Comprehensive Mechanisms

Reviews and Factors

in for Edible Oil
Food Science
and Oxidation
Food Safety Eunok Choe and David B. Min

ABSTRACT: Edible oil is oxidized during processing and storage via autoxidation and photosensitized oxidation, in
which triplet oxygen (3 O 2 ) and singlet oxygen (1 O 2 ) react with the oil, respectively. Autoxidation of oils requires radical
forms of acylglycerols, whereas photosensitized oxidation does not require lipid radicals since 1 O 2 reacts directly with
double bonds. Lipid hydroperoxides formed by 3 O 2 are conjugated dienes, whereas 1 O 2 produces both conjugated
and nonconjugated dienes. The hydroperoxides are decomposed to produce off-flavor compounds and the oil quality
decreases. Autoxidation of oil is accelerated by the presence of free fatty acids, mono- and diacylglycerols, metals such
as iron, and thermally oxidized compounds. Chlorophylls and phenolic compounds decrease the autoxidation of oil
in the dark, and carotenoids, tocopherols, and phospholipids demonstrate both antioxidant and prooxidant activity
depending on the oil system. In photosensitized oxidation chlorophyll acts as a photosensitizer for the formation
of 1 O 2 ; however, carotenoids and tocopherols decrease the oxidation through 1 O 2 quenching. Temperature, light,
oxygen concentration, oil processing, and fatty acid composition also affect the oxidative stability of edible oil.

Introduction ing orbitals has a permanent magnetic moment with 3 closely

Oxidative stability of oils is the resistance to oxidation during
processing and storage (Guillen and Cabo 2002). Resistance to
oxidation can be expressed as the period of time necessary to at-
tain the critical point of oxidation, whether it is a sensorial change
or a sudden acceleration of the oxidative process (Silva and others
2001). Oxidative stability is an important indicator to determine
oil quality and shelf life (Hamilton 1994) because low-molecular-
weight off-flavor compounds are produced during oxidation. The
off-flavor compounds make oil less acceptable or unacceptable
to consumers or for industrial use as a food ingredient. Oxidation
of oil also destroys essential fatty acids and produces toxic com-
pounds and oxidized polymers. Oxidation of oil is very important
in terms of palatability, nutritional quality, and toxicity of edible
oils.
Different chemical mechanisms, autoxidation and photosensi-
tized oxidation, are responsible for the oxidation of edible oils
during processing and storage depending upon the types of oxy-
gen. Two types of oxygen can react with edible oils. One is called
atmospheric triplet oxygen, 3 O 2 , and the other is singlet oxy-
gen,1 O 2 . 3 O 2 reacts with lipid radicals and causes autoxidation,
which is a free radical chain reaction. The chemical properties
of 3 O 2 to react with lipid radicals can be easily explained by the
molecular orbital of the oxygen as shown in Figure 1. The 3 O 2 in
the ground state with 2 unpaired electrons in the 2pπ antibond-
MS 20060292 Submitted 5/23/06, Accepted 7/13/06. Author Choe is with Dept.
of Food and Nutrition, The Inha Univ., Incheon, Korea. Author Min is with Dept.
of Food Science and Technology, The Ohio State Univ., Columbus, OH. Direct
inquiries to author Min (E-mail: min.2@osu.edu).
grouped energy states under a magnetic field and is called triplet
oxygen. 3 O 2 is a radical with 2 unpaired orbitals in the molecule.
It reacts with radical food compounds in normal reaction condi-
tions according to spin conservation. Photosensitized oxidation
of edible oils occurs in the presence of light, sensitizers, and at-
mospheric oxygen, in which 1 O 2 is produced.
The electron configuration in the 2pπ antibonding orbitals of
1
O 2 is shown in Figure 2. Since 1 orbital of the 2pπ antibond-
ing orbitals of1 O 2 has paired electrons and the other is com-
pletely empty, 1 O 2 has 1 energy level under a magnetic field
and is electrophilic. The nonradical electrophilic singlet oxygen
readily reacts with compounds with high electron densities, such
as the double bonds of unsaturated fatty acids. The 1 O 2 has an
energy of 93.6 kJ above the ground state of 3 O 2 (Korycka-Dahl
and Richardson 1978; Girotti 1998). High-energy 1 O 2 in solu-
tion is deactivated by transferring its energy to the solvent, and
its lifetime depends on the solvent. The lifetime of singlet oxygen
is about 2, 17, and 700 μs in water, hexane, and carbon tetra-
chloride, respectively (Merkel and Kearns 1972; Long and Kearns
1975).
Oxidation of edible oils is influenced by an energy input such
as light or heat, composition of fatty acids, types of oxygen, and
minor compounds such as metals, pigments, phospholipids, free
fatty acids, mono- and diacylglycerols, thermally oxidized com-
pounds, and antioxidants. Many efforts have been made to im-
prove the oxidative stabilities of oils by systematic studies on the
effects of these factors.
This article reviews the reaction mechanism, kinetics, and
oxidation products of autoxidation and photosensitized ox-
idation. Factors affecting the oxidation of edible oils, free
fatty acids, mono- and diacylglycerols, metals, phospholipids,


C 2006 Institute of Food Technologists Vol. 5, 2006—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY 169
CRFSFS: Comprehensive Reviews in Food Science and Food Safety

Molecular Figure 1 --- Molecular orbital of triplet oxygen, 3 O2

σ*
Atomic Atomic
π* π*

π π
2px 2py 2pz 2pz 2py 2px
σ

Ener gy σ*

2S σ 2S

σ*

1S 1S
σ

Table 1 --- Hydroperoxides of fatty acids by autoxidationa

Figure 2 --- Electronic configuration of 2pπ antibonding
orbital of singlet oxygen, 1 O2 Fatty acid Hydroperoxides at Relative amount (%)

Oleic acid C8 26∼28

C9 22∼25
C10 22∼24
C11 26∼28
pigments, thermally oxidized compounds, and antioxidants, are
also discussed. Linoleic acid C9 48∼53
C13 48∼53
Mechanisms of Autoxidation in Edible Oil Linolenic acid C9 28∼35
C12 8∼13
Autoxidation of oils, free radical chain reaction, includes initi- C13 10∼13
ation, propagation, and termination steps: C16 28–35
a Frankel (1985).
Initiation RH −→ R· + H·
Propagation R· + 3 O2 −→ ROO·
ROO· + RH −→ ROOH + R· 50 kcal/ mol. The energy required to remove hydrogen in C8 and
Termination ROO· + R· −→ ROOR C14 of linoleic acid is 75 kcal/ mol and the homolytic dissociation
R· + R· −→ RR energy between hydrogen and C17 or C18 is about 100 kcal/mol
(R : lipid alkyl) (Min and Boff 2002). The double bond adjacent to the carbon rad-
ical in linoleic acid shifts to the more stable next carbon and from
Autoxidation of oils requires fatty acids or acylglycerols to be the cis to the trans form. Autoxidation of linoleic and linolenic
in radical forms. Fatty acids or acylglycerols are in nonradical acids produces only conjugated products. The hydroperoxide po-
singlet states, and the reaction of fatty acids with radical state sitional isomers formed in the autoxidation of oleic, linoleic, and
atmospheric 3 O 2 is thermodynamically unfavorable due to elec- linolenic acids are shown in Table 1.
tronic spin conservation (Min and Bradley 1992). The hydrogen The lipid alkyl radical reacts with 3 O 2 and forms lipid peroxy
atom in the fatty acids or acylglycerols in edible oil is removed radical, another reactive radical. Reaction between lipid alkyl
and lipid alkyl radicals are produced in the initiation step. Heat, radical and 3 O 2 occurs very quickly at normal oxygen pres-
metal catalysts, and ultraviolet and visible light can accelerate sure and, consequently, the concentration of lipid alkyl radical
free radical formation of fatty acids or acylglycerols. The energy is much lower than that of lipid peroxy radical (Aidos and oth-
required to remove hydrogen from fatty acids or acylglycerols ers 2002). The lipid peroxy radical abstracts hydrogen from other
is dependent on the hydrogen position in the molecules. The lipid molecules and reacts with the hydrogen to form hydroper-
hydrogen atom adjacent to the double bond, especially hydro- oxide and another lipid alkyl radical. These radicals catalyze the
gen attached to the carbon between the 2 double bonds, is re- oxidation reaction, and autoxidation is called the free radical
moved easily. Hydrogen at C11 of linoleic acid is removed at chain reaction. Figure 3 shows the hydroperoxide formation in
170 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 5, 2006
Mechanisms and factors for edible oil oxidation

13 12 10 9 13 12 10 9 Figure 3 --- Hydroperoxide

formation in the
autoxidation of linoleic
acid
CH3(CH2)4 (CH2)7COOH CH3(CH2)4 (CH2)7COOH

-H -H

13 12 10 9 13 12 10 9

CH3(CH2)4 (CH2)7COOH CH3(CH2)4 (CH2)7COOH

13 12 10 9 13 12 10 9

CH3(CH2)4 (CH2)7COOH CH3(CH2)4 (CH2)7COOH

+3O2, H +3O2, H

HOO OOH
13 12 10 9 13 12 10 9

CH3(CH2)4 (CH2)7COOH CH3(CH2)4 (CH2)7COOH

13-Hydroperoxide 9-Hydroperoxide

the autoxidation of linoleic acid. The rates for the formation of
lipid peroxy radical and hydroperoxide depend only on oxygen
availability and temperature (Velasco and others 2003). When
radicals react with each other, nonradical species are produced
and the reaction stops.
The primary oxidation products, lipid hydroperoxides, are rel-
atively stable at room temperature and in the absence of metals.
However, in the presence of metals or at high temperature they are
readily decomposed to alkoxy radicals and then form aldehydes,
ketones, acids, esters, alcohols, and short-chain hydrocarbons.
The most likely pathway of hydroperoxide decomposition is a
homolytic cleavage between oxygen and the oxygen bond, in
which alkoxy and hydroxy radicals are produced. The activation
energy to cleave the oxygen–oxygen bond is 46 kcal/mol lower
than that to cleave the oxygen–hydrogen bond (Hiatt and others
1968). The alkoxy radical then undergoes homolytic β-scission of
the carbon–carbon bond and produces oxo-compounds and sat-
urated or unsaturated alkyl radicals (Figure 4). After electron rear-
Vol. 5, 2006—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY
rangement, the addition of hydroxyl radical, or hydrogen transfer,
the ultimate secondary lipid oxidation products are mostly low-
molecular-weight aldehydes, ketones, alcohols, and short-chain
hydrocarbons, as shown in Table 2.
The time for secondary product formation from the primary
oxidation product, hydroperoxide, varies with different oils. Sec-
ondary oxidation products are formed immediately after hy-
droperoxide formation in olive and rapeseed oils. However, in
sunflower and safflower oils, secondary oxidation products are
formed when the concentration of hydroperoxides is appreciable
(Guillen and Cabo 2002).
Most decomposition products of hydroperoxides are responsi-
ble for the off-flavor in the oxidized edible oil. Aliphatic carbonyl
compounds have more influence on the oxidized oil flavor due
to their low threshold values. Threshold values for hydrocarbons,
alkanals, 2-alkenals, and trans, trans-2,4-alkadienals are 90 to
2150, 0.04 to1, 0.04 to 2.5, and 0.04 to 0.3 ppm, respectively
(Frankel 1985). Hexanal (23.5%) and 2-decenal (34.3%), and
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CRFSFS: Comprehensive Reviews in Food Science and Food Safety

R1 Figure 4 --- Mechanisms of hydroperoxide

decomposition to form secondary oxidation
R2 products

O2 H

R2 CH CH CH R1

OOH

-
OH

B A
R2 CH CH CH R1 A

O
R2 CH CH CHO + R1
B

- R 3H
OH
A1 A2 R3

R2 CH CH + OHC R1
R2 OH R 2H
-
OH

B1 R 3H

R3
R2 CH CH OH
B2

R2 CH CHO R2 CH CH 2
2

2-heptenal (29.5%) and trans-2-octenal (18.1%), were the major
volatile compounds detected by the solid-phase microextraction
method in soybean and corn oils (peroxide value of 5), respec-
tively (Steenson and others 2002). Pentane, hexanal, propenal,
and 2,4-decadienal were present in high amounts in canola oil
stored uncovered at 60 ◦ C (Vaisey-Genser and others 1999).
Frankel (1985) reported that trans, cis-2,4-decadienal was the
most significant compound in determining the oxidized flavor
of oil, followed by trans, trans-2,4-decadienal, trans, cis-2,4-
heptadienal, 1-octen-3-ol, butanal, and hexanal. Hexanal, pen-
tane, and 2,4-decadienal were suggested and used as indicators
to determine the extent of the oil oxidation (Warner and others
1978; Przybylski and Eskin 1995; Choe 1997; Heinonen and oth-
ers 1997). Trans-2-hexenal, and trans, cis, trans-2,4,7-decatrienal
and 1-octen-3-one, were reported to give grass-like and fish-like
flavor in oxidized soybean oil, respectively (Min and Bradley
1992). No single flavor compound is mainly responsible for the
oxidized flavor of vegetable oils.
Singlet Oxygen Formation and Mechanisms
of Photosensitized Oxidation of Edible Oil
Oil oxidation is accelerated by light, especially in the presence
of sensitizers such as chlorophylls. Sensitizers in singlet state ab-
sorb light energy very rapidly, in picoseconds, and become ex-
cited. Excited singlet sensitizers can return to their ground state
via emission of light, internal conversion, or intersystem crossing
(Figure 5). Fluorescence and heat are produced by emission of
light and internal conversion, respectively. Intersystem crossing
results in excited triplet state of sensitizers.
Excited triplet sensitizers may accept hydrogen or an electron
from the substrate and produce radicals (type I) as shown in
Figure 6. Excited triplet sensitizers react with 3 O 2 and produce su-
peroxide anion by electron transfer. Superoxide anion produces
hydrogen peroxide, one of the reactive oxygen species by spon-
taneous dismutation, and the reaction of hydrogen peroxide with
superoxides results in singlet oxygen formation by Haber–Weiss
reaction in the presence of transition metals such as iron or copper

172 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 5, 2006

Mechanisms and factors for edible oil oxidation

Table 2 --- Secondary oxidation products of fatty acid methyl ester by autoxidationa
Class Oleic acid Linoleic acid Linolenic acid

Aldehydes Octanalb Pentanal Propanal

Nonanal Hexanal Butanal
2-Decenal 2-Octenal 2-Butenal
Decanal 2-Nonenal 2-Pentenal
2,4-Decadienal 2-Hexenal
3,6-Nonadienal
Decatrienal
Carboxylic acid Methyl heptanoate Methyl heptanoate Methyl heptanoate
Methyl octanoate Methyl octanoate Methyl octanoate
Methyl 8-oxooctanoate Methyl 8-oxooctanoate Methyl nonanoate
Methyl 9-oxononanoate Methyl 9-oxononanoate Methyl 9-oxononanoate
Methyl 10-oxodecanoate Methyl 10-oxodecanoate Methyl 10-oxodecanoate
Methyl 10-oxo-8-decenoate
Methyl 11-oxo-9-undecenoate
Alcohol 1-Heptanol 1-Pentanol
1-Octene-3-ol
Hydrocarbons Heptane Pentane Ethane
Octane Pentane
a Frankel (1985).

Figure 5 --- Excitation and deactivation of sensitizer

(Sen; sensitizers, ISC; intersystem crossing)

(Kellogg and Fridovich 1975):
O− − +
2 · + O2 · + 2H −→ H2 O2 + O2
−
H2 O2 + O−
2 · −→ HO · + OH + O2
1
The excitation energy of triplet sensitizers can be trans-
ferred onto adjacent 3 O 2 to form 1 O 2 by triplet–triplet anni-
hilation, and the sensitizers return to their ground singlet state
(type II). Kochevar and Redmond (2000) reported that a sensi-
tizer molecule may generate 103 to 105 molecules of 1 O 2 before
becoming inactive.
The rate of the type I or II processes depends on the kinds of
sensitizers and substrates (Chen and others 2001), and concentra-
tions of substrates and oxygen (Foote 1976). Phenols or amines,
which are readily oxidized, or readily reducible quinones favor
the type I process. On the other hand, olefins, dienes, and aro-
matic compounds, which are not so readily oxidized or reduced,
more often favor type II. Photosensitized oxidation of edible oil
follows the singlet oxygen oxidation pathway. 1 O 2 was suggested
to be involved in the initiation of the oil oxidation (Rawls and Van
Santen 1970; Lee and Min 1988).
1
O 2 either reacts chemically with other molecules or transfers
its energy to them. When 1 O 2 reacts with unsaturated fatty acids,
Vol. 5, 2006—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY
mostly allyl hydroperoxides are formed by ene reaction (Gollnick
1978), as shown in Figure 7.
Electrophilic 1 O 2 can directly react with high-electron-density
double bonds without the formation of alkyl radical, and form
hydroperoxides at the double bonds. When hydroperoxide is
formed, double bond migration and trans fatty acid occur, pro-
ducing both conjugated and nonconjugated hydroperoxides, as
shown in Table 3. Production of nonconjugated hydroperoxides
is not observed in the autoxidation. Figure 8 shows the oxidation
pathway of linoleic acid by 1 O 2 .
Hydroperoxides formed by 1 O 2 oxidation are decomposed by
the same mechanisms for the hydroperoxides formed by 3 O 2
in autoxidation. 1 O 2 oxidation produces more 2-decenal and
octane, two of the decomposition products of hydroperoxides,
in oleate than autoxidation does (Frankel 1985). The contents
of octanal and 10-oxodecanoate in autoxidized oleate were
higher than those of 1 O 2 -oxidized oleate. 2-Heptenal and 2-
butenal were noticeable in 1 O 2 -oxidized linoleic and linolenic
acids, whereas they were negligible in autoxidized linoleic and
linolenic acids. Heptenal was formed only in 1 O 2 -oxidized soy-
bean oil in the presence of chlorophyll and light (Min and others
2003).
A beany flavor, which is a unique and undesirable flavor in
soybean oil with low peroxide value, has been a problem for the
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CRFSFS: Comprehensive Reviews in Food Science and Food Safety

3
Sen* Figure 6 --- Reaction of triplet sensitizers with
substrates

Type I Type II

+ RH + 3O2

R + Sen H ( or R+ + Sen- ) 1
O2
3
+ O2

+ 3 O2 + RH

ROOH O2 + Sen+ ROOH

CH3(CH2)6 CH3(CH2)6 (CH2)6COOH OOH Figure 7 --- Formation of

(CH2)6COOH
1
O2 (CH2)6COOH
allyl hydroperoxide of
CH3(CH2)6
O oleic acid by ene
reaction
H O

CH3(CH2)6 (CH2)6COOH
OOH
1
O2 CH3(CH2)6 (CH2)6COOH
O
O H

last 70 years and studied extensively both nationally and inter- Table 3 --- Hydroperoxides of fatty acids by singlet oxygen oxidation
nationally (Chang and others 1966; Smouse and Chang 1967).
Relative
2-Pentylfuran and pentenylfuran were reported to be responsible
Fatty acid Hydroperoxides at amount (%)a Type of acid
for the beany flavor (Chang and others 1966, 1983; Smouse and
Chang 1967; Ho and others 1978; Smagula and others 1979), and Oleic acid C9 48
1
O 2 was involved in their formation from linoleic and linolenic C10 52
acids present in soybean oil, as shown in Figure 9 and 10 (Min and
others 2003). Min and others (2003) strongly indicated that the Linoleic acid C9 32 Conjugated
reversion flavor of soybean oil can be decreased or eliminated by C10 17 Nonconjugated
removing chlorophylls from the oil during processing. The soy- C12 17 Nonconjugated
bean oil industry currently removes effectively chlorophylls from C13 34 Conjugated
soybean oil using bleaching materials during the refining process,
and the beany flavor is no longer a serious problem in soybean Linolenic acid C9 23 Conjugated
oil. C10 13 Nonconjugated
C12 12 Conjugated
C13 14 Conjugated
Factors Affecting the Oxidation of Edible Oil C15 13 Nonconjugated
The oxidation of oil is influenced by the fatty acid compo- C16 25 Conjugated
sition of the oil, oil processing, energy of heat or light, the a Frankel (1985).

174 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 5, 2006

Mechanisms and factors for edible oil oxidation
1
O2
O (CH2)7COOH
CH3(CH2)4 (CH2)7COOH CH3(CH2)4
H (CH2)7COOH
O
1 OOH
O2
O
CH3(CH2)4
O H
1 OOH
O2
O
CH3(CH2)4
H O
OOH
1 OOH
O2
O
CH3(CH2)4
O H
concentration and type of oxygen, and free fatty acids, mono- and
diacylglycerols, transition metals, peroxides, thermally oxidized
compounds, pigments, and antioxidants. These factors interac-
tively affect the oxidation of oil and it is not easy to differentiate
the individual effect of the factors.
Fatty acid composition of oils
Oils that are more unsaturated are oxidized more quickly than
less unsaturated oils (Parker and others 2003). As the degree of
unsaturation increases, both the rate of formation and the amount
of primary oxidation compounds accumulated at the end of the
induction period increase (Martin-Polvillo and others 2004). Soy-
bean, safflower, or sunflower oil (iodine values > 130) stored in
the dark showed a significantly (P < 0.05) shorter induction pe-
riod than coconut or palm kernel oil whose iodine value is less
than 20 (Tan and others 2002). High oleic and high stearic oils
by gene silencing of the oilseeds or hydrogenated soybean oil
showed higher autoxidative stability (Evans and others 1973; Liu
and others 2002). The autoxidation rate greatly depends on the
rate of fatty acid or acylglycerol alkyl radical formation, and the
radical formation rate depends mainly on the types of fatty acid
or acylglycerol. The relative autoxidation rate of oleic, linoleic,
and linolenic acids was reported as 1:40 to 50:100 on the basis
of oxygen uptake (Min and Bradley 1992).
The difference in1 O 2 oxidation rate among fatty acids is lower
than that for autoxidation. The reaction rates between 1 O 2 and
stearic, oleic, linoleic, and linolenic acids are 1.2 × 104 , 5.3 ×
104 , 7.3 × 104 , and 10.0 × 104 M−1 s−1 , respectively (Vever-
Bizet and others 1989). The relative reaction rates of 1 O 2 with
oleic, linoleic, and linolenic acids are 1.0:1.4:1.9, respectively.
Soybean oil reacts with 1 O 2 at a rate of 1.4 × 105 M−1 s−1 in
methylene chloride at 20 ◦ C (Lee and Min 1991). The type of
polyunsaturated fatty acids, nonconjugated or conjugated dienes
or trienes, has little effect on the reaction between the lipid and
1
O 2 (Rahmani and Saari Csallani 1998).
Vol. 5, 2006—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY
OOH
Figure 8 --- Hydroperoxide
formation in linoleic acid
oxidation by singlet
CH3(CH2)4 oxygen
Conjugated
(CH2)7COOH
CH3(CH2)4 CH(CH2)6COOH
Nonconjugated
(CH2)7COOH
(CH2)7COOH
CH3(CH2)3CH
Nonconjugated
(CH2)7COOH
(CH2)7COOH
CH3(CH2)4
Conjugated
Oil processing
The oil-processing method affects the oxidative stability of an
oil. Crude soybean oil was the most stable to the oxidation fol-
lowed by deodorized, degummed, refined, and bleached oil dur-
ing 6 d storage at 55 ◦ C in the dark (Jung and others 1989). Higher
oxidative stability of crude oil than refined oil was suggested to
be partly due to higher concentrations of tocopherols in crude
oil (1670 ppm) than refined oil (1546 ppm). The induction time
in hexane-extracted rapeseed oil oxidation at 90 ◦ C was 10.5 ±
1.9 h compared with an induction time of 8.1 ± 0.7 h for pressed
rapeseed oil (Krygier and Platek 1999). Oxidative stability was
significantly lower in supercritical carbon dioxide-extracted wal-
nut oil than in pressed oil (Crowe and White 2003). Roasting of
safflower and sesame seeds before oil extraction improved the
oxidative stability of their oils (Yen and Shyu 1989; Lee and oth-
ers 2004), partly due to the Maillard products produced during
roasting. Some Maillard reaction products were reported to be
antioxidants. Oxidative stability increased as the roasting and ex-
pelling temperatures of the seeds increased.
Temperature and light
Autoxidation of oils and the decomposition of hydroperoxides
increase as the temperature increases (Shahidi and Spurvey 1996;
St. Angelo 1996). The formation of autoxidation products dur-
ing the induction period is slow at low temperature (Velasco
and Dobarganes 2002). The concentration of the hydroperox-
ides increases until the advanced stages of oxidation. The content
of polymerized compounds increases significantly at the end of
the induction period of autoxidation (Marquez-Ruiz and others
1996). The hydroperoxide decomposition rate of crude herring
oil stored at 50 ◦ C in the dark was higher than the formation rate
of hydroperoxide. The reverse phenomena were observed in the
same crude herring oil at 0 or 20 ◦ C in the dark (Aidos and others
2002).
Temperature has little effect on 1 O 2 oxidation due to the low ac-
tivation energy of 0 to 6 kcal/mole (Yang and Min 1994; Rahmani
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CRFSFS: Comprehensive Reviews in Food Science and Food Safety
(2-(2-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl) benzotriazole)
CH3 (CH2)4 CH CH CH2 CH CH CH2 (CH2)6 COOH or Tinuvin 326 (2-(3’-tert-butyl-2’-hydroxy-5’-methylphenyl)-5-
1
chlorobenzo-triazole), which is a UV absorber, into the trans-
O2 parent plastic bottles improved oxidative and sensory stability of
soybean oil under light (Pascall and others 1995; Azeredo and
others 2003).
CH3 (CH2)4 CH CH CH2 CH CH CH (CH2)6 COOH
O Oxygen
OH The oxidation of oil can often take place when oil, oxygen, and
catalysts are in contact. Both concentration and type of oxygen
affect the oxidation of oils. The oxygen concentration in the oil
CH3 (CH2)4 CH CH CH2 CH is dependent on the oxygen partial pressure in the headspace of
O the oil (Andersson 1998). A higher amount of oxygen is dissolved
1 in the oil when the oxygen partial pressure in the headspace is
O2
high. Oxidation of the oil increased with the amount of dissolved
oxygen (Min and Wen 1983). The solubility of oxygen is higher
CH3 (CH2)4 CH CH CH2 CH in the oil than in water, and also in crude oil than refined oil (Aho
and Wahroos 1967). One gram of soybean oil dissolves 55 μg
O O O oxygen at room temperature (Andersson 1998). The amount of
oxygen dissolved in oil is sufficient to oxidize the oil to a peroxide
value of approximately 10 meq/kg in the dark (Przybylski and
Eskin 1988). Min and Wen (1983) reported that the rate constants
CH3 (CH2)4 CH CH CH2 CH for oxygen disappearance in soybean oil containing 2.5, 4.5, 6.5,
O and 8.5 ppm dissolved oxygen during storage at 55 ◦ C in the dark
O O were 0.049, 0.058, 0.126, and 0.162 ppm/ h, respectively.
The effect of oxygen concentration on the oxidation of oil in-
+ 2 RH creased at high temperature and in the presence of light and met-
als such as iron or copper. Higher oxygen dependence of oil ox-
CH3 (CH2)4 CH CH2 CH2 CH + 2R idation at high temperature is due to low solubility of oxygen in
O the oil at high temperature (Andersson 1998). The oxygen has to
O be transported into the oil by diffusion when the oil is not stirred,
OH
such as during storage at low temperature. Convection is another
important pathway for oxygen penetration into the oil from the
CH3 (CH2)4 CH CH2 CH2 CH surface when the oil is stirred, for example, during processing at
O O high temperature.
Oil oxidation rate is independent of oxygen concentration at
sufficiently high oxygen concentrations, for example, above 10%
in the oxidation of methyl linoleate (Kacyn and others 1983).
CH3 (CH2)4 C CH2 CH2 CH When the oxygen content is low, the oxidation rate is dependent
O O on oxygen concentration and is independent of lipid concentra-
tion (Andersson 1998). The autoxidation rate of oil at more than
4% to 5% oxygen in the headspace was independent of oxy-
gen concentration and was directly dependent on the lipid con-
CH3 (CH2)4 C CH CH CH centration (Labuza 1971). However, the reverse was true at low
oxygen pressure of less than 4% in the headspace (Karel 1992).
OH OH The oxidation of rapeseed oil at 50 ◦ C in the dark, measured as
- H2O oxygen consumption or peroxide values, became faster as the
oxygen concentration increased at less than 0.5% oxygen in the
headspace, whereas the oxidation rate decreased with oxygen
concentration at more than 1% oxygen (Andersson and Lingnert
1999).
CH3 (CH2)4 Oxygen and edible oil can react more efficiently when an oil
O sample size is small or an oil sample has a high ratio of surface
to volume (Tan and others 2002; Kanavouras and others 2005).
Figure 9 --- Formation of 2-pentylfuran from linoleic acid by singlet oxygen oxidation When the surface-to-volume ratio increases, the relative rate of
oxidation is less oxygen-dependent with a low oxygen content.
The container surface can act as a reduction catalyst, and its
and Saari Csallani 1998). Light is much more important than tem- effect was shown to be proportional to the area of the container
perature in 1 O 2 oxidation. Light of shorter wavelengths had more in contact with the oils (Brimberg and Kamal-Eldin 2003).
detrimental effects on the oils than longer wavelengths (Sattar The interaction between temperature and oxygen concentra-
and others 1976). Reportedly, the effect of light on oil oxidation tion affects the volatile formation in rapeseed oil in the dark;
becomes less as temperature increases (Velasco and Dobarganes production of 2-pentenal and 1-pentene-3-one correlated posi-
2002). tively with oxygen concentration at 50 ◦ C, but negatively at 35 ◦ C
Because 1 O 2 oxidation occurs in the presence of light, the (Andersson and Lingnert 1999).
packaging of oils is very important. Transparent plastic bot- The reaction rate between lipid and oxygen is dependent on
tles increase oil oxidation. The incorporation of Tinuvin 234 the type of oxygen; the reaction rate of 1 O 2 with lipid is much
176 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 5, 2006
Mechanisms and factors for edible oil oxidation

O Figure 10 --- Formation of 2-pentenylfuran from linolenic

acid by singlet oxygen oxidation
CH3 CH2 CH CH CH2 CH CH CH2 CH CH CH2 (CH2)6 COH

1
O2
O
CH3 CH2 CH CH CH2 CH CH CH2 CH CH CH (CH2)6 COH
O
O
H
O
CH3 CH2 CH CH CH2 CH CH CH2 CH CH CH (CH2)6 COH
O

CH3 CH2 CH CH CH2 CH CH CH2 CH

O
1
O2

CH3 CH2 CH CH CH2 CH CH CH2 CH

O O
O
H

CH3 CH2 CH CH CH2 CH CH CH2 CH

O O

CH3 CH2 CH CH CH2 C CH2 CH2 CH

O O

CH3 CH2 CH CH CH2 C CH CH CH

OH OH

- H2O

CH3 CH2 CH CH CH2

O

Vol. 5, 2006—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY 177

CRFSFS: Comprehensive Reviews in Food Science and Food Safety
higher than that of 3 O 2 because 1 O 2 can directly react with lipids.
3
O 2 reacts with the radical state of lipids. Linoleates react with
1
O 2 at a rate 1,450 times faster than with 3 O 2 (Rawls and Van
Santen 1970).
Minor components present in oil
Edible oil consists of mostly triacylglycerols, but it also con-
tains minor components such as free fatty acids, mono- and
diacylglycerols, metals, phospholipids, peroxides, chlorophylls,
carotenoids, phenolic compounds, and tocopherols. Some of
them accelerate the oil oxidation and others act as antioxidants.
Free fatty acid and mono- and diacylglycerols. Crude oil con-
tains free fatty acids, and oil processing, such as refining, de-
creases the free fatty acid contents. Crude soybean oil contains
about 0.7% free fatty acids; however, refined oil contains 0.02%
free fatty acids (Jung and others 1989). Sesame oil extracted from
roasted sesame seeds contains 0.72% free fatty acids and bleach-
ing with acid clay decreases free fatty acid contents of the oil to
0.56% (Kim and Choe 2005). Free fatty acids are more suscepti-
ble to autoxidation than esterified fatty acids (Kinsella and others
1978). Free fatty acids act as prooxidants in edible oil (Miyashita
and Takagi 1986; Mistry and Min 1987a). They have hydrophilic
and hydrophobic groups in the same molecule and prefer to be
concentrated on the surface of edible oils. The hydrophilic car-
boxy groups of the free fatty acids will not easily dissolve in the
hydrophobic edible oil and are present on the surface of edible
oil. Mistry and Min (1987a) reported that free fatty acids decrease
the surface tension of edible oil and increase the diffusion rate of
oxygen from the headspace into the oil to accelerate oil oxidation.
Mono- and diacylglycerol, usually present at 0.07% to 0.11%
and 1.05% to1.20% in soybean oil, respectively, acted as proox-
idants to increase oxidation at 55 ◦ C in the dark (Mistry and Min
1987b; Mistry and Min 1988). The mono-and diacylglycerols,
which have hydrophilic hydroxy groups and hydrophobic hy-
drocarbons, decrease the surface tension of edible oil and in-
crease the diffusion rate of oxygen from the headspace to the
oil to accelerate the oxidation of oil. Mono- and diacylglyc-
erols should be removed from the oil during the oil-refining pro-
cess to improve the oxidative stability of edible oils (Mistry and
Min 1988).
Metals. Crude oil contains transition metals such as iron or
copper. For example, crude soybean oil contains 13.2 ppb and
2.80 ppm of copper and iron, respectively. However, refining re-
duces their contents. Edible oils manufactured without refining,
such as extra virgin olive oil and sesame oil, contain relatively
high quantities of transition metals (Table 4). Metals increase the
rate of oil oxidation due to the reduction of activation energy of
the initiation step in the autoxidation down to 63∼104 kJ/mol
(Jadhav and others 1996). Metals react directly with lipids to
produce lipid alkyl radicals. They also produce reactive oxygen
Table 4 --- Copper and iron contents in edible oils
Metal contenta
Oils Copper (ppb) Iron (ppm)
Cold-pressed sesame oilb 16 (3.0–38) 1.16 (0.18–1.52)
Crude soybean oilc 13.2 2.80
Virgin olive oilb 9.8 (1.0–79) 0.73 (nd–9.79)
Cold-pressed sunflower oilb 5.2 (2.2–8.5) 0.26 (0.22–0.31)
Refined olive oild 15 0.08
Refined soybean oilc 2.5 0.20
a Numbers in parentheses are the
b MAFF (1997).
ranges reported.
c Sleeter (1981).
d Leonardis and Macciola (2002).
178 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 5, 2006
species such as 1 O 2 and hydroxy radical from 3 O 2 and hydro-
gen peroxide, respectively (Andersson 1998). Lipid alkyl radical
and reactive oxygen species accelerate oil oxidation. Copper ac-
celerates hydrogen peroxide decomposition 50 times faster than
ferrous ion (Fe2+ ), and ferrous ion acts 100 times faster than ferric
ion (Fe3+ ):
Fe3+ + RH −→ Fe2+ + R− + H+
Fe2+ + 3 O2 −→ Fe3+ + O−
2·
+
O− −
2 · + O2 · + 2H −→ O2 + H2 O2
1
metal catalyst
H2 O2 + O−
2 −−−−−−−−→ HO· + OH− + 1 O2
Fe2+ + H2 O2 −→ Fe3+ + OH− + HO·
Metals also accelerate autoxidation of oil by decomposing hy-
droperoxides (Benjelloun and others 1991):
ROOH + Fe2+ (or Cu+ ) −→ RO· + Fe3+ (or Cu2+ ) + OH−
ROOH + Fe3+ (or Cu2+ ) −→ ROO· + Fe2+ (or Cu+ ) + H+
Fe2+ is much more active with a rate of 1.5 × 103 M−1 s−1
(Halliwell and Gutteridge 2001) than Fe3+ in decomposing the
lipid hydroperoxides to catalyze autoxidation (Mei and others
1998). Fe3+ also causes decomposition of phenolic compounds
such as caffeic acid in olive oil and decreases oil oxidative sta-
bility (Keceli and Gordon 2002).
Shiota and others (2006) reported that the prooxidant activity
of iron was suppressed by lactoferrin in fish oil or soybean oil
oxidation at 50 ◦ C to 120 ◦ C, possibly due to the iron-binding
ability of lactoferrin. Depletion of iron from the surroundings by
lactoferrin can suppress the iron-catalyzed oxidation of the oil.
Phospholipids. Crude oils contain phospholipids such as
phosphatidylethanolamine, phosphatidylcholine, phosphatidyli-
nositol, phsphatidylserine, and phosphatidic acid, but most
of them are removed by processing such as degumming.
Crude soybean oil contains phosphatidylcholine and phos-
phatidylethanolamine at 500.8 and 213.6 ppm, respectively.
However, refined, bleached, and deodorized (RBD) soybean
oil contains 0.86 and 0.12 ppm of phosphatidylcholine and
phosphatidylethanolamine, respectively (Yoon and others 1987).
Phospholipids act as antioxidants and prooxidants depending on
their concentration and presence of metals. Oxidation of docosa-
hexaenoic acid at 25 ◦ C to 30 ◦ C in the dark decreased when
mixed with phosphatiylcholine at a molar ratio of 1:1 (Lyberg
and others 2005).
The mechanism of the antioxidative effects of phospholipids
has not yet been elucidated in detail, but the polar group plays an
important role and the nitrogen-containing phospholipids such as
phosphatidylcholine and phosphatidylethanolamine are efficient
antioxidants under most conditions (King and others 1992). Phos-
pholipids decrease oil oxidation by sequestering metals, and con-
centration for the maximal antioxidant activity was between 3 and
60 ppm. Soybean oil oxidation decreased with addition of 5 to10
ppm phospholipids, and higher amount of phospholipids acted
as prooxidants. Yoon and Min (1987) reported that phospholipids
acted as antioxidants only in the presence of Fe2+ by chelating
iron. In purified soybean oil, which did not contain any met-
als, phospholipids worked as prooxidants. Phospholipids have
hydrophilic and hydrophobic groups in the same molecule. The
hydrophilic groups of the phospholipids are on the surface of oil
and hydrophobic group are in the edible oil. The phospholipids
decrease the surface tension of edible oil and increase the diffu-
sion rate of oxygen from the headspace to the oil to accelerate oil
Mechanisms and factors for edible oil oxidation
oxidation. Soybean oil oxidation in the dark at 60 ◦ C was the low-
est with phosphatidic acid and phosphatidylethanolamine, fol-
lowed by phosphatidylcholine, phosphatidylglycerol, and phos-
phatidylinositol (Yoon and Min 1987).
Chlorophylls. Chlorophylls are common pigments present in
edible vegetable oil. Virgin olive oil and rapeseed oil contain
chlorophyll at 10 ppm and 5 to 35 ppm, respectively (Salvador
and others 2001). Virgin olive oil also contains 4 to 15 ppm pheo-
phytin (Psomiadou and Tsimidou 2002). The chlorophyll concen-
trations in crude and bleached soybean oils are 0.30 and 0.08
ppm, respectively (Jung and others 1989). Chlorophylls are gen-
erally removed during oil processing, especially the bleaching
process (Table 5).
Chlorophylls and their degradation products, pheophytins and
pheophorbides, act as sensitizers to produce 1 O 2 in the presence
of light and atmospheric 3 O 2 , and accelerate the oxidation of oil
(Fakourelis and others 1987; Whang and Peng 1988; Gutierrez-
Rosales and others 1992). Pheophytins have a higher sensitizing
activity than chlorophylls, but lower than that of pheophorbides
(Endo and others 1984; Rahmani and Csallany 1998). Soybean oil
purified by silicic acid column chromatography did not contain
any chlorophylls and did not produce volatiles in the headspace
under light at 10 ◦ C, but purified soybean oil with added chloro-
phyll and RBD soybean oil produced headspace volatiles un-
der the same experimental conditions (Lee and Min 1988). Also,
appreciable amounts of volatiles were produced in soybean oil
containing chlorophyll only under light, but not in the dark. The
headspace volatile formation in soybean oil under light at 10 ◦ C
increased as the concentration of chlorophyll increased. Rahmani
and Csallani (1998) showed that the oxidation of virgin olive oil
containing pheophytin was accelerated by the illumination of
fluorescent light.
Although chlorophylls are strong prooxidants under light via
acting as a sensitizer to produce 1 O 2 , they act as antioxidants in
the dark possibly by donating hydrogen to free radicals (Endo and
others 1985; Francisca and Isabel 1992).
Thermally oxidized compounds. Processing of crude oils to re-
fined oils is generally performed at high temperature, and it
can produce oxidized compounds such as cyclic and noncyclic
carbon-to-carbon-linked dimers and trimers, hydroxy dimers, and
dimers and trimers joined through carbon-to-oxygen linkage. The
RBD soybean oil contains 1.2% thermally oxidized compounds
(Yoon and others 1988). Thermally oxidized compounds accel-
erated the soybean oil autoxidation at 55 ◦ C (Yoon and others
Table 5 --- Chlorophyll contents of canola oil during processing (ppm)a
Oil Chlorophyll a Pheophytin a
Extracted 1.88 3.31
Degummed 0.27 7.16
Refined 0.22 6.27
Bleached --- 0.56
a Suzuki and Nishioka (1993).
OH O O
ROO ROOH
Vol. 5, 2006—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY
1988). The acceleration of oil oxidation increases with the con-
centration of thermally oxidized compounds. Lipid hydroperox-
ides were also shown to act as prooxidants (Hahm 1988). The
oxidized compounds formed by hydroperoxide decomposition
can act as an emulsifier, which contain both hydrophilic and hy-
drophobic groups, lower surface tension in the oil, and increase
the introduction of oxygen into the oil to accelerate oil oxidation
(Min and Jung 1989).
Antioxidants. Edible oils naturally contain antioxidants such as
tocopherols, tocotrienols, carotenoids, phenolic compounds, and
sterols. Antioxidants are sometimes intentionally added to oil to
improve oxidative stability. Antioxidants are compounds that ex-
tend the induction period of oxidation or slow down the oxidation
rate. Antioxidants scavenge free radicals such as lipid alkyl rad-
icals or lipid peroxy radicals, control transition metals, quench
singlet oxygen, and inactivate sensitizers.
Antioxidants can donate hydrogen atoms to free radicals and
convert them to more stable nonradical products (Decker 2002).
The major hydrogen-donating antioxidants are monohydroxy or
polyhydroxy phenolic compounds with various aromatic ring
substitutions. Any compound whose reduction potential is lower
than that of a free radical can donate hydrogen to that radi-
cal unless the reaction is kinetically unfavorable. Standard 1-
electron reduction potentials of alkoxy, peroxy, and alkyl radicals
of polyunsaturated fatty acids are 1600, 1000, and 600 mV, re-
spectively (Buettner 1993). The standard reduction potential of
antioxidants is generally 500 mV or below. This clearly shows
that antioxidants react with lipid peroxy radicals before the per-
oxy radicals react with other lipid molecules to produce another
free radical. Any antioxidant radical produced from the reaction
with lipid peroxy radical has lower energy than the lipid peroxy
radical itself due to resonance structure (Figure 11).
Metal chelators such as phosphoric acid, citric acid, ascorbic
acid, and EDTA (ethylenediaminetetraacetic acid) decrease oil
oxidation in an indirect way. They can convert iron or copper
ions into insoluble complexes or can sterically hinder the forma-
tion of the complexes between metals and lipid hydroperoxides
(Halliwell and others 1995). Citric acid improved the sensory
quality of soybean oil containing 1 ppm iron during storage at
55 ◦ C (Min and Wen 1983). Citric acid is often added to oil in the
field to reduce its oxidation during storage before processing. Min
and Wen (1983) reported that the antioxidant effects of citric acid
increased as its content increased; and more than 150 ppm citric
acid was necessary to overcome the catalytic effect of 1 ppm iron.
Pheophytin b Pyropheophytin a Pyropheophytin b
1.34 16.57 3.13
1.07 9.40 1.84
1.12 9.13 1.79
0.32 0.21 0.25
O O Figure 11 --- Resonance
stabilization of an
antioxidant radical
179
CRFSFS: Comprehensive Reviews in Food Science and Food Safety
When oil contains 0.1 ppm or less iron such as in RBD oil, the
common practice of adding about 150 ppm citric acid to the oil
for the improvement of oxidative stability is not necessary (Min
and Wen 1983).
Some antioxidants quench 1 O 2 or excited sensitizers. 1 O 2 is
quenched physically and chemically. In physical quenching, 1 O 2
is converted into 3 O 2 by either energy transfer or charge transfer,
and there is no oxidation of antioxidants. In chemical quenching,
antioxidants react with 1 O 2 and produce oxidized antioxidants
(Min and Boff 2002).
Tocopherols
Tocopherols are the most important antioxidants present in ed-
ible oil. Animal fats also contain tocopherols, but at lower con-
centrations (Table 6). Among vegetable oils, soybean, canola,
sunflower, and corn oils contain relatively high amounts of to-
copherols. Palm oil does not have large amounts of tocopherols
(118 to 146 ppm); however, it contains a higher concentration
of tocotrienols, that is, α-, γ -, and δ-tocotrienols at 211, 353 to
372, and 56 to 67 ppm, respectively (Al-Saqer and others 2004).
Safflower oil also contains γ - and δ-tocotrienols in addition to
tocopherols at 3.8 to 7.0 and 7.5 to 8.4 ppm, respectively (Lee
and others 2004). Tocopherol contents of edible oils are affected
by the cultivar, processing, and storage of the oil (Deiana and
others 2002). Tocopherol contents of sesame oil range between
404 and 540 ppm depending on the cultivars (Mohamed and
Awatif 1998). The tocopherol contents of rapeseed oil are 794 and
749 ppm for hexane-extracted oil and pressed oil, respectively
(Krygier and Platek 1999). The refining process, especially de-
odorization, reduces tocopherol contents (Jung and others 1989;
Reische and others 2002; Eidhin and others 2003). The crude,
bleached, and deodorized soybean oil contains tocopherols at
1670, 1467, and 1138 ppm, respectively (Jung and others 1989).
In virgin olive oil, α-tocopherol concentration decreased with
storage time of the oil in the dark (Deiana and others 2002).
There was no tocopherol left in olive oil stored in the dark at
room temperature for 12 mo (Morello and others 2004).
Tocopherols compete with unsaturated fats and oils for lipid
peroxy radicals. Lipid peroxy radicals react with tocopherols
much faster at 104 to 109 M−1 s−1 than with lipids (10 to 60
M−1 s−1 ). One tocopherol molecule can protect about 103 to
108 polyunsaturated fatty acid molecules at low peroxide value
(Kamal-Elden and Appelqvist 1996). Tocopherols can transfer a
hydrogen atom at the 6-hydroxy group on its chroman ring to lipid
peroxy radical and scavenge the peroxy radicals. Tocopherol (T),
with a reduction potential of 500 mV, donates hydrogen to lipid
peroxy radicals (ROO·) that have a reduction potential of 1000
mV, and produces lipid hydroperoxide (ROOH) and tocopheroxy
radicals (T·). Tocopheroxy radicals are more stable than lipid per-
oxy radicals due to resonance structures. This ultimately slows
down the oil oxidation rate in the propagation stage of autoxida-
tion. Reaction rates of peroxy radicals in stearic and oleic acids
with α-tocopherol were reported to be 2.8 × 106 and 2.5 ×106
M−1 s−1 , respectively (Simic 1980). Tocopheroxy radicals can in-
teract with other compounds or each other, depending on the
lipid oxidation rates. Tocopheroxy radicals react with each other
at low lipid oxidation rates and produce tocopheryl quinone and
tocopherol. At higher oxidation rates, tocopheroxy radicals may
react with lipid peroxy radicals and produce tocopherol–lipid per-
oxy complexes ([T-OOR]); these can be hydrolyzed to tocopheryl
quinone and lipid hydroperoxide (Liebler and others 1990):
T + ROO− −→ T· + ROOH
T· + T· −→ T + Tocopheryl quinone
T· + ROO· −→ [T − OOR] −→ Tocopheryl quinone + ROOH
The effectiveness of tocopherols as antioxidants depends on
the isomers and concentration of tocopherols. Free radical scav-
enging activity of tocopherols is the highest in δ-tocopherol fol-
lowed by γ -, β-, and α-tocopherol (Reische and others 2002).
α-Tocopherol was more effective in reducing oil oxidation than
γ -tocopherol up to 200 ppm and less effective above this con-
centration (Yanishlieva and others 2002).
The optimal concentration of tocopherols as antioxidants is
dependent on their oxidative stability; the lower the oxidative
stability of the tocopherol, the lower the optimal concentration
of tocopherol for the maximal antioxidant activity. α-Tocopherol,
which is the least stable among tocopherol isomers, showed the
maximal antioxidant activity at 100 ppm in the oxidation of soy-
bean oil at 55 ◦ C in the dark, but the optimal concentrations of
γ - and δ-tocopherols as an antioxidant were 250 ppm and 500
ppm, respectively (Jung and Min 1990).
Tocopherols, particularly α-tocopherol, act as prooxidants
when present in high concentrations in vegetable oils via
propagation of free radicals, depending on the hydroperoxide

Table 6 --- Tocopherol contents of edible oil

Tocopherol (ppm)
Oil α β γ δ Total

Soybeana 116.0 34.0 737.0 275.0 1162

Canolaa 272.1 0.1 423.2 – 695.4
Sunflowera 613.0 17.0 18.9 – 648.9
Corna 134.0 18.0 412.0 39.0 603
Roasted sesameb 4 – 584 9 597
Rapeseedc 252 314 566
Safflowerd 386∼520 8.6∼12.4 2.4∼7.7 --- 397∼540
Olivee 168∼226 --- --- --- 168∼226
Beef tallowf 30.4 --- 3.8 --- 34.2
Lardg 18.0 --- --- --- 18.0
a Przybylski (2001).
b Kamal-Eldin and Andersson (1997).
c Velasco and others (2003).
d Lee and others (2004)
e Salvador and others (2001); Gutierrez and others (2001).
f Choe and Lee (1998).
g Drinda and Baltes (1999).

180 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 5, 2006

Mechanisms and factors for edible oil oxidation
concentration (Cillard and others 1980; Terao and Matsushita
1986; Jung and Min 1990). When the concentration of lipid per-
oxy radical is very low, the tocopheroxy radical abstracts hy-
drogen from the lipid and produces tocopherol and lipid alkyl
radical; however, the reaction rate is very low. Formation of
lipid alkyl radicals by tocopherols accelerates lipid oxidation,
which is called tocopherol-mediated peroxidation (Bowry and
Stocker 1993; Yamamoto 2001). The highest prooxidant activity
was shown in α-tocopherol followed by γ - and δ-tocopherol in
soybean oil autoxidation (Jung and Min 1990). Addition of 100
ppm α-tocopherol increased the oxidation of purified olive oil at
an early stage of autoxidation; however, α-tocopherol added to
moderately oxidized (POV = 15) purified olive oil or lard signifi-
cantly decreased the oil oxidation (Blekas and others 1995). The
threshold value for α-tocopherol as a prooxidant in virgin olive
oil oxidation was 60 to 70 ppm. When less α-tocopherol was ini-
tially present in the oil, the threshold value for prooxidant activity
was reached more quickly (Deiana and others 2002). Prooxidant
activity of α-tocopherol decreased as the temperature increased,
even at a high concentration (Marinova and Yanishlieva 1992).
Ascorbic acid (Asc) can reduce tocopheroxy radical and prevent
tocopherol-mediated peroxidation (Yamamoto 2001):
T· + RH −→ T + R·
R· + O2 −→ ROO·
T· + Asc −→ T + Dehydroascorbic acid
Oxidized tocopherols increase soybean oil oxidation and
prooxidant activity was the highest in oxidized α-tocopherol fol-
lowed by oxidized γ - and δ-tocopherol (Jung and Min 1992).
Prevention of tocopherol oxidation and removal of oxidized to-
copherols during oil processing are strongly recommended to
improve oil oxidative stability.
In addition to free radical scavenging activity, tocopherols de-
crease soybean oil oxidation under light by only 1 O 2 quenching
(Min and Lee 1988). 1 O 2 quenching rate by α-tocopherol was
reported to be 2.7 × 107 M−1 s−1 (Jung and others 1991). 1 O 2
quenching effect in soybean oil oxidation under light is depen-
dent on tocpherol concentration and the type; at 1 × 10−3 M,
the activity was in the decreasing order of α-, γ -, and δ- to-
copherol; however, there was no significant difference in 1 O 2
quenching activity among tocopherols at 4 × 10−3 M (Jung and
others 1991). Tocopherols can form a charge transfer complex
([T+ –1 O 2 ] 1 ) with 1 O 2 by electron donation to 1 O 2 . The singlet
state of tocopherol–1 O 2 complex undergoes intersystem crossing
into the triplet state ([T+ –1 O 2 ] 3 ) and produces less reactive 3 O 2
and tocopherol. Since this does not involve chemical reactions
between tocopherol and 1 O 2 , it is called physical quenching:
T + 1 O2 −→ [T+ − 1 O2 ]1 −→ [T+ − 1 O2 ]3 −→ T + 3 O2
Tocopherols react irreversibly with 1 O 2 in chemical quench-
ing and produce tocopherol hydroperoxydienone, tocopheryl
quinone, and quinone epoxide (Figure 12). The reaction rate of
tocopherols with 1 O 2 is affected by their structures. α-Tocopherol
showed the highest reaction rate of 2.1 × 108 M−1 s−1 , followed
by β-tocopherol with 1.5 × 108 M−1 s−1 , γ -tocopherol with 1.4 ×
108 M−1 s−1 , and δ-tocopherol with 5.3 × 107 M−1 s−1 (Mukai and
others 1991).
Carotenoids
Carotenoids are a group of tetraterpenoids consisting of iso-
prenoid units. Double bonds in carotenoids are conjugated forms
and usually are all trans forms. β-Carotene is one of the most
Vol. 5, 2006—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY
studied carotenoids. Edible oils, especially unrefined oils, con-
tain β-carotene. Crude palm oil and red palm olein contain 500
to 700 ppm carotenoids (Bonnie and Choo 2000). Virgin olive
oil contains 1.0 to 2.7 ppm β-carotene as well as 0.9 to 2.3 ppm
lutein (Psomiadou and Tsimidou 2002).
β-Carotene can slow down oil oxidation by light filtering, 1 O 2
quenching, sensitizer inactivation, and free radical scavenging.
Fakourelis and others (1987) reported that oxidation of olive oil
containing only β-carotene under light at 25 ◦ C was decreased
by filtering out some light energy, mainly between 400 and 500
nm. In the co-presence of chlorophylls, β-carotene decreased
the oxidation of soybean oil stored under light by 1 O 2 quenching
(Lee and Min 1988). 1 O 2 quenching by carotenoids is mainly
by energy transfer from 1 O 2 to carotenoids, without generating
oxidized products. Excited carotenoids return to the ground state
by giving off heat:
1
O2 + 1 Carotenoid −→ 3 O2 + 3 Carotenoid∗
3
Carotenoid∗ −→ Carotenoid + Heat
One mole of β-carotene can quench 250 to 1000 molecules of
1
O 2 at a rate of 1.3 × 1010 M−1 s−1 (Foote 1976). 1 O 2 quenching
of carotenoids is dependent on the number of conjugated dou-
ble bonds (Beutner and others 2001). Carotenoids having at least
9 conjugated double bonds act as an effective 1 O 2 quencher;
β-carotene, lycopene, and lutein are good 1 O 2 quenchers; how-
ever, phytoene, phytofluene, and ζ -carotene, which are precursor
compounds of lycopene, are not. The 1 O 2 quenching activity of
carotenoids increases as the number of conjugated double bonds
increases (Min and Boff 2002; Foss and others 2004). Lycopene
and α-carotene demonstrate higher 1 O 2 quenching ability than
β-carotene (Miller and others 1996).
Carotenoids inactivate excited sensitizers physically by absorb-
ing energy from sensitizers. The excited carotenoids return to the
ground state by transferring the energy to the oil (Stahl and Sies
1992). Lee and others (2003) reported that β-carotene with a
high 1-electron reduction potential of 1060 mV had great diffi-
culty in donating hydrogen to alkyl (E o = 600 mV) or peroxy
radical (E o = 770 to1440 mV) of polyunsaturated fatty acid. Nu-
clear magnetic resonance study showed that β-carotene did not
donate a hydrogen atom to quench these free radicals (Lee and
others 2003). However, β-carotene can donate hydrogen to hy-
droxy radical, which has a high reduction potential (2310 mV),
and produces a carotene radical (Car·). A carotene radical is a
fairly stable species due to delocalization of unpaired electrons
through its conjugated polyene system. At low oxygen concen-
tration, a carotene radical may react with other radicals such as
lipid peroxy radicals and form nonradical products (Burton and
Ingold 1984; Beutner and others 2001):
Car + HO· −→ Car· + H2 O
Car· + ROO· −→ Car − OOR
A lipid peroxy radical may be added to β-carotene and pro-
duce carotene peroxy radical (ROO–Car·), especially at higher
than 150 mm Hg of oxygen (Burton and Ingold 1984). Carotene
peroxy radical reacts with 3 O 2 and then with lipid molecules, and
produces lipid alkyl radicals, which propagate the chain reaction
of lipid oxidation (Iannone and others 1998):
ROO· + Car −→ ROO − Car·
ROO − Car· + 3 O2 −→ ROO − Car − OO·
ROO − Car − OO· + R H −→ ROO − Car − OOH + R ·
181
CRFSFS: Comprehensive Reviews in Food Science and Food Safety

CH3 CH3 Figure 12 --- Singlet oxygen

oxidation of α-tocopherol
HO 1 O
O2

H3C H3C O
O C16H33 C16H33
OOH
CH3 CH3

α-Tocopherol Hydroperxydienone
1
O2
CH3

HO
O
O
H3C O C16H33

CH3

α-Tocopherol endoperoxide

CH3 CH3
O
O O

+
H3C O H3C
C16H33 O C16H33
HO
CH3 CH3
α-Tocopheryl quinone α-Tocopheryl quinone epoxide

Antioxidant activity of β-carotene was not shown in soybean oil
stored in the dark (Lee and others 2003). During photosensitized
oxidation of soybean or rapeseed oil in open vessels, β-carotene
increased oil oxidation, but the co-presence of tocopherols de-
creased oxidation of the oil (Haila and Heinonen 1994). The an-
tioxidant activities of carotenoids by hydrogen donation remain
controversial.
β-Carotene may also donate electrons to free radicals and
become a β-carotene cation radical (Liebler 1993; Mortensen
and others 2001). The transfer of hydrogen or electrons from
carotenoids to free radicals depends on the reduction potentials
of the free radicals and chemical structures of the carotenoids,
especially the presence of oxygen-containing functional groups
(Edge and others 1997). The β-carotene cation radical has a rel-
atively high standard 1-electron reduction potential (1060 mV),
and does not readily react with oxygen to form peroxide (Edge
and others 2000). The β-carotene cation radical may react with
alkyl, alkoxy, or peroxy radicals formed in soybean oil during
oxidation. Lee and others (2003) reported that β-carotene was a
prooxidant in soybean oil oxidation in the dark due to the elec-
tron transfer mechanism in their 2, 2-diphenyl-1-picryl hydrazyl
and NMR study.
182 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 5, 2006
Carotenoids are degraded by hydroperoxides to hydroxyl- or
epoxycarotenes, and the degradation slows down at higher con-
centration; the rate of degradation of carotenes is lycopene >
β-carotene ≈ α-carotene (Anguelova and Warthesen 2000).
Other phenolic compounds
Phenolic compounds other than tocopherols in edible oils also
exert antioxidant activity. Sesame oil, which contains a high
amount of unsaturated fatty acids (iodine value = 109), has good
oxidative stability (Tan and others 2002). The autoxidation rate of
sesame oils at 60 ◦ C was much lower than that of corn oil, saf-
flower oil, and a mixture of soybean and rapeseed oils (Fukuda
and Namiki 1988). Roasted sesame oil was more stable for the
oxidation than unroasted sesame oil (Yoshida and Takagi 1997;
Yoshida and others 2000). The remarkable oxidative stability of
sesame oil is due to the presence of lignan compounds as well as
tocopherols (Yoshida 1994; Namiki 1995). Lignan compounds in
sesame oil include sesamin, sesamol, sesamolin, sesaminol, and
sesamolinol (Figure 13). Sesamin is the predominant lignan com-
pound in unroasted sesame oil (474 ppm) followed by sesamolin
(159 ppm). Sesamol concentration in unroasted sesame oil was
less than 7 ppm (Fukuda and others 1986; Dachtler and others
Mechanisms and factors for edible oil oxidation

O Figure 13 --- Phenolic

acids present in oils
O

O
OH

O
O O

O sesamol O sesamin

O
O
O

O sesamolin
O

O HO

O O

O sesaminol
OH
HO COOH OH
HO
HO OH HO

Caffeic acid Hydroxytyrosol Tyrosol

2003); however, roasted sesame oil contains a higher concen-
tration of sesamol (36 ppm) than unroasted oil (Kim and Choe
2005). Sesamol is produced by hydrolysis of sesamolin during
oil processing such as heating and bleaching (Fukuda and others
1985; Osawa and others 1985; Kim and Choe 2005). Sesamol is
converted to sesamol dimer and then to sesamol dimer quinone
(Kurechi and others 1981; Kikugawa and others 1983). Sesamol
and sesaminol showed higher antioxidant activity than sesamin
in sunflower oil autoxidation by scavenging radicals (Dachtler
and others 2003).
Sesamol acts as an antioxidant in the oxidation under light as
well as in the dark. The antioxidation by sesamol in chlorophyll-
sensitized photooxidation of soybean oil was lower than by α-
Vol. 5, 2006—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY
tocopherol, similar to δ-tocopherol, and higher than DABCO (di-
azabicyclo[2,2,2]octane) at the same molar concentration (Kim
and others 2003). The decrease of photooxidation of soybean oil
by sesamol was due to its 1 O 2 quenching, and the quenching rate
was 1.9 × 107 M−1 s−1 at 20 ◦ C (Kim and others 2003).
Sesame oil also contains phytosterols such as campesterol, stig-
masterol, β-sitosterol, and 4,5-avenasterol, with β-sitosterol as
the predominant sterol (Dachtler and others 2003). Sitosterol be-
haves partly as a prooxidant by increasing the solubility of oxygen
in the oil (Yanishlieva and Schiller 1983) and partly as a weak
antioxidant in sunflower oil and lard by competing with lipid
molecules for oxidation at the oil surface (Maestroduran and Bor-
japadilla 1993; Brimberg and Kamal-Eldin 2003).
183
CRFSFS: Comprehensive Reviews in Food Science and Food Safety
Table 7 --- Phenolic compounds in virgin olive oila
Phenolic alcohols 3,4-Dihydroxyphenyl ethanol (3,4-DHPEA, hydroxytyrosol), p-hydroxyphenylethanol (p-HPEA, tyrosol),
3,4-dihydroxyphenylethanol-glucoside
Phenolic acid and its derivatives Vanillic acid, syringic acid, p-coumaric acid, o-coumaric acid, gallic acid, caffeic acid, protocatechuic acid,
p-hydroxybenzoic acid, ferulic acid, cinnamic acid, 4-(acetoxyethyl)-1,2-dihydroxybenzene, benzoic acid
Secoiridoids Dialdehydic form of elenolic acid linked to 3,4-DHPEA, dialdehydic form of elenolic acid linked to p-HPEA,
oleuropein aglycon, ligstroside aglycon, oleuropein, p-HPEA derivative
Lignans 1-Acetoxypinoresinol, pinoresinol, 1-hydroxypinoresinol
Flavones Apigenin, luteolin
a Servili and Montedoro (2002).

Olive oil, which is very stable to autoxidation (Guillen ducing sugar of phosphatidylinositol, donates hydrogen or elec-
and Cabo 2002), contains phenolic compounds and toco- tron to tocopherols and delays the oxidation of tocopherols to to-
pherols. Phenolic compounds in olive oil include tyrosol copheryl quinone (Yoon and Min 1987). Sesamol and sesaminol
(4-hydroxyphenylethanol), hydroxytyrosol (3,4-dihydroxy- showed synergistic antioxidant activities with γ -tocopherol in the
phenylethanol), hydroxybenzoic acids, oleuropein, caffeic acid, autoxidation of sunflower oil (Dachtler and others 2003).
vanillic acid, p-coumaric acid, and derivatives of tyrosol and A combination of 11 ppm β-carotene, 30 ppm citric acid, 3
hydroxytyrosol (Papadopoulos and Boskou 1991; Tsimidou to 4 ppm Tinuvin P, and 150 to 200 ppm TBHQ decreased the
and others 1992), as shown in Table 7. Contents of tyrosol, oxidation rate of soybean oil during storage at 25 ◦ C under light
hydroxytyrosol, and phenolic acids in olive oil were 34.9, 37.8, for 6 mo (Azeredo and others 2004).
and 36.3 ppm, respectively (Keceli and Gordon 2002). The Synergism between antioxidants is affected by hydroperox-
phenolic compounds in olive oil acted as antioxidants mainly ide concentration. Olive oil autoxidation was lower when α-
at the initial stage of autoxidation (Deiana and others 2002) by tocopherol and phenolic compounds were used together than
scavenging free radicals and chelating metals (Chimi and others when used separately (Velasco and Dobarganes 2002); however,
1991). Hydroxytyrosol was the most effective antioxidant in α-tocopherol exerted an adverse effect on the antioxidation of
olive oil oxidation (Papadopoulos and Boskou 1991; Tsimidou olive oil by phenolic compounds such as tyrosol or oleuropein
and others 1992; Baldioli and others 1996). Among phenolic during the period of low hydroperoxide formation, for example,
compounds, o-diphenols such as caffeic acid are oxidized to less than 20 meq (Blekas and others 1995).
quinones by ferric ions and become ineffective in inhibiting
iron-dependent free radical chain reactions in oil (Keceli and
Gordon 2002). However, hydroxytyrosol, tyrosol, vanillic acids, Conclusions
and p-coumaric acid were not oxidized by the ferric ions. Fki Edible oil undergoes autoxidation and photosensitized oxi-
and others (2005) reported high radical scavenging effects of dation during processing and storage. The oxidation of edible
3,4-dihydroxyphenyl acetic acid present in olive mill wastewater oil produces off-flavor compounds and decreases oil quality.
on the oxidation of olive and husk refined oils. Chlorogenic acid Free fatty acids, mono- and diacylglycerols, metals, chlorophylls,
and caffeic acid are the principal phenols found in sunflower oil carotenoids, tocopherols, phospholipids, temperature, light, oxy-
(Leonardis and others 2003). Osborne and Akoh (2003) reported gen, oil processing methods, and fatty acid composition affect
prooxidant effects of polar phenolic acids such as quercetin and the oxidative stability of edible oil. To minimize the oxidation of
gallic acid on a canola oil and caprylic acid structured lipid in edible oil during processing and storage, it is recommended to
the presence of iron at pH 3.0, due to an increased ability to decrease temperature, exclude light and oxygen, remove metals
reduce iron. and oxidized compounds, and use appropriate concentrations of
antioxidants such as tocopherols and phenolic compounds.
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