M. J. Dennis

Analysis of polycyclic aromatic hydrocarbons in UK total diets

Analysis of UK total-diet samples for polycyclic aromatic hydrocarbons was carried out using a simplified sample clean-up and a high-performance liquid chromatography dual fluorescence detector system. The results indicate that cereals and oils/fats contribute the major part (approximately one third each) of the polycyclic aromatic hydrocarbons in these total diets. Fruit, sugars and vegetables provide much of the remainder (approximately one quarter) while meat, fish, milk and beverages make relatively minor contributions. These results are compared with others in the current literature on polycyclic aromatic hydrocarbons in foods. The levels in the UK diet seem to be at least as low as those found elsewhere.

Factors affecting the polycyclic aromatic hydrocarbon content of cereals, fats and other food products

Factors affecting polycyclic aromatic hydrocarbon (PAH) concentrations in oils and fats, cereals and related foodstuffs have been investigated. Levels of PAHs were low in retail fish and animal-derived oils and fats, such as butter, where the mean benzo(a)pyrene concentration was 0.06 microgram/kg. Higher and more variable amounts were present in retail vegetable oils for which the mean level of benzo(a)pyrene was 1.29 micrograms/kg. Margarine was the major dietary source of PAHs in the oils and fats total diet group accounting for 70% of the benzo(a)pyrene intake from these commodities. The levels of benzo(a)pyrene were less than 0.1 microgram/kg in white flour and similar amounts were found in bread showing that PAHs are not formed to any significant extent during baking of bread. Higher concentrations of up to 2.2 micrograms/kg benzo(a)pyrene were detected in cereal-derived products containing higher levels of edible oils such as pudding-based desserts, biscuits and cakes. The presence of vegetable oils as an ingredient also appeared to increase PAH levels in infant formulae as the mean benzo(a)pyrene content of 0.49 microgram/kg was four times higher than that found in skimmed milk. The mean value in the feed, after reconstituting the formulae with water, would however have been less than 0.1 microgram/litre. Investigations of rape seed drying showed no increase in any PAHs when cold, or electrically-heated air was used. Combustion gas drying had no effect for the larger PAHs such as benzo(a)pyrene but caused mean increases of between 41% and 126% for fluoranthene, pyrene and chrysene. These increases did not correlate with reductions in moisture content of the rape seed implying that the combustion conditions were more important to PAH contamination than the degree of exposure to combustion gases. Concentrations of these three PAHs and also benz(a)anthracene were all significantly reduced by up to a factor of five when crude oils were refined suggesting that carefully controlled direct drying need not contribute PAHs to refined oils and fats.

Investigation of ethyl carbamate levels in some fermented foods and alcoholic beverages.

An analytical procedure has been developed for the determination of trace amounts of ethyl carbamate in fermented foodstuffs and alcoholic beverages. Concentrations were generally below the 1-5 micrograms/kg detection limit in bread, cheese, yoghurt, beer, gin and vodka. Higher concentrations were found in the other alcoholic beverages examined, which included whisky, fruit brandy, liqueur, wine, sherry and port.

The determination of nitrate and nitrite in cured meat by HPLC/UV

A rapid strong anion exchange HPLC/UV procedure has been developed for the determination of nitrate and nitrite in a wide variety of cured meats. The accuracy of this technique has been confirmed by the good agreement achieved with the existing British Standard colorimetric method. The applicability and repeatability of the procedure has been established in a survey of over 200 samples. The agreement between duplicate determinations and their respective means averaged +/- 3.4% for nitrite and +/- 4.3% for nitrate as defined by the term [(a - b)/(a + b)] X 100% where a and b are the repeat determination values.

Estimation of nitropolycyclic aromatic hydrocarbons in foods

A method is described for the sample clean-up and estimation of nitropolycyclic aromatic hydrocarbons (nitro-PAH) in foods. The analysis involves the novel use of a coupled capillary gas chromatograph/thermal energy analyser and provides a detection limit for 1-nitropyrene of 12 pg (equivalent to 0.02 micrograms/kg for a 50-g sample). Only 3 out of 24 samples contained detectable quantities of nitro-PAHs; these were in the range 0.2-2.0 micrograms/kg. In contrast to the widespread occurrence of the parent PAHs in foodstuffs, the presence of nitro-derivatives appears to be minimal.

The determination of the flour improver potassium bromate in bread by gas chromatographic and ICP‐MS methods

The development and application of two methods for determining bromate in bread are described. A gas chromatographic (GC) method which relied on the formation of a volatile derivative of bromate gave a detection limit of 12 micrograms/kg. Duplicate analyses agreed well but recovery from breads spiked with bromate were low and averaged 30% for brown bread and 42% for white bread. Further studies indicated that this was caused by the derivatization reaction being suppressed by components of the sample and reagents used in their preparation. After taking both these factors into account, a recovery of 80% could be achieved. The GC method was used to carry out a survey of retail bread samples in 1989. Bromate was found in all six unwrapped breads analysed (median 35 micrograms/kg, range 17-317 micrograms/kg), whilst for 22 wrapped breads, seven were found to contain bromate (median < 12 micrograms/kg, range < 12-238 micrograms/kg). A second method of analysis employing inductively coupled plasma-mass spectrometry (ICP-MS) was developed which provided independent confirmation of the presence of bromate in these retail samples. The method gave a mean recovery of 71% from five spiked samples and a detection limit of 20 micrograms/kg. The GC and ICP-MS methods were compared by performing replicate analyses of a bread sample prepared with bromate-treated flour. Quantitative agreement between the two techniques was good. The precision of the ICP-MS technique (CV 12%) proved better than that found for the GC method (CV 18%). The Potassium Bromate (Prohibition as a Flour Improver) Regulation 1990 came into force on 1 April 1990 (Statutory Instrument 1990 Number 399).(ABSTRACT TRUNCATED AT 250 WORDS)

An investigation of the levels of N‐nitrosodimethylamine, apparent total N‐nitroso compounds and nitrate in beer

Over 170 retail samples of beer have been analysed for N-nitrosodimethylamine (NDMA), apparent total N-nitroso compounds (ATNC) and nitrate. Levels of NDMA ranged from below 0.1 up to 1.2 micrograms/kg with a mean of 0.2 micrograms/kg. ATNC was detected in 42% of the samples in concentrations of up to 569 micrograms (N-NO)/kg. The levels of nitrate ranged from less than 0.2 up to 143 mg/kg with a mean of 16.8 mg/kg. There was no correlation between the amounts of NDMA and ATNC found in the retail beers. Samples taken during the course of fermentation showed that NDMA was unaffected by the bacterial reduction of nitrate which causes ATNC formation. HPLC studies using a photolysis/chemiluminescence detector revealed that the ATNC in beer are highly polar species of as yet unknown identity.

N-nitroso compounds and polycyclic aromatic hydrocarbons in Icelandic smoked cured mutton

Five samples of Icelandic smoked cured mutton were analysed for volatile N-nitrosamines, N- nitrosoamino acids, total N-nitroso content and several polycyclic aromatic hydrocarbons. Levels varied considerably from sample to sample but generally the levels of polycyclic aromatic hydrocarbons and N-nitrosamines (as judged by N- nitrosoproline , N- nitrosohydroxyproline and total N-nitroso content) varied in the same way. It is suggested that in this product the smoking procedure is responsible for both groups of contaminants and that the curing process is relatively unimportant.

The effect of oxygen on nitrosamine formation in bacon

ZusammenfassungSpeck wurde in einer Luft- sowie einer Stickstoffatmosphäre gebraten and die Wirkung auf die Bildung von N-Nitrosodimethylamin und N-Nitrosopyrrolidin untersucht. Bei Stickstoff ergab sich eine 50–90%ige Verringerung der Konzentration beider Nitrosamine im Kochdampf. Die Ergebnisse werden im Hinblick auf die wahrscheinliche Rolle besprochen, welche das Stickstoffoxyd bei der Nitrosaminbildung während des Bratens von Speck spielt.SummaryBacon has been cooked in air and in nitrogen atmospheres and the effect on the formation of N-nitrosodimethylamine and N-nitrosopyrrolidine has been studied. Under nitrogen, reductions of 50%–90% were obtained in the concentrations of both nitrosamines in the cooking vapour. The results are discussed in terms of the likely role of nitric oxide in nitrosamine formation in cooking bacon.

Measurement of haloacetic acids and their decomposition in wine by capillary gas chromatography

A method has been developed for the analysis of haloacetic acids in wine involving solid-phase extraction followed by methylation and quantification by capillary gas chromatography with electron capture detection. Recoveries from spiked samples were greater than 85% for each of the acids and the limits of detection of the method were 100, 10 and 5 micrograms/litre for the chloroacetic, bromoacetic and iodoacetic acids, respectively. The haloacetic acids were not detected in a survey of over 30 retail samples. Separate stability studies showed that the concentration of chloroacetic acid added to wine was essentially unaffected by up to 90 days storage at 30 degrees C. Under the same conditions, however, less than 20% of bromoacetic acid and iodoacetic acid remained.