Analytical MethodsDevelopment of a matrix solid-phase dispersion-sonication extraction method for the determination of fungicides residues in ginseng extract
Introduction
Any of several plants of the genus Panax, especially Panax pseudoginseng of eastern Asia or Panax quinquefolius of North America, having small greenish flowers grouped in umbels, palmately compound leaves, and forked roots believed to have medicinal properties. Ginseng, the root of Panax Ginseng C.A. Meyer, is one of the most common herbal medicines in China (Attele et al., 1999, Gillis, 1997). It has been shown to exhibit both anti-stress and antioxidant activity and to exert various benefits relating to stress and the immune system (Kim et al., 1970, Simsek et al., 2007, Takahashi et al., 1992).
This plant of ginseng requires a longer growing time, and is highly susceptible to phyto-pathogen. Therefore, the ginseng employed often pesticides, such as pentachloronitrobenzene and procymidone, in the growing process. Being the longer half-life of these pesticides, and chronic adverse as well as bioaccumulation and genotoxic effect in biotic fat, the determination of pesticides residue is very important in ginseng products and its extracts (Ling et al., 1999, Manirakiza et al., 2000).
Scientific knowledge about chemical contamination of food has grown considerably in recent years. Until 15 years ago, this science was considered relatively young. Since then, this area of science has continued to develop, in particular becoming an established part of regulatory reviews of food safety across the world.
Furthermore, improper use of pesticides not only pollutes the cultivating soil, and ground water, but also leads to accumulation of pesticides in the plants. Therefore, from a healthcare perspective, safety issues considering the balance between adverse effects and therapeutic benefit must be dealt with, the need to extract and analyse residual contaminants in ginseng and its extract is an apparent problem (Ling et al., 1999, Nerdìn et al., 2002).
Procymidone, a dicarboximide fungicide, has been used in ginseng cultivation and residue is distinctively present in ginseng extract (Li, Kim, & Lee, 2007). Procymidone is found to act as androgen receptor and shows xenoendocrine disrupting properties in rats (Gray, 1998, Gray et al., 1999) and monkeys (Ostby et al., 1999). It was stated that it was very likely that humans would adversely be affected if the human foetus were exposed to sufficient levels during critical stages of neonatal life. Pentachloronitrobenzene, sometimes referred to as quintozene, is a commonly applied fungicidal treatment for control of a garden rot that affects many plants during cool and wet months. It has been widely used to protect ginseng crops. Pentachloroaniline and methylpentachloro-phenylsulphide are two main metabolism of pentachloronitrobenzene, and have been found residues in some vegetables (Lehotay & Ibrahim, 1995). Due to the toxicity, the use of these fungicides is strictly restricted or forbidden. Maximum Residue Limits (MRLs) of procymidone and pentachloronitrobenzene had been established in many countries for the ginseng, were not more than 0.1 mg kg−1, but no limits for pentachloroaniline and methylpentachloro-phenylsulphide in ginseng extract yet. Moreover, the analytical methods for the determination of pentachloroaniline and methylpentachloro-phenylsulphide residues in ginseng and its extracts have not been proposed.
Generally, pesticide analyses are carried out by gas chromatography (GC) or liquid chromatography (LC). These analytical techniques generally require critical steps such as liquid–liquid solvent extraction and series of cleanup procedures for sample preparation. Proper sampling largely determines the validity of an analytical sample for residue analysis. Although many suitable methods for the extraction of pesticides prior to the chromatographic separation have been developed, such as liquid–liquid extraction (LLE) (Fernández et al., 2001, Navarro et al., 2000, Sala et al., 1997, Strandberg and Ronald, 2001), solid-phase extraction (SPE) (Jiménez et al., 2001, Nozal et al., 2005, Wong et al., 2003, Young et al., 2001), solid-phase microextraction (SPME) (Carlo et al., 2004, Hwang and Lee, 2000, Zuin et al., 2004), stir bar sorptive extraction (SBSE) (Jiménez et al., 2001, Nozal et al., 2005, Wong et al., 2003, Young et al., 2001) and micro-porous membrane liquid–liquid extraction (MMLLE) (Hyötyläinen, Tuutijärvi, Kuosmanen, & Riekkola, 2002). Most routine methods used in pesticide residue analysis are often time and solvent consuming due to the steps involved in sample preparation before chromatographic analysis. The ginseng extract matrices had the complex nature in which the pesticide residues and other compounds such as saponins were present, and required a large sample (10–25 g). One alternative that simplifies the preparation of samples is matrix solid-phase dispersion (MSPD). This technique, based on the dispersion of the sample on an adsorbent, such as Florisil, C18, alumina, or silica, integrates sampling, extraction, and pre-concentration into a simple, single-step procedure. The dispersion of solid samples is previously done in a mortar, and then the mixture is transferred to the extraction columns (Kadenczki et al., 1992, Kristenson et al., 2006). In the case of liquid samples, the dispersion of the matrix in the adsorbent can be done directly in the extraction columns (Tadeo and Sánchez, 2003, Albero et al., 2003b). MSPD has many advantages over the traditional techniques, such as the use of smaller amounts of organic solvent, lower solvent cost and reduced toxic organic solvent. At present, MSPD has been successfully applied to the extraction of a wide range of drugs, pesticides, naturally occurring constituents, and other compounds from a wide variety of complex plant and animal samples (Barker, 2007, Bogialli and Di Corcia, 2007, Kristenson et al., 2006).
To the best of our knowledge, only a method using a Keele injector for GC–ECD or GC–MS analysis of procymidone residues in ginseng without performing solvent extraction and clean up procedures was reported (Li et al., 2007). In addition, in spite of the great number of MSPD publications, well-described and validated MSPD methods for the extraction of the most used fungicides applied to ginseng are scarce. The aim of this work was to develop a rapid MSPD method at low levels for the determination of procymidone, pentachloronitrobenzene, pentachloroaniline and methylpentachloro-phenylsulphide residues in ginseng extract.
Section snippets
Chemicals and materials
Pentachloronitrobenzene, pentachloroaniline, methylpentachloro-phenylsulphide and procymidone standards (98.85–99.2% purity) were purchased from Riedel-de Häen (Steinheim, Germany). Stock solutions (500 μg/mL) of each fungicide were prepared by dissolving 50 mg of the fungicide in 100 mL acetone and stored at 4 °C. Standard solutions containing 1.0, 0.5, 0.1, 0.05 and 0.01 μg/mL of each fungicide in acetone were used as chromatographic standards.
Ethyl acetate, acetone, dichloromethane and n-hexane
Matrix effect
The analysis of fungicides was accomplished using GC–μECD. The possible matrix effect on the chromatographic response was studied. When standards were prepared by spiking blank aqueous ginseng extract samples with known amounts of fungicides, higher peak areas were accomplished for the same fungicide concentration. Fig. 1 showed the different response obtained with standard mixtures prepared in acetone or with a blank aqueous ginseng extract sample. There was an evident matrix effect that
Conclusion
In this work, an efficient, fast and easy to perform analysis method based on MSPD was successfully applied to the analysis of pentachloronitrobenzene, pentachloroaniline, methylpentachloro-phenylsulphide and procymidone in ginseng extract. To our knowledge, this is the first time that these fungicide pesticides have been extracted from ginseng extract by MSPD and sonication-assisted extraction. The developed method uses a column so that the extraction and clean up are performed in a single
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