CN108562665B - Method for detecting acephate, diafenthiuron and metabolites thereof in soil - Google Patents
Method for detecting acephate, diafenthiuron and metabolites thereof in soil Download PDFInfo
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- CN108562665B CN108562665B CN201810352144.1A CN201810352144A CN108562665B CN 108562665 B CN108562665 B CN 108562665B CN 201810352144 A CN201810352144 A CN 201810352144A CN 108562665 B CN108562665 B CN 108562665B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Abstract
The invention discloses a method for detecting acephate, diafenthiuron and metabolites thereof in soil; in particular to detection of acephate and diafenthiuron and metabolites of acephate and diafenthiuron formamide. The experimental steps include dispersive solid-phase microextraction, effective extraction of 4 compounds from soil, and gas chromatographic separation and analysis. Experiments show that the invention has better precision (RSD is less than 3.40%) and accuracy (recovery rate range is 86.0% -106.0%), thereby being applicable to the analysis of the pesticide in the soil and the metabolite thereof.
Description
Technical Field
The invention relates to detection of residues in soil, in particular to a method for detecting acephate, diafenthiuron and metabolites thereof by using a gas chromatography.
Background
Acephate, also known as acephate, belongs to a low-toxicity insecticide. Acephate is an oral insecticide, has stomach toxicity and contact killing effects, can kill eggs, has a certain fumigating effect, is a slow-acting insecticide, is suitable for crops such as vegetables, tea trees, tobacco, fruit trees, cotton, rice, wheat, rape and the like, and is used for preventing and treating various chewing and piercing-sucking mouthparts pests, harmful mites and sanitary pests. Improper storage and use can cause poisoning of human and livestock. In contrast, the metabolite methamidophos belongs to a highly toxic pesticide, and is 40 degrees times of acephate. Therefore, the residue of acephate and its metabolite methamidophos in soil is very necessary. The structural formulas of the acephate and the methamidophos are as follows:
diafenthiuron is a novel thiourea insecticide and acaricide with the functions of contact poisoning, stomach toxicity, systemic absorption and fumigation, and has a certain ovicidal effect. Low toxicity, but high toxicity to fish and bee. Converting into substance with insecticidal activity under ultraviolet light, and has strong activity on pests with severe drug resistance on vegetables. Can be used for preventing and treating aphid, whitefly, leafhopper, noctuidae pests and mites on various crops and ornamental plants. The wettable powder is mainly prepared into liquid medicine for spraying to prevent and control vegetable plutella xylostella, cabbage caterpillar and cotton spider, the effective components are 20-30 g per mu, and the lasting period is 10-15 days. Researchers have detected diafenthiuron and its metabolites diafenthiuron-formamide and diafenthiuron-urea in tea and soil, but the ultra performance liquid chromatography-tandem mass spectrometry method used by the researchers has very high instrument cost. The structural formulae of diafenthiuron and diafenthiuron-carboxamide are as follows:
in the prior art, no document is available for simultaneously detecting the two pesticides and metabolites thereof, and for detecting metabolites of the pesticides, high-cost instruments such as mass spectra or tandem mass spectra are frequently used in the prior art, so that a simple and low-cost detection method is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provides a method for detecting acephate and diafenthiuron and metabolites thereof by using gas chromatography. The invention effectively extracts the compounds by a dispersive solid-phase extraction method, rapidly determines the content by utilizing a gas chromatography, and provides a simple and convenient detection method with low cost and good accuracy.
The invention is realized by the following technical scheme:
a method for detecting acephate, diafenthiuron and metabolites thereof by gas chromatography comprises the following steps:
step (1): sample preparation:
placing the mixed soil sample and a certain mass of sodium chloride into a conical flask with a plug, adding acetonitrile and deionized water, and carrying out ultrasonic bath; filtering, placing the filtrate in a separating funnel, adding sodium chloride, and oscillating; standing for layering, removing a water layer, taking an organic layer, and drying; concentrating, re-dissolving, and analyzing by sample injection.
Step (2): sample detection:
sampling the solution obtained in the step (1) by using an automatic sampler, detecting by using gas chromatography, and recording gas phase signal values of acephate, diafenthiuron and metabolites thereof;
and (3): and (4) analyzing results:
and (5) quantifying by a standard curve method according to the relation between the peak area and the mass concentration thereof in the chromatogram.
The mass of the soil sample in the above step (1) was 2g, the mass of the sodium chloride added was 0.5g, and the volume of the stoppered Erlenmeyer flask was 50 mL.
The volumes of acetonitrile and deionized water added in the step (1) were 20mL and 8mL, respectively.
The ultrasonic conditions in the step (1) are as follows: the ultrasonic power is 250W, and the ultrasonic time is 20 min.
The drying in the step (1) is carried out by adopting anhydrous sodium sulfate, and the using amount is 2 g.
The concentration and redissolution step in the step (1) is as follows: nitrogen was blown to near dryness and the residue was redissolved with methanol.
The gas chromatography conditions in the above step (2) were as follows: a chromatographic column: DB-624, 30 m.times.320. mu.m.times.1.8. mu.m; temperature rising procedure: the initial temperature is 50 deg.C, maintaining for 2min, increasing to 170 deg.C at a rate of 20 deg.C/min, maintaining for 5min, and increasing to 220 deg.C at a rate of 10 deg.C; the temperature of a sample inlet is 200 ℃; the sample volume was 1 μ L, split mode, split ratio was 20: 1.
The detection conditions in the step (2) are as follows: the temperature of the FID detector is 230 ℃, the carrier gas is helium, the flow rate is 4mL/min, and the flow rates of hydrogen and air are 40 mL/min and 450mL/min respectively.
Wherein, the metabolite of the acephate is methamidophos, and the metabolite of the diafenthiuron is diafenthiuron-formamide.
According to the technical scheme, the method for detecting the acephate, the diafenthiuron and the metabolites thereof by using the gas chromatography is established, has better accuracy, and is quick, automatic and practical; the blank of the prior art is supplemented.
The invention has better precision (RSD is less than 3.40%) and accuracy (recovery rate range is 86.0% -106.0%), therefore, the invention is suitable for analyzing the pesticide and the metabolite thereof in the soil.
Drawings
FIG. 1 is a chromatogram of four compound standards, wherein 1-4 are methamidophos, acephate, diafenthiuron and diafenthiuron-formamide.
Detailed Description
The design idea of the invention or simple substitution of the same belongs to the protection scope of the invention. The experimental procedures used below are, unless otherwise specified, all conventional procedures known in the art and the ingredients or materials used, if not specified, are all commercially available ingredients or materials.
The present invention is further specifically described below by way of examples 1-3.
Instrumentation and reagents used: GC-14C gas chromatograph with hydrogen flame ionization detector (Shimadzu corporation, Japan), DB-624, 30 m.times.320. mu.m.times.1.8. mu.m.
Acephate (the purity is more than or equal to 99.9%), methamidophos (the purity is more than or equal to 98%) and diafenthiuron (the purity is more than or equal to 99%) are analytically pure, diafenthiuron-formamide is entrusted to synthesis, and the HPLC purity is more than or equal to 98%; the experimental water is deionized water; other reagents used in the experiment were all commercially available.
Example 1
Preparation and determination of samples
First, preparation of sample
Placing the mixed soil sample of 2g and sodium chloride of 0.5g into a conical flask with a plug of 50mL, adding acetonitrile of 20mL and deionized water of 8mL, and carrying out ultrasonic bath for 20min (the power is 250W); filtering, placing the filtrate in a separating funnel, adding 0.5g of sodium chloride, and oscillating; standing for layering, removing a water layer, taking an organic layer, and drying; blowing nitrogen to near dryness, re-dissolving the residue with methanol, and analyzing by sample injection.
Second, measurement of sample
A chromatographic column: DB-624, 30 m.times.320. mu.m.times.1.8. mu.m; temperature rising procedure: the initial temperature is 50 deg.C, maintaining for 2min, increasing to 170 deg.C at a rate of 20 deg.C/min, maintaining for 5min, and increasing to 220 deg.C at a rate of 10 deg.C; the temperature of a sample inlet is 200 ℃; the sample volume was 1 μ L, split mode, split ratio was 20: 1.
The temperature of the FID detector is 230 ℃, the carrier gas is helium, the flow rate is 4mL/min, and the flow rates of hydrogen and air are 40 mL/min and 450mL/min respectively.
And (5) quantifying by a standard curve method according to the relation between the peak area and the mass concentration thereof in the chromatogram.
Example 2
The linear equation and the correlation coefficient of 4 samples within 0.05-5 mg/L are shown in Table 1.
TABLE 1
| Compound (I) | Linear equation of equations | Correlation coefficient |
| Acephate | y＝30.235x-0.6354 | 0.9998 |
| Methamidophos | y＝25.685x+0.9587 | 0.9995 |
| Diafenthiuron | y＝20.885-0.6531 | 0.9992 |
| Diafenthiuron carboxamide | y＝22.633+0.8853 | 0.9996 |
Example 3
Precision and accuracy of the method
The accuracy of the method is measured by performing three parallel tests on a soil sample. The results indicated a Relative Standard Deviation (RSD) of detection of less than 3.40%, including errors in sampling and GC detection.
The accuracy of the method is measured by the recovery rate of the added standard. Results are shown in table 2, with recovery ranging from 86.0% to 106.0%.
TABLE 2
The embodiments of the present invention are not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
Claims (6)
1. A method for detecting acephate, diafenthiuron and metabolites thereof in soil is characterized by comprising the following steps: step (1): sample preparation:
placing the mixed soil sample and a certain mass of sodium chloride into a conical flask with a plug, adding acetonitrile and deionized water, and carrying out ultrasonic bath; filtering, placing the filtrate in a separating funnel, adding sodium chloride, and oscillating; standing for layering, removing a water layer, taking an organic layer, and drying; concentrating, redissolving and analyzing by sample injection;
step (2): sample detection:
sampling the solution obtained in the step (1) by using an automatic sampler, detecting by using gas chromatography, and recording gas phase signal values of acephate, diafenthiuron and metabolites thereof;
and (3): and (4) analyzing results:
quantifying by a standard curve method according to the relation between the peak area and the mass concentration thereof in the chromatogram;
wherein, the gas chromatography conditions in the step (2) are as follows: a chromatographic column: DB-624, 30 m.times.320. mu.m.times.1.8. mu.m; temperature rising procedure: the initial temperature is 50 deg.C, maintaining for 2min, increasing to 170 deg.C at a rate of 20 deg.C/min, maintaining for 5min, and increasing to 220 deg.C at a rate of 10 deg.C; the temperature of a sample inlet is 200 ℃; the sample injection amount is 1 mu L, the split mode is adopted, the split ratio is 20:1, and the detection conditions in the step (2) are as follows: a FID detector, wherein the temperature of the detector is 230 ℃, the carrier gas is helium, the flow rate is 4mL/min, and the flow rates of hydrogen and air are 40 mL/min and 450mL/min respectively; and wherein the metabolite of acephate is methamidophos and the metabolite of diafenthiuron is diafenthiuron-formamide.
2. The method for detecting acephate and diafenthiuron and their metabolites in soil as claimed in claim 1, wherein the mass of the soil sample in the step (1) is 2g, the mass of the added sodium chloride is 0.5g, and the volume of the conical flask with the stopper is 50 mL.
3. The method for detecting acephate and diafenthiuron and their metabolites in soil as claimed in claim 1, wherein the volumes of acetonitrile and deionized water added in the step (1) are 20mL and 8mL, respectively.
4. The method for detecting acephate, diafenthiuron and metabolites thereof in soil according to claim 1, wherein the ultrasonic conditions in the step (1) are as follows: the ultrasonic power is 250W, and the ultrasonic time is 20 min.
5. The method for detecting acephate, diafenthiuron and their metabolites in soil as claimed in claim 1, wherein the drying in step (1) is performed using anhydrous sodium sulfate in an amount of 2 g.
6. The method for detecting acephate, diafenthiuron and metabolites thereof in soil according to claim 1, wherein the concentration and redissolution step in the step (1) is as follows: nitrogen was blown to near dryness and the residue was redissolved with methanol.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006125644A1 (en) * | 2005-05-24 | 2006-11-30 | Basf Aktiengesellschaft | Method for determining pesticide residues in soil or plant material |
| CN105669643A (en) * | 2013-12-05 | 2016-06-15 | 江西天人生态股份有限公司 | O-carboxamido benzamide derivative based on ryanodine receptor, and preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006125644A1 (en) * | 2005-05-24 | 2006-11-30 | Basf Aktiengesellschaft | Method for determining pesticide residues in soil or plant material |
| CN105669643A (en) * | 2013-12-05 | 2016-06-15 | 江西天人生态股份有限公司 | O-carboxamido benzamide derivative based on ryanodine receptor, and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Method validation of resistive heating—gas chromatography with flame photometric detection for the rapid screening of organophosphorus pesticides in fruit and vegetables;Katan Patel 等;《Journal of Chromatography A》;20040813;第1046卷(第1-2期);第225-234页 * |
| 柑桔木虱有效防治药剂田间筛选试验;邓明学 等;《农药》;20060731;第45卷(第7期);第486-490页 * |
| 气相色谱-串联质谱法测定茶叶中88种农药残留量;陈红平 等;《色谱》;20110531;第29卷(第5期);第409-416页 * |
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