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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.
Table 2
Statistical pesticide recovery and LOQs from herb matrices using d-SPE.
Table 2 (continued)
Pesticide's name RT (min) LOQ Fortication level (mg kg 1)
Table 2 (continued)
Pesticide's name RT (min) LOQ Fortication level (mg kg 1)
Table 2 (continued)
Pesticide's name RT (min) LOQ Fortication level (mg kg 1)
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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