CN105588911A - GC-Q-TOF/MS detection technology for 708 pesticide residues in bud vegetables - Google Patents

Abstract

The invention relates to the field of pesticide residue detection, and provides a detection method for screening 708 kinds of pesticide residues in sprout vegetables, and collects a full scan of fragment ions under specified conditions for pesticide standards in the GC-Q-TOF/MS primary mode Mass spectrogram, obtain the chemical molecular formula, retention time, accurate mass number of fragment ions, and ion abundance ratio of the pesticide, and import it into the PCDL software, correlate with the corresponding pesticide information, form a database, and measure the concentration of the sample to be tested under the same setting conditions The full-spectrum data is used to obtain the full-spectrum data; the sample determination results are retrieved through the accurate mass database, and the detected pesticides that meet the identification basis are accurately identified to obtain the types of pesticide residues in sprout vegetables. The invention uses the detection method established by GC-Q-TOF/MS high-resolution mass spectrometry to detect pesticide residues in sprout vegetables, preferably combined with specific pretreatment, and has the advantages of rapid, high-throughput, high-precision and high-reliability detection features. Qualitative detection and confirmation of 708 pesticides in sprout vegetables without the need for a standard as a control.

Description

GC-Q-TOF/MS detection technology for 708 kinds of pesticide residues in sprout vegetables

technical field

The invention relates to the field of pesticide residue detection, in particular to a detection method for screening 708 kinds of pesticide residues in sprout vegetables by using GC-Q-TOF/MS.

Background technique

Fruits and vegetables are closely related to people's lives, especially the nutritional value of sprout vegetables (mung bean sprouts, Chinese toon sprouts and grass heads, etc.) are favored by consumers. However, at present, there are more than 1100 kinds of pesticides and chemicals that may be used in the cultivation, growth and preservation of sprout vegetables. However, with the widespread use of pesticides, irregular behaviors such as excessive use, abuse and misuse have also occurred, making pesticide residues in agricultural products, which poses a potential threat to human health, and also has a negative impact on the import and export of agricultural products. adverse effects.

As early as 1976, the World Health Organization (WHO), the Food and Agriculture Organization (FAO) and the United Nations Environment Program (UNEP) jointly established the Global Environment Monitoring System/Food Project (Global Environment Monitoring System, GEMS/Food), aiming to grasp the status of food contamination in member countries , understand the intake of food pollutants, protect human health, and promote trade development. Now, all countries in the world have raised food safety to the strategic position of national security. Pesticide residue limit is one of the food safety standards and also the entry threshold for international trade. At the same time, the requirements for pesticide residues show a development trend of more and more varieties and stricter limits, that is, the threshold for pesticide residue limits established by international trade is getting higher and higher. Now the European Union has formulated 162,248 MRL standards for 839 pesticides, the United States has formulated 39,147 MRL standards for 351 pesticides, Japan has formulated more than 51,600 MRL standards for 579 pesticides, and my country has issued 3,650 MRL standards for 381 pesticides in 2014. MRL standard. At present, the uniform standard limit generally adopted in the world is 10 μg/kg. Therefore, both food safety and international trade call for high-throughput rapid pesticide residue detection technology, which undoubtedly provides opportunities and challenges for the majority of pesticide residue analysis workers. Among the current analytical techniques for pesticide residues, chromatography-mass spectrometry is the best analytical method to achieve high-throughput rapid detection of multiple residues.

At present, the analysis of pesticide residues is mainly based on gas chromatography, liquid chromatography, gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry. These detection techniques all first need pesticide standard control for qualitative. For example, for the detection of 100 kinds of pesticides, it is necessary to prepare corresponding 100 kinds of pesticide standard controls, and the pesticides other than these 100 kinds will be missed. In the actual work of pesticide and veterinary drug residue laboratories, most laboratories do not store hundreds of pesticide standard products. The reason is that pesticide standard products are not only expensive, but also valid for only 2-3 years, requiring repeated investment. There are only dozens of standard pesticides in general laboratories, and the types of pesticides that are routinely monitored are limited to these dozens, resulting in loopholes in food safety monitoring.

Contents of the invention

In order to overcome the above-mentioned defects, the team of the inventors has developed an accurate mass database of 708 pesticides and a GC-Q-TOF/MS detection technology for 708 pesticide residues in fruits and vegetables after years of painstaking research. In comparison, 708 kinds of pesticide residues in sprout vegetables can be quickly detected and detected, which meets the urgent need for high-throughput rapid detection of pesticide residues in agricultural products.

On the one hand, the present invention provides a GC-Q-TOF/MS detection method for detecting 708 kinds of pesticide residues in sprout vegetables, which is characterized in that: a TOF/MS database of 708 kinds of pesticides is established, and at the same time, the 708 kinds of pesticides are qualitatively detected and confirmed; the method includes the following steps:

(1) Prepare pesticide standard products into standard solutions of 1-5mg/L respectively, and measure the full-spectrum data of each standard solution by GC-QTOF/MS primary mode full-spectrum data under the set conditions, and obtain each pesticide respectively The chemical molecular formula, retention time, accurate mass number of fragment ions, ion abundance ratio;

(2) Import the full-spectrum data of the first-level model obtained in step (1), and the verified fragment ion full-scan mass spectrogram into the PCDL software, and correlate with the corresponding pesticide information to build a TOF/MS accurate mass database, For data retrieval and analysis;

(3) Determination of the full-spectrum data of pesticides in the test sample under the same setting conditions as step (1) sprout vegetables, obtain the chemical molecular formula, retention time, accurate mass number of fragment ions, and ion abundance of the pesticides contained in it. degree ratio;

(4) The results of the sample determination were retrieved from the accurate mass database, and the detected pesticides that met the identification basis were accurately identified, so as to obtain the types of pesticide residues in sprout vegetables.

Preferably, by carrying out pretreatment to sprout vegetables to obtain the assay sample of sprout vegetables, said pretreatment method comprises the following procedures:

Sample preparation: Sprout vegetable samples were extracted with 0.5-5 vol% acetic acid acetonitrile homogenate, dehydrated, centrifuged, concentrated, then purified by Carbon/NH ₂ column, acetonitrile + toluene eluted residual pesticides, concentrated and filtered Afterwards, the sample solution a to be tested is prepared.

The beneficial effects that the present invention has:

1. The present invention uses high-resolution fragment ion accurate mass number, retention time, ion abundance ratio and other compound information as identification standards, and establishes 708 kinds of pesticide detection and confirmation technology methods, which completely change the original method of using compound standards as references. The qualitative mode of the ratio is a fast, high-throughput, accurate and reliable new technology for the detection of pesticide residues that does not require standard controls.

2. The present invention realizes the qualitative detection and confirmation of 708 kinds of pesticide residues on the premise that there is no need for comparison with standard substances, which can greatly save the cost of purchasing standard substances, and is also more environmentally friendly and safer.

3. The present invention can complete the detection, characterization and confirmation of 708 kinds of pesticides within one hour. Compared with the traditional detection method, the work efficiency can be improved hundreds of times.

4. The present invention can extract and purify 708 kinds of pesticide residues in sprout vegetable samples at one time, and perform one-time sampling detection. Compared with traditional detection methods, it can save detection costs and improve work efficiency hundreds of times.

5. The pesticides in the sprout vegetable samples that can be tested in the present invention include one or more of the following substances: organophosphorus pesticides, carbamate pesticides, benzimidazole pesticides, sulfonylurea pesticides, nicotine Pesticides, pyrethroid pesticides and other types of pesticides and metabolites.

6. The GC-QTOF/MS detection technical indicators established by the present invention: the scanning range is 50-600m/z; the measured accurate mass can reach 0.0001m/z; the mass accuracy can be controlled within 20ppm; the scanning speed is 50-600m/z The z range is 5 times per second.

7. The present invention provides a high-resolution mass spectrometry detection technology that uses gas chromatography quadrupole time-of-flight mass spectrometry (GC-Q-TOF/MS) to quickly screen 708 kinds of pesticide residues in sprout vegetables. The analytical laboratory has been promoted and applied. After the detection and verification of more than 30 provinces and cities of sprout vegetable samples in the market, important residue detection data have been obtained.

8. Among the 708 kinds of pesticides detected at the same time, the detection sensitivity is all lower than the standard of 10 μg/kg, which meets the requirements of screening for MRL levels of pesticide residues in various countries.

Other features and advantages of the present invention will be described in detail in the detailed description that follows.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached picture:

Figure 1 is an example of the results of the most frequently detected pesticide (chlorpyrifos) by GC-Q-TOF/MS technology in commercially available mung bean sprouts samples in Shijiazhuang.

Figure 2 is the result of comparing the mass spectrum information of the most frequently detected pesticide (chlorpyrifos) detected by GC-Q-TOF/MS technology with mung bean sprouts samples sold in Shijiazhuang area and the database.

detailed description

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

The invention provides a GC-Q-TOF/MS detection method for detecting 708 kinds of pesticide residues in sprout vegetables, which is characterized in that: a TOF/MS database of 708 kinds of pesticides is established, and at the same time, 708 kinds of pesticide residues in sprout vegetables Pesticides are qualitatively detected and confirmed; the method includes the following steps:

(1) Prepare pesticide standard products into standard solutions of 1-5mg/L respectively, and measure the full-spectrum data of each standard solution by GC-QTOF/MS primary mode full-spectrum data under the set conditions, and obtain each pesticide respectively The chemical molecular formula, retention time, accurate mass number of fragment ions, ion abundance ratio;

(2) Import the full-spectrum data of the first-level model obtained in step (1), and the verified fragment ion full-scan mass spectrogram into the PCDL software, and correlate with the corresponding pesticide information to build a TOF/MS accurate mass database, For data retrieval and analysis;

(3) Determination of the full-spectrum data of pesticides in the test sample under the same setting conditions as step (1) sprout vegetables, obtain the chemical molecular formula, retention time, accurate mass number of fragment ions, and ion abundance of the pesticides contained in it. degree ratio;

(4) The results of the sample determination were retrieved from the accurate mass database, and the detected pesticides that met the identification basis were accurately identified, so as to obtain the types of pesticide residues in sprout vegetables.

Specifically, the GC-QTOF/MS database of the present invention is set up by taking Daofengsan (Phenthoate) as an example:

1) In the data collection interface, collect the fragment ion full-scan mass spectrum of Daofengsan (Phenthoate) standard (1-5mg/L) under the specified chromatographic mass spectrometry conditions through GC-QTOF/MS primary mode.

The chromatographic conditions are: chromatographic column: VF-1701MS (30m×0.25mm×0.25um) (J&WScientific, Folsom, CA); min to 200-280°C, then 20-50°C/min to 110-150°C, then 3-10°C/min to 200-280°C, then 5-15°C/min to 250- 320°C, keep for 3-10min, then cool down to 200-290°C at 5-20°C/min, keep for 1-5min; carrier gas: helium; purity ≥99.999%; 0.5-2mL/min; inlet temperature: 230-320°C; injection volume 1μL; injection method: splitless injection, solvent delay 2-10min. Preferably, chromatographic conditions: chromatographic column: VF-1701MS (30m × 0.25mm × 0.25um) (J&WScientific, Folsom, CA); chromatographic column temperature rise program: keep at 40°C for 1min, then raise the temperature to 130°C at 30°C/min, Then heat up to 250°C at 5°C/min, then heat up to 300°C at 10°C/min, keep for 5 minutes, then cool down to 280°C at 10°C/min, keep for 2 minutes; carrier gas: helium, purity ≥99.999%; Flow rate: 1.2mL/min; Injection port temperature: 290°C; Injection volume: 1 μL; Injection method: splitless injection, solvent delay 6min.

The mass spectrometry conditions are: ion source: EI (electron bombardment ionization source); ion source temperature: 230-330°C, electron bombardment source energy: 50-100eV; gas phase-mass spectrometry interface temperature: 200-320°C; 2-10 spectra are used for full scanning in TOF mode, and the mass number range is 50-600 amu. Preferably, mass spectrometry conditions: ion source: EI (electron bombardment ionization source); ion source temperature: 280°C, electron bombardment source energy: 70eV; gas phase-mass spectrometer interface temperature: 290°C; scan mode: 5 spectra per second The full scan of TOF mode is carried out in the same way, and the mass number range is 50-600 amu.

The full-scan mass spectrum of fragment ions is collected as the mass spectrum information of the Daofengsan (Phenthoate) standard substance, including chemical molecular formula of the compound, retention time, accurate mass number of fragment ions, and ion abundance ratio.

2) Call the target pesticide (Phenthoate) acquisition file in the AgilentMassHunter qualitative software (included with the instrument), and determine the target pesticide chromatographic peak.

3) Open the mass spectrum of the target pesticide and subtract the background, use the NIST11 low-resolution spectral library (included with the instrument) to search to obtain the compound information, and check whether the compound retrieved from the spectral library is consistent with the actual situation.

4) Check the mass spectrum, the mass spectrum of the target compound will display the fragment ion molecular formula and accurate mass number matched by the NIST11 low-resolution spectrum library, and make necessary modifications to the ion information through the "EditPeakAnnotion" window, such as the exact mass number deviation is too large Ion, it may mean that the Formula structure automatically calculated by the software is wrong. At this time, you can manually enter the correct information in the "Formula" column, or change "IronType" to Unknown.

5) The verified fragment ion full-scan mass spectrogram is imported into the PCDL software (included with the instrument), and is associated with Daofengsan information to build a TOF/MS database. For the mass spectrum information of 708 pesticides in the database, see Attached Table 1 for details.

Preferably, the pesticides are the 708 pesticides shown in Table 1. The method of forming these pesticides can be carried out in the manner of forming the TOF/MS database of Phenthoate as above.

According to the present invention, the method of correlating the mass spectrum information of the obtained standard substance with the corresponding pesticide through PCDL software can be carried out according to the instructions of the PCDL software, and the present invention will not repeat them here.

According to the present invention, preferably, the sprout vegetables are selected from the group consisting of horse mung bean sprouts, Chinese toon sprouts and grass head.

Table 1

According to the present invention, the determination of the full-spectrum data of the pesticides in the sample under the same setting conditions as the establishment of sprout vegetables, obtain the chemical molecular formula, retention time, accurate mass number of fragment ions, and ion abundance ratio of the pesticides contained in it. ;Call the established TOF/MS database, and search for the target compound qualitatively based on the TOF/MS database. The retention time deviation of the search parameters is limited to ±0.15min, and the accurate mass deviation is limited to ±20ppm. The deviation between the measured value of mass and other elements and the theoretical value in the TOF/MS database automatically gives the search matching score value of each detected ion. The average score of detected ions is the comprehensive score of the compound. It is stipulated that the score of each compound is > 60 and at least three ions are detected, which is positive detection. The method for qualitative detection of pesticide residues in agricultural products based on the TOF/MS database Accuracy is above 90%.

According to the present invention, by carrying out pretreatment to sprout vegetable to obtain the assay sample of sprout vegetable, described pretreatment method preferably comprises the following procedures:

Sprout vegetable samples are homogenized and extracted with acetonitrile solution containing 0.5-5 vol% acetic acid (abbreviated as 0.5-5 vol% acetic acid acetonitrile), dehydrated, centrifuged and concentrated, and then purified by Carbon/NH ₂ column, acetonitrile+ Residual pesticides were eluted with toluene, and the sample solution to be tested was made after re-concentration and filtration;

Wherein, preferably, the amount of the sprout vegetable sample is 5-20g, and the consumption of the 0.5-5% by volume of acetic acetonitrile is 30-50mL, and the consumption is preferably 35-45ml; Place in a centrifuge tube for homogenization. The extraction conditions of the homogenate are preferably: rotation speed 12000-15000rpm, time 0.5-2min.

Wherein, the dehydration is preferably achieved by adding 0.5-5 g of sodium chloride and 2-8 g of anhydrous magnesium sulfate to the acetic acid acetonitrile extract, and shaking for 4-6 minutes. Then the obtained dehydrated sample was centrifuged at 4000-4500 rpm for 1-10 min to obtain a supernatant, and 10-30 mL of the obtained supernatant was concentrated to 0.5-2 mL by rotary evaporation in a water bath at 20-60°C.

Wherein, the Carbon/NH ₂ column purification step is preferably as follows: add about 1-3 cm, preferably 2 cm high anhydrous sodium sulfate into the Carbon/NH ₂ column. First rinse the SPE column with 2-6mL, preferably 4mL acetonitrile+toluene (preferably 2.5-3.5:1, more preferably 3:1, v/v), and discard the effluent. When the liquid level reaches the top of the sodium sulfate, Quickly transfer the sample concentrate to the purification column, and connect it to a new heart bottle for reception. Then use 2-6mL, preferably 2mL acetonitrile+toluene (preferably 2.5-3.5:1, more preferably 3:1, v/v) to wash the sample solution bottle three times each time, and transfer the washing solution into the SPE column. Then use 20-30mL, preferably 25mL of acetonitrile+toluene (preferably 2.5-3.5:1, more preferably 3:1, v/v) to elute the pesticide, and combine the eluate into a heart bottle.

Wherein, the sample solution to be tested is further preferably prepared in the following manner. The eluate obtained above is concentrated in a 30-50°C water bath to about 0.5-2mL by rotation, and the concentrated solution is blown dry under nitrogen, adding Mix 1-5mL of acetonitrile + 0-5% formic acid water (2+(7-9), preferably 2+8, v/v), filter through a 0.18-0.22 μm, preferably 0.2 μm filter membrane, and then constant volume to obtain the Sample solution.

Specific embodiments of the present invention will be described in detail below.

Example 1

This example is used to illustrate the GC-Q-TOF/MS detection method for screening 708 kinds of pesticide residues in sprout vegetables provided by the present invention

(1) Weigh 10g of mung bean sprouts samples from Shijiazhuang area (accurate to 0.01g), add 40mL of 1% acetic acid in acetonitrile solution to an 80ml centrifuge tube, use a high-speed homogenizer at 13500r/min, homogenize and extract for 1min, add 1g of chlorinated Sodium, 4g of anhydrous magnesium sulfate, shake for 5min, centrifuge at 4200r/min for 5min, take 20mL of supernatant, condense to about 1mL by rotary evaporation in a 40°C water bath, and wait for purification.

(2) Add about 2cm high anhydrous sodium sulfate to the Carbon/NH ₂ column. Rinse the SPE column with 4 mL of acetonitrile + toluene (3+1, v/v) first, and discard the effluent. When the liquid level reaches the top of sodium sulfate, quickly transfer the concentrated sample solution to the SPE column, and then connect a new Heart bottle received. Then use 2 mL of acetonitrile + toluene (3+1, v/v) to wash the sample solution bottle three times each time, and transfer the washing solution into the SPE column. Connect a 50mL liquid reservoir to the column, use 25mL acetonitrile + toluene (3+1, v/v) to elute pesticides and related chemicals, combine them in a heart bottle, and concentrate in a 40°C water bath to about 0.5mL.

(3) The concentrated solution was blown dry under nitrogen, added 2 mL of acetonitrile + water (2+8, v/v) and mixed evenly, filtered through a 0.2 μm filter membrane and then constant volume to obtain the sample solution to be tested.

(4) GC-Q-TOF/MS operating conditions, separated and obtained the molecular formula, retention time, accurate mass number of fragment ions, and ion abundance ratio of each fragment ion of each pesticide in the mung bean sprouts sample.

Chromatographic conditions: chromatographic column: VF-1701MS (30m × 0.25mm × 0.25um) (J&WScientific, Folsom, CA); chromatographic column temperature program: keep at 40°C for 1min, then raise the temperature to 130°C at 30°C/min, then increase the temperature for 5 ℃/min to 250°C, then 10°C/min to 300°C, hold for 5 minutes, then 10°C/min to 280°C, hold for 2 minutes; carrier gas: helium, purity ≥99.999%; flow rate: 1.2 mL/min; Injection port temperature: 290°C; Injection volume: 1 μL; Injection method: splitless injection, solvent delay 6min.

Mass Spectrometry Conditions: Mass Spectrometry Conditions: Ion Source: EI (Electron Impact Ionization Source); Ion Source Temperature: 280°C, Electron Impact Source Energy: 70eV; GC-MS Interface Temperature: 290°C; Scanning Mode: 5 spectra per second The full scan of TOF mode is carried out in the same way, and the mass number range is 50-600 amu.

(5) Qualitatively retrieve the information obtained in step (4) based on the database in Table 1, the retention time deviation of the retrieval parameters is limited to ±0.5min, the accurate mass deviation is limited to ±100ppm, at least three fragment ions are detected, and according to each The deviation between the measured value of each element of the compound and the theoretical value in the database in Table 1 will automatically give a search matching score value, and the compound with a search matching score value > 60 is confirmed to have detected the target compound. The test results are shown in Table 2.

Taking chlorpyrifos with a high detection frequency as an example, as shown in Figure 1, 7 fragment ion information were detected in mung bean sprouts, searched in the database, compared with chlorpyrifos, the molecular weight deviation scores of the 7 fragment ions were all above 99 points, The retention time deviation was within 0 min, and the mass deviation of the most abundant fragment ion was -1.28ppm (as shown in Figure 2), which confirmed that chlorpyrifos was detected in mung bean sprouts.

Example 2

This example is used to illustrate the GC-Q-TOF/MS detection method for screening 708 kinds of pesticide residues in sprout vegetables provided by the present invention

According to the method in Example 1, the pesticide residues in the same batch of mung bean sprout samples are detected, and the difference is that the pretreatment steps are as follows:

(1) Accurately weigh 10.00g of sample into a centrifuge tube, add 50mL of water, and shake until the sample is fully soaked by water. After freezing for 10 min, pipette 50 mL of acetonitrile into a centrifuge tube, then place the centrifuge tube on a vortex mixer and vibrate at 2000 rpm for 1 min. Keep the centrifuge tube at -10°C for 10 minutes, then add 20g of anhydrous magnesium sulfate, 5g of sodium chloride, 5g of sodium citrate and 2.5g of sodium dihydrogen citrate into the centrifuge tube, and immediately place it on a vortex mixer , shake at 2000rpm for 2min, then centrifuge at 4000rpm for 10min to obtain supernatant.

(2) Pipette 1.0 mL of the supernatant into a 1.5 mL centrifuge tube, add 150 mg of anhydrous magnesium sulfate and 25 mg of PSA adsorbent, oscillate on a vortex mixer at 2000 rpm for 2 min, and centrifuge at 6000 rpm for 2 min. Take the supernatant and filter it through a 0.22 μm organic phase filter, pipette 200 μL, add 100 μL acetonitrile, and dilute to 1.0 mL with ultrapure water to obtain the sample solution to be tested.

The test results are shown in Table 2.

Table 2

It can be seen from the above data that the method of the present invention, especially the preferred method, can more effectively detect the types of pesticide residues in agricultural products, and also has a lower detection limit.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific implementation manners may be combined in any suitable manner if there is no contradiction. In order to avoid unnecessary repetition, various possible combinations are not further described in the present invention.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (10)

1. A method for detecting 708 kinds of pesticide residues in sprout vegetables by GC-Q-TOF/MS, characterized in that: 708 kinds of pesticide TOF/MS databases are established, and 708 kinds of pesticides in sprout vegetables are simultaneously Qualitative detection and confirmation; the method includes the following steps: (1) Prepare pesticide standard products into standard solutions of 1-5mg/L respectively, and measure the full-spectrum data of each standard solution by GC-QTOF/MS primary mode full-spectrum data under the set conditions, and obtain each pesticide respectively The chemical molecular formula, retention time, accurate mass number of fragment ions, ion abundance ratio; (2) Import the full-spectrum data of the first-level model obtained in step (1), and the verified fragment ion full-scan mass spectrogram into the PCDL software, and correlate with the corresponding pesticide information to build a TOF/MS accurate mass database, For data retrieval and analysis; (3) Determination of the full-spectrum data of pesticides in the test sample under the same setting conditions as step (1) sprout vegetables, obtain the chemical molecular formula, retention time, accurate mass number of fragment ions, and ion abundance of the pesticides contained in it. degree ratio; (4) The results of the sample determination were retrieved from the accurate mass database, and the detected pesticides that met the identification basis were accurately identified, so as to obtain the types of pesticide residues in sprout vegetables. 2. The method according to claim 1, wherein the pesticides are the 708 pesticides shown in Table 1. 3. The method according to claim 1, wherein the sprout vegetables are selected from the group consisting of mung bean sprouts, Chinese toon sprouts and grass heads. 4. method according to claim 1, wherein, the condition of measuring the full spectrum data of pesticide in every kind of standard solution comprises: (1) Chromatographic conditions: Chromatographic column: VF-1701MS; Chromatographic column temperature rise program: 30-50°C for 0.5-5min, then heat up to 110-150°C at 20-50°C/min, and then at 3-10°C/min Raise the temperature to 200-280°C, then raise the temperature to 250-320°C at 5-15°C/min, keep for 3-10min, then cool down to 200-290°C at 5-20°C/min, and keep for 1-5min; carrier gas: Helium; flow rate: 0.5-2mL/min; inlet temperature: 230-320℃: splitless injection, solvent delay 2-10min; (2) Mass spectrometry conditions: ion source: EI; ion source temperature: 230-330°C, electron bombardment source energy: 50-100eV; gas phase-mass spectrometry interface temperature: 200-320°C; scan mode: 2-10 sheets per second The spectrogram is used for full scan in TOF mode, and the mass number range is 50-600amu. 5. The method according to claim 1, wherein the TOF/MS accurate mass database can measure the retention time of the fragment ions obtained from the sample to be tested, the exact mass number, the measured value of the ion abundance ratio, and the TOF/MS The theoretical values of the corresponding elements of the fragment ions in the accurate mass database are searched and compared, and the score of each fragment ion is given, and then the average score is given, which is the matching score of the target compound; where, the retention time deviation of the fragment ions is set at ±0.5min, the accurate mass deviation is set to ±100ppm. 6. The method according to claim 5, wherein: the detected pesticides meeting the identification basis are accurately identified by the following method: Qualitative identification of pesticides is carried out through the score value given by the detection and coincidence of characteristic ions. The method procedure is: for the detection of target compounds in the sample, the retention time of the compound measured by time-of-flight mass spectrometry , the 7 fragment ions with the highest abundance, and the results of the fragment ion abundance ratio, compared with the TOF/MS database search, the result was that at least three fragment ions were detected, and the pesticides with a comprehensive score greater than 60 were identified as Pesticides were detected. 7. method according to claim 1, by carrying out pretreatment to sprout vegetables to obtain the mensuration test sample of sprout vegetables, described pretreatment method comprises the following procedures: Sample preparation: Sprout vegetable samples were extracted with 0.5-5 vol% acetic acid acetonitrile homogenate, dehydrated, centrifuged, concentrated, then purified by Carbon/NH ₂ column, acetonitrile + toluene eluted residual pesticides, concentrated and filtered Afterwards, the sample solution a to be tested is prepared. 8. The method according to claim 7, wherein: the sprout vegetable sample size is 5-20g; Preferably, the consumption of said 0.5-5% by volume of acetic acid acetonitrile is 30-50mL; Preferably, the extraction conditions of the homogenate are: the rotation speed is 12000-15000r/min, and the time is 0.5-5min; Preferably, the dehydration refers to adding 0.5-5g sodium chloride and 2-8g anhydrous magnesium sulfate to the 0.5-5% acetic acid acetonitrile extract, shaking for 1-10min; Preferably, the centrifugation refers to centrifugation at 3000-5000r/min for 1-10min; Preferably, the concentration refers to taking 10-30 mL of the centrifuged supernatant and concentrating it to about 0.5-2 mL by rotary evaporation in a water bath at 20-60°C. 9. The method according to claim 8, wherein: said Carbon/NH ₂ column purification steps are as follows: add about 1-3cm high anhydrous sodium sulfate in Carbon/NH ₂ column, first use 2-6mL certain proportion Rinse the SPE column with a mixture of acetonitrile and toluene, and discard the effluent. When the liquid level reaches the top of sodium sulfate, quickly transfer the sample concentrate to the purification column and receive it in the lower container; then use 2-6mL acetonitrile each time Wash the sample bottle three times with the mixed solution of toluene, and transfer the washing solution to the SPE column. Then use a certain volume of acetonitrile and toluene mixed solution of preferably 20-30ml to elute the pesticide, and combine the eluent in the container; Preferably, for the mixed solution of acetonitrile and toluene in a certain proportion, the volume ratio of acetonitrile:toluene is 2.5-3.5:1. 10. The method according to claim 8, wherein: the sample liquid a to be tested is made after reconcentration and filtration and refers to the eluent obtained in claim 9, which is concentrated in a 30-50° C. water bath by rotation to About 0.5-2mL, and dry the concentrated solution under nitrogen, add 1-5mL of a certain proportion of acetonitrile and 0-5% by volume of formic acid water mixed solution, mix well, filter through a 0.18-0.22μm filter membrane, and then constant volume, Obtain the sample solution a to be tested. Preferably, the mixed solution of acetonitrile and 0-5% by volume formic acid water in a certain proportion is acetonitrile: 0.1-5% by volume formic acid water 2: 7-9.