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.

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.

Solid-phase micro-extraction (SPME-GC) and sensors as rapid methods for monitoring lipid oxidation in nuts.

Dry foods with high fat content are susceptible to lipid oxidation, which involves a quality deterioration of the product, since this process is responsible for the generation of off-flavours. Hexanal is considered to be a good shelf-life indicator of such oxidation products. In addition, due to its high volatility, hexanal can be easily determined by fast headspace analytical techniques. For this reason an electronic nose comprising ten metal oxide semiconductors (MOS) and a solid-phase microextraction (SPME) coupled with gas chromatography and flame ionization detector (GC-FID) method were compared in order to determine hexanal formed in hazelnuts during storage under different conditions (room temperature, 40 degrees C, ultraviolet light, with and without oxygen scavenger). The results obtained by the two methods showed a good correlation, confirming the possibility of using a multi-sensor system as a screening tool for the monitoring of shelf-life and oxidation state of nuts.

Solid-phase microextraction method for the determination of hexanal in hazelnuts as an indicator of the interaction of active packaging materials with food aroma compounds.

Fatty foods are susceptible to lipid oxidation resulting in deterioration of product quality due to the generation of off-flavours. Hexanal is a good indicator of rancidity. Therefore, a method based on solid-phase microextraction (SPME) coupled to gas chromatograph with flame ionization detection was developed to determine hexanal formation in hazelnuts during storage. Optimum conditions were as follows: carboxen-polydimethylsiloxane 75 microm fibre, extraction time 10 min, equilibrium time 10 min and equilibrium temperature 60 degrees C. The effect of oxygen scavengers on the oxidation process was also evaluated by measuring hexanal formation in hazelnuts stored with/without oxygen absorber sachets. Oxygen scavengers were shown to reduce oxidation; however, analysis of the sachet revealed that other volatile compounds from the headspace were also absorbed.

Screening survey of deoxynivalenol in beer from the European market by an enzyme-linked immunosorbent assay.

Deoxynivalenol (DON) was analysed in 313 beer samples collected from the European retail market using a commercially available immunoassay kit (enzyme-linked immunosorbent assay, ELISA). The incidence rate was about 87%, while most samples (73%) had contamination levels lower than 20 ng m(-1). The contamination ranged between 4.0 and 56.7 ng ml(-1), with an average of 13.5 ng ml(-1). A statistically significant correlation between alcohol levels and DON contamination was found, as well as a significant difference between bottom, top and spontaneous fermenting beers. Twenty-seven beer samples were compared using a second ELISA kit and a good correlation was obtained between the two kits (r = 0.93). Although when compared with gas chromatography-mass spectrometry the ELISA tended to overestimate the results, a good correlation (r=0.94) between the two methods was observed. Monitoring of DON in beer is important considering that DON production is dependent on the weather and that it can contribute significantly to the tolerable daily intake of DON, especially for frequent beer consumers.

Urinary excretion of thromboxane and prostacyclin metabolites during chronic low-dose aspirin: evidence for an extrarenal origin of urinary thromboxane B2 and 6-keto-prostaglandin F1 alpha in healthy subjects.

In vivo biosynthesis of thromboxane and prostacyclin is currently evaluated by measuring urinary excretion of selected metabolites. Urinary thromboxane B2 (TXB2) and 6-keto-prostaglandin F1 alpha (6-keto-PGF1 alpha) (non-enzymatic hydrolysis products of thromboxane and prostacyclin) are thought to derive from renal biosynthesis of the parent compounds, while enzymatic metabolites such as 2,3-dinor-TXB2 and 2,3-dinor-6-keto-PGF1 alpha appear to be mainly derived from systemic (platelet) thromboxane and (vascular) prostacyclin, respectively. Using immunoaffinity extraction and high-resolution gas chromatography-negative ion chemical ionization mass spectrometry (HRGC-NICIMS), we measured the paired excretion of non-enzymatic and enzymatic metabolites of thromboxane and prostacyclin in healthy subjects before, during and after an eight-day schedule of oral low-dose aspirin (30 mg/day), a treatment known to inhibit platelet and perhaps vascular but not renal cyclooxygenase. Low-dose aspirin cumulatively reduced urinary excretion of TXB2 and 2,3-dinor-TXB2 (about 80% inhibition on day 8 of aspirin treatment, P less than 0.01), as well as 6-keto-PGF1 alpha and 2,3-dinor-6-keto-PGF1 alpha (about 45% inhibition on day 8 of aspirin treatment, P less than 0.01). Excretion of all metabolites recovered slowly after aspirin withdrawal. Urinary PGE2, taken as an index of renal cyclooxygenase activity, was not inhibited by aspirin. A highly significant correlation was found between paired excretion values of non-enzymatic vs. enzymatic metabolites of thromboxane and prostacyclin in all individuals studied (TXB2 vs. 2,3-dinor-TXB2 (r = 0.91 +/- 0.03); 6-keto-PGF1 alpha vs. 2,3-dinor-6-keto-PGF1 alpha (r = 0.92 +/- 0.06], irrespective of aspirin treatment. TXB2/2,3-dinor-TXB2 and 6-keto-PGF1 alpha/2,3-dinor-6-keto-PGF1 alpha mean ratios remained unchanged throughout the experiment. These data do not support the view that urinary TXB2 and 6-keto-PGF1 alpha derive mainly from renal biosynthesis in healthy subjects, but rather suggest that they may represent a fraction of systemic (platelet) thromboxane and (vascular) prostacyclin escaping metabolism. These data also suggest that chronic low-dose aspirin may partly inhibit vascular prostacyclin in addition to platelet thromboxane biosynthesis.