional camping saucepans were tested as an article for repeated use. In three subsequent release experiments with citric acid (5 g/L), artificial tap water and tomato puree as benchmark foodstuffs, the results were comparable to those of the uncoated wrought alloy aluminium trays.

N-nitrosamines migrating from food contact materials into food simulants: analysis and quantification by means of HPLC-APCI-MS/MS.

It was the aim of the work described here to develop a validated analytical method for the determination of N-nitrosamines in food simulants. Here, we present the validation of a liquid chromatography-atmospheric pressure chemical ionisation-tandem mass spectrometry method for the determination of 13 N-nitrosamines in the food simulants deionised water, 3% acetic acid and 10% ethanol. Method validation encompassed linearity, LOD, LOQ, recovery, precision and stability of the N-nitrosamines. The method was found to be sufficiently rugged and suitable for routine analysis. In addition, the developed method is on average 10 times more sensitive than the gas chromatography-thermal energy analyser (GC-TEA) method that is currently stipulated in Recommendation XXI for commodities based on natural and synthetic rubber issued by the German Federal Institute for Risk Assessment (BfR). The developed method was applied to determine the N-nitrosamine contents in migration solutions of 12 elastomer samples covering a range of different elastomer types. In 10 out of 12 samples, N-nitrosamines were determined. In most samples, the guidance value of 1 µg/dm2 specified in BfR Recommendation XXI was not exceeded. In conclusion, the analytical method presented here offers a useful alternative to the GC-TEA method currently stipulated in BfR Recommendation XXI. This is of wider relevance, since BfR recommendations are used for compliance assessment of Article 3, paragraph 1 a of the Regulation (EC) No. 1935/2004 with respect to their health safety.

Metal release from coffee machines and electric kettles.

The release of elemental ions from 8 coffee machines and 11 electric kettles into food simulants was investigated. Three different types of coffee machines were tested: portafilter espresso machines, pod machines and capsule machines. All machines were tested subsequently on 3 days before and on 3 days after decalcification. Decalcification of the machines was performed with agents according to procedures as specified in the respective manufacturer's manuals. The electric kettles showed only a low release of the elements analysed. For the coffee machines decreasing concentrations of elements were found from the first to the last sample taken in the course of 1 day. Metal release on consecutive days showed a decreasing trend as well. After decalcification a large increase in the amounts of elements released was encountered. In addition, the different machine types investigated clearly differed in their extent of element release. By far the highest leaching, both quantitatively and qualitatively, was found for the portafilter machines. With these products releases of Pb, Ni, Mn, Cr and Zn were in the range and beyond the release limits as proposed by the Council of Europe. Therefore, a careful rinsing routine, especially after decalcification, is recommended for these machines. The comparably lower extent of release of one particular portafilter machine demonstrates that metal release at levels above the threshold that triggers health concerns are technically avoidable.