Dithiocarbamate pesticides form an important class of organic fungicides used all over the world to control many diseases in a variety of crops. They are of low acute toxicity, but some of these compounds, namely the ethylenebisdithiocarbamates (EBDCs) (maneb, zineb, mancozeb, metiram, and nabam), can decompose to give ethylenethiourea (imidazolidine-2-thione, ETU) (Fig. 1).

Ethylenethiourea (ETU) in relation to use of ethylenebisdithiocarbamate (EBDC) fungicides

Column-switching with two C18 separation columns combined with UV detection at 233 nm has been used to determine ETU in ground water samples. The direct assay of ETU (limit of detection, 1 ppb) takes less than 10 min. For the determination of ETU down to a level of 0.1 ppb, preconcentration of ETU is achieved by a liquid-liquid extraction procedure allowing the analysis of at least 12 water samples per day. For both methods (1-ppb and 0.1-ppb level), the overall recovery (96 and 82%), the repeatability (4.5 and 4.3%) and the reproducibility (5.0 and 7.9%) are satisfactory (n=18 and 28, respectively). More than one hundred samples of ground water were analysed during a 10-month period; over 0.1 ppb of ETU (range, 0.1–300 ppb) was found in 30% of the samples tested.

Column-switching RPLC for the trace-level determination of ethylenethiourea in aqueous samples

Ethylenethiourea [imidazolidine-2-thione (ETU), Fig. 1] has been known to be a possible degradation product of ethylenebis(dithiocarbamate) (EBDC, Fig. 2) fungicides for over 30 years (Clarke et al. 1951, Fishbein and Fawkes 1965, Czegledi-Janko 1967, Bontoyan et al. 1972).

Review of Methods for the Determination of Ethylenethiourea (Imidazolidine-2-Thione) Residues

A robust and sensitive method for the determination of ethylenethiourea (ETU) and iso-propylenethiourea (i-PTU) in foods is reported. ETU and i-PTU were extracted by blending with dichloromethane (DCM) in the presence of sodium sulphate, sodium carbonate, thiourea and ascorbic acid. 2H4-ETU and n-PTU were used as internal standards. After filtration the DCM was removed by rotary evaporation and the extract re-dissolved in water before analysis by reversed-phase liquid chromatography with detection by atmospheric pressure chemical ionization-mass spectrometry using a double focusing mass spectrometer at a resolution of 5000. Mean recoveries of ETU and i-PTU from fruit-based, cereal-based and meat-based infant foods, potato chips and tinned potatos at 0.01 mg kg(-1) and from pizza and yoghurt at 0.02-0.1 mg kg(-1) were 95% and 97% respectively. Precision, including both repeatability and internal reproducibility, was in the range of 3.1-13.1%.

Determination of ethylenethiourea (ETU) and propylenethiourea (PTU) in foods by high performance liquid chromatography–atmospheric pressure chemical ionisation–medium-resolution mass spectrometry

The HPLC determination of ethylenethiourea (ETU, imidazolidine-2-thione) has been carried out by derivatisation with phenacyl halides to give imidazole-[2,1-b]thiazoles, which were separated on a polystyrenedivinylbenzene (PS-DVB) column A number of different phenacyl halides including p-phenyl-, and naphthyl, were studied and the p-nitro reagent was selected as the most suitable for residue analysis The analysis was more sensitive than direct HPLC analysis and had a limit of detection of 004 ng ETU

Determination of trace levels of ethylenethiourea by HPLC following derivatisation with phenacyl halides

A new gas chromatographic method reliable in the microgram range, was developed to measure ETU residues in various crops. Contrary to previously published procedures, this new method does not require prior derivatization of the ETU. The limit of sensitivity was shown to be 0.01 ppm using the flame photometric detector, FPD (sulfur mode, 394 nm).

A new gas chromatographic determination of ethylenethiourea residues without derivatization.

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A new gas chromatographic determination of ethylenethiourea residues without derivatization.