CN112014482A - Method for detecting herbicide residue in cereal grains and products thereof - Google Patents
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Abstract
The utility model provides a method for detecting herbicide residue in cereals and products thereof, relating to the field of pesticide detection, which comprises the steps of mixing a cereal oil substrate, water and acetonitrile formate, and carrying out first extraction to obtain a first extract; mixing the first extract with anhydrous magnesium sulfate and sodium chloride, and performing second extraction to obtain a second extract; centrifuging the second extract, taking supernatant as matrix extracting solution, mixing the matrix extracting solution with a purifying agent, purifying, and taking supernatant obtained after centrifuging the purified material as to-be-detected liquid; and (4) determining the solution to be detected by using ultra-high performance liquid chromatography-tandem mass spectrometry. The method can realize the simultaneous detection of 62 herbicides and has higher accuracy and repeatability.
Description
Technical Field
The disclosure relates to the field of pesticide detection, in particular to a method for detecting herbicide residues in cereals and products thereof.
Background
As the application of herbicides becomes more and more widespread, the problem of herbicide residue is also receiving increasing attention. Although the herbicide can effectively reduce the loss of crops, the negative effects brought by the herbicide are not small, and the environmental pollution and food residue caused by the herbicide directly threaten the health of human beings.
The problem of herbicide residue in cereals and processed products thereof is always present and needs to be solved. At present, the conventional pretreatment technology for detecting the multiple residues of the herbicide in the grains and the products thereof is mainly solid-phase extraction, and the detection mode is mainly to use liquid chromatography and liquid chromatography tandem mass spectrometry for detection. Because the substrates of the cereal grain and the processed products thereof are complex, and the conventional herbicide residue pretreatment technology has the defects of long solid phase extraction time consumption, low economy and environmental protection, low accuracy and poor repeatability, the development and establishment of the herbicide residue detection technology and the related pretreatment technology in the cereal grain and the processed products thereof are necessary.
Disclosure of Invention
The purpose of the disclosure is to provide a method for detecting herbicide residues in cereals and products thereof, the detection method can simultaneously detect 62 kinds of herbicide residues in cereals and products thereof, and has the advantages of high recovery rate, simple operation, economy and environmental protection.
To achieve the above objects, the present disclosure provides a method for detecting herbicide residue in cereal grains and products thereof, comprising the steps of:
s1, mixing the grain and oil substrate, water and the aqueous solution of acetonitrile formate according to the weight ratio of 1: 1: (1-3) mixing and performing a first extraction in the weight ratio to obtain a first extract; the concentration of the aqueous acetonitrile formate solution is 0.5-1.5% by volume;
s2, mixing the first extract with anhydrous magnesium sulfate and sodium chloride, and performing second extraction to obtain a second extract; the dosage of the anhydrous magnesium sulfate and the sodium chloride is 0.5-1g and 0.1-0.4g respectively relative to 1g of grain and oil substrate;
s3, centrifuging the second extract, taking supernatant as matrix extracting solution, mixing the matrix extracting solution with a purifying agent, purifying, and taking supernatant obtained after centrifuging the purified material as to-be-detected liquid; the purifying agent comprises anhydrous magnesium sulfate and nano zinc oxide, and relative to 1mL of the matrix extracting solution, the dosage of the anhydrous magnesium sulfate is 80-200mg, and the dosage of the nano zinc oxide is 20-100 mg;
and S4, measuring the solution to be measured by using ultra performance liquid chromatography-tandem mass spectrometry.
Preferably, in step S1, the grain and oil matrix, water and aqueous acetonitrile formate solution are mixed in a ratio of 1: 1: (1.75-2.25) and performing a first extraction; the concentration of the aqueous acetonitrile formate solution is 0.8-1.2% by volume;
in the step S2, the consumption of the anhydrous magnesium sulfate and the sodium chloride is 0.7-0.9g and 0.15-0.35g respectively relative to 1g of the grain and oil substrate;
in step S3, the amount of anhydrous magnesium sulfate is 130-160mg and the amount of nano zinc oxide is 40-60mg, relative to 1mL of the matrix extracting solution;
preferably, in step S1, the first extraction includes 20-100 seconds of vortexing; in step S2, the second extraction comprises vortexing in an ice-water bath for 20-100 seconds.
Preferably, the second extract is centrifuged at 4000-6000rpm for 3-10 minutes.
Preferably, the rotation speed of centrifugation of the material after purification treatment is 10000-.
Preferably, before the liquid to be detected is detected by ultra performance liquid chromatography-tandem mass spectrometry, the liquid to be detected is filtered by a filter membrane, and the pore diameter of the filter membrane is 0.22 micron or less.
Preferably, the grain and oil substrate is selected from at least one of soybean, peanut, rapeseed, corn, and sunflower seed.
Preferably, the herbicide in the herbicide residue is selected from the group consisting of 62 of: metsulfuron-methyl, rimsulfuron, mesosulfuron, bromoxynil octanoate, triasulfuron, imazethapyr, ethametsulfuron, imazaquin, diflufenican, pyraflufen, sulcotrione, sethoxydim, bromoxynil, propisochlor, s-metolachlor, chlorimuron-ethyl, propaquizasulfuron, alachlor, metsulfuron-methyl, thifensulfuron-methyl, dimethenamid-ethyl, chlorsulfuron, acetochlor, halosulfuron-methyl, clomazone, clethodim, pinoxaden, fomesafen, fenoxaprop-p-ethyl, molinate, butachlor, propachlor, propyzamide, bentazon, terbufos, fluxasulfuron-methyl, propafenone, clodinafop, bentazon, triclopyr, pyriftalid, triclopyr, pyraflufen-4 (sodium) clofenacet, pyributicarb, pyrafluazifop-ethyl, pyrafluazifop-4 (sodium) chloride, Metribuzin, 2, 4-D, chlortoluron, simazine, imazapic, isoproturon, pendimethalin, fluazifop-p-butyl, dicamba, haloxyfop-p-butyl, cyanazine and quizalofop-p-ethyl.
Preferably, the particle size of the nano zinc oxide is 20-40 nm.
By the method, the interference effect of other possible target compounds in the grains and the processed products thereof on the matrixes can be greatly reduced, so that the herbicide is effectively analyzed, the simultaneous detection of the herbicide in 62 in the grains and the processed products thereof 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
FIG. 1 is a diagram of average recovery rate (bar chart) and proportion (triangle) of qualified pesticide in recovery rate;
FIG. 2 is a matrix effect diagram of a grain and oil matrix.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. 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 herbicide residue in cereal grains and products thereof, comprising the steps of:
s1, mixing the grain and oil substrate, water and the aqueous solution of acetonitrile formate according to the weight ratio of 1: 1: (1-3) mixing and performing a first extraction in the weight ratio to obtain a first extract; the concentration of the aqueous acetonitrile formate solution is 0.5-1.5% by volume;
s2, mixing the first extract with anhydrous magnesium sulfate and sodium chloride, and performing second extraction to obtain a second extract; the dosage of the anhydrous magnesium sulfate and the sodium chloride is 0.5-1g and 0.1-0.4g respectively relative to 1g of grain and oil substrate;
s3, centrifuging the second extract, taking supernatant as matrix extracting solution, mixing the matrix extracting solution with a purifying agent, purifying, and taking supernatant obtained after centrifuging the purified material as to-be-detected liquid; the purifying agent comprises anhydrous magnesium sulfate and nano zinc oxide, and relative to 1mL of the matrix extracting solution, the dosage of the anhydrous magnesium sulfate is 80-200mg, and the dosage of the nano zinc oxide is 20-100 mg;
and S4, measuring the solution to be measured by using ultra performance liquid chromatography-tandem mass spectrometry.
Preferably, in step S1, the grain and oil substrate, water and the aqueous solution of acetonitrile formate are mixed in a ratio of 1: 1: (1.75-2.25) and performing a first extraction; the concentration of the aqueous acetonitrile formate solution is 0.8-1.2% by volume; more preferred grain and oil substrates, water and aqueous acetonitrile formate solutions are used in a ratio of 1: 1: (1.8-2.1), the concentration of the formic acid acetonitrile water solution is 0.9-1.1 volume percent; further preferably, the ratio of the grain and oil substrate to the water and acetonitrile formate solution is 1: 1: 2, the concentration of the aqueous acetonitrile formate solution was 1 vol%
Wherein, preferably, in the step S2, the consumption of the anhydrous magnesium sulfate and the sodium chloride is 0.7-0.9g and 0.15-0.35g respectively relative to 1g of the grain and oil substrate; more preferably 0.75-0.85 and 0.18-0.25; further preferably 0.8g and 0.2 g.
Wherein, preferably, in step S3, the amount of anhydrous magnesium sulfate is 130-160mg and the amount of nano zinc oxide is 40-60mg, relative to 1mL of the matrix extracting solution; more preferably 140-155mg and 45-55 mg; further preferably 150mg and 50 mg.
Preferably, in step S1, the first extraction includes 20-100 seconds of vortexing; in step S2, the second extraction comprises vortexing in an ice-water bath for 20-100 seconds.
Preferably, the second extract is centrifuged at 4000-6000rpm for 3-10 minutes.
Preferably, the rotation speed of centrifugation of the material after purification treatment is 10000-.
Preferably, before the liquid to be detected is detected by ultra performance liquid chromatography-tandem mass spectrometry, the liquid to be detected is filtered by a filter membrane, and the pore diameter of the filter membrane is 0.22 micron or less.
Preferably, the grain and oil substrate is selected from at least one of soybean, peanut, rapeseed, corn, and sunflower seed.
Preferably, the herbicide in the herbicide residue is selected from the group consisting of 62 of: metsulfuron-methyl, rimsulfuron, mesosulfuron, bromoxynil octanoate, triasulfuron, imazethapyr, ethametsulfuron, imazaquin, diflufenican, pyraflufen, sulcotrione, sethoxydim, bromoxynil, propisochlor, s-metolachlor, chlorimuron-ethyl, propaquizasulfuron, alachlor, metsulfuron-methyl, thifensulfuron-methyl, dimethenamid-ethyl, chlorsulfuron, acetochlor, halosulfuron-methyl, clomazone, clethodim, pinoxaden, fomesafen, fenoxaprop-p-ethyl, molinate, butachlor, propachlor, propyzamide, bentazon, terbufos, fluxasulfuron-methyl, propafenone, clodinafop, bentazon, triclopyr, pyriftalid, triclopyr, pyraflufen-4 (sodium) clofenacet, pyributicarb, pyrafluazifop-ethyl, pyrafluazifop-4 (sodium) chloride, Metribuzin, 2, 4-D, chlortoluron, simazine, imazapic, isoproturon, pendimethalin, fluazifop-p-butyl, dicamba, haloxyfop-p-butyl, cyanazine and quizalofop-p-ethyl.
Table 1: mass Spectrometry parameters for 62 herbicides
Preferably, the particle size of the nano zinc oxide is 20-40 nm.
The ultra-high performance liquid chromatography-tandem mass spectrometry detection method comprises the optimization of a mass spectrometry method and the optimization of a liquid phase method. The mass spectrometry method is partially detected in a dynamic multiple reaction monitoring (dMRM) mode, and is characterized by not less than 2 groups of characteristic ion pairs. The liquid phase method optimization mainly optimizes the gradient elution ratio of the mobile phase so as to obtain a TIC (time induced degradation) diagram with better pesticide dispersibility.
The present invention will be described in further detail below with reference to examples. In the following examples, the grain and oil substrate was a grain and oil substrate containing herbicides, specifically, a 1600 μ g/kg standard solution was prepared by dissolving 62 herbicides in acetonitrile, respectively, to obtain a herbicide solution, and the herbicide standard solution was mixed with a grain and oil substrate (soybean) without herbicides to obtain a soybean grain and oil substrate containing 62 herbicides at the same time (the final concentration of each pesticide was 1,5,10,50,100,200,500,800 μ g/kg) as the grain and oil substrate to be tested, to test the method of the present disclosure.
Experimental apparatus and reagents in the examples
UPLC-QQQ (ultra high performance liquid chromatography: 1200Infinity Series, Agilent technologies, Inc.; Triple quadrupole mass spectrometry: 6495Triple Quad LC/MS, Agilent technologies, Inc.); HPLC grade acetonitrile, methanol, acetic acid, mass spec grade formic acid were purchased from siemer feishel technologies (china) ltd; ZnO was purchased from Shanghai Aladdin Biotechnology GmbH; anhydrous magnesium sulfate, sodium chloride were purchased from: chemical agents of the national drug group, ltd.
The instrument conditions included: dynamic multiple reaction monitoring mode, capillary voltage: positive ion mode: 3.5KV, negative ion mode: 3.0KV, ion source temperature: the temperature of desolventizing gas is 325 ℃ at 150 ℃; the flow rate of the desolventizing agent is 900L/h; conical hole back blowing airflow 660L/h
Chromatographic conditions are as follows: eclipse Plus C18, 2.1x100mm, 1.8um
Mobile phase: a: 0.1% formic acid water
B: acetonitrile
Elution conditions (Table 2)
Example 1
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.
Comparative example 1
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 50mg of PSA, 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 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 50mg of GCB, 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 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 50mg Sep, 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 3 by using ultra performance liquid chromatography-tandem mass spectrometry; the grain and oil substrate without the herbicide is extracted and purified by the extraction and purification methods in the example 1 and the comparative examples 1-3 respectively to obtain extraction and purification liquid, and the extraction and purification liquid is mixed with the herbicide mixed liquid to be used as a substrate standard sample.
Calculating the recovery rate and the RSD according to the test results, and the calculation method of the recovery rate and the RSD comprises
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 62 herbicides is 70-120% and the ratio of the herbicides with RSD less than 20%, the results are shown in figure 1, it can be seen that when the purifying agent selects 150mg anhydrous magnesium sulfate and 5mg nano zinc oxide, the recovery rate and RSD are higher than the three groups of comparative examples, namely 150mg anhydrous magnesium sulfate, 50mg PSA, 150mg anhydrous magnesium sulfate, 50mg GCB, 150mg anhydrous magnesium sulfate and 50mg Sep, the purifying effect of 5mg nano zinc oxide is higher than that of 50mg PSA, 50mg GCB and 50mg Sep, namely the purifying effect of nano zinc oxide is obviously higher than that of PSA, GCB and Sep.
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 62 herbicide substrates in the soybean oil and grain substrate 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 above embodiments are merely illustrative of the preferred embodiments of the present disclosure, and do not limit the scope of the present disclosure, and various modifications and improvements can be made to the technical solutions of the present disclosure without departing from the design spirit of the present disclosure.
Claims (9)
1. A method for detecting herbicide residues in cereal grains and products thereof, the method comprising the steps of:
s1, mixing the grain and oil substrate, water and the aqueous solution of acetonitrile formate according to the weight ratio of 1: 1: (1-3) mixing and performing a first extraction in the weight ratio to obtain a first extract; the concentration of the aqueous acetonitrile formate solution is 0.5-1.5% by volume;
s2, mixing the first extract with anhydrous magnesium sulfate and sodium chloride, and performing second extraction to obtain a second extract; the dosage of the anhydrous magnesium sulfate and the sodium chloride is 0.5-1g and 0.1-0.4g respectively relative to 1g of grain and oil substrate;
s3, centrifuging the second extract, taking supernatant as matrix extracting solution, mixing the matrix extracting solution with a purifying agent, purifying, and taking supernatant obtained after centrifuging the purified material as to-be-detected liquid; the purifying agent comprises anhydrous magnesium sulfate and nano zinc oxide, and relative to 1mL of the matrix extracting solution, the dosage of the anhydrous magnesium sulfate is 80-200mg, and the dosage of the nano zinc oxide is 20-100 mg;
and S4, measuring the solution to be measured by using ultra performance liquid chromatography-tandem mass spectrometry.
2. The method of claim 1, wherein in step S1, the grain and oil substrate, the water, and the aqueous acetonitrile formate solution are mixed in a ratio of 1: 1: (1.75-2.25) and performing a first extraction; the concentration of the aqueous acetonitrile formate solution is 0.8-1.2% by volume;
in the step S2, the consumption of the anhydrous magnesium sulfate and the sodium chloride is 0.7-0.9g and 0.15-0.35g respectively relative to 1g of the grain and oil substrate;
in step S3, the amount of anhydrous magnesium sulfate is 130-160mg and the amount of nano zinc oxide is 40-60mg, relative to 1mL of the matrix extracting solution.
3. The method of claim 1 or 2,
in step S1, the first extraction includes 20-100 seconds of vortexing;
in step S2, the second extraction comprises vortexing in an ice-water bath for 20-100 seconds.
4. The method as claimed in claim 1 or 2, wherein the second extract is centrifuged at 4000-6000rpm for 3-10 minutes.
5. The method as claimed in claim 1 or 2, wherein the rotation speed of centrifugation of the purified material is 10000-15000rpm for 0.5-2 minutes.
6. The method of claim 1 or 2, wherein the method further comprises: and filtering the solution to be detected by using a filter membrane before detecting the solution to be detected by using ultra performance liquid chromatography-tandem mass spectrometry, wherein the pore diameter of the filter membrane is 0.22 micron or less.
7. The method of claim 1 or 2, wherein the grain oil substrate is selected from at least one of soy, peanut, canola, corn, and sunflower.
8. The method of claim 1 or 2, wherein the herbicide in the herbicide residue is selected from the group consisting of 62 of: metsulfuron-methyl, rimsulfuron, mesosulfuron, bromoxynil octanoate, triasulfuron, imazethapyr, ethametsulfuron, imazaquin, diflufenican, pyraflufen, sulcotrione, sethoxydim, bromoxynil, propisochlor, s-metolachlor, chlorimuron-ethyl, propaquizasulfuron, alachlor, metsulfuron-methyl, thifensulfuron-methyl, dimethenamid-ethyl, chlorsulfuron, acetochlor, halosulfuron-methyl, clomazone, clethodim, pinoxaden, fomesafen, fenoxaprop-p-ethyl, molinate, butachlor, propachlor, propyzamide, bentazon, terbufos, fluxasulfuron-methyl, propafenone, clodinafop, bentazon, triclopyr, pyriftalid, triclopyr, pyraflufen-4 (sodium) clofenacet, pyributicarb, pyrafluazifop-ethyl, pyrafluazifop-4 (sodium) chloride, Metribuzin, 2, 4-D, chlortoluron, simazine, imazapic, isoproturon, pendimethalin, fluazifop-p-butyl, dicamba, haloxyfop-p-butyl, cyanazine and quizalofop-p-ethyl.
9. The method according to claim 1 or 2, wherein the nano zinc oxide has a particle size of 20-40 nm.
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| CN113945655A (en) * | 2021-09-29 | 2022-01-18 | 中国农业科学院农产品加工研究所 | Method for detecting pesticide residue in cereal grains and oil products thereof |
| CN113945656A (en) * | 2021-09-29 | 2022-01-18 | 中国农业科学院农产品加工研究所 | Method for detecting pesticide and metabolite residues thereof in traditional Chinese medicinal materials |
| CN113820429A (en) * | 2021-10-15 | 2021-12-21 | 陕西西凤酒股份有限公司 | Method for simultaneously detecting tribenuron-methyl and 2-methyl-4-chloro by adopting liquid chromatograph-mass spectrometer |
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