Advance Food Chemistry

(FST-500)

Assignment Topic:

Rancidity and its types

Submitted To:

Mam Hina Saleem

Submitted By:

Umair Ahmad

2019-M.Phill-F.S-108

M.Phil. Food Science and Technology

UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE

Introduction to Rancidity
When food containing fat and oil come in contact with surrounding oxygen and these auto-oxidation leads
to bad smell and change in taste, the whole process is said to be rancidity. Most any food can technically
become rancid. The term particularly applies to oils. Oils can be particularly susceptible to rancidity
because their chemistry which makes them susceptible to oxygen damage.

Oxidation of fats is caused by a biochemical reaction between fats and oxygen. In this process the long-
chain fatty acids are degraded and short-chain compounds are formed. One of the reaction products is
butyric acid, which causes the typical rancid taste. Rancidification is the decomposition of fats, oils and
other lipids by hydrolysis or oxidation, or both. Hydrolysis will split fatty acid chains away from the glycerol
backbone in glycerides.

These free fatty acids can then undergo further auto-oxidation. Oxidation primarily occurs with
unsaturated fats by a free radical- mediated process. These chemical processes can generate highly
reactive molecules in rancid foods and oils, which are responsible for producing unpleasant and noxious
odors and flavors. These chemical processes may also destroy nutrients in food. Under some conditions
rancidity leads to the destruction of vitamins in food.

Types of Rancidity:
There are two types of rancidity:

1. Oxidative Rancidity:
The specific types of rancidity involving oxygen damage to foods are called “oxidative rancidity.” During
the process, oxygen molecules interact with the structure of the oil and damage its natural structure in a
way that can change its odor, its taste, and its safety for consumption, i.e. fat is oxidized and decomposes
into compounds with shorter carbon chains such as fatty acids, aldehydes, and ketones all of which are
volatile and contribute to the unpleasant odor of rancid fats. Oxidative rancidity leads to the formation of
both unpalatable and toxic compounds.

Three distinct classes of substance occurring in oxidized fat have been shown to be toxic:

(i) Peroxidised fatty acids (peroxidised fatty acids destroy both vitamin A and E in foods)

(ii) Polymeric material (under normal food processing conditions these appear in small enough
quantities to be insignificant).

(iii) Oxidized sterols (thought to be involved in the causation of atherosclerotic disease).

Oxidative rancidity, one of the major causes of quality deterioration in foods, is caused by the oxidative
deterioration of lipids by atmospheric oxygen. Lipids oxidize through a complex series of reactions giving
rise to a myriad of non-volatile and volatile compounds that are responsible for off-flavours even at
concentrations in the parts-per-billion range. . (J. Velasco, … G. Márquez-Ruiz, in Chemical Deterioration
and Physical Instability of Food and Beverages, 2010).

Lipid oxidation in foods

Oxidative rancidity, a major cause of food deterioration, leads to food quality degradation and product
rejection due to the formation of undesirable aroma and off-flavors, color fading, browning, or color
degradation. Another serious impact of oxidative rancidity is that it can pose health risks due to the
formation of oxidation products that are suspected to be toxic. These oxidation products can cause
oxidation damage in living organisms as well as mutagenesis and carcinogenesis (e.g., lipid peroxide,
malondialdehyde (MDA)). Lipid oxidation also reduces the nutritional value of the food.

Figure 11.2 illustrates that the oxidation of lipids proceeds through three different stages: initiation,
propagation, and termination. During the initiation stage, the lipid (RH) through action of catalysts, breaks
down to produce free radicals that react with other food components. More free radicals are formed
during the propagation phase, resulting in rapid degradation of food. These free radicals react with oxygen
to produce more free radicals to quickly oxidize lipid molecules. This rapid degradation of oils or lipids is
because of the ease of oxidation of free radicals to yield hydroperoxides and their breakdown compounds.
Hydroperoxides and secondary oxidation products (aldehydes, ketones, acids, etc.) are responsible for the
rancid aroma and off-notes in foods. The different factors affecting lipid oxidation are the presence of
oxygen and transition metal ions, moisture, heat, and light. To prevent, minimize, or slow down the rate
of lipid oxidation, oxygen and metal catalysts must be removed or sequestered to render them unreactive.
The food prone to oxidation must be stored at low temperatures and/or shielded from light. (Milda E.
Embuscado, in Handbook of Antioxidants for Food Preservation, 2015).
2. Hydrolytic Rancidity:
Fats are enzymatically hydrolyzed, the release of free fatty acids from glycerides, cause some rancid odor.
This process is called hydrolytic rancidity. Hydrolysis will split fatty acid chains away from the glycerol
backbone in glycerides. These free fatty acids can then undergo further auto-oxidation leads to oxidative
rancidity. (Mark Gibson, ... Pat Newsham, in Food Science and the Culinary Arts, 2018)

Hydrolytic rancidity develops when triglycerides in particular are hydrolyzed and free fatty acids are
released; the process sometimes requires a catalyst. It is also the reason short-chain fatty acids, such as
butter fats, are odorous. Rancidity in foods ranges from barely noticeable, indicating a loss of freshness—
to very severe complete with strong aromas (Sebranek and Neel, 2008). Small or slight degrees of
rancidity are much more common in foods, oils and fats than severe rancidity is, yet it is the slight rancidity
that is of much more concern. This is especially observable in meat—even though it is kept refrigerated
or even frozen, the polyunsaturated fat within meat will continue to oxidize and slowly become rancid.
This process starts from the moment of slaughter and continues under cool temperatures although it must
be said that, at refrigerated or even frozen temperatures, rancidity happens at a slower rate (see Section
9.2), (Gunstone, 2001).

Rancidity and shelf life

Rancidity is one of the most important quality parameters for nuts. The term rancidity refers to ‘off’
odours and flavours resulting from lipid oxidation or lipolysis (breakdown of oils chemically or by lipase
into constituent fatty acids) (Pike, 1998). Conditions prior to harvest, during drying and during storage can
induce such chemical changes in macadamia kernels (Mason et al., 1995; Kaijser et al., 2000). The high
oil content of macadamia makes them prone to rancidity, while the sugar and protein content makes
excessive browning of roasted kernels possible if drying and roasting methods are not appropriate
(Prichavudhi and Yamamoto, 1965; De la Cruz et al., 1966). Subjective detection of rancid off-flavours by
tasting is still used to determine nut quality (Fourie and Basson, 1989), and remains the ultimate measure
of rancidity. There are two important pathways leading to rancidity: oxidation and hydrolysis (Robards et
al., 1988).

What can be added to the recipe to prevent fat rancidity?

Rancidity can occur in many products or ingredients during storage. It affects taste and odor, and can have
an impact on nutritive value. Two major rancidification pathways are recognized in extruded products.
Enzymatic rancidity is catalyzed by the presence of certain enzymes (examples are peroxidases and
lipases). The heat treatment experienced during extrusion is usually sufficient to destroy these enzymes.
However, if ingredients containing these enzymes are stored in their raw or untreated state, they will
become rancid before extrusion and will contain rancidity by-products that will impact flavor and odor.
For many ingredients (especially whole seeds), it is important to heat treat the ingredient as quickly as
possible after the seed coat is broken as this action triggers the enzymes responsible for rancidity.
Extrusion is very effective in controlling enzymatic rancidity if the raw materials are processed
immediately after milling.

The second pathway responsible for rancidity is oxidation. Oxidative rancidity is a chemical reaction
catalyzed by heat, ultraviolet light, heavy metals and oxygen. Many of these factors are obviously present
during the extrusion process. Oxidative rancidity is best controlled by the addition of antioxidants and
‘oxygen scavengers’. Most antioxidants are added before extrusion even though there may be minor
destruction during the process depending on the time and temperatures employed. There is a growing
trend to utilize natural antioxidants such as mixed tocopherols, rosemary, and other unique ingredients.
Often an ‘antioxidant package’ containing antioxidants and oxygen scavengers are used in synergy.
Oxygen scavengers such as ascorbic and citric acid appear to increase the effectiveness of antioxidants.
(Mian N. Riaz, Galen J. Rokey, in Extrusion Problems Solved, 2012)

Factors influencing oxidative stability

It is important to be aware of the factors that influence oxidative stability to ensure the

longest shelf-life possible for oil.

1) Fatty acid composition

 The fatty acid composition gives important information regarding the stability of oil. Unsaturated fatty
acids such as oleic- (CI8: 1), linoleic- (CI8:2) and linolenic acid (18:3) are easier targets for oxidation (Frank,
Geil and Freaso, 1982; Lomanno and Nawar, 1982). Linoleic acid has been studied extensively and it has
been found to be 10-100 times more susceptible to oxidation than monoene or saturated fatty acids
(Selke, Rohwedder and Dutton, 1980). The degree of unsaturation affects the oil stability as seen in the
comparison of stored regular and low-linolenic canola oils (12.5 % and 2.5 % of 18:3 respectively)
(Malcolmson, Vaisey-Genser, Przybylski, Ryland, Eskin and Armstrong, 1996). The lowlinolenic canola oil
had a longer shelf-life than the regular canola oil. Oxidative stability of maize oils with increased total
saturated fatty acid composition was evaluated (Shen, Duvick, White and Pollak, 1999). Maize lines with
elevated saturated fatty acids (15-17 % compared to 13 % in traditional maize oil) have been developed.
The maize oils with elevated saturated fatty acids were more stable than the traditional maize oil. Similar
results were found when oxidative stability of soybean oils with increased palmitate (C 16:0) and reduced
linolenate 7 (C18:3) content were evaluated (Shen, Fehr, Johnson and White, 1997). Increasing 16:0
and/or reducing 18:3 lead to more oxidative stable soybean oils as measured by PV. The positioning of
the unsaturated fatty acids on the triglyceride also plays a role in lipid oxidative stability. The increased
concentration of unsaturated linoleic acid on the carbon-2 position of the triglyceride instead of the
carbon-1 and carbon-3 positions has a detrimental effect on the oxidative stability of oils (Neff and EI-
Agaimy, 1996).

2) Antioxidants
Antioxidants retard the onset of oxidation, thereby extending the shelf-life of fats and oils and food
products, but cannot prevent it. It is the same for synthetic antioxidants such as BHA, BHT, TBHQ and
natural antioxidants such as tocopherols. Antioxidants can act either as primary chain breaking
antioxidants, or as secondary preventative antioxidants (Gordon, 1990).

The best method used to prevent food item from rancidity is the addition of antioxidants. Antioxidants
are added to fat-containing foods in order to retard the development of rancidity due to oxidation.

There are five types of antioxidants:

(1) Natural antioxidants.

(2) Synthetic antioxidants.

(3) Semi-synthetic antioxidants – gallic acid, propylgallate.

(4) Metal chelators – citric acid, phosphoric acid.

(5) Oxygen scavengers – ascorbic acid.

Natural antioxidants include flavonoids, polyphenols, ascorbic acid (vitamin C) and tocopherols (vitamin
E). Synthetic antioxidants include butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT),
propyl-3, 4, 5-trihydroxybenzoate (also known as propyl gallate) and ethoxyquin. Natural antioxidants
tend to be short-lived, but synthetic antioxidants give longer shelf life and better action.

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 watery parts of foods. A combination of
water-soluble and fat- soluble antioxidants is ideal, usually in the ratio of fat to water.
 3) Oxygen availability
The availability of oxygen is an important rate-determining factor as oxidation cannot take place without
oxygen (Berger, 1994). The rate of lipid oxidation measured by hexanal formation increased with
increasing concentrations of oxygen (1.2 %, 4.5 %,10.0 %,15.4 %) in a closed system (Koelsch, Downes
and Labuza, 1991). It is also well known that samples with a high surface area in contact with air oxidise
more rapidly (Gordon, Mursi and Rossell, 1994). This is clearly illustrated in a study with extracted crude
sunflower oil stored under three different storage conditions; in a capped flask, open flask and capped
flask under nitrogen atmosphere (Crapiste, Brevedan and Carelli, 1999). There was little difference in the
oxidation rate between the open and capped flask, which indicates that oxidation rate 11 depends on the
relation between oil surface area exposed to air and sample volume, whereas the capped flask under
nitrogen showed very little oxidative activity. Oxygen can be replaced by utilising a protective gas practice
such as nitrogen blanketing that will protect oil in storage tanks, during bulk transport and when packaged
against oxidation (O'Brien, 1998).

4) Temperature
Temperature also has a big influence on shelf-life, as the rate of reaction of oxygen with fats roughly
doubles for every lOoC increase in temperature (Rossell, 1992; Berger, 1994). In a storage trial done by
Crapiste et al (1999) the PV and A V increased faster with higher storage temperatures of 30°C, 47°C and
67°C. The difference between storage at 50°C and 60°C of shortening blends is also clear as the PV at 60°C
increases much more rapidly than at 50°C (Berger, 1994). Sensory tests confirmed the results.

5) Light
Light has a promoting ifluence on oil oxidation through photo-oxidation (Hamilton, 1994). The mechanism
of oxidation by photosensitisation proceeds differently than normal free radical oxidation, as discussed
previously. Photosensitised oxidation involves activation of substrate, which subsequently reacts with
unsaturated fatty acids, for example sensitisedriboflavin that reacts with fatty acid double bonds (Frankel,
1985). As discussed by Frankel (1985), another mechanism of photos en siti sed oxidation is by singlet
oxygen. Selecting the most suitable type of packaging material for oils makes quite a difference in the
shelf-life. The rate of oxidation is slower in brown than in clear glass bottles (Tekin, Kaya and Oner, 1995).
Refined sunflower oil remains stable for two years when stored in highdensity polyethylene bottles and
sealed tins without developing pronounced off-flavours and odours. (Semwal and Arya, 1992). The
influence of different packaging materials on lipid oxidation in potato crisps exposed to fluorescent light
was examined and it was found that visible light with wavelengths longer than 380 nm could lead to
oxidation of the lipids in the crisps (Lennersten and Lingnert, 1998).