J Sci Food Agric 1997, 75, 281288

Crude Palm Oil Characteristics and Chlorophyll

Content
Y A Tan,1* C L Chong1 and K S Low2
1 Palm Oil Research Institute of Malaysia (PORIM), No 6, Persiaran Institusi, Bandar Baru Bangi, 43000
Kajang, Selangor Darul Ehsan, Malaysia
2 Laser and Opto-Electronics Laboratory, Institute of Advanced Studies, University of Malaya, Lembah
Pantai, 59100 Kuala Lumpur, Malaysia
(Received 17 June 1996 ; revised version received 6 January 1997 ; accepted 27 March 1997)

Abstract : The chlorophyll (CHL) content in palm oil extracted from oil palm
fruits, Elaeis guineensis, at various stages of ripeness was determined. It was
found that oils from ripe fruits of the same age contained dierent levels of CHL.
In addition it was noted that fruits from palms planted at the centre and those at
the edge of the eld seemed to ripen at dierent rates. Those at the centre of the
eld contained higher levels of CHL when compared with those of the same age
produced at the edge of the eld. This phenomenon could be due to topo-
graphical eects whereby the palms at the edge of the eld were exposed to much
more sunlight. This probably hastened the process of fruit ripening. A survey on
CHL levels in commercial CPO samples supplied by mills showed the presence
of CHL in all samples analysed. The range observed was between 250 and
1800 kg kg~1 with a mean value of 930 ^ 107 kg kg~1. This implied wide varia-
tions in the ripeness of palm fruits processed by the mills.

J Sci Food Agric 75, 281288 (1997)

No. of Figures : 4. No. of Tables : 2. No. of References : 20

Key words : quality, chlorophyll, ripeness, harvesting, oil extraction

INTRODUCTION on oxidative deterioration (Coe 1938 ; Endo et al 1984a

Crude palm oil (CPO) is extracted from the mesocarp of
the oil palm fruit, Elaeis guineensis. The natural orange
red colour of CPO is due to the presence of carotenoids
(500700 mg kg~1) in oil extracted from ripe palm
fruits. The other important group of pigments, though
present to a much lesser extent in CPO, are the green
chlorophylls (CHLs). These are the green pigments of
CHLa and CHLb as well as pheophytins (PHY) a and
b. During extraction of vegetable oils, a certain propor-
tion of CHLs is solubilised and remains in the extract
(Dahlen 1973). In CPO, the colour of CHLs is visually
masked by the higher levels of carotenoids.
CHLs are also photosensitisers. This group of chemi-
cal species absorbs light to activate or sensitise either
the unsaturated oils or molecular oxygen to induce
photosensitised oxidation. The adverse eects of CHLs
* To whom correspondence should be addressed.
281
( 1997 SCI. J Sci Food Agric 0022-5142/97/$17.50. Printed in Great Britain
c ; Kirisakis and Dugan 1985), hydrogenation (Abraham
and Deman 1963 ; Koritala 1975) and bleachability
(Dahlen 1973) of vegetable oils are well documented.
However, there is very little information on the levels of
CHLs in, and their eects on, CPO. A level of 827 ppb
was quoted by Strecker et al (1990) and Ikemefuna and
Adamson (1984) studied the changes in CHL content in
ripening palm fruits.
This paper reports the rst part of our investigation
which was on the determination of CHL content in oil
extracted from fruits of varying ripeness and the average
level of CHL in CPO extracted by palm oil mills.
MATERIALS AND METHODS
Oil samples
Commercial CPO was obtained from local mills. CPO
from palm fruits at various stages of maturity was
282
extracted from identied fruit bunches in palms located
at our PORIM/UKM Research Station. Crude palm oil
was extracted from all the fruits on a bunch.
Reagents/apparatus
Standard reagents and apparatus as required in the
method for the analyses outlined in the following sec-
tions were used.
Instruments
The instruments used were the Hitachi 150-20 UV
visible spectrophotometer, Hewlett Packard 5890 Series
II chromatograph and Rancimat 679 (Metrohm Ltd,
Herisau, Switzerland).
Analytical methods
The oil samples were analysed by methods as follows.
Free fatty acids (FFA) by AOCS Method Cc 5a-40
(AOCS 1992) ; oxidative status measuring peroxide
value (PV) by AOCS Cd 8-53 (AOCS 1992), absorbance
at 233 and 269 nm (A , A ) using PORIM Test
233 269
Method p 2.15 (PORIM 1990) which is a modied
version of IUPAC Method 2.505 ; (IUPAC 1987) ; Ran-
cimat induction period by the method of Laubli and
Bruttel (1986) using 25 g of oil sample and a tem-
perature of 110C ; carotene content was quantied
using PORIM Test Method p 2.6 (PORIM 1990) which
is quite similar to that proposed by Cocks and Van
Rede (1966) and the fatty acid composition (FAC) of the
oil samples were determined following conditions of
sample preparation and analyses recommended by
IUPAC 2.322 and IUPAC 2.303 (IUPAC 1987), respec-
tively.
The Deterioration of Bleachability Index (DOBI)
values of the CPO samples were determined by the
method of Swoboda (1980, 1982). This method is also
given in PORIM Test Method p 29 (PORIM 1990).
The DOBI value is the ratio of the spectrophotometric
measurement of absorbance at 446 nm to that at
269 nm, for a solution of CPO in a hydrocarbon
solvent (iso-octane).
All analyses of the oil samples were run in duplicate
and the results averaged.
Spectrophotometric determination of CHL pigments in
vegetable oils
This spectrophotometric method (Holasova et al 1990)
is for the determination of total CHL pigments,
expressed as PHYa, in crude vegetable oils.
Y A T an, C L Chong, K S L ow
The CHL pigments are determined by measuring the
absorbance at 670 nm, correcting the result for the
background absorption, and calculating the content
with use of the absorptivity of PHYa, which is the main
CHL pigment in crude vegetable oils. The oil samples
were heated to a temperature 5C higher than the
melting point. All turbid samples were ltered prior to
the analysis. The sample was then measured at 630 nm,
670 nm and 710 nm in a 10-mm glass cuvette against
air instead of a reference cell.
The content of CHL pigments was expressed in
mg kg~1 of PHYa which was equal to
C \ 3453(A 05A 05A )l~1
670 630 710
where C is the content of CHL pigments in mg of
PHYa in 1 kg of oil, A is the absorbance at the respec-
tive wavelength (nm), and l is the thickness of the spec-
trophotometer cell (cm).
Monitoring of fruit maturation
A total of eight palms of Elaeis guineensis species and
tenera variety were selected for monitoring the matu-
ration of fruits. CPO from fruits of the tagged palms
were then extracted at the required stage of maturity.
These seven-year-old palms were located at Field 231 of
the PORIM/UKM Research Station. All the palms
chosen for this study were of the tenera variety. Flowers
ready for pollination, near pollination or already pol-
linated were identied by painting the three fronds
nearest to the inorescence. The owers turn red a few
days (23 days) after being pollinated. Flowers which
were still enclosed by bracts were considered about a
week or so from pollination. Flowers ready for pol-
lination exude a sweet smell similar to that of aniseed
and were pale yellow in colour. The palms with the
chosen owers were then tagged with aluminium strips
(10 cm ] 100 cm, painted in dierent colours). The
strips were placed around the palm trunks. CPO from
fruits of the tagged palms were then extracted at the
required stage of maturity.
Two sets of experiments were carried out. The experi-
ments were so designed such that pollination of owers
and harvesting of palm fruits were at the same time
period of each experimental year. Thus, the rst set
monitored fruits from October 1992 to April 1993 and
the second set from November 1993 to May 1994. This
schedule eliminated the eects of rainfall and sunshine
on the rate of fruit maturity.
Harvesting and extraction of crude palm oil
At the required stages of maturity, which were set at 18,
19, 20, 21, 22 and 23 weeks after pollination, the marked
fruit bunches were harvested and sterilised in an auto-
Crude palm oil characteristics and chlorophyll content 283

clave (Sakura Neoclave ASV-302) at a temperature of extracted from young fruits showed a much reduced
120C and a pressure of 12 kg cm~2 for 40 min. The oxidative stability in terms of short Rancimat induction
palm fruit is a sessile drupe borne on a large compact periods. The induction period of the oils in this series
bunch. On the average, one fruit bunch from our experi- agreed with this observation except for 22nd week CPO
ments held about 1000 to 1500 fruits and all the fruits which showed an exceptionally low induction period.
were oil extracted. The sterilised fruits were manually Since this sample also showed a high concentration of
stripped o the bunch and the mesocarp separated from carotenoids as well as high PV and FFA values, it was
the nut with a knife. The mesocarp was then heated in suspected that the fruits were actually overripe.
the microwave oven for 10 min and the CPO was The FFA of the CPO samples were all below 2%,
extracted from the mesocarp with a hydraulic hand carotene content ranged from a low of 279 mg kg~1 to
press. Heating removes water and at the same time a high of 937 mg kg~1, CHL content from nil to
liquees the oil trapped in the mesocarp bres. A centri- 12 517 kg kg~1, DOBI in the region of 1540, induc-
fuge set at 60C and 660 ] g was used to separate the tion period of 718185 h, A of around 0812 and
233
extracted CPO from the bres and other solid impur- A between 017 and 018. The PV of all the samples
269
ities. were rather high, ranging from 373 to 92. Except for
The CPO was then decanted o, ltered through a CPO from fruits harvested at 22nd week, the oxidative
Whatman No 4 lter paper in a Buchner funnel and status of the other CPO samples was about the same.
vacuum dried to remove remaining traces of water. In The FAC of the CPO samples are shown in Table 1.
this manner, CPO was extracted from fruits ranging It is established that oils in young fruits contain a
from 18 to 23 weeks of maturity. All the oils were higher amount of unsaturated fatty acids than oils from
poured into Beatson bottles, ushed with nitrogen, older fruits. This table shows that the oil with the
capped tightly and kept in the cold room set at 5C highest unsaturation and therefore highest IV was that
before analyses. from the 19th week CPO and the 22nd week CPO had
the lowest IV.
The contents of CHL and carotene pigments, PV,
Determination of average levels of chlorophylls in A and A absorbances, DOBI and Rancimat
233 269
commercial crude palm oil samples induction periods of the CPO extracted from fruits in
the second experiment are also shown in Fig 1. The oxi-
Commercial samples of CPO were collected randomly dative status of this set of CPO samples was found to
from mills and reneries in Malaysia. The levels of CHL be much better than that shown by the CPO extracted
in these samples were quantied using the spectro- from the rst experiment. The PVs were much lower (all
photometric method. Values given are means of dupli- below 2 meq kg~1), and much lower A and A
233 269
cate analyses. values were also observed. It has been reported by Siew
et al (1989) that CPO quality is not dependent on sea-
sonal variations provided adequate steps were taken to
ensure quality consistency during oil extraction. Thus,
RESULTS AND DISCUSSION dierences in oil quality from theses two sets of experi-
ments could not be due to biological or environmental
Characteristics of CPO extracted from fruits at various
stages of maturity TABLE 1
Fatty acid composition (wt% as methyl esters) and iodine
The CPO extracted from the fruits at varying stages of value (calculated) of curde palm oil extracted from fruits
maturity are referred to as 19th week CPO, 20th week ranging from 19th to 22nd week of maturity
CPO, 22nd week CPO and 23rd week CPO, according
to the age of the fruits from which the oil was extracted. Fatty acid 19th week 20th week 21st week 22nd week
Some of the identity and quality characteristics of the
C tra tr tr tr
CPO extracted from the fruits at various stages of 12> 0
C 06 08 07 13
development are graphically presented in Fig 1. All 14> 0
C 397 438 394 440
values given are means of duplicate analyses. 16> 0
C 02 02 02 01
Figure 1 shows the CHL and carotene contents of the 16>1
C 33 35 44 47
18> 0
CPO extracted from fruits harvested in the rst experi- C 433 403 417 388
18>1
ment. As expected, the oils extracted from the older C 125 111 130 106
18> 2
fruits contained a higher level of carotene pigments and C 03 01 02 01
18> 3
oils from younger fruits a higher content of CHL pig- C 01 02 03 03
20> 0
ments. CPO extracted from fruits of age 22 weeks did Iodine value 587 538 582 516
not show any CHL pigments. Past observations
(unpublished data) have indicated that all CPO a tr, trace.
284 Y A T an, C L Chong, K S L ow

Fig 1. Characteristics of CPO extracted from dierent age fruits (data from two sets of experiments).

variation between the 2 years. A possible reason for this
could be that in this second experiment the whole
bunch of fruits was sterilised in one cycle using a larger
size autoclave. Sterilisation in the rst trial was carried
out in a smaller autoclave where a bunch of fruits was
sterilised in batches and three rounds of sterilisation
cycle were needed to complete sterilisation of one whole
bunch of fresh fruits. In addition, a longer sterilisation
cycle was needed before the set conditions for sterilisa-
tion were reached. Thus the longer processing time
could account for the poorer oxidative state of the CPO
samples in the rst experiment.
Crude palm oil characteristics and chlorophyll content 285

The Rancimat induction period of the sample
increased with increasing age of the fruits. The expected
trend of pigment level was increasing carotenoids with
increasing maturity, accompanied by decreasing level of
CHLs.
Figure 1 also shows the dierences in the character-
istics between the CPO from these two experiments.
The FAC of the CPO samples in this second experiment
also showed the expected trend of higher IV in oils from
younger fruits (Table 2).
From Fig 1, a preliminary conclusion was that there
were correlations among CHL content, carotene
content, DOBI and Rancimat induction period.
Longer induction periods appeared to be associated
with lower CHL content and higher levels of carot-
enoids and high DOBI. Thus CPO extracted from
young fruits which contained CHLs and much lesser
amounts of carotene than ripe fruits, is expected to
possess an inferior oxidative stability to begin with, and
this instability may be magnied with storage.
were expected because the bunch consists of fruits
which do not ripen simultaneously. Furthermore, there
is considerable variation both between bunches within a
palm and between palms, over the duration of time
when all fruits ripen (Rao et al 1983).
An interesting feature found in this study was that
palms planted at the edge of a eld and those planted at
the centre of the eld produced fruits which ripened at
dierent rates, with those at the edge ripening at a faster
rate. This conclusion was drawn from the observation
that when two bunches of fruits of the same age, one
from a palm in the inner eld and the other from one at
the edge of the eld, were compared ; CPO extracted
from the former was found to contain a much higher
level of CHL. Figure 3 depicts this dierence in chlo-
rophyll content of fruits from dierent palms in dierent
locations.
Levels of CHL in commercial CPO

Commercial harvesting will result in a mixture of fruit

CHL content in CPO from fruits of varying stages of
maturity
Figure 2 is a graphical representation of the level of
CHL content in CPO extracted from fruits 17th to 24th
week after pollination. Each column represents the
mean chlorophyll content of oil extracted from two
bunches of palm fruits harvested from palms planted in
the same eld. The expected trend of decreasing CHL
content with increasing ripeness of fruits was noted.
However, there was a rather wide variation in the
content of CHL in CPO extracted from fruits of the
same ripeness. For example, the CHL pigments of the
sample of 18th week CPO ranged from below 1000 to
12 793 kg kg~1. One sample of CPO from 22nd week
fruits contained over 1000 kg kg~1 CHL while there
was no CHL in another sample. These observations
bunches at various stages of ripeness. The ideal time for
harvesting is at the time in the life of each bunch when
oil yield and oil quality are in optimal balance. Whether
this is also correlated with the time when CHL is at the
minimal level, is being investigated.
The degree of ripeness may be estimated from the
colour of the fruits. The colour of unripe fruits is black
to reddish black, while that of its pericarp is light
yellow ; the pericarp of ripe fruits, on the other hand, is
orange.
Figure 4 shows the distribution of CHL content in
eighteen samples of CPO obtained from local mills and
reneries. A notable feature of this survey was that there
was no sample devoid of CHL and the average level of
CHL content was around 930 ^ 107 kg kg~1 which
was in agreement with the level of 827 ppb cited by
Strecker et al (1990). The presence of CHL in CPO from

TABLE 2
Fatty acid composition (wt% as methyl esters) and iodine value (calculated) of crude palm oil
extracted from fruits ranging from 19th to 23rd week of maturity

Fatty acid 19th week 20th week 21st week 22nd week 23rd week

C tr tr tr tr 01
12> 0
C 03 05 07 06 06
14> 0
C 399 371 370 401 403
16> 0
C 03 01 01 02 02
16>1
C 43 48 53 49 49
18> 0
C 421 432 436 427 426
18>1
C 125 137 127 107 107
18> 2
C 03 02 02 03 02
18> 3
C 03 04 03 04 03
20> 0
Iodine value 577 607 593 551 550
286 Y A T an, C L Chong, K S L ow

Fig 2. Variation of chlorophyll content in CPO from fruits at varying stages of maturity.

Fig 3. Chlorophyll content of CPO from fruits of palms planted at the centre (I) and the edge (II) of the eld. Mean values of oil
extracted from two bunches of palm fruit.
Crude palm oil characteristics and chlorophyll content
Fig 4. Variation of chlorophyll content in 18 commercial CPO samples.
ripe fruits is also consistent with the ndings of Ikemu-
funa and Adamson (1984) which indicated that CHL
did not disappear completely in ripe palm fruits.
ACKNOWLEDGEMENT
We thank the Director-General of PORIM for per-
mission to publish this paper.
REFERENCES
Abraham V, Deman J M 1986 Hydrogenation of canola oil as
aected by chlorophyll. J Am Oil Chem Soc 63 (9) 1185
1188.
AOCS 1992 Official Method and Recommended Practices of the
AOCS (4th edn). American Oil Chemists Society, Cham-
paign, Illinois, USA.
Coe M R 1938 Photochemical studies of rancidity : The
mechanism of rancidication. Oil and Soap 9 230.
Cocks L V C, van Rede C 1966 L aboratory Handbook for Oil
and Fat Analysis, Academic Press, London, pp 276277.
Dahlen J A H 1973 Chlorophyll content monitoring of
Swedish rapeseed and its signicance in oil quality. J Am
Oil Chem Soc 50 312A327A.
Endo Y, Usuki R, Kaneda T 1984a Prooxidant activities of
chlorophylls and their decomposition products on the
photooxidation of methyl linoleate. J Am Oil Chem Soc
61 (4) 781784.
287
Endo Y, Usuki R, Kaneda T 1984b Pheophtin sensitized
photooxidation of methyl linoleate. Jpn Oil Chem (Y uko-
gaku) 33 (7) 447448.
Endo Y, Usuki R, Kaneda T 1984c The photooxidative alter-
ation of chlorophylls in methyl linoleate and prooxidant
activity of their decomposition products. J Agric Bio Chem
48 (4) 985989.
Holasova M, Parizkova H, Porkorny J 1990 Spectro-
photometric determination of chlorophyll pigments in crude
vegetable oils. L a Rivista Italiana Delle Sostanze Grasse Vol
LXVII, October.
Ikemefuna J, Adamson I 1984 Chlorophyll and changes in
ripening palm fruit, Elaeis guineensis. Phytochem 23 (7)
14131415.
IUPAC 1987 Standard Methods for the Analysis of Oils, Fats
and Derivatives (7th edn). IUPAC, Applied Chem Division,
Commission on Oils and Fats Derivatives, Blackwell Scien-
tic Publications, Oxford, UK.
Kiritsakis A, Dugan L R 1985 Studies in photooxidation of
olive oil. J Am Oil Chem Soc 62 (5) 892896.
Koritala S 1975 Selective hydrogenation of soybean oil : VII.
Poisons inhibitors for copper catalysis. J Am Oil Chem Soc
52 240243.
Laubli M W, Brutell P A 1986 Determination of the oxidative
stability of fats and oils : Comparison between the active
oxygen method (AOCS Cd 1227) and the Rancimat
method. J Am Oil Chem Soc 63 792795.
PORIM 1990 T est Methods. Compiled by the Palm Oil
Research Institute of Malaysia, Bandar Baru Bangi, Sel-
angor Darul Ehsan, Malaysia.
Rao V, Soh A C, Corley R H, Lee C H, Rajanaidu N, Tan Y
P, Chin C W, Lim K C, Tan S T, Lee T P, Ngui M 1983 A
Critical Reexamination of the Methods of Bunch Quality
Analysis in Oil Palm Breeding (PORIM Occasional Paper
9). Palm Oil Research Institute of Malaysia, Bandar Baru
Bangi, Selangor Darul Ehsan, Malaysia.
288
Siew W L, Mohammad N, Rahman A A, Sabli F 1989 Quality
index for crude palm oil. PORIM Report PO (149d) 89,
Palm Oil Research Institute of Malaysia, Bandar Baru
Bangi, Selangor Darul Ehsan, Malaysia.
Strecker L R, Hasman J M, Maza A 1990 W orld Conference
Proceedings on Edible Fats and Oils Processing : Basic Prin-
Y A T an, C L Chong, K S L ow
ciples and Modern Practices, ed Erickson D R. American
Oil Chemists Society, Champaign, Illinois, pp 5155.
Swoboda P A T 1980 Chemical changes causing deterioration
in palm oil quality. PORIM Bull 1 48.
Swoboda P A T 1982 Bleachability and the DOBI. PORIM
Bull 5 2838.