CN115097033A - Method for rapidly detecting pesticide residues in fruits and vegetables - Google Patents

Method for rapidly detecting pesticide residues in fruits and vegetables Download PDF

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Publication number
CN115097033A
CN115097033A CN202210692543.9A CN202210692543A CN115097033A CN 115097033 A CN115097033 A CN 115097033A CN 202210692543 A CN202210692543 A CN 202210692543A CN 115097033 A CN115097033 A CN 115097033A
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China
Prior art keywords
fruits
sample
vegetables
temperature
pesticide residues
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CN202210692543.9A
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Chinese (zh)
Inventor
李丽蓉
李鹏飞
代诗卉
杨凡
丁盛
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Yunnan Fuer Quality Inspection Co ltd
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Yunnan Fuer Quality Inspection Co ltd
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Priority to CN202210692543.9A priority Critical patent/CN115097033A/en
Publication of CN115097033A publication Critical patent/CN115097033A/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • G01N30/14Preparation by elimination of some components
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/62Detectors specially adapted therefor
    • G01N30/72Mass spectrometers
    • G01N30/7206Mass spectrometers interfaced to gas chromatograph
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • G01N2030/062Preparation extracting sample from raw material

Abstract

The invention provides a method for rapidly detecting pesticide residues in fruits and vegetables, and belongs to the technical field of pesticide residue analysis and detection. The method comprises the steps of sample pretreatment and sample determination, the invention realizes the enrichment and purification of the sample by utilizing the accelerated solvent extraction technology, and combines the GC-MS/MS technology, thereby rapidly and accurately determining various residual pesticides in the fruit and vegetable products. Meanwhile, the detection method provided by the invention also has the advantages of simple and rapid operation, and good sensitivity and precision, and provides reference for further reducing pesticide residues in fruits and vegetables.

Description

Method for rapidly detecting pesticide residues in fruits and vegetables
Technical Field
The invention relates to the technical field of pesticide residue analysis and detection, in particular to a method for rapidly detecting pesticide residues in fruits and vegetables.
Background
The pesticide plays an important role in improving the crop yield, but the pesticide abuse easily causes the pesticide residue to exceed the standard, influences the food safety and harms the human health. As a big country of agricultural products, China has a very large demand on fruits and vegetables, so that the supervision of the agricultural products is increasingly strong. Pesticide residue detection projects are increasing, pesticide residue quantity requirements are demanding, and pesticide residue detection technologies and detection working strength face significant tests.
Solid Phase Microextraction (SPME) is an efficient sample pretreatment means, and compared with the traditional sample extraction method, the method has the greatest advantage that pesticide residues in fruits and vegetables can be subjected to in-situ extraction, so that the sample pretreatment step is greatly simplified. Gas Chromatography-Mass spectrometry (Gas Chromatography-Mass spectrometry) is a combination of Gas Chromatography (GC) and Mass Spectrometry (MS), the Gas Chromatography becomes an ideal sample injector of the Mass spectrometry, a sample is gasified and injected through a Gas Chromatography injection port and separated through a capillary column before entering the Mass spectrometer, and meanwhile, the Mass spectrometer is also regarded as an ideal detector of the Gas Chromatography, and has the main characteristics of wide application range, high sensitivity and strong identification capability. Therefore, the gas chromatography-mass spectrometry combined technology has high identification capability of mass spectrum and high separation capability of gas chromatography. The gas chromatography-mass spectrometer is one of the most commonly used pesticide residue detection instruments at present, and generally, a gas chromatograph can be used for analyzing and detecting samples, and most of the gas chromatography-mass spectrometer can be used for quantitative and qualitative detection.
The application number is CN 201910788612.4 discloses a method for measuring 179 pesticide residues in fruits and vegetables, and although the method can measure various pesticide residues through a gas chromatography-mass spectrometer and a liquid chromatography-mass spectrometer, the method has the defects of complex sample treatment operation, long consumed time, large reagent dosage, more interference components in the measuring process and the like.
Disclosure of Invention
In view of the above, the present invention provides a method for rapidly detecting pesticide residues in fruits and vegetables, comprising the following steps:
1) sample preparation: crushing fresh fruits and vegetables, pulping to obtain fruit and vegetable pulp, and freezing and storing;
2) sample pretreatment: accurately weighing 10g of fruit and vegetable pulp, mixing the fruit and vegetable pulp with 10-20g of diatomite, putting the mixture into an extraction tank, adding a mixed solution of dichloromethane and acetone into the extraction tank, setting the system pressure to be 10-20 MPa, extracting at the temperature of 100-130 ℃ for 2-5 min, quickly flushing a sample with a solvent, and purging with nitrogen to collect about 20ml of all extracting solution; then 1g NaCl and 4g MgSO were added 4 Vigorously shaking for 1min, standing for purification, collecting supernatant 2mL, adding 50mg PSA, vortexing for 2min, and processing at 9000r/min -1 Centrifuging for 5min, accurately sucking 1mL of centrifuged supernatant into a test tube, adding 1mL of acetone, mixing, and filtering with 0.22 μm filter membrane to obtain extract;
3) subjecting the extract obtained in the step 2) to gas chromatography-tandem mass spectrometry under the following conditions:
gas chromatography conditions:
(1) and (3) chromatographic column: AgilentHP-INNOWAX (60m 0.32mm 0.25um) is a chromatographic column;
(2) sample inlet temperature: 280 ℃;
(3) the temperature programming conditions were as follows: the initial temperature is 40 ℃, the holding time is 1min, the temperature is increased to 120 ℃ at the heating rate of 10 ℃/min, the holding time is 5min, then the temperature is increased to 350 ℃ at the heating rate of 15 ℃/min, and the holding time is 1 min;
(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 ml/min;
(5) sample introduction amount: 1 mu L of the solution;
(6) and (3) sample introduction mode: no split-flow sample introduction;
tandem mass spectrometry conditions:
(1) electron bombardment source: 70 eV;
(2) ion source temperature: 230 ℃;
(3) MSD transmission line temperature: 280 ℃.
Preferably, the storage conditions for said freezing in step 1) are-18 ℃.
Preferably, the volume ratio of the dichloromethane to the acetone in the step 2) is 1-2: 1.
preferably, the diatomaceous earth in step 2) has a particle size of 50-80 mesh.
The invention also aims to provide application of the method for rapidly detecting the pesticide residue in the fruits and the vegetables.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, a step of extraction solvent exchange process is added before sample purification to remove part of polar components, so that the purification effect of the sample is greatly improved, meanwhile, the sample to be detected and a certain amount of diatomite are uniformly mixed, on one hand, an inert material can play a role in dispersion, on the other hand, the diatomite also plays a role in drying to absorb part of water in the sample, and the dried sample is favorable for penetration of a solvent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The test methods or test methods described in the following examples are all conventional methods unless otherwise specified; the starting materials and auxiliaries are, unless otherwise specified, obtained from customary commercial sources or prepared in customary manner.
Example 1
A method for rapidly detecting pesticide residues in fruits and vegetables comprises the following steps:
1) sample preparation: mincing and homogenizing spinach to obtain a sample to be detected, and freezing and storing at-18 ℃;
2) sample pretreatment: precisely weighing 10g of sample to be detected, fully mixing the sample with 10g of diatomite with the granularity of 50 meshes, and filling the mixture into a containerAdding 50ml of mixed solution of extraction solvent V (dichloromethane) and V (acetone) in a ratio of 1: 1 into an extraction pool, setting the system pressure at 20MPa and the temperature at 130 ℃, extracting for 2min, then rapidly flushing a sample with the extraction solvent, purging with nitrogen, and collecting about 20ml of all extraction solution; then 1g of NaCl and 4g of MgSO were added 4 Violently oscillating for 1min, standing for purification, taking 2mL of supernate, adding 50mg PSA, vortexing for 2min, centrifuging for 5min at 9000r/min-1, accurately sucking 1mL of centrifuged supernate into a test tube, adding 1mL of acetone, uniformly mixing, and filtering with a 0.22-micron filter membrane to obtain an extract;
3) subjecting the extract obtained in step 2) to gas chromatography-tandem mass spectrometry under the following conditions:
gas chromatography conditions:
(1) a chromatographic column: AgilentHP-INNOWAX (60m 0.32mm 0.25um) is a chromatographic column;
(2) sample inlet temperature: 280 ℃;
(3) the temperature programming conditions were as follows: the initial temperature is 40 ℃, the holding time is 1min, the temperature is increased to 120 ℃ at the heating rate of 10 ℃/min, the holding time is 5min, then the temperature is increased to 350 ℃ at the heating rate of 15 ℃/min, and the holding time is 1 min;
(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 ml/min;
(5) sample injection amount: 1 mu L of the solution;
(6) and (3) sample introduction mode: no split-flow sample introduction;
tandem mass spectrometry conditions:
(1) electron bombardment source: 70 eV;
(2) ion source temperature: 230 ℃;
(3) MSD transmission line temperature: 280 ℃.
Example 2
A method for rapidly detecting pesticide residues in fruits and vegetables comprises the following steps:
1) sample preparation: mincing and homogenizing peach to obtain a sample to be detected, and freezing and storing at-18 ℃;
2) sample pretreatment: accurately weighing 10g of sample to be detected, fully mixing the sample with 15g of diatomite with the granularity of 60 meshes, and filling the mixture into an extraction tankThen adding 60ml of mixed solution of extraction solvent V (dichloromethane) and V (acetone) in a ratio of 2: 1 into an extraction pool, setting the system pressure to be 10MPa and the temperature to be 100 ℃, extracting for 5min, then rapidly flushing a sample with the extraction solvent, purging with nitrogen, and collecting about 20ml of all extraction solution; then 1g NaCl and 4g MgSO were added 4 Violently oscillating for 1min, standing for purification, taking 2mL of supernatant, adding 50mg PSA, vortexing for 2min, centrifuging for 5min at 9000r/min-1, accurately sucking 1mL of centrifuged supernatant into a test tube, adding 1mL of acetone, mixing uniformly, and filtering with a 0.22 mu m filter membrane to obtain an extract;
3) subjecting the extract obtained in step 2) to gas chromatography-tandem mass spectrometry under the following conditions:
gas chromatography conditions:
(1) a chromatographic column: agilent HP-INNOWAX (60m 0.32mm 0.25um) as column;
(2) sample inlet temperature: 280 ℃;
(3) the temperature programming conditions were as follows: the initial temperature is 40 ℃, the holding time is 1min, the temperature is increased to 120 ℃ at the heating rate of 10 ℃/min, the holding time is 5min, then the temperature is increased to 350 ℃ at the heating rate of 15 ℃/min, and the holding time is 1 min;
(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 ml/min;
(5) sample introduction amount: 1 mu L of the solution;
(6) and (3) sample introduction mode: no split-flow sample introduction;
tandem mass spectrometry conditions:
(1) electron bombardment source: 70 eV;
(2) ion source temperature: 230 ℃;
(3) MSD transmission line temperature: 280 ℃.
Example 3
A method for rapidly detecting pesticide residues in fruits and vegetables comprises the following steps:
1) sample preparation: mincing celery and homogenizing to obtain a sample to be detected, and freezing and storing at-18 ℃;
2) sample pretreatment: accurately weighing 10g of sample to be detected, fully mixing the sample with 20g of diatomite with the granularity of 80 meshes, and then filling the mixture into an extraction tankThen adding 90ml of mixed solution of extraction solvent V (dichloromethane) and V (acetone) in a ratio of 2: 1 into an extraction pool, setting the system pressure at 15MPa and the temperature at 100 ℃, extracting for 4min, then rapidly flushing the sample with the extraction solvent, and collecting about 20ml of all extraction solution after nitrogen purging; then 1g NaCl and 4g MgSO were added 4 Violently oscillating for 1min, standing for purification, taking 2mL of supernate, adding 50mg PSA, vortexing for 2min, centrifuging for 5min at 9000r/min-1, accurately sucking 1mL of centrifuged supernate into a test tube, adding 1mL of acetone, uniformly mixing, and filtering with a 0.22-micron filter membrane to obtain an extract;
3) subjecting the extract obtained in step 2) to gas chromatography-tandem mass spectrometry under the following conditions:
gas chromatography conditions:
(1) a chromatographic column: AgilentHP-INNOWAX (60m 0.32mm 0.25um) as a column;
(2) sample inlet temperature: 280 ℃;
(3) the temperature programming conditions were as follows: the initial temperature is 40 ℃, the holding time is 1min, the temperature is increased to 120 ℃ at the heating rate of 10 ℃/min, the holding time is 5min, then the temperature is increased to 350 ℃ at the heating rate of 15 ℃/min, and the holding time is 1 min;
(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 ml/min;
(5) sample introduction amount: 1 mu L of the solution;
(6) and (3) sample introduction mode: no split-flow sample introduction;
tandem mass spectrometry conditions:
(1) electron bombardment source: 70 eV;
(2) ion source temperature: 230 ℃;
(3) MSD transmission line temperature: 280 ℃.
The specific types of the residual pesticides on the fruits and the vegetables can be simultaneously determined through the experiment, and reference can be provided for further reducing the residual quantity of the pesticides in the fruits and the vegetables.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (5)

1. A method for rapidly detecting pesticide residues in fruits and vegetables is characterized by comprising the following steps:
1) sample preparation: crushing fresh fruits and vegetables, pulping to obtain fruit and vegetable pulp, and freezing and storing;
2) sample pretreatment: accurately weighing 10g of fruit and vegetable pulp, mixing with 10-20g of diatomite, putting into an extraction tank, adding a mixed solution of dichloromethane and acetone into the extraction tank, setting the system pressure to be 10-20 MPa, extracting at 100-130 ℃ for 2-5 min, rapidly flushing a sample with a solvent, and purging with nitrogen to collect about 20ml of all extracting solution; then 1g NaCl and 4g MgSO were added 4 Vigorously shaking for 1min, standing for purification, collecting supernatant 2mL, adding 50mg PSA, vortexing for 2min, and processing at 9000r/min -1 Centrifuging for 5min, accurately sucking 1mL of centrifuged supernatant into a test tube, adding 1mL of acetone, mixing, and filtering with 0.22 μm filter membrane to obtain extract;
3) subjecting the extract obtained in step 2) to gas chromatography-tandem mass spectrometry under the following conditions:
gas chromatography conditions:
(1) a chromatographic column: agilent HP-INNOWAX (60m 0.32mm 0.25um) as column;
(2) sample inlet temperature: 280 ℃;
(3) the temperature programming conditions were as follows: the initial temperature is 40 ℃, the holding time is 1min, the temperature is increased to 120 ℃ at the heating rate of 10 ℃/min, the holding time is 5min, then the temperature is increased to 350 ℃ at the heating rate of 15 ℃/min, and the holding time is 1 min;
(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 ml/min;
(5) sample introduction amount: 1 mu L of the solution;
(6) and (3) sample introduction mode: no split-flow sample introduction;
tandem mass spectrometry conditions:
(1) electron bombardment source: 70 eV;
(2) ion source temperature: 230 ℃;
(3) MSD transmission line temperature: at a temperature of 280 ℃.
2. The method for rapidly detecting pesticide residues in fruits and vegetables according to claim 1, wherein the freezing preservation condition in the step 1) is-18 ℃.
3. The method for rapidly detecting pesticide residues in fruits and vegetables according to claim 1, wherein the volume ratio of the dichloromethane to the acetone in the step 2) is 1-2: 1.
4. the method for rapidly detecting pesticide residues in fruits and vegetables according to claim 1, wherein the particle size of the diatomite in the step 2) is 50-80 meshes.
5. The application of the method for rapidly detecting pesticide residues in fruits and vegetables is characterized in that the method according to any one of claims 1 to 4 is applied to detection of pesticide residues in fruits and vegetables.
CN202210692543.9A 2022-06-17 2022-06-17 Method for rapidly detecting pesticide residues in fruits and vegetables Pending CN115097033A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004340627A (en) * 2003-05-13 2004-12-02 Saika Gijutsu Kenkyusho Analytical system for residual chemical substance
CN101852698A (en) * 2009-04-02 2010-10-06 天津市农业科学院中心实验室 Method for treating pesticide residue sample in Chinese medicinal material before measurement
CN108020609A (en) * 2017-11-28 2018-05-11 浙江公正检验中心有限公司 Quick determination method that is a kind of while measuring 34 kinds of pesticide residues in fruits and vegetables
CN111380980A (en) * 2020-04-21 2020-07-07 深圳市深大检测有限公司 Method for detecting pesticide residue on fruits and vegetables
CN111521709A (en) * 2020-03-09 2020-08-11 山东商业职业技术学院 GC-MS (gas chromatography-Mass spectrometer) detection method for 25 pesticide residues in pepper
CN113219093A (en) * 2021-05-06 2021-08-06 河北百润环境检测技术有限公司 Method for detecting pyridaphenthion, pyridaben, cypermethrin and lambda-cyhalothrin in soil or sediment
CN114324619A (en) * 2020-09-30 2022-04-12 江苏省理化测试中心 Method for measuring residual quantity of prochloraz and metabolites thereof in cereal grains and application

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004340627A (en) * 2003-05-13 2004-12-02 Saika Gijutsu Kenkyusho Analytical system for residual chemical substance
CN101852698A (en) * 2009-04-02 2010-10-06 天津市农业科学院中心实验室 Method for treating pesticide residue sample in Chinese medicinal material before measurement
CN108020609A (en) * 2017-11-28 2018-05-11 浙江公正检验中心有限公司 Quick determination method that is a kind of while measuring 34 kinds of pesticide residues in fruits and vegetables
CN111521709A (en) * 2020-03-09 2020-08-11 山东商业职业技术学院 GC-MS (gas chromatography-Mass spectrometer) detection method for 25 pesticide residues in pepper
CN111380980A (en) * 2020-04-21 2020-07-07 深圳市深大检测有限公司 Method for detecting pesticide residue on fruits and vegetables
CN114324619A (en) * 2020-09-30 2022-04-12 江苏省理化测试中心 Method for measuring residual quantity of prochloraz and metabolites thereof in cereal grains and application
CN113219093A (en) * 2021-05-06 2021-08-06 河北百润环境检测技术有限公司 Method for detecting pyridaphenthion, pyridaben, cypermethrin and lambda-cyhalothrin in soil or sediment

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Application publication date: 20220923