Residual pesticide extraction solution applied to agricultural product, rapid extraction method for agricultural product source liquid using residual pesticide extraction solution, and agricultural product residual pesticide inspection method

Abstract

To provide a residual pesticide extraction solution applied to an agricultural product, a rapid extraction method for an agricultural product source liquid using the residual pesticide extraction solution, and an agricultural product residual pesticide inspection method.SOLUTION: A residual pesticide extraction solution contains an acid solution and an acetone solution, and a content of the acid solution is 0.5 to 3 vol%. A rapid extraction method for an agricultural product source liquid includes the steps of: subjecting an agricultural product sample to homogenization processing; then mixing the residual pesticide extraction solution with the homogenized sample to form a sample solution; and subsequently using a column filled with mixed powder therein to remove moisture and impurities in the sample solution to obtain the agricultural product source liquid. An agricultural product residual pesticide inspection method includes the steps of: using the rapid extraction method for the agricultural product source liquid to obtain the agricultural product source liquid; and directly introducing the agricultural product source liquid to a liquid chromatography tandem type mass analyzer or a gas chromatography tandem type mass analyzer to inspect a residual agricultural pesticide.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a technology for testing agricultural products for pesticide residues, and in particular to a pesticide residue extraction solution to be applied to agricultural products, a method for rapid extraction of an undiluted agricultural product sample solution using the pesticide residue extraction solution, and a method for testing agricultural products for pesticide residues. [Background technology]

[0002] Pesticide residues in agricultural products are usually tested using liquid chromatography tandem mass spectrometers (LC / MS-MS) or gas chromatography tandem mass spectrometers (GC / MS-MS). Before using the above analytical instruments, the QuEChERS (Quick Easy Cheap Effective Rugged Safe) method is generally used to obtain sample stock solutions for testing from agricultural products. However, in order to increase the testing speed, rapid extraction kits have been used in recent years for pesticide residue testing in agricultural products, and U.S. Patent No. 9581579 (Patent No. 6377182) is a typical example.

[0003] In the process of using a rapid extraction kit to test agricultural products for pesticide residues, it is necessary to add an extraction solvent to the homogenized agricultural product sample to obtain the sample stock solution. Currently, the suitable extraction solvents are mainly acetonitrile solution or acetonitrile solution containing acetic acid. The problem is that acetonitrile is a toxic chemical that poses risks to environmental pollution and human health. In addition, there is another problem that the sample stock solution extracted using an extraction solvent containing acetonitrile cannot be tested using a gas chromatography tandem mass spectrometer (GC / MS-MS) unless it undergoes a solvent replacement process. Therefore, how to solve the above problem has been a long-standing concern in the pesticide testing industry. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] U.S. Pat. No. 9,581,579 [Patent Document 2] Patent No. 6377182 Summary of the Invention [Problem to be solved by the invention]

[0005] The object of the present invention is to provide a pesticide residue extraction solution to be applied to agricultural products, a method for rapid extraction of an agricultural product sample stock solution using the pesticide residue extraction solution, and a method for testing agricultural products for pesticide residues, which can solve the above-mentioned problems caused by the use of acetonitrile solution as an extraction solvent in the prior art. [Means for solving the problem]

[0006] More specifically, the pesticide residue extraction solution of the present invention contains an acidic solution and an acetone solution, and the content of the acidic solution is 0.5 to 3 vol %.

[0007] In one embodiment, the content of the acidic solution in the pesticide residue extraction solution of the present invention is 1 vol%.

[0008] In one embodiment, the acidic solution of the pesticide residue extraction solution of the present invention is formic acid, acetic acid, or a combination thereof.

[0009] The method for rapid extraction of an undiluted agricultural produce sample of the present invention includes the steps of: performing a homogenization treatment on an agricultural produce sample to obtain a homogenized sample; mixing the homogenized sample with the above-mentioned pesticide residue extraction solution of the present invention to form a sample solution; and removing moisture and impurities in the sample solution using a column filled with the mixed powder to obtain an undiluted agricultural produce sample solution.

[0010] In one embodiment, the agricultural product sample used in the present invention is a vegetable or fruit, the homogenized sample is 1 gram, and the pesticide residue extraction solution is 5 milliliters. Preferably, the present invention further comprises the step of shaking the homogenized sample and the pesticide residue extraction solution of the present invention for 30 seconds to mix and form a sample solution.

[0011] In one embodiment, the method for rapid extraction of raw agricultural produce samples of the present invention includes the step of adding deionized water into a homogenized sample, where the agricultural produce sample is a grain or an agricultural product that has undergone drying processing. Preferably, the homogenized sample used in the method for rapid extraction of raw agricultural produce samples of the present invention is 0.5 grams, and the pesticide residue extraction solution is 5 milliliters. More preferably, the method for rapid extraction of raw agricultural produce samples of the present invention further includes the step of mixing the pesticide residue extraction solution and the homogenized sample by vigorously shaking them for 30 seconds to form a sample solution.

[0012] The agricultural product pesticide residue testing method of the present invention includes the steps of obtaining an agricultural product sample stock solution using any of the above-mentioned rapid extraction methods for an agricultural product sample stock solution of the present invention, and directly introducing the agricultural product sample stock solution into a liquid chromatography tandem mass spectrometer or a gas chromatography tandem mass spectrometer to perform pesticide residue testing. [Brief description of the drawings]

[0013] [Figure 1] 1 is a flowchart showing one embodiment of a method for testing agricultural products for residual pesticides according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] As shown in FIG. 1, one embodiment of the agricultural product pesticide residue testing method of the present invention includes the following steps:

[0015] Step a: A homogenization process is performed on the produce sample to obtain a homogenized sample.

[0016] Step b: Mix the residual pesticide extraction solution with the homogenized sample to form a sample solution. Here, the residual pesticide extraction solution includes an acidic solution and an acetone solution, and the preferred content of the acidic solution is 0.5-3 vol%, more preferably 1 vol%. The acidic solution can be, but is not limited to, formic acid, acetic acid, or a combination thereof. In addition, in another embodiment, the residual pesticide extraction solution is composed only of an acidic solution and an acetone solution, and does not contain other components.

[0017] Step c: Using a column filled with the mixed powder to remove water and impurities in the sample solution to obtain the raw agricultural product sample solution. In this embodiment, the column filled with the mixed powder can be selected from, but is not limited to, the rapid extraction kit of U.S. Patent No. 9,581,579.

[0018] Step d: The agricultural product sample stock solution is directly introduced into a liquid chromatography tandem mass spectrometer (LC / MS-MS) or a gas chromatography tandem mass spectrometer (GC / MS-MS) to perform a pesticide residue test. For example, 1 milliliter of the agricultural product sample stock solution is directly introduced into the aforementioned analytical equipment to perform a pesticide residue test.

[0019] In step a, the produce sample may be, but is not limited to, fresh vegetables or fruits, or dried grains or other produce that has undergone a drying process. In this embodiment, the produce sample is a homogenized sample that has been homogenized with a stirring homogenizer (blender) to produce fine particles.

[0020] In step b, the pesticide residue extracting solution and the homogenized sample are vigorously shaken together for a predetermined time to mix them as much as possible to form a homogenous sample solution. In this embodiment, the produce sample is fresh vegetables or fruits, the homogenized sample is 1 gram, the pesticide residue extracting solution is 5 milliliters, and the shaking time is 30 seconds, but is not limited thereto.

[0021] In another embodiment, the agricultural product sample is dried grain or other agricultural product that has been subjected to drying processing, and the homogenized sample needs to be added with an appropriate amount of deionized water and left for a predetermined appropriate time (e.g., 10 minutes, etc.). Then, the homogenized sample to which the deionized water has been added and the residual pesticide extracting solution are vigorously shaken together for a predetermined time to mix the two as much as possible to form a homogenous sample solution. In this another embodiment, the homogenized sample is 0.5 grams, the residual pesticide extracting solution is 5 milliliters, the deionized water is 1 milliliter, and the shaking time is 30 seconds, but is not limited thereto.

[0022] In step c, the sample solution is placed in the column, and then the sample solution is pressurized by the piston rod to pass the sample solution through the mixed powder in the column at a predetermined flow rate. The predetermined flow rate is preferably 0.01 to 0.2 mL / sec, and more preferably 0.05 mL / sec. Alternatively, a vacuum evacuation method may be used to pass the sample solution through the mixed powder in the column at a predetermined flow rate. The mixed powder can adsorb a portion of the moisture in the sample solution, and can also adsorb a portion of the impurities in the sample solution, particularly impurities that interfere with the measurement results obtained by the above-mentioned analytical equipment.

[0023] The time for pressurizing the sample solution using the piston rod can usually be less than one minute. In the above embodiment, the sample solution is dripped from the column at a rate of one drop per second, and the time required for pressurizing the sample solution is about 30 seconds. That is, after about 30 seconds of pressurization, the sample solution is entirely filtered by the mixed powder and discharged from the column, forming the agricultural product sample stock solution.

[0024] In step d, 1 milliliter of the agricultural product sample stock solution is introduced into the above-mentioned analytical instrument, and the above-mentioned analytical instrument is used to test the pesticide residue status in the agricultural product sample stock solution. In addition, one embodiment of the rapid extraction method for agricultural product sample stock solution of the present invention includes the above-mentioned steps a to c, and the description thereof is omitted here.

[0025]

Table 1a

[0026]

Table 1b

[0027]

Table 1c

[0028]

Table 1d

[0029]

Table 1e

[0030]

Table 1f

[0031]

Table 1g

[0032]

Table 1h

[0033] Tables 1a-1h show the results of pesticide residue testing performed on produce samples using the method of the present invention and the control method. The produce sample was bok choy, and contained 198 pesticide standards with known concentrations. These pesticide standards include acaricides (e.g., Clofentezine, Ethion), fungicides (e.g., Iprobenfos, Penconazole), herbicides (e.g., Bromacil, Alachlor), insecticides (e.g., Fenobucarb, Diflubenzuron), nematicides (e.g., Fenamiphos, Fosthiazate), plant growth regulators (e.g., Paclobutrazol), and other pesticides (e.g., Piperonyl butoxide). The details are shown in Tables 1a to 1h, and will not be described here.

[0034] In Tables 1a to 1h, the extraction solvent used in the method of the present invention is a residual pesticide extraction solution, and the content of acetic acid therein is 1 vol%, with the remainder being an acetone solution. The control method is the same as the method of the present invention, except for the points described below. The extraction solvent used in the control method is a mixed solution composed of acetic acid and acetonitrile solution, and the content of acetic acid is 1 vol%, with the remainder being an acetonitrile solution. Note that ND in Tables 1a to 1h and the following Table 2 indicates that the peak signal-to-noise ratio (PSNR) is less than 10 and the recovery rate cannot be calculated.

[0035] Table 2 shows the statistical results based on Tables 1a to 1h.

[0036] [Table 2]

[0037] As can be seen from Table 2, the recovery rate (Recovery) of 178 kinds of pesticides was within the standard range of 70% to 120% in the present invention. Meanwhile, in the control method, the recovery rate of only 165 kinds of pesticides was within this standard range. In addition, the recovery rate of one pesticide was 50% or less, and the recovery rate of another pesticide was in the range of more than 50% and less than 60% in the present invention. The recovery rates of two pesticides were more than 60% and less than 70%, and the recovery rates of six other pesticides were in the range of more than 120% and less than 140%, and the recovery rates of two pesticides were more than 140%. Overall, it can be said that the pesticide recovery rate of the present invention is superior to that of the control method. In addition, since the present invention uses a residual pesticide extraction solution that does not contain acetonitrile as the extraction solvent in step b, the raw agricultural product sample solution can be directly introduced into the above-mentioned analytical equipment, and there is no need to perform solvent replacement beforehand. Furthermore, since the present invention does not use acetonitrile, which is a toxic chemical substance, there is no risk of environmental pollution or harm to human health. [Explanation of symbols]

[0038] Steps a~d

Claims

1. A method for rapid extraction of an undiluted agricultural product sample, comprising: subjecting the produce sample to a homogenization process to obtain a homogenized sample; mixing the homogenized sample with a pesticide residue extraction solution to form a sample solution; and removing moisture and impurities from the sample solution using a column filled with the mixed powder to obtain an original agricultural product sample solution. The method for rapid extraction of an undiluted solution of an agricultural product sample, wherein the residual pesticide extraction solution contains an acidic solution and an acetone solution, and the content of the acidic solution is 0.5 to 3 vol %.

2. 2. The method for rapid extraction of an undiluted agricultural product sample liquid according to claim 1, wherein the content of the acidic solution is 1 vol %.

3. 2. The method for rapid extraction of an original solution of an agricultural product sample according to claim 1, wherein the acidic solution is formic acid, acetic acid or a combination thereof.

4. 2. The method for rapid extraction of raw agricultural product samples according to claim 1, wherein the agricultural product sample is a vegetable or fruit, the homogenized sample is 1 gram, and the pesticide residue extraction solution is 5 milliliters.

5. 5. The method for rapid extraction of raw agricultural produce samples according to claim 4, wherein the pesticide residue extraction solution and the homogenized sample are mixed together by shaking them for 30 seconds to form the sample solution.

6. 2. The method for rapid extraction of raw liquid of agricultural produce samples according to claim 1, further comprising the step of adding deionized water to the homogenized sample, wherein the agricultural produce sample is a grain or an agricultural produce that has undergone a drying process.

7. 7. The method for rapid extraction of raw agricultural produce samples according to claim 6, wherein the homogenized sample is 0.5 grams, the pesticide residue extraction solution is 5 milliliters, and the deionized water is 1 milliliter.

8. 8. The method of claim 7, further comprising the step of mixing and shaking the pesticide residue extraction solution and the homogenized sample together for 30 seconds to form the sample solution.

9. A method for testing agricultural products for residual pesticides, comprising: Obtaining an original agricultural product sample solution using the rapid extraction method according to any one of claims 1 to 8; A step of directly introducing the agricultural product sample stock solution into a liquid chromatography tandem mass spectrometer or a gas chromatography tandem mass spectrometer to perform a pesticide residue test; A method for inspecting agricultural product for residual pesticides, comprising:

10. A residual pesticide extraction solution for application to agricultural products, comprising an acidic solution and an acetone solution, the content of the acidic solution being 0.5 to 3 vol %.

11. The pesticide residue extraction solution according to claim 10, characterized in that the content of the acidic solution is 1 vol %.

12. 12. The pesticide residue extraction solution according to claim 10 or 11, characterized in that the acidic solution is formic acid, acetic acid or a combination thereof.

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