Rancidification

Last updated

Rancidification is the process of complete or incomplete autoxidation or hydrolysis of fats and oils when exposed to air, light, moisture, or bacterial action, producing short-chain aldehydes, ketones and free fatty acids. [1]

Contents

When these processes occur in food, undesirable odors and flavors can result. In processed meats, these flavors are collectively known as warmed-over flavor. In certain cases, however, the flavors can be desirable (as in aged cheeses). [2]

Rancidification can also detract from the nutritional value of food, as some vitamins are sensitive to oxidation. [3] Similar to rancidification, oxidative degradation also occurs in other hydrocarbons, such as lubricating oils, fuels, and mechanical cutting fluids. [4]

Pathways

Five pathways for rancidification are recognized: [5]

Hydrolytic

Hydrolytic rancidity refers to the odor that develops when triglycerides are hydrolyzed and free fatty acids are released. This reaction of lipid with water may require a catalyst (such as a lipase, [6] or acidic or alkaline conditions) leading to the formation of free fatty acids and glycerol. In particular, short-chain fatty acids, such as butyric acid, are malodorous. [7] When short-chain fatty acids are produced, they serve as catalysts themselves, further accelerating the reaction, a form of autocatalysis. [7]

Oxidative

Oxidative rancidity is associated with the degradation by oxygen in the air.

Free-radical oxidation

The double bonds of an unsaturated fatty acid can be cleaved by free-radical reactions involving molecular oxygen. This reaction causes the release of malodorous and highly volatile aldehydes and ketones. Because of the nature of free-radical reactions, the reaction is catalyzed by sunlight. [7] Oxidation primarily occurs with unsaturated fats. For example, even though meat is held under refrigeration or in a frozen state, the poly-unsaturated fat will continue to oxidize and slowly become rancid. The fat oxidation process, potentially resulting in rancidity, begins immediately after the animal is slaughtered and the muscle, intra-muscular, inter-muscular and surface fat becomes exposed to oxygen of the air. This chemical process continues during frozen storage, though more slowly at lower temperature. Oxidative rancidity can be prevented by light-proof packaging, oxygen-free atmosphere (air-tight containers) and by the addition of antioxidants. [7]

Enzyme-catalysed oxidation

A double bond of an unsaturated fatty acid can be oxidised by oxygen from the air in reactions catalysed by plant or animal lipoxygenase enzymes, [6] producing a hydroperoxide as a reactive intermediate, as in free-radical peroxidation. The final products depend on conditions: the lipoxygenase article shows that if a hydroperoxide lyase enzyme is present, it can cleave the hydroperoxide to yield short-chain fatty acids and dicarboxylic acids (several of which were first discovered in rancid fats).

Microbial

Microbial rancidity refers to a water-dependent process in which microorganisms, such as bacteria or molds, use their enzymes such as lipases to break down fat. [6] Pasteurization and/or addition of antioxidant ingredients such as vitamin E, can reduce this process by destroying or inhibiting microorganisms. [6]

Food safety

Despite concerns among the scientific community, there is little data on the health effects of rancidity or lipid oxidation in humans. [8] [9] Animal studies show evidence of organ damage, inflammation, carcinogenesis, and advanced atherosclerosis, although typically the dose of oxidized lipids is larger than what would be consumed by humans. [10] [11] [12]

The free radical pathway for the first phase of the oxidative rancidification of fats. Lipid peroxidation.svg
The free radical pathway for the first phase of the oxidative rancidification of fats.

Antioxidants are often used as preservatives in fat-containing foods to delay the onset or slow the development of rancidity due to oxidation. Natural antioxidants include ascorbic acid (vitamin C) and tocopherols (vitamin E). Synthetic antioxidants include butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), TBHQ, propyl gallate and ethoxyquin. The natural antioxidants tend to be short-lived, [13] so synthetic antioxidants are used when a longer shelf-life is preferred. The effectiveness of water-soluble antioxidants is limited in preventing direct oxidation within fats, but is valuable in intercepting free radicals that travel through the aqueous parts of foods. A combination of water-soluble and fat-soluble antioxidants is ideal, usually in the ratio of fat to water.

In addition, rancidification can be decreased by storing fats and oils in a cool, dark place with little exposure to oxygen or free radicals, since heat and light accelerate the rate of reaction of fats with oxygen. Antimicrobial agents can also delay or prevent rancidification by inhibiting the growth of bacteria or other micro-organisms that affect the process. [1]

Oxygen scavenging technology can be used to remove oxygen from food packaging and therefore prevent oxidative rancidification.

Oxidative stability measurement

Oxidative stability is a measure of oil or fat resistance to oxidation. Because the process takes place through a chain reaction, the oxidation reaction has a period when it is relatively slow, before it suddenly speeds up. The time for this to happen is called the "induction time", and it is repeatable under identical conditions (temperature, air flow, etc.). There are a number of ways to measure the progress of the oxidation reaction. One of the most popular methods currently in use is the Rancimat method.

The Rancimat method is carried out using an air current at temperatures between 50 and 220 °C. The volatile oxidation products (largely formic acid [14] ) are carried by the air current into the measuring vessel, where they are absorbed (dissolve) in the measuring fluid (distilled water). By continuous measurement of the conductivity of this solution, oxidation curves can be generated. The cusp point of the oxidation curve (the point where a rapid rise in the conductivity starts) gives the induction time of the rancidification reaction, [15] and can be taken as an indication of the oxidative stability of the sample.

The Rancimat method, the oxidative stability instrument (OSI) and the oxidograph were all developed as automatic versions of the more complicated AOM (active oxygen method), which is based on measuring peroxide values [15] for determining the induction time of fats and oils. Over time, the Rancimat method has become established, and it has been accepted into a number of national and international standards, for example AOCS Cd 12b-92 and ISO 6886.

See also

Related Research Articles

Antioxidants are compounds that inhibit oxidation, a chemical reaction that can produce free radicals. Autoxidation leads to degradation of organic compounds, including living matter. Antioxidants are frequently added to industrial products, such as polymers, fuels, and lubricants, to extend their useable lifetimes. Food are also treated with antioxidants to forestall spoilage, in particular the rancidification of oils and fats. In cells, antioxidants such as glutathione, mycothiol or bacillithiol, and enzyme systems like superoxide dismutase, can prevent damage from oxidative stress.

<span class="mw-page-title-main">Fatty acid</span> Carboxylic acid

In chemistry, particularly in biochemistry, a fatty acid is a carboxylic acid with an aliphatic chain, which is either saturated or unsaturated. Most naturally occurring fatty acids have an unbranched chain of an even number of carbon atoms, from 4 to 28. Fatty acids are a major component of the lipids in some species such as microalgae but in some other organisms are not found in their standalone form, but instead exist as three main classes of esters: triglycerides, phospholipids, and cholesteryl esters. In any of these forms, fatty acids are both important dietary sources of fuel for animals and important structural components for cells.

A preservative is a substance or a chemical that is added to products such as food products, beverages, pharmaceutical drugs, paints, biological samples, cosmetics, wood, and many other products to prevent decomposition by microbial growth or by undesirable chemical changes. In general, preservation is implemented in two modes, chemical and physical. Chemical preservation entails adding chemical compounds to the product. Physical preservation entails processes such as refrigeration or drying. Preservative food additives reduce the risk of foodborne infections, decrease microbial spoilage, and preserve fresh attributes and nutritional quality. Some physical techniques for food preservation include dehydration, UV-C radiation, freeze-drying, and refrigeration. Chemical preservation and physical preservation techniques are sometimes combined.

<span class="mw-page-title-main">Triglyceride</span> Any ester of glycerol having all three hydroxyl groups esterified with fatty acids

A triglyceride is an ester derived from glycerol and three fatty acids. Triglycerides are the main constituents of body fat in humans and other vertebrates, as well as vegetable fat. They are also present in the blood to enable the bidirectional transference of adipose fat and blood glucose from the liver, and are a major component of human skin oils.

Essential fatty acids, or EFAs, are fatty acids that humans and other animals must ingest because the body requires them for good health but cannot synthesize them.

An unsaturated fat is a fat or fatty acid in which there is at least one double bond within the fatty acid chain. A fatty acid chain is monounsaturated if it contains one double bond, and polyunsaturated if it contains more than one double bond.

<span class="mw-page-title-main">Linseed oil</span> Oil obtained from the dried, ripened seeds of the flax plant

Linseed oil, also known as flaxseed oil or flax oil, is a colourless to yellowish oil obtained from the dried, ripened seeds of the flax plant. The oil is obtained by pressing, sometimes followed by solvent extraction.

<span class="mw-page-title-main">Stearic acid</span> Eighteen-carbon straight-chain fatty acid

Stearic acid is a saturated fatty acid with an 18-carbon chain. The IUPAC name is octadecanoic acid. It is a waxy solid with the formula CH3(CH2)16CO2H. Its name comes from the Greek word στέαρ "stéar", which means tallow. The salts and esters of stearic acid are called stearates. As its ester, stearic acid is one of the most common saturated fatty acids found in nature following palmitic acid. The triglyceride derived from three molecules of stearic acid is called stearin.

<span class="mw-page-title-main">Drying oil</span> Oil that hardens after exposure to air

A drying oil is an oil that hardens to a tough, solid film after a period of exposure to air, at room temperature. The oil hardens through a chemical reaction in which the components crosslink by the action of oxygen. Drying oils are a key component of oil paint and some varnishes. Some commonly used drying oils include linseed oil, tung oil, poppy seed oil, perilla oil, and walnut oil. Their use has declined over the past several decades, as they have been replaced by alkyd resins and other binders.

<span class="mw-page-title-main">Saponification value</span> Milligrams of a base required to saponify 1g of fat

Saponification value or saponification number represents the number of milligrams of potassium hydroxide (KOH) or sodium hydroxide (NaOH) required to saponify one gram of fat under the conditions specified. It is a measure of the average molecular weight of all the fatty acids present in the sample in form of triglycerides. The higher the saponification value, the lower the fatty acids average length, the lighter the mean molecular weight of triglycerides and vice versa. Practically, fats or oils with high saponification value are more suitable for soap making.

<span class="mw-page-title-main">Lipid peroxidation</span>

Lipid peroxidation is the chain of reactions of oxidative degradation of lipids. It is the process in which free radicals "steal" electrons from the lipids in cell membranes, resulting in cell damage. This process proceeds by a free radical chain reaction mechanism. It most often affects polyunsaturated fatty acids, because they contain multiple double bonds in between which lie methylene bridges (-CH2-) that possess especially reactive hydrogen atoms. As with any radical reaction, the reaction consists of three major steps: initiation, propagation, and termination. The chemical products of this oxidation are known as lipid peroxides or lipid oxidation products (LOPs).

In chemistry, a saturated compound is a chemical compound that resists addition reactions, such as hydrogenation, oxidative addition, and binding of a Lewis base. The term is used in many contexts and for many classes of chemical compounds. Overall, saturated compounds are less reactive than unsaturated compounds. Saturation is derived from the Latin word saturare, meaning 'to fill'.

In chemistry, the iodine value is the mass of iodine in grams that is consumed by 100 grams of a chemical substance. Iodine numbers are often used to determine the degree of unsaturation in fats, oils and waxes. In fatty acids, unsaturation occurs mainly as double bonds which are very reactive towards halogens, the iodine in this case. Thus, the higher the iodine value, the more unsaturations are present in the fat. It can be seen from the table that coconut oil is very saturated, which means it is good for making soap. On the other hand, linseed oil is highly unsaturated, which makes it a drying oil, well suited for making oil paints.

The smoke point, also referred to as the burning point, is the temperature at which an oil or fat begins to produce a continuous bluish smoke that becomes clearly visible, dependent upon specific and defined conditions. Smoke point values can vary greatly, depending on factors such as the volume of oil utilized, the size of the container, the presence of air currents, the type and source of light as well as the quality of the oil and its acidity content, otherwise known as free fatty acid (FFA) content. The more FFA an oil contains, the quicker it will break down and start smoking. The lower the value of FFA, the higher the smoke point. However, the FFA content typically represents less than 1% of the total oil and consequently renders smoke point a poor indicator of the capacity of a fat or oil to withstand heat.

<span class="mw-page-title-main">Sunflower oil</span> Oil pressed from the seed of Helianthus annuus

Sunflower oil is the non-volatile oil pressed from the seeds of the sunflower. Sunflower oil is commonly used in food as a frying oil, and in cosmetic formulations as an emollient.

Autoxidation refers to oxidations brought about by reactions with oxygen at normal temperatures, without the intervention of flame or electric spark. The term is usually used to describe the gradual degradation of organic compounds in air at ambient temperatures. Many common phenomena can be attributed to autoxidation, such as food going rancid, the 'drying' of varnishes and paints, and the perishing of rubber. It is also an important concept in both industrial chemistry and biology. Autoxidation is therefore a fairly broad term and can encompass examples of photooxygenation and catalytic oxidation.

<span class="mw-page-title-main">Triolein</span> Chemical compound

Triolein is a symmetrical triglyceride derived from glycerol and three units of the unsaturated fatty acid oleic acid. Most triglycerides are unsymmetrical, being derived from mixtures of fatty acids. Triolein represents 4–30% of olive oil.

The chronic endothelial injury hypothesis is one of two major mechanisms postulated to explain the underlying cause of atherosclerosis and coronary heart disease (CHD), the other being the lipid hypothesis. Although an ongoing debate involving connection between dietary lipids and CHD sometimes portrays the two hypotheses as being opposed, they are in no way mutually exclusive. Moreover, since the discovery of the role of LDL cholesterol (LDL-C) in the pathogenesis of atherosclerosis, the two hypotheses have become tightly linked by a number of molecular and cellular processes.

Warmed-over flavor is an unpleasant characteristic usually associated with meat which has been cooked and then refrigerated. The deterioration of meat flavor is most noticeable upon reheating. As cooking and subsequent refrigeration is the case with most convenience foods containing meat, it is a significant challenge to the processed food industry. The flavor is variously described as "rancid," "stale," and like "cardboard," and even compared to "damp dog hair." Warmed-over flavor is caused by the oxidative decomposition of lipids in the meat into chemicals which have an unpleasant taste or odor. This decomposition process begins after cooking or processing and is aided by the release of naturally occurring iron in the meat.

<span class="mw-page-title-main">Cooking oil</span> Oil consumed by humans, of vegetable or animal origin

Cooking oil is plant or animal liquid fat used in frying, baking, and other types of cooking. Oil allows higher cooking temperatures than water, making cooking faster and more flavorful, while likewise distributing heat, reducing burning and uneven cooking. It sometimes imparts its own flavor. Cooking oil is also used in food preparation and flavoring not involving heat, such as salad dressings and bread dips.

References

  1. 1 2 Lück, Erich; von Rymon Lipinski, Gert-Wolfhard (2000). "Foods, 3. Food Additives". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a11_561. ISBN   3527306730.
  2. Thomas, Alfred (2000). "Fats and Fatty Oils". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a10_173. ISBN   3527306730.
  3. Termes, Waldemar (1990). Naturwissenschaftliche Grundlagen der Lebensmittelzubereitung. Hamburg: Behr's Verlag. pp. 50–37. ISBN   978-3-925673-84-9.
  4. Klemchuk, Peter P. (2000). "Antioxidants". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a03_091. ISBN   3527306730.
  5. Freeman, I. P. (2000). "Margarines and Shortenings". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a16_145. ISBN   978-3-527-30673-2.
  6. 1 2 3 4 Robin Koon (4 August 2009). "Understanding rancidity of nutritional lipids". Natural Products Insider. Retrieved 7 April 2019.
  7. 1 2 3 4 Sergey, Bylikin (January 2014). Chemistry : course companion. Horner, Gary; Murphy, Brian; Tarcy, David (2014 ed.). Oxford. ISBN   978-0-19-839212-5. OCLC   862091138.
  8. Cameron-Smith, David; Albert, Benjamin B.; Cutfield, Wayne S. (23 November 2015). "Fishing for answers: is oxidation of fish oil supplements a problem?". Journal of Nutritional Science. 4: e36. doi:10.1017/jns.2015.26. ISSN   2048-6790. PMC   4681158 . PMID   26688722.
  9. EFSA Panel on Biological Hazards (2010). "Scientific Opinion on Fish Oil for Human Consumption. Food Hygiene, including Rancidity". EFSA Journal. 8 (10): 1874. doi: 10.2903/j.efsa.2010.1874 .
  10. Albert, Benjamin B.; Cameron-Smith, David; Hofman, Paul L.; Cutfield, Wayne S. (2013). "Oxidation of Marine Omega-3 Supplements and Human Health". BioMed Research International. 2013: 464921. doi: 10.1155/2013/464921 . PMC   3657456 . PMID   23738326.
  11. Kanner, Joseph (2007). "Dietary advanced lipid oxidation endproducts are risk factors to human health". Molecular Nutrition & Food Research. 51 (9): 1094–1101. doi:10.1002/mnfr.200600303. PMID   17854006.
  12. Falade, A. O.; Oboh, G.; Okoh, A. I. (2017). "Potential health lmplications of the consumption of thermally-oxidized cooking oils – a review". Polish Journal of Food and Nutrition Sciences (in Polish). 67 (2): 95–105. doi: 10.1515/pjfns-2016-0028 .
  13. Rahmawati S, Bundjali B (2009). "Kinetics of the oxidation of vitamin C". Prosiding Seminar Kimia Bersama UKM-ITB. VIII (9–11): 535–546.
  14. Allen, J.C.; Hamilton, R.J. (1994). Rancidity in Foods. Springer-Verlag GmbH. p. 47. ISBN   978-0-8342-1287-9.
  15. 1 2 Miraliakbari, H. (2007). Tree nut oils: chemical characteristics, oxidation and antioxidants. Library and Archives Canada. p. 31. ISBN   978-0-494-19381-5.[ permanent dead link ]

Further reading