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J. Mass Spectrom. Soc. Jpn.

Vol. 54, No. 6, 2006

Determination of Total Hydroperoxides in Oxidized


Vegetable Oils Based on Triphenylphosphine Oxidation
Using Electron Ionization Mass Spectrometry
Yoshiyuki MD8=>96 and Shigeo N6@6BJG6
Department of Material and Life Chemistry, Kanagawa University, Yokohama, JAPAN
A method for determining the peroxide value (POV) of oxidized vegetable oil using electron ionization mass
spectrometry (EI-MS) was developed. The range of POV measured by the method developed in this study is 0
100 meq/kg, which is a matter of interest for those involved in the vegetable oil industry. This method consists
of three steps: the hydroperoxides in the sample oxidize triphenylphosphine (TPP), which produces triphenylphosphine oxide (TPPO); the TPPO concentration in the reaction solution is determined by EI-MS; and the
POV of the sample is obtained from the calibration curve, which correlates the POV from the iodometric method
with the TPPO concentration. The oxidation reaction of TPP was obtained by mixing TPP, oxidized vegetable
oil, 3,5-di-t-butyl-4-hydroxy toluene (antioxidant), and the mixed solvent of chloroform and methanol in a test
tube. The test tube was tightly sealed and then stored in the dark at 60 for 60 min. The resultant solution was
poured into a test tube for the EI and ionized using an ionization energy of 20 eV. The ion strength of the TPPO
dehydride molecule, by which the TPPO concentration was obtained, was determined using the maximum value
of the selected ion current chromatogram peak. The calibration curve was prepared from the POV obtained from
the iodometric method and the TPPO concentration obtained by this method, using a moderately oxidized
vegetable oil. For samples of air-oxidized cotton seed oil, olive oil, soybean oil, and sa%ower oil, the POV
obtained from the TPPO concentration using the calibration curve showed good agreement with that obtained
by the iodometric method.
(Received July 28, 2006; Accepted September 15, 2006)

1.

Introduction

Vegetable oils lose a signicant amount of their commercial value following air-oxidation and, moreover,
have been shown to have an adverse e#ect on the
living body when used to prepare food.1) It is well
known that hydroperoxides, which are formed by air
oxidation, play a role in these phenomena and that the
decomposition and formation are autocatalytically repeated.2) Therefore, it is important that a method be
developed to obtain the total trace amount of hydroperoxides (peroxide value, POV).3) The recognized
methods for determining the POV are basic indirect
chemical methods using iodine that were established
by the American Oil Chemists Society4) and Japanese
Oil Chemists Society.5) These methods are comparatively simple, considerably sensitive, highly reliable,
and excel in reproducibility. However, they are laborintensive and consume a considerably large quantity
of solvent, which raises environmental concerns.
Recently, various methods using di#erent equipment have been developed in place of the iodometric
method. Analysis of hydroperoxide can be achieved
using infrared spectroscopy6) and Fourier transform
infrared spectroscopy7) based on the OOH stretching
at 3400 cm1 and 3600 cm1. As for the method to
Correspondence to: Yoshiyuki MD8=>96, Department of
Material and Life Chemistry, Kanagawa University, 327
1 Rokkakubashi, Kanagawa-ku, Yokohama 2218686,
JAPAN, e-mail: mochiy01@kanagawa-u.ac.jp

obtain the oxidation-reduction potential of hydroperoxide, the use of the polarograph method8) and electrochemical method9) have been reported. Furthermore, a method using ultraviolet absorptiometry9) of
the conjugated double bond formed by the relocation
of hydroperoxide, was reported. An indirect method to
measure the amount of compound oxidized by hydroperoxides and the iodometric method were proposed.
Fourier transform infrared spectroscopy,10) ultraviolet
absorptiometry,11) and Fourier transform near-infrared
spectroscopy,12) in which the absorption band of the
triphenylphosphine oxide (TPPO) produced by the oxidation of triphenylphosphine (TPP) is measured, were
also reported. Other proposed methods include measuring the luminescence of luminol and the uorometry
of diphenyl-1-pyrenyl-phosphineoxide.13)
It is impossible to directly determine the POV of
hydroperoxides in oxidized vegetable oils using conventional spectrometry as many unspecied molecular
species exist. Moreover, it is very di$cult to ionize the
thermally hypersensitive hydroperoxide. Consequently, a method to obtain the total amount of hydroperoxides by mass spectrometry has not previously been
studied. As hydroperoxide reacts stoichiometrically
with TPP and produces TPPO,11)13) it can be considered
appropriate to adopt an indirect method in which the
amount of the related ions such as [TPPO], [TPPO
H], and base peak etc. of TPPO produced by the ionization of TPPO is used for measuring the POV by mass
spectrometry.
We have examined various problems which occurred

235

Y. Mochida & S. Nakamura

due to the electron ionization (EI) of TPPO and veried


this method with air-oxidized samples of commercially
available cotton seed oil, olive oil, soybean oil, and
sa%ower oil.
2.

Experiments

2.1 Samples and reagents


Cumene hydroperoxide was purchased from Nippon
Oil & Fats Co., Ltd. (Tokyo, Japan). Triphenylphosphine (purity 98), triphenylphosphine oxide (purity
98), and 2,6-di-t-butyl-p-cresol (antioxidant) were obtained from Tokyo Kasei Kogyo Co., Ltd. (Tokyo,
Japan). Analytical grade chloroform and methanol
were obtained from Wako Pure Chemical Co., Ltd.
(Osaka, Japan). Olive oil, soybean oil, and cotton seed
oil were purchased from Uryou Yakuhin Kogyo Co.,
Ltd. (Tokyo, Japan). Sa%ower oil was obtained from
Rinoru Oil Mills Co., Ltd. (Tokyo, Japan).
2.2 Preparation of samples
An undiluted solution (TPPO/CM solution) used in
determining the calibration curve of the TPPO concentration was produced by dissolving 6.00 mg of TPPO
and 200 mg of antioxidant in 10 mL of chloroform/
methanol (CM) solvent (2 : 1 (v/v) chloroform : methanol). This solution was diluted with CM solvent so that
the TPPO/CM solution contains TPPO concentrations
of 0.156, 0.312, 0.625, 1.250, and 2.500 mg/10 mL. The
TPP/CM solution was prepared by dissolving 200 mg
of TPP and 200 mg of antioxidant in 10 mL of the CM
solvent. This solution was prepared immediately
before use. Sample solutions of the oxidized vegetable
oil used for ionization were prepared by adding 200 mg
of the oxidized vegetable oil, 200 mg of antioxidant,
and 10 mL of the TPP/CM solution to a test tube (10

Fig. 1.

mm*50 mm) with a screw cap, and then tightly


sealed. They were allowed to react in the dark at 60
for 60 min. The oxidized vegetable oil was prepared by
spreading the vegetable oil to a thickness of about 1.0
mm in the scale (diameter: 15 cm*), placing the lid on
with a gap to allow circulation of air, and moderately
oxidizing the oil by exposing it to outdoor sunlight.
2.3 Mass spectrometry
All mass spectra were obtained using a Hitachi M2000-type double-focusing mass spectrometer (Tokyo,
Japan). Five microliters of the solution containing the
sample was injected into the EI sample tube in which
quartz cotton was packed and the sample tube was
inserted into the ionization chamber after the solvent
was evaporated under reduced pressure. The ionization was carried out under the following conditions: an
ionization voltage of 20 eV, an ionization current of
100 mA, an ion source temperature of 200, and the
maximum current to be supplied to the instrument for
heating of the EI sample tube. The scan interval was
0.8 s and the data was collected from 12 to 36 s.
2.4 Other measurements
The surface of the sample holder materials in the EI
sample tube was observed with a eld-emission scattering microscope (S-4000) obtained from Nissei Sangyo
Co., Ltd. (Tokyo, Japan). Determination of the chemical
POV of the hydroperoxides was carried out on the
samples by standard iodometry4), 5) based on the following equations:
ROOH2I2HI2ROHH2O
2Na2S2O3I22NaINa2S4O6
The POV is dened as the milliequivalent of peroxide

EI mass spectra of triphenylphosphine (TPP) and triphenylphosphine oxide (TPPO). Electron energy: TPO was
carried out at 20 eV (spectrum A), and TPPO was carried out at 70 eV (spectrum B) and 20 eV (spectrum C).
236

Determination of Peroxide Values Using EI-MS

per kg of the sample (according to the American Oil


Chemists Society method4)).
3.
3.1

Results and Discussion

Mass spectra of triphenylphosphine and triphenylphosphine oxide


In this method, the amount of TPPO generated by
the reaction of excess TPP with the hydroperoxide of
the oxidized vegetable oil was analyzed by EI-MS. Consequently, the appearance and the intensity of the related ions (molecular, dehydride, and fragment ions
etc.) of TPP and TPPO, which a#ect the determination
of the POV, was examined. As for TPP, 1.0 mL of the
solution, which was prepared by dissolving TPP in the
CM solvent, was injected into the EI sample tube, and
ionized after the solvent was evaporated under reduced
pressure. A molecular ion and many fragment-ions
were observed at an electron energy of 70 eV. Conversely, the number of fragment-ions decreased at an
electron energy of 20 eV, and [TPP] was observed as
a base peak (Fig. 1A). A similar test was carried out for
TPPO (see Fig. 1B) and [TPPOH] appeared as a base
peak and many other ions were observed at an electron
energy of 70 eV but ions other than [TPPOH]
drastically decreased at an electron energy of 20 eV
(Fig. 1C). There was no signicant di#erence between
the results obtained at 20 eV and 70 eV. Based on the
above results, the peak obtained for [TPPOH] at an
electron energy of 20 eV was adopted for measuring
the POV.
3.2 Oxidation reaction of triphenylphosphine
caused by cumene hydroperoxide and air
The measurement of POV based on TPPO produced
by the reaction of hydroperoxide in the oxidized vegetable oil and TPP is adopted as the method which uses

Fig. 2.

infrared spectroscopy, near-infrared spectroscopy,


uorometry, etc. Consequently, it seems that the oxidation of TPP by hydroperoxide in the sample does not
pose a problem. Cumene hydroperoxide11) or t-butyl
hydroperoxide,10) which can be easily obtained, were
used as the hydroperoxide source to prepare the
calibration curves of TPPO for these techniques. In the
EI-MS method, the forming process of TPPO by pure
hydroperoxide and the appearance of the ionization of
hydroperoxide, TPP, and TPPO should be veried. The
formation of TPPO was achieved by adding 1 mol of
TPP and 2 mols of cumene hydroperoxide to the CM
solvent and keeping it in the dark at 60 for 60 min.
One microliter of this solution was injected into the EI
sample tube in which quartz cotton was packed, and
the ionization was carried out after the solvent was
evaporated under reduced pressure. Figure 2A shows
the selected ion current chromatogram of the obtained
[TPPOH] and [TPP]. No TPP molecular ion was
detected even at a sensitivity 50 times the ionic
strength of [TPPOH] suggesting that TPP was denitely converted to TPPO. Only [TPPOH], which is
used to measure the POV, was clearly observed from
the mass spectrum with a scan number of 2737 (Fig.
2B).
TPP in the solution state is easily oxidized and therefore, the e#ect of air and dissolved air in the solution
during a series of operation processes must be determined. Adequate amounts of TPP and CM solvent
were injected into the test tubes and kept in the dark at
room temperature or 60 for 60 min and then examined by mass spectrometry.
Figure 3 shows the selected ion current chromatogram of [TPP] and [TPPOH]. Figure 3A indicates that a large amount of [TPPOH] was produced

Selected ion current chromatogram of the dehydride molecule of TPPO and mass spectrum of TPPO produced
from TPP with cumene hydroperoxide. Mass spectrum B) multiplied scan number 2737 of the selected ion
current chromatogram A). Next number of expresses magnication of ion strength. TPPO was obtained by
adding TPP (20 mg) and cumene hydroperoxide (40 mg) to the CM solvent (2 : 1 chloroform : methanol, 10 mL) and
keeping it in the dark at 60 for 60 min.
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Y. Mochida & S. Nakamura

Fig. 3.

Selected ion current chromatogram of TPP a#ected during the preparation of ionization solution by dissolved air
in solution or by atmosphere. The nitrogen substitution was not carried out for the solutions and the experiment
parts. The preparation of the ionization solution is the same as in Fig. 2. The reactions were carried out at room
temperature A) and at 60 B) and C) for 60 min. Antioxidant, 3,5-di-t-butyl-4-hydroxy toluene, was added for C).
Next number of expresses magnication of ion strength.

Fig. 4.

Scattering microscope images of sample holder materials.

at room temperature. It was determined that TPP in


the solution was oxidized by the air or the dissolved air
during the process. Figure 3B indicates that the e#ect
of the dissolved air in the solution was greater at 60.
Usually, in order to prevent the e#ect of air, the operation is carried out in an anaerobic atmosphere and by
nitrogen gas substitution in the experimental apparatus and solution. However, this operation creates problems in relation to the evaporation of the volatile solvent, the deterioration of the working environment,

and complexity. Akasaka et al.14) reported that the


addition of antioxidant to the reaction solution did not
prevent oxidation during a series of operating processes, and oxidation of the oxidized vegetable oil and
TPP. We also examined the e#ect of the addition of
antioxidant on the mass spectrum by keeping the
TPP-CM solution in the dark at 60 for 60 min. The
addition of antioxidant was valid though the generation of a small amount of TPPO (appearance of [TPPO
H]) was recognized (Fig. 3C), as it did not a#ect the

238

Determination of Peroxide Values Using EI-MS

Fig. 5.

Typical selected ion current chromatogram patterns of the dehydride molecule, [TPPOH], of desorbed TPPO
from asbestos for Gooch crucible and active carbon used as sample holder materials. The ionization solution was
TPPO (20 mg) added to CM solvent (5 mL).

Fig. 6.

The scattering microscope images of the quartz wool after repeated injection and ionization of the ionization
solution. Usual amount of the injection is 1 mL. The preparation of the ionization solution of A) and B) is by
adding TPPO (20 mg) to CM solvent (10 mL). See Fig. 2 for cumene hydroperoxide-TPP-CM solution for ionization
solution of C).

selected ion current chromatogram pattern of [TPPO


H].
3.3 E#ect of sample holder material
The results of the ionization of TPPO showed poor
reproducibility as the selected ion current chromatogram pattern of [TPPOH] changed each time. It
was assumed that this phenomenon was caused by the
sample holder material which a#ected the desorption
of the sample. We examined the e#ect of sample holder
materials, the quartz wool, asbestos wool for the Gooch
crucible, and active carbon. The scattering micrographs of the sample holder materials (Fig. 4) show a
remarkably small granular convexoconcave surface
for the active carbon and many needle-like prongs for
the asbestos wool used for the Gooch crucible and the
quartz wool. The quartz wool had a thicker and longer
shape and smaller prongs while the asbestos wool used
for the Gooch crucible revealed a groove along the axis
of the needle. The state of desorption of TPPO from the
sample holder material was determined by the selected
ion current chromatogram pattern of [TPPOH] obtained from the ionization of the TPPO solution, which
was prepared by dissolving 20 mg of TPPO in 50 mL of
CM solvent. The pattern obtained with the asbestos
wool exhibited multiple peaks (Fig. 5A), which can be
attributed to the irregular spiky desorption of TPPO in
the grooves. Active carbon, which has a wider adsorption area, exhibited a more remarkable tendency, and

the pattern of a continuous pulse-shaped desorption


was obtained (Fig. 5B). On the other hand, the pattern
obtained for the quartz wool sample holder exhibited a
single peak. This phenomenon is attributed to the fact
that quartz wool has neither groove nor pores to
strongly retain the TPPO and many small bosses existing on the surface had a positive e#ect on the desorption (Fig. 4). However, leading and tailing, which
indicated that the desorption did not start and nish
quickly, were observed with the selected ion current
chromatogram pattern. Similarly, a non-desorption
material was observed when the TPPO solutions were
repeatedly ionized without exchanging the quartz
wool sample holder (Fig. 6). The amount of residue was
small after undergoing ionization ve times (Fig. 6B),
and was large after 50 times (Fig. 6A). The amount of
residue was also examined when hydroperoxide, TPP,
and TPPO coexisted (Fig. 6C). The TPPO solution
including 20 mg of cumene hydroperoxide and 20 mg
of TPP was ionized after reacting in the dark at 60
for 60 min. The residue after ten repetitions exhibited
the same number, but larger peaks, compared to the
case without hydroperoxide.
Consequently, the
number of iterations to ensure good reproducibility
can be estimated as 10, though it may be inuenced by
the TPPO concentration. However, the quartz wool
sample holder should be changed every time if
reproducibility is important.

239

Y. Mochida & S. Nakamura

Fig. 7.

EI sample tubes used for EI method. A), B), D), E), and F) are handmade products and C) is a manufacturers
product.

Fig. 8.

Adaptation between the peroxide value (POV) by iodimetric method and TPPO concentration by a correction
curve. The [TPPOH] intensity of oxidized vegetable oil obtained by the EI-MS method was matched with the
[TPPOH] intensity obtained from the correction curve of TPPO, and a scale of the POV obtained with
iodimetric method was graduated to x axis in equal increments. The ionization of the TPPO-CM solution used 5
mL of the solution of CM solvent (10 mL) containing TPPO (6 mg) and antioxidant (200 mg). See Fig. 2 for the
preparation of the CM solvent. The ionization of oxidized vegetable oil used 5 mL of the solution of oxidized
vegetable oil (200 mg), antioxidant (200 mg), and CM solvent (10 mL), reacted in the test tube with screw stopping
(10 mm*50 mm) in the dark at 60 for 60 min. The preparation of the oxidized vegetable oil was carried out
by oxidizing the oil in an open plate and in outdoor sunlight.

3.4

E#ect of shape of the EI sample tube and heating method


The desorption of TPPO was a#ected by the heating
rate of the EI sample tube. A selected ion current
chromatogram of [TPPOH] with little leading and
tailing was obtained under the condition of ash heat-

ing (operated at the maximum dissipation of the equipment). The shape of the EI sample tube also signicantly inuenced desorption. Figure 7 shows examples of various types of handmade sample tubes. The
straight type (Fig. 7A) and the barrel type (Fig. 7B)
exhibited almost the same behavior as the

240

Determination of Peroxide Values Using EI-MS

Table 1.

Comparison of POVs Determined by EI-MS Method and Iodometric Method


Oxidized vegetable oil

Value

Cotton seed oil


1

[TPPOH] intensity/()
POVTPPO/(meq/kg)
POVIodine/(meq/kg)

Soybean oil
5

0.11
0.21 0.66 1.05 1.14
4.0
14
37
60
63
4.0
17
37
60
62

Sa%ower oil
4

0.06
0.33 0.69
2.15
2.0
18
40
122
1.5
20
40
120

0.06
0.65 1.54
2.0
36
87
2.0
30
87

Olive oil
1

0.21 0.73
12
42
12
38

See Fig. 8 for the preparation and ionization of the oxidized vegetable oil (analyte). [TPPOH] intensity: [TPPOH]
intensity is obtained from TPO in the sample by EI-MS method. POVTPPO : POV is determined from the correction curve of
TPPO concentration. POVIodine : POV is determined by iodometric method.

manufacturers product (Fig. 7C), and the appearance


of ion products was unstable. However, the shapes
shown in Fig. 7D and Fig. 7E exhibited a stable behavior of ion production, and reproducibility was improved suggesting that a long and thick tube body
provides a good result. When a tungsten wire was
wound around the heat supply section of the EI sample
tube (Fig. 7F) in order to transmit the heat throughout
the EI sample tube and allow uniform evaporation of
TPPO, the shape of the selected ion current chromatogram of [TPPOH] became an isosceles triangle.
3.5 Calibration curve of TPPO, and correlation
between the POV by iodometric method and
TPPO concentration by calibration curve
Six milligrams of TPPO in the undiluted solution
(TPPO-CM solution), which was prepared for making
the calibration curve of the TPPO concentration, was
determined by assuming that 200 mg of the sample
(POV was 200 meq/kg or less) was necessary for the
oxidation reaction of TPP. That is, if the main component, glyceride, of the vegetable oil is triolein, 200 mg
of triolein mono hydroperoxide, which has a POV of
200 meq/kg, can produce 5.56 mg of TPPO from TPO.
A calibration curve showing [TPPOH] intensity
compared to the TPPO concentration (mg/10 mL) of
the diluted TPPO-CM solution was prepared using the
peak value of the pattern (triangle) of the selected ion
current chromatogram of [TPPOH]. The base
length of this triangle remained similar at di#erent
TPPO concentrations. Consequently, the peak height
value was proportional to the TPPO concentration.
The linear regression plots (star symbol) are shown in
Fig. 8. The correlation coe$cient was r0.999.
The TPPO concentration (mg/10 mL) obtained by
this method from the oxidized vegetable oil with di#erent component molecular species corresponds to the
POV (meq/kg) obtained by the iodimetric method.
Four vegetable oils with di#erent oxidation degrees
were examined. The calibration curve prepared by
comparing the [TPPOH] intensity obtained by this
method with the [TPPOH] intensity from the
calibration curve of TPPO matched for the oxidized
vegetable oil, and then the POV obtained by the
iodometric method was plotted for comparison with
the TPPO concentration obtained from the calibration
curve. The results are shown in Fig. 8 together with
the calibration curve of TPPO; the correlation coe$cient was r0.999. Various oxidized vegetable oils are
indicated by the solid symbol along with the star

symbol for the TPPO concentration, and the x-axis is


the POV (meq/kg). The results proved that the POV of
the other oxidized vegetable oils had a good correlation
with the TPPO concentration of the diluted TPPO-CM
solution.
3.6 Measurement of samples
For the moderately oxidized samples (olive oil,
soybean oil, cotton seed oil, and sa%ower oil), the POV
obtained from the calibration curve approximately
coincided with the POV obtained by the iodometric
method. The correlation coe$cient of these samples
(including the samples used to prepare the calibration
curves) was r0.727. When the points, which obviously deviated from the straight line, were excluded, the
correlation coe$cient was r0.997 (see Table 1). The
removal of solvent under reduced pressure from the
ionization solution injected into the EI sample tube is
considered to be the cause of the error because, the
ionization solution containing the sample increased in
viscosity and was liable to boil suddenly while being
concentrated. In addition, the errors were caused by
the amount of quartz wool packed in the EI sample
tube and the method used to pack it.
4.

Conclusion

The POV (200 meq/kg or less) of the sample, which


contained various hydroperoxides of di#erent molecular species, was determined by the EI-MS method. The
sample solution for ionization was prepared by adding
the sample, TPP, antioxidant, and CM solvent to the
test tube, tightly sealing the test tube, and allowing it
to react in the dark at 60 for 60 min. The POV was
determined from the peak value of the triangular
selected ion current chromatogram pattern of the
TPPO dehydride molecule, which was obtained from
the EI of the sample. The correlation coe$cient of the
calibration curve for TPPO was r0.999. In addition,
the correlation coe$cient of the sample was r0.997.
Based on the method using EI-MS to obtain the POV
by measuring the amount of TPPO, produced by the
oxidation of TTP by the sample, we are convinced that
we have solved various problems inherent in the ionization process and developed a practical method for
POV measurement.
Acknowledgment
We are grateful to Mr. Kenji Ogihara, School of Engineering, Kanagawa University, for his help in the scattering microscope analyses.

241

Y. Mochida & S. Nakamura

8)

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Keywords: EI-MS, Peroxide value, Hydroperoxides, Iodometry, Triphenylphosphine

242