Article

pubs.acs.org/JAFC

Dispersive Micro-Solid-Phase Extraction of Herbicides in Vegetable

Oil with Metal−Organic Framework MIL-101
Na Li,† Liyuan Zhang,‡ Li Nian,§ Bocheng Cao,† Zhibing Wang,∥ Lei Lei,† Xiao Yang,† Jiaqi Sui,†
Hanqi Zhang,† and Aimin Yu*,†
†
College of Chemistry, Jilin University, Qianjin Street 2699, Changchun 130012, P. R. China
‡
College of Food, Heilongjiang Bayi Agricultural University, Xinfeng Lu 5, Daqing 163319, P. R. China
§
Institude of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South
China University of Technology, Guangzhou 510640, P. R. China
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∥
College of Chemistry and Life Science,Changchun University of Technology, Yanan Street 2055, Changchun 130012, P. R. China
*
S Supporting Information
Downloaded via UNIV TEKNOLOGI MARA on March 16, 2023 at 14:02:30 (UTC).

ABSTRACT: Dispersive microsolid-phase extraction based on metal−organic framework has been developed and applied to the
extraction of triazine and phenylurea herbicides in vegetable oils in this work. The herbicides were directly extracted with
MIL-101 from diluted vegetables oils without any further cleanup. The separation and determination of herbicides were carried
out on high performance liquid chromatography. The effects of experimental parameters, including volume ratio of n-hexane to
oil sample, mass of MIL-101, extraction time, centrifugation time, eluting solvent, and elution time were investigated. The
Student’s t test was applied to evaluate the selected experimental conditions. The limits of detection for the herbicides ranged
from 0.585 to 1.04 μg/L. The recoveries of the herbicides ranged from 87.3 to 107%. Our results showed that the present
method is rapid, simple, and effective for extracting herbicides in vegetable oils.
KEYWORDS: metal−organic framework (MOF), MIL-101, vegetable oil, herbicide, dispersive microsolid-phase extraction

■ INTRODUCTION
Vegetable oils have been used for thousands of years in cooking
and play a more and more important role in human diet.
Nowadays, vegetable oils are considered as essential food-
stuffs because of their high nutrition value. The positive effect
of vegetable oils on health has prompted demands worldwide.
To increase yields, pesticides are widely used on oil crops at
various stages of cultivation to protect against weeds and pests.
However, the pesticide residues can persist into the harvest
stage, and thus the contamination of oil seeds or fruits1−3 and
oil products1,4−10 is possible. The presence of pesticides in
vegetable oils can affect the oil quality and pose a risk to human
health. As a major group of pesticide, herbicides are used widely
for weed control. The European Union has established max-
imum residue limits (MRLs) of some herbicides in oil seeds
and fruits.11 However, some herbicides were found in vegetable
oils.1,4,6−8 In the report by Sanchez et al.,6 triazine and phenylurea
herbicides ranging from 5.6 to 190.4 μg/kg were found in virgin
olive oils and 120.1 μg/kg of simazine was found in one oil
sample. The determination of herbicide residues in vegetable
oils is necessary.
Analytical problems associated with high-fat foods are well-
known. Sample preparation methods for vegetable oils require
the removal of fat to eliminate interferents and protect ana-
lytical systems.12 The common methods for the extraction of
pesticides in vegetable oils are liquid−liquid extraction (LLE)
followed by the cleanup. Liquid−liquid partition,5 low tempera-
ture fat precipitation,2,4 gel-permeation chromatography
(GPC),6 solid phase extraction (SPE),8,9,13,14 dispersive SPE
(DSPE),15−18 and matrix solid phase dispersion (MSPD)7,19−21
are usually applied in the cleanup. To achieve sufficient cleanup,
the combination of a variety of cleanup procedures was applied.
The LLE followed by low temperature fat precipitation and
DSPE was applied to the extraction of pesticides in soybean oil
and peanut oil.15,16 Low temperature fat precipitation followed
by SPE or MSPD was used to clean up the extract of palm
oil.13,19 These methods are usually time and solvent consuming,
expensive, and complex. To simplify the sample preparation
process, the direct extraction of analytes in oil samples has been
investigated. The pesticides in vegetable oils could be directly
determined on the basis of the cleanup by liquid chromatog-
raphy and size-exclusion chromatography.10,22 However, the
acquisition and maintenance cost of the instrument was
considerable. MSPD using sulfuric acid-impregnated silica as
dispersant was applied to the one-step extraction of pesticides
and polychlorobiphenyls from vegetable oils.23 In contrast to
the conventional methods, the direct adsorption of pesticides
from oil solution is attractive and potential. The molecularly
imprinted solid phase extraction24 was developed for the direct
extraction of fenthion in diluted olive oil. The novel sorbents
could be used for the rapid, simple, and effective extraction of
targets in oil samples.
MIL-101, first reported in 2005, was built up from a hybrid
supertetrahedral building unit and the unit was prepared with
terephthalate ligands and trimeric chromium octahedral
Received: August 25, 2014
Revised: January 26, 2015
Accepted: February 10, 2015
Published: February 10, 2015

© 2015 American Chemical Society 2154 DOI: 10.1021/jf505760y

J. Agric. Food Chem. 2015, 63, 2154−2161
Journal of Agricultural and Food Chemistry
clusters.25 MIL-101 has some advantages of large pore windows,
mesoporous pores (2.9−3.4 nm), accessible coordinative un-
saturated sites, and excellent chemical stability. These proper-
ties make it attractive in analytical applications, especially in
chromatographic separation and sample pretreatment. MIL-101
has been explored as stationary phase for liquid chromatog-
raphy.26 In sample treatment, MIL-101 has been successfully
used as sorbent to extract targets in aqueous samples.27−29
Hasen et al. used MIL-101 to extract naproxen and clofibric
acid from aqueous solution.28 Hu et al. reported the application
of MIL-101 packed microcolumn for the extraction of naproxen
and its metabolite in urine samples.29 The adsorption extraction
with MIL-101 in nonpolar system is also attractive. In our
previous work, MIL-101 was successfully used to clean up the
extract of peanuts and a large mass of fat was separated.3 Com-
pared with conventional sorbents, MIL-101 shows better
extraction efficiency in nonpolar solution. Thus, the MIL-101
could be potentially applied to the direct extraction of
pesticides in vegetable oil and the sample preparation process
can be effectively simplified and accelerated.
Herein, the dispersive microsolid-phase extraction (d-μ-SPE)
based on MIL-101 was developed for extracting herbicides
in vegetable oils. The herbicides were extracted directly with
MIL-101 from diluted vegetable oils, and no further cleanup
operation is needed. The fat remaining in sample solution was
easily removed after centrifugation. The herbicides were
separated and determined by HPLC. The operation is quick
and simple, and the results are satisfactory.
■
MATERIAL AND METHODS
Chemicals. Fenuron, simeton, simazine, atraton, chlortoluron,
secbumeton, and terbumeton were obtained from National Institute
for the Control of Pharmaceutical and Biological Products (Beijing,
China). Standard stock solutions for the herbicides (200 μg/mL)
were prepared by dissolving 2.0 mg of the standard in 10.0 mL of
acetonitrile. All of the stock standard solutions were stored in a
refrigerator at 4 °C. Working and mixed working standard solutions
were prepared by diluting stock standard solutions with acetonitrile.
Chromatographic grade acetonitrile was purchased from Fisher Scien-
tific Company (Pittsburgh, PA, USA). Cr(NO3)3·9H2O (>99.0%)
were purchased from XLong chemical Co., Ltd. (Guangdong, China).
1,4-Benzenedicarboxylic acid (H2BDC, ≥98.5%) was purchased from
Tianjin Guangfu Fine Chemical Research Institute (Tianjin, China).
Hydrofluoric acid (HF, ≥40%) was purchased from Nanjing Chemical
Reagent Co., Ltd. (Nanjing, China). Pure water was obtained with a
Milli-Q water purification system (Millipore Co., USA). Primary
secondary amine (PSA), C18, and graphitized carbon black (GCB)
were purchased from Beijing Agela Technologies Inc. (Beijing, China).
All of the other reagents (analytical-reagent grade) were purchased
from Beijing Chemical Factory (Beijing, China).
Instruments. Chromatographic separation and determination
of the herbicides were carried out on an Agilent 1100 series liquid
chromatograph (Agilent Technologies Inc., USA) equipped with
photodiode array detector (DAD) and quaternary gradient pump.
Eclipse XDB-C18 column (3.5 μm, 4.6 mm × 150 mm, Agilent, USA)
was used.
The KQ3200E ultrasonic cleaner was purchased from Kunshan
Ultrasonic Instrument Co., Ltd. (Kunshan, China). The frequency and
output power of the ultrasonic cleaner are 40 kHz and 150 W, respec-
tively. An Allegra 64 R centrifuge was purchased from Beckman Coulter.
The X-ray diffraction (XRD) patterns were recorded on a Rigaku
D/max-2550 diffractometer equipped with a graphite monochromator
(Rigaku, Japan) and Cu Kα radiator (λ = 1.5418 Å). Transmission
electron microscopic (TEM) characterization was performed on a
Tecnai G2 F20 S-Twin (Philips, Holland). BET surface area was mea-
sured on an ASAP 2020 micropore physisorption analyzer (Micromeritics,
2155
Article
Norcross, GA, USA) using nitrogen adsorption at 77 K. The synthesis and
characterization of MIL-101 was consistent with our previous work.3
Sample Preparation. Vegetable oils were collected from local
markets. Soybean oil (sample 1), corn oil (sample 2), sunflower oil
(sample 3), and peanut oil (sample 4) were used. All samples were
stored at room temperature.
Four fresh spiked samples containing triazine and phenylurea
herbicides were prepared by adding the mixed working standard solu-
tion into the samples, shaking for 10 min, and standing for 1 h. The
aged spiked sample of soybean oil was prepared by the method
mentioned above except that the spiked soybean oil sample was kept
in sealed bottle and stored for 1, 2, 3, and 4 weeks at 4 °C, respectively.
In the “Analysis of Samples” section, four oil samples (sample 1−4)
were used. The other experiments were performed with soybean oil
sample (sample 1) only.
Extraction Procedure. d-μ-SPE. A 2 mL of vegetable oil sample
was added into 25 mL centrifuge tube and diluted with 10 mL of
n-hexane. Subsequently, 7 mg of MIL-101 was added into the tube and
the ultrasonic extraction was carried out for 15 min. The mixture was
centrifuged for 3 min at 8720g, and the supernatant was decanted.
Then 0.5 mL of n-hexane was added into the tube and followed by the
same procedure as mentioned above. The analytes were eluted from
MIL-101 with 1.5 mL of methanol in an ultrasonic bath for 1 min. The
mixture was centrifuged for 10 min at 8720g, and the supernatant was
dried under nitrogen stream. The residue was dissolved in 200 μL of
methanol. The resulting solution was filtered with 0.22 μm PTFE filter
and referred to as analytical solution. Then 20 μL of the analytical
solution was injected into the HPLC system.
QuEChERS Procedure. The quick, easy, cheap, effective, robust, and
safe (QuEChERS) procedure was performed according to Sobhanzadeh
et al.;18 2 mL of vegetable oil and 5 mL of water were added into a
25 mL centrifuge tube. Then, 7 mL of acetonitrile, 2.8 g of anhydrous
magnesium sulfate, and 0.7 g of sodium chloride were added into the
tube. The tube was vigorously shaken for 1 min. The mixture was
centrifuged at 1395g for 1 min. The tube was horizontally stored in
freezer at −20 °C for 2 h. Then the supernatant was transferred into a
PTFE centrifuge tube containing 750 mg of anhydrous magnesium
sulfate, 250 mg of PSA, 250 mg of C18 sorbent, and 250 mg of GCB.
After shaking for 30 s, the mixture was centrifuged at 1395g for 1 min.
The supernatant was evaporated to dryness and reconstituted in
200 μL of methanol. The resulting solution was filtered with 0.22 μm
PTFE filter and referred to as analytical solution. Then 20 μL of the
analytical solution was injected into the HPLC system.
HPLC Analysis. The HPLC analysis was conducted in gradient
mode. Mobile phases A and B were water and acetonitrile, respectively.
The gradient conditions are as follows: 0−8 min, 30−45% B; 8−10
min, 45% B; 10−15 min, 45−50% B; 15−19 min, 50−72% B. The
column temperature was kept at 30 °C, and the flow rate of mobile
phase was kept at 0.5 mL/min. Injection volume of analytical solution
was 20 μL. The monitoring wavelengths were 244 nm for fenuron and
chlortoluron and 222 nm for the other herbicides.
Statistics. The Student’s t-test was applied to the evaluation of the
reasonableness of the selected experimental parameters. The t is
calculated from
x1 − x 2
t=
1 1
S
n1
+ n2
(n1 − 1)S12 + (n2 − 1)S22
S=
n1 + n2 − 2
where x1 and x2 are the mean recoveries obtained under two experi-
mental conditions, n1 and n2 are the sample sizes, s1 and s2 are the stan-
dard deviations, and (n1 + n2 − 2) is degree of freedom.
■
RESULTS AND DISCUSSION
Optimization of d-μ-SPE. In the study, some experimental
parameters that affect the extraction efficiency were investigated
DOI: 10.1021/jf505760y
J. Agric. Food Chem. 2015, 63, 2154−2161
Journal of Agricultural and Food Chemistry
and optimized. All optimization experiments were carried out
by analyzing the spiked soybean oil sample in triplicate.
Effect of Volume Ratio of n-Hexane to Oil Sample. The
dilution has a significant effect on the extraction efficiency. In
this work, vegetable oil sample was diluted with n-hexane. The
results are shown in Figure 1. The recoveries of herbicides
Figure 1. Effect of volume ratio of n-hexane to oil sample on
recoveries of herbicides from soybean oil. Mass of MIL-101, 7 mg;
extraction time, 15 min; centrifugation time, 3 min; eluting solvent,
1.5 mL of methanol; spiked concentration, 50 μg/L.
increase with the increase of the volume ratio of n-hexane to
oil sample. The highest recoveries are obtained when the
volume ratio is 5:1, and the recoveries change slightly with the
further increase of the volume ratio. The reason could be that
the viscosity of oil sample decreases with the increase of the
volume of n-hexane, which is beneficial to the dispersion of
sorbent and thus improvement of the extraction efficiency. In
addition, the fat and other impurities are easily dissolved in
nonpolar solvent (n-hexane). Consequently, the increase of
n-hexane volume is beneficial to the removal of impurities.
Therefore, the selected volume ratio of n-hexane to oil sample
was 5:1.
Effect of Mass of MIL-101. The effect of mass of MIL-101 in
the range of 0.5−12 mg on recoveries was investigated. The
results shown in Figure 2 indicate that the recoveries of
Figure 2. Effect of mass of MIL-101 on recoveries of herbicides from
soybean oil. Volume ratio of n-hexane to oil sample, 5:1; extraction
time, 15 min; centrifugation time, 3 min; eluting solvent, 1.5 mL of
methanol; spiked concentration, 50 μg/L.
2156
Article
herbicides increase with the increase of mass of MIL-101 from
0.5 to 5 mg and change slightly when the mass of MIL-101 is
more than 5 mg. To ensure sufficient extraction, 7 mg of
MIL-101(Cr) was selected in the following experiments.
Effect of Extraction Time and Centrifugation Time. The
effect of extraction time ranging from 1 to 30 min was inves-
tigated. The results are shown in Figure 3. The recoveries of
Figure 3. Effect of extraction time on recoveries of herbicides from
soybean oil. Volume ratio of n-hexane to oil sample, 5:1; mass of
MIL-101, 7 mg; centrifugation time, 3 min; eluting solvent, 1.5 mL of
methanol; spiked concentration, 50 μg/L.
herbicides increase when extraction time increases from 1 to
15 min and change slightly with the further increase of extrac-
tion time. The recoveries increase rapidly within 10 min and
increase slightly from 10 to 15 min. Therefore, the extraction
time was selected as 15 min. The effect of centrifugation
time was investigated in the range of 1−10 min. The effect of
centrifugation time on the recoveries of herbicides is slight. The
rapid separation of MIL-101 from sample solution may be due
to the low density of sample solution. Therefore, 3 min was
selected as centrifugation time.
Effect of Eluting Solvent and Elution Time. In this work,
methanol and acetonitrile were used as eluting solvents in the
volume range of 0.5−2 mL. The results shown in Figure 4
indicate that the recoveries of analytes increase with increasing
Figure 4. Effect of eluting solvent on recoveries of herbicides from
soybean oil. Volume ratio of n-hexane to oil sample, 5:1; mass of
MIL-101, 7 mg; extraction time, 15 min; centrifugation time, 3 min;
spiked concentration, 50 μg/L.
DOI: 10.1021/jf505760y
J. Agric. Food Chem. 2015, 63, 2154−2161
Journal of Agricultural and Food Chemistry Article

Table 1. Calibration Lines, Linearity Ranges, and Detection Limits for Determination of Herbicides in Vegetable Oil Samples
analyte calibration line correlation coefficient linearity range (μg/L) LOD (μg/L)
fenuron y = (2.07 ± 0.00411)x + (0.206 ± 0.483) 0.9999 3.90−250 1.04
simeton y = (3.36 ± 0.0257)x + (1.81 ± 3.02) 0.9997 2.00−250 0.720
simazine y = (3.29 ± 0.0149)x + (1.92 ± 1.75) 0.9999 2.00−250 0.609
atraton y = (3.30 ± 0.0356)x + (2.75 ± 4.19) 0.9994 2.00−250 0.576
chlortoluron y = (2.08 ± 0.0156)x + (2.66 ± 1.84 0.9997 3.90−250 0.974
secbumeton y = (3.06 ± 0.0240)x + (0.723 ± 2.83) 0.9997 2.00−250 0.637
terbumeton y = (3.10 ± 0.0202)x − (2.92 ± 2.38) 0.9998 2.00−250 0.585

Table 2. Recoveries of Herbicides from Soybean Oil Sample the increase of elution time. So, 1 min of elution time was
and Intra- and Interday Precision of the d-μ-SPE Methoda selected.
Statistical Analysis. To evaluate the reasonableness of
analytes intraday precision interday precision
the selected experimental parameters, the Student’s t test was
fenuron 98.9 ± 4.28 100 ± 3.39 applied and the t values were calculated (the detailed information
simeton 96.2 ± 2.65 101 ± 2.39 was listed in Supporting Information, Table 1). The results indicate
simazine 102 ± 1.63 101 ± 1.77 that the difference between the selected value and the near value of
atraton 99.0 ± 1.33 99.4 ± 4.38
the experimental parameters are significant (P < 0.01). So the
chlortoluron 99.4 ± 4.46 97.8 ± 1.72
selected experimental parameters should be reasonable.
secbumeton 95.8 ± 1.95 99.4 ± 3.02
Evaluation of the Present Method. Analytical Perform-
terbumeton 101 ± 1.67 99.2 ± 2.23
ance. The calibration curves were constructed by plotting the
a
The values in the table are mean recovery ± standard deviation peak areas measured versus the concentrations of analytes in
(%, n = 5). the spiked oil samples. The linear regression equations and
correlation coefficients are listed in Table 1. The limits of
the volume of eluting solvent and change slightly when detection (LODs) were calculated based on the signal-to-noise
the volume of eluting solvent is larger than 1.5 mL. The (S/N) ratio of 3. The LODs for triazine and phenylurea
recoveries obtained with methanol are slightly higher than herbicides range from 0.585 to 1.04 μg/L.
those obtained with acetonitrile. As methanol is cheaper Repeatability was evaluated by determining target analytes in
than acetonitrile, 1.5 mL of methanol was selected as eluting spiked oil samples at spiked concentration of 50 μg/L. The
solvent. The eluting of analytes was carried out in ultrasonic intraday precision was obtained by analyzing a sample five
bath. The effect of elution time ranging from 0.5 to 5 min times during a working day. The interday precision was
was studied. There is no significant change in recoveries with obtained by analyzing the same sample over five working days.

Table 3. Recoveries of Herbicides from Aged Soybean Oil Samples at Two Different Spiking Levelsa
added (μg/L) stored time (week) fenuron simeton simazine atraton chlortoluron secbumeton terbutmeton
10.0 1 99.8 ± 3.57 99.9 ± 3.18 105 ± 3.05 102 ± 3.71 100 ± 0.314 99.9 ± 3.77 105 ± 2.28
2 96.1 ± 0.973 97.8 ± 3.18 101 ± 0.407 97.6 ± 0.586 97.2 ± 3.14 95.1 ± 2.93 104 ± 2.51
3 96.6 ± 6.16 99.5 ± 3.37 103 ± 0.813 99.2 ± 3.12 97.8 ± 0.941 94.2 ± 5.45 104 ± 3.19
4 95.0 ± 2.60 95.6 ± 1.87 102 ± 1.42 99.7 ± 1.95 95.8 ± 2.51 93.2 ± 0.629 101 ± 1.82

100 1 100 ± 1.16 100 ± 0.445 104 ± 1.58 103 ± 2.00 101 ± 1.57 102 ± 1.31 107 ± 4.14
2 96.9 ± 1.25 97.3 ± 2.47 101 ± 0.684 97.7 ± 0.306 98.2 ± 2.80 97.2 ± 5.92 104 ± 5.30
3 98.7 ± 0.892 98.6 ± 2.41 100 ± 3.49 97.2 ± 3.03 98.8 ± 0.643 98.3 ± 4.03 104 ± 5.68
4 95.9 ± 2.61 97.2 ± 0.465 99.5 ± 4.04 99.1 ± 1.67 96.7 ± 1.41 95.6 ± 0.645 102 ± 2.33
a
The values in the table are mean recovery ± standard deviation (%, n = 3).

Table 4. Recoveries of Herbicides from Fresh Vegetable Oil Samples at Two Different Spiking Levelsa
sample added (μg/L) fenuron simeton simazine atraton chlortoluron secbumeton terbumeton
1 10.0 101 ± 3.57 98.6 ± 5.05 99.2 ± 6.10 102 ± 2.73 97.8 ± 2.82 96.3 ± 4.19 102 ± 2.74
100 102 ± 0.693 99.5 ± 2.26 99.7 ± 0.963 102 ± 2.59 98.3 ± 1.57 98.2 ± 4.09 99.1 ± 1.95

2 10.0 98.9 ± 7.46 92.5 ± 2.06 96.6 ± 1.22 100 ± 3.71 94.5 ± 5.02 95.9 ± 3.56 99.9 ± 2.74
100 88.3 ± 1.09 94.0 ± 1.71 92.6 ± 3.69 97.7 ± 0.730 87.3 ± 3.76 90.9 ± 1.23 95.7 ± 2.17

3 10.0 103 ± 7.79 99.9 ± 3.93 93.4 ± 4.88 102 ± 1.17 95.4 ± 1.25 93.8 ± 4.40 103 ± 4.79
100 98.2 ± 2.26 97.6 ± 0.587 97.2 ± 1.86 104 ± 1.21 96.2 ± 1.20 96.1 ± 1.75 97.7 ± 3.01

4 10.0 97.0 ± 1.62 102 ± 0.562 102 ± 3.66 95.6 ± 4.69 96.9 ± 1.57 93.8 ± 5.66 99.0 ± 5.47
100 93.9 ± 3.96 91.9 ± 5.80 103 ± 4.84 99.3 ± 2.58 97.1 ± 6.19 93.4 ± 2.09 100 ± 6.06
a
The values in the table are mean recovery ± standard deviation (%, n = 3).

2157 DOI: 10.1021/jf505760y

J. Agric. Food Chem. 2015, 63, 2154−2161
Journal of Agricultural and Food Chemistry Article

Figure 5. Chromatograms of extracts of soybean oil sample 1 (A) and spiked sample 1 (B) prepared by the d-μ-SPE method, and of soybean oil
sample 1 (C) and spiked sample 1 (D) prepared by QuEChERS method. 1, fenuron; 2, simeton; 3, simazine; 4, atraton; 5, chlortoluron; 6,
secbumeton; 7, terbumeton.

The results are listed in Table 2. The recoveries of intra- and
interday range from 95.8 to 102%, with standard deviations
ranging from 1.33 to 4.46%. The results indicate that the
present method has good repeatability.
The long-term stability of the analytes in the sample was
evaluated by analyzing one aged spiked sample of soybean oil.
The recoveries of herbicides in aged spiked sample of soybean
oil are listed in Table 3. It can be seen that the recoveries of
herbicides range from 93.2 to 107%, with standard deviations
ranging from 0.306 to 6.16%. It can be deduced that the
herbicides in soybean oil are stable for at least 4 weeks.
Analysis of Samples. The target analytes were not found in
vegetable oil samples. The practical applicability of the present
2158
method was evaluated by determining herbicides from four
fresh spiked vegetable oils. The recoveries of herbicides in fresh
spiked vegetable oil samples listed in Table 4 range from 87.3
to 104%, with standard deviations ranging from 0.562 to 7.79%.
The results indicate that the present method provides satis-
factory recoveries and acceptable precision at two concen-
tration levels. The chromatograms of sample 1 and spiked
sample 1 are shown in Figure 5.
Comparison with QuEChERS Method. For further evalua-
tion, the present method was compared with QuEChERS
method developed by Sobhanzadeh et al.18 The chromatograms
of the extracts obtained by QuEChERS method are shown in
Figure 5. The resolutions of the peaks obtained by the present
DOI: 10.1021/jf505760y
J. Agric. Food Chem. 2015, 63, 2154−2161
Journal of Agricultural and Food Chemistry Article

method range from 2.04 to 24.6, and the selectivity ranges

this work
this work
from 1.05 to 2.07. The resolutions of the peaks obtained by

ref

14
33

34
18

20

21

19
35
1

7
QuEChERS method range from 1.89 to 14.3, and the selectivity
ranges from 1.04 to 1.42. In Figure 5, the chromatograms of the
extracts obtained by QuEChERS method are much dirtier than

not reported

not reported
a

1.31−1.49a
0.585−1.04
1.64−2.48

0.01−3.5b
6.4−7.5b

0.6−1.0b

0.2−1.4b

1.5−2.0b
1.5−5.0b
0.2−2b
those obtained by the present method. So the selectivity of

1−5b
LOD
the present method is higher than that of QuEChERS method.
The high selectivity of the present method can be attributed to
the reverse extraction way in which the analytes are adsorbed,
while the fat and most of the interferents remain in sample

2.83−6.68
2.83−7.64

4.60−9.75
RSD (%)

4.9−15.8

5.3−13.4
4.3−13.4
1.1−7.7
2−10

5−10
3−5

3−6
2−4
<15
solution. The large windows of MIL-101(Cr) make the
introduction of the analytes into the cages easy.3 The analytes
were adsorbed on MIL-101 mainly by the coordination
interaction between heteroatoms in analytes and the unsatu-

recovery (%)

not reported
51.62−92.65

76.1−104.2
76.1−107.4
81.8−110.7
88.2−99.5

69.5−73.3
93.4−102
rated metal sites, π−π interaction between the analytes and

84−106

92−109
81−111

83−104
47−80
terephthalic acid molecules of the framework, and the
π-complexation between the π-electrons of analytes and
Lewis acid sites in the pore of MIL-101. The analytes with
log Kow from 1.07 to 2.94 are relatively polar (the log Kow was

LC/TOF-MS
LC-TOF-MS

LC-TOF-MS
LC-TOF-MS
GC-MS/MS
LC-MS/MS

LC-MS/MS

LC-MS/MS
detection
obtained from SciFinder scholar database). MOFs with open

GC-NPD
LC-DAD
LC-DAD

GC-MS

LC-UV
metal sites have great potential for enhancing adsorption of
molecules with polarity.30−32 The report by Huang and co-
workers demonstrated that MIL-101 has high affinity to the

low temperature fat precipitation (2 h) followed DSPE: 50 mg MgSO4 + 250 mg PSA +

low temperature fat precipitation (2 h) + DSPE: 4 g MgSO4 + 250 mg PSA + 250 mg

volatile organic compounds containing heteroatom, especially

low temperature fat precipitation (4 h) followed DSPE: 100 mg MgSO4 + 500 mg

the amines, and the surface of the MIL-101 is energetically
heterogeneous.31 Fu et al. also reported that the interaction

low temperature fat precipitation (4 h) followed MSPD: 2 g PSA + 2 g GCB

between the open metal sites of MIL-101 and the polar analytes

DSPE: 750 mg MgSO4 + 250 mg PSA + 250 mg C18 + 250 mg GCB

with electron-rich functional groups is very strong in nonpolar
solvent.32 The strong coordination interaction between the
unsaturated metal sites of MIL-101 (electron acceptor) and the
heteroatoms of analytes (electron donor) could have an
Table 5. Comparison of the Present Method with Other Methods Reported in Literature

important impact on the extraction process. Consequently,

the herbicides in oil sample solution can be adsorbed effectively
cleanup procedure

MSPD: 2 g aminopropyl-bonded silica + 2 g florisil

MSPD: 2 g aminopropyl-bonded silica + 2 g florisil

on MIL-101. Methanol, as a polar solvent, has strong dissolving
ability toward analytes. Methanol, as a proton donor, could

LLP: 1.5 mL water + 1.5 mL ethyl acetate

also chelate with the open metal sites of MIL-101 and weaken
low temperature fat precipitation (12 h)

the interaction between MIL-101 and the analytes.32 So the

MSPD: 2 g PSA + 2 g Florisil/GCB

analytes can be easily eluted. The sensitivity of the method was
SPE: 500 mg ENVI-Carb cartridge

evaluated by LODs. In Table 5, the LODs obtained by the

250 mg C18 + 250 mg GCB

present method are lower than those obtained by QuEChERS

the unit of LOD is μg/L. bthe unit of LOD is μg/kg. cACN: acetonitrile.
method. The accuracy was evaluated by the recovery of
C18 + 250 mg GCB

herbicides in spiked soybean oil samples. The results listed in

Table 5 indicate that the two methods both provide acceptable
accuracy. The comparison of the two methods on sample pre-
paration process was also conducted and is shown in Table 5.
Florisil

Therefore, compared with QuEChERS method, the present

GPC

method has some advantages in selectivity, sensitivity, sorbent

and solvent consumption, operation procedure, and time
consumption. So the present method is suitable to the
LLE: 10 mL ACN containing 1%

LLE: 35 mL ACN saturated with

LLE: 35 mL ACN saturated with

DLLME: 90 μL [C6mim][FeCl4]

extraction of herbicides in vegetable oils.

d-μ-SPE: 7 mg MIL-101(Cr)

The present method was further compared with the reported

QuEChERS: 10 mL ACN
QuEChERS: 10 mL ACN
QuEChERS: 7 mL ACNc

methods for the determination of triazine and phenylurea

extraction

herbicides in edible vegetable oils.1,6,7,14,18−21,33−35 The results

virgin olive oil LLE: 20 mL ACN
LLE: 10 mL ACN

LLE: 10 mL ACN

LLE: 10 mL ACN
LLE: 10 mL ACN
petroleum ether

petroleum ether

are shown in Table 5. The LODs obtained by the present

method are lower than these obtained by most methods. The
acetic acid

results indicate that the present method provides satisfactory

sensitivity. In addition, compared with the other methods, the
present method is quicker and simpler in terms of short
extraction time and no additional cleanup step.
vegetable oil
vegetable oil

vegetable oil

In the work, a d-μ-SPE method based on MIL-101 was

rapeseed oil

soybean oil
matrix

developed for directly extracting triazine and phenylurea

palm oil

palm oil
olive oil

olive oil
olive oil

olive oil

olive oil

herbicides from diluted vegetable oils. A large mass of fat is

easily separated. The experimental results indicated that the
a

2159 DOI: 10.1021/jf505760y

J. Agric. Food Chem. 2015, 63, 2154−2161
Journal of Agricultural and Food Chemistry
present method has high selectivity, sensitivity, and accuracy.
The present method is quick, simple, and effective, which
shows great potential in the routine analysis of herbicides in
vegetable oils. It would be an applicable method to extract
contaminants in high-fat samples and also be a useful cleanup
procedure for non- or low-fat samples by varying experimental
parameters. The direct adsorption of analytes from oil samples
is an attractive strategy to remove fat and improve method
performance and MOFs are promising sorbents. It provides
inspiration for the application of MOFs with unique structure
and functions to the extraction of various contaminants in
nonpolar system.
■
ASSOCIATED CONTENT
* Supporting Information
S
Comparison of experimental parameters for dispersive micro-
solid-phase extraction of herbicides from vegetable oil using the
Student’s t test. This material is available free of charge via the
Internet at http://pubs.acs.org.
■ AUTHOR INFORMATION
Corresponding Author
*Phone: +86 431 85168399. Fax: +86 431 85112355. E-mail:
analchem@jlu.edu.cn.
Funding
This work was supported by the National Natural Science
Foundation of China (21207047).
Notes
The authors declare no competing financial interest.
■
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2161 DOI: 10.1021/jf505760y

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