CN113804794A - Method for detecting pesticide residues in grease-rich sample based on composite SPE - Google Patents
Method for detecting pesticide residues in grease-rich sample based on composite SPE Download PDFInfo
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Abstract
The invention discloses a method for detecting pesticide residues in a grease-rich sample based on composite SPE (solid phase extraction), which relates to the field of pesticide residue detection in a grease-containing sample, and comprises a PSA/C18 composite column, an edible blend oil sample, a pork sample, a milk sample and a soybean sample, wherein the method for detecting the pesticide residues in the grease-rich sample based on the composite SPE comprises the following steps; step 1: extracting a sample, and filtering a sample extracting solution through a PSA/C18 composite column, wherein PSA in the PSA/C18 composite column is silica gel bonded ethylenediamine-N-propyl microspheres which have weak anion exchange and normal phase retention effects and can be used for removing fatty acids (such as oleic acid, palmitic acid and linoleic acid), organic acids, partial pigments, metal ions, saccharide interferents and the like which influence detection in a food matrix, C18 is silica gel bonded octadecyl microspheres which retain nonpolar compounds through hydrophobic effect, and the oil and impurities in the food can be filtered by combining the two, so that the data deviation of pesticide residue detection is reduced, and the accuracy of the pesticide residue detection is improved.
Description
Technical Field
The invention relates to the field of pesticide residue detection in an oil-containing sample, in particular to a method for detecting pesticide residue in an oil-rich sample based on composite SPE.
Background
The development of agricultural industrialization makes the production of agricultural products depend on exogenous substances such as pesticides, antibiotics and hormones. The pesticide in agricultural products in China is used at a high level, and the unreasonable use of the substances can lead to the overproof pesticide residues in the agricultural products, influence the edible safety of consumers, cause the consumers to have diseases and abnormal development in serious cases, even directly cause poisoning and death, influence the trade of the agricultural products due to the overproof pesticide residues, and highly attach importance to the pesticide residue problem in various countries in the world, the increasingly strict limit standards are set for pesticide residues in various agricultural and sideline products, so that the export of Chinese agricultural products faces severe challenges, the rapid detection methods of the pesticide residues are various, one of the gas chromatography mass spectrometry is adopted as the gas chromatography mass spectrometry, the existing gas chromatography mass spectrometry can detect most of food pesticide residues, however, in some foods containing grease, grease cannot be effectively filtered, so that the data deviation of pesticide residue detection is large, and the accuracy of pesticide residue detection is affected.
Disclosure of Invention
The invention aims to solve the problems and designs a method for detecting pesticide residues in a grease-rich sample based on a composite SPE.
The technical scheme of the invention is that the method for detecting the pesticide residues in the oil-rich sample based on the composite SPE comprises a PSA/C18 composite column, an edible blend oil sample, a pork sample, a milk sample and a soybean sample, wherein the method for detecting the pesticide residues in the oil-rich sample based on the composite SPE comprises the following steps;
step 1: extracting a sample:
extracting an edible blend oil sample:
a1: weighing 1g of edible blend oil sample, adding 15mL of acetonitrile, oscillating for 5min, centrifuging at 6000rpm for 2min, and collecting supernatant;
a2: adding 15mL of acetonitrile to the lower layer, repeating the A1 step for one time, collecting the supernatant, and combining the supernatant collected by A1 and the supernatant collected by A1;
a3: distilling the supernatant collected from A2 under reduced pressure in 35 deg.C water bath to dryness, adding 1mL acetonitrile, ultrasonic dissolving to obtain edible blend oil sample extractive solution, and purifying.
Pork sample extraction:
b1: weighing 2g of pork sample, adding 4g of sodium chloride and 15mL of acetonitrile, oscillating for 5min, centrifuging at 6000rpm for 2min, and collecting supernatant;
b2: adding 15mL of acetonitrile to the lower layer, repeating the step B1 for one time, collecting the supernatant, and combining the supernatant collected by B1 and the supernatant collected by B1;
b3: distilling the supernatant collected in B2 under reduced pressure in a water bath at 35 ℃ until the supernatant is dried, adding 1mL of acetonitrile, and ultrasonically dissolving to obtain a pork sample extract to be purified.
Extracting a milk sample:
c1: weighing 5g of milk sample, adding 15mL of acetonitrile, oscillating for 3min, adding 2mL of 200g/L lead acetate solution and 4g of sodium chloride, oscillating for 2min, centrifuging at 6000rpm for 2min, and collecting supernatant;
c2: adding 15mL of acetonitrile to the lower layer, repeating the C1 step for extraction once, collecting the supernatant, and combining the supernatant collected by C1 and the supernatant collected by C1;
c3: distilling the supernatant collected by C2 under reduced pressure in a water bath at 35 ℃ until the supernatant is dried, adding 1mL of acetonitrile, and ultrasonically dissolving to obtain a milk sample extract to be purified.
Extracting a soybean sample:
d1: weighing 2g of sample, adding 5mL of water, soaking for 10min, adding 25mL of acetonitrile, oscillating for 10min, centrifuging at 6000rpm for 2min, and collecting supernatant;
d2: adding 25mL and 15mL of acetonitrile into the lower layer, repeating the step D1 for two times, combining three supernatants obtained by extracting twice in the steps D1 and D1;
d3: and distilling the supernatant collected by the D2 under reduced pressure in a water bath at 35 ℃ until the supernatant is dried, adding 1mL of acetonitrile, and performing ultrasonic dissolution to obtain a soybean sample extracting solution to be purified.
Step 2: purification
a, activating: adding 10mL of acetonitrile into a PSA/C18 composite column, and discarding the effluent liquid;
b, loading: adding edible blend oil sample extract, pork sample extract, milk sample extract or soybean sample extract into PSA/C18 composite column, and collecting effluent;
c, elution: adding 20mL of acetonitrile into a PSA/C18 composite column, and collecting effluent;
d, re-dissolving: and (4) distilling the effluent liquid of the b and the c under reduced pressure in a water bath at 35 ℃ until the effluent liquid is dry, adding 1mL of acetonitrile, and uniformly mixing for GC-MS analysis.
And step 3: detection by chromatograph
Respectively putting the purified edible blend oil sample extract, pork sample extract, milk sample extract and soybean sample extract obtained in the step 2 into a GC-MS instrument for analysis, wherein the chromatographic conditions are as follows:
a chromatographic column: DM-5MS,30 m.times.0.32 mm.times.0.25. mu.m
Sample inlet temperature: 240 ℃ C
Temperature rising procedure: the initial temperature is 70 ℃, the temperature is kept for 2min, the temperature is raised to 150 ℃ at the speed of 25 ℃/min, then the temperature is raised to 200 ℃ at the speed of 3 ℃/min, then the temperature is raised to 280 ℃ at the speed of 8 ℃/min, and the temperature is kept for 12 min.
Carrier gas: helium, flow rate: 1.46mL/min
And (3) sample introduction mode: non-shunting sample introduction
Sample introduction amount: 1.0 μ L
Ion source temperature: 230 deg.C
Interface temperature: 280 deg.C
Solvent retardation: 5.9min
Preferably, the PSA/C18 composite column comprises a column tube with the volume of 12mL, the PSA is arranged at the upper layer and has the mass of 1g, the sieve plate is arranged at the middle, and the C18 is arranged at the lower layer and has the mass of 2 g.
Preferably, the step 1 may further include:
a3: distilling the supernatant collected from A2 to about 5mL under reduced pressure in a water bath at 35 ℃ for purification;
b3: distilling the supernatant collected from B2 to about 5mL under reduced pressure in a water bath at 35 ℃ for purification;
c3: distilling the supernatant collected from C2 to about 5mL under reduced pressure in a water bath at 35 ℃ for purification;
d3: the supernatant collected from D2 was distilled to about 5mL under reduced pressure at 35 ℃ water bath to be purified.
Preferably, the method for detecting pesticide residues in the oil-rich sample based on the composite SPE is suitable for the edible blend oil, pork, milk, dichlorvos in soybeans, fenamiphos, trifluralin, phorate, alpha-hexachlorobenzene, dimethoate, beta-hexachlorocyclohexane, lindane, quintozene, disulfoton, delta-hexachlorocyclohexane, chlorothalonil, chlorfenap, iprobenfos, chlorpyrifos-methyl, methyl parathion, heptachlor, tolclofos-methyl, pyrazofos-methyl, pirimiphos-methyl, aldrin, malathion, fenthion, trichlorphon, chlorpyrifos, parathion, pyrimidylphos, epoxy heptachlor, triadimenol, procymidone, methidathion, alpha-thiodan, chlordane, dieldrin, profenofos, p '-DDE, endrin, beta-thiodan, p' -DDD, o, p-DDT, ethion, And (3) detecting triazophos, endosulfan, p' -DDT, thiophenium, thiotepa, cyfluthrin, cypermethrin, fenvalerate, difenoconazole and deltamethrin.
Preferably, the PSA is silica gel bonded ethylene diamine-N-propyl microspheres.
Preferably, the C18 is silica gel bonded octadecyl microsphere.
Advantageous effects
According to the method for detecting the pesticide residues in the grease-rich sample based on the composite SPE, which is manufactured by the technical scheme of the invention, a sample extracting solution is filtered through a PSA/C18 composite column, wherein PSA in the PSA/C18 composite column is silica gel bonded ethylenediamine-N-propyl microspheres which have weak anion exchange and normal phase retention effects, fatty acids (such as oleic acid, palmitic acid and linoleic acid), organic acids, partial pigments, metal ions, saccharide interferents and the like which influence detection in a food matrix are removed, C18 is silica gel bonded octadecyl microspheres, and nonpolar compounds are retained through hydrophobic effects, and the oil and impurities in the food can be filtered by combining the two, so that the data deviation of pesticide residue detection is reduced, and the accuracy of pesticide residue detection is improved.
Drawings
FIG. 1 is a table of a selected ion monitoring set according to the present invention.
FIG. 2 is a graph of various pesticide residue standards (10ug/mL) TIC of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
The method for detecting pesticide residues in oil-rich samples based on composite SPE is suitable for dichlorvos, fenamiphos, trifluralin, phorate, a-hexachlorophene, hexachlorobenzene, dimethoate, beta-hexachlorocyclohexane, lindane, quintozene, ethoprophos, delta-hexachlorocyclohexane, chlorothalonil, chlorfenap, iprobenfos, methyl chlorpyrifos, methyl parathion, heptachloro, methyl cumylphos, pyraclofos, fenitrothion, pirimiphos-methyl, aldrin, malathion, fenthion, trichlorofol, chlorpyrifos, parathion, pyrimidylphosphonium, epoxy heptachloro, triadimenol, procymidone, methidathion, a-endosulfan, dibromide, p '-DDE, isotridecyl, beta-endosulfan, p' -DDD, o, p-DDT, ethion, triazophos, p-D, p-DDT, ethoprophos, triazophos, chlorpyrifos, prochlor, prochloraz, p, prochloraz, p, prochlorvinphos, p, prochlorvinphos, p, prochlorvinphos, prochloraz, prochlorvinphos, prochloraz, p, prochloraz, prochlorvinphos, prochloraz, p, prochlorvinphos, p, prochloraz, p, prochloraz, p, prochlorvinphos, prochloraz, p, And (3) detecting endosulfate, p' -DDT, thiophenyl, thiotepa, cyfluthrin, cypermethrin, fenvalerate, difenoconazole and deltamethrin.
Example 1:
step 1: extracting a sample:
extracting an edible blend oil sample:
a1: weighing 1g of edible blend oil sample, adding 15mL of acetonitrile, oscillating for 5min, centrifuging at 6000rpm for 2min, and collecting supernatant;
a2: adding 15mL of acetonitrile to the lower layer, repeating the A1 step for one time, collecting the supernatant, and combining the supernatant collected by A1 and the supernatant collected by A1;
a3: distilling the supernatant collected from A2 under reduced pressure in 35 deg.C water bath to dry, adding 1mL acetonitrile, ultrasonic dissolving to obtain edible blend oil sample extractive solution, and purifying, or distilling the supernatant to about 5mL in 35 deg.C water bath in PSA/C18 composite column.
Step 2: purification
The PSA/C18 composite column comprises 12mL column tube, PSA at the upper layer with mass of 1g, sieve plate in the middle, C18 at the lower layer with mass of 2g, PSA as silica gel bonded ethylenediamine-N-propyl microsphere, and C18 as silica gel bonded octadecyl microsphere.
a, activating: adding 10mL of acetonitrile into a PSA/C18 composite column, and discarding the effluent liquid;
b, loading: adding edible blend oil sample extract into PSA/C18 composite column, and collecting effluent;
c, elution: adding 20mL of acetonitrile into a PSA/C18 composite column, and collecting effluent;
d, re-dissolving: and (4) distilling the effluent liquid of the b and the c under reduced pressure in a water bath at 35 ℃ until the effluent liquid is dry, adding 1mL of acetonitrile, and uniformly mixing for GC-MS analysis.
And step 3: detection by chromatograph
And (3) putting the purified edible blend oil sample extracting solution obtained in the step (2) into a GC-MS instrument for analysis, wherein the chromatographic conditions are as follows:
a chromatographic column: DM-5MS,30 m.times.0.32 mm.times.0.25. mu.m
Sample inlet temperature: 240 ℃ C
Temperature rising procedure: the initial temperature is 70 ℃, the temperature is kept for 2min, the temperature is raised to 150 ℃ at the speed of 25 ℃/min, then the temperature is raised to 200 ℃ at the speed of 3 ℃/min, then the temperature is raised to 280 ℃ at the speed of 8 ℃/min, and the temperature is kept for 12 min.
Carrier gas: helium, flow rate: 1.46mL/min
And (3) sample introduction mode: non-shunting sample introduction
Sample introduction amount: 1.0 μ L
Ion source temperature: 230 deg.C
Interface temperature: 280 deg.C
Solvent retardation: 5.9min
Electron impact ionization source (EI): ion monitoring mode (SIM) was selected and group monitoring is shown in table 1.
Example 2:
step 1: extracting a sample
Pork sample extraction:
b1: weighing 2g of pork sample, adding 4g of sodium chloride and 15mL of acetonitrile, oscillating for 5min, centrifuging at 6000rpm for 2min, and collecting supernatant;
b2: adding 15mL of acetonitrile to the lower layer, repeating the step B1 for one time, collecting the supernatant, and combining the supernatant collected by B1 and the supernatant collected by B1;
b3: distilling the supernatant collected from B2 under reduced pressure in 35 deg.C water bath to dry, adding 1mL acetonitrile, ultrasonic dissolving to obtain pork sample extractive solution, and purifying, or distilling the supernatant under reduced pressure in 35 deg.C water bath to about 5mL in PSA/C18 composite column.
Step 2: purification
The PSA/C18 composite column comprises 12mL column tube, PSA at the upper layer with mass of 1g, sieve plate in the middle, C18 at the lower layer with mass of 2g, PSA as silica gel bonded ethylenediamine-N-propyl microsphere, and C18 as silica gel bonded octadecyl microsphere.
a, activating: adding 10mL of acetonitrile into a PSA/C18 composite column, and discarding the effluent liquid;
b, loading: adding the pork sample extracting solution into a PSA/C18 composite column, and collecting effluent;
c, elution: adding 20mL of acetonitrile into a PSA/C18 composite column, and collecting effluent;
d, re-dissolving: and (4) distilling the effluent liquid of the b and the c under reduced pressure in a water bath at 35 ℃ until the effluent liquid is dry, adding 1mL of acetonitrile, and uniformly mixing for GC-MS analysis.
And step 3: detection by chromatograph
And (3) respectively putting the pork sample extracting solution purified in the step (2) into a GC-MS instrument for analysis, wherein the chromatographic conditions are as follows:
a chromatographic column: DM-5MS,30 m.times.0.32 mm.times.0.25. mu.m
Sample inlet temperature: 240 ℃ C
Temperature rising procedure: the initial temperature is 70 ℃, the temperature is kept for 2min, the temperature is raised to 150 ℃ at the speed of 25 ℃/min, then the temperature is raised to 200 ℃ at the speed of 3 ℃/min, then the temperature is raised to 280 ℃ at the speed of 8 ℃/min, and the temperature is kept for 12 min.
Carrier gas: helium, flow rate: 1.46mL/min
And (3) sample introduction mode: non-shunting sample introduction
Sample introduction amount: 1.0 μ L
Ion source temperature: 230 deg.C
Interface temperature: 280 deg.C
Solvent retardation: 5.9min
Electron impact ionization source (EI): ion monitoring mode (SIM) was selected and group monitoring is shown in table 1.
Example 3:
step 1: extracting a sample:
extracting a milk sample:
c1: weighing 5g of milk sample, adding 15mL of acetonitrile, oscillating for 3min, adding 2mL of 200g/L lead acetate solution and 4g of sodium chloride, oscillating for 2min, centrifuging at 6000rpm for 2min, and collecting supernatant;
c2: adding 15mL of acetonitrile to the lower layer, repeating the C1 step for extraction once, collecting the supernatant, and combining the supernatant collected by C1 and the supernatant collected by C1;
c3: distilling the supernatant collected from C2 under reduced pressure in 35 deg.C water bath to dry, adding 1mL acetonitrile, ultrasonic dissolving to obtain milk sample extractive solution, and purifying, or distilling the supernatant under reduced pressure in 35 deg.C water bath to about 5mL in PSA/C18 composite column.
Step 2: purification
The PSA/C18 composite column comprises 12mL column tube, PSA at the upper layer with mass of 1g, sieve plate in the middle, C18 at the lower layer with mass of 2g, PSA as silica gel bonded ethylenediamine-N-propyl microsphere, and C18 as silica gel bonded octadecyl microsphere.
a, activating: adding 10mL of acetonitrile into a PSA/C18 composite column, and discarding the effluent liquid;
b, loading: adding the milk sample extracting solution into a PSA/C18 composite column, and collecting effluent;
c, elution: adding 20mL of acetonitrile into a PSA/C18 composite column, and collecting effluent;
d, re-dissolving: and (4) distilling the effluent liquid of the b and the c under reduced pressure in a water bath at 35 ℃ until the effluent liquid is dry, adding 1mL of acetonitrile, and uniformly mixing for GC-MS analysis.
And step 3: detection by chromatograph
And (3) respectively putting the milk sample extract purified in the step (2) into a GC-MS instrument for analysis, wherein the chromatographic conditions are as follows:
a chromatographic column: DM-5MS,30 m.times.0.32 mm.times.0.25. mu.m
Sample inlet temperature: 240 ℃ C
Temperature rising procedure: the initial temperature is 70 ℃, the temperature is kept for 2min, the temperature is raised to 150 ℃ at the speed of 25 ℃/min, then the temperature is raised to 200 ℃ at the speed of 3 ℃/min, then the temperature is raised to 280 ℃ at the speed of 8 ℃/min, and the temperature is kept for 12 min.
Carrier gas: helium, flow rate: 1.46mL/min
And (3) sample introduction mode: non-shunting sample introduction
Sample introduction amount: 1.0 μ L
Ion source temperature: 230 deg.C
Interface temperature: 280 deg.C
Solvent retardation: 5.9min
Electron impact ionization source (EI): ion monitoring mode (SIM) was selected and group monitoring is shown in table 1.
Example 4:
step 1: extracting a sample:
extracting a soybean sample:
d1: weighing 2g of sample, adding 5mL of water, soaking for 10min, adding 25mL of acetonitrile, oscillating for 10min, centrifuging at 6000rpm for 2min, and collecting supernatant;
d2: adding 25mL and 15mL of acetonitrile into the lower layer, repeating the step D1 for two times, combining three supernatants obtained by extracting twice in the steps D1 and D1;
d3: distilling the supernatant collected from D2 under reduced pressure in 35 deg.C water bath to dry, adding 1mL acetonitrile, ultrasonic dissolving to obtain semen glycines sample extractive solution, and purifying, or distilling the supernatant to about 5mL in 35 deg.C water bath in PSA/C18 composite column.
Step 2: purification
The PSA/C18 composite column comprises 12mL column tube, PSA at the upper layer with mass of 1g, sieve plate in the middle, C18 at the lower layer with mass of 2g, PSA as silica gel bonded ethylenediamine-N-propyl microsphere, and C18 as silica gel bonded octadecyl microsphere.
a, activating: adding 10mL of acetonitrile into a PSA/C18 composite column, and discarding the effluent liquid;
b, loading: adding the soybean sample extracting solution into a PSA/C18 composite column, and collecting effluent;
c, elution: adding 20mL of acetonitrile into a PSA/C18 composite column, and collecting effluent;
d, re-dissolving: and (4) distilling the effluent liquid of the b and the c under reduced pressure in a water bath at 35 ℃ until the effluent liquid is dry, adding 1mL of acetonitrile, and uniformly mixing for GC-MS analysis.
And step 3: detection by chromatograph
And (3) respectively putting the purified soybean sample extract in the step (2) into a GC-MS instrument for analysis, wherein the chromatographic conditions are as follows:
a chromatographic column: DM-5MS,30 m.times.0.32 mm.times.0.25. mu.m
Sample inlet temperature: 240 ℃ C
Temperature rising procedure: the initial temperature is 70 ℃, the temperature is kept for 2min, the temperature is raised to 150 ℃ at the speed of 25 ℃/min, then the temperature is raised to 200 ℃ at the speed of 3 ℃/min, then the temperature is raised to 280 ℃ at the speed of 8 ℃/min, and the temperature is kept for 12 min.
Carrier gas: helium, flow rate: 1.46mL/min
And (3) sample introduction mode: non-shunting sample introduction
Sample introduction amount: 1.0 μ L
Ion source temperature: 230 deg.C
Interface temperature: 280 deg.C
Solvent retardation: 5.9min
Electron impact ionization source (EI): ion monitoring mode (SIM) was selected and group monitoring is shown in table 1.
The addition recovery results of various pesticide residues detected by GC-MS in example 1, example 2, example 3 and example 4 are as follows:
as shown in FIG. 2, the mass spectrum of the test sample was obtained by the measurement according to the detection method of example 1, and it was found that 60 types of agricultural residues were separated with good separation effect. The test results of embodiments 2, 3 and 4 are similar to those of embodiment 1, and are not repeated herein
The technical solutions described above only represent the preferred technical solutions of the present invention, and some possible modifications to some parts of the technical solutions by those skilled in the art all represent the principles of the present invention, and fall within the protection scope of the present invention.
Claims (6)
1. A method for detecting pesticide residues in a grease-rich sample based on composite SPE is characterized by comprising a PSA/C18 composite column, an edible blend oil sample, a pork sample, a milk sample and a soybean sample, wherein the method for detecting the pesticide residues in the grease-rich sample based on the composite SPE comprises the following steps;
step 1: extracting a sample:
extracting an edible blend oil sample:
a1: weighing 1g of edible blend oil sample, adding 15mL of acetonitrile, oscillating for 5min, centrifuging at 6000rpm for 2min, and collecting supernatant;
a2: adding 15mL of acetonitrile to the lower layer, repeating the A1 step for one time, collecting the supernatant, and combining the supernatant collected by A1 and the supernatant collected by A1;
a3: distilling the supernatant collected from A2 under reduced pressure in 35 deg.C water bath to dryness, adding 1mL acetonitrile, ultrasonic dissolving to obtain edible blend oil sample extractive solution, and purifying.
Pork sample extraction:
b1: weighing 2g of pork sample, adding 4g of sodium chloride and 15mL of acetonitrile, oscillating for 5min, centrifuging at 6000rpm for 2min, and collecting supernatant;
b2: adding 15mL of acetonitrile to the lower layer, repeating the step B1 for one time, collecting the supernatant, and combining the supernatant collected by B1 and the supernatant collected by B1;
b3: distilling the supernatant collected in B2 under reduced pressure in a water bath at 35 ℃ until the supernatant is dried, adding 1mL of acetonitrile, and ultrasonically dissolving to obtain a pork sample extract to be purified.
Extracting a milk sample:
c1: weighing 5g of milk sample, adding 15mL of acetonitrile, oscillating for 3min, adding 2mL of 200g/L lead acetate solution and 4g of sodium chloride, oscillating for 2min, centrifuging at 6000rpm for 2min, and collecting supernatant;
c2: adding 15mL of acetonitrile to the lower layer, repeating the C1 step for extraction once, collecting the supernatant, and combining the supernatant collected by C1 and the supernatant collected by C1;
c3: distilling the supernatant collected by C2 under reduced pressure in a water bath at 35 ℃ until the supernatant is dried, adding 1mL of acetonitrile, and ultrasonically dissolving to obtain a milk sample extract to be purified.
Extracting a soybean sample:
d1: weighing 2g of sample, adding 5mL of water, soaking for 10min, adding 25mL of acetonitrile, oscillating for 10min, centrifuging at 6000rpm for 2min, and collecting supernatant;
d2: adding 25mL and 15mL of acetonitrile into the lower layer, repeating the step D1 for two times, combining three supernatants obtained by extracting twice in the steps D1 and D1;
d3: and distilling the supernatant collected by the D2 under reduced pressure in a water bath at 35 ℃ until the supernatant is dried, adding 1mL of acetonitrile, and performing ultrasonic dissolution to obtain a soybean sample extracting solution to be purified.
Step 2: purification
a, activating: adding 10mL of acetonitrile into a PSA/C18 composite column, and discarding the effluent liquid;
b, loading: adding edible blend oil sample extract, pork sample extract, milk sample extract or soybean sample extract into PSA/C18 composite column, and collecting effluent;
c, elution: adding 20mL of acetonitrile into a PSA/C18 composite column, and collecting effluent;
d, re-dissolving: and (4) distilling the effluent liquid of the b and the c under reduced pressure in a water bath at 35 ℃ until the effluent liquid is dry, adding 1mL of acetonitrile, and uniformly mixing for GC-MS analysis.
And step 3: detection by chromatograph
Respectively putting the purified edible blend oil sample extract, pork sample extract, milk sample extract and soybean sample extract obtained in the step 2 into a GC-MS instrument for analysis, wherein the chromatographic conditions are as follows:
a chromatographic column: DM-5MS,30 m.times.0.32 mm.times.0.25. mu.m
Sample inlet temperature: 240 ℃ C
Temperature rising procedure: the initial temperature is 70 ℃, the temperature is kept for 2min, the temperature is raised to 150 ℃ at the speed of 25 ℃/min, then the temperature is raised to 200 ℃ at the speed of 3 ℃/min, then the temperature is raised to 280 ℃ at the speed of 8 ℃/min, and the temperature is kept for 12 min.
Carrier gas: helium, flow rate: 1.46mL/min
And (3) sample introduction mode: non-shunting sample introduction
Sample introduction amount: 1.0 μ L
Ion source temperature: 230 deg.C
Interface temperature: 280 deg.C
Solvent retardation: 5.9 min.
2. The method for detecting the pesticide residue in the grease-rich sample based on the composite SPE as claimed in claim 1, wherein the PSA/C18 composite column comprises a column tube with a volume of 12mL, PSA on the upper layer with a mass of 1g, a sieve plate in the middle, and C18 on the lower layer with a mass of 2 g.
3. The method for detecting the pesticide residues in the grease-rich sample based on composite SPE as claimed in claim 1, wherein the step 1 further comprises:
a3: distilling the supernatant collected from A2 to about 5mL under reduced pressure in a water bath at 35 ℃ for purification;
b3: distilling the supernatant collected from B2 to about 5mL under reduced pressure in a water bath at 35 ℃ for purification;
c3: distilling the supernatant collected from C2 to about 5mL under reduced pressure in a water bath at 35 ℃ for purification;
d3: the supernatant collected from D2 was distilled to about 5mL under reduced pressure at 35 ℃ water bath to be purified.
4. The method for detecting pesticide residues in an oil-rich sample based on the composite SPE as claimed in claim 1, wherein the method for detecting pesticide residues in an oil-rich sample based on the composite SPE is suitable for edible blend oil, pork, milk, dichlorvos in soybean, dichlorvos, trifluralin, phorate, a-hexachlorobenzene, dimethoate, beta-hexachlorocyclohexane, lindane, quintozene, fosetyl, delta-hexachlorocyclohexane, chlorothalonil, chlorfenap, iprobenfos, chlorpyrifos-methyl, parathion-methyl, heptachloro, tolclofos-methyl, picrophos, fenide-fenitrothion, pirimiphos-methyl, aldrin, malathion, fenthion, dicofol, chlorpyrifos, parathion, pyrimidophosphorus-methyl, heptachloro-epoxy, triadimenol, procymidone, methidathion, a-thion, chlordane, dicofol, p' -DDE, The detection of the reagent of the Dildrin, beta-endosulfan, p '-DDD, o, p-DDT, ethion, triazophos, endosulfan, p' -DDT, thiophenium, thiotepa, cyfluthrin, cypermethrin, fenvalerate, difenoconazole and deltamethrin.
5. The method for detecting the pesticide residue in the grease-rich sample based on the composite SPE as claimed in claim 2, wherein the PSA is silica gel bonded ethylenediamine-N-propyl microspheres.
6. The method for detecting the pesticide residues in the grease-rich sample based on the composite SPE as claimed in claim 2, wherein the C18 is silica gel bonded octadecyl microspheres.
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