Peroxide Value 1997 %» ee ee ee ee eS eS Se eeeroxide value is usually applied to D )edible product including edible tallow and associated products such as margarine shortenings and frying fat. It is also applied to the fat in meat and meat products. It is used as an indicator of the extent of oxidative rancidity. It is affected by the age of raw material as well as oxidation of fats during processing and storage. Although peroxide value is usually used in association with edible product, it may also be specified for tallow and meat meal used in petfood products because it reflects the palatability of fats and oils. Fats are oxidised at the sites of unsaturated bonds in fatty acid chains. Oxidation of the unsaturated bonds results in a variety of compounds being formed including free radicals and hydroperoxides. At the onset of oxidation, peroxides increase but they are eventually oxidised to aldehydes and ketones and peroxide levels fall in the later stages of oxidation. The peroxide value test does not specifically measure peroxides. It measures all material capable of oxidising potassium iodide. The amount of potassium iodide oxidised in the test can be influenced by the way the test is conducted. The ‘method shown below is based on the American Oil Chemist Society (AOCS) official method. Application ‘The test applies to all fats and oils but is intended mainly for use with edible fats. Apart from being used as an indicator of rancidity, itis also used to ‘measure the stability of fats in tests designed to ‘measure the rate of change of peroxide value. Peroxide value can be measured in fat containing ‘materials such as meat, meat products and meat meal. The fat first has to be extracted from these materials by solvents such as a chloroform and ‘methanol mixture. Peroxides in oxidised fats are unstable and are themselves oxidised to other compounds. Thus the peroxide value of fats may increase and subsequently decline. For this reason, peroxide value is most appropriate as a measure of the onset of rancidity in relatively fresh fats. For fats that have been stored of a long time and fats that are components of meat and other food products, the degree of rancidity is assessed by peroxide value in combination with other measurements such as thiobarbituric acid (TBA) value Fats oxidation is a self-catalysing reaction. This means that the compounds formed at the start of oxidation promote further oxidation and cause an inerease in the rate of reaction. Oxidation and development of peroxide value should proceed slowly in fresh tallow but if fresh tallow is contaminated by small amounts of stale tallow eg; from dirty tanks or product lines, the oxidised ‘material in the stale tallow will promote and accelerate oxidation in the fresh tallow. Thus high peroxide values are usually caused by dirty processing and tallow handling equipment. Oxidation is also catalysed by metal ions and high peroxide values may be caused by tallow coming into contact with brass or copper. Outline of Method Fat is mixed with a solvent and potassium iodide is added to the solution of fat. Peroxides and other oxidising material in the fat react with the iodide to liberate iodine. The reaction proceeds for a specified time and is then stopped by diluting the reaction mixture. The amount of iodine liberated under the specific conditions of the test is measured by titration with sodium thiosulphate. The amount of iodide liberated is expressed as mill-equivalents (meq) of peroxide per 100g of sample. Precautions 8 The amount of iodine liberated in the test is sensitive to the conditions used such ‘as the time the peroxides are allowed to react with iodide, the reaction temperature and pH, and the presence other catalytic agents. ‘To obtain reproducible results, the precise conditions of the test must be followed. 1 Sodium thiosulphate must be accurately standardised. It should be made up from concentrated sohution and care must be taken to avoid contaminating or diluting the standard solution. 1 The potassium iodide solution must be saturated ie, there must be undissolved cxystals of iodide in the container. It must be stored in the dark and tested to ensure that it contains no iodine, a1 Solutions should be made with recently boiled distilled water to eliminate the possibility of oxidation of iodide by dissolved oxygen. Alternative Methods ‘The AOGS official method should be followed precisely to measure peroxide value in fats. Equipment Suppliers ‘The equipment and reagents used in the peroxide value tests are readily available from laboratory suppliers Method Equipment a Balance with 0.1g sensitivity 12 250ml stoppered conical flask 110ml graduated measuring pipette 250ml burette 1 Boss head, clamp and stand for the burette 250ml measuring cylinder Reagents 1 Acetic acid ~ chloroform solution ‘Mix 300ml of glacial acetic acid with 200ml of chloroform. Prepare this mixture in a fume cupboard to avoid inhaling chloroform fumes. 1 Potassium iodide solution ‘Mix about 38g of potassium iodide with about 25ml of recently boiled distilled water. Store the saturated solution in a dark cupboard or in a flask wrapped with aluminium foil. Check the solution before use to ensure there are undissolved crystals in the mixture indicating that the solution is saturated. The solution can be tested for the presence of iodine by mixing 0.5ml with the acetic acid-chloroform solvent, and adding 2 drops of starch solution, Ifa blue colour appears which requires more than 1 drop of 0.1M sodium thiosulphate to discharge, prepare a fresh solution of iodide. .0-0-1M-sodium-thiosulphate-solution 0.0.01M sodium thiosulphate solution prepared by diluting 10.0ml of 0.1M sodium thiosulphate to 100ml with recently boiled distilled water (required for samples with PV less than 10 meq/1000g) 12 1% starch indicator solution: dissolve 10g, soluble starch in 100ml of distilled water Procedure 1. Weigh 5.0g of melted fat in a 250ml stoppered conical flask. While the fat is still liquid, add 30m of acetic acid-chloroform solution and swirl the flask to dissolve the fat in the solvent. 2. Add 0.5ml of saturated potassium iodide solution from a Im! graduated pipette. 3, Stopper the flask and allow the mixture to stand with occasional shaking for exactly 1 minute. After 1 minute, add 30ml of distilled water. 4, Add about 5 drops of starch indicator solution, Titrate with 001M sodium thiosulphate solution, Shake the flask vigorously during the titration to extract iodine from the chloroform layer. The end-point is when the purple colour disappears. For peroxide values > 10 meq/1000g, titrate with 0.1M sodium thiosulphate 5, Perform a blank determination of the reagents. The blank titration should not exceed 0.1ml of 0.01M sodium thiosulphate, Calculation Peroxide value (meq/1000g) _ (A-B) x Mx 1000 ae [tration value of sample (ml of thiosulphate) ‘Where: Titration value of blank =B (an! of thiosulphate) Molatity of sodium thiosulphate = M Weight of sample (g) =WReferences ‘Official Methods and Recommended Practices of the American Oil Chemist's Society’ (1993) Edited by D. Firestone. AOAG Press, Illin¢ Additional information Additional help and advice are available from Food Science Australia, Meat Industry Services Section: Phone Fax Jan Eustace (07) 32142517 (07) 32142103 Nell McPhail (07) 3214 2119 (07) 32142103 Bill Spooncer (02) 4567 7952 (02) 4567 8952 Chris Sentence (08) 8370 7466 (08) 8370 7568 Processing and Product Innovation Meat & Livestock Australia Tel: (02) 9463 9166 Fax: (02) 9463 9182 Email: ppi@mla.com.au