CN114252311A - Method for carrying out in-situ rapid detection pretreatment on pesticide residues in vegetables and fruits - Google Patents
Method for carrying out in-situ rapid detection pretreatment on pesticide residues in vegetables and fruits Download PDFInfo
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- 238000001514 detection method Methods 0.000 title claims abstract description 38
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 18
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- 238000002203 pretreatment Methods 0.000 claims abstract description 16
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- 239000000919 ceramic Substances 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000019262 disodium citrate Nutrition 0.000 claims description 3
- 239000002526 disodium citrate Substances 0.000 claims description 3
- 229940079896 disodium hydrogen citrate Drugs 0.000 claims description 3
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 238000001471 micro-filtration Methods 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 235000011083 sodium citrates Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 2
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- 238000011084 recovery Methods 0.000 description 10
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- 239000005874 Bifenthrin Substances 0.000 description 1
- 239000005946 Cypermethrin Substances 0.000 description 1
- 239000005892 Deltamethrin Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000273928 Zingiber officinale Species 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960001591 cyfluthrin Drugs 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/405—Concentrating samples by adsorption or absorption
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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
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
- G01N2001/2873—Cutting or cleaving
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Abstract
The invention discloses a method for carrying out in-situ rapid detection pretreatment on pesticide residues in vegetables and fruits, which comprises the following steps of: chopping a vegetable or fruit sample, mashing the chopped vegetable or fruit sample into homogenate, and placing the homogenate into a polyethylene bottle; an extraction step: weighing a homogeneous sample, adding acetonitrile, shaking, filtering by using filter paper, and collecting filtrate; adding an extraction salt bag into the filtrate, violently shaking, standing at room temperature, and layering the solution; a purification step: and (5) sucking the supernatant, purifying the supernatant by a filtration type purification column for one time, and then passing the supernatant through a microporous filter membrane for determination. Compared with the traditional QuEChERS pretreatment method, the method disclosed by the invention has the advantages that a novel rapid filtration method is used as a purification method, and the centrifugation step is omitted by standing after filtration and naturally layering to realize extraction of a target substance. The invention has simple operation and high processing speed, does not need to borrow other auxiliary instruments, and is suitable for being used as a pretreatment method for on-site in-situ rapid detection.
Description
Technical Field
The invention belongs to the food detection technology, in particular to a pesticide detection method, and specifically relates to a method for carrying out in-situ rapid detection pretreatment on pesticide residues in vegetables and fruits.
Background
The pesticide residue detection generally comprises 2 parts of sample pretreatment and instrument analysis, wherein the sample pretreatment is a key step influencing the accuracy and precision of a detection result and is a research focus of pesticide residue detection. The appropriate pretreatment method can improve the sensitivity, detection range, precision and accuracy of the detection technology.
The currently used methods for sample pretreatment at home and abroad include Solid Phase Extraction (SPE) [ Wu L, Cao ZY, Mou RX. Agric Sci Technol,2017,18(8): 1526-. However, these pretreatment methods are time consuming, have poor purification performance, and require frequent maintenance of the apparatus. Therefore, how to accelerate the pretreatment and improve the purification effect can be one of the important technical bottlenecks in the field of pesticide residues. The QuEChERS (Quick, easy, chemical, effective, rugged, safe) method is originally a sample pretreatment method which is proposed by Anastasiades and the like in 2003 and is applied to various pesticide residues in fruits and vegetables, integrates the traditional liquid-liquid extraction (LLE) and SPE methods, and becomes a first-choice pretreatment method for detecting the pesticide residues. However, the QuEChERS method is not perfect, and as a general pretreatment method, the QuEChERS method tends to take the whole extraction effect of various pesticides into consideration, and cannot take the effects of both the purification effect and the recovery rate into consideration. The rapid filtration purification (m-PFC) is a method for purifying interfering substances in a matrix, which has been developed based on the QuEChERS method. The Pan-Ping team [ Han Y, Song L, Liu S.food Chemistry,2018:258-267] [ HanYT, Song L, Pan CP.J.Chromatogr.B 2016,1031, 99-108 ] uses the rapid filtration type purification method for dispersed solid-phase extraction, obviously improves and optimizes the QuEChERS method, and is verified on nearly hundreds of pesticides and various representative matrixes, particularly has obvious purification effect on vegetable and fruit matrixes. Compared with the classical QuEChERS method, the method has obvious advantages in the aspects of application range, interfering substance removal, matrix effect, test cost and the like. Deep human research on more complex substrates such as shallot, ginger, garlic and leek shows that the purification effect of the dispersed solid phase extraction by using the rapid filtration type purification method is obviously superior to that of the traditional solid phase material. The m-PFC column can remove phytochrome, lipid, some sugar, sterol, phenol, wax, alkaline interferent, organic acid, etc., and has dehydration function. Meanwhile, the method saves the steps of vortex and centrifugation during purification, thereby greatly shortening the purification time. At present, the method is successfully applied to the detection of pesticide residue in vegetables.
The QuEChERS method and the m-PFC method have the potential to become pretreatment methods for in-situ rapid analysis, but both the QuEChERS method and the m-PFC method require centrifugation during pretreatment. The use of centrifuges limits their application in the field of rapid in situ analysis. Therefore, it is important to develop a more convenient and faster pretreatment method.
The invention further improves and optimizes the m-PFC method, and develops a pretreatment method which has more practicability and is suitable for in-situ analysis. The method is combined with gas chromatography to verify 10 pyrethroid pesticides in vegetables. The verification results of recovery rate, linearity, matrix effect, detection limit, precision, accuracy and the like show that the method is feasible.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a method for carrying out in-situ rapid detection pretreatment on pesticide residues in vegetables and fruits, and the method for carrying out in-situ rapid detection pretreatment on the pesticide residues in the vegetables and fruits overcomes the defects that the detection pretreatment on the pesticide residues in the vegetables and fruits in the prior art needs large-scale instruments and is not suitable for in-situ detection.
The invention provides a method for carrying out in-situ rapid detection pretreatment on pesticide residues in vegetables and fruits, which comprises the following steps:
(1) a step of preparing a sample: chopping a vegetable or fruit sample, fully and uniformly mixing, directly putting into a tissue mashing machine, mashing into homogenate, and putting into a polyethylene bottle; (also shearing after removing root, or peeling, shearing skin, and directly placing into polyethylene bottle.)
(2) An extraction step: weighing 10g of a homogeneous sample, adding 20mL of acetonitrile, shaking for 2min, filtering with filter paper, collecting filtrate (the sample subjected to shearing treatment does not need to be filtered), adding an extraction salt bag and 1 ceramic proton into the filtrate, violently shaking for 1min, standing at room temperature for 1-3min, and layering the solution;
(3) a purification step: sucking 1.5mL of supernatant, passing through a filtration type purification column, purifying for the first time, and then passing through a 0.22 mu m microporous filter membrane for determination;
furthermore, in the detection process, the pretreatment sample can be smashed into homogenate, and also can be cut into pieces or skin-taking and cutting into pieces.
Furthermore, in the detection process, the homogeneous sample needs to be filtered before being added into the extraction salt bag, and the sheared sample does not need to be filtered.
Furthermore, the extraction salt package component comprises 4g of anhydrous magnesium sulfate, 1g of sodium chloride, 1g of sodium citrate and 0.5g of disodium hydrogen citrate.
Furthermore, after the extraction salt packet and 1 ceramic proton are added, solution layering can be realized by standing for 1-3min at room temperature without centrifugation.
Further, the m-PFC purification column is divided into two types, one type is suitable for a simple matrix, and the other type is suitable for a complex matrix. Different m-PFC purification columns are respectively used for the simple matrix and the complex matrix.
Further, sampling of vegetables and fruits was performed according to GB/T8855. The sample sampling site was performed as specified in GB 2763. 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; for samples which are slender, flat or have different component contents in each part, small pieces can be cut at different positions or cut into small pieces for post-treatment; cutting the obtained sample, mixing, sampling by quartering method or directly mashing in tissue mashing machine to obtain homogenate, and placing into polyethylene bottle.
Further, m-PFC columns, m-PFC purification columns (simple) applied to simple substrates, and m-PFC purification columns (complex) applied to complex substrates, are specifically classified in Table 1.
TABLE 1 LUMTECH MPFC-QuEChERS Ultrafiltration purification column comparison Table
The principle of the invention is as follows: after the acetonitrile extracting solution is filtered, anhydrous magnesium sulfate and sodium chloride are added, the layering of the solution can be quickly realized without centrifugation by utilizing the water absorption characteristic of the anhydrous magnesium sulfate, and then plant pigments, lipids, certain sugars, sterol, phenol, wax, alkaline interferents, organic acids and other substances are removed by utilizing an m-PFC column. The new method completely omits the steps of vortex and centrifugation, shortens the pretreatment time and simplifies the pretreatment steps.
The invention further improves and optimizes the QuEChERS pretreatment method. Compared with the traditional QuEChERS pretreatment method, the method utilizes a novel rapid filtration method as a purification method, and simultaneously realizes extraction of a target object by standing and natural layering after filtration to realize omission of a centrifugation step. The method is simple to operate, high in processing speed, free of other auxiliary instruments, low in reagent and material consumption and low in cost, and is very suitable for being used as a pretreatment method for on-site in-situ rapid detection. And finally, verifying the feasibility of the method by taking 10 pyrethroid pesticides as target objects and gas chromatography as a detection method.
Compared with the prior art, the invention has remarkable technical progress. The detection pretreatment method provided by the invention is simple and easy to operate, few in used instruments, high in recovery rate and good in stability, can realize extraction and purification of pesticide residues in vegetables and fruits without any auxiliary instrument, and is suitable for in-situ use on a basic site.
Drawings
FIG. 1 is a gas chromatogram of 10 pyrethroid insecticides. 1-bifenthrin, 2-fenpropathrin, 3-cyhalothrin, 4-permethrin, 5-cyhalothrin, 6-cypermethrin, 7-cyhalothrin, 8-fenvalerate, 9-cyfluthrin, 10-deltamethrin.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention will be further explained and illustrated with reference to specific examples.
Example 1
The invention relates to a method for carrying out in-situ rapid detection pretreatment on pesticide residues in vegetables and fruits, which comprises the following steps:
first, sample preparation
Chopping a vegetable or fruit sample, and directly putting the chopped vegetable or fruit sample into a tissue mashing machine to be mashed into homogenate. (also, the roots can be removed and the skin can be cut into pieces or peeled and then cut into pieces.)
Further, sampling of vegetables and fruits was performed according to GB/T8855. The sample sampling site was performed as specified in GB 2763. 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; for samples which are slender, flat or have different component contents in each part, small pieces can be cut at different positions or cut into small pieces for post-treatment; cutting the obtained sample, mixing, sampling by quartering method or directly mashing in tissue mashing machine to obtain homogenate, and placing into polyethylene bottle.
Second, extraction
10g of a homogeneous sample is weighed, 20mL of acetonitrile is added, the mixture is shaken for 2min and then filtered by filter paper, and the filtrate is collected (the cut sample does not need to be filtered). Adding the extraction salt package and 1 ceramic proton into the filtrate, shaking vigorously for 1min, and standing at room temperature for 1-3 min.
Further, the extraction salt package component consists of 4g of anhydrous magnesium sulfate, 1g of sodium chloride, 1g of sodium citrate and 0.5g of disodium hydrogen citrate.
Third, purification
Sucking 1.5mL of supernatant, purifying by a filtration type purification column (m-PFC column) for one time, and then passing through a 0.22 mu m microporous membrane to obtain a filtrate to be detected.
Fourthly, measurement
Taking 10 pyrethroid pesticides as target substances, and directly measuring the acetonitrile extraction filtrate by gas chromatography. The reference conditions are as follows.
The instrument comprises the following steps: agilent 7890A;
a chromatographic column: HP-5MS (30m 320um 0.25 um);
temperature rising procedure: the initial temperature was 100 deg.C, programmed at 25 deg.C/min to 220 deg.C, and held for 2 min. Then the temperature is programmed to 240 ℃ at a speed of 10 ℃/min and kept for 6 min. Then the temperature is programmed to 260 ℃ at 4 ℃/min and kept for 2 min. Finally, the temperature is increased to 300 ℃ by a program of 10 ℃/min and kept for 2 min;
a detector: an ECD; detector temperature: 300 ℃;
flow rate of carrier gas: n is a radical of2:1mL/min；
And (3) sample introduction mode: no shunt sampling; sample introduction amount: 1.0 uL; sample inlet temperature: at 220 ℃.
Example 2:
a fresh cucumber sample is directly put into a tissue triturator to be mashed into homogenate after being cut into pieces and put into a polyethylene bottle. Weighing 10g of sample in a 50mL plastic centrifuge tube, adding 20mL of acetonitrile, shaking for 2min, filtering with filter paper, collecting filtrate, adding an extraction salt package and 1 ceramic homogeneous proton into the filtrate, violently shaking for 1min, standing at room temperature for 1-3min, and allowing the solution to stratify. 1.5mL of supernatant was taken, purified once by an m-PFC purification column (simple), and passed through a 0.22 μm microfiltration membrane for gas chromatography.
Example 3:
fresh cucumber samples were peeled, chopped and placed directly in polyethylene bottles. Weighing 10g of cucumber peel into a 50mL plastic centrifuge tube, adding 20mL of acetonitrile, shaking for 2min, adding an extraction salt bag and 1 ceramic homogeneous proton, shaking vigorously for 1min, standing at room temperature for 1-3min, and allowing the solution to stratify. 1.5mL of supernatant was taken, purified once by an m-PFC purification column (simple), and passed through a 0.22 μm microfiltration membrane for gas chromatography.
Example 4:
a fresh green vegetable sample is removed from roots, cut up, directly put into a tissue triturator, triturated into homogenate and put into a polyethylene bottle. Weighing 10g of sample into a 50mL plastic centrifuge tube, adding 20mL of acetonitrile, shaking for 2min, filtering with filter paper, collecting filtrate, adding an extraction salt package and 1 ceramic homogeneous proton into the filtrate, violently shaking for 1min, standing for 1-3min at room temperature, absorbing 1.5mL of supernatant, purifying by a m-PFC purification column (complex) once, and filtering by a 0.22 mu m microporous membrane for gas chromatography determination.
Example 5:
a fresh green vegetable sample is cut into pieces after roots are removed, and then is directly placed into a polyethylene bottle. Weighing 10g of chopped green vegetable leaves into a 50mL plastic centrifuge tube, adding 20mL of acetonitrile, shaking for 2min, adding an extraction salt bag and 1 ceramic proton, shaking vigorously for 1min, standing at room temperature for 1-3min, absorbing 1.5mL of supernatant, purifying by a m-PFC purification column (simple) for one time, and filtering by a 0.22 mu m microporous membrane for gas chromatography determination.
According to calculation, the detection limit (LOD, S/N ═ 3) of 10 pyrethroid pesticides is between 0.0001 and 0.007mg/kg, the quantitative limit (LOQ, S/N ═ 10) is between 0.0002 and 0.02, the recovery rate of 10 pyrethroid pesticides is better (70 to 120 percent), and the RSD is between 0.7 and 9.9 percent. The results show that this pretreatment method is feasible.
TABLE 2.4 measurement results of examples
Example 6:
cucumber and green vegetables are selected as substrates, 10 pyrethroid pesticide standard substances with the amount of 0.1mg/kg are added, 10 pyrethroid pesticide residues are measured after the treatment is respectively carried out according to the method, the national standard GB 3200.113-2018 and the standard NY/T761-2008, and the results are shown in Table 3.
As can be seen from Table 3, for simple substrates, the recovery rate of the rapid detection method ranges from 84% to 94%, the recovery rate of the NY/T761-2008 and the recovery rate of the GB 3200.113-2018 standard method respectively ranges from 87% to 94% and from 88% to 98%, and the RSD is less than 5%; for complex substrates, the recovery rate range of the rapid detection method is 71-111%, the recovery rate ranges of the NY/T761-2008 and GB 3200.113-2018 standard methods are 82-106% and 74-100%, the RSD is less than 10%, and the actual detection requirements are met. The recovery rate difference of the 3 methods is small, and the accuracy is basically consistent. However, compared with the NY/T761-2008 and GB23200.113 standard methods, the rapid detection method does not need other auxiliary instruments, the pretreatment time can be controlled within 10min, and the method is more convenient and shorter in use time than the standard methods. Therefore, the quick detection method can accurately realize the pretreatment of extraction and purification of 10 pyrethroid pesticides in vegetables in a short time.
Table 310 pyrethroid pesticide residue detection methods comparison (n ═ 6)
Claims (6)
1. A method for carrying out in-situ rapid detection pretreatment on pesticide residues in vegetables and fruits is characterized by comprising the following steps:
(1) a step of preparing a sample: chopping a vegetable or fruit sample, fully and uniformly mixing, directly putting into a tissue mashing machine, mashing into homogenate, and putting into a polyethylene bottle; or cutting into pieces after removing root or peeling, and placing into polyethylene bottle;
(2) an extraction step: weighing 10g of a homogeneous sample, adding 20mL of acetonitrile, shaking for 2min, filtering with filter paper, and collecting filtrate; adding extraction salt bag and homogenizer into the filtrate, shaking vigorously for 1min, standing at room temperature for 1-3min, and layering the solution;
(3) a purification step: 1.5mL of the supernatant was taken through a filtration column, purified once and then passed through a 0.22 μm microfiltration membrane for measurement.
2. The method as claimed in claim 1, wherein the pre-treated sample is crushed into homogenate, or cut into pieces or peeled and cut into pieces during the detection process.
3. The method as claimed in claim 1, wherein the pre-treatment of vegetables and fruits for in-situ rapid detection comprises filtering the homogenized sample before adding the extraction salt bag, and filtering the cut sample.
4. The method for the in-situ rapid detection pretreatment of pesticide residues in vegetables and fruits according to claim 1, wherein the extraction salt package component comprises 4g of anhydrous magnesium sulfate, 1g of sodium chloride, 1g of sodium citrate and 0.5g of disodium hydrogen citrate.
5. The method for the in-situ rapid detection pretreatment of pesticide residues in vegetables and fruits according to claim 1, wherein the extraction salt package and 1 ceramic homogenous proton are added, and then the mixture is left standing at room temperature for 1-3min without centrifugation.
6. The method for the in-situ rapid detection pretreatment of pesticide residues in vegetables and fruits according to claim 1, wherein the sampling amount of vegetables and fruits is performed according to GB/T8855, and the sampling position of the samples is performed according to GB 2763.
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| CN202111253143 | 2021-10-27 | ||
| CN202111253143X | 2021-10-27 |
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