Palm oil carotenoids

Choo Yuen May

Abstract in the world’s oil supply was 10.1%, and it is expected

that by the year 2000 palm oil will be as important as
Crude palm oil is the richest natural plant source of soy-bean oil, contributing 21.1% of the world’s total oils
carotenoids in terms of retinol (provitamin A) equivalent. and fats [3].
This article reports on
» the carotenoids found in palm oil, its fractions,
The composition of palm oil
byproducts, and derivatives from the Elaeis guineensis
and E. oleifera palms, including their hybrids and a Palm oil consists mainly of glycerides made up of a
back-cross, as well as the carotenoids of pressed palm range of fatty acids. Triglycerides constitute the major
fibres, second-pressed oil, palm leaves, and palm- component, with small proportions of diglycerides and
derived alkyl esters; monoglycerides. Palm oil also contains other minor
» two novel procedures for preparing highly concentrated constituents, such as free fatty acids and non-glyceride
sources of carotenoids (>80,000 ppm), by recovery by components. This composition determines the oil’s
palm alkyl esters, and by retention and concentration chemical and physical characteristics.
in deacidified and deodorized red palm oil; The fatty acid composition of crude Malaysian
» the carotenoid content and profiles of the above palm oil is given in table 1 [4]. About 50% of the fatty
sources obtained by high-performance liquid acids are saturated, 40% mono-unsaturated, and 10%
chromatography; and polyunsaturated. It contains adequate amounts of n-6, 18:2
essential fatty acid. In its content of monounsaturated 18:1
» nutritional effects of palm oil carotenoids and their
acid, palm oil is similar to olive oil, which is as effective
potential applications for health promotion and
as the more polyunsaturated oils in reducing blood
disease prevention.
cholesterol and the risk of coronary heart disease [5].
Crude palm oil contains approximately 1% of minor
Introduction components: carotenoids, vitamin E (tocopherols
Palm oil is derived from the mesocarp of the oil palm and tocotrienols), sterols, phospholipids, glycolipids,
fruit. Its physical and chemical properties are quite terpenic and aliphatic hydrocarbons, and other trace
distinct from those of oil obtained from the kernel inside impurities [6] (table 2). The most important are
the nut. The oil palm Elaeis guineensis originated in West carotenoids and vitamin E, both of which possess
Africa. The current planting material in Malaysia is a important physiological properties.
cross of the dura and pisifera varieties known as tenera, The iodine value is between 50 and 56.
all belonging to the E. guineensis species.
TABLE 1. Fatty acid composition of Malaysian palm oil
The oil palm is the most prolific oil-producing plant;
the national average oil yield in Malaysia is 3.8 tons per % of total acids
hectare per year, with 11% of that quantity being palm Acid Range Mean
kernel oil, a co-product. The production of palm oil
12:0 0.1-1.0 0.2
in the world for 1991 was 11.41 million tons, of which
Malaysia (53.8%) and Indonesia (23.3%) were the two 14:0 0.9-1.5 1.1
major producers [1]. Both countries are expected to 16:0 41.8-46.8 44.0
increase production, with Malaysia estimated to reach 16:1 0.1-0.3 0.1
8.38 million tons and Indonesia more than 4.48 million 18:0 4.2-5.1 4.5
tons by 1995 [2]. In 1984 the market share of palm oil

Food and Nutrition Bulletin, vol. 15, no. 2 © 1994, The United Nations University. 1
2 Palm oil carotenoids

18:1 37.3-40.8 39.2 TABLE 3. Retinol equivalents (RE) of red palm oil
compared with other foods
18:2 9,1-11.0 10.1
18:3 0.0-0.6 0.4 Relative qualitya
REb
20:0 0.2-0.7 0.4 >RPO < RPO
Source: Ref.4. Fish liver oils (preformed retinol)
Halibut 900,000 30
TABLE 2. Minor components of crude palm oil
Shark 180,000 6
ppm Cod 18,000 1.7
Carotenoids [7] 500-700 Fruits and vegetables (carotene derived)
Tocopherol and tocotrienols [4, 8] 600-1,000 Red palm oil 30,000
Sterols [9] 326-527 Carrots 2,000 15
Phospholipids [10,11] 5-130 a Leafy vegetables 685 44
Triterpene alcohol [12, 13] 40-80 a Apricots 250 120
Tomatoes 100 300
Methyl sterols [13] 40-80
Bananas 30 1,000
Squalene [14, 15] 200-500
Orange juice 8 3,750
Aliphatic alcohols [7] 100-200
Source: Ref. 24.
Aliphatic hydrocarbon [14, 15] 50 a. Per 100 B edible portion (µg).
b. Times greater or less than red palm oil (RPO).
a. Estimated

Carotenoids Sources of palm carotenoids

The carotenoids, whose name is derived from the fact Palm species and hybrids
that they constitute the major pigment in the carrot
Although palm forests are found in West Africa, oil palms
root, Daucus carota, are undoubtedly among the most
are actually cultivated in East Africa, South America,
widespread and important pigments in living organisms.
Malaysia, and Java [25-27]. Palm oil from the Far East and
They are present in numerous vegetable Oils, including
from Zaire contains 500-800 ppm of carotenes, whereas
yellow maize (corn) oil, groundnut oil, soy-bean oil,
that from Côte d’Ivoire and especially Benin contains
rapeseed oil, linseed oil, olive oil, barley oil, sunflower-
1,000-1,600 ppm, but the oil yield is less [25, 26, 28]. Oil
seed oil, and cotton-seed oil [16-22]. The concentration
from the tenera variety that is widely planted in Malaysia
of carotenoids in these vegetable oils is generally low, less
has a carotenoid content of about 500-700 ppm [6].
than 100 ppm.
Other oil palm species, such as Elaeis oleifera (or E.
Of the vegetable oils that are widely consumed,
melanococca), a South American palm, have been found
palm oil contains the highest known concentration
to contain a higher concentration of carotenes (4,600
of agriculturally derived carotenoids [23]. In fact,
ppm) [29]. Hybrids of E oleifera x E. guineensis also
crude palm oil is the world’s richest natural plant
produce oils with high concentrations of carotenoids.
source of carotenes in terms of retinol (provitamin A)
The following values have been found for the total
equivalent. It contains about 15 to 300 times as many
carotenoid content of oil from different species, varieties,
retinol equivalents as carrots, leafy green vegetables,
and hybrids: E. guineensis var. pisifera (P), 428 ppm; var.
and tomatoes, which are considered to have significant
dura (D), 997 ppm; E. oleifera (O), 4,592 ppm; the hybrid
quantities of provitamin A activity [24] (table 3). It is
O x P. 1,430 ppm; O x D, 2,324 ppm; and the back-cross
these carotenoids that impart an orangey-red colour to
OD x P, 896 ppm (table 4). E. oleifera oil has the highest
crude palm oil.
carotenoid content and E. guineensis oil the lowest, with
Currently, interest is focusing on the nutritional the hybrids and the back-cross having intermediate
aspects of carotenoids. Since they are likely to grow in concentrations. It can be seen from the table that the
importance and value, their recovery from palm oil and species and hybrids are comparable with regard to the
its by-products is important. major components, α- and ß-carotene.
Choo Yuen May 3

TABLE 4. Carotenoid composition (percentages) of palm oil from different species and sources

E. guineensis E Hybrids Back Second Red

Pressed Carotenoid
pisifera dura oleifera cross OD pressed palm
tenera O x P O x D fibre oil concentrate
(P) (D) (O) xP oil oil
Phytoene 1.27 1.68 2.49 1.12 1.83 2.45 1.30 11.87 6.50 1.5 2.0
Phytofluene 0.06 0.90 1.24 tr tr 0.15 tr 0.40 1.63 0.3 1.2
Cis-β -carotene 0.68 0.10 0.15 0.48 0.38 0.55 0.42 0.49 0.28 0.9 0.8
β -carotene 56.02 54.39 56.02 54.08 60.53 56.42 51.64 30.95 31.10 49.9 47.4
α -carotenes 35.16 33.11 24.35 40.38 32.78 36.40 36.50 19.45 20.68 33.3 37.0
Cis-α-carotene 2 49 1.64 0.86 2.30 1.37 1.38 2.29 1 77 1.70 5.5 6. 9
ζ -carotene a
0.69 1.12 2.31 0.36 1.13 0.70 0.36 7.56 4.62 1.7 1.3
δ -carotene 0.83 0.27 2.00 0.09 0.24 0.22 0.14 6.94 2.13 0.6 0.6
γ -carotene b
0 33 0.48 1.16 0.08 0.23 0.26 0.1 9 2.70 2.48 1.3 0.5
Neurosporeneb 0.29 0.63 0.77 0.04 0.23 0.08 0.08 3.38 1.88 0.1 tr
β -zeacarotene 0.74 0.97 0.56 0.57 1.03 0.96 1.53 0.37 0.58 1.3 0.5
α -zeacarotene 0.23 0.21 0.30 0.43 0.35 0.40 0.52 tr 0.15 0.4 0.3
Lycopenec 1.30 4.50 7.81 0.07 0.05 0.04 0.02 14.13 26.45 3.4 1.5
Total (pmp) 673 428 997 4,592 1,430 2,324 896 5,162 2,510 80,560 545
tr = trace.
a. With two cis isomers.
b. With one as isomer.
c. With three cis isomers.

Extraction methods and by-products
Carotenoids from commercial crude palm oil are
concentrated during extraction and fractionation. A
new system of extraction based on a double-pressing
technique has been implemented recently by several
mills in Malaysia [30]. The oil from the second pressing
has a higher concentration of carotenoids. This can be
attributed to the fact that the first pressing is carried out
at lower pressure to avoid cracking the nuts, and relatively
more oil is extracted compared with carotenoids. After
removal of the nuts, the fibre is subjected to higher
pressure, and more carotenoids are extracted from the
mesocarp together with some residual oil left by the
first pressing. The advantages of double pressing over
the conventional single pressing are a lower loss of oil
in fibre, a higher kernel extraction rate, less wear on the
screw worm and cages, and reduction of contamination
of crude palm oil by kernel oil.
Carotenoids may also be concentrated in an
industrial process called fractionation [31, 32]. Palm
oil is a semi-solid fat at ordinary room temperature due
to the presence of solid, fully saturated triglycerides
and the high-melting-point mono-oleoglycerides and
monolinologlycerides dispersed throughout the liquid
dioleoglycerides and other more unsaturated glycerides.
Fractionation extends the uses of palm oil; the products
obtained are liquid oil (olein, 70%-80%) and solid
fat (stearin, 20%-30%). The liquid oil is designated
for cooking, and the solid fraction can be used as a
component of harder frying fats, for the production of
margarine, vanaspati, and as a cocoa butter substitute.
The carotenoid content in the palm olein (lower-melting-
point) fraction is enriched 10%-20%, as shown in table 5.
TABLE 5. Carotenoid content of various palm oil fractions
ppm
Crude palm oil 630-700
Crude palm olein 680-760
Crude palm stearin 380-540
Residual oil from fibre 4,000-6,000
Second-pressed oil 1,800-2,400
Total carotenoids estimated at 446 nm.
A carotenoid-rich oil can be obtained from the
pressed fibre of the oil palm fruit [33, 34] which normally
is burnt as fuel in palm oil mills. The pressed fibre
contains about 5%-6% of residual oil, and the extracted
oil contains 4,000-6,000 ppm of carotenes, six times the
concentration in crude palm oil. The carotenoid content
of the residual oil in the pressed fibre from hybrid oil
palms is even higher, 6,0007,000 ppm [33]
Oil palm leaves also contain carotenoids, at
1,900 ppm [35].
4 Palm oil carotenoids

Carotenoid profiles
The total carotenoids in palm oil are usually determined by
ultraviolet-visible spectroscopy at 446 nanometres as ppm of
ß-carotene. However, because of their complex composition,
various analytical methods have been employed to determine
their profile. Earlier studies used column chromatography
with different absorbents [36-38]. More recently,
reverse-phase high-performance liquid chromatography
(HPLC) has proved to have several advantages for separating
the carotenoids in the oil [29, 39, 40]. By this method, the
major carotenoids are α - and ß-carotenes, which constitute
about 80%-90% of the total carotenoid content (table 4),
The others are γ-carotene, phytofluene, phytoene, lycopene,
neurosporene, ζ-carotene, α-zeacarotene, ß-zeacarotene,
δ-carotene, and some xanthophylls such as zeaxanthin,
α-carotene-5,8-epoxide, and ß-carotene-5,6-epoxide [29,
36, 40] (fig. 1).

FIG. 1. HPLC chromatograms of palm oil carotenoids run at different wavelengths. (1) Presumed xanthophylls; (2) lyco-
pene-bans and three cis isomers (a denotes cis isomers); (3) and cis isomers; a -zeacarotene; (4) ß-zeacarotene; (5) neuros-
porene-trans (6) -carotene; (10) a d -carotene; (7) g -carotene-bans and as isomers; (8) z -carotene-bans and two cis isomers;
(9) cis-a -carotene; (11) ß-carotene; (12) phytofluene; (13) cis-ß-carotene; (14) phytoene.
The carotenoid profile for the oil extracted from [44-47], selective solvent extraction [48], molecular
fibre has a slightly different chemical composition. distillation [49], and transesterification followed by
The major carotenoids are still a- and b-carotene, but distillation of esters [5053]. Most of the methods are
they constitute only about 50% of the total. Phytoene, difficult to perform, inefficient, or costly.
lycopene, g-carotene, and d-carotene are present at Recently, volatile methyl esters have been produced
higher concentrations [33]. The carotenoid profile of the on a large scale from palm oil for oleochemical or
second-pressed oil is similar to that of the fibre oil. diesel substitution [54-59]. This mild reaction converts
the palm oil triglycerides to esters, leaving the valuable
New methods for the recovery and minor components unchanged [57, 60] and allowing for
concentration of carotenoids recovery of the carotenoids. The carotenoids have been
concentrated or recovered from the volatile esters by
In addition to the work on carotenoid-rich palm oils various methods, such as adsorption [60], solvent-solvent
described above, studies are being carried out to obtain an extraction [52], and distillation [61].
oil with high concentrations of palm-based carotenoids
One method involves the selective adsorption of
for nutrition and health applications. Numerous
carotenoids obtained from reverse-phase adsorption
extraction methods have been developed, including
material [60], with the esters of higher polarity being
saponification [41, 42], urea processing [43], adsorption
first eluted out from the column. A recovery rate of
Choo Yuen May
greater than 90% can be achieved, with a carotenoid
concentration of 8,000-9,000 ppm (table 6), both of
which are higher than those obtained by other methods.
The column can be regenerated and reused more than
fifty times without any loss of activity.
TABLE 6. Results of various methods of carotenoid
recovery and concentration
Carotenoid
content Recovery rate (%)
(ppm)a
Through methyl ester
carbon-18 reverse
8,000-9,000 > 90
phase adsorption
carbon adsorption 5,000-7,000 < 50
vacuum distillation >20,784 <46
molecular distillation > 80,000 > 80
From crude palm oil
activated carbon
3,700-5,600 < 80
adsorption
molecular distillation 1,290-1,990 - α-carotene, γ -carotene, and ß-zeacarotene, which are
Source: Ref. 33.
a. Total carotenoids estimated at 446 nm.
Another method involves distillation of the volatile
alkyl ester using normal vacuum or molecular distillation
[61, 62]. Residual concentrates of 2.0% carotenoids
can be achieved by normal vacuum distillation, with
recovery of about 46%. These residual carotenoids can be
further concentrated to 8.4% by normal-phase column
chromatography, and at the same time other separated
minor components are being concentrated [61]. Total
tocopherol and tocotrienol content is increased to
37% and sterols to 32%, with recovery of 65% and 82%
respectively, based on the crude methyl ester. An oil with
a final carotenoid concentration of 80,000 ppm has been
achieved through molecular distillation. A carotene with
a concentration of 72% has been obtained through both
molecular distillation and column adsorption [63].
In the current technology of physical refining,
the carotenoids in crude palm oil undergo thermal
decomposition during deodorization-deacidification
(240°C-270°C). As a result, the processed product,
normally known as refined, bleached, and deodorized
(RBD) palm oil, contains no carotenoids at all. In view
of this, a process to prepare carotene-enriched palm
oil has been developed [64] that involves degumming
of the oil with phosphoric acid, followed by treatment
with bleaching earth. The treated oil is then subjected
to deodorization and deacidification at a mild reaction
temperature to remove odoriferous materials as well
as free fatty acids. More than 80% of the carotenoids
5
originally present in the crude palm oil are retained.
Analysis by HPLC shows that the profile of the carotenoids
is similar to that of the starting material, again indicating
that carotenoids are not destroyed during the process.
The quality of this red palm oil is good. According to
a sensory panel, it is suitable for food preparation. This
process has been demonstrated successfully on a pilot-
plant scale, with 80% of the carotenoids and vitamin E
originally present in the crude palm oil being retained.
It should be noted that in this process the triglycerides
remain intact, unlike that described above in which all
the triglycerides are converted to alkyl esters. However,
the former process can yield a higher concentration of
carotenoids after the alkyl esters are removed.
Palm oil carotenoids in nutrition
Carotenes as provitamin A
Carotenes, in particular ß-carotene, have long been
known for their provitamin A activity, as they can
be transformed into vitamin A in vivo. In addition,
present in crude palm oil, have similar activity. The
vitamin A equivalents of α-, ß-, and γ -carotenes and
ß-zeacarotene are 0.9, 1.67, 0.75, and 0.42 respectively.
Crude palm oil has long been used by Africans as a
source of vitamin A. Elsewhere in the world, however,
it is not considered acceptable as a result of its content
of free fatty acids. On the other hand, RBD palm oil,
which is marketed for consumption worldwide, contains
practically no carotenoids, as they have been destroyed
during refining. As a result, the process mentioned
above [64] was developed to produce a deodorized and
deacidified red palm oil as a more widely acceptable
source of vitamin A.
Nutritional and toxicological studies
Carotenoids as antioxidants
ß-carotene has long been known to be an efficient
quencher of singlet oxygen and, as such, is an effective
antioxidant. α -carotene and lycopene are also effective
singlet oxygen quenchers, as demonstrated in a recent
study on singlet oxidation of lipids, cholesterol, and low-
density lipoprotein (author’s unpublished data, 1992). In
the presence of palm oil carotenoids, no oxidation products
increased. This area of work is important, as research
findings show that three micronutrients, ß-carotene and
vitamins E and C, have protective properties against
free radical damage that is believed to be responsible for
numerous degenerative diseases such as atherosclerosis,
arthritis, and carcinogenesis. In fact, α - and ß-carotenes,
lycopene, and phytoene have anticancer properties,
6
with a-carotene ten times as potent as ß-carotene as an
anticancer agent [65]. ß-carotene has also been reported
to have anti-atherosclerotic effects [66].
A study was performed to determine the tissue
distribution of carotenoids in palm oil and to correlate
their accumulation with protection against oxidative
stress in rats [67]. After two weeks of feeding, ß-carotene
in the liver increased from 7.3 to 30 ng per gram of
wet tissue. After ten weeks, α -carotene and lycopene
were 74 and 49 ng per gram of wet tissue respectively.
The ß-carotene content in heart and hind-limb skeletal
muscles increased after ten weeks to 17 and 6 ng per gram
of wet tissue respectively. No carotenoids were detected
in the brain, adipose tissue, and skin during the period of
feeding. After in vitro induction of lipid peroxidation in
liver homogenates by an azo-initiator of peroxyl radicals,
an inverse correlation between tissue carotenoid level
and accumulation of lipid peroxidation products was
observed: α -carotene>lycopene > ß-carotene.
Toxicology study
The carotenoid concentrate prepared by molecular
distillation [62] was subjected to a toxicological study
(H. T. Khor, D. Tan, Y. M. Choo, 1992). Four groups
of Sprague-Dawley rats (12 rats per group) were fed a
semi-purified diet supplement with 0.2% palm oil-based
carotenoid concentrate (20,000 ppm), methyl ester, ethyl
ester, and a control diet for 16 weeks. Histopathological
examinations showed the major organs such as the heart,
lungs, adrenals, kidneys, liver, and spleen to be normal
for all groups. No extensive or significant amount of fat
was deposited in the heart and coronary vessels, and the
aorta was normal in all groups. It was concluded that
the carotenoid concentrate and other diets do not have
toxicological effects on the major organs of male rats.
The carotenoid concentrate [62] has also undergone
studies of oral cancer in animals (K. H. Ng, personal
communication, 1992).
The Food and Agriculture Organization has recently
accepted and included palm oil carotenoids as a
permissible food colourant.
Forms for ingestion
Carotenoid concentrate obtained by molecular
distillation has been prepared in three different physical
forms for potential nutrition and health applications [68]:
capsules (both soft and hard), powder, and emulsion.
The powder can be made into tablets or placed in hard
capsules. Preliminary results of stability tests show that
the powdered carotenoids were not as stable as the
concentrate in soft capsules during storage for one year
at ambient temperature (28°C-32°C). This could be due
Palm oil carotenoids
to greater exposure of the powder to light and air, leading
to increased oxidation or degradation of the carotenoids.
However, the carotenoid content of the powder declined
only slightly (<4%) when it was kept in a freezer at -50°C
for one year.
Conclusion
Crude palm oil is the richest natural plant source of
carotenoids in terms of retinol equivalent. Analysis
by HPLC shows that these carotenoids are rich in α
-and ß-carotenes. Besides their provitamin A activity,
carotenoids are good singlet oxygen quenchers, which
leads to their role in minimizing or preventing photo-
oxidation and thus diseases in which free radicals are
implicated.
Two novel methods are effective in producing
carotenoid-rich products such as carotenoid
concentrate with concentrations greater than 80,000
ppm, and deacidified and deodorized red palm oil. This
concentrate has been tested for toxicological effects and
found to be safe.
In view of the importance of carotenoids for health
and disease prevention, methods have been developed
to present it in different forms for pharmaceutical
applications.
Oil palm (Elaeis guineensis and E. oleifera) products
are good and viable sources of carotenoids.
Acknowledgements
The author thanks the Director-General of PORIM
for permission to publish this paper. Thanks are also
extended to the Malaysian Palm Oil Promotion Council
for its invitation to contribute to the present collection
of studies.
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