CN114965799A - Method for rapidly determining residual quantity of various pesticides in food - Google Patents
Method for rapidly determining residual quantity of various pesticides in food Download PDFInfo
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- CN114965799A CN114965799A CN202210919954.7A CN202210919954A CN114965799A CN 114965799 A CN114965799 A CN 114965799A CN 202210919954 A CN202210919954 A CN 202210919954A CN 114965799 A CN114965799 A CN 114965799A
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- G—PHYSICS
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- 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
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- 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
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- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
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Abstract
The invention belongs to the field of pesticide residue analysis methods, and particularly relates to a method for rapidly determining residual quantities of various pesticides in food. The method can effectively avoid various interferences and matrix effects of sample introduction in the sample, has the characteristics of accurate quantification, simple and rapid operation, small solvent consumption, sensitivity and the like, and belongs to an environment-friendly green chemical analysis method.
Description
Technical Field
The invention belongs to the field of pesticide residue analysis methods, and particularly relates to a method for rapidly determining various pesticide residues in food.
Background
The GC-MSMS has the advantages of high analysis speed, high selectivity, low detection limit and the like, is gradually an effective tool for people to detect the pesticide residue, and a GC-MSMS pesticide residue detection standard method is correspondingly proposed in many countries. However, the accuracy of the result is greatly influenced by the existence of matrix effect in the detection, and the analysis value is often deviated from the true value. The matrix effect in GC-MSMS detection is mainly caused by interaction of various chemical bonds of pesticides with a sample matrix and the surface of a glass liner tube at a sample inlet. This phenomenon cannot be eradicated and only various methods have been used to reduce the matrix effect.
The commonly used matrix effect compensation methods are: the substrate purification is matched with an isotope labeling method, a substrate matching calibration method, an analysis protective agent method and the like.
The matrix purification is usually performed by adopting a solid phase extraction method, a Quechers method and the like after extraction, so that the pesticide and matrix components can be separated to different degrees, the detection equipment can be greatly protected by purifying the matrix for many times, but the detection cost is increased and the recovery rate of some pesticides is reduced due to excessive purification steps. Isotope internal standard method is most effective in application, but is very expensive in multi-residue analysis, and is not suitable for detecting various pesticide residues. The matrix matching calibration method is adopted by most standard methods at home and abroad, but has the defects that matrix matching needs to be carried out on each sample matrix, different matrixes cannot be mixed, pure negative matrixes are difficult to obtain, and a lot of workload is additionally added for experiments with multiple matrix types. The analysis protectant method is a compromise method of a matrix matching method, wherein a special high-polarity compound is mixed into a sample extract and a calibration solution and interacts with a system active site to improve the response value of a pesticide standard substance in a solvent to the maximum extent so as to enable the response value to reach a response value similar to that of the matrix matching method, and the method is capable of screening and analyzing pesticide residues in samples of different matrix types by using a standard substance prepared by a pure solvent and is inferior to the matrix matching method in quantitative accuracy.
Disclosure of Invention
The invention aims to provide a method for rapidly determining the residual quantity of various pesticides in food, which overcomes the problems in the prior art and can rapidly and accurately determine the residual quantity of various pesticides in food in a short time.
In order to achieve the purpose, the technical route of the invention is as follows: after the sample is extracted, the ultracentrifugation method is adopted to remove the macromolecular protein, waxy esters and other impurity components in the matrix, effectively extract the pesticide components, avoid using various purification fillers in the conventional purification method to reduce the cost and simultaneously avoid the loss of the pesticide; and then, three-section sample injection is adopted, so that the mixed matrix is interacted with the active site of the system before pesticide, more pesticide components are ensured to enter a chromatographic column and a detector, the purposes of improving sensitivity and accurately quantifying are achieved, and the maintenance cost and the maintenance frequency of the instrument are reduced.
The technical scheme for solving the technical problems comprises the following steps:
(1) purifying an extracting solution: 5-15 g of sample is subjected to oscillation extraction by using 10-30 ml of 0.1-1.0% acetonitrile acetate solution, 0.4-1.2 g of anhydrous magnesium sulfate and 0.1-0.3 g of anhydrous sodium acetate are mixed to extract salt, the salt is subjected to oscillation layering to obtain an extracting solution, and the extracting solution is subjected to ultracentrifugation at the rotating speed of 10-15 ten thousand revolutions per minute for 3-5 minutes to obtain an ultraclean extracting solution.
After the pesticide components in the sample are extracted, the sample is tested on a machine without purification treatment, the co-extract can aggravate the pollution of a precision instrument and increase the maintenance cost of the precision instrument, meanwhile, the co-extract can introduce more matrix effects to distort the quantitative result, and the conventional method adopts various fillers or solid-phase extraction columns for purification. When the rotating speed of the centrifuge rotor is more than 10 ten thousand revolutions per minute, the maximum centrifugal force is 70 ten thousand times of the ordinary centrifugal force, and some impurities such as macromolecular protein, waxy esters and the like can overcome the defects of diffusion and sedimentation. Various purification fillers and extraction columns in the conventional purification method are not needed, the effect of separating pesticide components from impurities is achieved, meanwhile, the pesticide loss and the cost increase are avoided, and the lower quantitative limit of 0.001-0.005 mg per kilogram is reached.
(2) Three-stage sample injection standard substance: combining 6 negative matrixes of spinach, ginger, apple, cucumber, wheat and white radish in equal proportion, mixing the mixed negative matrixes with a standard substance mixture with a certain concentration, and mixing the negative matrixes with the standard substance mixture according to the weight ratio of 1: 3, absorbing according to a volume ratio, isolating the middle by using 0.1 microliter of air, carrying out sample injection successively in layers, using a solvent emptying mode and a temperature programming mode at an injection port, carrying out GC-MSMS detection, respectively obtaining an instrument response value, and taking the concentration and the area as a calibration curve. The 6 negative matrixes are combined in equal proportion, the quantitative results of the 6 negative matrixes are consistent with the quantitative results of 27 single matrixes on 186 pesticides, the relative errors of the quantitative results are less than 5%, the recovery rate of the simulated standard sample is 89.5% -103.6%, the mixed matrix can be used as a universal matrix to replace 27 single matrixes and pesticide mixed standards or samples to be fed in a three-stage mode respectively, and the quantitative detection requirements are met. Wherein the 27 kinds of substrates comprise spinach, woad, green stem vegetable, leek, root mustard, cauliflower, ginger, white radish, taro, carrot, potato, Chinese yam, burdock, green Chinese onion, vegetable pepper, pumpkin, green sword bean, tomato, sweet pea, cucumber, wheat, corn, apple, strawberry, blueberry and peach.
(3) Three-stage sample introduction test sample: treating a sample to be detected according to the step (1), and mixing 6 mixed negative matrixes and the sample to be detected according to the proportion of 1: 3, absorbing by volume ratio, isolating by 0.1 microliter of air in the middle, injecting samples successively in layers, measuring the response area of the target by using a solvent emptying and temperature programming mode at an injection port, and calculating a corresponding measured value by using the calibration curve obtained in the step (2).
The matrix or the analysis protective agent and the standard substance are uniformly mixed and then are subjected to sample injection, the chances of adsorption of the matrix or the analysis protective agent and the standard substance with active sites of a system are equal, the three-stage sample injection is to inject the matrix into a sample injection port before the standard substance and preferentially act on the active sites of the system, an air layer plays a role in isolating the matrix layer from a standard substance layer, the active sites are prevented from being simultaneously adsorbed with the matrix or the analysis protective agent and the standard substance, and the sensitivity and the accuracy of a target object are effectively improved. Within the concentration range of 1.0-100.0 nanograms per milliliter, the linear correlation coefficients R2 of the obtained 186 pesticides are all larger than 0.997, and are superior to matrix matching standard curves respectively made for different matrix types in the traditional method, so that the working intensity is greatly reduced, and the labor and the detection cost are saved while the quantification is accurate.
In conclusion, the beneficial effects of the invention are as follows: the ultracentrifugation technology is applied to the field of pesticide residue detection, so that the pretreatment of the sample is simple, the purification effect is superior to that of the traditional method, and the loss of a target object is avoided; the three-stage sample introduction mode of 'mixed matrix + air + standard sample or test sample' is adopted, various interferences and matrix effects in the sample are effectively avoided, complicated steps of respectively preparing matrix matching standard products by different matrixes, adding analysis protective agents and the like in the traditional method are avoided, 186 pesticide residues in 27 samples such as spinach and the like can be accurately quantified simultaneously, the simulated addition recovery rate reaches 89.5% -103.6%, the relative standard deviation of parallel samples is less than 11.5%, and the method has the characteristics of accurate quantification, high robustness, simplicity and quickness in operation, small solvent consumption, sensitivity and the like, and belongs to an environment-friendly green chemical analysis method.
Detailed Description
The following description is made in conjunction with the principles and features of the present invention, the examples of which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
According to the invention, 6 negative samples of spinach, ginger, apple, cucumber, wheat and white radish are extracted, ultracentrifuged and mixed in equal proportion to obtain a negative matrix extracting solution for later use.
Preparing 186 pesticide mixed standard products by using chromatographic pure acetonitrile for later use, injecting samples in a mode of 1 microliter of the mixed negative matrix, 0.1 microliter of air and 3 microliter of pesticide mixed standard products, using a solvent emptying and temperature programming mode for an injection port, detecting by GC-MSMS, and making a calibration curve according to the concentration and the response area of each pesticide for sample detection and quantification.
The following examples further illustrate the invention using a sample to simulate the manner in which pesticides are added.
Taking negative kohlrabi, strawberry and rice samples, homogenizing and crushing uniformly, adding 3 mixed standards with different concentrations into the kohlrabi, strawberry and rice samples respectively, wherein the adding concentrations are 5 micrograms per kilogram, 10 micrograms per kilogram and 50 micrograms per kilogram, and freezing and storing in a refrigerator at the temperature of 18 ℃ below zero for later use.
Example 1
And taking the kohlrabi sample subjected to simulated labeling, and detecting the content of pesticide residue in the kohlrabi sample.
(1) Respectively weighing 10.0 g of kohlrabi sample into a 50 ml plastic centrifuge tube, repeating each content level for 10 times, adding 20 ml of 1.0% acetic acid acetonitrile, fully and uniformly mixing in a vortex manner, adding 4 g and 1 g of anhydrous magnesium sulfate and anhydrous sodium acetate respectively, after violent oscillation and standing for layering, transferring the supernatant into a 2 ml centrifuge tube, and centrifuging for 3min at the rotating speed of 10-15 million revolutions per minute on an ultracentrifuge to obtain the ultra-clean extract of the sample.
(2) The method comprises the steps of adopting a mode of '1 microliter of 6 mixed negative matrixes +0.1 microliter of air +3 microliter of sample ultra-clean extracting solution' for sample injection, detecting by GC-MSMS, comparing the detected result of 186 pesticides with the theoretical addition amount, and specifically showing in table 1 that the recovery rate is 89.6-103.5%, and the relative standard deviation of 10 parallel detection samples of each addition concentration is less than 11.2%.
Example 2
The above mock-scaled strawberry and rice samples were taken and the experiment was repeated according to the same procedure as described in example 1, the weight of the strawberry sample was increased to 15 g, the weight of the rice sample was reduced to 5 g, the amount of 1.0% acetonitrile acetate was adjusted to 30 ml, and the mass of the anhydrous magnesium sulfate and anhydrous sodium acetate added was increased to 6 g and 1.5 g, respectively. Compared with the theoretical addition amount, the recovery rate of 186 pesticide residues obtained by GC-MSMS detection is 89.5-103.6%, and the relative standard deviation of 10 parallel detection samples of each addition concentration is less than 11.5%.
The average recovery and relative standard deviation RSD of the 186 pesticide residue contents obtained in the above 2 examples are shown in table 1.
Table 1 recovery and relative standard deviation of simulated addition of 186 pesticides in food (n = 10)
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A method for rapidly determining the residual quantity of various pesticides in food is characterized by comprising the following steps:
(1) purifying an extracting solution: extracting a sample by using acetic acid acetonitrile, adding anhydrous magnesium sulfate and anhydrous sodium acetate extraction salt, oscillating and layering, and ultracentrifuging supernate to obtain an ultraclean extracting solution;
(2) three-stage sample injection standard substance: 6 mixed negative matrices and a gradient concentration standard mixture were used, according to 1: 3, respectively absorbing the volume ratio, isolating the middle by using 0.1 microliter of air, successively injecting samples in layers, detecting by GC-MSMS, and fitting a calibration curve by area and concentration;
(3) three-stage sample introduction test sample: the negative matrix and test sample were mixed using 6 types of media according to 1: 3, respectively absorbing the components in a volume ratio, isolating the middle by using 0.1 microliter of air, successively injecting samples in layers, detecting by GC-MSMS (gas chromatography-metal mass spectrometry), and accurately quantifying by combining a calibration curve.
2. The method for rapidly determining the residual quantity of various pesticides in food according to claim 1, wherein the ultracentrifugation is performed at a rotation speed of 10 to 15 ten thousand rpm for 3 to 5 minutes.
3. The method as claimed in claim 1, wherein the 6 kinds of mixed negative substrates are 6 kinds of mixed negative substrates obtained by subjecting 6 kinds of samples without pesticide residue, such as spinach, ginger, apple, cucumber, wheat and white radish, to respective extractive solutions, ultracentrifugation and purification to obtain 6 kinds of ultra-clean extractive solutions, and mixing the 6 kinds of ultra-clean extractive solutions at equal ratio.
4. The method for rapidly determining the residual quantity of various pesticides in food according to claim 1, wherein in the three-stage sample injection standard substance, a sample injection needle sucks 6 mixed negative matrixes with 3 microliters of gradient concentration standard substance mixture, 0.1 microliter of air and 1 microliter of gradient concentration standard substance mixture in sequence; the sequence of the inlet to the instrument was 1. mu.l of 6 mixed negative matrices, 0.1. mu.l of air, 3. mu.l of a graded concentration mixture of the standard.
5. The method for rapidly determining the residual quantity of various pesticides in food according to claim 1, wherein in the three-stage sample injection test sample, a sample injection needle sucks 6 mixed negative matrixes of 3 microliters of test sample, 0.1 microliter of air and 1 microliter of sample injection needle in sequence; the sequence of entry into the instrument was 1. mu.l of 6 mixed negative matrices, 0.1. mu.l of air, and 3. mu.l of assay sample.
6. The method for rapidly determining the residual amount of various pesticides in food according to any one of claims 1 to 5, which is applied to quantitative determination of 186 pesticides in 27 plant-derived foods such as spinach, woad, caulis et folium Brassicae Capitatae, leek, kohlrabi, cauliflower, ginger, radish, taro, carrot, potato, yam, burdock, welsh onion, bell pepper, pumpkin, green sword bean, tomato, sweet pea, cucumber, wheat, corn, apple, strawberry, blueberry and peach.
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Cited By (1)
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| CN116660425A (en) * | 2023-07-18 | 2023-08-29 | 山东杰诺检测服务有限公司 | Method for rapidly determining various pesticide residues in fruits and vegetables and application thereof |
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