CN113945655A - Method for detecting pesticide residue in cereal grains and oil products thereof - Google Patents
Method for detecting pesticide residue in cereal grains and oil products thereof Download PDFInfo
- Publication number
- CN113945655A CN113945655A CN202111155218.0A CN202111155218A CN113945655A CN 113945655 A CN113945655 A CN 113945655A CN 202111155218 A CN202111155218 A CN 202111155218A CN 113945655 A CN113945655 A CN 113945655A
- Authority
- CN
- China
- Prior art keywords
- extract
- silica gel
- magnesium sulfate
- anhydrous magnesium
- matrix
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present disclosure relates to a method for detecting pesticide residues in cereals and oil products thereof, comprising the steps of: s1, mixing the matrix to be detected, water and an acetonitrile aqueous solution of formic acid, and performing first extraction to obtain a first extract; s2, mixing the first extract with anhydrous magnesium sulfate and sodium chloride, and performing second extraction to obtain a second extract; s3, performing first centrifugation on the second extract, taking supernatant as matrix extracting solution, mixing the matrix extracting solution with a purifying agent, performing purification treatment, and performing second centrifugation on the purified material to obtain supernatant as to-be-detected liquid; the purifying agent comprises anhydrous magnesium sulfate, ethylenediamine-N-propyl silanized silica gel and octadecylsilane bonded silica gel; and S4, determining the solution to be detected by using ultra performance liquid chromatography-tandem mass spectrometry and gas chromatography-tandem mass spectrometry. The method is simple to operate, high in accuracy and good in repeatability.
Description
Technical Field
The application relates to the field of food detection, in particular to a method for detecting pesticide residues in grains and oil products thereof.
Background
Due to the reasons of multiple varieties, long growth period, susceptibility to diseases and insect pests and the like, grain and cereal agricultural products need to be applied with various pesticides to ensure the growth of the crops. However, the use of pesticides also brings problems to the safety of agricultural products, and particularly, pesticide residues in agricultural products exceed the standard and are always the core problem of the safety of grain and cereal agricultural products at present or even in a later period of time due to multiple varieties, high toxicity, wide application range and high use technology difficulty. Due to the influence of homologues, isomers, degradation products and metabolites of pesticides, the analysis of pesticide residues in cereals has the problems of complex matrix, more components to be detected and the like.
The traditional pretreatment of pesticide residue analysis generally comprises three aspects of sample extraction, purification and concentration, and the pretreatment technology has the defects of low accuracy and poor repeatability due to the complex substrate of grain and cereal agricultural products. Therefore, there is a need in the art for a suitable pesticide residue detection method for detecting various pesticide residues in cereal grains and oil products thereof.
Disclosure of Invention
The purpose of the disclosure is to provide a method for detecting 131 pesticide residues in grains and oil products thereof, which is simple to operate, high in accuracy and good in repeatability.
In order to achieve the above objects, the present disclosure provides a method for detecting pesticide residues in cereal grains and oil products thereof, comprising the steps of:
s1, mixing the matrix to be detected, water and an acetonitrile aqueous solution of formic acid, and performing first extraction to obtain a first extract;
s2, mixing the first extract with anhydrous magnesium sulfate and sodium chloride, and performing second extraction to obtain a second extract;
s3, performing first centrifugation on the second extract, taking supernatant as matrix extracting solution, mixing the matrix extracting solution with a purifying agent, performing purification treatment, and performing second centrifugation on the purified material to obtain supernatant as to-be-detected liquid;
s4, determining the liquid to be detected by using ultra-high performance liquid chromatography-tandem mass spectrometry and gas chromatography-tandem mass spectrometry
The purifying agent comprises anhydrous magnesium sulfate, ethylenediamine-N-propyl silanized silica gel and octadecylsilane bonded silica gel; wherein the weight ratio of the anhydrous magnesium sulfate, the ethylenediamine-N-propylsilanized silica gel and the octadecylsilane chemically bonded silica is 1: 0.5-2: 0.5-2.
Optionally, in step S1, the weight ratio of the substrate to be tested, water and the aqueous solution of acetonitrile formate is 1: 1-2: 2-3; the concentration of the aqueous acetonitrile formate solution is 0.5 to 2.0 vol%.
Optionally, in step S2, the amount of anhydrous magnesium sulfate is 0.5-1g and the amount of sodium chloride is 0.1-0.4g relative to 1g of the substrate to be tested.
Alternatively, in step S3, the amount of anhydrous magnesium sulfate is 100-200mg, the amount of ethylenediamine-N-propylsilanized silica gel is 10-400mg, and the amount of octadecylsilane chemically bonded silica gel is 10-400mg, relative to 1mL of the matrix extract.
Preferably, the amount of the anhydrous magnesium sulfate is 120-180mg, the amount of the ethylenediamine-N-propylsilanized silica gel is 50-100mg, and the amount of the octadecylsilane bonded silica gel is 50-100mg, relative to 1mL of the matrix extracting solution.
Optionally, in step S1, the first extraction comprises vortexing for 1-5 minutes; in step S2, the second extraction comprises vortexing in an ice-water bath for 1-5 minutes.
Optionally, the conditions of the first centrifugation comprise: the rotating speed is 4000-; the conditions of the second centrifugation include: the rotation speed is 10000-.
Optionally, the method further comprises: and filtering the liquid to be detected by using a filter membrane before detecting the liquid to be detected by using ultra performance liquid chromatography-tandem mass spectrometry and gas chromatography-tandem mass spectrometry, wherein the pore diameter of the filter membrane is 0.22 micron or less.
Optionally, the substrate to be tested is selected from at least one of soybean, peanut, rapeseed and corn.
Optionally, the pesticide in the pesticide residue is selected from the group consisting of 131: propoxur, dichlorvos, metocloprid, chlorfenvinphos, phosmet, phorate, terbufos, alpha-hexahexa, gamma-hexa, beta-hexa, ethion, delta-hexa, diazinon, tefluthrin, phosphamidon, methyl parathion, methyl chlorpyrifos, heptachloro, propargite, pyraclofos, fenitrothion, malathion, aldrin, fenthion, chlorpyrifos, disulfoxide, parathion, trichlorfon, isocrotophos, chlorfenphos, chlorfenapyr, endosulfan, thion, methidathion, o, p '-DDE, dieldrin, miticide, profenofos, p' -DDE, o, p '-DDD, isodifen, chlorfenapyr, o, p' -DDT, p '-DDD, p' -DDT, furethrin, methoprene, aldicarb, Spiromesifen, bifenthrin, fenpropathrin, cyhalothrin, mirex, fluthrin, permethrin, pyridaben, cyfluthrin, cypermethrin, fenvalerate, etofenvalerate, cyfluthrin, deltamethrin, acetamiprid, aldicarb sulfone, aldicarb sulfoxide, benalathion-, buprofezin, thionophos, carbaryl, carbofuran, 3-hydroxycarbcarb, chlorantraniliprole, clothianidin, cyantraniliprole, diflubenzuron, dimethoate, disulfoton sulfone, emamectin benzoate, fenamiphos, etoxazole, fenamiphos sulfone, fenamiphos sulfoxide, fenpyroxim, fenpyroxynil, fipronil sulfoxide, disulfoton, fipronil sulfone, flonicamid, flufenide, phoxim, fosthiazate, hexythiazox, imidacloprid, pyraflufenpyr, flufenpyr, fipronil sulfoxide, phoxim, fenpyr, fenpyrad, fenpyr, fenpyrad, fenpyr, fenpyrad, fenpyr, fenthion, fenpyrad, fenpyr, fenthion, fenpyr, indoxacarb, isoxathion, methomyl, monocrotophos, pymetrozine/pyrazinone, spinosad, thiamethoxam, triazophos, methiocarb, methamidophos, methoxyfenozide, nitenpyram, omethoate, phorate sulfoxide, pirimicarb, pirimiphos-methyl, pyriproxyfen, rotenone, spinetoram, spirotetramat, tebufenozide, tebufenpyrad, thiacloprid, triazophos, trichlorfon, chlorbenzuron, sulphoxide phosphorus-, lufenuron, chlorfluazuron, systemic phos and spirodiclofen.
Through the technical scheme, the method disclosed by the invention can greatly reduce the interference effect of other possible target compounds in grains and oil products, so that the pesticide residue is effectively analyzed, the simultaneous detection of 131 pesticides in grains and oil products can be realized, and the accuracy and the repeatability are higher.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
FIG. 1 is a bar graph of the average recovery of example 1 and comparative examples 1-5;
FIG. 2 is a bar graph of the relative standard deviations of example 1 and comparative examples 1-5;
FIG. 3 is a matrix effect graph of the grain and oil matrix to be tested.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a method for detecting pesticide residues in cereals and oil products thereof, comprising the following steps:
s1, mixing the matrix to be detected, water and an acetonitrile aqueous solution of formic acid, and performing first extraction to obtain a first extract;
s2, mixing the first extract with anhydrous magnesium sulfate and sodium chloride, and performing second extraction to obtain a second extract;
s3, performing first centrifugation on the second extract, taking supernatant as matrix extracting solution, mixing the matrix extracting solution with a purifying agent, performing purification treatment, and performing second centrifugation on the purified material to obtain supernatant as to-be-detected liquid;
s4, determining the liquid to be detected by using ultra-high performance liquid chromatography-tandem mass spectrometry and gas chromatography-tandem mass spectrometry
The purifying agent comprises anhydrous magnesium sulfate, ethylenediamine-N-propyl silanized silica gel and octadecylsilane bonded silica gel; wherein the weight ratio of the anhydrous magnesium sulfate, the ethylenediamine-N-propylsilanized silica gel and the octadecylsilane chemically bonded silica is 1: 0.5-2: 0.5-2.
The method of the present disclosure uses anhydrous magnesium sulfate, ethylenediamine-N-propylsilanized silica gel, and octadecylsilane bonded silica gel as a purifying agent, and the purifying agent is used in which the weight ratio of the anhydrous magnesium sulfate, the ethylenediamine-N-propylsilanized silica gel, and the octadecylsilane bonded silica gel is 1: 0.5-2: 0.5 to 2; the purifying agent can effectively extract and purify pesticides and the like in grains and oil products thereof, greatly reduce the interference effect of other possible target compounds in the grains and the oil products thereof on matrixes, effectively analyze pesticide residues, realize the simultaneous detection of 131 pesticides in the grains and the oil products thereof, and have higher accuracy and repeatability.
According to the disclosure, in step S1, the weight ratio of the substrate to be tested, water and the aqueous acetonitrile formate solution may be 1: 1-2: 2-3; the concentration of the aqueous acetonitrile formate solution may be 0.5 to 2.0 vol%.
According to the present disclosure, in step S2, the amount of anhydrous magnesium sulfate may be 0.5 to 1g and the amount of sodium chloride may be 0.1 to 0.4g, relative to 1g of the substrate to be tested.
According to the disclosure, in step S3, the amount of anhydrous magnesium sulfate may be 100-200mg, the amount of ethylenediamine-N-propylsilanized silica gel may be 10-400mg, and the amount of octadecylsilane bonded silica gel may be 10-400mg, relative to 1mL of the matrix extract. Further preferably, in order to obtain better purification and extraction effects, the amount of anhydrous magnesium sulfate may be 120-180mg, the amount of ethylenediamine-N-propylsilanized silica gel may be 50-100mg, and the amount of octadecylsilane bonded silica gel may be 50-100mg, relative to 1mL of the matrix extract.
According to the present disclosure, in step S1, the first extraction may include vortexing for 1-5 minutes; in step S2, the second extraction may include vortexing in an ice-water bath for 1-5 minutes.
According to the present disclosure, the conditions of the first centrifugation may include: the rotating speed is 4000-; the conditions of the second centrifugation may include: the rotation speed is 10000-.
According to the present disclosure, the method may further comprise: and filtering the liquid to be detected by using a filter membrane before detecting the liquid to be detected by using ultra performance liquid chromatography-tandem mass spectrometry and gas chromatography-tandem mass spectrometry, wherein the pore diameter of the filter membrane is 0.22 micron or less.
According to the present disclosure, the substrate to be tested may be selected from at least one of soybean, peanut, rapeseed, and corn.
According to the present disclosure, the pesticide in the pesticide residue may be selected from the group consisting of 131: propoxur, dichlorvos, metocloprid, chlorfenvinphos, phosmet, phorate, terbufos, alpha-hexahexa, gamma-hexa, beta-hexa, ethion, delta-hexa, diazinon, tefluthrin, phosphamidon, methyl parathion, methyl chlorpyrifos, heptachloro, propargite, pyraclofos, fenitrothion, malathion, aldrin, fenthion, chlorpyrifos, disulfoxide, parathion, trichlorfon, isocrotophos, chlorfenphos, chlorfenapyr, endosulfan, thion, methidathion, o, p '-DDE, dieldrin, miticide, profenofos, p' -DDE, o, p '-DDD, isodifen, chlorfenapyr, o, p' -DDT, p '-DDD, p' -DDT, furethrin, methoprene, aldicarb, Spiromesifen, bifenthrin, fenpropathrin, cyhalothrin, mirex, fluthrin, permethrin, pyridaben, cyfluthrin, cypermethrin, fenvalerate, etofenvalerate, cyfluthrin, deltamethrin, acetamiprid, aldicarb sulfone, aldicarb sulfoxide, benalathion-, buprofezin, thionophos, carbaryl, carbofuran, 3-hydroxycarbcarb, chlorantraniliprole, clothianidin, cyantraniliprole, diflubenzuron, dimethoate, disulfoton sulfone, emamectin benzoate, fenamiphos, etoxazole, fenamiphos sulfone, fenamiphos sulfoxide, fenpyroxim, fenpyroxynil, fipronil sulfoxide, disulfoton, fipronil sulfone, flonicamid, flufenide, phoxim, fosthiazate, hexythiazox, imidacloprid, pyraflufenpyr, flufenpyr, fipronil sulfoxide, phoxim, fenpyr, fenpyrad, fenpyr, fenpyrad, fenpyr, fenpyrad, fenpyr, fenthion, fenpyrad, fenpyr, fenthion, fenpyr, indoxacarb, isoxathion, methomyl, monocrotophos, pymetrozine/pyrazinone, spinosad, thiamethoxam, triazophos, methiocarb, methamidophos, methoxyfenozide, nitenpyram, omethoate, phorate sulfoxide, pirimicarb, pirimiphos-methyl, pyriproxyfen, rotenone, spinetoram, spirotetramat, tebufenozide, tebufenpyrad, thiacloprid, triazophos, trichlorfon, fenoxuron, sulphoxate, lufenuron, chlorfluazuron, systemic phos and spirodiclofen, the mass spectrum parameters of the above 131 insecticides are shown in Table 1.
TABLE 1
The detection of the ultra-high performance liquid chromatography-tandem mass spectrometry and the gas chromatography-tandem mass spectrometry comprises the optimization of a mass spectrometry method and the optimization of a gas phase method and a liquid phase method. The mass spectrometry part is detected in a dynamic multi-reaction monitoring mode, and is characterized by not less than 2 groups of characteristic ion pairs. The liquid phase method optimization is mainly based on mobile phase gradient elution ratio optimization, and the gas phase method optimization is mainly based on temperature rise program optimization, so that a TIC graph with good pesticide dispersibility is obtained.
The present disclosure is further illustrated by the following examples. The raw materials used in the examples are all available from commercial sources. In the following examples, the substrate to be tested was a grain and oil substrate containing an insecticide, and specifically, the method of the present disclosure was tested by dissolving 131 insecticides in acetonitrile to prepare a standard solution of 10mg/L, then obtaining an insecticide standard intermediate solution, mixing the insecticide standard intermediate solution with a grain and oil substrate (soybean) without insecticide to obtain a soybean grain and oil substrate simultaneously containing 131 insecticides (each pesticide was obtained to a final concentration of 1, 5, 10, 50, 100, 500 μ g/L).
Experimental apparatus and reagents in the examples
UPLC-QQ (ultra high performance liquid chromatography: 1200Infinity Series, Agilent technologies, Inc.; triple quadrupole mass spectrometry: 6470LC/TQ, Agilent technologies, Inc.); gas chromatography/tandem triple quadrupole mass spectrometer (Agilent7890B-7000C, GC-MS/MS);
HPLC grade acetonitrile, methanol, acetic acid, mass spec grade formic acid were purchased from siemer feishel technologies (china) ltd; anhydrous magnesium sulfate, sodium chloride were purchased from: chemical agents of the national drug group, ltd.
The conditions of the liquid chromatography-tandem mass spectrometry instrument comprise: dynamic multiple reaction monitoring mode, capillary voltage: positive ion mode: 3.5KV, negative ion mode: 4.0KV, ion source temperature: the temperature of desolventizing gas is 350 ℃; the flow rate of the desolventizing agent is 11L/min; temperature of sheath gas: at 260 ℃.
Chromatographic conditions are as follows: poroshell 120 EC-octadecylsilane bonded silica chromatography column (3.0 x 100mm,2.7 μm).
Mobile phase: a: 0.1% formic acid water
B: acetonitrile
The specific elution conditions are shown in Table 2
TABLE 2
| Time (min) | A(％) | B(％) |
| 0 | 85 | 15 |
| 0.2 | 85 | 15 |
| 4 | 50 | 50 |
| 5 | 50 | 50 |
| 12 | 2 | 98 |
| 14.5 | 2 | 98 |
| 15 | 85 | 15 |
| 15.5 | 85 | 15 |
Gas chromatography conditions: rtx-5MS quartz capillary column (30 m.times.0.25 mm.times.0.25 μm, RESTEK, USA); temperature of the column: initial 50 ℃, carrier gas: helium, purity not less than 99.999%, flow rate: 0.8 mL/min; sample inlet temperature: injecting samples at 250 ℃: 1 mu L of the solution; and (3) sample introduction mode: no shunt sampling; electron bombardment source: 70 eV; ion source temperature: 280 ℃; transmission line temperature: 280 ℃; solvent retardation: 3.0min, and the specific temperature rise conditions are shown in Table 3.
TABLE 3
| Step (ii) of | Heating rate/min | Final temperature C | |
| 1 | / | 50 | 1 |
| 2 | 40 | 140 | 0 |
| 3 | 8 | 240 | 0 |
| 4 | 12 | 300 | 5 |
Example 1
Accurately weighing 5g of grain and oil matrix into a 50mL centrifuge tube, adding 10mL of water and 15mL of 1 vol% acetonitrile formate, performing vortex extraction for 1min, adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, immediately shaking up, performing ice-water bath, and performing vortex for 1 min. The mixture was centrifuged at 4000rpm for 1 minute, and the supernatant was used as a matrix extract. Taking 1mL of matrix extracting solution, adding 150mg of anhydrous magnesium sulfate, 50mg of ethylenediamine-N-propylsilanized silica gel and 50mg of octadecylsilane chemically bonded silica, centrifuging at 12000rpm for 1 minute, taking supernate, filtering through a 0.22 mu m filter membrane, and adding the supernate into a sample injection vial to serve as a solution to be detected.
Comparative example 1
Accurately weighing 5g of grain and oil matrix into a 50mL centrifuge tube, adding 10mL of water and 15mL of 1 vol% acetonitrile formate, performing vortex extraction for 1min, adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, immediately shaking up, performing ice-water bath, and performing vortex for 1 min. The mixture was centrifuged at 4000rpm for 1 minute, and the supernatant was used as a matrix extract. Taking 1mL of matrix extracting solution, 50mg of ethylenediamine-N-propylsilanized silica gel and 50mg of octadecylsilane chemically bonded silica, centrifuging at 12000rpm for 1 minute, taking supernate, filtering through a 0.22 mu m filter membrane, and adding the supernate into a sample injection vial to serve as a solution to be detected.
Comparative example 2
Accurately weighing 5g of grain and oil matrix into a 50mL centrifuge tube, adding 10mL of water and 15mL of 1 vol% acetonitrile formate, performing vortex extraction for 1min, adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, immediately shaking up, performing ice-water bath, and performing vortex for 1 min. The mixture was centrifuged at 4000rpm for 1 minute, and the supernatant was used as a matrix extract. Taking 1mL of matrix extracting solution, adding 150mg of anhydrous magnesium sulfate and 50mg of ethylenediamine-N-propylsilanized silica gel, centrifuging at 12000rpm for 1 minute, taking supernate, filtering through a 0.22 mu m filter membrane, and adding the supernate into a sample injection vial to serve as a solution to be detected.
Comparative example 3
Accurately weighing 5g of grain and oil matrix into a 50mL centrifuge tube, adding 10mL of water and 15mL of 1 vol% acetonitrile formate, performing vortex extraction for 1min, adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, immediately shaking up, performing ice-water bath, and performing vortex for 1 min. The mixture was centrifuged at 4000rpm for 1 minute, and the supernatant was used as a matrix extract. Taking 1mL of matrix extracting solution, adding 150mg of anhydrous magnesium sulfate and 50mg of octadecylsilane chemically bonded silica, centrifuging at 12000rpm for 1 minute, taking supernate, filtering through a 0.22-micron filter membrane, and adding the supernate into a sample injection vial to serve as a solution to be detected.
Comparative example 4
Accurately weighing 5g of grain and oil matrix into a 50mL centrifuge tube, adding 10mL of water and 15mL of 1 vol% acetonitrile formate, performing vortex extraction for 1min, adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, immediately shaking up, performing ice-water bath, and performing vortex for 1 min. The mixture was centrifuged at 4000rpm for 1 minute, and the supernatant was used as a matrix extract. 1mL of the substrate extract was added with 150mg of anhydrous magnesium sulfate, centrifuged at 12000rpm for 1 minute, and the supernatant was filtered through a 0.22 μm filter and then added to a sample vial as a test solution.
Comparative example 5
Accurately weighing 5g of grain and oil matrix in a 50mL centrifuge tube, adding 5mL of water and 10mL of 1 vol% acetonitrile formate, performing vortex extraction for 1min, adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, immediately shaking up, performing ice-water bath, and performing vortex for 1 min. Centrifuged at 12000rpm for 1 minute, and the supernatant was used as a substrate extract. Taking 1mL of matrix extracting solution, adding 150mg of anhydrous magnesium sulfate and 5mg of nano zinc oxide, centrifuging at 12000rpm for 1 minute, taking supernate, filtering through a 0.22 mu m filter membrane, and adding the supernate into a sample injection vial to serve as a solution to be detected.
Test example 1
Respectively testing the to-be-tested solutions obtained in the test example 1 and the comparative examples 1 to 4 by using ultra performance liquid chromatography-tandem mass spectrometry; the grain and oil substrate without the insecticide is extracted and purified by the extraction and purification methods in the example 1 and the comparative examples 1 to 5 respectively to obtain the extraction and purification solution, and the extraction and purification solution is mixed with the insecticide mixed solution to be used as a substrate standard sample.
And calculating the recovery rate and the RSD according to the test result, wherein the calculation method of the recovery rate and the RSD comprises the following steps:
recovery rate ═ C test solution x dilution times "/" C matrix standard "× 100
Relative Standard Deviation (RSD) ═ Standard Deviation (SD)/arithmetic mean of calculated results (X) × 100%
The average recovery rate of 131 insecticides was 60% to 130% and the RSD was < 20%, and the results are shown in fig. 1, and it can be seen that when the purification agent was selected in example 1, the recovery rate and relative standard deviation were higher than those of comparative examples 1 to 5, the purification effect was more significant when 150mg of anhydrous magnesium sulfate, 50mg of ethylenediamine-N-propylsilanized silica gel, and 50mg of octadecylsilane bonded silica gel were used in combination.
Calculating the matrix effect according to the test result, wherein the Matrix Effect (ME) is calculated by the following formula:
ME(％)＝Ssubstrate/SSolvent(s)×100％
The matrix effect is negligible when ME is 80% -120%, ME < 80% shows matrix-weakening effect, ME > 120% shows matrix-strengthening effect. The effect of 131 insecticide matrices in the soybean oil matrix is shown in figure 2. From fig. 2, it can be seen that the matrix effect is not significant for the methods of the present disclosure.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. A method for detecting pesticide residues in cereal grains and oil products thereof, comprising the steps of:
s1, mixing the matrix to be detected, water and an acetonitrile aqueous solution of formic acid, and performing first extraction to obtain a first extract;
s2, mixing the first extract with anhydrous magnesium sulfate and sodium chloride, and performing second extraction to obtain a second extract;
s3, performing first centrifugation on the second extract, taking supernatant as matrix extracting solution, mixing the matrix extracting solution with a purifying agent, performing purification treatment, and performing second centrifugation on the purified material to obtain supernatant as to-be-detected liquid;
s4, determining the liquid to be detected by using ultra-high performance liquid chromatography-tandem mass spectrometry and gas chromatography-tandem mass spectrometry;
the purifying agent comprises anhydrous magnesium sulfate, ethylenediamine-N-propyl silanized silica gel and octadecylsilane bonded silica gel; wherein the weight ratio of the anhydrous magnesium sulfate, the ethylenediamine-N-propylsilanized silica gel and the octadecylsilane chemically bonded silica is 1: 0.5-2: 0.5-2.
2. The method according to claim 1, wherein in step S1, the weight ratio of the substrate to be tested, water and the aqueous acetonitrile formate solution is 1: 1-2: 2-3; the concentration of the aqueous acetonitrile formate solution is 0.5 to 2.0 vol%.
3. The method according to claim 1, wherein in step S2, the amount of anhydrous magnesium sulfate is 0.5 to 1g and the amount of sodium chloride is 0.1 to 0.4g, relative to 1g of the substrate to be tested.
4. The method as claimed in claim 1, wherein in step S3, the amount of anhydrous magnesium sulfate is 100-200mg, the amount of ethylenediamine-N-propylsilanized silica gel is 10-400mg, and the amount of octadecylsilane bonded silica gel is 10-400mg, relative to 1mL of the matrix extract.
5. The method as claimed in claim 4, wherein the amount of anhydrous magnesium sulfate is 120-180mg, the amount of ethylenediamine-N-propylsilanized silica gel is 50-100mg, and the amount of octadecylsilane bonded silica gel is 50-100mg, relative to 1mL of the matrix extract.
6. The method of claim 1, wherein,
in step S1, the first extraction comprises vortexing for 1-5 minutes;
in step S2, the second extraction comprises vortexing in an ice-water bath for 1-5 minutes.
7. The method of claim 1, wherein,
the conditions of the first centrifugation include: the rotating speed is 4000-;
the conditions of the second centrifugation include: the rotation speed is 10000-.
8. The method of claim 1, wherein the method further comprises: and filtering the liquid to be detected by using a filter membrane before detecting the liquid to be detected by using ultra performance liquid chromatography-tandem mass spectrometry and gas chromatography-tandem mass spectrometry, wherein the pore diameter of the filter membrane is 0.22 micron or less.
9. The method according to claim 1, wherein the substrate to be tested is selected from at least one of soybean, peanut, rapeseed, and corn.
10. The method of claim 1 wherein the pesticide in the pesticide residue is selected from the group consisting of 131: propoxur, dichlorvos, metocloprid, chlorfenvinphos, phosmet, phorate, terbufos, alpha-hexahexa, gamma-hexa, beta-hexa, ethion, delta-hexa, diazinon, tefluthrin, phosphamidon, methyl parathion, methyl chlorpyrifos, heptachloro, propargite, pyraclofos, fenitrothion, malathion, aldrin, fenthion, chlorpyrifos, disulfoxide, parathion, trichlorfon, isocrotophos, chlorfenphos, chlorfenapyr, endosulfan, thion, methidathion, o, p '-DDE, dieldrin, miticide, profenofos, p' -DDE, o, p '-DDD, isodifen, chlorfenapyr, o, p' -DDT, p '-DDD, p' -DDT, furethrin, methoprene, aldicarb, Spiromesifen, bifenthrin, fenpropathrin, cyhalothrin, mirex, fluthrin, permethrin, pyridaben, cyfluthrin, cypermethrin, fenvalerate, etofenvalerate, cyfluthrin, deltamethrin, acetamiprid, aldicarb sulfone, aldicarb sulfoxide, benalathion-, buprofezin, thionophos, carbaryl, carbofuran, 3-hydroxycarbcarb, chlorantraniliprole, clothianidin, cyantraniliprole, diflubenzuron, dimethoate, disulfoton sulfone, emamectin benzoate, fenamiphos, etoxazole, fenamiphos sulfone, fenamiphos sulfoxide, fenpyroxim, fenpyroxynil, fipronil sulfoxide, disulfoton, fipronil sulfone, flonicamid, flufenide, phoxim, fosthiazate, hexythiazox, imidacloprid, pyraflufenpyr, flufenpyr, fipronil sulfoxide, phoxim, fenpyr, fenpyrad, fenpyr, fenpyrad, fenpyr, fenpyrad, fenpyr, fenthion, fenpyrad, fenpyr, fenthion, fenpyr, indoxacarb, isoxathion, methomyl, monocrotophos, pymetrozine/pyrazinone, spinosad, thiamethoxam, triazophos, methiocarb, methamidophos, methoxyfenozide, nitenpyram, omethoate, phorate sulfoxide, pirimicarb, pirimiphos-methyl, pyriproxyfen, rotenone, spinetoram, spirotetramat, tebufenozide, tebufenpyrad, thiacloprid, triazophos, trichlorfon, chlorbenzuron, sulphoxide phosphorus-, lufenuron, chlorfluazuron, systemic phos and spirodiclofen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111155218.0A CN113945655A (en) | 2021-09-29 | 2021-09-29 | Method for detecting pesticide residue in cereal grains and oil products thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111155218.0A CN113945655A (en) | 2021-09-29 | 2021-09-29 | Method for detecting pesticide residue in cereal grains and oil products thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113945655A true CN113945655A (en) | 2022-01-18 |
Family
ID=79329860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111155218.0A Pending CN113945655A (en) | 2021-09-29 | 2021-09-29 | Method for detecting pesticide residue in cereal grains and oil products thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113945655A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104502504A (en) * | 2014-12-30 | 2015-04-08 | 郭庆龙 | Method for measuring residual amount of chlorantraniliprole in vegetables and fruits |
| CN104535692A (en) * | 2015-01-19 | 2015-04-22 | 山东出入境检验检疫局检验检疫技术中心 | LC-MS/MS (liquid chromatography-mass spectrometry/mass spectrometry) determination method of residual amount of tetrachlorantraniliprole in fruits and vegetables |
| CN108896694A (en) * | 2018-07-05 | 2018-11-27 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of remaining LC-QToF-MS Screening analysis method of pesticide in animal food |
| CN112014482A (en) * | 2019-05-29 | 2020-12-01 | 中国农业科学院农产品加工研究所 | Method for detecting herbicide residue in cereal grains and products thereof |
| CN112034053A (en) * | 2019-06-03 | 2020-12-04 | 中国农业科学院农产品加工研究所 | Method for detecting pesticide residues in traditional Chinese medicinal materials |
| CN112834647A (en) * | 2020-12-31 | 2021-05-25 | 中国检验检疫科学研究院 | Method for determining 297 pesticide residues by combining pretreatment technology of high-oil complex matrix sample with GC-MSMS (gas chromatography-metal-semiconductor mass spectrometry) |
-
2021
- 2021-09-29 CN CN202111155218.0A patent/CN113945655A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104502504A (en) * | 2014-12-30 | 2015-04-08 | 郭庆龙 | Method for measuring residual amount of chlorantraniliprole in vegetables and fruits |
| CN104535692A (en) * | 2015-01-19 | 2015-04-22 | 山东出入境检验检疫局检验检疫技术中心 | LC-MS/MS (liquid chromatography-mass spectrometry/mass spectrometry) determination method of residual amount of tetrachlorantraniliprole in fruits and vegetables |
| CN108896694A (en) * | 2018-07-05 | 2018-11-27 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of remaining LC-QToF-MS Screening analysis method of pesticide in animal food |
| CN112014482A (en) * | 2019-05-29 | 2020-12-01 | 中国农业科学院农产品加工研究所 | Method for detecting herbicide residue in cereal grains and products thereof |
| CN112034053A (en) * | 2019-06-03 | 2020-12-04 | 中国农业科学院农产品加工研究所 | Method for detecting pesticide residues in traditional Chinese medicinal materials |
| CN112834647A (en) * | 2020-12-31 | 2021-05-25 | 中国检验检疫科学研究院 | Method for determining 297 pesticide residues by combining pretreatment technology of high-oil complex matrix sample with GC-MSMS (gas chromatography-metal-semiconductor mass spectrometry) |
Non-Patent Citations (7)
| Title |
|---|
| 李建勋等: "QuEChEＲS-超高效液相色谱-飞行时间 质谱法快速 筛查蔬菜中 154 种农药残留", 食品发酵工业, vol. 45, no. 19, pages 239 - 248 * |
| 林玉婵;陈孟君;杨钦沾;符靖雯;吴燕梅;黄子敬;: "气相色谱-串联质谱法测定黄秋葵中107种农药残留量", 理化检验(化学分册), no. 09 * |
| 范广宇等: "气相色谱 - 串联质谱法同时测定花生中 97 种农药", 粮食与油脂, vol. 32, no. 6, pages 71 - 73 * |
| 蒋治国;王博超;殷雪琰;堵燕钰;罗漪涟;: "在线凝胶渗透色谱/气相色谱-串联质谱法测定蔬菜中49种农药残留组分", 安徽农学通报, no. 22 * |
| 邵丽等: "QuEChERS-三重四极杆液相色谱质谱联用法 快速筛查花生中 52 种农药残留", 食品安全质量检测学报, vol. 12, no. 15, pages 6078 - 6079 * |
| 韩梅;侯雪;邱世婷;焦颖;: "QuEChERS-超高效液相色谱-四极杆/静电场轨道阱高分辨质谱测定蔬菜中61种农药残留", 农药, no. 10 * |
| 黄玉宾;郭琳琳;刘峰;: "超高效液相色谱-串联三重四极杆质谱法快速测定蔬菜和水果中8种氨基甲酸酯类农药残留", 河北农业科学, no. 02 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cazorla-Reyes et al. | Single solid phase extraction method for the simultaneous analysis of polar and non-polar pesticides in urine samples by gas chromatography and ultra high pressure liquid chromatography coupled to tandem mass spectrometry | |
| CN102735784B (en) | Method for simultaneously determining one hundred pesticide residuals in traditional Chinese medicine through ultrahigh performance liquid chromatography-tandem quadrupole mass spectrum | |
| CN111630391A (en) | Triple quadrupole mass spectrometer for detecting MRM parent-child ion pairs of pesticide residues | |
| CN107478737B (en) | Method for detecting residual quantity of 80 pesticides in white spirit | |
| Walorczyk et al. | Development and validation of a multi-residue method for the determination of pesticides in honeybees using acetonitrile-based extraction and gas chromatography–tandem quadrupole mass spectrometry | |
| Balinova et al. | Solid-phase extraction on sorbents of different retention mechanisms followed by determination by gas chromatography–mass spectrometric and gas chromatography–electron capture detection of pesticide residues in crops | |
| CN112730693B (en) | Method for determining pesticide residue in feed by liquid phase-tandem mass spectrometry technology | |
| De Gerónimo et al. | A simple and rapid analytical methodology based on liquid chromatography-tandem mass spectrometry for monitoring pesticide residues in soils from Argentina | |
| Li et al. | Residue analysis of tetraniliprole in rice and related environmental samples by HPLC/MS | |
| CN113009057B (en) | Method for detecting neonicotinoid insecticides and metabolites in urine by solid phase extraction-ultra-high performance liquid chromatography-tandem mass spectrometry | |
| CN112881544B (en) | Method for rapidly determining various pesticide residues in ecological textile based on liquid chromatography-triple quaternary lever-tandem mass spectrometry technology | |
| Zhang et al. | Disposable pipette extraction (DPX) coupled with liquid chromatography–tandem mass spectrometry for the simultaneous determination of pesticide residues in wine samples | |
| CN113945655A (en) | Method for detecting pesticide residue in cereal grains and oil products thereof | |
| CN109298111A (en) | In fruits and vegetables a variety of agricultures it is residual and meanwhile detection method | |
| CN112858542A (en) | Liquid chromatography-mass spectrometry method for determining atrazine, imidacloprid and metabolites thereof in leaves | |
| CN111855830A (en) | Method for detecting strawberry pesticide residues based on color-quality combination technology | |
| Zhang et al. | Development of a PRiME cleanup procedure for the purification of avermectins in grass carps and liquid chromatography-tandem mass spectrometry analysis | |
| Liu et al. | Determination of aminoglycoside fungicide Validamycin A in rice plant by Quick, Easy, Cheap, Effective, Rugged, and Safe approach using ultra high performance liquid chromatography-electrospray ionization-tandem mass spectrometry | |
| CN114236009B (en) | Screening method for recessive prohibited chemicals added in pesticide preparation | |
| CN115372493A (en) | Method for detecting 24 pesticide residues in traditional Chinese medicine and application | |
| Wang et al. | Degradation properties and identification of metabolites of 6-Cl-PMNI in soil and water | |
| CN113607861A (en) | Analysis method for detecting 48 pesticide residues in vegetables through liquid chromatography tandem mass spectrometry by combining magnetic stirring with sol-gel | |
| CN111474278B (en) | Method and kit for detecting metabolites of macrolide compounds | |
| Zhu et al. | Screening of multiclass pesticide residues in maca and Moringa oleifera by a modified QuEChERS sample preparation procedure and UPLC-ESI-MS/MS analysis | |
| CN111965276A (en) | Method for detecting residual quantity of spinosad A, spinosad D, clothianidin and thiamethoxam in cucurbita pepo |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |