Survey of ethyl carbamate in fermented foods sold in the United Kingdom in 2004.

Results are presented of a survey of fermented foods and beverages sold in the United Kingdom for levels of ethyl carbamate (urethane) carried out to expand the range of food types sold in the United Kingdom for which data regarding ethyl carbamate are available. Samples were analyzed by in-house validated methods, which included measurement uncertainty estimates. The samples comprised 75 fermented liquids (beers, wines, fortified wines, spirits, liqueurs, soy sauces, and vinegars) and 25 fermented solid foods (cheeses, yogurts, soybean products, sauerkraut, yeast extract, olives, and Christmas pudding). Ethyl carbamate was not detected in the beers or the cider. Wines contained between 11 and 24 microg/kg and sake between 81 and 164 microg/kg. Fortified wines contained ethyl carbamate at levels between 14 and 60 microg/kg. Only two of five liqueurs contained ethyl carbamate. Most soy sauces and vinegars did not contain ethyl carbamate. No ethyl carbamate was detected in cheeses, yogurts, olives, or soybean-based products. Single samples of sauerkraut, yeast extract, and Christmas pudding contained low levels (29, 41, and 20 microg/kg ethyl carbamate, respectively).

Determination of 1,3-dichloropropanol in soy sauce and related products by headspace gas chromatography with mass spectrometric detection: interlaboratory study.

An interlaboratory study was performed to evaluate the effectiveness of a headspace gas chromatography (GC) method for the determination of 1,3-dichloro-propan-2-ol (1,3-DCP) in soy sauce and related products at levels above 5 ng/g. The test portion is mixed with an internal standard (d5-1,3-DCP) and ammonium sulfate in a sealed headspace vial. After achieving equilibrium, the headspace is sampled either by gas-tight syringe or solid-phase microextraction (SPME) and analyzed by GC with mass spectrometric detection. 1,3-DCP is detected in the selected-ion mode (monitoring m/z 79 and 81 for 1,3-DCP and m/z 82 for the deuterated internal standard) and quantified by measurement against standards. Test materials comprising soy, dark soy, mushroom soy, and teriyaki sauces, both spiked and naturally contaminated, were sent to 9 laboratories in Europe, Japan, and the United States; of these, 5 used SPME and 4 used syringe headspace analysis. Test portions were spiked at 5.0, 10.0, 20.0, 100.0, and 500.0 ng/g. The average recovery for spiked blank samples was 108% (ranging from 96-130%). Based on results for spiked samples (blind pairs at 5, 10, 20, 100, and 500 ng/g) as well as a naturally contaminated sample (split-level pair at 27 and 29 ng/g), the relative standard deviation for repeatability (RSDr) ranged from 2.9-23.2%. The relative standard deviation for reproducibility (RSDR) ranged from 20.9-35.3%, and HorRat values of between 1.0 and 1.6 were obtained.

Progress towards the characterisation of faecal compounds.

Intestinal nitrosation produces ATNCs (Apparent Total N-nitroso Compounds) and these have been linked with an increased risk of colon cancer from eating red meat. Modern LC-MS instrumentation makes direct detection of ATNC components in faecal water a possibility. The difficulty is in determining which of the many compounds present are N-nitrosamines before embarking on efforts to characterise them. We have assumed that any in vivo nitrosation of alimentary tract contents will be non-specific and depend on the amount and basicity of amine present, with concentration of nitrosating agent being the limiting factor. By further nitrosating faecal waters (and ileostomy fluids) we can increase the amount of ATNC and readily access these compounds. The amount and the number of nitrosamines generated depend on the concentration of individual amines present. By derivatisation separately using both 14N and 15N labelled nitrite, we demonstrated that inspecting chromatograms in parallel for a unit mass difference provides a novel and practicable means for identifying unknown ATNC in faecal and ileostomy samples. MS procedures were linked with the traditional approaches of thermal energy analyser (TEA), preparative HPLC, visualisation of nitrosamines with Griess reagent and degradation of N-nitroso compounds by UV irradiation. We have demonstrated that this approach is repeatable and have used it to identify 30 putative N-nitroso compounds (as protonated parent masses [M + H]+ at: 242, 258, 312, 313, 333, 348, 365, 377, 382, 386, 392, 412, 414, 421, 434, 442, 466, 467, 483, 493, 572, 582, 625, 636, 637, 656, 662, 752, 808, and 870.