Food Chemistry 113 (2009) 692700

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Analytical Methods

Analysis of synthetic antioxidants and preservatives

in edible vegetable oil by HPLC/TOF-MS
Li Xiu-Qin a, Ji Chao b, Sun Yan-Yan c, Yang Min-Li a, Chu Xiao-Gang a,*
a

Institute of Food Safety, Chinese Academy of Inspection and Quarantine, Jia 3, Gaobeidian North Road, Beijing 100123, PR China
College of Food Science and Technology, Jiang Nan University, Wuxi 214036, PR China
c
School of Pharmacy, Shenyang Pharmaceutical University, Shenyang 110016, PR China
b

a r t i c l e

i n f o

Article history:
Received 21 February 2008
Received in revised form 14 July 2008
Accepted 19 July 2008

Keywords:
Synthetic antioxidants
Synthetic preservatives
Analysis
Edible vegetable oil
HPLC/TOF-MS

a b s t r a c t
The application of high performance liquid chromatography time-of-ight mass spectrometry (HPLC/
TOF-MS) for the qualitation and quantitation of 11 synthetic antioxidants and preservatives in edible vegetable oil samples is reported here. The qualitation by HPLC/TOF-MS is accomplished with the accurate
mass of the deprotonated molecules [M H] , along with the accurate mass of their main fragment ion. In
order to obtain sufcient sensitivity for quantitation purposes (using deprotonated molecule), segment
programme of fragmentor voltage is designed in negative ion mode. The mass accuracy typically obtained
is routinely better than 5 ppm. The 11 compounds behave linearly in the 0.055.0 mg/kg concentration
range, with correlation coefcient >0.997. The recoveries at the tested concentrations of 0.12.0 mg/kg
are 65.8106.9%, with coefcients of variation <8.1%. The method illustrated is suitable for routine qualitative and quantitative analyses of synthetic antioxidants and preservatives in edible vegetable oils.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
Synthetic antioxidants are widely used as food additives to prevent rancidication, owing to their high performance, low cost and
wide availability. Therefore, many synthetic antioxidants such as
butylated hydroxyanisole (BHA), tertiary butyl hydroquinone
(TBHQ), 2,4,5-trihydroxybutyrophenone (THBP), di-tertbutyl-4hydroxymethylphenol (IONOX-100), propyl gallate (PG), octyl gallate (OG), nordihydroguaiaretic acid (NDGA) and 4-hexylresorcinol
(4HR) are used in edible vegetable oil and cosmetics (Guan, Chu,
Fu, & Ye, 2005; Guo, Xie, Yan, Wan, & Wu, 2006). Preservatives such
as 2-naphthol (2NL), 4-phenylphenol (OPP) and 2.4-dichlorophenoxyacetic acid (2,4-DA), are commonly used in vegetable and fruit
to keep fresh. Propyl gallate and butylated hydroxyanisole, as synthetic phenolic antioxidants, display high chemical activity for suppressing chain initiation, or breaking chain propagation of the
peroxidation of unsaturated fatty acids. Their molecular structures
are shown in Fig. 1. Although they are powerful in protecting product quality in food distribution, excess antioxidants added to food
might produce toxicities or mutagenicities, and thus endanger the
health of people (Williams 1993, 1994). In most countries, the content of phenolic antioxidants in processed food is strictly limited.
So there are still genuine needs to establish an effective and convenient qualitation and quantitation method for analytically moni* Corresponding author. Tel.: +86 01 85778904; fax: +86 01 85752995.
E-mail address: lixq_sypu@yahoo.com (C. Xiao-Gang).
0308-8146/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodchem.2008.07.072

toring the proper use of prohibited antioxidants and the

superscale use of permitted antioxidants. The methods mainly reported for the determination of antioxidants and preservatives in
foods, cosmetics and pharmaceuticals were based on high performance liquid chromatography (HPLC) (Borremans, Van, Roos, &
Goeyens, 2004; Christian & Liliane, 2002; Karovicova & Simko,
2000; Lozano et al., 2005), gas chromatography (GC) (Gonzlez,
Gallego, & Valcarcel, 1999; Mu, Xu, & Li, 2007; Yang, Lin, & Choong,
2002), ion chromatography (IC) (Lian, Li, Wu, & Tian, 2005), capillary electrophoresis (CE) (Driouich, Takayanagi, Oshima, & Motomizu, 2000; Jaworska, Szulinska, & Wilk, 2005; Labat, Kummer,
Dallet, & Dubost, 2000; Lin, Chou, Sheu, & Shgu, 2000; Memon,
Bhanger, & Khuhawer, 2005; Xiang, Gao, & Xu, 2007), high performance liquid chromatography electrospray mass spectrometry
(HPLCMS) (Lee, Lin, Li, & Tsai, 2006); and gas chromatography
mass spectrometry (GCMS) (Guo, Xie, Yan, & Wan, 2007). In many
instances more than one additive is added to foodstuff which often
contains many kinds of food additives including antioxidants and
preservatives. Therefore, analytical methods that can simultaneously determine antioxidants and preservatives are advantageous. But most of the methods only allow food antioxidants or
preservatives to be determined, respectively. Boyce (1999) reported simultaneous determination of antioxidants including
butylated hydroxyanisole and butylated hydroxytoluene, preservatives including methylparaben and ethylparaben, and sweeteners
permitted as additives in food by mixed micellar electrokinetic capillary chromatography. In the last few years the role of HPLCMS

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L. Xiu-Qin et al. / Food Chemistry 113 (2009) 692700

HO

HO

HO

C O

HO

C O

HO
Octyl gallate (OG)

HO

Propyl gallate (PG)

MW=282.1467

MW=212.0685

OCH3

OH

OH

OH

Butylated hydroxyanisole (BHA)

Tertiary butylhydroquinone (TBHQ)

MW=180.1150

MW=166.0994

OH

O
C

OH

OH
CH3

OH

Di-tertbutyl-4-hydroxymethylphenol

2,4,5-Trihydroxybutyrophenone (THBP)

(IONOX-100) MW=236.1776

MW=196.0736

OH

Cl
Cl

OH

O CH2
COOH

OH
OH

Nordihydroguaiaretic acid (NDGA)

2.4-Dichlorophenoxyacetic acid (2,4-DA)

MW= 302.1518

MW=219.9694

OH

OH

OH

OH

4-Hexylresorcinol (4HR)
MW=194.1307

2-Naphthol(2-NL)
MW=144.0575

2-Phenylphenol (OPP)
MW=170.0732

Fig. 1. Molecular structures of 11 synthetic antioxidants and preservatives.

and related techniques is increasingly built up as an enabling tool in

food analysis for quality control. However, to the best of our knowledge, so far no people has reported the application of time-of-ight
mass spectrometry combined with high performance liquid chromatography for simultaneous determination of a group of antioxidants
(8 kinds) and preservatives (3 kinds) in foodstuff.
In this study, we have explored potential usefulness of high performance liquid chromatography time-of-ight mass spectrometry
(HPLC/TOF-MS) for accurate qualitative and quantitative analysis
of antioxidants and preservatives in edible vegetable oil. Recently,
HPLC/TOF-MS has been proven to be a sensitive and selective
method for the determination and conrmation of pesticide residues in vegetables and fruits (Thurman, Ferrer, & Fernandez-Alba,
2005; Ferrer, Garca-Reyes, Mezcua, Thurman, & Fernandez-Alba,
2005). The proposed methodology reported here consists of a preliminary liquidliquid extraction step using acetonitrile as extraction solvent which was saturated with hexane. Finally, mass
spectrometric qualitation and quantitation of the selected analytes
are achieved using HPLC/TOF-MS in negative ionisation mode. The
analytical methodology developed for the qualitation and quanti-

tation of 11 antioxidants and preservatives is applied to 19 kinds

of edible vegetable oil samples. The identication by time-of-ight
was accomplished with the determination of accurate mass of the
deprotonated molecule ([M H] ), along with accurate mass of a
characteristic fragment ion and the characteristic chlorine isotope
cluster present in some compounds studied. Several analytical
parameters, such as sensitivity, linearity, precision, mass accuracy,
selectivity, and limits of detection (LODs) are evaluated. In general,
this methodology of HPLC/TOF-MS for routine quantitative analyses of antioxidants and preservatives can be applied in most of edible oil.
2. Materials and methods
2.1. Chemicals
Reference compounds (butylated hydroxyanisole (BHA), tertiary butylhydroquinone (TBHQ), 2,4,5-trihydroxybutyrophenone
(THBP), di-tertbutyl-4-hydroxymethylphenol (IONOX-100), propyl
gallate (PG), octyl gallate (OG), 2-naphthol (2-NL), 4-phenylphenol

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L. Xiu-Qin et al. / Food Chemistry 113 (2009) 692700

(OPP), 4-hexylresorcinol (4HR), 2.4-dichlorophenoxyacetic acid

(2,4-DA) and nordihydroguaiaretic acid (NDGA) were purchased
from Fluka (Buchs, Switzerland) and Aldrich (Sigma-Aldrich, Steinheim, Germany). All reference compounds have a purity of P98.0%.
HPLC grade acetonitrile and hexane were obtained from Merck
(Darmstadt, Germany). Water was puried using a Milli-Q Ultrapure water purication system (Millipore, Bedford, MA, USA).
About 0.1 g (accurately weighed to 0.0001 g) of all reference
compounds were individually weighed into a 100 mL amber volumetric ask and dissolved with ethanol. Standard mixtures of all
analytes at different concentration levels were prepared by dilution using 4:1 methanol/water to establish the linearity range
and the calibration curves. Standards and samples were passed
through a 0.22 lm nylon lter (Pall Corporation, USA) before injection into the HPLC/TOF-MS system.
2.2. Sample preparation
Nineteen test samples including fteen samples of olive oil, four
samples of rap oil, peanut oil, corn oil and sunower seed oil were
purchased from local supermarkets in Beijing, PR China. About
0.25 g (accurately weighed to 0.0001 g) of edible vegetable oil were
weighed into a 10 mL glass centrifuge tube using an adventurer
electronic balance, and 3 mL acetonitrile which was saturated with
hexane was added. The mixture was homogenised for 5 min at
1800 rpm with a MS2 mini shaker. It was then centrifuged for
5 min at 4000 rpm with a TDL-5-A low-speed tabletop centrifuge.
The acetonitrile phase was collected and the oil phase was subsequently extracted twice in this way by acetonitrile. All the acetonitrile phases were combined into a 10 mL capacity ask, diluted to
the mark with acetonitrile, then analysed by HPLC/TOF-MS.
2.3. HPLC/TOF-MS analyses
The separation of selected analytes was carried out using an
HPLC system (consisting of a vacuum degasser, an autosampler,
and a binary pump; Agilent Series 1100, Agilent Technologies, San-

ta Clara, CA) equipped with a reversed phase C18 analytical column

of 150 mm  2.1 mm and 3.5 lm particle size (Zorbax Eclipse
XDB-C18). Column temperature was maintained at 35 C. The injected sample volume was 20 lL. Mobile phases B was acetonitrile
and mobile phase A was water. The optimised chromatographic
condition in negative ion mode was: 010 min, 1030% B; 10
12 min, 3060% B; 1225 min, 6090% B; 2526 min, return to initial conditions; a 10 min post-run was used after each analysis.
The ow-rate used was 0.2 mL/min. This HPLC system was connected to a time-of-ight mass spectrometer, Agilent MSD TOF
(Agilent Technologies, Santa Clara, CA), equipped with an electrospray interface operating in negative ion, using the following operation parameters: capillary voltage 3500 V; nebulizer pressure
35 psig; drying gas 9 L/min; gas temperature 350 C; fragmentor
voltage segment: 03.5 min, 130 V; 3.515 min, 170 V; 15
20 min, 200 V; 2021 min, 150 V; 2126 min, 200 V; skimmer
voltage: 60 V; octopole DC 1 34.5 V; octopole RF: 250 V. LC/MS
accurate mass spectra were recorded across the range 50
1050 m/z. The data recorded was processed with Applied Biosystem/MDSSCIEX Analyst QS software (Frankfurt, Germany) with
accurate mass application specic additions from Agilent MSD
TOF software. The instrument performed the accurate mass internal mass calibration automatically using a dual-nebulizer ion
source combined with an automated calibrate delivery system,
which introduced the internal reference masses (121.0509 and
922.0098 in positive ion mode; 112.9856 and 1033.9881 in negative ion mode) at approximately 600 lL/h.
3. Results and discussion
3.1. HPLC/TOF-MS analyses of antioxidants and preservatives
Edible vegetable oil is one of the most complex food matrices
due to the presence of numerous interferences that show up in
full-scan mode. For this reason, HPLC/TOF-MS parameters were
optimised by exploring the fragmentation of the analytes studied.
Under the optimised instrumental parameters (nebulizer and dry-

Table 1
Effect of the fragmentor voltages on CID fragmentation for HPLC/TOF-MS and accurate mass measurements for the deprotonated molecules
Compounds

2,4-DA
PG
THBP
TBHQ
2-NL
NDGA
OPP
BHA
4HR

OG
IONOX-100
a
b

MW

218.9
160.9
211.1
124.1
195.1
124.1
165.1
151.1
143.0
115.0
301.1
109.1
169.0
141.1
179.1
164.1
193.1
179.1
164.1
149.1
281.1
124.1
235.1
217.2

Parent and daughter ion

C8H5Cl2O3
C6H3OCl2
C10H11O5
C6H4O3
C10H11O4
C6H4O3
C10H13O2
C9H11O2
C10H7O
C9H7
C18H21O4
C6H5O2
C12H9O
C11H9
C11H15O2
C10H12O2
C12H17O2
C11H15O2
C10H12O2
C9H9O2
C15H21O5
C6H4O3
C15H23O2
C15H21O

Relative abundance

tR(min)

100 V

130 V

150 V

170 V

200 V

230 V

111.1a
2.9%b
23.2

13.7

28.9

95.5

17.5

19.4

19.4
1.6%
56.4

8.9

23.5

117.0
11%
25.0

14.9

35.2

109.8

25.8

21.9

23.4
3.89%
68.5

9.0

25.4

63.2
100%
23.7

11.1

33.0

111.9

21.3

22.9

18.8
16.38%
67.1

9.8

28.5

9.2
100%
32.8
0.1%
18.7

40.8

118.0

49.2

51.2

17.7
100%
123.2
3.99%
3.18%

13.1

28.1

2.6
100%
18.9
17%
14.2
4.1%
13.7
7.6%
73.1
1.9%
64.2

39.9

0.9
100%
67.7
7.04%
6.0%

23.3

23.1

0.0
100%
5.4
100%
6.0

5.9

49.7
18.6%
55.6
1.7%
30.5
6.99%
0.0
100%
25.1

33.5%
16.9%
22.3
4.5%
13.4
35.4%

The value equal to the peak area of parent ion in extraction ion chromatogram/105 (Ai/105).
The value refer to the relatively abundance of daughter ion in different fragmentor voltage.

Error
mDa

ppm

2.34

0.0231

0.1

4.40

0.4972

2.4

7.06

0.0174

0.1

9.74

0.3033

1.8

13.96

0.5384

3.8

18.45

1.1329

3.8

19.75

0.7885

4.7

20.53

0.1465

0.8

20.69

0.0035

0.1

21.32

0.2476

0.9

21.49

0.7537

3.2

L. Xiu-Qin et al. / Food Chemistry 113 (2009) 692700

ing nitrogen ow rates, vaporiser and drying temperatures), the effect of the fragmentor voltage was studied in order to obtain additional information from characteristics fragments of the
compounds studied. The in-source collisionally induced dissociation (CID) fragmentation is greatly enhanced at high fragmentor
voltage. This provided highly valuable structural information since
the accurate mass of the characteristic fragment ion could be used
along with that of the deprotonated molecule for conrmation purposes. The relative peak area response value (Ai/105) of the deprotonated molecules and the relative abundances for the main
fragments of the antioxidants and preservatives studied are summarised in Table 1 at six different voltages: 100, 130, 150, 170,
200 and 230 V. In negative ion mode: 2,4-DA in general required
lower fragmentor voltages (130 V) for fragmentation as can be
observed in Table 1. As Fig 2a shows if the voltages exceed
170 V, the deprotonated molecule of 2,4-DA would disappear and
the fragment ion (m/z 193) would turn to base peak. As can be

695

seen from Fig 2b, BHA shows good fragmentation at 150 V and
the mother ion would disappear and the fragment ion (m/z 164)
would become base peak when the voltage exceeded 150 V. As
shown in Table 1, the others compounds show good response values at 170 V except OG which shows a good response value at
200 V. However, most compounds show lower fragmentation at
170 V, even at a higher fragmentor voltage of 200 V. Moreover
their response values of mother ions notablely were decreased
when the voltage was 200 V. Therefore, in order to obtain sufcient
sensitivity for quantitative purposes (using the deprotonated molecule) and additional qualitative spectra information, a segment
programme for fragmentor voltage was designed for further analyses in negative ion mode. According to the intensity of deprotonated molecule and fragment ion and retention time of analytes,
the fragmentor voltage segment: 03.5 min, 130 V; 3.515 min,
170 V; 1520 min, 200 V; 20.021.0 min, 150 V; 21.026 min,
200 V.

Fig. 2a. HPLC/TOF-MS accurate mass spectrum of the deprotonated molecules and fragment ion for 2,4-DA at different fragmentor voltages.

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L. Xiu-Qin et al. / Food Chemistry 113 (2009) 692700

Fig. 2b. HPLC/TOF-MS accurate mass spectrum of the deprotonated molecules and fragment ion for BHA at different fragmentor voltages.

The mass accuracies obtained for both the deprotonated molecules and their characteristic fragment ions for the selected antioxidants and preservatives are shown in Table 1 (using an edible
vegetable oil matrix matched standard spiked at 0.8 mg/kg for each
compound). The effect of the concentration level on the accuracy of
the mass measurements of the selected antioxidants and preservatives was evaluated at different concentration levels within the
range 0.055.0 mg/kg. No signicant differences were observed
in the mass accuracy obtained with the matrix-matched standards
compared with that obtained with standards in pure solvent, with
average mass accuracy values better than 5 ppm of error for most
of antioxidants and preservatives. This fact illustrates the capability of accurate mass measurements in the unequivocal conrmation of these species in edible vegetable oil matrices at different
concentration levels.
In order to explore the feasibility of HPLC/TOF-MS for quantitative analyses in edible vegetable oil, as a complex matrix, the analytical performance of the proposed methodology was studied.

3.2. Linearity
To carry out this study, solutions with six levels of concentration within the range of 0.055.0 mg/kg were prepared. Analysis
was performed in triplicate. Quantitation was carried out using
the peak area from the extracted ion chromatogram (EIC) of the
deprotonated molecule with a mass window of 0.01 Da. The linearity range, correlation coefcient and linear equations were listed in
Table 2. As observed, the linearity of the analytical response within
the studied range of 2 orders of magnitude is excellent, with correlation coefcients higher than 0.997 in all cases.
3.3. Precision
Assay precision of the method was evaluated intra-and interday by analysis of six replicates of standard solution for two concentrations in 3 days. The intra- and inter-day precision was assessed by analysing standard solution. The intra-day precision

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L. Xiu-Qin et al. / Food Chemistry 113 (2009) 692700

Table 2
Linear equations, correlation coefcients, LOD for the 11 synthetic antioxidants and preservatives and recovery of the spiked analytes from edible vegetable oil
Compounds

Equations

Linear range (mg/kg)

LOD (mg/kg)

Maximum levela(mg/kg)

Spiked level (mg/kg)

Recovery (%)

RSD (%)

2,4-DA

Y = 7670.7X + 24807

0.9988

0.051.0

0.001

PG

Y = 608.67X

20483

0.9995

0.050.8

0.02

100

THBP

Y = 2417.4X

2E+06

0.9972

0.85.0

0.2

0.02% of lipid

TBHQ

Y = 3560.8X

637429

0.9998

0.25.0

0.03

200

2-NL

Y = 7663.7X

34120

0.9999

0.055.0

0.001

70

NDGA

Y = 3970.6X

645785

0.9996

0.25.0

0.03

1000

OPP

Y = 3162.8X

30903

0.9997

0.051.0

0.005

12

BHA

Y = 1500.5X

36878

0.9995

0.050.8

0.03

200

4HR

Y = 8337.9X

79589

0.9991

0.051.0

0.001

OG

Y = 4093.7X

3E+06

0.9996

0.85.0

0.2

70

IONOX-100

Y = 1853.4X + 38783

0.9995

0.050.8

0.001

0.02% of lipid

0.1
0.8
0.8
2.0
0.8
2.0
0.1
0.8
0.1
0.8
0.1
0.8
0.1
0.8
0.1
0.8
0.1
0.8
0.8
2.0
0.1
0.8

91.2
98.8
86.6
94.6
80.4
84.3
65.8
74.2
102.6
92.6
94.4
91.3
87.2
97.3
84.6
81.8
78.5
106.9
96.2
81.9
82.5
86.2

4.6
5.7
5.1
6.3
7.2
5.1
4.7
5.1
5.9
5.6
3.4
4.8
0.1
0.8
0.1
0.8
0.1
0.8
0.8
2.0
0.1
0.8

Maximum level refer to the maximum permitted quantity was added in food.

was between 4.31% and 7.07% and the inter-day precision was between 9.1% and 14.5%. The result shows good reproducibility and
precision of method.
3.4. Recovery
The recovery of the method was studied at the concentration
levels of 0.12.0 mg/kg where a known concentration of the analytes was added to a determined amount of placebo and it was calculated by the concentration of the analytes recovered in relation
to that added. The results obtained for the accuracy study (recovery method) from 6 samples (n = 3 for each concentration level)
are presented in Table 2 for the 11 compounds. As shown in Table
2, it can be concluded that the recovery study of the antioxidants
and preservatives in the edible vegetable oil matrix was correct,
therefore, the proposed analytical method was sufciently accurate. As an example, a typical total ion chromatogram of a spiked
edible vegetable oil sample at 0.8 mg/kg together with the extracted ion chromatogram used for quantication purposes is
shown in Fig. 3.
3.5. Limits of detection
The limits of detection (LODs) were estimated with concentration levels giving a signal-to-noise ratio of about 3. The results
are shown in Table 2. As observed, the limits of detection obtained
are much lower than the maximum residue level established for
these antioxidants and preservatives. Due to the high complexity
of this matrix, it is difcult to fulll these values with other techniques (i.e. LC/UV and GC/MS). In this sense, analyses using
HPLC/TOF-MS benet from the use of narrow mass windows for
quantitation purposes, which results in enhanced signal-to-noise
ratio, thus providing lower detection limits.
3.6. Selectivity using HPLC/TOF-MS
Selectivity is the ability to separate or isolate the response of
the target compounds from matrix ions. High selectivity for the
target compounds can be achieved using the high resolving power
of time-of-ight measurements. This feature reinforces the usefulness of TOF mass spectrometers applied to analyses of antioxidants

and preservatives in foodstuff. Fig. 4 showed an example of the

selectivity achieved by TOF-MS. As shown in Fig. 4a, retention time
of NDGA were 18.48 min in total ion chromatogram of standards.
As shown in Fig. 4b, there is also peak at the similarly retention
time (18.51 min) in total ion chromatogram of sample matrix.
But when function of extracted ion was applied at a narrow amu
window (0.01 Da), the peak of NDGA was not found. Therefore, it
showed the main interference disappears leading to a more selective identication for the target compound when the extracted ion
is selected at a 0.01 Da window. Furthermore, this selectivity improves the signal-to-noise ratio leading to better method detection
limits overall.
3.7. Sample determination
To evaluate the effectiveness of the proposed method, it was applied to the analysis of a total of nineteen samples of edible vegetable oil. Fortunately, in most cases, most antioxidants and
preservatives were not found and only TBHQ, PG and IONOX-100
were found at concentration levels near the limit of detection (below these food additives maximum residue level). Furthermore,
the total amounts of synthetic antioxidants and preservatives in
all of the samples were below the critical value dened in Chinese
National Standard.

4. Conclusion
A new analytical method has been developed and applied in
routine for screening and quantitation antioxidants and preservatives in edible vegetable oil. This is a real example that illustrates
the usefulness of routine accurate mass measurement capabilities
of HPLC/TOF-MS, with a unique feature, which can aid in solving
this kind of daily analytical problem. In fact, when one deals with
this kind of samples with the possibility of isobaric interferences
due to the complexity of matrix, the use of mass spectrometric
techniques with high selectivity is absolutely necessary. In this
sense, the selectivity of HPLC/TOF-MS relies on the resolving power
of the instrument on the m/z-axis, which enables the discrimination between the target species and isobaric interferences within
0.01 Da of mass difference.

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L. Xiu-Qin et al. / Food Chemistry 113 (2009) 692700

Fig. 3. Total ion chromatogram (TIC) is corresponding to the analysis of a spiked oil sample with antioxidants and preservatives (0.8 mg/kg) by HPLC/TOF-MS and the
extracted ion chromatogram (XIC) for each corresponding deprotonated molecule. Window = 0.01 Da; negative ion mode.

L. Xiu-Qin et al. / Food Chemistry 113 (2009) 692700

699

Fig. 4. Total ion chromatogram and extracted ion mass spectrum of sample. (a). Total ion chromatogram of standard and mass spectrum of standard peaks(NDGA) at
18.48 min; (b). Total ion chromatogram of sample and mass spectrum of suspected peaks at 18.51 min.

Acknowledgements
The authors wish to express their deep sense of gratitude to Dr
Jerry Zweigenbaum and Yan Yan Fang of Agilent Technologies Inc.
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