Concerns have been raised regarding the human health effects of endocrine disrupting chemicals (EDCs), many of which are associated with and leaching from plastics. As infants are particularly vulnerable to EDCs, we have investigated whether plastic teethers for babies represent a relevant source of exposure. Applying effect-directed analysis, we use bioassays to screen teethers, toys used to soothe a baby's teething ache, for endocrine activity and chemical analysis to identify the causative compounds. We detected significant endocrine activity in two of 10 plastic teethers. Those samples leached estrogenic and/or antiandrogenic activity as detected in the Yeast Estrogen Screen and Yeast Antiandrogen Screen. After sample fractionation, gas chromatography-mass spectrometry non-target screening revealed that methyl-, ethyl- and propylparaben were responsible for the observed estrogenic and antiandrogenic activity in one product. The second product is likely to contain at least six different antiandrogenic compounds that remain so far unidentified. This study demonstrates that plastic teethers can be a source of infant exposure to well-established and unknown EDCs. Because of their limited value to the product, but potential toxicity, manufacturers should critically revisit the use of parabens in plastic teethers and further toys. Moreover, plastic teethers might leach EDCs that escape routine analysis and, thus, toxicological evaluation. The resulting uncertainty in product safety poses a problem to consumers, producers and regulators that remain to be resolved.

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Alkyl esters of p-hydroxybenzoic acid (parabens) are well-known to be used as preservatives in pharmaceuticals, cosmetics, and food products due to their antimicrobial effect. However, parabens are also known to act as endocrine disruptors. Thus, if manufactures of consumer goods use parabens particularly in products for infants and young children, this application should be considered as critical and should be thoroughly investigated, at least if an intake into the body cannot be excluded. The present work describes an analytical method for the analysis of methyl-, ethyl-and n-propylparaben (MeP, EtP and n-PrP) in plastic and gel material from baby teethers filled with cooling gel. Measurements were performed with gas chromatography-quadrupole mass spectrometry (GC-qMS) on N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) derivatized parabens. Samples were prepared applying ultrasonic assisted extraction (UAE) using methanol as the solvent. For quantification, a stable isotope dilution assay (SIDA) was used that showed good recoveries for spiked gel material, which ranged from 82 to 119%. The baby teether analyses showed that parabens were present in all considered plastic and gel samples. Furthermore, in all gel samples (2E,4E)-hexa-2,4-dienoic acid (sorbic acid) was identified as an additional preservative.a Mean concentration value with range (number in brackets) from two independently prepared samples; LOD: limit of detection; LOQ: limit of quantication; SD: standard deviation. b Mean value and standard deviation (number in brackets) from repeatability test (intra-day precision, n ¼ 5). c Same product as no. 1 but different lot number purchased about one year later. Fig. 1 GC-qMS chromatograms of target screening for methylparaben (MeP), ethylparaben (EtP) and n-propylparaben (n-PrP) with the internal standard methylparaben-d 4 (MeP-d 4 ). (A) Calibration level 50 mg 10 mL À1 and (B) gel sample extract of baby teether no. 3.This journal is

A method for the analysis of the homologous series of alkanals, (E)-2-alkenals, and (E,E)-2,4-alkadienals is described utilizing a headspace solid-phase microextraction (HS-SPME) step and on-fiber derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) hydrochloride. Oxime derivatives formed on the fiber are desorbed in the gas chromatographic injector and analyzed by comprehensive 2-D GC coupled to quadrupole MS (GC x GC-qMS). Selecting specific fragment ions within the electron impact mass spectra of the oxime derivatives provides a suitable method for the target analysis of these aldehyde classes, which furthermore benefits from the increased separation efficiency by GC x GC. The analysis of higher molecular weight aldehydes is described in wine and grape seed oil as examples. Quantification of the aldehydes utilizes a stable isotope dilution analysis (SIDA) assay with octan-d(16)-al as isotopomeric internal standard. Besides the selectivity and sensitivity of aldehyde analysis using PFBHA derivatives, critical aspects on background level contamination and repeatability of the sample preparation method are discussed. Optimization of GC x GC-qMS parameters allowed a considerable saving of the cryogenic medium, involving additional (unmodulated) conditioning runs, rendering the method more amenable to routine analysis.