[Determination of ethylenethiourea residues in tea using precolumn derivatization with ultra-performance liquid chromatography-tandem mass spectrometry].

A method based on precolumn derivatization along with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the determination of ethylenethiourea residues in tea. The sample was extracted using acetonitrile; the extracting solution was purified by matrix-dispersed solid phase extraction and precolumn derivatization using 9-fluorenylmethyl chloroformate (FMOC-CL). The UPLC separation was carried out on an Acquity BEH C18 column (100 mm×2.1 mm, 1.7 µm) and quantified using the isotope internal standard method. The mobile phase was 0.1% (v/v) formic acid and acetonitrile. For tea samples, the detection limit of this method was 1.3 µg/kg and the limit of quantitation was 4.2 µg/kg. The recoveries were in the range 97.7%-107.5% with relative standard deviation (RSD) of 2.1%-10.0% (n=6). The linear correlation coefficient (r) was 0.9993 over the concentration range 1.0-203.4 µg/L. This method showed high sensitivity, good reproducibility, and qualitative and quantitative accuracy, and could be suitable for the detection of ethylenethiourea residues in tea.

Combined determination and confirmation of ethylenethiourea and propylenethiourea residues in fruits at low levels of detection.

In this work, a new method for the determination of ethylenethiourea (ETU) and propylenethiourea (PTU) in fruits and vegetables is presented. Different extraction and purification techniques, including matrix solid phase dispersion (MSPD) and solid-liquid extraction (SLE), followed by a clean-up step by solid phase extraction (SPE), were compared. The determination of ETU and PTU was performed by high performance liquid chromatography with diode array detection (HPLC/DAD) or by gas chromatography with mass spectrometry detection (GC/MS). The effect of several parameters on the extraction, separation and detection was studied. The proposed method based on solid-liquid extraction with acetonitrile, clean-up with Envicarb II/PSA cartridges and subsequent analysis by HPLC/DAD was characterised and applied to the analysis of fruits and vegetables from different countries. Analytes recoveries were between 71% and 94% with relative standard deviations (RSDs) ranging from 8% to 9.5%. Quantification limits obtained for ETU and PTU with the HPLC/DAD method were 7 and 16 µg kg⁻¹ in strawberries (fresh weight), respectively. For apples, they were 11 and 25 µg kg⁻¹, respectively.

A rapid determination method for ethylenethiourea in potato and cucumber by modified QuEChERS - high performance liquid chromatography-tandem mass spectrometry.

A rapid and sensitive analytical method for the determination of ethylenethiourea (ETU) in potatoes and cucumbers is developed. This method employs modified QuEChERS followed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) analysis. ETU was extracted by alkaline acetonitrile (containing 1%NH(3).H(2)0), separated on a ZIC-pHILIC column, confirmed by multiple reaction monitoring (MRM) mode with electrospray ionisation source. This modified procedure showed satisfactory recovery (90.6-103.5%) fortified at the range of 0.005-0.05 mg kg(-1) with relative standard deviation (RSD)<7%. The limits of detection (LOD) and the limits of quantification (LOQ) were 0.002 mg kg(-1) and 0.005 mg kg(-1), respectively. Matrix effect and HILIC retention mechanism were also evaluated. The method was finally applied to detect ETU in potato and cucumber samples collected at harvest period. Residues of ETU were detected in four cucumber samples with the level lower than LOQ.

Determination of ethylenethiourea in food commodities by a two-step derivatization method and gas chromatography with electron-capture and nitrogen-phosphorus detection.

Ethylenethiourea (ETU) is a decomposition product from ethylene-bis-dithiocarbamates (EBDCs), the most widely used class of fungicides in the world. ETU has been classified as a possible human carcinogen. The maximum permitted residue level (MRL) in the European Union was set at 0.05 ppm. Gas chromatographic determination of ETU can be achieved only after derivatization. ETU is extracted from food samples and cleaned up by a combination of two-step derivatization and liquid-liquid partitioning. In the first step, ETU is derivatized with benzyl chloride to form S-benzyl ETU, which is then trifluoroacetylated to form the final product, which is amenable to GC. The determination is carried out with capillary gas chromatography using electron-capture (ECD) and nitrogen-phosphorus detection (NPD) as selective detection methods in parallel. The responses of ECD and NPD were found to be of the same order of magnitude. Therefore, the parallel response was found to be a useful criterion for peak identification down to the limit of detection. Reproducibility of the two-step derivatization of ETU to form trifluoroacetylated S-benzyl ETU was found to be satisfactory. The recoveries from apple, pear, tomato and a common baby food, at various concentration levels, were found to be between 82-92%, with a limit of detection of less than 1 ppb. Commercial samples, submitted for routine monitoring of dithiocarbamates (DTC) were also monitored in our laboratory for the presence of ETU. Four of the twenty samples found positive for DTC were also found to be contaminated with ETU in the range of 0.01 to 0.37 ppm. Three of these food samples were found to contain ETU residues above the MRL of 0.05, while those food samples containing DTC residues between 0.2 and 0.8 ppm were all below the MRL of DTC. No relation exists between the DTC residues concentration and the level of ETU. The screening data were further confirmed by electron impact mass spectrometry in selected ion monitoring mode. Chromatograms of ETU residue analyses are presented to demonstrate the extremely sensitive detection method with real food samples.

1-Phenyl-5-vinyl-2-imidazolidinethione, a proposed causative agent of Spanish toxic oil syndrome: synthesis, and identification in one of a group of case-associated oil samples.

A method is described for the synthesis and characterization of N-(2-hydroxy-3-butenyl)-N'-phenylthiourea, and its cyclization product, 1-phenyl-5-vinyl-2-imidazolidinethione (PVIZT). Fourteen coded oil samples associated with toxic oil syndrome cases in Spain were examined by gas chromatography-electron impact mass spectrometry for the presence of PVIZT. Although these samples were obtained from households where cases of toxic oil syndrome had been recorded, they differed extremely with regard to their anilide and sulphur contents. In one sample PVIZT was detected at an estimated concentration of 1 mg/kg.