CN116660425B - Method for rapidly determining various pesticide residues in fruits and vegetables and application thereof - Google Patents
Method for rapidly determining various pesticide residues in fruits and vegetables and application thereof Download PDFInfo
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Classifications
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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
- 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
- G01N30/60—Construction of the column
- G01N30/6034—Construction of the column joining multiple columns
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention belongs to the technical field of food detection methods, and relates to a method for rapidly determining various pesticide residues in fruits and vegetables and application thereof, wherein the method comprises the steps of (1) extracting a sample; (2) immersion solid phase microextraction; (3) micro negative pressure combined chromatography. The invention combines solid phase microextraction with micro negative pressure combined chromatographic column and is applied to fruit and vegetable pesticide residue detection; for 280 pesticides in 30 fruits and vegetables, after a sample is subjected to extraction and high-speed centrifugation by a small amount of extracting solution, the sample is automatically enriched by adopting immersed solid-phase microextraction, an instrument sample inlet is subjected to high-temperature analysis, a micro negative pressure combined chromatographic column is subjected to quick separation detection within 7 minutes, the quantitative limit of the method is 1.0 microgram per kilogram, the simulated addition recovery rate reaches 91.3% -106.5%, the relative standard deviation of parallel samples is less than or equal to 8.9%, the sensitivity is high, the quantitative accuracy and the durability are high, the robustness is high, the reagent consumption is low, the generated waste liquid and waste are less, and the cost is low, so that the method is an environment-friendly green chemical analysis method.
Description
Technical Field
The invention belongs to the technical field of food detection methods, and particularly relates to a method for rapidly determining various pesticide residues in fruits and vegetables and application thereof.
Background
The existing pesticide residue detection standard method has different operation steps: after the sample is extracted by various reagents, the sample is purified by various solid phase extraction columns or matrix dispersion solid phase extraction materials, and the purified liquid is concentrated or replaced by a solvent and then is injected into a detection instrument for qualitative and quantitative determination. The method has the advantages of more operation steps, large consumption of reagent consumables, more waste liquid and waste, large waste treatment consumption, high environmental pressure, higher cost of manpower and material resources consumption and no compliance with the concept of low-carbon economic sustainable development.
With the development of scientific instruments and techniques, nondestructive detection of multiple residues becomes possible, and qualitative and semi-quantitative ultra-rapid screening of pesticide residues in samples can be performed by only a few milligrams of samples and tens of microliters of organic solvents. The technology is still in the research stage, and the method accuracy, reliability and matrix representativeness still need to be further studied. At present, the gas chromatography-mass spectrometry/mass spectrometry (GC-MS/MS method) has the advantages of high selectivity, high accuracy and the like, and is still a necessary tool for detecting pesticide residues. In particular, in order to improve the column efficiency and ensure the separation effect, the temperature programming is generally adopted, more than hundred pesticides are generally separated into a plurality of groups for sample injection analysis during simultaneous analysis, or the temperature gradient is slowed down to improve the separation degree, and the time for collecting data through instrument analysis is still longer. The research of the rapid gas chromatographic analysis is not to improve the temperature rising speed, shorten the length of the chromatographic column, reduce the inner diameter of the chromatographic column and the like, but is not beneficial to the multi-component separation analysis. The recommended chromatographic column inner diameter of all the existing commercial gas chromatographic mass spectrometers is generally 0.1-0.25 mm, and the maximum is not more than 0.32 mm, because the chromatographic column with the too large inner diameter has an influence on a vacuum system, the vacuum degree of a vacuum cavity is reduced, the ion transmission efficiency is reduced, the ion reaction and high-voltage discharge are increased, the spectrum information is complicated, the sensitivity of the instrument is reduced, the service life of internal vacuum components is prolonged, and the mass spectrometry analysis is not facilitated.
Common solid phase microextraction modes include immersion solid phase microextraction and headspace solid phase microextraction. The headspace solid-phase microextraction method is mainly used for analyzing volatile or semi-volatile aroma substances or peculiar smell components, and has poor extraction effect on substances which are difficult to volatilize. Immersion solid phase microextraction is a process in which quartz fibers coated with an extraction stationary phase are inserted directly into a sample matrix, and target components are transferred directly from the sample matrix into the extraction stationary phase. However, due to compatibility of the extracted fiber material and the solvent, the service life and the range of the extraction head are limited, and the extraction head is only used for analyzing some substances in a sample diluted by water and more than 10 times of water or analyzing the residue of a certain type of medicine. The research of self-made extraction fiber heads is relatively more, but the commercial finished product types are very few due to the limitations of process maturity, stability, durability, applicability and the like of the extraction adsorbent, and the commercial solid-phase extraction fiber materials on the market at present mainly comprise Polydimethylsiloxane (PDMS), polyacrylate (PA), polydimethylsiloxane/polydivinylbenzene (PDMS/DVB), polydivinylbenzene/wide-range activated carbon/polydimethylsiloxane (DVB/carbon WR/PDMS).
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for rapidly determining various pesticide residues in fruits and vegetables and application thereof, which greatly reduces the usage amount of reagents, reduces wastes, is more friendly to people and environment, and rapidly and accurately determines 280 pesticide residues in fruits and vegetables within 7 minutes, and the specific technical scheme is as follows:
a method for rapidly determining various pesticide residues in fruits and vegetables comprises the following steps:
(1) And (3) extracting a sample: adding the extracting solution into a sample for vortex extraction, and centrifuging at a rotating speed of 5-8 ten thousand revolutions per minute to obtain a clarified extracting solution;
(2) Immersion solid phase microextraction: transferring 2 ml of the clarified extract obtained in the step (1) into a 10 ml headspace bottle, aging for 3-5 minutes under the protection of nitrogen at 230-260 ℃ in the extraction and sample injection procedures, cooling for 2-5 minutes at room temperature, fully soaking an extraction fiber head below the liquid level, extracting and enriching, wherein the extraction temperature is 55-65 ℃, the stirring speed is 200-450 revolutions per minute, the extraction time is 15-30 minutes, and the sample injection port is 220-250 ℃ for 3-5 minutes;
(3) Micro negative pressure combined chromatographic analysis: combining three sections of chromatographic columns with different inner diameter specifications, wherein the chromatographic columns comprise a column I without a coating film, a column II without a coating film and a column III with an inner wall coated with 5% phenyl/polydimethylsiloxane stationary phase coating to play a main separation role; a back-blowing gas controller is added between the first column and the second column, and the third column is communicated into the mass spectrum vacuum cavity; setting configuration parameters of the first column and the second column, wherein the third column is not set at all; the temperature programming condition of the column temperature box is that the temperature is kept at 60-70 ℃ for 0.5-1 min, and then the temperature is raised to 310-320 ℃ per min at 50-60 ℃ for 1-2 min.
After a small amount of extracting solution is extracted from the sample, 5-8 ten thousand revolutions per minute of ultracentrifugation is adopted to thoroughly separate the extracting solution from solid impurities, meanwhile, some macromolecular proteins, waxy esters and other impurities can overcome centrifugal sedimentation generated by diffusion, and on the basis of more extracted target substances, less co-extracted impurity components are introduced, so that 280 compounds can have recovery rate of more than 91.3%; and various purifying fillers in the conventional purifying method are avoided, so that the cost is reduced.
The invention adopts immersion solid phase microextraction, and the types and the quantity of the adopted immersion extracted target species are obviously more than those of a headspace type; compared with a liquid direct sample injection method, the solid-phase microextraction method is 5-10 times higher in the absolute response area and the signal-to-noise ratio of 280 pesticides, so that the lower relative matrix sample injection amount of the solid-phase microextraction method can meet the requirement of limiting quantity, the lower sample injection amount means that the matrix effect can be reduced, the service life of the chromatographic column is prolonged, the frequent cutting of the chromatographic column is not needed to keep peak shape and sensitivity, the maintenance frequency of an instrument sample injection port, an ion source and the like is reduced, and the running cost is saved. The extraction temperature, the extraction time and the stirring rate adopted by the invention can further improve the recovery efficiency and the recovery stability of the target analyte.
In the micro negative pressure combined chromatographic analysis, three sections of chromatographic columns with different inner diameter specifications are connected, a back-blowing gas controller is added between the first column and the second column, and the specifications of the two chromatographic columns are only correctly configured when an instrument is matched, so that the flow and pressure limiting effect is achieved, and instrument software and the controller accurately and stably control the carrier gas flow rate and pressure at the front end of the chromatographic column; the third column is not matched with the instrument software, and any setting of the third column cannot be seen in the instrument configuration, so that the invisible effect is achieved. The third column is communicated into the vacuum cavity of the mass spectrum to provide micro negative pressure in the third column, so that the third column becomes a part of the vacuum cavity, the viscosity of carrier gas is reduced, the vapor pressure of analytes is also reduced, chromatographic peak separation is accelerated, and compared with the traditional chromatographic column, the peak width of each analyte is reduced from 5-8 seconds to 2-3 seconds, the peak shape is sharper, and the signal to noise ratio is higher. The speed is improved by at least 4 times under the condition of not changing the instrument, so that the ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry method can be achieved at the same time level, the quality of the result is improved, and the robustness is greatly enhanced.
Further, the extracting solution is a uniformly mixed solution of acetonitrile, methanol, isopropanol, deionized water and the like in proportion.
Acetonitrile and hydroenergy are mixed in arbitrary proportion, and its penetrability is extremely strong, can permeate to the inside of tissue cell, and can salt out from water when the salt of certain concentration exists to extract the residual medicine in the food, in the detection field of medicine residue in the food, be the best choice, can have better extraction efficiency to most compounds. However, for some polar compounds with strong water solubility, the extraction efficiency is lower, the polar compounds are more lost in the salting-out process, the addition of methanol and water with stronger polarity can improve the extraction efficiency of the polar compounds, the isopropanol can be mutually dissolved with other solvents to play a transitional role, the salting-out layering of the mixed extract can not be caused even if the salt of the food exists, and the target substances can be uniformly distributed in the mixed solvent, so that more compounds can be better dissolved and extracted.
Further, the sample is 1.0-2.0 g, and the extracting solution is 2-10 ml.
Further, in the step (2), the extraction fiber head is selected from composite polydivinylbenzene/activated carbon/polydimethylsiloxane (DVB/carbon WR/PDMS). Of the 4 commercial extraction fiber heads, DVB/carbon WR/PDMS fibers gave the best extraction results.
Further, the film thickness of the extraction fiber head was 120 micrometers, and the fiber head was 10 millimeters long.
Further, the column is 1 m long and 0.25 mm in inner diameter; column two is 5 m long, and the inner diameter is 0.1 mm; the three columns were 15 m long with an inner diameter of 0.53 mm and an inner wall coating of 1 micron.
The detector in gas chromatography, almost all forms of mass spectrometry require a vacuum system, and all existing GC-MS/MS instruments and software-inherent electronic pressure control systems (EPC) are required to compensate the vacuum of the detector according to the type of carrier gas, the inside diameter of the column, the film thickness, the vacuum outlet conditions, etc., so that the carrier gas flow rate and pressure can be accurately controlled. Therefore, the inner diameter of the chromatographic column recommended by all the existing GC-MS/MS instruments is 0.1-0.25 mm and is not more than 0.32 mm, and because the use of the large-caliber capillary column combined with the vacuum outlet can increase the pressure in the ion source of the MS system to a level exceeding the allowable limit, the vacuum system is influenced, the vacuum degree of the vacuum cavity is reduced, so that the ion transmission efficiency is reduced, the molecular ion reaction and high-voltage discharge are increased, the spectrum information is complicated, the sensitivity of the instrument is reduced, the service life of internal vacuum components is prolonged, and the like, so that the mass spectrometry is not facilitated.
The invention connects 3 sections of chromatographic columns with different inner diameter specifications, wherein the inner diameter of the column I is 0.25 millimeter, the inner diameter of the column II is 0.1 millimeter, and the invention better plays the role of limiting flow and pressure, so that the instrument software and the controller can more accurately and stably control the flow rate and pressure of the carrier gas at the front end of the chromatographic column. The three inner diameters of the column are 0.53 mm, and the column is not matched with instrument software, so that a stealth effect is achieved, and the quality of results and the robustness can be improved.
The invention also provides an application of the method for rapidly determining the residual quantity of various pesticides in fruits and vegetables in quantitative determination of 280 pesticides in 30 fruits and vegetables, namely white radish, spinach, green pepper, strawberry, green onion, kohlrabi, tomato, carrot, cauliflower, cucumber, leek, blueberry, potato, pumpkin, burdock, oyster mushroom, apple, green sword bean, green stem vegetable, chinese yam, fruit corn, chinese cabbage, peach, melon, sweet pea, potato, lettuce, watermelon, taro and onion.
The beneficial effects of the invention are as follows:
the method combines solid-phase micro-extraction with micro-negative pressure combined chromatographic column, is applied to detection of pesticide residues in fruits and vegetables, and aims at 280 pesticides in 30 fruits and vegetables, after a sample is subjected to extraction and high-speed centrifugation by a small amount of extracting solution, the sample is automatically enriched by adopting immersed solid-phase micro-extraction, and is subjected to high-temperature analysis by an instrument sample inlet, the micro-negative pressure combined chromatographic column is subjected to quick separation detection within 7 minutes, the quantitative limit of the method is 1.0 microgram per kilogram, the simulated addition recovery rate reaches 91.3% -106.5%, the relative standard deviation of parallel samples is less than or equal to 8.9%, the sensitivity is high, the quantitative accuracy and the durability are high, the robustness is high, the reagent consumption is low, the generated waste liquid and waste are few, the cost is low, and the method belongs to an environment-friendly green chemical analysis method.
Detailed Description
The principles and features of the present invention are described below in connection with examples, which are set forth only to illustrate the present invention and not to limit the scope of the invention.
The following examples are further illustrated using samples to simulate the addition of pesticides.
Taking negative spinach, oyster mushroom and watermelon samples, homogenizing and crushing uniformly, respectively adding 3 mixed markers with different concentrations into the spinach, oyster mushroom and watermelon samples, adding 1 microgram per kilogram, 2 micrograms per kilogram and 10 micrograms per kilogram, and freezing and storing in a refrigerator at-18 ℃ for later use.
Example 1:
a method for rapidly determining various pesticide residues in spinach takes the spinach subjected to simulated labeling as a sample, and comprises the following steps:
(1) And (3) extracting a sample: adding 2.0 g of the spinach sample subjected to the simulation and standard addition, adding 10.0 ml of extracting solution prepared by mixing acetonitrile, methanol, isopropanol, deionized water and the like in proportion, carrying out vortex extraction for 2 minutes, and then centrifuging at a rotating speed of 5 ten thousand-8 ten thousand rpm for Zhong Chaosu minutes for 2 minutes to obtain clarified extracting solution;
(2) Immersion solid phase microextraction: transferring 2.0 ml of the clarified extract obtained in the step (1) into a 10 ml headspace bottle, selecting composite polydivinylbenzene/activated carbon/polydimethylsiloxane (DVB/carbon WR/PDMS, film thickness 120 microns, fiber head length 10 mm), extracting the fiber head, setting an extraction and sample injection program, aging for 5 minutes under the protection of nitrogen at 260 ℃, cooling for 2 minutes at room temperature, fully soaking the extracted fiber head below the liquid level, extracting and enriching, wherein the extraction temperature is 65 ℃, the stirring speed is 350 revolutions per minute, the extraction time is 15 minutes, and the sample injection port is used for analyzing for 3 minutes at 250 ℃;
(3) Micro negative pressure combined chromatographic analysis: combining 3 sections of chromatographic columns with different specifications, wherein the column is 1 m long and 0.25 mm in inner diameter, and no coating film exists; column two is 5 m long, the inner diameter is 0.1 mm, and no coating film exists; the column was 15 m long with an inner diameter of 0.53 mm and an inner wall coating of 1 micron of 5% phenyl/polydimethylsiloxane stationary phase. The temperature programming conditions of the column temperature box are as follows: the temperature was kept at 60℃for 1 minute, and then at 50℃per minute to 310℃for 1 minute. The GC-MS/MS dynamic retention time multi-reaction monitoring mode is characterized in that the measured 280 pesticide detection results are compared with the theoretical addition amount, the detailed table 1 is shown, the recovery rate is 91.3% -106.5%, and the relative standard deviation of 8 parallel detection samples with each addition concentration is less than or equal to 8.9%.
Example 2:
a method for rapidly determining various pesticide residues in oyster mushrooms, which takes the oyster mushrooms subjected to simulated labeling as a sample, comprises the following steps:
(1) And (3) extracting a sample: adding 2.0 g of the oyster mushroom sample subjected to the simulation and standard addition, adding 10.0 ml of extracting solution prepared by mixing acetonitrile, methanol, isopropanol and deionized water in equal proportion, performing vortex extraction for 2 minutes, and then performing centrifugation at Zhong Chaosu per minute at a rotating speed of 5 ten thousand-8 ten thousand revolutions for 2 minutes to obtain clarified extracting solution;
(2) The procedure of the immersion solid phase microextraction and (3) the micro negative pressure combined chromatography is the same as in example 1, and will not be repeated here. The measured 280 pesticides are compared with the theoretical addition amount, the detailed table 1 shows that the recovery rate is 92.4% -105.7%, and the relative standard deviation of 8 parallel detection samples with each addition concentration is less than or equal to 7.5%.
Example 3:
a method for rapidly measuring various pesticide residues in watermelons, taking the watermelons subjected to simulated and standard addition as a sample, comprises the following steps:
(1) And (3) extracting a sample: 1.0 g of the simulated standard-added watermelon sample is added with 2.0 ml of extracting solution mixed by acetonitrile, methanol, isopropanol, deionized water and the like in proportion, vortex-extracted for 2 minutes, and then centrifuged for 2 minutes at a speed of 5 ten thousand-8 ten thousand rpm for Zhong Chaosu, so as to obtain clarified extracting solution;
(2) The procedure of the immersion solid phase microextraction and (3) the micro negative pressure combined chromatography is the same as in example 1, and will not be repeated here. The detected 280 pesticides are compared with the theoretical addition amount, the detailed table 1 shows that the recovery rate is 95.7% -104.7%, and the relative standard deviation of parallel samples is less than or equal to 8.4%.
Table 1 simulated addition recovery and relative standard deviation (n=8) of 280 pesticides in fruit and vegetable
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By adopting the measuring method, 280 pesticides in 27 fruits and vegetables including white radish, green pepper, strawberry, green onion, kohlrabi, tomato, carrot, cauliflower, cucumber, leek, blueberry, potato, pumpkin, burdock, apple, green sword bean, green stem vegetable, yam, fruit corn, woad, peach, melon, sweet pea, potato, lettuce, taro and onion are detected, the simulated addition recovery rate reaches 91.3% -106.5%, and the relative standard deviation of parallel samples is less than or equal to 8.9%.
In conclusion, the measuring method has the advantages of high sensitivity, accurate quantification, high durability and robustness, less reagent consumption, less waste liquid and waste, and low cost, and belongs to an environment-friendly green chemical analysis method.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (6)
1. The method for rapidly determining the various pesticide residues in the fruits and the vegetables is characterized by comprising the following steps:
(1) And (3) extracting a sample: adding the extracting solution into a sample for vortex extraction, and centrifuging at a rotating speed of 5-8 ten thousand revolutions per minute to obtain a clarified extracting solution;
(2) Immersion solid phase microextraction: transferring 2 ml of the clarified extract obtained in the step (1) into a 10 ml headspace bottle, aging for 3-5 minutes under the protection of nitrogen at 230-260 ℃ in the extraction and sample injection procedures, cooling for 2-5 minutes at room temperature, fully soaking an extraction fiber head below the liquid level, extracting and enriching, wherein the extraction temperature is 55-65 ℃, the stirring speed is 200-450 revolutions per minute, the extraction time is 15-30 minutes, and the sample injection port is 220-250 ℃ for 3-5 minutes;
(3) Micro negative pressure combined chromatographic analysis: combining three sections of chromatographic columns with different inner diameter specifications, wherein the chromatographic columns comprise a column I without a coating film, a column II without a coating film and a column III with an inner wall coated with a 5% phenyl/polydimethylsiloxane stationary phase coating; a back-blowing gas controller is added between the first column and the second column, and the third column is communicated into the mass spectrum vacuum cavity; setting configuration parameters of a first column and a second column, wherein the third column is not provided; the temperature programming condition of the column temperature box is that the temperature is kept at 60-70 ℃ for 0.5-1 min, and then the temperature is raised to 310-320 ℃ per minute at 50-60 ℃ for 1-2 min; the column is 1 m long and 0.25 mm in inner diameter; column two is 5 m long, and the inner diameter is 0.1 mm; the three columns are 15 m long, the inner diameter is 0.53 mm, and the thickness of the inner wall coating film is 1 micron.
2. The method for rapidly determining multiple pesticide residues in fruits and vegetables according to claim 1, wherein the extracting solution is a mixed solution of acetonitrile, methanol, isopropanol, deionized water and the like uniformly mixed in proportion.
3. The method for rapidly determining multiple pesticide residues in fruits and vegetables according to claim 1, wherein the sample is 1.0-2.0 g, and the extracting solution is 2-10 ml.
4. The method for rapidly determining pesticide residues in fruits and vegetables according to claim 1, wherein in the step (2), the extraction fiber head is a composite polydivinylbenzene/activated carbon/polydimethylsiloxane extraction fiber head.
5. The method for rapidly determining multiple pesticide residues in fruits and vegetables according to claim 4, wherein the thickness of the extraction fiber head is 120 micrometers, and the length of the extraction fiber head is 10 millimeters.
6. The use of the method for rapidly determining multiple pesticide residues in fruits and vegetables according to any one of claims 1 to 5 in quantitative determination of 280 pesticides in 30 fruits and vegetables, namely white radish, spinach, green pepper, strawberry, green onion, kohlrabi, tomato, carrot, cauliflower, cucumber, leek, blueberry, potato, pumpkin, burdock, oyster mushroom, apple, green sword bean, green peduncle, yam, fruit corn, woad, peach, melon, sweet pea, potato, lettuce, watermelon, taro and onion.
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