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).
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a b s t r a c tThe increasing availability and use of sports supplements is of concern as highlighted by a number of studies reporting endocrine disruptor contamination in such products. The health food supplement market, including sport supplements, is growing across the Developed World. Therefore, the need to ensure the quality and safety of sport supplements for the consumer is essential. The development and validation of two reporter gene assays coupled with solid phase sample preparation enabling the detection of estrogenic and androgenic constituents in sport supplements is reported. Both assays were shown to be of high sensitivity with the estrogen and androgen reporter gene assays having an EC 50 of 0.01 ng mL −1 and 0.16 ng mL −1 respectively.The developed assays were applied in a survey of 63 sport supplements samples obtained across the Island of Ireland with an additional seven reference samples previously investigated using LC-MS/MS. Androgen and estrogen bio-activity was found in 71% of the investigated samples. Bio-activity profiling was further broken down into agonists, partial agonists and antagonists. Supplements (13) with the strongest estrogenic bio-activity were chosen for further investigation. LC-MS/MS analysis of these samples determined the presence of phytoestrogens in seven of them. Supplements (38) with androgen bio-activity were also selected for further investigation. Androgen agonist bio-activity was detected in 12 supplements, antagonistic bio-activity was detected in 16 and partial antagonistic bio-activity was detected in 10. A further group of supplements (7) did not present androgenic bio-activity when tested alone but enhanced the androgenic agonist bio-activity of dihydrotestosterone when combined.The developed assays offer advantages in detection of known, unknown and low-level mixtures of endocrine disruptors over existing analytical screening techniques. For the detection and identification of constituent hormonally active compounds the combination of biological and physio-chemical techniques is optimal.
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