CN111983063A - Method for measuring various pesticide residues in sea buckthorn products by gas chromatography-tandem mass spectrometry - Google Patents
Method for measuring various pesticide residues in sea buckthorn products by gas chromatography-tandem mass spectrometry Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 17
- 238000004885 tandem mass spectrometry Methods 0.000 title claims abstract description 16
- 240000000950 Hippophae rhamnoides Species 0.000 title 1
- 241000229143 Hippophae Species 0.000 claims abstract description 42
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000000575 pesticide Substances 0.000 claims abstract description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
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- 235000011083 sodium citrates Nutrition 0.000 claims abstract description 8
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 6
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- 239000012086 standard solution Substances 0.000 claims description 14
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- 239000000126 substance Substances 0.000 claims description 13
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Classifications
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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
-
- 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
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7206—Mass spectrometers interfaced to gas chromatograph
-
- 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
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
Abstract
The invention relates to the technical field of pesticide residue determination, and discloses a method for determining various pesticide residues in a sea buckthorn product by gas chromatography-tandem mass spectrometry. The method adopts gas chromatography-tandem mass spectrometry (GC-MS/MS) to simultaneously determine various residual pesticides in the seabuckthorn product, and has the advantages of simple and quick operation, and good sensitivity, precision and recovery rate; the invention takes 1% acetic acid acetonitrile as the extracting solution, can make the sample in the slightly acidic environment, improve the recovery rate of the pesticide which is easy to degrade under the alkaline condition; the method takes 5g of magnesium sulfate, 1.5g of sodium chloride, 1g of sodium citrate and 0.5g of disodium citrate trihydrate as extraction solvents, further improves the extraction effect and the recovery rate, and improves the final detection sensitivity and precision.
Description
Technical Field
The invention relates to the technical field of pesticide residue determination, in particular to a method for determining various pesticide residues in a sea buckthorn product by gas chromatography-tandem mass spectrometry.
Background
The sea-buckthorn is a very unique resource in a plurality of plateau special biological resources in Qinghai province, has the ecological benefit of preventing water and soil loss, is drought-resistant and sand-resistant, can live on saline-alkali soil, and has high nutritional and medicinal effects. The main diseases of sea-buckthorn are xerosis, and common insect pests include spring looper, apple leaf roller moth, sea-buckthorn aphid, trunk-boring insect pest willow moth and the like. In order to prevent serious destructive diseases of sea buckthorn and prevent invasion of pathogenic bacteria, various pesticides are applied to plants. Because various pesticide preparations are widely applied in China, common pests and pathogenic bacteria in seabuckthorn crops have resistance and drug resistance to pesticides in different degrees, when various pesticides are used for preventing and treating the pests, the using dosage of the pesticides is increased for improving the preventing and treating effect, so that the residues of the pesticides on the seabuckthorn crops are caused.
The sea-buckthorn is a general name of plants and fruits thereof, the sea-buckthorn is a medicine-food homologous plant, roots, stems, leaves, flowers and fruits of the sea-buckthorn, particularly sea-buckthorn fruits contain rich nutrient substances and bioactive substances, and the sea-buckthorn fruit can be widely applied to many fields of national economy such as food, medicine, light industry, aerospace, farming and herding fish industry. The medicinal value, the food therapy value and the beauty value of the sea-buckthorn make the sea-buckthorn more and more popular with people in the field of food therapy medicines. In order to guarantee the rights and health of consumers, all seabuckthorn products must be detected by food pesticide residues.
Disclosure of Invention
Based on the problems, the invention provides a method for measuring various pesticide residues in a sea buckthorn product by using a gas chromatography-tandem mass spectrometry (GC-MS/MS).
In order to solve the technical problems, the invention provides a method for measuring various pesticide residues in a sea buckthorn product by gas chromatography-tandem mass spectrometry, which comprises the following steps:
s1: weighing 10g of sample to be detected, putting the sample to be detected in a 50mL centrifuge tube, adding 10mL of 1% acetic acid acetonitrile and ceramic homogenous proton, performing vortex oscillation for 3min, adding an extraction solvent, performing vortex oscillation for 1min, centrifuging at 0 ℃ and 10000r/min for 10min, adding 7mL of supernatant into a 15mL purification tube filled with a purifying agent, performing vortex oscillation for 1min, centrifuging at 0 ℃ and 10000r/min for 10min, absorbing 2mL of supernatant into a 10mL test tube, drying in a 40 ℃ water bath with nitrogen, adding 20 mu L of internal standard solution, performing constant volume with 1mL of acetone, and passing through a 0.2 mu m organic filter membrane to obtain an extract;
s2: subjecting the extract obtained in step S1 to GC-MS measurement under the following conditions:
gas chromatography conditions:
(1) a chromatographic column: back-blowing EPC by an Agilent HP-5MS ultranert column and a pre-column H2, wherein the Agilent HP-5MS ultranert column has the following dimensions: 15m × 0.25 μm × 250 μm, and the size of the pre-column H2 blowback EPC is: 14.83. mu. m.times.250. mu. m.times.0.25. mu.m;
(2) sample inlet temperature: 280 ℃;
(3) the temperature programming conditions were as follows:
(4) carrier gas: helium is selected as carrier gas, the purity of the carrier gas is more than or equal to 99.999 percent, and the flow rate is 1.2 ml/min;
(5) sample introduction amount: 1 μ L
(6) And (3) sample introduction mode: no split-flow sample introduction is carried out, and after 2min, a split-flow valve and a spacer purge valve are opened;
tandem mass spectrometry conditions:
(1) electron bombardment source: 70eV
(2) Ion source temperature: 300 deg.C
(3) MSD transmission line temperature: 280 deg.C
Further, the extraction solvent in step S1 is a mixture of 5g of magnesium sulfate, 1.5g of sodium chloride, 1g of sodium citrate, and 0.5g of disodium bicitrate trihydrate.
Further, the depurative in the step S1 was a mixture of 1200mg of magnesium sulfate, 120mg of PSA and 400mg of C18.
Further, the internal standard solution in step S1 is an epoxy heptachlor solution, and the preparation method of the epoxy heptachlor solution is as follows: 3.5mg of epoxy heptachloride is weighed into a 100mL volumetric flask and the volume is fixed to the scale with toluene.
Further, the types of pesticides detected, the retention time, the quantitative ion pair, the qualitative ion and the collision energy of the related chemicals and the internal standard compound of each pesticide are shown in table 1:
TABLE 1
Compared with the prior art, the invention has the beneficial effects that: the method adopts gas chromatography-tandem mass spectrometry (GC-MS/MS) to simultaneously determine various residual pesticides in the seabuckthorn product, and has the advantages of simple and quick operation, and good sensitivity, precision and recovery rate; the invention takes 1% acetic acid acetonitrile as the extracting solution, can make the sample in the slightly acidic environment, improve the recovery rate of the pesticide which is easy to degrade under the alkaline condition; the method takes 5g of magnesium sulfate, 1.5g of sodium chloride, 1g of sodium citrate and 0.5g of disodium citrate trihydrate as extraction solvents, further improves the extraction effect and the recovery rate, and improves the final detection sensitivity and precision.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Example 1:
the method for measuring various pesticide residues in the sea buckthorn product by using the gas chromatography-tandem mass spectrometry comprises the following steps:
s1: weighing 10g of sample to be detected in a 50mL centrifuge tube, adding 10mL of 1% acetonitrile acetate and ceramic homogenous proton, performing vortex oscillation for 3min, then adding an extraction solvent, wherein the extraction solvent is a mixture of 5g of magnesium sulfate, 1.5g of sodium chloride, 1g of sodium citrate and 0.5g of disodium bicitrate trihydrate, performing vortex oscillation for 1min, performing centrifugation at 0 ℃ and 10000r/min for 10min, then adding 7mL of supernatant into a 15mL purification tube filled with a purifying agent, wherein the purifying agent is a mixture of 1200mg of magnesium sulfate, 120mg of PSA and 400mg of C18, performing vortex oscillation for 1min, performing centrifugation at 0 ℃ and 10000r/min for 10min, absorbing 2mL of supernatant into a 10mL test tube, performing blow drying in a 40 ℃ water bath by using nitrogen, adding 20 mu L of internal standard solution, performing volume fixing by using 1mL of acetone, and passing through a 0.2 mu m organic filter membrane to obtain an extract; the internal standard solution in this example is an epoxy heptachlor solution, and the preparation method of the epoxy heptachlor solution is as follows: weighing 3.5mg of epoxy heptachlor in a 100mL volumetric flask, and metering the volume to the scale with toluene;
s2: subjecting the extract obtained in step S1 to GC-MS measurement under the following conditions:
gas chromatography conditions:
(1) a chromatographic column: back-blowing EPC by an Agilent HP-5MS ultranert column and a pre-column H2, wherein the Agilent HP-5MS ultranert column has the following dimensions: 15m × 0.25 μm × 250 μm, and the size of the pre-column H2 blowback EPC is: 14.83. mu. m.times.250. mu. m.times.0.25. mu.m;
(2) sample inlet temperature: 280 ℃;
(3) the temperature programming conditions were as follows:
(4) carrier gas: helium is selected as carrier gas, the purity of the carrier gas is more than or equal to 99.999 percent, and the flow rate is 1.2 ml/min;
(5) sample introduction amount: 1 μ L
(6) And (3) sample introduction mode: no split-flow sample introduction is carried out, and after 2min, a split-flow valve and a spacer purge valve are opened;
tandem mass spectrometry conditions:
(1) electron bombardment source: 70eV
(2) Ion source temperature: 300 deg.C
(3) MSD transmission line temperature: 280 deg.C
The types of pesticides tested, the retention time of the chemicals related to each pesticide and the internal standard compound, the quantitative ion pair, the qualitative ion and the collision energy are shown in table 1:
TABLE 1
Example 2:
the samples to be detected in the embodiment are sea buckthorn fruit juice, sea buckthorn fruit wine and sea buckthorn fruit vinegar, and the experimental samples are respectively collected from Qinghai Qinghua Bo-Ming biotechnology limited and Qinghai Kangpu bioengineering limited.
The experimental reagents used in this example are shown in table 2:
TABLE 2 Experimental reagent consumables, Specifications and manufacturers
The experimental apparatus used in this example is shown in table 3:
TABLE 3 Experimental instruments, models and manufacturers
The concentration of the pesticide and related chemical standards used in this example was 10 μ g/mL, as detailed in Table 4:
TABLE 4
The standard solution of this example was prepared as follows:
(1) mixing of standard solutions
Dividing the pesticide and the related chemicals into two groups according to the properties and the retention time of the pesticide and the related chemicals, wherein the concentration of the pesticide and the related chemicals is 10 mug/mL; putting 1mL of the mixed standard solution into a 10mL volumetric flask, fixing the volume to a scale with acetone, and storing in a refrigerator at-18 ℃ for later use, wherein the validity period is 1 month;
(2) preparing an internal standard solution: accurately weighing 3.5mg of epoxy heptachloride in a 100mL volumetric flask, and metering the volume to the scale with toluene;
(3) mixing standard working solutions
The mixed standard working solution of the pesticide, the related chemicals and the related chemicals is diluted into series of standard working solutions of 5ng/mL, 10ng/mL, 20ng/mL, 50ng/mL and 100ng/mL by acetone step by step, and the mixed standard working solution is kept in a refrigerator at the temperature of minus 18 ℃ away from light for standby;
(4) matrix mixed standard working solution
The pesticide and related chemicals matrix mixed standard working solution is prepared by respectively adding 40 μ L of internal standard solution and serial standard working solutions diluted step by step into 1.0mL of sample blank matrix extracting solution, mixing uniformly to prepare matrix mixed standard working solution, and using the matrix mixed standard working solution as it is.
The chromatographic conditions used in this example were as follows:
(1) a chromatographic column: agilent HP-5MS ultra nert column (15 m.times.0.25 μm.times.250 μm) and pre-column H2 blowback EPC (14.83 m.times.250 μm.times.0.25 μm);
(2) temperature at sample inlet
Sample inlet temperature: 280 ℃;
(3) temperature programmed condition
(4) Carrier gas
Helium is used as carrier gas, the purity is more than or equal to 99.999 percent, and the flow rate is as follows: 1.2 mL/min;
(5) sample introduction amount: 1 mu L of the solution;
(6) and (3) sample introduction mode: and (4) no split-flow sample introduction is carried out, and the split-flow valve and the spacer purge valve are opened after 2 min.
The mass spectrometry conditions used in this example were as follows:
electron bombardment source: 70 eV;
ion source temperature: 300 ℃;
MSD transmission line temperature: 280 ℃;
the types of pesticides detected, the retention times of the related chemicals and internal standard compounds of each pesticide, the quantitative ion pair, the qualitative ion and the collision energy were the same as the related parameters in table 1 in example 1 of this document.
The pretreatment method for the sea buckthorn juice, the sea buckthorn fruit wine and the sea buckthorn fruit vinegar in the embodiment comprises the following steps:
weighing 10g of uniformly mixed sample in a 50mL centrifuge tube, adding 10mL of 1% acetonitrile acetate and ceramic homogenous proton, carrying out vortex oscillation for 3min, adding 5g of magnesium sulfate, 1.5g of sodium chloride, 1g of sodium citrate and 0.5g of disodium bicitrate trihydrate, carrying out vortex oscillation for 1min, centrifuging at 0 ℃ and 10000r/min for 10min, then adding 7mL of supernatant into a 15mL purification tube filled with 1200mg of magnesium sulfate, 120mg of PSA and 400mg of C18, carrying out vortex oscillation for 1min, centrifuging at 0 ℃ and 10000r/min for 10min, accurately absorbing 2mL of supernatant into a 10mL test tube, blowing nitrogen in a 40 ℃ water bath to be nearly dry, accurately adding 20 mu L of internal standard solution, fixing the volume with 1mL of acetone, and passing through a 0.2 mu m organic filter membrane.
In the experimental process, acetonitrile, 1% acetonitrile acetate and acetone are respectively adopted to extract various pesticide residues in the sea buckthorn product, and the result shows that 1% acetonitrile acetate is used as an extracting solution, so that a sample can be in a slightly acidic environment, and the recovery rate of some pesticides which are easily degraded under an alkaline condition is improved, so that 1% acetonitrile acetate is used as an extracting solution in the embodiment; meanwhile, in the embodiment, the extraction effects of the formula of 5g of magnesium sulfate, 1.5g of sodium chloride, 1g of sodium citrate and 0.5g of disodium citrate trihydrate and the formula of 6g of magnesium sulfate, 1.5g of sodium acetate and 0.5g of disodium citrate trihydrate as extraction solvents are respectively considered, and experimental results show that some pesticides (such as cyfluthrin, dicofol, dimethoate and the like) with higher acid-base sensitivity in the first formula in the sea buckthorn fruit juice, the sea buckthorn fruit wine and the sea buckthorn fruit vinegar are better in extraction effect and higher in recovery rate, so the extraction formula is selected in the embodiment: 5g magnesium sulfate, 1.5g sodium chloride, 1g sodium citrate, 0.5g disodium citrate trihydrate; in the embodiment, two purification methods are also adopted to compare three matrix samples of the sea-buckthorn fruit juice, the sea-buckthorn fruit vinegar and the sea-buckthorn fruit wine with the standard concentration of 0.1mg/kg, and the first scheme is as follows: 600mg magnesium sulfate, 400mg PSA, 200mg GCB; scheme II: 1200mg magnesium sulfate, 120mg PSA, 400mg C18, three matrix samples that the experiment adopted all use sea buckthorn as raw materials, because C18 decontaminant can remove fat, lipoid, flavone and other non-polar impurities in the sea buckthorn, therefore C18 decontaminant has better purifying effect, three samples in the experiment are the matrix of lighter colour, it can not make the pesticide have better recovery rate to add GCB, can reduce the recovery rate of some pesticides on the contrary, therefore purify and need not add GCB, PSA decontaminant has extremely strong purification ability, can purify the polar material in the sample matrix, because PSA has extremely strong polar adsorption, too much use also can cause the absorption to some pesticides, so select the purification scheme: 1200mg magnesium sulfate, 120mg PSA, 400mgC 18.
In this example, the blank sample matrix extract was used as a diluent for a standard solution to prepare matrix standard mixed working solutions with concentrations of 5ng/mL, 10ng/mL, 20ng/mL, 50ng/mL, and 100 ng/mL. The matrix standard solution and the sample solution are detected under the same instrument condition, so that the influence of matrix effect can be reduced. The corresponding values and contents of the 75 pesticides in the matrix are all in a good linear relationship, and the details are shown in table 5:
table 575 kinds of linear ranges, linear equations and correlation coefficients of pesticide residues
The average recovery and relative standard deviation of the 75 matrix samples of this example are shown in table 6:
TABLE 675 mean recoveries and relative standard deviations of matrix samples (n ═ 6)
The above is an embodiment of the present invention. The embodiments and specific parameters in the embodiments are only for the purpose of clearly illustrating the process of verifying the invention and are not intended to limit the scope of the invention, which is defined by the claims, and all the equivalent structural changes made by applying the content of the specification of the invention should be covered by the scope of the invention.
Claims (5)
1. The method for measuring various pesticide residues in the sea buckthorn product by using the gas chromatography-tandem mass spectrometry is characterized by comprising the following steps of:
s1: weighing 10g of sample to be detected, putting the sample to be detected in a 50mL centrifuge tube, adding 10mL of 1% acetic acid acetonitrile and ceramic homogenous proton, performing vortex oscillation for 3min, adding an extraction solvent, performing vortex oscillation for 1min, centrifuging at 0 ℃ and 10000r/min for 10min, adding 7mL of supernatant into a 15mL purification tube filled with a purifying agent, performing vortex oscillation for 1min, centrifuging at 0 ℃ and 10000r/min for 10min, absorbing 2mL of supernatant into a 10mL test tube, drying in a 40 ℃ water bath with nitrogen, adding 20 mu L of internal standard solution, performing constant volume with 1mL of acetone, and passing through a 0.2 mu m organic filter membrane to obtain an extract;
s2: subjecting the extract obtained in step S1 to GC-MS measurement under the following conditions:
gas chromatography conditions:
(1) a chromatographic column: back-blowing EPC by an Agilent HP-5MS ultranert column and a pre-column H2, wherein the Agilent HP-5MS ultranert column has the following dimensions: 15m × 0.25 μm × 250 μm, and the size of the pre-column H2 blowback EPC is: 14.83. mu. m.times.250. mu. m.times.0.25. mu.m;
(2) sample inlet temperature: 280 ℃;
(3) the temperature programming conditions were as follows:
(4) carrier gas: helium is selected as carrier gas, the purity of the carrier gas is more than or equal to 99.999 percent, and the flow rate is 1.2 ml/min;
(5) sample introduction amount: 1 μ L
(6) And (3) sample introduction mode: no split-flow sample introduction is carried out, and after 2min, a split-flow valve and a spacer purge valve are opened;
tandem mass spectrometry conditions:
(1) electron bombardment source: 70eV
(2) Ion source temperature: 300 deg.C
(3) MSD transmission line temperature: 280 ℃.
2. The method for determining various pesticide residues in a seabuckthorn product according to claim 1, wherein the extraction solvent in step S1 is a mixture of 5g magnesium sulfate, 1.5g sodium chloride, 1g sodium citrate and 0.5g disodium citrate trihydrate.
3. The method for determining various pesticide residues in a seabuckthorn product by gas chromatography-tandem mass spectrometry as claimed in claim 1, wherein the scavenger in step S1 is a mixture of 1200mg magnesium sulfate, 120mg PSA and 400mg C18.
4. The method for determining various pesticide residues in a seabuckthorn product by gas chromatography-tandem mass spectrometry as claimed in claim 1, wherein the internal standard solution in the step S1 is an epoxy heptachlor solution, and the preparation method of the epoxy heptachlor solution is as follows: 3.5mg of epoxy heptachloride is weighed into a 100mL volumetric flask and the volume is fixed to the scale with toluene.
5. The method for determining various pesticide residues in a seabuckthorn product by gas chromatography-tandem mass spectrometry as claimed in claim 1, wherein the retention time, the quantitative ion pair, the qualitative ion and the collision energy of the detected pesticide species, the related chemicals of each pesticide and the internal standard compound are shown in table 1:
TABLE 1
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