Comparison of migration from polyethersulphone and polycarbonate baby bottles

This work presents two analytical methods developed for measuring three components of polyethersulphone (PES) and applying them to the migration testing of 30 baby bottles made of PES. The study also provides migration results under the same conditions for bisphenol A (BPA) from 40 polycarbonate baby bottles using a well-established method adapted to low concentrations. For PES bottles, migration of diphenyl sulphone (DPS), 4,4′-dichlorodiphenyl sulphone (DCPS) and 4,4′-dihydroxydiphenyl sulphone (DHPS; also known as bisphenol S) was carried out using two different analytical methods with detection limits of 0.1–0.3?µg/kg, and, therefore, much below their respective European Commission Directive 2002/72/EC legislative migration limits of 50–3000?µg/kg, respectively. In parallel, 40 bottles made of polycarbonate were analysed for the migration of BPA using a method validated at EU level and modified to give a lower detection limit of 0.1?µg/kg. Migration tests were conducted into the simulant for milk 50% EtOH (as per Commission Regulation No. 321/2011 of 1 April 2011) according to the test conditions from the guidelines on test conditions for articles in contact with foodstuffs (with a focus on kitchenware) prepared by the EU Reference Laboratory and its network of National Reference Laboratories. None of the 30 bottles made of PES released any detectable amounts of DCPS or DHPS and only two bottles released a very low amount of DPS of ～1?µg/kg in the milk food simulant compared to a regulatory limit of 3000?µg/kg. For PC bottles, 32 bottles of 40 (80%) did not release BPA above the LOD of 0.1?µg/kg (in any of the three migration tests performed on each bottle). The other 20% of bottles exhibited only very minor migration, where the highest level in the first migration test was 1.83?µg/kg and most bottles did not release detectable BPA in the second and third test. Only one bottle, with a migration level of 1.08?µg/kg, in the first test still showed a detectable level in the last migration test (i.e. 0.42?µg/kg). It is important to note that the legal limit (European Commission Directive 2002/72/EC) was still 600?µg/kg for polycarbonate bottles at the time of purchase, preceding the precautionary ban taking effect from 1 June 2011 (Commission Directive 2011/8/EU; Commission Regulation No. 321/2011). This confirms that the likelihood of migration of BPA is very low and remains at very minute amounts. The results also suggest the absence of release from PES bottles based on the set of bottles investigated.     

Identification and quantification of the migration of chemicals from plastic baby bottles used as substitutes for polycarbonate

The results of a study on the analytical identification and quantification of migration of chemicals from plastics baby bottles found in the European Union market made of materials that are now present as substitutes for polycarbonate (PC) are reported. A total of 449 baby bottles with a focus on first age or sets of bottles were purchased from 26 European Union countries, Canada, Switzerland and the USA. From this collection, which contained several duplicates, a total of 277 baby bottles were analysed. The materials included different types of plastic such as PC, polyamide (PA), polyethersulphone (PES), polypropylene (PP), but also silicone, and from the United States a co-polyester marketed under the trade name Tritan?. The bottles were subjected to the conventional migration test for hot fill conditions, i.e. 2?h at 70°C. The simulant used was that specified in European Union legislation (2007/19/EC) for milk, i.e. 50% ethanol. In a first phase 1, migration was conducted since the scope of this investigation was a screening rather than a true compliance testing check. Second and third migrations were performed on selected articles when migrated substances exceeded limits specified in the legislation. In order to verify some materials, a portion of the bottle was cut to run an FT-IR fingerprint to confirm the nature of the polymer. The migration solutions in general showed a low release of substances. Results showed that bottles made of PP and silicones showed a greater number of substances in the migration solutions and in greater quantity. Chemicals from PP included alkanes, which could be found in >65% of the bottles at levels up to 3500?μg?kg?1; and benzene derivatives in 17% of the baby bottles and found at levels up to 113?μg?kg?1. Some substances were found on a regular basis such as plasticisers, esters and antioxidants (e.g. tris(2,4-di-tert-butylphenyl)phosphate, known as Irgafos 168. Some substances found were not included in the Community positive list, which means that those should not be found even in the first migration. Such substances included 2,6-di-isopropylnaphthalene (DIPN), found in 4% of the bottles at levels up to 25?μg?kg?1, 2,4-di-tert-butyl phenol (in 90% of the bottles at levels up 400?μg?kg?1). Moreover, bisphenol A (BPA) was detected and quantified in baby bottles made of PA, but limited to one brand and model specific (but labelled BPA free). Results for baby bottles made of silicone also indicated the presence of components, e.g. potentially coming from inks (benzophenone, diisopropyl naphtahalene - DIPN, which could come for example from the presence of instruction leaflets in the bottles). In the case of silicone, phthalates were also found in relevant concentrations, with levels for DiBP and DBP from the first migration test of 50-150?μg?kg?1 and DEHP at levels 25-50?μg?kg?1.     

Migration of bisphenol A from polycarbonate baby bottles under real use conditions

Migration of the potential endocrine disrupter, bisphenol A (BPA), from 31 polycarbonate (PC) baby bottles into aqueous food simulants was studied under real repetitive use, using a sensitive and fully validated liquid chromatographic method with fluorescence detection. Confirmation of the presence of BPA was performed by liquid chromatography–mass spectrometry (LC–MS). The effects of cleaning in a dishwasher or with a brush, sterilization with boiling water and the temperature of migration were examined. It was shown that temperature was the crucial factor for the migration of BPA from the plastic bottles to water. All samples released BPA in the concentration range 2.4–14.3 µg kg^?1 when filled with boiled water and left at ambient temperature for 45 min. The decrease of BPA release in the sterilization water and in the food simulant over 12 cycles of use indicated that the hypothesis of polymer degradation in water is dubious. Estimated infantile dietary exposure, regarding the use of PC baby bottles, ranged between 0.2 and 2.2 µg kg^?1 bw day^?1, which is below the Tolerable Daily Intake of 50 µg kg^?1 bw recently established by EFSA.     

Migration of bisphenol A from polycarbonate baby bottles purchased in the Spanish market by liquid chromatography and fluorescence detection

During the last decade the safety of bisphenol A (BPA) monomer in polycarbonate baby bottles has drawn the attention of both the public and the scientific community. This paper presents the results of BPA migration from polycarbonate baby bottles bought in the Spanish market, into simulant B (3% acetic acid), 50% ethanol and into real food (reconstituted infant formula). Furthermore, it was also the objective of this study to assess the suitability of 50% ethanol as a simulant for infant formula. BPA was analysed by a multi-analyte liquid chromatography method with fluorescence detection and mass spectrometry confirmation. The method was in-house validated and accredited by the national accreditation body. The validation results for this analyte in the previous mentioned matrices were: LOD?=?0.004–0.007?mg?kg^–1; LOQ (validated)?=?0.03?mg?kg^–1; RSD%?=?3.4–5.8; and recovery?=?106.6–118.2%. A collection of 72 different baby bottle samples from 12 different brands were analysed. Baby bottle material was identified by FTIR. The migration test conditions used were those recommended for baby bottles in the Guidelines on testing conditions for articles in contact with foodstuffs (with a focus on kitchenware), prepared by the European network of laboratories for food-contact materials. In most of the migration assays the results were below the LOD. In four of the commercial brands there was detectable migration into the simulant 50% ethanol and BPA was detected in only two samples of infant formula (0.01?mg?kg^–1). Migration results obtained were in compliance with European Union regulations.     

Development and application of a non-targeted extraction method for the analysis of migrating compounds from plastic baby bottles by GC-MS

In 2011, the European Union prohibited the production of polycarbonate (PC) baby bottles due to the toxic effects of the PC monomer bisphenol-A. Therefore, baby bottles made of alternative materials, e.g. polypropylene (PP) or polyethersulphone (PES), are currently marketed. The principal aim of the study was the identification of major compounds migrating from baby bottles using a liquid–liquid extraction followed by GC/MS analysis. A 50% EtOH in water solution was selected as a simulant for milk. After sterilisation of the bottle, three migration experiments were performed during 2 h at 70°C. A non-targeted liquid–liquid extraction with ethyl acetate–n-hexane (1:1) was performed on the simulant samples. Identification of migrants from 24 baby bottles was done using commercially available WILEY and NIST mass spectra libraries. Differences in the migrating compounds and their intensities were observed between the different types of plastics, but also between the same polymer from a different producer. Differences in the migration patterns were perceived as well between the sterilisation and the migrations and within the different migrations. Silicone, Tritan? and PP exhibited a wide variety of migrating compounds, whereas PES and polyamide (PA) showed a lower amount of migrants, though sometimes in relatively large concentrations (azacyclotridecan-2-one up to 250 µg kg^?1). Alkanes (especially in PP bottles), phthalates (dibutylphthalate in one PP bottle (±40 µg kg^?1) and one silicone bottle (±25 µg kg^?1); diisobutylphthalate in one PP (±10 µg kg^?1), silicone (up to ±80 µg kg^?1); and Tritan? bottle (±30 µg kg^?1)), antioxidants (Irgafos 168, degradation products of Irganox 1010 and Irganox 1076), etc. were detected for PP, silicone and Tritan? bottles. Although the concentrations were relatively low, some compounds not authorised by European Union Regulation No. 10/2011, such as 2,4-di-tert-butylphenol (10–100 µg kg^?1) or 2-butoxyethyl acetate (about 300 µg kg^?1) were detected. Migrating chemicals were identified as confirmed (using a standard) or as tentative (further confirmation required).     

Dietary exposure assessment of infants to bisphenol A from the use of polycarbonate baby milk bottles

The residual bisphenol A (BPA) levels in 28 different brands of polycarbonate (PC) baby milk bottles available in the Singapore market were measured. With a detection limit of 3 mg/kg, BPA residues were detected in 19 out of the 28 PC baby milk bottles at levels between 4.01 and 141 mg/kg, with a mean of 28.1 ± 31.4 mg/kg and a median of 17.2 mg/kg. The potential migration of BPA from each of the 28 PC milk bottles was also measured using food-simulating solvents and time conditions recommended by the US Food and Drug Administration (US FDA), but using temperatures more severe than actual use. The highest upper-bound mean BPA migration levels of 0.64 ± 0.48 µg/in² in 10% ethanol at 70°C and 0.43 ± 1.25 µg/in² in corn oil at 100°C were observed after incubating cut portions of the milk bottles for 240 h. With this migration data and using US FDA's procedure for estimation of dietary exposure, the worst-case dietary exposure assessment for the intake of BPA by infants between birth and three months of age was below the oral Reference Dose of 0.05 mg/kg bw/day established by the US Environmental Protection Agency. This study showed that the dietary exposure to BPA from actual uses of PC milk bottles is unlikely to pose a health risk in infants.     

Primary aromatic amine migration from polyamide kitchen utensils: method development and product testing

A rapid and sensitive LC-MS/MS method for the identification, quantification and confirmation of six primary aromatic amines (PAAs) was developed and validated to ISO 17025:2005. From a literature survey, 57 frequently used PAA compounds were identified and subsequently reduced to six – aniline, 4,4′-MDA, 3,3′-DMB, 2,4-TDA, 2,6-TDA and o-T – based on results from migration studies on a range of utensils. Low LOQs of between 0.075 and 0.496?µg?l^?1 were determined for the six analytes, thereby quantifying well below the legal limit of 10?µg?kg^?1 total PAAs. Furthermore, low measurement uncertainties were calculated for the analytical method, in the range of 3.15–3.20%. Mean recoveries were between 98% and 102% and spanned over ±12% at 95% CI. Following the analysis of 84 black polyamide kitchen utensils, the migration of PAAs detected was significant and is therefore of concern. The six analytes identified, quantified and confirmed in this survey could be utilised as possible markers for the identification of PAA migration, thereby improving the time and cost-efficiency of food control laboratories.     

Release of bisphenol A from polycarbonate baby bottles: water hardness as the most relevant factor

The concentrations of bisphenol A (BPA) in the content of polycarbonate baby bottles reported by scientific literature were almost always clearly below 1 μg/l, but in a German consumer journal they reached 157 μg/l. These high values were interpreted as a result of microwave heating, but here they are shown to be the result of testing with tap water. Since BPA is primarily released by degradation of the polycarbonate, rather than by migration from the polymer, testing with food simulants (distilled water or distilled water/ethanol) is not appropriate. Degassing of tap water during boiling causes the pH to increase and the water to become more aggressive. BPA concentrations may reach 50 μg/l if a polycarbonate bottle is sterilized by boiling water in it (well feasible only by means of microwave heating) and this same water is used to prepare a beverage. Increased concentrations are also observed when boiling-hot beverages with a high pH are filled into the bottle, such as boiled plain water or tea. Respecting simple rules, the BPA concentrations can be kept below 0.5 μg/l.     

Migration of polyolefin oligomeric saturated hydrocarbons (POSH) into food

POSH are polyolefin oligomeric saturated hydrocarbons, such as oligomers from polyethylene or polypropylene. POSH that have migrated into foods are easily mistaken for mineral oil-saturated hydrocarbons (MOSH). In fact, both POSH and MOSH largely consist of highly isomerised branched and possibly cyclic hydrocarbons, both forming humps of unresolved components in gas chromatography. Chromatograms are reported to show typical elution patterns of POSH and help analysts distinguishing POSH from MOSH as far as possible. Since the structures of the POSH are not fundamentally different from those of the MOSH, it would be prudent to apply the evaluation of the MOSH. However, the migration is frequently beyond that for which safety has been demonstrated. This is shown for a few examples, particularly for powdered formula for babies.     

Methods for the analysis of melamine and related compounds in foods: a review

In recent years, two adulteration incidents concerning the addition of melamine (MEL) and related compounds to dairy products and vegetable proteins have occurred in China. These episodes prompted numerous governmental and private laboratories to develop or implement methods for the analysis of a wide variety of food products for MEL and related compounds, including cyanuric acid, ammeline, and ammelide. Methods have been developed for both screening and quantitation purposes; procedures used in the methods range from sensitive hyphenated chromatographic-mass spectrometric techniques to immunoselective assays. Various issues are encountered during the analysis of MEL and related compounds in food products. These issues include contamination, matrix effects, and analyte instability, and their severity varies according to the method used, and matrices and analytes examined.     

Linear and cyclic oligomers in polybutylene terephthalate for food contact materials

Polybutylene terephthalate (PBT) is a polyester (PES) gaining more importance on the food contact material (FCM) market. However, little is known about the potential migration of PBT oligomers which are formed during polymer production. In this work, PBT pellets and a slotted spoon manufactured from this material by injection moulding were analysed on extractable oligomers and their migration potential into hydrophilic foods. Overall 27 oligomers (cycles and linears) could be identified in different extracts by HPLC-DAD/ESI-MS data, but without confirmation by reference substances. The oligomers were quantified by HPLC-DAD using bis(2-hydroxyethyl) terephthalate (BHET) as external standard and the total amount of oligomers isolated by reprecipitation from the pellets and the spoon were 0.69 and 0.71%, respectively. While cyclic oligomers made up for approximately 90% of the extractable oligomers, linear oligomers proved to be more relevant for migration into aqueous foodstuffs. Furthermore, it was shown that hydrolysis of oligomers can take place in water at elevated temperatures. Consequently, the qualitative and quantitative composition of PBT oligomers in aqueous foods from FCMs does not only depend on migration but also on hydrolysis. Migration testing of the PBT spoon under repeat use conditions with water at 100°C for 2 h resulted in 0.29 mg item^?1 of linear oligomers and 0.05 mg item^?1 of the cyclic PBT dimer in the third migrate.     

Feasibility study for the development of certified reference materials for specific migration testing. Part 1: Initial migrant concentration and specific migration

The paper describes a project with the main objective of developing the know how to produce certified reference materials (CRMs) for specific migration testing. Certification parameters discussed are the initial concentration of the migrant in the polymer (C_P,0) and the specific migration into a food simulant under certain temperature/time conditions. Sixteen preliminary candidate CRMs were defined and produced. The most important polymers (low- and high-density polyethylene (LDPE and HDPE), polypropylene (PP), polystyrene (PS), polyethylene terephtalate (PET), plasticized polyvinyl chloride (PVC), rigid PVC, polyamides (PA)) and additives as well as monomers representing different physicochemical properties as target substances for migration were chosen. The stability and homogeneity of the migrants in the materials were tested and methods for the determination of the certification parameters were developed and validated. From the 16 materials produced, the six most suitable CRM candidates (LDPE//Irganox 1076/Irgafos 168, LDPE//1,4-diphenyl-1,3-butadiene (DPBD), HDPE//Chimassorb 81/Uvitex OB, PP homo//Irganox 1076/Irgafos 168, HIPS, 1% mineral oil//styrene, PA 6//caprolactam) were selected. The feasibility of CRM production for the six candidate materials was demonstrated and a trial certification exercise was performed with participation of all four partner laboratories. All six materials showed suitable properties for future production as certified reference materials.     

Liquid chromatography-tandem mass spectrometry determination of N-nitrosamines released from rubber or elastomer teats and soothers

A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method as an alternative to a gas chromatography-thermal energy analyser (GC-TEA) method recommended by the European Committee on Standardization (CEN) was validated for the simultaneous determination of eight N-nitrosamines released into artificial saliva from rubber or elastomer teats and soothers. N-nitroso-dipropylamine-d₁₄ (NDPA-d₁₄) was used as internal standard for accurate quantification. The method was validated with relatively good analytical results, including sufficiently low limits of detection (0.1–2?µg?kg^?1 of sample) and good linearity (r ^2?>?0.99) throughout the studied concentration ranges. Intra- and inter-day precisions expressed with the relative standard deviation (RSD, %) were 3.4–8.0% and 4.4–11.3%, which were below the performance criteria based on one-half of the value derived from the Horwitz value. It was also found that the LC-MS/MS method is sufficiently rugged and successfully applicable to its routine analysis for the compliance test of Commission Directive 93/11/EEC.     

Determination of microbial transglutaminase in meat and meat products

Transglutaminase is an enzyme that can be used to cross-link pieces of meat, fish or meat products. The resulting product gives the optical impression of an intact chunk of meat. The usage of transglutaminase as a food additive is permitted in some countries. However, its utilisation has to be declared to ensure transparency for consumers. This paper describes two orthogonal analytical methods suited for the detection of technological relevant transglutaminase concentrations (around 25?mg pure enzyme in 1?kg of product) in meat and meat products. The mass spectrometry-based approach relies on a previous digestion with Achromobacter lyticus protease and LC-MS/MS separation and detection. Sufficient selectivity was obtained by monitoring four different peptides. The orthogonal (complementary and independent), ELISA-based approach relies on two commercially available bacterial transglutaminase-specific antibodies, combined to a sandwich ELISA. The two methods were tested by analysing some 60 samples obtained from the market.     

Further insights into the mechanism of migration from the PVC gaskets of metal closures into oily foods in glass jars

Factors influencing migration from the gaskets of metal closures into oily foods were investigated. Tightening of the lid has an effect presumably through the deformation of the gasket, the amount of oil adhering to the latter, and the proportion of its surface being covered by oil. The substantial difference observed in the migration determined with the jar in an upright or a reversed position is partly related to this. The nature of the plasticizer determines the saturation in the partitioning process between the gasket and the small amount of oil in contact with the gasket as well as the adherence of oil (wettability). If saturation is rapidly reached, the frequency of exchanging the oil by shaking of the jar is an important factor. A complete exchange of the oil in contact with the gasket requires vigorous and persisting shaking, presumably because of the high viscosity and the hindered access to the angle between the gasket and the jar rim. The limited data available on long-term performance suggest that migration accelerates after roughly one year of storage. It is concluded that the extrapolation of long-term migration from short-term data presupposes a deeper investigation of the course of migration over years.     

Migration of melamine from can coatings cross-linked with melamine-based resins,into food simulants and foods

Resins based on melamine-formaldehyde and related analogues such as methylolated melamine are used to cross-link coatings used inside food cans and on the metal closures of glass jars. Thirteen commercially coated cans and closures representing 80% of the European market were tested using simulants under realistic industrial heat-processing conditions for canned and jarred foods. The food simulants and the retort conditions used were 3% acetic acid for 1?h at 100°C and 10% ethanol for 1?h at 130°C. The highest migration level seen for melamine into simulant was 332?µg?kg^?1. There was no detectable migration of the melamine analogues cyanuric acid (<1?µg?kg^?1) or ammelide (<5?µg?kg^?1) from any sample. Twelve of the thirteen samples released no detectable ammeline (<5?µg?kg^?1) but the coating giving the highest release of melamine did also release ammeline at 8?µg?kg^?1 with the higher of the two process temperatures used. Migration experiments into food simulant and foods themselves were then conducted using two experimental coatings made using amino-based cross-linking resins. Coated metal panels were exposed to the food simulant 10% (v/v) aqueous ethanol and to three foodstuffs under a range of time and temperature conditions both in the laboratory and in a commercial food canning facility using proprietary time and temperature conditions. The highest migration into a food was 152?µg?kg^?1 from the first coating processed for a long time at a moderate sterilisation temperature. The highest migration into simulant was also from this coating at 220?µg?kg^?1 when processed at 134°C for 60?min, dropping to 190?µg?kg^?1 when processed at 123°C for 70?min. Migration from the second coating was quite uniformly two to three times lower under all tests. These migration results were significantly higher than the levels of melamine extractable using 95% ethanol at room temperature. The experiments show that commercial canning and retorting can be mimicked in an acceptable way using laboratory tests with an autoclave or a simple pressure cooker. The results overall show there is hydrolytic degradation of the melamine cross-linked resins to release additional melamine. There is a strong influence of the temperature of heat treatment applied with foods or simulants but only a minor influence of time of heating and only a minor influence, if any, of food/simulant acidity.     

Determination of cyanidin-3-glucoside (red kernel food colour) in beverages by high performance liquid chromatography and a study of its degradation by quadruple time-of-flight mass spectrometry

A method for the determination of cyanidin-3-glucoside (red kernel colour, RKC) in various matrices, including carbonated soft drinks, fruit-based soft drinks, sugar confectionery and milk-based drinks, by high performance liquid chromatography (HPLC) based on UV–Vis detection (at 520?nm) have been developed. Pre-treatment procedures for various matrices have been optimised. For soft drinks, the pH values were adjusted to 2.0, and sugar confectionery and milk-based drinks were extracted with 30 and 50% methanol in 0.1% formic acid (pH?～?2.5) aqueous solutions, respectively. The limits of detection for the established methods ranged from 0.2?mg/kg for soft drinks to 2.0?mg/kg for the sugar confectionery and milk-based drinks with the relative standard deviations lower than 7%, which satisfy the method performance requirements for quality control for the beverages. The stability of the colourant RKC under various thermal and pH conditions was investigated by quadruple time-of-flight mass spectrometry (Q-TOF-MS). The main colourant component of RKC, cyanidin-3-glucoside (Cyd-3-Glu), lost the glucose entity under thermal treatment. A new component was identified when RKC degraded under various pH conditions and a degradation pathway is proposed. The results will assist in understanding the degradation mechanism of the colourant Cyd-3-Glu.     

Determination of furan in jarred baby food purchased from the Spanish market by headspace gas chromatography-mass spectrometry (HS-GC-MS)

The aim of this paper is to offer a method based on headspace gas chromatography-mass (HS-GC-MS) spectrometry technique in-house validated and use to estimate furan concentrations in jarred baby-food samples purchased from the Spanish market. The validation was performed according to ISO 17025 and European Food Safety Authority (EFSA) requirements and the results obtained (limit of detection (LOD) = 0.05 µg kg^?1; limit of quantification (LOQ) = 4 µg kg^?1, lowest validated level; relative standard deviation (RSD) = 3.1–10.5%; recoveries = 85.4–101.5%) confirm that this method is fit for the routine analysis of furan in jarred baby food control. Furan was analysed in 39 different baby-food samples and the mean levels varied between 64.6 µg kg^?1 (rice and chicken samples) and less than or equal to the LOQ (fruit-based samples). The mean concentrations found for the different matrices were 5.0, 37.8, 25.2, 33.8 and 30.5 µg kg^?1 for fruit, vegetables, meat/vegetables, fish/vegetables and dairy-containing baby foods, respectively. According to the statistical analyses, fruit-based baby-food samples had significantly lower concentrations of furan. Mean values for the other matrices were at least five times higher, and this is in accordance with the levels reported in other studies.     

Saturated and aromatic mineral oil hydrocarbons from paperboard food packaging: estimation of long-term migration from contents in the paperboard and data on boxes from the market

In the absence of a functional barrier, mineral oil hydrocarbons from printing inks and recycled fibres tend to migrate from paper-based food-packaging materials through the gas phase into dry food. Concentrations easily far exceed the limit derived from the acceptable daily intake (ADI) of the Joint FAO/WHO Expert Committee on Food Additives (JECFA). Since the estimation of long-term migration into the food by testing at 40°C for 10 days is difficult, it seems preferable (and easier) to use the mineral oil content in the paperboard. Evaporation experiments showed that hydrocarbons eluted up to about n-C₂₄ are sufficiently volatile for relevant migration into dry food: in worst-case situations, about 80% migrate into the packed food. The extraction of the paperboard was optimised to give good recovery of the relevant hydrocarbons, but to discriminate against those of high molecular mass which tend to disturb gas chromatographic analysis in on-line coupled normal phase HPLC-GC-FID. Even though some of the relevant hydrocarbons had already evaporated, the average concentration of?<?C₂₄ mineral oil saturated hydrocarbons (MOSH) in the paperboard boxes of 102 products from the Swiss and Italian market was 626?mg?kg^?1. Nearly 15% of investigated boxes still contained more than 1000?mg?kg^?1?<?C₂₄ MOSH up to over 3000?mg?kg^?1 (maximum?=?3500?mg?kg^?1). This amount of MOSH in the board have the potential of contaminating the packed food at a level exceeding the limit, derived from the JECFA ADI, hundreds of times.     

Endogenous steroid profiling by gas chromatography-tandem mass spectrometry and multivariate statistics for the detection of natural hormone abuse in cattle

For years it has been suspected that natural hormones are illegally used as growth promoters in cattle in the European Union. Unfortunately there is a lack of methods and criteria that can be used to detect the abuse of natural hormones and distinguish treated from non-treated animals. Pattern recognition of steroid profiles is a promising approach for tracing/detecting the abuse of natural hormones administered to cattle. Traditionally steroids are analysed in urine as free steroid after deconjugation of the glucuronide (and sulphate) conjugates. The disadvantage of this deconjugation is that valuable information about the steroid profile in the sample is lost. In this study we develop a method to analyse steroids at very low concentration levels (ng l^?1) for the free steroid, glucuronide and sulphate conjugates in urine samples. This method was used to determine concentrations of natural (pro)hormones in a large population (n?=?620) of samples from male and female bovine animals and from bovine animals treated with testosterone-cypionate, estradiol-benzoate, dihydroepiandrosterone and pregnenolone. The data acquired were used to build a statistical model applying the multivariate technique ‘Soft Independent Modeling of Class Analogy’ (SIMCA). It is demonstrated that by using this model the results of the urine analysis can indicate which animal may have had illegal treatment with natural (pro)hormones.