Running Head: RANCIDITY 1

Rancidity: Types, Mechanism, Examples, and Prevention

Rachel A. Alamilla

Department of Math and Science, Saint John’s College Junior College

BIO 140-1: Biochemistry

Ms. Lucero Cob

February 17, 2021

Abstract

Rancidification has been an issue for multiple food companies all over the world due to

the susceptibility of lipids, especially unsaturated fats and oils, to oxidize into toxic products that

degrade and produce odours; these products can cause consumers to experience vitamin

deficiencies as well as the loss of “good” fats. However, as the years passed and science became

more developed, multiple studies have been conducted in order to obtain a better understanding

of rancidity, its mechanisms and its effects which allow industries to prevent their products from

going rancid as their sales may greatly decrease because of it. Rancidity is both a health and

economic issue and due to extensive research, scientists have been able to describe how it

happens and how to avoid it. Additionally, this research discusses rancidity as well as its types,

mechanisms, preventions and the factors that influence these reactions.

Rancidity: Types, Mechanism, Examples, and Prevention

Although rancidity mainly refers to the oxidation of fats and oils, the term is used

collectively when referring to both its oxidation and hydrolysis as they both affect the shelf life

of foods containing these components as well as their nutritive value. Moreover, unsaturated fats,

both polyunsaturated and monounsaturated, tend to be more susceptible to rancidification (G.

Talbot, 2011) due to the fact that they contain higher amounts of methylene groups adjacent to a

double bond as opposed to saturated fats since they do not have double bonds; this then allows

the oxidation rate of the unsaturated fats and oils to be considerably high.

Rancidification has a high level of concern, especially amongst industries that

manufacture products containing fats and oils as their shelf life is greatly limited as an effect of

this occurrence. Multiple factors play a role in how the shelf life is affected due to rancidity.

According to Talbot (2011), the chemical composition, the storage conditions and the amount of

pro-oxidants and antioxidants present in the oil are all important factors that affect the shelf life

of a product. The chemical composition refers to the rate of unsaturation of the fat since the

increase of unsaturation causes an increase in the oxidation rate in terms of rancidity.

Additionally, whether or not the unsaturation is in cis or trans configuration can also affect the

oxidation rate. For instance, oleic and cis acids have a higher rate of oxidation than elaidic acid

or trans isomers (Sonnatag 1979). The second factor, which are the storage conditions, can also

greatly affect the shelf life of these products. For example, the presence of oxygen in the

atmosphere, an increase in temperature, agitation when stirring and the presence of light can all

affect the shelf life of fats and oils since their oxidation rates increase. Lastly, minor components

called pro-oxidants and antioxidants in fats and oils also impact their shelf life; pro-oxidants

catalyse oxidation while antioxidants inhibit it. This is why copper, manganese and iron are
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avoided within the inside of storage tanks where these products are placed since the metal ions

can catalyse an oxidation reaction. All these factors trigger an increase in oxidation which in turn

allows the food to go “rancid” and causes food spoilage since undesirable flavors and odours are

developed.

Not only does rancidification negatively affect the shelf life of fats and oils, but it also

decreases its nutritional value. Whenever unsaturated fats and oils oxidize, they produce toxic

substances that destroy vitamins like linoleic acid, tocopherol and vitamins A, D and K which

are all fat-soluble. In addition, multiple foods composed of them decrease in its content when

exposed to air— or when oxidized. However, this outcome is not exclusive to fat-soluble

vitamins since biotin, which is a water soluble vitamin is also affected by oxidation as well as

other dietary essentials (Quakenbush, 1945). Since the potency of the vitamins in these products

are being affected by the rancidification of fats and oils, it can cause vitamin deficiencies which

trigger dermatitis, anaemia, reproductive failure and death in animals (Quakenbush, 1945).

Additionally, the ingestion of rancid fats can also cause diseases such as arteriosclerosis, heart

disease and carcinogenesis (Koon, 2009).

The rancidification of fats and oils can take place in two different forms: oxidative, which

is when unsaturated fats are exposed to oxygen, or hydrolytic, which is when triglycerides are

hydrolyzed into fatty acids and glycerol using enzymes. Although both processes result in

rancidity, the products they break into are completely different. Oxidative rancidity can be split

into three sub groups: autoxidation, photo-oxidation and enzyme catalyzed oxidation. (Talbot,

2011).

Autoxidation is also referred to as self-catalysed in which pro-oxidants, like metals,

speed up the oxidation process while antioxidants inhibit it. In addition, this process is composed
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of four parts: initiation, propagation I, propagation II and termination; this produces

hydroperoxides that later break into aldehydes that produce the bad odour associated with

rancidity. In the initiation phase, a hydrogen atom which is usually from a methylene group

adjacent to a double bond in a fatty acid of a triglyceride is broken off as a free radical; this

phase is often referred to as the induction period as it takes a long time. Due to the triglyceride

free radical’s reactive nature, they instantly react with other compounds. In propagation I, the

triglyceride free radical reacts with oxygen to produce a hydroperoxy free radical. In propagation

II, this then reacts with another hydrogen atom in the triglyceride to form a hydroperoxide which

is mainly stable; however, this results in an additional triglyceride free radical which reacts with

another oxygen radical and produces more hydroperoxide while the reaction propagates. The

final part of autoxidation is when the hydroperoxides produced breaks down into aldehydes

which then cause bad odours and the rancidification of food.

Unlike autoxidation, photo-oxidation does not have an induction period and takes place

in the presence of light and a photosensitizer which can be metals like copper or molecules like

chlorophyll; many pigments in food categorize as a photosensitizers. In addition, there are two

types of photo-oxidation; in type one, the sensitizer is turned into its excited triplet state with the

assistance of light. This then produces hydroperoxide, just like in autoxidation, as the triplet state

sensitizer reacts with a lipid substrate either through electron transfer or by a hydrogen atom and

then a triplet oxygen in order to form radicals. However, photo-oxidation differs from

autoxidation since it cannot be inhibited by antioxidants. In the second type of photo-oxidation,

the triplet state sensitizer reacts with a triplet oxygen via energy transfer and produces a single

oxygen that is not a radical that is highly reactive and reacts with unsaturated lipid. Just like type

one, type two cannot be inhibited by an antioxidant (Frankel, 2012).

Although enzyme-catalyzed oxidation is not much of an issue in a commercial aspect,

many plants and animals contain an enzyme within their tissues called lipoxygenase which

serves as a catalyst for oxidation in seeds. This allows hydroperoxides to form inside the seed

before extraction and if the oil is not properly refined when they get manufactured, their

hydroperoxides that later break into aldehydes come along when the oil is packaged. Oftentimes,

oil marketed as “virgin” oil may contain these rancid qualities such as virgin rapeseed oil (Talbot,

2011).

The second type of rancidity is called hydrolytic rancidity and it requires enzymes. There

are two types; the first type involves the production of ketoacids from a reaction between a

triglyceride and water along with heat. Since keto acids are unstable, they lose carbon dioxide

and form methyl ketones as well as hydroxy fatty acids. These then aid in the formation of alpha

lactones and beta lactones. In addition, the chain length of the methyl ketone determines the

flavour and odour of the food. The second type requires an active lipase that originates from

bacteria and water to break down triglycerides into glycerol and the free fatty acids (Koon,

2009). These fatty acids then undergo autoxidation in order to further deteriorate; the triglyceride

is firstly converted to a diglyceride, then a monoglyceride and lastly, glycerol. In addition, this

kind of rancidity is more of a concern in animal fats rather than vegetable fats. Enzymes like

Lipoxygenase are mainly present in oils; however, lipase is only present when they have been

contaminated by microbes that produce it. Since enzymes are made of protein, they greatly

depend on the pH and temperature in order to properly function. Just like in the first type, the

second type also depends on the chain length of the fatty acid for the type of flavouring and

odour produced.
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Although these types of rancidification processes occur naturally, there are many ways to

prevent them from occurring in order to avoid consumers from experiencing unhealthy

symptoms. However, each type of rancidification has different methods of prevention since some

methods may not work for all the various types. For instance, antioxidants are great preventive

measures of rancidity and there are three different types which are: Oxygen Scavengers, Free

Radical Scavengers and Chelating Agents. Oxygen scavengers react with oxygen; an example of

this would be ascorbic acid. Free radical scavengers react with free radicals to prevent them from

oxidizing other fatty acids; an example of these are extracts from spices and herbs. Lastly,

chelating agents, like citric acid, form chelate complexes with trace metals present in products

containing fat to prevent them from acting as catalysts for these reactions. Many industries have

utilized these methods in order to prevent autoxidation from taking place in their products; for

instance, BHT (butylated hydroxytoluene) is a common antioxidant used and it works by

preventing autocatalytic reactions through converting the peroxy radicals to hydroperoxides.

Although antioxidants are fairly effective, rancidification through photo-oxidation cannot be

avoided with antioxidants (Talbot, 2011). Another method of preventing oxidation is by ensuring

no oxygen is present within the product either by using air-tight packaging or by using nitrogen;

for example, various kinds of chips are half-filled with nitrogen in order to prevent the oxygen

from forming hydroperoxides in rancidification. As mentioned earlier, agitation can also have an

effect on oxidation; therefore, it is recommended that agitation when storing oils is kept as

minimal as possible. Additionally, photo-oxidation is mainly avoided for virgin bottled oils, since

it is not much of a problem in bulk oils and boxed fats. This is done by keeping the oils in dark

areas in order to prevent light from providing energy for the reaction. High temperatures are also

known for increasing oxidation rates, so, bulk oils are recommended to be kept in temperatures
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that are not past 10°C of their melting point in order to prevent crystallization when storing; in

addition, storing fat and oil-containing foods in the fridge also helps in preventing

rancidification. According to Ramezanzadeh (1998), products that contain hydrolytic enzymes

can be stabilized with microwave heat since it destroys bacteria that possesses these enzymes,

which in turn, reduce free fatty acids. Additionally, low temperatures in a fridge also prevent the

growth of bacteria. Since unsaturated fats are mainly affected by rancidity, many companies use

complete hydrogenation in order to convert the unsaturated fats to saturated fats since they are

less susceptible to rancidity, which in turn, allows oils to be used in high temperatures. However,

this method can result in the production of trans fat due to partial hydrogenation that causes

cardiovascular diseases since HDL cholesterol is being lowered while LDL cholesterol and

triglyceride levels are being increased.

Conclusion

Rancidification consists of two main types, hydrolytic and oxidative and it mainly affects

unsaturated fats and oils. Oxidative rancidity is caused by the exposure of oxygen and is made up

of three types: autoxidation, photo-oxidation and enzyme-catalyzed oxidation while hydrolytic

rancidity is caused by hydrolytic enzymes in microbes. These reactions produce toxic products

such as hydroperoxides which later break into aldehydes and ketones that can cause bad odour,

loss in vitamin content and diseases due to vitamin deficiencies. Additionally, many factors such

as light, high temperatures, agitation, pro-oxidants, antioxidants and bacteria can all influence the

oxidation of oils. However, it can be prevented by storing oils in dark areas, using nitrogen,

air-tight packaging, using antioxidants, refrigerating as well as microwaving. With the

knowledge acquired through research, many industries now package their foods in various ways

that prevent rancidity in order to improve the health of consumers. For example, some products

like peppermints are stored in vacuum packaging and products such as chips are packaged with

nitrogen to avoid oxidation. It is important to use these preventative measures as it can decrease

the risk of individuals attaining deficiency diseases like anaemia and dermatitis since rancid

foods destroy vitamin content.

References

Frankel, E. N. (2012). Photooxidation of unsaturated fats. Lipid Oxidation, 51–66.

https://doi.org/10.1533/9780857097927.51

Koon, R. (2009, August 4). ‘Understanding Rancidity of Nutritional Lipids,’ Natural Products

Insider, Retrieved from https://www.naturalproductsinsider.com/regulatory/

understanding-rancidity-nutritional-lipids

Quackenbush, F.W. Oil Soap (1945) 22: 336. https://doi.org/10.1007/BF02641182

Ramezanzadeh, F. M. (1998) “Prevention of Hydrolytic and Oxidative Rancidity and

Nutrient Losses in Rice Bran During Storage.” LSU Historical Dissertations and Theses.

6860. https://digitalcommons.lsu.edu/gradschool_disstheses/6860

Sonntag (1979). `Reactions of fats and fatty acids'. Bailey's Industrial Oil and Fat Products. Ed.

Swern D. Vol. 1, 4th edn, 138. John Wiley & Sons, New York

Talbot, G. (2011). The stability and shelf life of fats and oils. Food and Beverage Stability and

Shelf Life, 683–715. https://doi.org/10.1533/9780857092540.3.683