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Safety evaluation of certain food additives - ipcs inchem

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SULFITES: ASSESSMENT OF DIETARY EXPOSURE 223<br />

(INS 227), potassium bisulfite (INS 228) and sodium thiosulfate (INS 539). Sulfites<br />

are added to <strong>food</strong>s such as processed meats, dried fruit, wine, beer, fruit and<br />

vegetable juices, water-based flavoured drinks and processed fish and sea<strong>food</strong>s,<br />

with the major functions <strong>of</strong> preservation and inhibition <strong>of</strong> browning reactions. The<br />

ability <strong>of</strong> sulfites to prevent further oxidation <strong>of</strong> polyphenols is especially important<br />

in wine production, where these components are considered to contribute to the<br />

taste, texture and colour <strong>of</strong> the final product (Burroughs, 1981; Ough, 1986). Sulfites<br />

may also occur naturally in some <strong>food</strong>s, especially in fermented ones, as a result<br />

<strong>of</strong> endogenous formation by yeast during the fermentation process (Taylor et al.,<br />

1986).<br />

Sulfites may be present in <strong>food</strong> as sulfurous acid, inorganic sulfites and a<br />

variety <strong>of</strong> reversibly and irreversibly combined forms. They react rapidly with a<br />

variety <strong>of</strong> <strong>food</strong> constituents, including reducing sugars, aldehydes, ketones and<br />

proteins, to form various combined sulfites, such as the highly stable<br />

hydroxysulfonate adducts. The amount <strong>of</strong> compound in each <strong>of</strong> these states is<br />

dependent on a number <strong>of</strong> factors, including the <strong>food</strong> matrix and the pH. Sulfites<br />

reversibly bound may dissociate into free sulfite when the <strong>food</strong> pH is raised above<br />

10 or when acidified solutions are heated until boiling (Ough, 1986; Fazio & Warner,<br />

1990; Lück & Jager, 1997). Adducts irreversibly bound are usually formed by the<br />

reaction <strong>of</strong> sulfites with alkanes or aromatic compounds, giving rise to sulfonic acids,<br />

which are not recovered when the sulfited <strong>food</strong> is submitted to alkaline conditions<br />

or upon distillation in acid medium. The fraction <strong>of</strong> sulfites that does not bind to <strong>food</strong><br />

constituents is called “free sulfite”, constituting a mixture <strong>of</strong> sulfur dioxide, bisulfite<br />

and sulfite ions in a dynamic equilibrium. This fraction is rapidly converted to<br />

molecular sulfur dioxide when the sulfited <strong>food</strong> is acidified (Wedzicha, 1992). As<br />

sulfites react with a variety <strong>of</strong> <strong>food</strong> constituents and some are lost during processing<br />

and storage, their use levels may not represent the amount needed to ensure an<br />

effective residual level through the shelf life <strong>of</strong> the product and may not reflect<br />

the concentration remaining in a <strong>food</strong> at the time <strong>of</strong> ingestion (Taylor et al., 1986;<br />

Annex 1, reference 137). The fate <strong>of</strong> added sulfites is highly dependent on the<br />

chemical nature <strong>of</strong> the <strong>food</strong>, the type and extent <strong>of</strong> storage conditions, the<br />

permeability <strong>of</strong> the package and the level <strong>of</strong> addition. The combination with organic<br />

constituents, the equilibrium between the various inorganic forms, the volatilization<br />

<strong>of</strong> sulfur dioxide and the oxidation to sulfates are all important reactions, and their<br />

relative importance will depend mostly on the <strong>food</strong> involved (Fazio & Warner,1990).<br />

2.2 Analytical methods<br />

Analytical methods for the determination <strong>of</strong> sulfites in <strong>food</strong> have been<br />

reviewed (Fazio & Warner, 1990; Karavicová & Simko, 1996). Published methods<br />

are generally based on the known chemistry and reactivity <strong>of</strong> sulfites with the matrix<br />

and require some means <strong>of</strong> recovering sulfur dioxide. They fall into two basic<br />

categories: methods that require an initial distillation <strong>of</strong> the test sample to free the<br />

sulfur dioxide, and those that use a non-distillation reaction to achieve the same<br />

end-point (Wedzicha et al., 1984; Wedzicha, 1992). Several methods use acidic or<br />

basic solutions (AOAC International, 1995a, 1995b, 1995c, 1995d, 1995e, 1995f),

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