Detection method for compound herbicides containing chlorpyrifos and triclopyralid butoxyethyl ester

Abstract

This invention discloses a method for detecting a compound herbicide of chlorpyrifos and triclopyroxyacetate butoxyethyl ester, comprising the following steps: S1 Sample pretreatment: prepare standard sample 1 of chlorpyrifos and standard sample 2 of triclopyroxyacetate butoxyethyl ester for later use; dilute the sample to be tested for later use; S2 Mobile phase preparation: mix organic solvent and water to prepare the mobile phase; S3 Inject standard sample 1 and the diluted sample to be tested twice, and inject standard sample 2 sequentially into a high-performance liquid chromatograph (HPLC) for detection using a gradient elution program. This method can achieve stable peak elution of chlorpyrifos and triclopyroxyacetate butoxyethyl ester, avoiding errors in the calculation of the peak area ratio of the two components due to excessively large or small peak areas, and can separate chlorpyrifos and triclopyroxyacetate butoxyethyl ester in a short time, improving detection efficiency.

Description

Technical Field

[0001] This invention relates to the field of measurement and testing, specifically to a method for detecting a compound herbicide consisting of atrazine and triclopyralid butoxyethyl ester. Background Technology

[0002] The herbicide combination of atrazine and triclopyralid butoxyethyl ester exhibits good weed control efficacy. However, the mixture of atrazine and triclopyralid butoxyethyl ester shows some instability, necessitating testing of the active ingredient after production to ensure efficacy. However, solvents, emulsifiers, and dispersants in the finished product can interfere with the detection of the active ingredient. Traditional detection methods involve separately detecting atrazine and triclopyralid butoxyethyl ester, resulting in low efficiency. Therefore, developing a method for the simultaneous detection of atrazine and triclopyralid butoxyethyl ester is crucial.

[0003] Chinese invention patent CN103308641A discloses a high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS / MS) method for determining three amide herbicides in tobacco and tobacco products. This method involves extracting pesticide residues using matrix dispersion solid-phase extraction (MS / MS) and directly determining the pesticide residue levels in tobacco and tobacco products using HPLC-MS / MS. The pretreatment process is simple and rapid, reducing interference from impurities such as pigments in tobacco, but it requires tandem detection with mass spectrometry. CN117434181A discloses a method for detecting herbicides and their metabolites in grains and oilseeds. This method uses acidic acetonitrile as the extractant and inorganic salts for dehydration and salting out. It uses dispersion solid-phase extraction purification followed by HPLC-MS / MS for qualitative and quantitative analysis of pesticide metabolite residues in grains, but the steps are cumbersome and the process is complex. Summary of the Invention

[0004] To develop a method for simultaneously detecting chlorpyrifos and triclopyroxyacetyl butoxyethyl ester, a first aspect of the present invention provides a method for detecting a compound herbicide of chlorpyrifos (also known as aminopyridine acid) and triclopyroxyacetyl butoxyethyl ester, comprising the following steps:

[0005] S1 Sample pretreatment: Take cyprodinium to prepare standard sample 1, take triclopyralid butoxyethyl ester to prepare standard sample 2 for later use, and take the sample to be tested after dilution for later use.

[0006] S2 prepares the mobile phase by mixing organic solvent and water;

[0007] S3 is injected twice in the order of standard sample 1, diluted test sample, and standard sample 2 into the high performance liquid chromatograph. The high performance liquid chromatograph uses the mobile phase configured in S2 for liquid chromatography detection under gradient elution program.

[0008] In a preferred embodiment, the high-performance liquid chromatograph is an Agilent 1260II with a VWD detector.

[0009] In a preferred embodiment, the herbicide compounded with cyprodinil and triclopyralid butoxyethyl ester is an emulsifiable concentrate, wherein the technical concentration of cyprodinil in the compound herbicide is 100-500 g / L, and the technical concentration of triclopyralid butoxyethyl ester in the compound herbicide is 100-300 g / L.

[0010] In a preferred embodiment, the technical concentration of atrazine in the compound herbicide is 300 g / L; the technical concentration of triclopyralid butoxyethyl ester in the compound herbicide is 100 g / L.

[0011] In a preferred embodiment, the concentration of atrazine in standard sample 1 is 0.3-0.8 g / L, and the concentration of triclopyralid butoxyethyl ester in standard sample 2 is 0.3-0.8 g / L.

[0012] In a preferred embodiment, the concentration of atrazine in standard sample 1 is 0.5 g / L, and the concentration of triclopyralid butoxyethyl ester in standard sample 2 is 0.5 g / L.

[0013] In a preferred embodiment, the concentration of the diluted sample to be tested is 1-3 g / L.

[0014] In a preferred embodiment, the concentration of the diluted sample to be tested is 2 g / L.

[0015] During the experiment, the inventors discovered that the emulsifiable concentrate herbicide formulated with chlorpyrifos and triclopyroxyacetate butoxyethyl ester exhibited unstable efficacy after actual mixing. Therefore, it was necessary to test the actual content of chlorpyrifos and triclopyroxyacetate butoxyethyl ester in the emulsifiable concentrate herbicide before it left the factory to ensure it achieved the specified efficacy. In actual testing, the inventors found that the chlorpyrifos content was relatively high in the formulated product. The concentration of the test sample needed to be controlled at 2 g / L to ensure stable peak elution of both chlorpyrifos and triclopyroxyacetate butoxyethyl ester, avoiding errors in calculating the peak area ratio due to excessively large or small peak areas.

[0016] In a preferred embodiment, methanol is used as the diluent to dilute the sample to be tested.

[0017] During the experiment, the inventors discovered that when methanol was used as a diluent, the sample was clear, while when acetonitrile was used as a diluent, the sample was turbid. The uneven dissolution would affect the accuracy of subsequent tests.

[0018] In a preferred embodiment, the volume ratio of organic solvent to water in the mobile phase is (30-90):(70-10); the organic solvent is methanol or acetonitrile; and the pH of the mobile phase is adjusted to 2-4 using phosphoric acid. Preferably, the pH of the mobile phase is adjusted to 3 using phosphoric acid.

[0019] Preferably, the organic solvent is methanol.

[0020] During the experiment, the inventors discovered that it is also necessary to control the mobile phase to be a mixture of methanol and water, and to adjust the pH to 3 with phosphoric acid to ensure stable dissolution of the sample. If an aqueous solution of acetonitrile is used for injection, the compound emulsifiable concentrate herbicide will become turbid, affecting the accuracy of detection. The reason may be that the solubility of aminopyridine acid and triclopyroxyacetic acid butoxyethyl ester is different. When diluting the sample for injection, it is necessary to coordinate the dissolution effect of the two components to avoid turbidity caused by insufficient dissolution of a single component, which would affect the peak accuracy of liquid chromatography.

[0021] In a preferred embodiment, the chromatographic column in the high-performance liquid chromatograph is selected from Agilent EclipsePlus C. 18 5μm 4.6×150mm column, Agilent Poroshell 120EC-C 18 4μm 4.6×100mm column, Agilent Eclipse XDB-C 18 At least one of the following: 5μm 4.6×150mm chromatographic column.

[0022] As a preferred embodiment, the high-performance liquid chromatograph uses an Agilent Eclipse Plus C1000 series HPLC system. 18 When using a 5μm 4.6×150mm column, the gradient elution program is as follows: 0.00 min, methanol-water ratio 50:50; 5.00 min, methanol-water ratio 50:50; 5.50 min, methanol-water ratio 90:10; 14.00 min, methanol-water ratio 90:10; 14.50 min, methanol-water ratio 50:50; then run for 5 min.

[0023] As a preferred embodiment, the high-performance liquid chromatograph is an Agilent Eclipse XDB-C. 18 When using a 5μm 4.6×150mm column, the gradient elution program is as follows: 0.00 min, methanol-water ratio 50:50; 5.00 min, methanol-water ratio 50:50; 5.50 min, methanol-water ratio 90:10; 16.50 min, methanol-water ratio 90:10; 17.00 min, methanol-water ratio 50:50; then run for 5 min.

[0024] As a preferred embodiment, the high-performance liquid chromatograph is an Agilent Poroshell 120EC-C. 18 When using a 4μm 4.6×100mm column, the gradient elution program is as follows: 0.00 min, methanol-water ratio 30:70; 5.00 min, methanol-water ratio 30:70; 5.50 min, methanol-water ratio 90:10; 12.50 min, methanol-water ratio 90:10; 13.00 min, methanol-water ratio 30:70; followed by a 5 min run.

[0025] The inventors employed gradient elution to separate aminochloropyridine acid and triclopyroxyacetic acid butoxyethyl ester during the experiment, thus accelerating the analysis speed. An Agilent Poroshell 120EC-C analyzer was used. 18 The chromatographic column configurations of 0.00 min (ethanol-water ratio 30:70), 5.00 min (ethanol-water ratio 30:70), 5.50 min (ethanol-water ratio 90:10), 12.50 min (ethanol-water ratio 90:10), and 13.00 min (ethanol-water ratio 30:70) enable rapid separation of aminochloropyridine acid and triclopyroxyacetic acid butoxyethyl ester, with good separation from impurity peaks, clear peak shapes, and accurate data.

[0026] As a preferred embodiment, the formula for calculating the mass fraction X of atrazine in the sample to be tested is as follows:

[0027] In the formula:

[0028] A1—The average peak area of ​​atrazine in standard solution 1;

[0029] A2—The average value of the area of ​​the toxic phytotoxicity in the sample to be tested;

[0030] m1—mass of atrazine standard solution 1, in g;

[0031] m2—mass of the sample to be tested for atrazine, in grams;

[0032] P—mass fraction of chlorhexidine in standard solution 1, %.

[0033] As a preferred embodiment, the formula for calculating the mass fraction X of triclopyroxyacetic acid butoxyethyl ester in the sample to be tested is as follows:

[0034] In the formula:

[0035] A1—The average peak area of ​​triclopyroxyacetic acid butoxyethyl ester in standard solution 2;

[0036] A2—The average area of ​​triclopyroxyacetic acid butoxyethyl ester in the sample to be tested;

[0037] Mass of m1—Triclopyroxyacetic acid butoxyethyl ester standard solution 2, g;

[0038] Mass of the m2-triclopyroxyacetic acid butoxyethyl ester sample to be tested, g;

[0039] P—Mass fraction of triclopyroxyacetic acid butoxyethyl ester in standard solution 2, %.

[0040] A second aspect of the present invention provides an application of a detection method for a compound herbicide of atrazine and triclopyralid butoxyethyl ester, applicable to the detection of a compound herbicide of atrazine and triclopyralid butoxyethyl ester in emulsifiable concentrate formulations.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] (1) In the detection method of the compound herbicide of chlorpyrifos and triclopyroxyacetic acid butoxyethyl ester described in this invention, the concentration of the sample to be tested is 2 g / L, so that chlorpyrifos and triclopyroxyacetic acid butoxyethyl ester can achieve stable peaks, and avoid errors in the calculation of the peak area ratio of the two components due to excessively large or small peak areas.

[0043] (2) The detection method of the compound herbicide of chlorpyrifos and triclopyroxyacetic acid butoxyethyl ester described in this invention controls the mobile phase to be a mixture of methanol and water, and adjusts the pH to 3 with phosphoric acid, which can make the sample stable and dissolve, and avoid the problem of inaccurate detection caused by uneven dissolution.

[0044] (3) The detection method of the compound herbicide of chlorpyrifos and triclopyroxyacetic acid butoxyethyl ester described in this invention uses gradient elution to separate chlorpyrifos and triclopyroxyacetic acid butoxyethyl ester, which speeds up the analysis.

[0045] (4) The detection method for the compound herbicide of chlorpyrifos and triclopyralid butoxyethyl ester described in this invention is performed using Agilent Eclipse XDB-C. 18 A 5μm 4.6×150mm column, combined with a suitable gradient elution program, can separate toxicazine and triclopyralid butoxyethyl ester in a short time, improving detection efficiency.

[0046] (5) The detection method of the compound herbicide of chlorpyrifos and triclopyroxyacetic acid butoxyethyl ester described in this invention can simultaneously perform qualitative and quantitative detection of chlorpyrifos and triclopyroxyacetic acid butoxyethyl ester, which saves time, effort, reagents and energy. Attached Figure Description

[0047] Figure 1 The liquid chromatogram of Example 3;

[0048] Figure 2 The liquid chromatogram of Example 4;

[0049] Figure 3 The liquid chromatogram of Example 8;

[0050] Figure 4 This is the liquid chromatogram of Example 10. Detailed Implementation

[0051] Example A

[0052] Example 1

[0053] A method for detecting a compound herbicide consisting of atrazine and triclopyralid butoxyethyl ester, comprising the following steps:

[0054] S1 Sample pretreatment: Take cyprodinium to prepare standard sample 1, take triclopyralid butoxyethyl ester to prepare standard sample 2 for later use, and take the sample to be tested after dilution for later use.

[0055] S2 prepares the mobile phase by mixing organic solvent and water;

[0056] S3 was injected twice into the high-performance liquid chromatograph in the order of standard sample 1, diluted test sample, and standard sample 2, and detected by liquid chromatography using a gradient elution program.

[0057] The high-performance liquid chromatograph is an Agilent 1260II with a VWD detector.

[0058] The technical concentration of atrazine in the compound herbicide is 300 g / L; the technical concentration of triclopyralid butoxyethyl ester in the compound herbicide is 100 g / L.

[0059] The concentration of atrazine in standard sample 1 is 0.5 g / L, and the concentration of triclopyralid butoxyethyl ester in standard sample 2 is 0.5 g / L.

[0060] The concentration of the diluted sample was 2 g / L. The diluent for diluting the sample was methanol.

[0061] The diluted test sample

[0062] The mobile phase is methanol and water, and the pH is adjusted to 3 using phosphoric acid.

[0063] The high-performance liquid chromatograph used an Agilent Eclipse Plus C18 5μm 4.6×150mm column. The gradient elution program is as follows:

[0064] 0.00 min, methanol-water ratio 50:50; 5.00 min, methanol-water ratio 50:50; 5.50 min, methanol-water ratio 70:30; 25.00 min, methanol-water ratio 70:30; 25.50 min, methanol-water ratio 50:50; then run for 5 min.

[0065] Flow rate: 1.000 mL / min; Detection wavelength: 230 nm; Injection volume: 5 μL

[0066] Under these conditions, the retention time of the toxic atrazine in the sample was 2.324 min. The peak of triclopyroxyacetate butoxyethyl ester had not yet appeared by the end of the run. The methanol:water ratio was then adjusted to 70:30, but the peak still hadn't appeared after 49 min. At 49 min, the methanol:water ratio was adjusted to 80:20, and at 55 min, it was adjusted to 90:10. The peak of triclopyroxyacetate butoxyethyl ester appeared at 58.325 min. The detection efficiency was low, and the detection time was long.

[0067] Example 2

[0068] A method for detecting a compound herbicide of chlorpyrifos and triclopyralid butoxyethyl ester, the specific implementation method is the same as in Example 1, except that the gradient elution procedure is as follows:

[0069] 0.00 min, methanol-water ratio 50:50; 5.00 min, methanol-water ratio 50:50; 5.50 min, methanol-water ratio 80:20; 31.00 min, methanol-water ratio 80:20; 31.50 min, methanol-water ratio 50:50; then run for 5 min.

[0070] Under these conditions, the retention time of atrazine in the sample was 2.318 min, and the retention time of triclopyroxyacetic acid butoxyethyl ester was 29.073 min. The peak shape of atrazine was not very good, with a slight tail, while the peak shape of triclopyroxyacetic acid butoxyethyl ester was very good.

[0071] Example 3

[0072] A method for detecting a compound herbicide of chlorpyrifos and triclopyralid butoxyethyl ester, the specific implementation method is the same as in Example 1, except that the gradient elution procedure is as follows:

[0073] At 0.00 min, the methanol-water ratio was 50:50; at 5.00 min, the methanol-water ratio was 50:50; at 5.50 min, the methanol-water ratio was 90:10; at 14.00 min, the methanol-water ratio was 90:10; at 14.50 min, the methanol-water ratio was 50:50; followed by a 5-minute run. The liquid chromatography spectrum is shown below. Figure 1 .

[0074] The theoretical concentration of the diluted test sample is 30 wt% toxicazine + 10 wt% triclopyralid butoxyethyl ester.

[0075] Based on the peak area of ​​the detection spectrum, the detection results were calculated using the formula as follows: Toxicity: 29.8 wt%; Triclopyralid butoxyethyl ester: 10.1 wt%.

[0076] Under these conditions, the retention time of atrazine in the sample was 2.316 min, showing good separation from the two impurity peaks at 1.648 min and 4.648 min. The retention time of triclopyroxyacetic acid butoxyethyl ester was 12.809 min, also showing good separation from the previous 14 impurity peaks, with the elution time of the 14th impurity peak being 11.519 min. The peak shape of atrazine was not very good, showing slight tailing, while the peak shape of triclopyroxyacetic acid butoxyethyl ester was very good.

[0077] Summary: Solution A uses Agilent Eclipse Plus C. 18 In Example 1, with a 5μm 4.6×150mm column, the low methanol ratio of the mobile phase (70%) resulted in a late elution time for triclopyroxyacetic acid butoxyethyl ester. In Example 2, with a methanol ratio of 80%, the elution time for triclopyroxyacetic acid butoxyethyl ester was also late (29.073 min). In Example 3, with a mobile phase ratio of 90%, the elution time for triclopyroxyacetic acid butoxyethyl ester was 12.809 min, which was short and showed good separation from the 14th impurity peak (elution time 11.519 min), indicating the best results.

[0078] Example B

[0079] Example 4

[0080] A method for detecting a compound herbicide of chlorpyrifos and triclopyralid butoxyethyl ester, the specific implementation method being the same as in Example 1, except that the chromatographic column in the high-performance liquid chromatograph is an Agilent Eclipse XDB-C. 18 A 5μm 4.6×150mm column was used. The gradient elution program was as follows:

[0081] At 0.00 min, the methanol-to-water ratio was 50:50; at 5.00 min, the methanol-to-water ratio was 50:50; at 5.50 min, the methanol-to-water ratio was 90:10; at 16.50 min, the methanol-to-water ratio was 90:10; at 17.00 min, the methanol-to-water ratio was 50:50; followed by a 5-min run. See the liquid chromatography spectrum. Figure 2 .

[0082] The theoretical concentration of the diluted test sample is 30 wt% toxicazine + 10 wt% triclopyralid butoxyethyl ester.

[0083] Based on the peak area of ​​the detection spectrum, the detection result was calculated using the formula as follows: Toxifen: 30wt% Triclopyralid butoxyethyl ester: 10wt%.

[0084] Example B uses the same column length and inner diameter as Example A, so a methanol-water ratio of 90:10 was directly selected. Under these conditions, the retention time of atrazine in the sample was 2.347 min, and the resolution of the three impurity peaks at 1.600 min, 2.020 min, and 5.729 min was very good. The retention time of triclopyroxyacetic acid butoxyethyl ester was 15.724 min, and the resolution of the previous 14 impurity peaks was also very good, with the elution time of the 14th impurity peak being 13.644 min. The peak shapes of atrazine and triclopyroxyacetic acid butoxyethyl ester were both very good under this column.

[0085] Example C

[0086] Example 5

[0087] A method for detecting a compound herbicide of chlorpyrifos and triclopyralid butoxyethyl ester, the specific implementation method being the same as in Example 1, except that the chromatographic column in the high-performance liquid chromatograph is an Agilent Poroshell 120EC-C. 18 A 4μm 4.6×100mm column was used with the following gradient elution program:

[0088] 0.00 min, methanol-water ratio 50:50; 5.00 min, methanol-water ratio 50:50; 5.50 min, methanol-water ratio 90:10; 16.50 min, methanol-water ratio 90:10; 17.00 min, methanol-water ratio 50:50; then run for 5 min.

[0089] Under these conditions, the retention time of atrazine in the sample was 1.559 min, and the peak showed a bulge indicating the presence of impurities. The retention time of triclopyroxyacetic acid butoxyethyl ester was 11.842 min.

[0090] Example 6

[0091] A method for detecting a compound herbicide of atrazine and triclopyralid butoxyethyl ester, the specific implementation method is the same as in Example 5, except that the gradient elution procedure is as follows:

[0092] 0.00 min, methanol-water ratio 40:60; 5.00 min, methanol-water ratio 40:60; 5.50 min, methanol-water ratio 80:20; 16.50 min, methanol-water ratio 80:20; 17.00 min, methanol-water ratio 40:60; then run for 5 min.

[0093] Under these conditions, the retention time of atrazine in the sample was 2.002 min, preceded by an impurity with a peak length of 1.624 min. The atrazine peak shape was poor, with a tail at the peak tip, which was the impurity. Triclopyroxyacetic acid butoxyethyl ester did not produce a peak after running under these conditions. After 30 min, the methanol and water were adjusted to 90:10, and the triclopyroxyacetic acid butoxyethyl ester produced a peak at 32.3 min.

[0094] Example 7

[0095] A method for detecting a compound herbicide of atrazine and triclopyralid butoxyethyl ester, the specific implementation method is the same as in Example 5, except that the gradient elution procedure is as follows:

[0096] 0.00 min, methanol-water ratio is 30:70; 5.00 min, methanol-water ratio is 30:70; 5.50 min, methanol-water ratio is 80:20; 35.00 min, methanol-water ratio is 80:20; 35.50 min, methanol-water ratio is 30:70; then run for 5 min.

[0097] Under these conditions, the retention time of atrazine in the sample was 2.841 min, showing good separation from the three impurity peaks, including the one at 2.030 min. The retention time of triclopyroxyacetic acid butoxyethyl ester was 25.941 min, also showing good separation from the previous 13 impurity peaks, with the elution time of the 13th impurity peak at 15.840 min. Both atrazine and triclopyroxyacetic acid butoxyethyl ester exhibited good peak shapes.

[0098] Example 8

[0099] A method for detecting a compound herbicide of atrazine and triclopyralid butoxyethyl ester, the specific implementation method is the same as in Example 5, except that the gradient elution procedure is as follows:

[0100] 0.00 min, methanol-water ratio is 30:70; 5.00 min, methanol-water ratio is 30:70; 5.50 min, methanol-water ratio is 90:10; 12.50 min, methanol-water ratio is 90:10; 13.00 min, methanol-water ratio is 30:70; then run for 5 min.

[0101] Under these conditions, the retention time of chlortetracycline in the sample was 2.821 min, showing excellent separation from the impurity peak at 2.019 min. The retention time of triclopyroxyacetic acid butoxyethyl ester was 11.828 min, also showing excellent separation from the preceding 14 impurity peaks. The elution time of the 14th impurity peak was 11.558 min, and the separation between triclopyroxyacetic acid butoxyethyl ester and this impurity peak was >1.5. Both chlortetracycline and triclopyroxyacetic acid butoxyethyl ester showed good peak shapes. See the liquid chromatography diagram. Figure 3 .

[0102] The theoretical concentration of the diluted test sample is 30 wt% toxicazine + 10 wt% triclopyralid butoxyethyl ester.

[0103] Based on the peak area of ​​the detection spectrum, the detection result was calculated using the formula as follows: Toxicity: 30wt% Triclopyralid butoxyethyl ester: 10.1wt%.

[0104] Summary: Example C uses Agilent Poroshell 120EC-C. 18 In Example 5, using a 4μm 4.6×100mm column, the initial methanol-to-water ratio of 50:50 was too high, resulting in poor separation between the toxaphene and impurity peaks. In Example 6, the initial methanol-to-water ratio of 40:60 was also too high, leading to poor separation between the toxaphene and impurity peaks. Later, the methanol-to-water ratio of 80:10 was too low, resulting in no peak of triclopyroxyacetic acid butoxyethyl ester within the specified running time. In Example 7, the initial methanol-to-water ratio of 30:70 resulted in excellent separation between the toxaphene and impurity peaks. Later, the methanol-to-water ratio of 80:10 resulted in no peak of triclopyroxyacetic acid butoxyethyl ester. The elution time of oxyethyl ester was 25.941 min, which is not short, and it showed good separation from the 13th impurity peak (elution time of 15.840 min). In Example 8, the mobile phase initially had a methanol-water ratio of 3:70, and the separation between toxicant and the impurity peak was very good. Later, in a methanol-water ratio of 90:10, the elution time of triclopyroxyacetic acid butoxyethyl ester was 11.828 min, which was just right, and it showed good separation from the 14th impurity peak (elution time of 11.558 min). Therefore, the mobile phase ratio of Example 7 under this column in Example C is the most optimal.

[0105] Example D

[0106] Example 9

[0107] A method for detecting a compound herbicide of chlorpyrifos and triclopyralid butoxyethyl ester, the specific implementation method being the same as in Example 1, except that the chromatographic column in the high-performance liquid chromatograph is an Agilent ZORBAX SB-C. 18 The following gradient elution program was used with a 5μm 4.6×250mm column:

[0108] 0.00 min, methanol-water ratio is 55:45; 5.00 min, methanol-water ratio is 55:45; 5.50 min, methanol-water ratio is 90:10; 19.50 min, methanol-water ratio is 90:10; 20.00 min, methanol-water ratio is 55:45; then run for 5 min.

[0109] Under these conditions, the retention time of atrazine in the sample was 3.709 min, and the retention time of triclopyralid butoxyethyl ester was 17.076 min. Atrazine peak showed severe tailing.

[0110] Example 10

[0111] A method for detecting a compound herbicide of chlorpyrifos and triclopyralid butoxyethyl ester, the specific implementation method is the same as in Example 9, except that the gradient elution procedure is as follows:

[0112] 0.00 min, methanol-water ratio is 55:45; 8.00 min, methanol-water ratio is 55:45; 8.50 min, methanol-water ratio is 90:10; 21.00 min, methanol-water ratio is 90:10; 21.50 min, methanol-water ratio is 55:45; then run for 5 min.

[0113] Under these conditions, the retention time of toxicazine in the sample was 3.720 min, and the retention time of triclopyralid butoxyethyl ester was 20.061 min. The peak shape of toxicazine was not good, with severe tailing. The last of the 13 impurity peaks had a elution time of 17.676 min and was well separated from triclopyralid butoxyethyl ester. See the liquid chromatography diagram. Figure 4 .

[0114] The theoretical concentration of the diluted test sample is 30 wt% toxicazine + 10 wt% triclopyralid butoxyethyl ester.

[0115] Based on the peak area of ​​the detection spectrum, the detection results were calculated using the formula as follows: Toxicity: 29.5 wt%; Triclopyralid butoxyethyl ester: 9.9 wt%.

[0116] Summary: Option D uses Agilent ZORBAX SB-C 18 With a 5μm 4.6×250mm column, the mobile phases of Example 8 and Example 9 both exhibited severe peak tailing in the toxicant determination, and neither was the optimal choice.

[0117] Example E

[0118] Example 11

[0119] A method for detecting a compound herbicide of chlorpyrifos and triclopyralid butoxyethyl ester, the specific implementation method being the same as in Example 1, except that the chromatographic column in the high-performance liquid chromatograph is a Finome Luna C10 ... 18 A 5μm 4.6×250mm chromatographic column was used, with the following mobile phase: methanol to water ratio of 50:50.

[0120] Under these conditions, the retention time of atrazine in the sample was 5.252 min, and the atrazine peak showed severe tailing.

Claims

1. A method for detecting a compound herbicide of atrazine and triclopyralid butoxyethyl ester, characterized in that, Includes the following steps: S1 Sample pretreatment: Take cyprodinium to prepare standard sample 1, take triclopyralid butoxyethyl ester to prepare standard sample 2 for later use, and take the sample to be tested after dilution for later use. S2 prepares the mobile phase by mixing organic solvent and water; S3 is injected into the high-performance liquid chromatograph in the following order: standard sample 1, diluted test sample, and standard sample 2. The high-performance liquid chromatograph uses the mobile phase prepared in S2 to perform liquid chromatography detection under gradient elution program. The volume ratio of organic solvent to water in the mobile phase is (30-90):(70-10); the organic solvent is methanol or acetonitrile; the pH of the mobile phase is adjusted to 2-4 using phosphoric acid. The chromatographic column in the high-performance liquid chromatograph is selected from Agilent Eclipse Plus C. 18 5μm 4.6×150mm column, Agilent Poroshell 120 EC-C 18 4μm 4.6×100mm column, Agilent Eclipse XDB-C 18 At least one of the following: 5μm 4.6×150mm chromatographic column; The high-performance liquid chromatograph used is an Agilent Eclipse Plus C. 18 When using a 5μm 4.6×150mm column, the gradient elution program is as follows: 0.00 min, methanol-water ratio 50:50; 5.00 min, methanol-water ratio 50:50; 5.50 min, methanol-water ratio 90:10; 14.00 min, methanol-water ratio 90:10; 14.50 min, methanol-water ratio 50:50; then run for 5 min. The high-performance liquid chromatograph used is an Agilent Poroshell 120 EC-C. 18 When using a 4μm 4.6×100mm column, the gradient elution program is as follows: 0.00 min, methanol-water ratio 30:70; 5.00 min, methanol-water ratio 30:70; 5.50 min, methanol-water ratio 90:10; 12.50 min, methanol-water ratio 90:10; 13.00 min, methanol-water ratio 30:70; followed by a 5 min run.

2. The detection method for the compound herbicide of atrazine and triclopyralid butoxyethyl ester according to claim 1, characterized in that, The herbicide compounded with cyprodinil and triclopyralid butoxyethyl ester is an emulsifiable concentrate, wherein the technical concentration of cyprodinil in the compound herbicide is 100-500 g / L; and the technical concentration of triclopyralid butoxyethyl ester in the compound herbicide is 100-300 g / L.

3. The detection method for the compound herbicide of atrazine and triclopyralid butoxyethyl ester according to claim 1, characterized in that, The concentration of atrazine in standard sample 1 is 0.3-0.8 g / L, and the concentration of triclopyralid butoxyethyl ester in standard sample 2 is 0.3-0.8 g / L.

4. The detection method for the compound herbicide of atrazine and triclopyralid butoxyethyl ester according to claim 1, characterized in that, The concentration of the diluted sample to be tested is 1-3 g / L.

5. The application of a detection method for a compound herbicide of atrazine and triclopyralid butoxyethyl ester according to any one of claims 1-4, characterized in that, It is used in the detection of compound herbicides containing emulsifiable concentrates of chlorpyrifos and triclopyralid butoxyethyl ester.

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