Paul Brereton

The effects of domestic cooking on the levels of 3-monochloropropanediol in foods

The results are reported of a study to determine the effect of domestic cooking procedures on the level of 3-monochloropropane-1,2-diol (3-MCPD) in selected foods. Samples of 23 foods comprising stock cubes, gravies, a cake mix, batters, breads, cheese and meats were subjected to a range of cooking procedures including grilling, toasting and microwaving. The resulting levels of 3-MCPD were compared with those present in the foods before cooking. Grilling and toasting produced substantial increases in the 3-MCPD content of bread, forming up to 0.3mg/kg, and of most cheeses, resulting in levels of up to about 0.1mg/kg. Microwave cooking produced elevated 3-MCPD levels in some cheeses. Frying laboratoryproduced batters increased 3-MCPD levels to about 0.1mg/kg whereas a retail batter contained no detectable 3-MCPD when fried. The remaining foods showed little or no discernible increase on cooking.

Survey of 3-monochloropropane-1,2-diol (3-MCPD) in selected food groups, 1999-2000

A survey of the levels of 3-monochloropropane-1,2-diol (3-MCPD) in a range of selected food products available in the UK is reported. The survey was carried out on behalf of the Food Standards Agency (FSA) to identify the food groups that might provide a significant contribution to 3-MCPD exposure from the diet. Three hundred samples comprising meat, dairy, cereal, soup and miscellaneous products were purchased from retail outlets and analysed using a GC-MS procedure, which had been formally validated by an earlier collaborative trial. 3-MCPD was detected in 89 (30%) of the samples. Three samples, all crackers, contained levels of 3-MCPD > 0.1mg kg-1, the highest level being 0.134mg kg-1. Levels of 3-MCPD were generally slightly higher in foods after cooking. In all cases where 3-MCPD was detected in cooked foods, it was also present in the uncooked sample.

3-Monochloropropane-1,2-diol (3-MCPD) in soy sauces and similar products available from retail outlets in the UK

A survey of the level of 3-monochloropropane-1,2-diol (3-MCPD) in soy sauces and similar products available in the UK is reported. The survey was carried out by the Joint Ministry of Agriculture, Fisheries and Food/Department of Health Food Safety and Standards Group (JFSSG) to check for compliance with the Food Advisory Committees (FAC) recommended limit for 3-MCPD of 0.01mg/kg following reports that soy sauces in several European countries had been found to contain high levels (up to 124mg/kg) of 3-MCPD. Forty samples of soy sauce and similar products purchased from retail outlets were analysed using a GC-MS procedure which had been formally validated by an earlier collaborative trial. 3-MCPD was undetectable in 21 (52%) of samples analysed in the survey, with a further five samples containing very low levels of between 0.01 and 0.02mg/kg. Five samples (13%) contained 3-MCPD at levels in the range 0.020-1mg/kg while nine samples (23%) were found to contain 3-MCPD at levels greater than 1mg/kg, with the highest level being 30.5mg/kg.

Effects of storage time and temperature on the concentration of ethyl carbamate and its precursors in wine.

A 3-year study was carried out on the effects of time and temperature on the concentration of ethyl carbamate in wine. The study monitored the changing concentration of ethyl carbamate and of urea and citrulline, which are two major precursors of ethyl carbamate in wine. In addition to the formation of ethyl carbamate, both urea and citrulline decayed in other reactions. Kinetic analysis was carried out to model the formation of ethyl carbamate and its dependence on the concentrations of ethanol, urea and citrulline. This led to the development of an equation that can be used to predict the concentration of ethyl carbamate in wine at the point of consumption, resulting from any given storage time and temperature profile. The results were in good agreement with data obtained from similar studies.

Survey of chloropropanols in soy sauces and related products purchased in the UK in 2000 and 2002

The results of surveys to investigate the levels of 3-monochloropropane-1,2-diol (3-MCPD) and 1,3-dichloropropanol (1,3-DCP) in UK retail samples of soy sauces and similar products are reported. The products, sampled in 2000 and 2002, were analysed for 3-MCPD using an established solvent extraction technique with a reporting limit of 0.01 mg kg−1, which also detected 2-monochloropropane-1,2-diol (2-MCPD), and for 1,3-DCP by an automated headspace method with a reporting limit of 0.005 mg kg−1, which also detected 2,3-dichloropropanol (2,3-DCP). In the 2000 survey, 3-MCPD was quantified in 32 of 100 samples. After normalization to 40% dry matter, it was quantified at or above 0.02 mg kg−1 in 25 of the samples and in excess of 1 mg kg−1 in 16 samples, the highest containing 82.8 mg kg−1. 2-MCPD was found in 26 samples, at up to 17.6 mg kg−1 after normalization to 40% dry matter. The presence of 1,3-DCP was detected in 17 of the samples, at levels between 0.006 and 0.345 mg kg−1. 1,3-DCP was only detected where 3-MCPD was present, but the levels of 1,3-DCP and 3-MCPD were not correlated. 2,3-DCP was detected in 11 samples at levels ranging from 0.006 to 0.043 mg kg−1. In the 2002 survey, 3-MCPD was quantified (> 0.01 mg kg−1) in only eight of 99 samples and 2-MCPD in three samples. After normalization to 40% dry matter, 3-MCPD was present at or above 0.02 mg kg−1 in seven of these, the maximum level being 35.9 mg kg−1. 1,3-DCP was detected in this sample alone, at 0.017 mg kg−1.

Statistical modelling as an aid to the design of retail sampling plans for mycotoxins in food

A study has been carried out to assess appropriate statistical models for use in evaluating retail sampling plans for the determination of mycotoxins in food. A compound gamma model was found to be a suitable fit. A simulation model based on the compound gamma model was used to produce operating characteristic curves for a range of parameters relevant to retail sampling. The model was also used to estimate the minimum number of increments necessary to minimize the overall measurement uncertainty. Simulation results showed that measurements based on retail samples (for which the maximum number of increments is constrained by cost) may produce fit-for-purpose results for the measurement of ochratoxin A in dried fruit, but are unlikely to do so for the measurement of aflatoxin B1 in pistachio nuts. In order to produce a more accurate simulation, further work is required to determine the degree of heterogeneity associated with batches of food products. With appropriate parameterization in terms of physical and biological characteristics, the systems developed in this study could be applied to other analyte/matrix combinations.

An improved method for the measurement of added vegetable fats in chocolate.

A method for identifying refined vegetable fats added to chocolate (cocoa butter equivalents, CBEs) was combined with established quantitative methods for determining the level of vegetable fat added to cocoa butter with the aim of providing improved precision. The identification of fats was based on the analysis of sterol and triterpene alcohol degradation products formed during the processing of the fat. The procedure was able to successfully discriminate between 95% of pairs of fats from a set (33) of CBE-type vegetable fats. Subsequent analysis of 80 mixtures of four CBEs with chocolate successfully identified, on cross-validation, 94% of the samples. Combining the qualitative procedure with established quantitative methodology, based on the analysis of triacylglycerols, improved the method precision from ± 2.1% to ± 0.3% (5% addition of CBE at 95% confidence). Identifying the fat analytically permits the use of quantitative methods for determining the level of added fat in chocolate that have improved precision in comparison with the measurement of an unidentified fat. This may obviate the need to use factory inspection as a means to identify the ingredients of a product and monitor compliance with proposed legislation.

Identification of steroidal hydrocarbons in refined confectionery fats by gas chromatography–mass spectrometry

Steroidal hydrocarbon degradation products (steradienes) of sterols formed during the bleaching of confectionery fats were isolated by a new rapid silica column technique. The steradienes were separated by gas chromatography with mass spectrometric detection. Refined mango butter contained predominantly a sterene which was unrelated to the major desmethyl sterols. Dehydration products of triterpene alcohols were isolated from stearin fractions of refined shea butter which is used in the manufacture of chocolate.

Development and single-laboratory validation of an HPLC method for the determination of cyclamate sweetener in foodstuffs

A method for the determination of cyclamate has been developed and single-laboratory validated for a range of foodstuffs including carbonated and fruit-juice drinks, fruit preserves, spreads, and dairy desserts. The method uses the peroxide oxidation of cyclamate to cyclohexylamine followed by derivatization with trinitrobenzenesulfonic acid and analysis by a modified reversed-phase high-performance liquid chromatography-ultraviolet light (HPLC-UV). Cycloheptylamine is used as an internal standard. The limits of detection were in the range 1–20 mg kg−1 and the analysis was linear up to 1300 mg kg−1 cyclamic acid in foods and up to 67 mg l−1 in beverages. Analytical recovery was between 82% and 123%, and results were recovery corrected. Precision was within experimentally predicted levels for all of the matrices tested and Horrat values for the combined standard uncertainty associated with the measurement of cyclamate between 0.4 (water-based drinks) and 1.7 (spreads). The method was used successfully to test three soft drink samples for homogeneity before analytical performance assessment. The method is recommended for use in monitoring compliance and for formal testing by collaborative trial.

Collaborative trials of the sampling of two foodstuffs, wheat and green coffee.

Two foodstuffs, wheat and green coffee, have been sampled from bulk lots by multiple samplers in the sampling analogue of a collaborative trial. For wheat the variation between samplers, contributing to the standard deviation of sampling reproducibility, was significant for two analytes. No significant sampling reproducibility variation was found in the coffee results, although significant sampling repeatability variation was detected.