J Sci Food Agric 79 :300306 (1999)

Journal of the Science of Food and Agriculture

Dissimilarity of the oxidations of rapeseed and

butter oil triacylglycerols and their mixtures in
the absence of tocopherols
Anna-Maija Lampi* and Vieno Piironen
Department of Applied Chemis try and Microbiology , Univers ity of Hels inki , Viikki -D , PO Box 27 , FIN -00014 Hels inki , Finland

Abstract : Although fatty acid composition is the most important attribute used to control oxidation
stability, all edible oils are a ected by lipid oxidation irrespective of whether they are highly unsaturated or not. The aim of the study was to compare the oxidation of rapeseed oil (RO) and butter oil
(BO) triacylglycerols (TAGs) and their mixtures containing 10% or 20% of the other. Oxidation of the
TAGs at 40C was followed by formation of primary and secondary products. Statistical methods were
used to interpret the data. The RO and BO TAGs and their mixtures began to oxidise without any
induction periods. In the RO TAGs more hydroperoxides and p-anisidine reactive compounds were
formed than in the BO TAGs. The BO TAGs oxidised more than would be expected by their fatty acid
composition. High susceptibility of BO TAGs to oxidation was caused by the easy breakdown of their
hydroperoxides. Heptadienal and heptenal were specic products of oxidised RO TAGs and heptanal
and nonenal of oxidised BO TAGs. Mixtures of RO and BO TAGs behaved according to which was
dominant in the mixture. However, as little as 10% of RO or BO TAG introduced its specic oxidation
products to the mixture.
( 1999 Society of Chemical Industry

Keywords : rapeseed oil ; butter oil ; peroxide value ; anisidine value ; volatile aldehydes

INTRODUCTION
Lipid oxidation in edible oils and fats is associated
with the unsaturation of the oils, especially with diunsaturated and polyunsaturated acyl groups.1 In
vegetable oils, many attempts have been made to
improve their stability by reducing the content of
linolenyl groups and replacing them by oleyl or saturated acyl groups.2h4 A recommended way to study
the stability of vegetable oils at ambient temperatures, ie not higher than 60C, is to follow the
contents of primary prroducts, eg by peroxide value
(PV), and of secondary products by sensory or headspace analysis.5 Generally, these two measurements
correlate well with each other, but in some studies no
correlation has been found.2,3 Sensory quality of
vegetable oils is considered acceptable when
2 ] PV ] anisidine value (AnV) is below 10.6
Lipid oxidation is a signicant problem also in
butter fat, although butter fat contributes only about
300 g kg~1 of mono-unsaturated and \40 g kg~1 of
di-unsaturated and polyunsaturated acyl groups. In
dairy products, lipid oxidation is associated with
sensory properties because o-avours are detected
at PVs as low as 1 meq kg~1.7,8 Even small increases
in unsaturation decrease the oxidative stability of
butter fat.7 Recently several experiments have shown

that the fatty acid composition of butter fat can be

altered by adding unsaturated lipids to feeds without
aecting the sensory quality. However, no commercial applications are available so far.9
Because of the dierences in their fatty acid compositions, the oxidation in vegetable and butter oils
cannot be similar. Their oxidation stabilities have
not been compared, although consumers use spreads
produced from them similarly. Even less is known
about the oxidation of versatile vegetable and butter
oil blends.
In order to study the oxidation susceptibility of
oils and their mixtures, we decided to use chromatographically puried triacylglycerols (TAGs) as the
oxidising material. With the TAGs it is possible to
understand what would happen in the oils if no antior pro-oxidants were present, thereby focusing on
the oxidising mateial.
The aim of the work was to study and compare the
oxidation of rapeseed oil (RO) and butter oil (BO)
TAGs and their mixtures at an ambient temperature.
Oxidation of the TAGs was followed by measurements of PV, AnV and contents and the proles of
their volatile aldehydes. With these indexes of oxidation we wanted to demonstrate which reactions of
oxidation were the most important ones and which

* Corres pondence to : Anna-Maija Lampi, Department of Applied

Chemis try and Microbiology, Viikki-D, PO Box 27, FIN-00014,
Univers ity of Hels inki, Hels inki, Finland

Contract/grant s pons or : Academy of Finland

(Received 27 November 1997 ; revis ed vers ion received 25 March
1998 ; accepted 12 June 1998 )

( 1999 Society of Chemical Industry. J Sci Food Agric 00225142/99/$17.50

300

Oxidation of rapeseed and butter oil triacylglycerols

products were typical for each material. Moreover,

we wanted to determine how increasing the unsaturation of BO TAG by adding RO TAG aected stability and vice versa.
MATERIALS AND METHODS
TAG materials
TAGs were puried from commercial rapeseed (van
der Berg, Helsinki, Finland) and butter oils (Valio
Ltd, Seina joki, Finland) by a multilayer chromatographic method.10 RO and BO TAGs were oxidised
as such and as mixtures containing 10% and 20% of
the other TAG. The fatty acid compositions of the
TAGs were analysed from transesteried samples by
capillary gas chromatography (GC) as described
earlier11 and expressed as g kg~1 of methyl esters
(Table 1). Each TAG material was prepared and oxidised in duplicate.
As c-tocopherol was the most critical compound in
the purication of oils, the purity of each TAG
material was conrmed by analysing their tocopherol
contents by normal phase high performance liquid
chromatography (HPLC) with uorescence detection.10 The TAGs contained 1 lg g~1 of ctocopherol and no other tocopherols (determination
limit 1 lg g~1). Indexes of oxidation status of the
TAGs were also measured as described below. The
TAGs had PV \ 0.6 meq kg~1, AnV 0.7, and contained volatile aldehydes \16 nmol g~1. There were
no free fatty acids, mono-acylglycerols or diacylglycerols, or complex lipids in the TAGs, as
checked by silica gel thin-layer chromatograpy. Total
sterol contents of the RO and BO TAGs were 4.0
and 0.2 mg g~1 analysed from trimethylsilyl ether
derivatised samples by capillary GC.12
Oxidation
Oxidation experiments with 5.0 g aliquots of TAGs
were carried out in 1.7 cm (id) vials at 40C in closed
Erlenmeyer asks in the dark for 14 days. At regular
intervals two vials were withdrawn and the TAGs
were combined for analysis of oxidation status.
Measurements of oxidation status
The oxidation status of the TAGs were characterised
by PV and AnV measurements and by analysing
Table 1. Contents of major uns aturated fatty acids in
rapes eed oil (RO) and butter oil (BO) TAGs

TAG material

RO
90%
80%
20%
10%
BO

RO
RO
RO
RO

Fatty acid content (g kg 1)

Oleic

Linoleic

Linolenic

550
520
480
290
260
22

220
200
180
57
37
17

100
89
79
23
13
4

J Sci Food Agric 79 :300306 (1999)

volatile aldehydes. PV detects hydroperoxides, which

are primary products. AnVs and volatile aldehydes
are indexes of secondary products of oxidation. PVs
were measured by a modied ferric thiocyanate
method13 and AnVs by an AOCS method (AOCS
Cd 18-90)14 both with a UV-VIS spectrophotometer.
Volatile aldehydes were liberated from 3.0 g aliquots of the TAGs by purging samples with a nitrogen ow (80 ml min~1) for 16 h at 50C and collected
in two successive chemical traps containing 2.5 g l~1
2,4-dinitrophenyl hydrazine in 2 M HCl. 2,4-dinitrophenyl hydrazone derivatives (DNPH) of the aldehydes were analysed by reversed phase HPLC
according to Lampi et al15 except for the use of an
external standard method for quantitation. The performance of the HPLC system was tested daily by
three mixtures containing DNPHs at three concentration
levels
ranging
from
2 ] 10~6
to
1 ] 10~4 mol l~1. Calibration curves for three aldehyde groups, alkanals, alkenals and alkadienals, were
calculated from all the DNPH mixture analyses.
Quantitation was based on the molar absorptivities of
alkanal-, alkenal- and alkadienal-DNPHs being
21 000 (j \ 357 nm), 27 500 (j \ 374 nm) and 27 500
(j \ 391 nm), respectively.16
Recovery studies of volatile aldehydes were made
by spiking 0.337 lg g~1 of aldehydes into RO and
BO before purging and comparing the amounts of
aldehydes found with those found when the same
amounts of aldehydes were added directly into the
chemical traps.
All chemical analyses of oxidation status were
made of duplicate samples. The precision of duplicate determinations were calculated as P
\
0.95
t (0.05) ] S , where P
was the maximum relative
l
r
0.95
random error at the 95% level, t (0.05) was the 5%
l
value of t-distribution with l degrees of freedom and
S was the relative standard deviation of the determir
nations.17 The repeatability of multiple analyses was
expressed as a coefficient of variation (CV%). The
error of calibration curves was calculated as an estimate error standard deviation (SD) of the slopes.18
Statistical analyses
Dierences between the oxidation status of the
materials at particular times were conrmed by
analysis of variance. Hydroperoxide formation and
breakdown in the materials were compared with each
other by linear regression analysis. Principal component analysis (PCA) was used to compress the data
for graphical interpretation of the data. All statistical
analyses were made by a Survo 84C integrated statistical system.19 A signicance level of p \ 0.05 was
used.
RESULTS AND DISCUSSION
Reliability of the methods
Calibration curves for PV determination were made
once a month and the estimate error SD of the slopes
301

AM Lampi, V Piironen

were ^1.0%. The accuracy of the UV/VISspectrophotometer was conrmed twice with potassium dichromate solutions. The P
s of PVs and
0.95
AnVs were 7.3% and 4.0%, respectively.
The HPLC method could separate all aldehydeDNPHs efficiently except for a pair of heptadienaland hexanal-DNPHs (Fig 1). Although the selectivity (a \ k@2/k@1) for the pair was only 1.041.05,
UV-detection with ve wavelengths conrmed
proper analysis of the two compounds. The peak
symmetry of heptanal-DNPH was chosen as the criterion for the usefulness of the column. When the
peak symmetry rose [ 1.5, the column was discarded. The estimate of error SD of the calibration
curves of alkanal-, alkenal- and alkadienal-DNPHs
were 0.4%, 1.5% and 2.0%, respectively. The HPLC
analysis was stable throughout the experiments,
because the CV% of the peak area of
10 ] 10~6 mol l~1 heptanal-DNPH solution was
5.6% when measured daily (N \ 31).
Recovery tests of added aldehydes in RO and BO
showed that alkanals with 7 and 8 carbon atoms were
most efficiently liberated from the matrix, reaching
recoveries of 88% ^ 8% and 88% ^ 7% from RO
and 94% ^ 15% and 101% ^ 16% from BO (Figs
2(a) and (b)). Higher aldehydes gave smaller recoveries, which could be explained by their low air to
vegetable oil partition coefficients.20 The DNPHs of
aldehydes with less than ve carbon atoms are to
some extent water-soluble,21 which reduces their
extraction yield from the chemical trap and decreases
their recoveries. Therefore, propanal, a typical
breakdown product of linolenyl groups, could not be
measured with the method. In accordance with our
results, Lee et al22 found that it is difficult to trap
aldehydes with less than ve carbon atoms in adsorbents such as 2,6-diphenyl-p-phenylene oxide and to
liberate aldehydes with more than nine carbon atoms
from oils at 50C. The recoveries of pentanal and
hexanal were 6% and 13% smaller from RO than
from BO, but there were not signicant dierences
in the higher aldehydes. The recoveries of added

Figure 1. HPLC chromatogram (j \ 360 nm) of volatile aldehyde

DNPHs of 20% RO TAGs mixture after 14 days of oxidation at
40C (PV \ 58 meq kg1 ; AnV \ 12 ; volatile
aldehydes \ 180 nmol g1). C6 : 0, hexanal ; C7 : 0, heptanal ;
C7 : 1, heptenal ; C9 : 1, nonenal ; C7 : 2, heptadienal.

302

Figure 2. Recoveries of added : (a) alkanals (6 lg g1) from RO ;

(b) alkanals (3 lg g1) from BO ; (c) added 7 carbon atoms
aldehydes (0.337 lg g1) from RO.

heptanal and heptenal were stable at the level of 0.3

35 lg g~1 (corresponding to 3310 nmol g~1 of
heptanal) but that of heptadienal decreased below
7 lg g~1 (Fig 2(c)). The determination limit of aldehydes was 1 nmol g~1. Above 5 nmol g~1 the P
s
0.95
of hexanal, heptanal and total aldehydes were 16%,
21% and 20%, respectively.
Oxidation of the TAGs
Oxidation of the six TAG materials began without
any induction periods when measured by PV (Fig
3(a)), which is a typical feature when no antioxidants
are present. PV results of the replicate oxidation
experiments of the six materials deviated ^10%
(range 0.0426%) from the means shown in Fig. 3(a).
The rate of the formation of primary products was
higher in the 80100% RO TAGs than in the other
materials. Analysis of variance showed that there
were remarkable dierences between the oxidation of
dierent materials already at 3 days of oxidation
when the PVs ranged from 6.5 to 19 meq kg~1.
F-tests for equality of PVs were rejected, because the
J Sci Food Agric 79 :300306 (1999)

Oxidation of rapeseed and butter oil triacylglycerols

Figure 3. Average oxidation curves of s ix TAG materials from

replicate experiments . (a) Peroxide values (PV), (b) anis idine
values (AnV), (c) volatile aldehydes . ], RO TAG ; \, 90% RO
TAG ; L, 80% RO TAG ; ], 20% RO TAG ; K, 10% RO TAG ; ,
BO TAG.

F(5,6) values varied from 14.7 to 74.8. At the end of

the experiment, there were 3.8 times as much hydroperoxides in the RO TAGs (PV \ 117 meq kg~1) as
in the BO TAGs (PV \ 32 meq kg~1). All the
materials were in the expanding phase of oxidation
after 14 days and no decline in PVs was found.
At the beginning of oxidation, there were no major
dierences in the formation of secondary products
between the six TAG materials as measured by AnV
(Fig 3(b)). Generally, AnVs of the two replicate oxidation experiments deviated ^12% (range 0.06
45%) from the means. In the 80100% RO TAGs
the rate of secondary product formation was slow
during 3 days and increased after 7 days of oxidation.
The rate in the BO TAGs was constant. It was only
after 14 days of oxidation that the F-test value for
equality of AnVs (F(5,6) \ 21.0) indicated that there
were statistically signicant dierences between the
materials. The nal AnVs ranged from 9.6 to 19.
J Sci Food Agric 79 :300306 (1999)

More volatile aldehydes were produced in the BO

TAGs than in the RO TAGs (Fig 3(c)). The deviation of the replicate oxidation experiments of the
materials from the means was ^11% (range 0.3
32%), which is similar to those of PVs and AnVs.
Volatile aldehydes began to be formed without a lag
phase which is contradictory to the formation of secondary products measured by AnV. Analysis of
variance showed signicant dierences between the
materials after 3, 10 and 14 days of oxidation. At the
end of the experiment there was 1.8 times as much
volatile aldehydes in the BO TAGs (310 nmol g~1) as
in the RO TAGs (170 nmol g~1). Smaller recoveries
of pentanal and hexanal from RO TAGs compared
to BO TAGs and the methods inability to measure
propanal could not explain the dierences in the
volatile aldehyde content of the materials.
The order of susceptibility to oxidation was dierent when dierent indexes of oxidation were looked
at. When the decomposition of hydroperoxides to panisidine reactive compounds and volatile aldehydes
were explained by their formation measured by PV,
all linear regressions were signicant. The t of the
linear regression was especially signicant when only
one material was analysed at a time (0.930.99). Differences between the materials were shown, too. The
higher stability of RO TAG hydroperoxides compared to that of BO TAG hydroperoxides was
evident when the slopes between PV explaining AnV
or volatile aldehydes were compared. The slopes of
RO TAGs were 0.15 and 1.3 and those of BO TAGs
0.29 and 8.6, respectively. When the slopes were
considered, the mixtures behaved according to which
TAG was dominant.
BO TAGs were much more susceptible to oxidation that could be accounted for by their fatty acid
composition. Moreover, unsaturated phospholipids
that are associated with initiation of lipid oxidation
in milk fat and butter were lacking in the BO
TAGs.8 However, once started lipid oxidation does
occur in the more saturated neutral lipids as shown
by Badings7 and Christensen and Holmer.23
Fast oxidation of BO TAGs has to be a consequence of the unstability of the hydroperoxides. As
hydroperoxides were decomposed, new reactive
species were created, catalysing oxidation. It has
been found earlier that formation of volatile aldehydes in oxidising anhydrous milk fat occurs at the
same time that oxygen is consumed in hydroperoxide
formation,24 yet the reason for the instability of BO
TAG hydroperoxides is not known.
Generally, addition of 10% or 20% of the other
TAG material did not aect the overall oxidation
pattern of the TAGs. The eect of addition of RO
TAGs to BO TAGs was dierent on formation of
primary and secondary products, because PVs
increased and volatile aldehyde contents decreased.
Addition of BO TAGs to RO TAGs also had versatile eects. Black25 showed that adding vegetable oil
to milk fat changed the oxidative avour stability of
303

AM Lampi, V Piironen

the milk-fat-based product. The fair agreement

between sensory analysis and PV of the vegetable oil
became poor when 20% of vegetable oil was added to
milk fat, which means that the ratio of formation and
decomposition rates of hydroperoxides was changed.
Similarly, Frankel and Huang4 showed that in vegetable oils with varying linolenate contents, the
analysis of PV and hexanal formation gave contradictory results about the susceptibility to oxidation of
the oils.
Volatile aldehyde profiles of the TAGs
The proles and the amounts of volatile aldehydes of
oxidised RO and BO TAGs were dierent (Table 2).
The proportion of unsaturated aldehydes was greater
in RO than in BO TAGs, which was expected
because more allyl acyl groups were involved in RO
TAGs. This nding also explained the higher AnVs
of RO TAGs compared to those of BO TAGs,
because AnV is more sensitive to unsaturated than
saturated aldehydes (AOCS Cd 18-90).14 In all of
the TAGs containing RO, hexanal was the major
volatile aldehyde, but heptanal was the major
product in BO TAGs. Heptadienal was a specic
product of RO TAGs and heptanal and nonenal of
BO TAGs. The prole of RO TAGs resembled that
of canola oil26 and the prole of BO TAGs that of
BO.7,27
When volatile aldehyde proles of the RO and BO
TAGs were compared with the proles of oxidised
unsaturated acyl groups, the involvement of individual acyl groups of the TAGs in oxidation were conrmed. Heptadienal, which was the specic product
of the RO TAGs, is a typical product of linolenyl
groups.22,28 Hexanal is typically the major product
from linoleyl groups, but it is formed from other acyl
groups, too.21 The breakdown product of oleyl
groups consist of saturated aldehydes,7,28 which
were found predominantly in BO TAGs but also in
RO TAGs.
Analyses of volatile aldehydes showed that in the
BO TAGs they were oleyl hydroperoxides that
decomposed and that these hydroperoxides decomposed quickly. This is in contradiction of the theory
that the more unsaturated an acyl hydroperoxide is,
the easier it decomposes. Our results are supported
by Brimberg,29 who showed that with monounsaturated substrates, part of oxygen is consumed
by secondary oxidation reactions almost from the

beginning. She also stated that methyl oleate hydroperoxides decompose at about the same rate as
methyl linoleate hydroperoxides, which partly supports our nding of the fast decomposition of BO
TAG hydroperoxides. Also, Lee et al22 found that in
low linolenate soybean oil the amount of oleyl group
specic products were higher than expected from the
relative rate of oxidation of oleyl groups.
As little as 10% of BO TAGs in a mixture was
enough to result in heptanal formation and similarly
10% of RO TAGs in a mixture in heptadienal formation. Minor amounts of specic volatile aldehydes of
both of the TAGs were present in the mixture.
Volatile aldehyde proles changed during oxidation. Generally, the proportion of saturated aldehydes increased and those of unsaturated aldehydes
decreased at later phases of oxidation. The dierence
was most evident in the percentages of hexanal and
heptadienal (Fig 4). Hexanal has been shown to be
the predominate end product, because higher
unsaturated aldehydes continue to decompose and
produce it.30 In all the TAG containing RO the nal
hexanal contents varied from 35% to 40% of all the

Figure 4. Proportions of hexanal and heptadienal in oxidis ing

TAGs . ], RO TAGs ; \, 90% RO TAGs ; L, 80% RO TAGs ; ],
20% RO TAGs ; K, 10% RO TAGs ; , BO TAGs .

Aldehydes (nmol g 1)

TAG material

Table 2. Volatile aldehyde

profiles of rapes eed oil
(RO) and butter oil (BO)
TAGs oxidis ed for
14 days at 40C

304

RO
90%
80%
20%
10%
BO

RO
RO
RO
RO

Hexanal

Heptanal

Heptenal

60
54
53
81
81
86

1
4
5
32
48
102

37
35
30
24
22
18

Nonenal

Heptadienal

2
10
16
25

34
30
26
6
13
7

Others
39
25
31
46
50
76

J Sci Food Agric 79 :300306 (1999)

Oxidation of rapeseed and butter oil triacylglycerols

volatile aldehydes. In BO TAG the increase was less

than in the other materials and the nal percentage
of hexanal was only 27%.
Characteristic of the oxidation of the TAGs
The data from six materials, ve time points and 19
indicators of oxidative status (PV, AnV and 16 volatile aldehydes and their sum) were subjected to PCA
to facilitate the interpretation of multivariate data.
The rst factor described 43%, the second 25% and
the third 10% of the total variation in the data. From
the score plot marked with material codes (Fig 5(a))
the two rst factors seemed to separate the high-inRO TAGs from the high-in-BO TAGs. When the
score plot was marked with oxidation times (Fig

5(b)) the rst factor was shown to be related to the

oxidation time. The corresponding plot of loadings
(Fig 5(c)) showed that heptanal and nonenal were
highly correlated with the BO TAGs and heptadienal, heptenal, PV and AnV were highly correlated
with oxidised RO TAGs. At the same time, the loadings of hexanal and total aldehydes were the lowest
in the rst factor but near the origin in the second
factor, which means that their values were highly
related to the extent of oxidation, but they were poor
in separating the dierent materials from each other.
The PCA analysis further showed that analysis of
individual aldehydes is important in order to dierentiate the oxidation of RO and BO TAGs without
tocopherols. Although total aldehyde and hexanal
contents indicated that the materials were oxidising,
these analyses could not be used to identify which of
the TAGs was oxidising.
CONCLUSIONS
RO and BO TAGs were readily oxidised at 40C.
Mixtures of the TAG materials behaved according to
the TAG that was dominant. Thus unsaturation of
BO TAGs can be signicantly increased by mixing it
with RO TAGs without decreasing its oxidative stability to a large extent. Neither does addition of BO
TAGs to RO TAGs improve its oxidative stability.
However, adding as little as 10% of one TAG to a
mixture introduced specic oxidation products of
this TAG to the mixture.
The unexpectedly high susceptibility of BO TAGs
to oxidation has to be caused by the easy breakdown
of its hydroperoxides as shown by formation of volatile aldehydes. Analysis of volatile aldehydes showed
that it was the oleyl hydroperoxides of BO TAGs
and linoleyl and linolenyl hydroperoxides that were
broken down in RO TAGs.
PCA proved to be an efficient means to detect
which of the indexes of oxidation dierentiate the
oxidation of RO and BO TAGs and to show the
similarities between them. In addition to having
general indexes of primary and secondary oxidation
products it is very important to include specic products such as heptadienal, heptenal, heptanal and
nonenal in an analysis to obtain a clear picture of the
oxidation.
The next phase of this study will be experiments
with added antioxidants in the puried TAGs in
order to better understand and control the oxidation
mechanisms of these materials. In addition, a study
of formation and distribution of hydroperoxides in
these TAGs would further assist interpretation of
oxidation in natural fats and oils.

Figure 5. Res ults from PCA on all the data from oxidis ed TAGs .
Score plots of the two firs t factors explaining 68% of the variation
in the data. In s core plot (a) s amples are marked with material
codes (], RO TAGs ; \, 90% RO TAGs ; L, 80% RO TAGs ; ],
20% RO TAGs ; K, 10% RO TAGs ; , BO TAGs ) and in (b)
s amples are marked with oxidation times in days . In (c) loading
plots of s everal oxidation s tatus indexes are plotted.

J Sci Food Agric 79 :300306 (1999)

ACKNOWLEDGEMENTS
The authors would like to thank Leena Kataja and
Pirkko Loikkanen for technical assistance. This work
was nancially supported by the Academy of
Finland.
305

AM Lampi, V Piironen

REFERENCES
1 Porter NA, Caldwell SE and Mills KA, Mechanisms of free
radical oxidation of unsaturated lipids. Lipids 30 :277290
(1995).
2 Liu H-R and White PJ , Oxidation stability of soybean oils
with altered fatty acid compositions. J Am Oil Chem Soc
69 :528532 (1992).
3 Przybylski R, Malcolmson LJ , Eskin NAM, Durance-Tod S,
Mickle J and Carr R, Stability of low linolenic acid canola
oil to accelerated storage at 60C. Food Sci Technol 26 :205
209 (1993).
4 Frankel EN and Huang S-W, Improving the oxidative stability
of polyunsaturated vegetable oils by blending with higholeic sunower oil. J Am Oil Chem Soc 71 :255259 (1994).
5 Frankel EN, In search of better methods to evaluate natural
antioxidants and oxidative stability in food lipids. Trends
Food Sci & Technol 4 :220225 (1993).
6 Rossel J B, Measurement of rancidity, in Rancidity in Foods, Ed
by Allen J C and Hamilton RJ , Chapman & Hall, Glasgow,
pp 2253 (1994).
7 Badings HT, Cold-storage defects in butter and their relation
to the autoxidation of unsaturated fatty acids. Neth Milk
Dairy J 24 :147256 (1970).
8 Richardson T and Korycka-Dahl M, Lipid oxidation, in
Developments In Dairy Chemistry 2, Lipids, Ed by Fox PF,
Applied Science Publishers, London, pp 241363 (1983).
9 Bear RJ , Production and utilization of dairy cows milk and
products with increased unsaturated fatty acids, in Progress
in Dairy Science, Ed by Phillips CJ C, CAB International,
Oxon, pp 247261 (1996).
10 Lampi A-M, Hopia A, Ekholm P and Piironen V, Method for
the preparation of triacylglycerol fractions from rapeseed
and other oils for autoxidation studies. Food Sci Technol
25 :386388 (1992).
11 Hyvo nen L, Lampi A-M, Varo P and Koivistoinen P, Fatty
acid analysis, TAG equivalents as net fat value, and nutritional attributes of commercial fats and oils. J Food Comp
Anal 6 :2440 (1993).
12 Toivo J , Kalo P, Piironen V and Varo P, Determination of
sterols in edible oils using solid phase extraction in sample
preparation, in 87th AOCS Annual Meeting, Indianapolis,
April 28May 1, 1996. Abstracts, p 18 (1996).
13 Shantha NC and Decker EA, Rapid, sensitive, iron-based
spectrophotometric methods for determination of peroxide
values of food lipids. J AOAC Int 77 :421424 (1994).
14 AOAC, Official method Cd 18-90, p-Anisidine value, in Official Methods and Recommended Practices of the AOCS, 4th
edn, American Oil Chemists Society, Champaign, pp 12
(1990).
15 Lampi A-M, Piironen V, Hopia A and Koivistoinen P, Characterization of the oxidation of rapeseed and butter oil tri-

306

16

17

18
19

20

21

22

23

24

25
26

27

28

29

30

acylglycerols by four analytical methods. Food Sci Technol

30 :807813 (1997).
Perkampus HH, Sandeman I and Timmons CJ , UV Atlas of
Organic Compounds Vol V, Butterworths Verlag Chemie,
Dortmund (1971).
Minkkinen P, Monitoring the precision of routine analyses by
using duplicate determinations. Anal Chim Acta 191 :369
376 (1986).
Caulcutt R and Boddy R, Statistics for Analytical Chemists,
Chapman and Hall, New York, pp 8083 (1983).
Mustonen S, Survo, An Integrated Environment for Statistical
Computing and Related Areas, Survo Systems, Helsinki, pp
1494 (1992).
Buttery RG, Guandagni DG and Ling LC, Flavor compounds : Volatilities in vegetable oil and oil-water mixtures.
Estimation of odor thresholds. J Agric Food Chem 21 :198
201 (1973).
Reindl B and Stan H-J , Determination of volatile aldehydes in
meat as 2,4-dinitrophenylbydrazones using reversed-phase
high-performance liquid chromatography. J Agric Food
Chem 30 :849854 (1982).
Lee I, Fatemi SH, Hammond EG and White PJ , Quantitation
of avor volatiles in oxidized soybean oil by dynamic head
space analysis. J Am Oil Chem Soc 72 :539546 (1995).
Christensen TC and Holmer G, Lipid oxidation determination
in butter and dairy spreads by HPLC. J Food Sci 61 :486
489 (1996).
Moreau DL and Rosenberg M, Oxidative stability of anhydrous milkfat microencapsulated in whey proteins. J Food
Sci 61 :3943 (1996).
Black RG, Oxidative avour stability of milkfat-vegetable oil
blends. Aust J Dairy Technol 31 :2226 (1976).
Raghavan SK, Connell DR and Khayat A, Canola oil avor
quality evaluation by dynamic headspace gas chromatography, in Lipid in Food Flavors, Amer Chem Soc Symp Ser
558, Ed by Ho CT and Chen Q, American Chem Soc,
Washington, pp 292300 (1994).
Day EA and Lillard DA, Autoxidation of milk lipids. I. Identication of volatile monocarbonyl compounds from autoxidized milk fat. J Dairy Sci 43 :585597 (1960).
Grosch W, Reactions of hydroperoxides Products of low
molecular weight, in Autoxidation of Unsaturated Lipids,
Food Science and Technology. A Series of Monographs, Ed by
Chan HW, Academic Press, London, pp 95139 (1987).
Brimberg U, On the kinetics of the autoxidation of fats. II.
Monounsaturated substrates. J Am Oil Chem Soc 70 :1063
1067 (1993).
Shieberle P and Grosch W, Model experiments about the formation of volatile carbonyl compounds. J Am Oil Chem Soc
58 :602607 (1981).

J Sci Food Agric 79 :300306 (1999)