The formation and analysis of n‐nitrosamines

Abstract

The assessment of the potential carcinogenic risk to human health of the small quantities of N-nitrosamines formed in some foodstuffs depends on the availability of information on the routes by which they can be formed and of analytical methods having adequate sensitivity and selectivity for their determination. The present state of knowledge on these two aspects is reviewed in this paper.Demonstrations that a large number of N-nitrosamines are carcinogenic when fed to experimental animals1 have prompted investigations into their potential significance in human cancer. Chemical aspects of these studies have centred on attempts to ascertain which N-nitrosamines are likely to be present in food and the environment and upon the development of analytical methods for their determination. This paper reviews progress made in elucidating the parameters involved in the formation of N-nitrosamines, with particular reference to their possible presence in food and their formation in vivo, and the development of analytical methods of sufficient sensitivity and specificity to permit determination of them at the very low concentrations at which they are likely to be found. Formation of N-nitrosaminesThe principal chemical reaction involved in the formation of N-nitrosamines in circumstances relevant to human cancer is that of secondary amines with nitrous acid. The former are present at low concentrations in proteinaceous foods and the latter can arise from sodium nitrite used as a preservative or from enzymic reduction of nitrate which is commonly present in small quantities in water and foods and is also used in conjunction with nitrite in food preservation.Mirvishz studied the nitrosation of dimethylamine in aqueous solution as a function of pH. Figure 1 shows the pH dependence; the extent of reaction is a maximum at pH 3.4 and falls off at both higher and lower pH values. The nitrosating species is Nz03, derived from non-ionised nitrous acid and the reaction is therefore second order with respect to nitrous acid concentration. The Nz03 reacts with unprotonated amine and the reaction is first order with respect to the latter. Thus the reaction rate can be expressed as Rate= kl[R2NH][HN02l2 (1) a Presented at the SCI/IFST Symposium "The Role of Nitrate/Nitrite in Food", London, March 1975.

Electrocatalytic oxidation and determination of nitrite on carbon paste electrode modified with oxovanadium(IV)-4-methyl salophen

“…The potential for nitrite to be metabolised to carcinogenic N-nitroso compounds [1,2] and its widespread presence in food products and beverages has necessitated its monitoring [1][2][3][4][5]. Nitrite is used as a food preservative (E249, E250) and its salts are known to occur in high quantity in soil [6][7][8][9].…”

Mechanism of N-nitrosopyrrolidine formation in bacon

“…At present, there are many methods available which are capable of measuring volatile nitrosamines at the microgram/kilogram level. Excellent reviews have been presented by Foreman and Goodhead (1975) and Scanlan (1975).…”

Determination of volatile N-nitrosamines in bacon cook-out fat by nitrite release and thin-layer chromatography of fluorescent amine derivatives

“…Lower limits of detection of IV-nitrosodimethylamine (NDMA) and IV-nitrosopyrrolidine (NPYR) are in the order of 5 gg/kg (ppb). The technique has been compared with a high-resolution gas chromatography-mass spectrometry method and gave comparable results.A number of methods are now available for the determination of volatile IV-nitrosamines in foodstuffs and these have been reviewed recently (Foreman and Goodhead, 1975). In spite of the fact that the need for screening methods has been repeatedly emphasized (Goodhead and Gough, 1975), work on this type of method has been somewhat limited.…”

“…A number of methods are now available for the determination of volatile IV-nitrosamines in foodstuffs and these have been reviewed recently (Foreman and Goodhead, 1975). In spite of the fact that the need for screening methods has been repeatedly emphasized (Goodhead and Gough, 1975), work on this type of method has been somewhat limited.…”