This study describes the validation and application of two independent analytical methods for the determination of glyphosate in breast milk. They are based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS), respectively. For LC-MS/MS, sample preparation involved an ultrafiltration followed by chromatography on an anion exchange column. The analysis by GC-MS/MS involved an extraction step, cleanup on a cation exchange column, and derivatization with heptafluorobutanol and trifluoroacetic acid anhydride. Both methods were newly developed for breast milk and are able to quantify glyphosate residues at concentrations as low as 1 ng/mL. The methods were applied to quantify glyphosate levels in 114 breast milk samples, which had been collected from August to September of 2015 in Germany. The mothers participated at their own request and thus do not form a representative sample. In none of the investigated samples were glyphosate residues above the limit of detection found.
Food and contaminated indoor environments are the most relevant sources of human exposure to polyhalogenated chemicals. This study analyzed for the first time fat residues in kitchen hoods for contaminations with polyhalogenated compounds. A wide range of contaminants was detected in all kitchen hoods (n = 15) and most of them could be quantified. Between 0.2 and 18 μg polyhalogenated chemicals/g fat were detected, with chlorinated paraffins being the most relevant contaminant group. Aside from the chlorinated paraffins, each kitchen hood fat sample showed a distinct fingerprint. A wide range of old and current-use brominated flame retardants were also detected in the samples. In addition to these contaminants originating from their use in indoor equipment, residues of organochlorine pesticides and semi-volatile halogenated natural products verified that cooking of food, accompanied with the release of contaminants from the heated food, was another relevant source of contamination. Re-analyses of two samples after 3 months only resulted in small variations in contaminant pattern and concentrations. Therefore, fat from kitchen hoods is proposed as an easily accessible matrix to assess contamination of these hazardous polyhalogenated chemicals.
Polybrominated diphenyl ethers (PBDEs) are environmental contaminants regularly detected in biota and food. Seafood has been identified as the major dietary source for human uptake. Fish is predominantly consumed after cooking, and this process may alter the actual human intake of contaminants. This study thus aimed to investigate the fate of PBDEs in this cooking process. Heating of fish fortified with 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether (BDE-209) at typical cooking conditions (200 °C, in plant oil) resulted in a decrease of its concentration in favor of the formation of lower brominated congeners. After 15 min, ∼25% of BDE-209 was transformed into nona- to octabrominated congeners. The major transformation route was BDE-209 → BDE-206 → BDE-196 and BDE-199. Low amounts of heptabrominated congeners as well as one hexabromodibenzofuran and a heptabromodibenzofuran isomer were also detected. However, penta- and tetrabrominated diphenyl ethers were not observed, and heating of BDE-47 did not produce new transformation products.
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