ABSTRACT
An ultra performance liquid chromatography (UPLC)-tandem mass spectrometry (MS/MS) method was developed for the determination of the Alternaria toxins tenuazonic acid, alternariol, alternariol monomethyl ether, altenuene, altertoxin I and tentoxin. Owing to its instability, altenusin could not be determined. The sample preparation includes an acidic acetonitrile/water/methanol extraction, followed by SPE clean-up step, before injection into the UPLC-MS/MS system. The separation was made on an Acquity UPLC column using a water/acetonitrile gradient with ammonium hydrogen carbonate as a modifier. Matrix compounds of real samples led to enhancement as well as suppression of the target compounds, depending on analyte and matrix. The recoveries were between 58 and 109% at a level of 10 µg/kg. Eighty-five tomato products, consisting of peeled and minced tomatoes, soup and sauces, tomato purées and concentrates, ketchup as well as dried and fresh tomatoes, were taken from the Swiss market in 2010. Tenuazonic acid was found most frequently (81 out of 85 samples) and in the highest levels of up to 790 µg/kg. Alternariol and alternariol monomethyl ether were found in lower concentrations, ranging from <1 to 33 µg/kg for alternariol and <5 to 9 µg/kg for alternariol monomethyl ether. Only a few samples were positive for altenuene and tentoxin. Altertoxin I was never detected.
ABSTRACT
A new sensitive method has been successfully developed and validated for the simultaneous determination and quantification of nine estrogenic UV filters (benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-4, 4,4-dihydroxybenzophenone, ethyl-4-aminobenzoate, 2-ethyl-hexyl-4-trimethoxycinnamate, 3-(4-methylbenzylidene)-camphor, 3-benzylidene-camphor) in different environmental matrices. After optimisation of extraction conditions for the best recovery of polar to lipophilic compounds from fish tissue and a subsequent lipid clean-up in HPLC, fish extraction recoveries exceeded 72% for all nine UV filters. Identification and quantification of compounds was performed for lipophilic UV filters with gas chromatography-electroionisation-mass spectrometry and for polar and mid-polar compounds with liquid chromatography coupled to electrospray ionisation mass spectrometry. Instrumental detection limits (IDL) varied between 5 and 260 pg injected and method detection limits (MDL) were in the low ng/g lipids range for all test compounds. The described analytical methods are shown to be useful to screen for estrogenic UV filters in environmental samples such as fish and polar organic chemical integrative samplers.
