CN115598250A - Method for rapidly determining pesticide residue of agricultural product mixed sample - Google Patents
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- CN115598250A CN115598250A CN202211274851.6A CN202211274851A CN115598250A CN 115598250 A CN115598250 A CN 115598250A CN 202211274851 A CN202211274851 A CN 202211274851A CN 115598250 A CN115598250 A CN 115598250A
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Abstract
The invention discloses a method for rapidly determining pesticide residue of a mixed sample of agricultural products, and particularly relates to the technical field of food safety, wherein a mixed sample method is used for detecting pesticide residue, so that the detection efficiency is improved by 2-9 times, and the detection limit of the method is one order of magnitude lower than that of a common method; the project method comprises the steps that cyfluthrin, cyhalothrin, cypermethrin and the like are used in large amount and are often detected, and meanwhile, overproof varieties are often found; the method uses the isotope parent ion pair technology of chlorine, and can detect important components such as cyfluthrin, cyhalothrin, cypermethrin and the like; in the re-dissolving step after nitrogen blowing, the adopted special solvents are acetone: water: methanol was added as 20:30:50, this kind of special proportion solvent can reach the effect of dissolving multiple component pesticide, removes impurity such as chlorophyll simultaneously, reaches the recovery rate height, and the low purpose of being convenient for detect of matrix effect.
Description
Technical Field
The invention relates to the technical field of food safety, in particular to a method for rapidly determining pesticide residue of a mixed sample of agricultural products.
Background
At present, four practical situations exist in the field of agricultural product pesticide residue detection:
1. the liquid chromatogram tandem mass spectrum detection quantity of pesticide residue of agricultural products in China is large, and the total quantity is estimated to be more than 100 ten thousand samples per year.
2. The current universal liquid chromatography tandem mass spectrometry detection method is long in time consumption and high in cost.
The widely used GB23200.121-2021 'liquid chromatogram-mass spectrum combination method for determining the residual quantity of 331 pesticides and metabolites thereof in national food safety standards plant-derived food' and GB 20769-2008 'determination of the residual quantity of 405 pesticides in fruits and vegetables-liquid chromatogram tandem mass spectrum method' have the advantages of accuracy, accuracy and large flux; the defect is that the single-sample detection consumes long time, and 30 minutes are needed for pure operation; the cost of a single sample is high.
3. The detection standard exceeding rate of agricultural product pesticide residue is lower and is below 3 percent; for example, in 2021, the pesticide residue exceeding rate of more than 2000 agricultural products in China is 0.91% monitored by Ministry of agriculture; 2600 parts of agricultural products in Guangdong province in 2021 have the detection standard exceeding rate of 2.5 percent; the pesticide residue exceeding rate of 682 parts of agricultural products in the Baoan district of 2021 is 1.5%.
4. The existing universal liquid chromatography-tandem mass spectrometry pesticide residue detection method does not comprise large usage amount of cyfluthrin, cyhalothrin and the like, and the like which are often detected and exceed the standard.
Therefore, the method for rapidly determining the pesticide residue of the agricultural product mixed sample has important significance.
Disclosure of Invention
In order to overcome the defects, the invention provides a method for rapidly measuring the pesticide residue of a mixed sample of agricultural products, and solves the technical problem.
In order to achieve the purpose, the invention provides the following technical scheme: a method for rapidly measuring pesticide residue of a mixed sample of agricultural products comprises the following steps:
A. preparing a single sample;
randomly sampling 1kg of edible fungi, tropical and subtropical fruits (edible peels), randomly sampling 1.5kg of aquatic vegetables, stem vegetables, bean vegetables, stone fruits, tropical and subtropical fruits (inedible peels), randomly sampling 4-6 individuals (the sampling amount is not less than 1 kg) of melon vegetables and common fruits, and randomly sampling 2kg of other vegetables and fruits; for smaller individual samples, all treatment was done after sampling; for larger basically uniform samples of individuals, the samples can be divided or cut into small blocks on a symmetry axis or a symmetry plane for post-treatment; cutting the sample, mixing, pulverizing part or all of the sample with tissue masher, and placing into polyethylene bottle;
B. mixing and preparing a sample;
mixing 2-10 single samples to form a mixed sample for detection;
C. extracting and purifying;
weighing 20g of sample, putting the sample into a 80mL plastic centrifuge tube, adding 20mL of acetonitrile and 1 ceramic homogeneous proton, violently shaking for 1min, adding 8g of anhydrous magnesium sulfate, 2g of sodium chloride, 2g of sodium citrate dihydrate and 1g of disodium citrate sesquihydrate, violently shaking for 1min, and centrifuging at 4500r/min for 5min; quantitatively sucking the supernatant into a plastic centrifuge tube containing a water removing agent and a purifying material; for a sample with a darker color, adding GCB into the centrifugal tube, and uniformly mixing for 1min in a vortex manner; centrifuging at 4500r/min for 5min;
D. nitrogen blowing and concentrating;
2mL of supernatant is sucked, and after nitrogen blowing, the volume is fixed to 0.5mL and the supernatant is filtered through a microporous filter membrane to be measured;
E. redissolving;
dissolving various types of pesticides by using a special solvent, and removing chlorophyll impurities to reduce a matrix effect;
F. film-passing and machine-loading;
the special solvent is acetone: water: methanol was added as 20:30: and mixing at a ratio of 50.
As a further scheme of the invention: and B, weighing 30.0 g of each single sample in the step B, forming a mixed sample by 2-10 single samples, and fully and uniformly mixing the mixed samples.
As a further scheme of the invention: and D, adopting a nitrogen blowing instrument in the nitrogen blowing process in the step D, adopting a vortex oscillator for vortex mixing in the step C, and adopting a liquid chromatogram-series triple quadrupole mass spectrometer equipped with an electrospray ion source as a machine in the step F.
As a further scheme of the invention: and C, quantitatively absorbing the supernatant in the step C, wherein the dosage of the extracted liquid per milliliter is 150mg of anhydrous magnesium sulfate, 25mgPSA and GCB, and the dosage of the GCB is 2.5mg per milliliter according to the content of the extracted liquid in a centrifugal tube.
The abbreviation of N-propylethylenediamine adsorbent is PSA, the abbreviation of graphitized carbon black GCB.
The invention has the beneficial effects that:
1. the invention uses the mixed sample method to detect the pesticide residue and improves the detection efficiency by 2 to 9 times, and the detection limit of the project method is one order of magnitude lower than that of the common method;
2. the project method comprises the steps that cyfluthrin, cyhalothrin, cypermethrin and the like are used in large amount and are often detected, and meanwhile, overproof varieties are often found; the method uses the isotope parent ion pair technology of chlorine, and can detect important components such as cyfluthrin, cyhalothrin, cypermethrin and the like;
3. in the re-dissolving step after nitrogen blowing, the adopted special solvents are acetone: water: methanol was added as 20:30:50, the special proportion solvent can achieve the effect of dissolving various components of pesticides, simultaneously remove impurities such as chlorophyll and the like, and achieve the purposes of high recovery rate, low matrix effect and convenient detection.
In a word, the method has high efficiency and low detection limit, and brings important components such as cyfluthrin, cyhalothrin, cypermethrin and the like into the method.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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.
Example (b):
a method for rapidly measuring pesticide residue of an agricultural product mixed sample comprises the following steps:
A. preparing a single sample;
randomly sampling 1kg of edible fungi, tropical and subtropical fruits (edible peels), randomly sampling 1.5kg of aquatic vegetables, stem vegetables, bean vegetables, stone fruits, tropical and subtropical fruits (inedible peels), randomly sampling 4-6 individuals (the sampling amount is not less than 1 kg) of melon vegetables and common fruits, and randomly sampling 2kg of other vegetables and fruits; for smaller individual samples, all treatment was done after sampling; for a large and basically uniform sample, the sample can be divided or cut into small blocks on a symmetry axis or a symmetry plane for post-treatment; cutting the sample, mixing, pulverizing part or all of the sample with tissue masher, and placing into polyethylene bottle;
B. mixing and preparing a sample;
mixing 2-10 single samples to form a mixed sample for detection;
C. extracting and purifying;
weighing 20g of sample, putting the sample into a 80mL plastic centrifuge tube, adding 20mL of acetonitrile and 1 ceramic homogeneous proton, violently shaking for 1min, adding 8g of anhydrous magnesium sulfate, 2g of sodium chloride, 2g of sodium citrate dihydrate and 1g of citric acid disodium salt sesquihydrate, violently shaking for 1min, and centrifuging at 4500r/min for 5min; quantitatively sucking the supernatant into a plastic centrifuge tube containing a water removing agent and a purifying material; for a sample with a darker color, adding GCB into the centrifugal tube, and uniformly mixing for 1min in a vortex manner; centrifuging at 4500r/min for 5min;
D. nitrogen blowing and concentrating;
2mL of supernatant fluid is sucked, and after nitrogen blowing, the volume is fixed to 0.5mL and the solution is filtered through a microporous filter membrane to be measured;
E. re-dissolving;
dissolving various types of pesticides by using a special solvent, and removing chlorophyll impurities to reduce a matrix effect;
F. passing through a film and loading on a machine;
the special solvent is acetone: water: methanol was added as 20:30: and mixing at a ratio of 50.
And B, weighing 30.0 g of each single sample in the step B, forming a mixed sample by 2-10 single samples, and fully and uniformly mixing the mixed samples.
And D, adopting a nitrogen blowing instrument in the nitrogen blowing process in the step D, adopting a vortex oscillator for vortex mixing in the step C, and adopting a liquid chromatogram-tandem triple quadrupole mass spectrometer as a machine in the step F and matching an electrospray ion source.
And C, quantitatively absorbing the supernatant in the step C, wherein the dosage of the anhydrous magnesium sulfate and 25mgPSA in each milliliter of extracting solution is 2.5mg in each milliliter of extracting solution according to the content of the extracting solution in a centrifugal tube.
Mixing 2-10 samples, detecting the mixed sample, judging whether the detection result is qualified or not by using the national standard GB 2763, and judging whether the sample is negative or not to be qualified; carrying out repeated detection on positive samples in each original sample again, and judging whether the original samples are qualified or not after the repeated detection;
test one: and (4) exceeding the standard rate: 1.6% of 430 mixed sample detection results of 109 pesticide residues in vegetables and fruits; and (3) finding that 7 samples exceed the standard, wherein the standard exceeding rate is as follows: 1.6 percent.
Detection efficiency table for different mixed numbers of 430 samples:
430 samples were tested (superscript rate is less than or equal to 2%) and mixed samples were concluded:
2 samples are mixed, only 230 samples need to be detected, and the efficiency is 1.9 times that of a single sample;
3 samples are mixed, only 172 samples need to be detected, and the efficiency is 2.5 times that of a single sample;
4 samples are mixed, only 139 samples need to be detected, and the efficiency is 3.1 times that of a single sample;
5 samples are mixed, only 122 samples need to be detected, and the efficiency is 3.6 times that of a single sample;
mixing 10 samples, only 111 samples need to be detected, and the efficiency is 3.9 times that of a single sample.
And (2) test II: and (4) exceeding the standard rate: 0.9% of 790 vegetable and fruit 109 pesticide residue mixed sample detection result table; and (3) finding that 7 samples exceed the standard, wherein the standard exceeding rate is as follows: 0.9 percent.
Detection efficiency table for different mixed numbers of 790 samples:
the mixed sample conclusion of 790 sample detections (0.9% out of standard):
2 samples are mixed, only 230 samples need to be detected, and the efficiency is 1.9 times that of a single sample;
3 samples are mixed, only 172 samples need to be detected, and the efficiency is 2.7 times that of a single sample;
4 samples are mixed, only 139 samples need to be detected, and the efficiency is 3.5 times that of a single sample;
5 samples are mixed, only 122 samples need to be detected, and the efficiency is 3.8 times that of a single sample;
10 samples were mixed and only 111 samples were tested, with an efficiency 4.7 times that of the single sample.
In the actual detection test, 10 samples are mixed for detection, and the detection efficiency of the mixed samples is 3.9 to 4.7 times that of the single detection.
And (3) testing three: detection efficiency of different mixed numbers of 300 samples with standard exceeding rate of 2.3%
300 samples are detected (the superscript rate is less than or equal to 1 percent) and mixed samples are concluded:
2 samples are mixed, only 160 samples need to be detected, and the efficiency is 1.9 times that of a single sample;
3 samples are mixed, only 118 samples need to be detected, and the efficiency is 2.6 times that of a single sample;
mixing 4 samples, only 99 samples need to be detected, and the efficiency is 3.1 times that of a single sample;
5 samples are mixed, only 90 samples need to be detected, and the efficiency is 3.6 times that of a single sample;
mixing 10 samples, only 95 samples need to be detected, and the efficiency is 3.2 times that of a single sample.
The points to be finally explained are: although the present invention has been described in detail with reference to the general description and the specific embodiments, on the basis of the present invention, the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (4)
1. A method for rapidly measuring pesticide residue of a mixed sample of agricultural products is characterized by comprising the following steps:
A. preparing a single sample;
randomly sampling 1kg of edible fungi, tropical and subtropical fruits (edible peels), randomly sampling 1.5kg of aquatic vegetables, stem vegetables, bean vegetables, stone fruits, tropical and subtropical fruits (edible peels), randomly sampling 4-6 individuals of melon vegetables and common fruits (the sampling amount is not less than 1 kg), and randomly sampling 2kg of other vegetables and fruits; for smaller individual samples, all treatment was done after sampling; for larger basically uniform samples of individuals, the samples can be divided or cut into small blocks on a symmetry axis or a symmetry plane for post-treatment; cutting the sample, mixing, pulverizing part or all of the sample with tissue masher, and placing into polyethylene bottle;
B. mixing and preparing a sample;
mixing 2-10 single samples to form a mixed sample for detection;
C. extracting and purifying;
weighing 20g of sample, putting the sample into a 80mL plastic centrifuge tube, adding 20mL of acetonitrile and 1 ceramic homogeneous proton, violently shaking for 1min, adding 8g of anhydrous magnesium sulfate, 2g of sodium chloride, 2g of sodium citrate dihydrate and 1g of disodium citrate sesquihydrate, violently shaking for 1min, and centrifuging at 4500r/min for 5min; quantitatively sucking the supernatant into a plastic centrifuge tube containing a water removing agent and a purifying material; for a sample with a darker color, adding GCB into the centrifugal tube, and uniformly mixing for 1min in a vortex manner; centrifuging at 4500r/min for 5min;
D. nitrogen blowing and concentrating;
2mL of supernatant is sucked, and after nitrogen blowing, the volume is fixed to 0.5mL and the supernatant is filtered through a microporous filter membrane to be measured;
E. re-dissolving;
dissolving various types of pesticides by using a special solvent, and removing chlorophyll impurities to reduce a matrix effect;
F. passing through a film and loading on a machine;
the special solvent is acetone: water: methanol was added as 20:30:50 in proportion.
2. The method for rapidly measuring the pesticide residue of the agricultural product mixed sample according to claim 1, which is characterized in that: and B, weighing 30.0 g of each single sample in the step B, forming a mixed sample by 2-10 single samples, and fully and uniformly mixing the mixed samples.
3. The method for rapidly measuring the pesticide residue of the agricultural product mixed sample according to claim 1, which is characterized in that: and D, adopting a nitrogen blowing instrument in the nitrogen blowing process in the step D, adopting a vortex oscillator for vortex mixing in the step C, and adopting a liquid chromatogram-tandem triple quadrupole mass spectrometer equipped with an electrospray ion source as a machine in the step F.
4. The method for rapidly measuring the pesticide residue of the agricultural product mixed sample according to claim 1, which is characterized in that: and C, quantitatively absorbing the supernatant in the step C, wherein the dosage of the extracted liquid per milliliter is 150mg of anhydrous magnesium sulfate, 25mgPSA and GCB, and the dosage of the GCB is 2.5mg per milliliter according to the content of the extracted liquid in a centrifugal tube.
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| CN202211274851.6A CN115598250A (en) | 2022-10-18 | 2022-10-18 | Method for rapidly determining pesticide residue of agricultural product mixed sample |
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