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Microchemical Journal 95 (2010) 4349

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Microchemical Journal
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m i c r o c

A multiresidue method for the determination 234 pesticides in Korean herbs using
gas chromatography mass spectrometry
Thanh Dong Nguyen a,b, Kyung Jun Lee a, Myoung Hee Lee c, Gae Ho Lee a,
a
Department of Chemistry, Chungnam National University, Daejeon, Republic of Korea
b
Institute of Environmental Technology, Vietnam Academy of Science and Technology, Hanoi, Vietnam
c
Department of Cosmetic Science, Daejeon Health Sciences College, Daejeon, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: A rapid, specic and sensitive multiresidue method based on dispersive solid phase extraction sample
Received 11 September 2009 preparation and gas chromatography with the mass spectrometric detection for the analysis of 234
Received in revised form 24 September 2009 pesticides in Korean herbs (Acanthopanax senticosus, Morus alba L., Hovenia dulcis) has been developed.
Accepted 24 September 2009
Method recoveries were found to be between 62 and 119% with relative standard deviation lower than 21%
Available online 1 October 2009
for all compounds in the concentration range of 0.05 to 0.400 mg kg 1. Limits of quantication of most
Keywords:
compounds are below 0.050 mg kg 1. The data demonstrate that this method was successfully used for
Dispersive solid phase extraction analysis of 234 pesticides in Korean herbs.
Gas chromatography 2009 Elsevier B.V. All rights reserved.
Mass spectrometric detection
Korean herbs

1. Introduction organic solvent and the use of no chlorinated solvents; and little lab
ware is used and safety for lab workers have been proved [9,10]. Based
The traditional Korean herbs (Acanthopanax senticosus, Morus alba on modied d-SPE sample preparation and GC-MS determination,
L., Hovenia dulcis) have been used from ancient time. In recent day, analytical methods have been developed and validated for rice [11],
11,302 oriental medicine clinics [1] in Korea show the important role rice paddy [12], cabbage and radish [13] in previous studies.
of Korean herbs in Korean health care. During growing and post Modied d-SPE sample preparation and GC-MS determination
harvest times, herbs can be contaminated by chemical contaminants, have been studied and developed in this work for the determination
such as pesticides [2,3]. The presence of pesticides in herbs can be very of 234 pesticides in some Korean herbs (A. senticosus, M. alba L.,
problematic because the herbs are used for patients. In order to ensure H. dulcis). To the best of our knowledge no publication has documented
consumer safety, the authorities in Korea has set maximum residue the method of analysis of pesticide residues in A. senticosus, M. alba L.
limits (MRLs) in herbs for some pesticides [4]. and H. dulcis.
The determination of pesticides in herbs of unidentied pesticide-
treatment history is a formidable task, because it involves the 2. Experimental
identication and quantication of several hundred possible single
compounds or combinations in the presence of complex matrices. The 2.1. Materials and standards
conventional sample preparation methods commonly used are time
consuming, labor-intensive and costly in terms of expensive solvents The standard pesticides were bought from Wako (Osaka, Japan),
and clean-up materials [5,6]. Furthermore, the detection methods such Chemservice (West Chester, PA, USA) and Dr. Ehrenstorfer (Ausberg,
as GC-ECD [7] and GC-NPD [8] show a limited range of pesticide analysis Germany). The purities of the standard pesticides were from 97.4% to 99%.
and occurrence of false positive and inaccurate quantitation caused by Internal standards [naphthalene-d8, acenaphthene-d10, phenanthrene-
the interferences of unknown substances that are co-eluting in the same d10, uoranthene-d10 and triphenyl phosphate (TPP)] were purchased
retention time with analyzed pesticides. Thus, the development of new from C/D/N Isotopes Inc. (Quebec, Canada) and Chemservice (West
methods in sample preparation and measurement is needed. Chester, PA, USA). Glacial acetic acid (HAc) and solvents of pesticide
The advantages of the dispersive solid phase extraction (d-SPE) analytical grade were purchased from J.T. Baker (Philipsburg, NJ, USA).
method are high recovery for wide polarity and volatility range of Puried water was 18M (ultra-pure water, Sinhan Science Tech,
pesticides; high sample throughput; the use of smaller amounts of Daejeon, Korea). Anhydrous MgSO4 and NaCl were obtained from Wako
(Osaka, Japan). Primary secondary amine (PSA) and graphite carbon
Corresponding author. Tel.: + 82 0428216553; fax: + 82 0428217506. black (GCB) sorbents were obtained from Varian (Varian, Harbor City, CA)
E-mail address: ghlee@cnu.ac.kr (G.H. Lee). and from Supelco (Bellefonte, PA, USA), respectively.

0026-265X/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.microc.2009.09.012
44 T.D. Nguyen et al. / Microchemical Journal 95 (2010) 4349

Stock standard solutions of 2.00 mg mL 1 were prepared in MeCN 2.5 g homogenized sample was spiked prior to the determination
and MeOH and stored at 20 C. Intermediate and working standard procedure by the addition of a mixture of standard pesticides solution
solutions of a mixture of pesticides and internal standard solution was to give 0.050, 0.100 and 0.400 mg kg 1 of each compound. Spiking
prepared in MeCN. samples were left to stand for around 3 h to allow pesticide absorption
onto the sample. They were then prepared according to the
2.2. Apparatus determination procedure described above.

A Shimadzu 2010 (Shimadzu, Kyoto, Japan) gas chromatograph


2.5. Preparation of calibration standards
equipped with a split-splitless auto-injector model AOC-20i, an auto
sampler model AOC-20s and a MS-QP 2010 (Shimadzu, Kyoto, Japan)
Calibration standards in a blank matrix of the herbal samples being
series mass selective detector were used for the analysis of the pesticides
analyzed were prepared by adding respective spiking solution and
studied. A fused silica capillary column (J&W DB 5MS), 5% phenyl
internal standard solution to blank extract, to produce a nal con-
polysiloxane as non-polar stationary phase (30 m 0.25 mm i.d.) and
centration of 0.050, 0.100, 0.200 and 0.40 mgkg 1 and 0.100 mgkg 1
0.25 m lm thickness, supplied by Agilent (Palo Alto, CA, USA) was used
for internal standards. Calibration standards in solvent were prepared in
for the GC separation, with helium as carrier gas at a constant ow at
the same manner, replacing blank extract with acetonitrile.
1.7mL min 1. The temperature program used was as follows: initial
temperature, 65 C held for 1 min, then at the rate of 15 Cmin 1 to
135 C, 10 Cmin 1 to 145 C, 5 C min 1 to 150 C, 2.5 C min 1 to 3. Results and discussion
220 C, 7.5 Cmin 1 to 227.5 C and 12.5 C min 1 to 300 C and then
maintaining this temperature at 4.5 min. The temperature of the injection 3.1. Gas chromatographic determination
port was 260 C and a 1 L volume was injected in splitless mode.
A mass range of m/z 50700 was scanned to conrm the retention Analysis was performed in the SIM mode based on the use of one
times of analytes. For determination of the pesticide residues, a target and two qualier ions. Pesticides were identied according to
selected ion monitoring (SIM) mode was performed. To conrm retention times, target and qualier ions. The quantitation was based
pesticide ions tentatively identied by SIM, one quantication and on the peak area ratio of the target ion divided by the internal
two identication ions were monitored for each compound. The standards. Table 1 summarizes some of the pesticides studied with
interface temperature was 280 C. The peak areas were calculated their target and qualier ions used in SIM mode to analyze pesticides
based on the respective quantication ion. Groupings were dened to in some Korean herbs.
increase the sensitivity of the MS analysis.
A Glas-Col Multi Pulse Votexer (Glas-Col, Terre Haute, USA), the 3.2. Quantitation
Hanil Refrigerated Centrifuge (Hanil Science Industrial, Incheon,
Korea), an Ecospin 3180C (Biotron, Daejeon, Korea) vacuum concen- Calibration curves were constructed for each compound using four
trator and an IlShin DF (IlShin Lab Co, Daejeon, Korea) refrigerator different concentration levels. Four internal standards were employed
were used for the sample preparation stages. at the beginning of the sample preparation stage to help control the
signicant losses of the analytes during extraction. Adding TPP at the
2.3. Sample preparation last stage of sample preparation was to control the amount of sample
injection in gas chromatography. According to their polarities and
2.3.1. Korean herbs volatilities, 234 pesticides were divided into groups to increase the
A. senticosus, M. alba L. and H. dulcis samples were taken from sensitivity of studied pesticides. For identication of pesticides, the
herbal markets in Korea. retention time and three ions (one for quantitation and two for
identication) with the assistance of the NIST's pesticide library were
2.3.2. Procedure used.
From the grinded and homogenized sample of A. senticosus,
M. alba L. and H. dulcis, 2.5 g was weighted into a 50 mL Teon
centrifuge tube; 10 mL of water was added; a mixture of four internal 3.3. Method validation
standards (naphthalene-d8, acenaphthene-d10, phenanthrene-d10,
and uoranthene-d10) was added and extracted with 10 mL of MeCN 3.3.1. Linearity
(HAc 0.5%) for 1 min with a vortex mixer. Then the sample tubes were Correlation coefcients were greater than0.99 from 0.050 mg kg 1
kept in a refrigerator for 30 min. When the temperature of the mixed to 0.400 mg kg 1 for all pesticides.
samples reached 4 C, 4 g MgSO4 and 1 g NaCl were added and then
vortexed immediately for 1 min and then the extract was centrifuged
for 5 min at 4000 rpm at 4 C. Two milliliters of prepared aliquot was Table 1
sampled from the upper layer into a 5 mL micro-centrifuge vial Quantitation and identication ions of some pesticides.
containing 50 mg primary secondary amine (PSA), 300 mg MgSO4,
Pesticide's name Observed ions Pesticide's name Observed ions
30 mg GCB and again vortexed for 1 min and then centrifuged for (m/z) (m/z)
5 min at 4000 rpm at 4 C. From the upper layer of the prepared
Anilofos 226, 125, 184 Fluacrypyrim 103, 426, 352
sample, an aliquot of 1.2 mL was transferred into a 1.8 mL Eppendorf Azinphos-methyl 160, 132, 105 Heptachlor-epoxide 353, 388, 351
vial and put into a vacuum concentrator to dryness. Finally, 0.25 mL of Benalaxyl 148, 206, 325 Isoprothiolane 118, 204, 290
MeCN containing 0.1 mg L 1 of triphenyl phosphate (TPP) was added Bifenox 341, 310, 189 Methoprene 73, 111, 153
to dissolve the residue and then 1 L of this solution was injected onto Buprofezin 105, 305, 172 Metolcarb 108, 107, 90
Cadusafos 159, 213, 127 Oxyuorfen 252, 302, 300
the gas chromatography mass spectrometry system.
Carbosulfan 160, 118, 323 Pretilachlor 238, 176, 262
Chlordance-cis 373, 375, 337 Propiconazole 259, 173, 191
2.4. Recovery studies Deltamethrin 253, 208, 172 Quizalofop ethyl 372, 299, 243
Disulfoton 88, 274, 186 Silauofen 286, 179, 258
A. senticosus, M. alba L. and H. dulcis samples with no pesticides Ethauralin 316, 276, 333 Terrazole 211, 183, 213
Etrimfos 292, 181, 277 Zoxamide 187, 242, 299
detected previously were used for the fortication experiments. A
T.D. Nguyen et al. / Microchemical Journal 95 (2010) 4349 45

Table 2
Statistical pesticide recovery and LOQs from herb matrices using d-SPE.

Pesticide's name RT (min) LOQ Fortication level (mg kg 1)

(mg kg 1) Acanthopanax senticosus Morus alba L. Hovenia dulcis

0.050 0.100 0.400 0.050 0.100 0.400 0.050 0.100 0.400

Acephate 9.023 0.060 94 15 89 9 92 4 69 7 76 7 88 4 75 11 82 11 84 11


Acetochlor 19.719 0.006 81 11 89 11 90 9 92 11 87 10 90 9 81 11 85 10 105 8
Acrinathrin 42.477 0.045 81 6 92 8 97 9 96 7 90 9 98 7 110 13 91 10 93 7
Alachlor 20.225 0.008 85 12 88 11 90 7 95 9 99 8 96 6 93 11 101 10 90 6
Aldrin 22.481 0.012 80 7 86 12 85 10 87 7 94 9 94 6 98 10 92 8 92 5
Benalaxyl 33.974 0.006 84 7 94 10 93 9 97 5 93 9 95 8 91 7 96 9 93 7
Benfuracarb 7.263 0.068 91 7 90 7 86 6 91 11 93 4 90 4 70 7 75 6 97 5
Bensultap 7.055 0.030 85 13 94 7 88 10 86 13 99 7 96 6 68 5 103 6 90 4
Bentazon 19.732 0.075 66 11 79 9 90 5 88 7 99 7 104 5 66 3 88 9 109 6
BHC-alpha 14.497 0.006 82 12 84 9 91 8 85 7 89 6 91 7 86 17 90 10 81 7
BHC-beta 15.795 0.006 88 10 90 13 89 8 84 17 84 8 89 6 84 10 96 9 92 9
BHC-delta 17.857 0.006 78 13 82 11 88 8 97 13 89 10 82 7 89 9 99 7 85 6
BHC-gamma 16.21 0.006 85 12 83 9 90 8 83 8 91 7 91 7 77 17 90 11 82 8
Bifenthrin 38.177 0.006 81 9 90 9 93 10 104 7 98 10 94 8 89 10 99 10 93 7
Bitertanol 40.799 0.012 66 12 63 7 74 7 77 4 71 9 111 13 88 9 84 12 99 5
Bromopropylate 37.905 0.030 80 8 88 9 93 10 87 9 87 8 96 8 89 10 99 9 103 8
Buprofezin 30.109 0.006 80 10 91 12 91 9 93 11 103 10 94 8 89 9 99 10 85 8
Butachlor 27.808 0.009 80 10 89 10 92 9 93 6 99 9 94 7 87 7 102 8 91 8
Cadusafos 14.285 0.006 86 11 86 10 91 8 91 11 85 7 91 8 93 9 92 9 88 8
Captafol 36.093 0.075 71 16 72 9 89 4 71 13 79 11 84 12 93 14 97 9 84 6
Captan 25.819 0.075 72 14 75 11 90 6 82 11 91 11 90 10 71 10 77 7 85 6
Carbophenothion 34.162 0.010 71 10 80 10 94 9 78 10 90 10 92 10 82 12 106 8 101 7
Carboxin 29.914 0.015 84 15 89 10 93 8 89 16 90 9 99 8 77 11 97 11 105 8
Carfentrazone-ethyl 34.495 0.075 75 9 87 10 93 9 84 9 93 9 96 8 85 10 101 9 96 8
Chinomethionat 26.596 0.015 77 7 85 12 91 8 93 11 91 9 98 7 85 10 98 7 101 8
Chlofennapyl 30.862 0.006 79 11 88 10 91 10 102 8 100 9 93 9 87 9 94 7 87 6
Chlofentezine 5.911 0.015 83 10 94 10 96 9 86 8 104 6 96 5 84 7 88 7 85 8
Chlordance-cis 27.487 0.025 77 13 79 11 80 9 90 8 98 8 90 8 85 9 87 7 87 5
Chlordane-trans 26.64 0.018 77 14 80 12 80 8 104 13 101 8 95 9 84 8 86 8 85 4
Chlorfenvinphos 25.791 0.025 76 13 85 13 93 8 94 13 98 9 95 8 75 7 107 8 96 7
Chloruazuron 7.434 0.075 85 11 104 7 91 8 89 10 91 8 96 4 82 10 92 6 91 3
Chlorobenzilate 31.813 0.006 78 9 89 9 91 5 97 10 96 7 95 9 90 10 91 9 88 5
Chlorothalonil 17.058 0.015 76 19 71 12 87 4 80 9 83 7 85 11 69 9 74 9 82 7
Chlorpropham 13.556 0.024 82 12 85 10 90 8 98 4 86 8 91 8 88 15 90 8 84 8
Chlorpyrifos 22.787 0.009 76 15 83 11 89 8 82 7 88 7 94 8 84 7 93 7 86 6
Chlorpyrifos-methyl 19.691 0.006 75 12 79 11 88 7 84 17 88 8 86 8 86 8 99 8 86 7
Cinosulfuron 23.957 0.045 76 15 82 9 92 7 81 6 88 8 98 9 87 8 88 12 106 7
Cyuthrine 41.621 0.015 71 6 81 10 100 9 70 9 72 10 96 9 77 10 94 8 108 10
Cyhalofop-butyl 39.668 0.025 82 12 90 10 96 8 81 7 83 9 102 7 90 7 103 11 113 10
Cyhalothrin 39.942 0.012 73 10 82 8 98 9 75 9 83 9 98 9 74 8 95 9 101 7
Cypermethrin 42.121 0.045 74 7 86 10 96 9 74 9 78 10 99 9 72 8 89 9 102 9
Cyprodinil 24.97 0.015 84 10 90 10 90 8 93 12 99 8 99 8 88 9 101 9 94 8
Deltamethrin 43.812 0.075 64 7 77 9 94 6 64 9 68 10 96 10 73 8 93 9 111 9
Diazinon 17.268 0.012 87 13 83 9 92 7 88 16 88 7 87 9 79 4 78 10 90 7
Dichlouanid 22.044 0.030 75 10 88 13 89 9 78 11 83 9 78 10 75 11 106 8 86 7
Dichlorobenil 7.772 0.006 92 12 94 8 82 9 84 13 93 8 99 6 87 7 100 6 89 5
Dichlovos 6.635 0.006 71 10 74 4 86 9 65 15 70 18 72 11 71 13 79 5 81 4
Diclofop-methyl 36.287 0.009 66 6 76 10 92 7 70 11 76 15 89 13 82 9 98 11 109 8
Dicloran 15.131 0.060 78 14 94 10 91 7 89 11 81 8 93 9 94 12 87 10 92 8
Dicofol 23.581 0.012 88 9 97 9 95 10 71 10 79 8 83 7 94 8 100 9 96 7
Dieldrin 29.259 0.006 84 13 88 10 89 9 102 11 106 9 98 8 93 13 100 11 89 8
Diethofencarb 23.358 0.030 82 8 91 9 88 9 97 9 94 8 96 8 93 15 111 10 97 10
Difenconazole 43.426 0.070 66 8 78 7 96 5 63 8 66 4 94 9 69 6 87 12 112 7
Dimepiperate 26.16 0.010 76 11 84 11 91 9 89 11 98 9 95 8 86 11 104 8 92 8
Dimethenamid 19.376 0.006 83 10 91 11 90 8 84 12 94 17 95 7 93 12 102 8 89 7
Dimethipin 15.916 0.015 88 10 90 11 95 8 89 13 84 7 87 9 94 8 95 9 86 10
Dimethoate 15.252 0.045 77 18 78 11 107 6 80 17 77 7 81 13 75 15 82 13 80 10
Dimethromorph 44.167 0.015 80 12 92 8 96 3 75 5 70 7 99 8 86 10 96 15 102 13
Dimethylvinphos 22.92 0.015 75 14 77 10 90 8 84 13 89 9 89 10 91 8 108 8 91 8
Diniconazole 31.913 0.015 74 14 85 8 96 9 84 8 86 8 100 7 89 8 104 10 114 10
Diphenamid 24.229 0.012 83 10 90 10 92 9 88 10 92 8 94 8 91 9 104 9 97 9
Diphenylamine 12.76 0.015 90 11 88 9 91 8 84 6 89 7 93 7 96 11 96 9 91 6
Disulfoton 17.654 0.006 74 11 80 11 87 8 84 16 87 14 89 6 83 8 98 8 91 5
Dithiopyr 21.324 0.008 81 11 87 10 87 9 108 8 106 8 97 7 91 9 100 9 86 9
Edifenphos 34.2 0.012 79 12 79 10 92 8 74 14 81 10 88 10 88 11 105 9 96 8
Endosulfan 25.068 0.060 81 14 86 11 87 8 108 8 98 9 90 4 86 12 93 7 86 4
Endosulfan-sulfate 34.12 0.006 77 5 81 10 91 9 94 8 92 8 90 10 88 15 94 6 91 5
Endrine 30.588 0.012 74 9 85 9 89 9 93 7 96 10 91 9 87 10 97 7 91 5
EPN 37.81 0.030 64 8 63 15 99 8 72 11 76 8 111 10 85 5 108 12 106 8
Esfenvalarate 14.664 0.015 83 13 113 7 79 17 82 8 85 11 92 8 73 10 71 17 102 9
Esprocarb 22.292 0.060 80 10 83 10 79 9 101 7 100 8 94 7 89 9 97 7 89 5

(continued on next page)


46 T.D. Nguyen et al. / Microchemical Journal 95 (2010) 4349

Table 2 (continued)
Pesticide's name RT (min) LOQ Fortication level (mg kg 1)

(mg kg 1) Acanthopanax senticosus Morus alba L. Hovenia dulcis

0.050 0.100 0.400 0.050 0.100 0.400 0.050 0.100 0.400

Ethauralin 13.364 0.015 79 10 79 9 99 7 82 6 82 9 93 10 83 18 100 10 92 11


Ethiofencarb 8.89 0.075 85 8 84 8 88 13 103 9 88 8 99 4 84 11 87 7 92 4
Ethion 32.611 0.012 70 12 78 9 99 9 78 10 85 8 91 10 85 12 111 11 106 9
Ethoprophos 13.019 0.010 86 12 85 9 91 8 79 10 84 8 91 8 94 9 94 8 89 8
Etoxazole 38.392 0.008 78 10 90 11 96 11 89 3 97 8 99 8 87 13 103 10 101 10
Etrimfos 18.146 0.010 77 10 81 10 89 8 79 14 88 14 83 5 88 10 105 7 89 9
Fenamidone 38.343 0.009 78 7 90 9 97 10 86 4 90 8 101 7 90 13 99 9 106 8
Fenarimol 39.877 0.012 79 10 91 9 95 9 89 7 89 8 98 9 84 9 87 8 95 6
Fenazaquin 38.605 0.008 80 3 91 9 95 9 90 8 93 9 97 7 86 10 99 9 101 6
Fenbuconazole 41.487 0.030 63 6 78 7 107 5 66 18 65 8 95 10 84 11 92 13 110 9
Fenhexamide 34.594 0.005 89 11 104 10 92 8 93 7 82 7 102 7 95 10 91 11 102 7
Fenitrothion 21.76 0.030 71 14 75 11 114 7 72 10 82 8 89 9 83 14 114 9 104 12
Fenobucarb 12.318 0.006 86 9 87 10 91 8 69 14 87 6 90 8 84 10 78 11 83 6
Fenothiocarb 27.867 0.009 89 19 89 9 91 7 94 9 92 8 97 7 84 10 90 9 90 6
Fenoxanil 31.194 0.015 71 8 75 9 91 13 79 13 91 7 106 7 71 16 93 17 110 6
Fenoxycarb 38.237 0.015 80 17 84 9 95 7 84 5 82 9 98 9 90 11 98 10 109 9
Fenpropathrin 38.47 0.012 83 8 90 9 96 9 84 11 94 9 96 9 87 8 90 10 91 7
Fensulfothion 31.965 0.025 68 6 78 17 108 6 71 16 74 12 92 15 100 20 113 13 116 14
Fenthion 23.076 0.006 76 13 82 11 90 8 89 12 94 10 92 9 89 10 104 8 90 8
Ferinzone 27.029 0.060 69 18 78 6 108 7 77 9 80 6 93 13 74 15 95 12 97 13
Fipronil 25.592 0.015 72 10 80 11 97 8 79 7 86 6 96 9 81 9 107 9 108 8
Fluacrypyrim 33.872 0.070 81 8 91 9 93 11 108 12 98 11 94 9 70 19 97 10 89 6
Fluazifop-butyl 31.844 0.050 85 6 90 12 92 9 94 5 98 8 97 7 89 13 107 12 97 9
Fludioxonil 29.011 0.015 78 10 87 9 95 8 89 11 84 9 100 7 92 8 98 8 110 9
Flufenacet 23.647 0.015 81 12 89 10 92 9 91 14 91 10 85 8 85 17 99 9 84 6
Flufenoxuron 18.539 0.025 84 10 91 11 78 7 82 7 76 11 101 7 66 4 74 8 101 10
Fluoromide 15.094 0.050 69 15 67 12 111 5 72 13 79 7 80 5 88 10 98 12 71 9
Fluquinconazole 40.991 0.012 75 12 85 9 95 8 77 7 77 9 99 9 93 9 98 10 114 9
Flusilazole 30.081 0.006 74 9 85 9 96 9 86 5 91 8 98 8 87 9 99 10 97 9
Flutolanil 28.998 0.015 92 9 94 9 93 10 84 12 88 8 97 7 96 9 100 8 100 8
Fluvalinate 43.075 0.030 63 13 73 4 103 9 86 11 86 4 108 9 81 18 88 11 93 9
Folpet 26.165 0.030 66 17 72 10 105 6 65 12 84 9 90 11 77 14 110 9 104 10
Fosthiazate 24.264 0.045 80 12 78 11 92 7 66 17 76 10 84 13 90 11 114 9 95 8
Furathiocarb 38.978 0.015 74 5 87 10 97 10 75 10 83 9 98 8 87 8 105 10 109 9
Heptachlor 20.332 0.006 73 8 81 9 87 8 101 7 100 9 97 6 91 10 95 8 87 6
Heptachlor-epoxide 25.064 0.010 79 11 83 11 84 9 101 13 100 8 94 8 85 10 91 7 87 5
Hexaconazole 28.705 0.045 63 11 63 12 66 6 104 9 106 7 91 10 76 8 81 7 94 4
Hexaumuron 8.775 0.075 84 15 113 12 87 13 84 10 88 9 93 8 75 19 85 7 84 16
Hexythiazox 26.912 0.060 77 7 92 12 100 12 86 5 84 9 101 7 93 12 107 11 116 12
Imazalil 28.861 0.012 66 15 77 8 92 7 87 6 89 8 98 7 96 9 100 8 100 8
Indanofan 38.34 0.045 71 8 81 10 99 10 68 11 84 11 93 11 92 12 108 9 105 11
Iprobenfos 18.578 0.012 75 11 84 11 89 8 85 10 91 13 93 9 88 9 104 7 93 7
Iprodione 35.537 0.030 77 9 88 9 95 9 87 7 89 8 98 7 92 10 108 9 111 10
Isazophos 17.873 0.012 83 21 88 5 89 8 84 8 84 10 88 5 74 9 76 17 88 10
Isophenphos 25.733 0.020 77 10 80 12 82 7 85 8 98 7 95 8 82 9 110 11 92 8
Isoprocarb 10.846 0.008 85 12 88 12 92 9 85 7 88 8 90 7 95 9 94 7 86 8
Isoprothiolane 29.173 0.030 82 7 90 10 91 9 96 13 99 9 95 8 88 11 94 9 88 6
Kresoxim-methyl 30.529 0.006 92 13 96 9 92 9 95 8 98 9 94 8 87 9 96 8 87 7
Linuron 21.997 0.045 71 15 73 10 90 7 82 12 91 9 91 10 85 11 102 8 91 5
Lufenuron 8.773 0.075 69 8 106 8 98 6 85 9 85 7 86 7 79 16 71 9 83 6
Malathion 22.622 0.030 74 14 79 10 99 7 82 12 93 9 90 10 86 10 110 9 91 9
Mecarbam 26.083 0.045 75 13 83 11 93 8 78 10 96 9 94 9 79 14 100 7 89 8
Mefenacet 39.446 0.030 76 7 83 9 92 7 73 13 73 9 94 10 89 7 104 9 116 9
Mepanipyrim 28.215 0.009 71 9 81 9 95 9 76 8 86 8 98 8 80 10 113 10 112 9
Mepronil 33.593 0.006 84 10 92 8 94 9 94 5 84 9 100 7 92 9 98 12 108 8
Metalaxyl 20.781 0.006 87 9 93 12 89 9 101 9 94 9 94 6 94 8 98 10 91 9
Metconazole 38.489 0.045 63 10 70 8 97 9 71 10 81 10 96 9 82 12 98 9 103 8
Methabenzthiarzuron 13.728 0.020 101 17 101 9 82 12 83 11 88 9 95 7 78 8 67 6 77 8
Methamidophos 6.529 0.018 82 12 86 10 91 5 92 11 85 7 90 4 79 5 85 7 93 3
Methidathion 26.798 0.012 72 15 76 10 95 7 79 14 90 10 89 11 86 9 104 8 87 8
Methoprene 27.323 0.030 79 11 81 11 77 10 89 10 95 9 90 8 84 9 97 8 88 6
Methyl pentachlorophenyl sulde 21.558 0.006 81 13 82 9 82 9 106 7 96 8 98 6 88 4 87 9 93 6
Metobromuron 18.844 0.015 74 15 76 11 89 6 79 19 85 16 92 7 89 10 103 8 92 6
Metolachlor 22.546 0.005 82 9 89 10 90 9 95 11 96 9 92 8 92 9 102 8 91 8
Metolcarb 9.487 0.015 93 9 97 9 87 6 104 10 96 6 93 5 80 18 88 9 87 5
Metribuzin 19.772 0.012 79 10 83 9 93 8 87 9 85 9 94 7 88 10 105 11 97 8
Molinate 10.983 0.005 94 14 88 7 91 7 83 16 86 8 97 7 97 10 97 7 98 5
Monocrotophos 14.231 0.045 84 15 87 10 88 9 67 16 67 9 83 13 91 11 80 14 88 4
Myclobutanil 29.866 0.006 76 9 88 9 96 9 83 7 91 7 99 7 86 14 96 13 102 8
Napropamid 28.386 0.045 86 10 93 9 93 9 96 7 95 8 99 7 93 9 106 10 99 10
Nitrapyrin 9.245 0.012 88 10 93 8 85 8 97 10 90 6 94 6 81 11 105 8 88 6
Novaliuron 6.904 0.075 98 16 106 6 94 7 79 11 81 9 87 6 78 13 80 3 79 8
Ofurace 33.4 0.010 81 16 92 8 98 9 93 8 80 6 96 10 92 11 88 12 93 6
Omethoate 9.325 0.075 72 19 83 9 90 10 89 10 90 7 104 3 78 11 88 8 103 10
T.D. Nguyen et al. / Microchemical Journal 95 (2010) 4349 47

Table 2 (continued)
Pesticide's name RT (min) LOQ Fortication level (mg kg 1)

(mg kg 1) Acanthopanax senticosus Morus alba L. Hovenia dulcis

0.050 0.100 0.400 0.050 0.100 0.400 0.050 0.100 0.400

op-DDD 29.731 0.006 80 10 88 9 90 10 87 7 101 9 93 8 91 9 101 9 90 8


op-DDT 32.224 0.006 80 8 89 10 93 10 97 6 95 8 91 8 91 11 100 9 93 8
o-Phenylphenol 10.524 0.030 87 11 87 10 90 7 86 6 90 8 93 7 94 9 94 8 90 6
Oryzalin 40.645 0.075 78 6 74 9 103 6 62 9 64 9 88 7 70 13 90 12 86 14
Oxadiazone 29.9 0.006 84 9 90 10 89 10 108 9 105 9 94 8 87 9 95 7 88 5
Oxadixyl 32.181 0.012 80 15 88 9 94 8 95 17 81 8 94 5 93 10 91 14 99 9
Oxamyl 10.686 0.060 74 9 83 11 84 12 89 14 86 8 110 5 81 16 73 14 85 6
Oxyuorfen 30.39 0.030 68 15 71 10 99 8 74 10 77 7 96 8 81 9 96 5 103 7
Pachlobutrazol 27.373 0.006 75 9 83 8 95 9 88 9 89 8 97 8 90 12 105 9 102 10
Parathion 23.307 0.030 72 9 68 11 78 11 74 9 84 7 92 10 83 12 91 6 99 7
Parathion-methyl 20.096 0.045 70 14 74 11 109 4 73 11 80 5 90 10 81 9 114 8 102 11
Penconazole 25.31 0.006 74 9 83 8 104 8 78 21 78 9 105 5 98 13 104 4 105 11
Pencycuron 16.079 0.025 89 11 87 10 90 7 92 11 88 8 91 8 84 9 96 10 88 7
Penthoate 26.063 0.012 73 13 80 9 91 8 83 11 98 10 94 10 81 8 105 8 88 8
Pentoxazone 39.199 0.018 82 7 92 9 94 9 99 7 94 8 97 7 89 8 85 8 86 5
Permethrine 40.935 0.012 82 4 92 9 96 10 90 7 89 9 97 7 94 8 101 8 103 7
Phenamiphos 28.773 0.025 75 8 84 9 92 9 77 8 80 9 99 8 91 9 108 11 115 11
Phorate 14.426 0.010 82 13 82 10 91 8 89 12 88 7 89 8 89 12 80 9 92 10
Phosalone 39.053 0.030 78 5 81 11 95 8 64 12 77 11 90 12 102 10 107 12 105 8
Phosmet 37.541 0.030 71 12 75 9 96 8 64 9 75 12 84 14 93 11 116 10 98 10
Phosphamidone 19.408 0.045 75 16 77 11 95 7 67 18 81 13 90 8 96 11 119 10 91 11
Phoxim 5.863 0.060 72 8 75 8 100 10 94 15 103 6 88 4 83 5 94 7 93 4
Pirimicarb 18.602 0.006 81 10 88 10 89 8 89 16 92 14 94 7 89 9 103 8 92 8
Pirimiphos-ethyl 24.576 0.006 78 14 84 9 91 8 92 7 99 8 94 9 86 11 107 11 89 9
Pirimiphos-methyl 21.802 0.006 75 11 80 12 89 8 91 8 102 9 96 8 91 10 109 11 92 9
pp-DDD 29.791 0.006 80 10 88 9 90 10 99 7 95 9 89 5 82 8 85 5 89 8
pp-DDE 29.374 0.006 83 10 90 10 87 9 91 12 104 8 97 7 89 10 96 8 88 6
pp-DDT 34.803 0.006 71 8 80 11 90 9 90 7 96 8 94 10 85 10 104 9 98 6
Pretilachlor 29.122 0.006 82 9 90 10 94 10 111 8 97 9 94 8 89 10 104 8 95 9
Probenazole 21.849 0.060 70 13 75 11 102 6 73 13 83 12 89 10 80 10 106 10 91 9
Prochloraz 41.095 0.060 63 9 80 9 86 13 72 10 74 12 82 12 88 10 116 13 88 9
Procymidone 26.196 0.006 88 10 89 10 88 9 77 10 103 10 95 9 88 18 95 10 85 5
Profenofos 29.24 0.030 77 11 80 11 91 8 92 13 94 10 93 8 88 11 101 9 89 6
Prometryn 21.099 0.008 83 11 88 7 90 8 96 6 98 9 96 8 94 10 105 8 93 9
Propamocarb HCl 8.672 0.070 76 13 90 8 87 8 66 16 75 6 84 7 77 12 105 6 94 6
Propanil 19.517 0.045 80 14 86 9 90 7 84 13 85 9 99 7 92 12 95 8 101 8
Propargite 36.362 0.015 67 14 89 12 91 14 84 7 94 10 96 6 68 11 106 10 93 8
Propiconazole 34.558 0.045 70 10 78 8 98 9 80 6 86 8 98 8 76 12 101 9 109 8
Propisochlor 20.57 0.004 79 11 88 10 89 8 98 9 101 9 95 8 89 11 100 9 87 7
Propoxur 12.374 0.009 83 13 83 11 93 6 81 4 87 7 87 9 79 9 76 8 79 8
Pymetrozine 29.268 0.060 68 19 79 8 102 10 68 10 76 7 84 9 72 10 87 12 96 6
Pyraclofos 40.46 0.045 69 10 73 11 98 8 63 9 67 3 84 15 94 14 112 10 100 10
Pyraclostrobin 40.685 0.075 83 10 93 8 104 4 114 10 106 7 111 8 80 10 74 6 100 7
Pyraufen-ethyl 35.62 0.030 79 7 90 10 91 9 92 8 94 9 97 7 88 9 101 8 98 8
Pyrazophos 40.084 0.015 69 6 78 9 104 9 62 13 76 10 93 12 85 11 111 10 112 10
Pyributicarb 37.318 0.006 75 8 86 10 96 10 78 7 92 8 98 8 80 11 102 9 103 8
Pyridaben 41.07 0.006 75 7 86 9 95 9 79 7 80 9 100 8 86 11 98 9 110 7
Pyridalyl 42.367 0.045 78 7 89 7 96 10 79 6 75 8 96 6 92 10 101 8 119 11
Pyridaphenthion 37.499 0.060 65 8 79 9 108 8 68 7 72 10 93 13 87 9 114 9 114 11
Pyrimethanil 17.263 0.005 92 12 88 10 91 7 98 8 89 8 91 8 96 9 101 8 92 7
Pyriproxyfen 39.517 0.008 78 6 93 9 94 10 90 7 90 9 97 8 88 9 96 9 97 7
Pyroquilon 16.79 0.012 93 13 90 10 93 7 89 16 82 10 93 8 96 9 98 10 95 5
Quintozene 15.874 0.015 77 15 74 11 84 8 88 9 82 8 95 8 87 6 92 4 98 9
Quizalofop ethyl 42.131 0.040 81 14 89 9 95 7 80 6 79 10 100 9 90 10 99 10 112 9
Sanmarton 42.919 0.075 76 7 88 9 96 9 79 8 78 9 100 8 84 9 84 9 98 8
Silauofen 42.477 0.020 82 5 94 10 96 10 94 6 89 9 100 7 91 9 98 10 104 9
Simazine 15.744 0.030 84 13 86 12 93 7 89 10 84 8 93 12 78 10 92 10 90 6
Spirodiclofen 40.66 0.005 92 12 95 9 80 10 92 13 97 11 87 8 67 9 73 6 65 4
Tebuconazole 35.826 0.012 70 15 81 11 99 9 74 11 80 7 101 8 85 15 103 11 116 9
Tebufenozide 39.998 0.075 81 7 91 9 98 9 80 10 77 9 99 9 98 12 90 9 98 8
Tebufenpyrad 38.626 0.010 84 11 94 9 95 10 91 8 93 9 100 7 92 9 106 10 107 10
Tebupirimfos 18.594 0.025 78 9 83 9 89 8 89 17 90 19 93 6 91 12 102 9 91 9
Teubenzuron 6.729 0.075 87 20 109 5 90 8 97 14 98 9 87 6 71 11 82 5 73 5
Terbufos 16.693 0.012 79 14 81 9 92 8 90 7 87 7 91 8 85 16 102 10 95 7
Terbuthylazine 16.766 0.009 85 13 87 11 91 8 87 12 85 8 81 10 79 9 86 9 87 5
Terrazole 9.303 0.025 81 9 90 8 86 9 81 17 92 8 98 6 106 6 101 7 92 5
Tetraconazole 23.794 0.030 75 9 83 9 94 9 84 12 92 7 91 8 86 11 106 10 97 8
Tetradifon 38.791 0.006 80 10 90 9 92 10 99 11 91 8 96 9 92 9 94 9 101 7
Thiabendazole 25.719 0.045 84 18 81 8 92 13 68 8 65 6 90 11 81 12 101 17 114 13
Thiazopyr 22.698 0.008 96 9 107 9 74 8 85 11 83 7 100 7 76 16 82 12 88 7
Thiuzamide 29.968 0.045 81 9 90 9 93 9 97 10 95 7 95 8 91 8 102 8 99 8
Thiobencarb 22.819 0.006 85 14 88 10 88 8 92 10 96 8 97 7 89 9 100 9 93 6
Thiocyclam hydrogenoxalate 10.22 0.040 80 9 81 8 91 8 87 8 84 8 93 7 71 9 96 8 98 10

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48 T.D. Nguyen et al. / Microchemical Journal 95 (2010) 4349

Table 2 (continued)
Pesticide's name RT (min) LOQ Fortication level (mg kg 1)

(mg kg 1) Acanthopanax senticosus Morus alba L. Hovenia dulcis

0.050 0.100 0.400 0.050 0.100 0.400 0.050 0.100 0.400

Thiometon 14.982 0.006 82 13 80 10 90 7 90 14 88 7 87 8 88 8 88 9 80 10


Tokuthion 28.891 0.015 74 11 83 10 90 9 92 8 98 8 94 8 85 10 103 8 94 8
Tolclofos-methyl 20.129 0.006 77 13 83 11 88 9 95 6 99 10 93 8 88 12 99 8 89 7
Tolyuanid 25.474 0.012 69 16 75 12 80 8 78 13 90 8 87 12 74 9 83 6 84 8
Triadimefon 23.536 0.006 71 14 86 8 94 8 81 20 92 7 95 7 86 15 104 14 96 11
Triadimenol 26.876 0.006 109 11 104 15 98 11 84 5 88 7 97 8 92 8 112 8 110 10
Tri-allate 18.083 0.015 80 10 86 11 86 8 88 20 87 12 90 3 88 9 95 7 90 5
Triazamate 27.431 0.060 99 9 97 11 89 10 98 10 101 9 92 8 78 8 86 9 84 5
Triazophos 33.674 0.025 66 9 76 9 106 9 71 16 77 10 89 12 90 13 114 10 107 9
Trichlorfon 5.151 0.075 76 9 91 7 89 10 90 9 94 7 98 6 88 12 100 7 91 6
Triumizole 25.067 0.012 82 11 82 10 82 9 105 8 94 7 87 9 77 7 79 9 82 4
Triumuron 9.337 0.030 94 9 105 9 83 9 84 7 97 7 96 5 88 17 89 14 92 5
Triuralin 13.794 0.030 79 13 77 8 94 6 83 13 81 9 92 7 90 8 94 12 86 2
Vamidothion 27.469 0.075 73 18 79 8 110 7 68 12 71 9 76 17 85 8 106 11 93 9
Vinclozoline 19.73 0.060 73 17 68 9 103 6 69 9 94 6 103 6 66 9 90 8 109 9
Zoxamide 26.429 0.025 85 5 98 11 95 9 89 8 92 6 110 4 78 11 72 8 110 8
Mean percent recovery RSD of pesticides in herb samples at 0.050, 0.100 and 0.400 mg kg 1 fortication levels (n = 3).

3.3.2. Limit of quantitation Of which, 11 samples (4.9%) were found to be positive with pesticides as
Limits of quantication (LOQs) of the proposed method were presented in Table 3, however, all found pesticides were under their
calculated by considering a value 10 times that of background noise. MRLs. It is necessary to point out that the pp-DDE was founded in one
For most of the compounds, the LOQs are below 0.050 mg kg 1 as sample, and this pesticide belongs to the chlorinated pesticide group
shown in Table 2. and is a product of the breakdown of DDTa banned pesticide for
agricultural use worldwide under the Stockholm Convention.
3.3.3. Recovery
Satisfactory recoveries (from 62 to 119%) with RSDs b 21% were
4. Conclusions
obtained from three commodities spiked (n = 3) at 0.050, 0.100 and
0.400 mg kg 1 as shown by the data in Table 2.
A simple and rapid method was developed to determine the
residues of 234 pesticides in Korean herbs (A. senticosus, M. alba L.,
3.4. Application on real sample
H. dulcis). This method using d-SPE sample preparation and GC-MS
analysis showed a high sensitivity and conrmatory power necessary
A total of 224 Korean herb samples (including A. senticosus, M. alba
for the determination of pesticide residues at the levels required in
L., and H. dulcis) were collected from domestic markets from December
Korea's MRL for Korean herbs. The proposed method not only allowed
2007 till March 2009 and analyzed following the described procedure.
the simultaneous determination and conrmation of a very large
number of pesticides which was acceptable in terms of recovery and
detection limit but also showed useful in routine analysis due to it
being fast and easy to carry out.
Table 3
Pesticide residues found in herb samples and their concentrations.
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