International Biodeterioration& Biodegradation(1994)345 354

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Degradation of the Lauric Acid Oils*

Judith L. K i n d e r l e r e r
Food Research Centre, Sheffield Hallam University, Sheffield S1 IWB, UK

(Received 14 September 1994; accepted 8 November 1994)

ABSTRACT

The composition, properties, uses and degradation of the lauric acid oils
have been discussed. Coconut and palm kernel oil contain approximately
40% medium chain f a t t y acids (C6.'0-C12:0). The medium chain f'atty
acids in these oils are readily degraded by .filamentous .fungi belonging to
the following genera, Penicillium, Aspergillus, C l a d o s p o r i u m , F u s a r i u m ,
T r i c h d e r m a and M o n a s c u s to give the methyl ketone one carbon atom less.
This type of spoilage has been described as ketonic rancidity.
Ketonic rancidity caused by Penicillium c r u s t o s u m can be controlled by
the total absence o f fungal spores, a temperature less than 4°C, water
activity less than 0.91; the addition of sorbic acid at lO00mg/kg or by the
absence o f oxygen. Coconut oil is a better substrate for ketonic rancidity
than palm kernel oil due to the higher concentration of medium chain f a t t y
acids in the former.

INTRODUCTION

The lauric acid oils are oils in which the triacylglycerols have a high
concentration of lauric acid (C12:0) and myristic acid (C14:0). The two
principal lauric acid oils of commerce are coconut (CNO) and palm kernel
(PKO). These oils are produced in the tropical regions of South East Asia
and Africa. Coconut oil is produced from the endosperm of the nut of the
coconut Cocos nucifera and palm kernel oil from the endosperm of the oil

*Presented at the Spring 1993 meeting of the Biodeterioration Society in Stratford-upon-

Avon, UK, organised by Mr Roy Sowden of Biomet Laboratories Ltd.

345
346 J. L. Kinderlerer

palm fruit E l a e i s g u i n e e n s i s . Both plants are members of the Palmae. In

this paper, the composition, properties, uses and degradation of the lauric
acid oils will be discussed.

COMPOSITION AND PROPERTIES

The fatty acid composition of the lauric acid oils is given in Table 1. Coco-
nut oil has a higher concentration of medium chain fatty acids (C6:0-
C12:0) than palm kernel. With any natural commodity, the chemical
composition will vary with cultivar, geographic region and year of harvest.
It is possible that, in the future, the lauric acid oils will be produced from
temperate crops such as rape seed as a result of genetic seed engineering.
Both oils contain a low concentration of unsaturated fatty acids. This is
reflected in the low iodine values, 8.5 g iodine per 100 g for coconut oil and
18 g iodine per 100 g oil for palm kernel oil, respectively (Pantzaris, 1986).
Two properties of the lauric acid oils are important. Firstly, they have a
sharp melting point, below body temperature (25-27cC). Secondly, a low
iodine value which makes these oils relatively resistant to oxidative rancid-
ity. These properties mean that the lauric acid oils are widely used as a raw
materials in the food industry and as a feedstock for oleochemicals.

I N D U S T R I A L USES O F T H E L A U R I C A C I D OILS

In the food industry the lauric acid oils are used in the manufacture of
synthetic creams and whipped toppings, in filled milks and in coffee
whiteners, and as a replacement for milk-fat in non-dairy ice cream. In

TABLE I
Fatty Acid Composition of Coconut and Palm Kernel Oil (g per 100 g oil")
Fatty acid Coconut oil Palm kernel oil
Caproic 6:0 0.5
Caprylic 8:0 7.7 3.1
Capric 10:0 5.9 3.2
Lauric 12:0 46-3 38.7
Myristic 14:0 15.6 14-6
Palmitic 16:0 8.3 7.7
Stearic 18:0 3. l 2.0
Oleic 18:1 5.7 12-3
Linoleic 18:2 1-8 2-3
"Kinderlerer (1992).
 Degradation ~1"the laurie acid oils 347

addition these oils are used as confectionery fats in toffees, cocoa butter
substitutes, and as an enrobing fat for ice cream. They are used in cooking
as a frying oil, as a fat in margarine and as an ingredient in biscuits, both
in the dough and as the fat in the filling cream. More palm kernel oil is
used by the food industry than coconut oil.
In the oleochemicals industry the lauric acid oils are used in the
production of ionic (soap) and non-ionic (alcohol ethoxylate) detergents.
They are used as a feedstock for the manufacture of quaternary ammo-
nium compounds which are incorporated into fabric softeners and hair
conditioners. They are used as a starting material for the manufacture of
the following: emulsifiers, glycerol monostearate, diacetyl tartaric esters of
monoglycerides, sorbitan esters (the Spans), polyoxyethylene sorbitan
esters (the Tweens) and lastly in the production of glycerol. More coconut
oil is used by the olechemical industry than palm kernel oil.
The figures for the total value o f imports of the lauric acid oils into the U.K.
for the years 1983-1988 are given in Table 2. These figures account for
approximately 10% (by volume) of the vegetable oil market. The situation is
somewhat different for the United States of America (Table 3). More coconut
oil is imported into the USA than palm kernel oil, unlike the U K where the
reverse is true. These differences may reflect the traditional suppliers,
Malaysia in the case of the UK, and the Philippines in the case of the USA.
Obviously it is important that commodities of this type are stable.

D E G R A D A T I O N O F T H E L A U R I C A C I D OILS

Microbial growth on commodities can result in a significant loss of

biological material with a concomitant production of microbial metabo-

TABLE2
UK I m p o r t s o f L a u r i c A c i d O i l s ~ r 1 9 8 3 1988"

Year P K O vahw C N O value

( $ ( U S ) x 106 ) ( $ ( U S ) x 106 )

1983 32.7 26.7

1984 38.4 45-7
1985 42.9 34-9
1986 25.9 18.6
1987 28-7 23-3
1988 26.4
Average 32.5 29.8

"Commodity Yearbook, 1990.

348 J. L. Kinderlerer

TABLE 3
United States Imports of Lauric Acid Oils for 1983 1988"

Year P K O value C N O value

( $ ( U S ) x 106 ) ( $ ( U S ) x 106 )

1983 61.1 224.4

1984 93.5 344.3
1985 91.2 279,4
1986 62-7 173,7
1987 72.9 187,0
1988 110.0
Average 81.9 241,7

"Commodity Yearbook, 1990.

lites which contribute to off-odours and off-tastes. During microbial

spoilage, food commodities can become overheated and discoloured.
These changes result in a significant financial loss. All tropical food
products have a significant mycoflora due to methods of production.
Fungi are a major cause of spoilage in stored commodities and probably
rank second to insects as a cause of deterioration and loss (Pitt & Hock-
ing, 1985).
Rancidity is a subjective term which is used to describe the unpalatable
odour of edible fats and oils following oxidative or hydrolytic changes.
These processes can occur in raw foodstuffs, refined or edible oils and
processed foods containing edible oils. Traditionally two types of rancidity
have been described. The first is hydrolytic rancidity, where triacylglycer-
ols are hydrolysed to give free fatty acids. This reaction is catalysed by
lipase enzymes (triacylglycerol acyl hydrolase EC.3.1,1.3) which are wide-
spread in the fungal kingdom. The second is oxidative rancidity which
involves the oxidation of mono-, di- and polyunsaturated fatty acids to
give hydroperoxides. This reaction involves a classic free radical mechan-
ism. The fatty acid hydroperoxides are cleaved adjacent to the double
bond to give a variety of end-products. Fat hydroperoxides are tasteless
and odourless, but their decomposition products have a great impact on
flavour. Both free radical mechanisms and reactions catalysed by lipoxy-
genase (linoleate:oxygen oxidoreductase EC.I.13.11.12) enzymes have
been implicated. Lipoxygenase enzymes are widespread in the plant and
fungal kingdoms. A third type of rancidity has been described. This
rancidity involves the fungal conversion of medium chain fatty acids (C6-
C~2) to the methyl ketone one carbon atom less (Kinderlerer, 1992). The
inter-relationships between the different types of rancidity are given in
Fig. 1.
 Degradation of the lauric acid oils 349

TRIACYLGLYCEROLS
l.Oxia-tion / ysis
(photoor¢ ~

TRIACYLGLYCEROLS FREE FATTY ACIDS

HYDROPEROXlDES + GLYCEROL
LONG C H A I N MEDIUMCHAIN
. / ~ \ \ ~ 3.Metabotism
2.H y d r o ~ t.O×idalion \\ ~by moulds
(photo or ¢nz)'mlc)~

/
\ \
\
FREE FATTY ACID HYDROPEROXIDES METHYL KETONES
& SECONDARYALCOHOLS

SECONDARY & TERTIARY PRODUCTS

Fig. 1. General reaction scheme to show the interrelationships between oxidative (l)+
hydrolytic (2), and (3) ketonic rancidity. Adapted from Kinderlerer (1992).

Relatively little research has been undertaken on ketonic rancidity in

the lauric acid oils. The ability of fungi to convert medium-chain length
fatty acids or triacylglycerols containing these acids to the methyl ketone
one carbon atom less has been known for a long time. Early work prior to
1948 has been reviewed by Foster in his classic work on the chemical
activities of fungi (Foster, 1949).
Three lines of research have been undertaken on the bioconversion of
medium-chain length fatty acids. The first involved studying rancidity and
spoilage in oil seeds such as coconut and palm kernel or in products
containing coconut or palm kernel oil. A variety of different fungal species
have been used in this work (Stokoe, 1928; Kinderlerer & Kellard, 1984;
Kellard et al., 1985; Kinderlerer, 1987; Yagi et al., 1989; Kinderlerer &
Hatton, 1991). The second involves a study of flavour development in blue
and white mould-ripened cheese. Two Penicillium species (P. roquefortii
and P. camembertii have been used in this work. The following reviews
explore aspects of flavour development in mould-ripened cheeses (Hawke,
1966; Kinsella & Hwang, 1976; Lenoir, 1984). Lastly the bioconversion of
free medium chain fatty acids by fungi to give fine flavour chemicals.
Aspects of this have been reviewed by Kinderlerer (1993). Six fungal
350 J. L. Kinderlerer

genera Aspergillus, Penicillium and their corresponding teleomorphic

genera, Trichoderma, Cladosporium, Fusarium and Monascus have been
used in this work.
Conversion of triacylglycerols to methyl ketones involves two reactions.
The first reaction involves lipolysis of triacylglycerols containing medium-
chain length fatty acids to release free fatty acids. Considerable evidence
exists that free fatty acids are relatively toxic (Kinderlerer, 1993). High
concentrations of free Patty acids (FFAs) are unusual in living tissues.
Their occurrence is usually due to the action of endogenous lipase
enzymes after tissue damage has taken place. In stored palm kernels,
however, high concentrations of free fatty acids can result from fungal
growth (Dart & Dede, 1987). The second reaction involves the conversion
of free medium chain fatty acids to the methyl ketone one carbon atom
less. Thus lauric acid (C12:0) is converted to 2-undecanone (C11:0), capric
acid (C10:0) is converted to 2-nonanone (C,~) and caprylic acid (C8:0) is
converted to 2-heptanone (Cv).
Most workers have demonstrated a 1:1 conversion of free medium-
chain length fatty acid to the methyl ketone one carbon atom less. In some
circumstances it appears that more than one methyl ketone can be
produced from a single fatty acid. Okumura and Kinsella (1984) found
that 2-undecanone, 2-nonanone and 2-heptanone were produced from
oleic acid (18:2) and 2-nonanone and 2-undecanone from lauric acid
(C12:0) by Penicillium camemhertii in a synthetic milk medium. King and
Clegg (1979) found a similar situation with Penicillium roqu~}lf~rtii.

CONTROL OF KETONIC RANCIDITY

Most preservation factors operate through the inhibition or slowing of

microbial growth. Both extrinsic factors related to the environment and
intrinsic factors related to the food are used (Mossel, 1983). Modern
methods of food preservation would favour using a number of extrinsic
and intrinsic factors together rather than one alone (Gould et al., 1983).
Both conidia (spores) and fungal mycelium can convert acylated
medium chain fatty acids in simple and mixed triacylglycerols to give the
methyl ketone one carbon atom less than the parent fatty acid (Hatton &
Kinderlerer, 1991; Kinderlerer & Hatton; 1991). In a study on methods
for controlling ketonic rancidity in the lauric acid oils, Kinderlerer &
Hatton (1991), used a common spoilage Peniciilium, Penicillium crusto-
sum. This species has been isolated from many foodstuffs including nuts,
meat and fruit (Frisvad, 1988). Ketonic rancidity can be controlled by
temperature. Figure 2 demonstrates that no growth or ketone formation
 D e g r a d a t i o n o f the lauric a c i d oils 351

80C
IM1281919 ~,~
//-,.,~

~60C
t/ \
v
•

•,a200

0 --+ 1-'6 1'5 ab 2'5 3b 3s - 40

Incubation Temperature/°C
Fig. 2. The effect of temperature on ketone production by two strains of Penieillium crusto-
sum grown on coconut and palm kernel oil in liquid suspensionculture. Kinderlerer & Hatton
(1991), reprinted with kind permission of Blackwell'sScientificPublishers, Oxford, UK.

took place at less than 4°C nor at temperatures greater than 37~'C after
72h growth of two strains of P e n i c i l l i u m c r u s t o s u m on coconut oil and
palm kernel oil. Neither growth nor ketone production took place at water
activities (aw) of less than 0.91, where sodium chloride ( 1 5 % m / v ) was
used to control water activity (Fig. 3). Ketone production was not
observed in the absence of oxygen. In all experiments the final pH tended
to pH 6-5 7.0 irrespective of the initial pH (Hatton & Kinderlerer, 1991),
thus the pH did not appear to be useful in controlling ketone production,
due to the ability of the fungus to alter its environment. The preservative,
sorbic acid at 1000mg/kg inhibited ketone production (Fig. 4) although
some sorbic acid was converted to pentadiene (Kinderlerer & Hatton,
1990). The fatty acid composition of the oil is important. Coconut oil
contains more medium chain fatty acids than palm kernel oil (Table 1).
This is reflected in the greater yield of methyl ketones (Fig. 5).

CONCLUSIONS

Coconut and palm kernel oil can undergo an unusual type of r a n c i d i t y - -

ketonic rancidity. Ketonic rancidity is caused by conversion of medium
352 J. L. Kinderlerer

Boo ~'--=- !
leo : IMI281919 /
,.C I ..e3... / E
.~0 ICO: IM1342844
~
/// ..,"
.......

600 b--~-,. ..
I PKO : IM1342844
~ - +j2~t.....-+..~

~)

.~
400"

.
..........
..+..+."
. ........

/
~
f. .!
..+,+."

b.~ +.,.,+'"

,,~ 200- ..........

O .-""+" ,,/"
[.~ ,.....' ,++++"~/,
. .," ............................ +"~/

- A

0.91 0.92 0,93 0.94 095 0.96 0,97 0.98

Water Activity (aw )

Fig. 3. The effect of water activity on ketone production by two strains of Penicillium
c r u s t o s u m grown on coconut and palm kernel oil in liquid suspension culture. Kinderlerer
& Hatton (1991), reprinted with kind permission of Blackwell's Scientific Publishers,
Oxford, UK.

8001 ~'-0: IM1291919

2t~ li\
I~\
.~
.... ~'
I--A-
I pKO: IM1281919
~J // "k I -..-~-.
.~ 6oo-mi\

J+ .......... ,...

o 5 6 g 1'o 13 1~ 1'6 +'8 ~d

Sorbic Acid / (mmol/liLre)

Fig. 4. The effect of sorbic acid on ketone production by two strains of Penicillium crus-
t o s u m grown on coconut and palm kernel oil in liquid suspension culture. Kinderlerer &
Hatton (1991), reprinted with kind permission of Bl'ackwell's Scientific Publishers, Oxford,
UK.
 Degradation t~[the laurie acid oils 353

Ketone yield from 1 g substrate at

25°C

.=
[ ] PKO
5 ITrace • CNO
('~ , I I t

0 1O0 200 300 400 500 600

Concentration Ketone (micromole/g)

Fig. 5. The effect of substrate on ketone production at 25"C by Penicillium crustosum.

Data derived from Kinderlerer & Hatton (1991).

chain fatty acids or triacylglycerols containing medium chain fatty acids,

by filamentous fungi belonging to the following genera, Penicillium,
Aspergillus, Cladosporium, Fusarium, Trichoderma and Monascus, to the
methyl ketone one carbon atom less than the parent fatty acid. Ketonic
rancidity has been described as an oxidative variant of the hydrolytic type
of rancidity.

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Dart, R. K. & Dede, E. B. (1987). The free fatty acids of palm kernel oil
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Frisvad, J. C. (1988). Fungal species and their production of mycotoxins. In Intro-
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