CN112379022A - Detection method for rapidly screening various pesticides and biotoxins in aquatic product - Google Patents

Detection method for rapidly screening various pesticides and biotoxins in aquatic product Download PDF

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CN112379022A
CN112379022A CN202011277373.5A CN202011277373A CN112379022A CN 112379022 A CN112379022 A CN 112379022A CN 202011277373 A CN202011277373 A CN 202011277373A CN 112379022 A CN112379022 A CN 112379022A
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CN112379022B (en
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张宪臣
王勇
杨威
李勇
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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
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Abstract

The invention discloses a detection method for rapidly screening various pesticides and biotoxins in aquatic product products, which comprises the following steps: (1) preparing a standard solution; (2) QuEChERS extraction and purification of samples: (3) concentrating; (4) ultra-high performance liquid chromatography-high resolution mass spectrometer analysis. The method disclosed by the invention is used for pretreating aquatic products by utilizing QuEChERS, and simultaneously, high-flux measurement is carried out on the residual quantities of 93 pesticides and 16 biotoxins in the aquatic products by combining and utilizing an ultra-high performance liquid chromatography-quadrupole/electrostatic field orbit trap mass spectrometry (UPLC-Q active Orbitrap HRMS).

Description

Detection method for rapidly screening various pesticides and biotoxins in aquatic product
Technical Field
The invention relates to a detection method for rapidly screening various pesticides and biotoxins in aquatic products, belonging to the technical field of food chemical analysis.
Background
With the improvement of the living standard of people, the proportion of aquatic products and products thereof in the living standard of people is increasing day by day, and the safety problem of the aquatic products becomes the focus of social attention. Among many factors influencing the quality safety of aquatic products, pesticide and biotoxin residues are one of the main reasons, and after the pesticide is used in the production and processing of crops such as fruits, vegetables and grains, the residues of the pesticide can enter the aquatic products through the food chain and the environment, so that the human health is influenced. Biotoxins are toxic chemical substances produced by the organism itself, such as animals, plants, marine organisms, microorganisms, and the like, which have toxic effects on other biological species. Since biotoxins are widely present in the field of food safety, the hazard degree of biotoxins is higher than that of synthetic pollutants, phytotoxins, food additives, pesticide residues and the like, and the biotoxins are usually present in trace amounts in food matrixes, so that the biotoxins pose great potential threats to the dietary health of human beings.
The detection method of pesticides and biotoxins in aquatic products mainly comprises an enzyme-linked immunosorbent assay, a high performance liquid chromatography, a gas chromatography-tandem mass spectrometry (GC-MS/MS), a liquid chromatography-tandem mass spectrometry (LC-MS/MS) and a liquid chromatography-high resolution mass spectrometry. Wherein, the enzyme-linked immunosorbent assay is easy to generate false positive results and cross reaction; the high performance liquid chromatography has poor anti-interference capability and low sensitivity and cannot meet the requirement of a standard limit value; the GC-MS method needs to perform complicated derivatization treatment on a sample; the LC-MS/MS technology does not need derivatization treatment, has better selectivity, sensitivity and specificity under the condition of meeting the simultaneous detection of multiple components, makes up the defects of the previous methods, but is difficult to completely clarify the structural cleavage information of the compound, has defects in qualitative accuracy and is easy to generate false positive results. The pretreatment method for detecting pesticides and biotoxins in aquatic products and products thereof comprises solid phase extraction, matrix solid phase dispersion extraction, rapid solvent extraction, microwave-assisted extraction, molecular imprinting technology, QuEChERS and the like. The application of QuEChERS in detecting pesticides and biotoxins in aquatic products and products thereof is increasing due to the advantages of rapidness, simplicity, cheapness, effectiveness, durability, safety, reliability and the like, but the QuEChERS is easy to generate a matrix effect and can influence the detection limit and selectivity of the method and the accurate quantification of a test result.
The quadrupole/electrostatic field orbit trap high-resolution mass spectrometer (Q-active) has the advantages of high resolution and good quantitative capability, is different from a triple quadrupole low-resolution mass spectrometer which carries out quantitative analysis through an ion pair of a target object in a multi-reaction monitoring mode, can directly quantify the high-resolution mass spectrometer by utilizing the accurate molecular weight of a parent ion of the target object, does not need to optimize the daughter ions and related parameters one by one for the target object, can greatly reduce the time of a detection method for multi-target object analysis, and can well avoid the phenomenon that the low-resolution mass spectrometer is easy to generate false positive due to matrix interference. However, due to the complex fish matrix containing various components such as fat, protein and the like, the detection lower limit of the target compound in Q-active by the conventional processing method can not meet the requirements of related national sanitary standards and announcements due to the interference of the matrix.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a detection method for rapidly screening various pesticide and biotoxin residues in aquatic products by using a QuEChERS-UPLC-Q active Orbitrap MS.
In order to achieve the purpose, the invention adopts the following technical scheme:
a detection method for rapidly screening various pesticides and biotoxins in aquatic product products is characterized by comprising the following steps:
(1) preparing a standard solution:
preparing standard stock solution, accurately weighing standard substances, dissolving the standard substances in respective 5mL volumetric flasks by using acetonitrile, fixing the volume to a scale, preparing the standard stock solution with the mass concentration of 1mg/mL, and storing the standard stock solution in a refrigerator at 4 ℃;
preparing mixed standard working solution, accurately sucking a proper amount of stock solution, and preparing mixed standard working solution with corresponding concentration of 1 microgram/mL by using acetonitrile;
(2) QuEChERS extraction and purification of samples:
accurately weighing 5.00g of uniformly crushed aquatic product sample to 0.01g, adding 1mL of water, adding into a 50mL centrifuge tube with a plug,1.0g of sodium chloride and 10mL of acetonitrile, performing vortex oscillation for 2min, performing ultrasonic extraction for 10min, centrifuging for 10min at 13000r/min at 5 ℃, transferring supernatant into a container, and putting 600-1200 mg of MgSO (MgSO) in advance4Swirling and oscillating for 5min in a 15mL centrifuge tube containing 50-200 mg of n-propyl ethylenediamine (PSA) and 20-100 mg of Graphitized Carbon Black (GCB), centrifuging for 10min at 13000r/min at 5 ℃, and transferring the supernatant into a 30mL glass tube to obtain a sample extracting solution;
(3) concentration: concentrating the sample extractive solution at 40 deg.C under reduced pressure with a parallel quantitative concentrator, dissolving the residue with methanol water solution (methanol: water 25:75, v/v) by vortex, filtering the extractive solution with 0.2 μm filter membrane, and measuring with ultra high performance liquid chromatography-high resolution mass spectrometer;
(4) ultra-high performance liquid chromatography-high resolution mass spectrometer analysis.
Wherein the standard substances weighed in the step (1) are as follows:
carbaryl (purity is more than or equal to 98.9 percent), carbofuran (purity is more than or equal to 98.3 percent), 3-hydroxy carbofuran (purity is more than or equal to 98.0 percent), isoprocarb (purity is more than or equal to 98.5 percent), methomyl (purity is more than or equal to 99.1 percent), omethoate (purity is more than or equal to 99.0 percent), acetamiprid (purity is more than or equal to 98.1 percent), chlorsulfuron (purity is more than or equal to 98.5 percent), diniconazole (purity is more than or equal to 99.0 percent), edifenphos (purity is more than or equal to 99.0 percent), fenpyroximate (purity is more than or equal to 99.4 percent), imazalil (purity is more than or equal to 99.0 percent), metalaxyl (purity is more than or equal to 98.7 percent), paclobutrazol (purity is more than or equal to 99.0 percent), phoxim (purity is more than or equal to 98.0 percent), pirimibencarb (purity is more than or equal to 98.7 percent), thiabendazole (purity, Carbendazim (purity is more than or equal to 99.0%), pyrimethanil (purity is more than or equal to 99.0%), fenamiphos (purity is more than or equal to 98.5%), phosphosulfolane (purity is more than or equal to 99.0%), aldicarb (purity is more than or equal to 99.2%), aldicarb sulfoxide (purity is more than or equal to 99.0%), alachlor (purity is more than or equal to 99.5%), chlorpyrifos (purity is more than or equal to 99.0%), chlorpyrifos-methyl (purity is more than or equal to 99.9%), dichlorvos (purity is more than or equal to 99.2%), dimethoate (purity is more than or equal to 98.5%), ethion (purity is more than or equal to 99.0%), fenpropathrin (purity is more than or equal to 99.0%), fenfluroxypyr (purity is more than or equal to 99.0%), fluvalinate (purity is more than or equal to 99.0%), fluvalicarb-99.5%), pyrithion (purity is more than or equal to 99.0%), fluvalicarb (purity is more than or equal to 99., Myclobutanil (purity 100%), parathion (ethyl parathion) (purity more than or equal to 99.5%), phorate (purity more than or equal to 98.9%), pirimiphos (purity more than or equal to 99.0%), profenofos (purity more than or equal to 98.2%), quinalphos (purity more than or equal to 96.0%), tebufenpyrad (purity more than or equal to 99.5%), tetraconazole (purity more than or equal to 99.6%), methidathion (purity more than or equal to 99.1%), azathion (purity more than or equal to 97.8%), butoxycarb (purity more than or equal to 91.3%), clothianidin (purity more than or equal to 98.9%), fenamidone (purity more than or equal to 96.9%), furalaxyl (purity more than or equal to 98.5%), monocrotophos (purity more than or equal to 99.0%), pyraclostrobin (purity more than or equal to 93.9%), phos (purity more than or equal to 99.8%), chlordiazepoxide (purity more than or equal to 97.8%), and bensulide (purity more than or equal to 99.3%), pyrazosulfuron-2.8%) Propiconazole (purity is more than or equal to 99.0 percent), simetryn (purity is more than or equal to 98.9 percent), thidiazuron (purity is more than or equal to 99.0 percent), antimycin (purity is more than or equal to 99.0 percent), chlordimeform (purity is more than or equal to 97.1 percent), fenpropathrin (purity is more than or equal to 98.0 percent), oxydisup (purity is more than or equal to 95.7 percent), thiophosphoryl sulfone (purity is more than or equal to 98.0 percent), thiophosphoryl sulfoxide (purity is more than or equal to 99.5 percent), cyhalothrin (purity is more than or equal to 98.4 percent), iprobenfos (purity is more than or equal to 97.5 percent), phenthoate (purity is more than or equal to 98.1 percent), phorate (purity is more than or equal to 95.7 percent), methrin-sulfofenvalerate (purity is more than or equal to 93.6 percent), fenphos (purity is more than or equal to 98.7 percent), triazophos (purity is more than or equal to 99.2 percent), diclofenoxaprop-ethyl (purity is more than or equal, The compound bactericide is prepared from the following raw materials, by weight, diclofop-methyl (the purity is more than or equal to 99.8%), barnyard grass dicamba (the purity is more than or equal to 92.1%), aflatoxin B1 (the purity is more than or equal to 99.6%), aflatoxin B2 (the purity is more than or equal to 99.0%), aflatoxin G1 (the purity is more than or equal to 99.0%), aflatoxin G2 (the purity is more than or equal to 99.0%), aflatoxin M1 (the purity is more than or equal to 99.9%), aflatoxin M2 (the purity is more than or equal to 99.5%), patulin (the purity is more than or equal to 99.1%), HT-2 toxin (the purity is more than or equal to 99.0%), T-2 toxin (the purity is more than or equal to 99.0%), zearalenone (the purity is more than or equal to 99.3%), aflatoxin (the purity is more than or equal to 99.6%), deoxynivalenol (the purity is more than or equal to 95.0%), diacetyl fusanol (.
In the invention, the QuEChERS purification filler is MgSO4N-propylethylenediamine and graphitized carbon black, preferably with 900mg MgSO4100mg of n-propylethylenediamine and 50mg of graphitized carbon black.
In the concentration step of the invention, the condensation temperature of a parallel quantitative concentrator is 5 ℃, and the vacuum degree is reduced in a gradient way of 250mbar, 10min, 100mbar, 10min and 20mbar until the concentration is dry. The conventional concentration method can destroy the structure of target compounds and reduce the recovery rate of the target compounds, and the target compounds can be effectively protected by using the equipment, so that the influence of pretreatment on the recovery rate of the target compounds is reduced.
The parameters of the ultra-high performance liquid chromatography-high resolution mass spectrometer are as follows:
and (3) chromatography: watersatitis T3C18150mm X2.1 mm, 3.3 μm; column temperature: 40 ℃; sample introduction amount: 10 mu L of the solution; mobile phase: a was a 5mmol 0.1% aqueous ammonium formate solution and B was a 5mmol 0.1% methanolic ammonium formate solution. Gradient elution procedure for 0-2.0 min, keeping 25% of B; 2.0-7.0 min, linearly changing the proportion of the mobile phase B from 25% to 65%; 7.0-8.0 min, linearly changing the proportion of the mobile phase B from 65% to 90%; keeping 90% of B for 8.0-12.0 min; keeping 25% of B for 12.1-15 min;
mass spectrum: the temperature of a heating electrospray ion source is 350 ℃, the ion transmission temperature is 320 ℃, the sheath gas is 40 units, the auxiliary gas is 40 units, the capillary voltage is 3.2KV, and the temperature of an ion transmission pipe is 325 ℃; fullscan/ddms2 Scan mode: the collection range is 80-1000 Da, and positive and negative switching collection is carried out; the resolution of the primary mass spectrum is 70000FWHM, and the resolution of the secondary mass spectrum is 17500 FWHM; the collision cell energy NCE was 20, 40, 60 eV.
In the research, the accurate mass number of ion fragments is calculated through primary full scanning and secondary ion full scanning of a mass spectrometer, and the mass spectrometer is fitted with a mass spectrum to determine that each substance to be detected has 1 monitoring ion pair for qualitative confirmation.
The mass analysis parameters for each target compound as determined are shown in table 1.
Table 1: mass analysis parameters of each compound
Figure BDA0002779532390000051
Figure BDA0002779532390000061
Figure BDA0002779532390000071
Figure BDA0002779532390000081
Figure BDA0002779532390000091
Figure BDA0002779532390000101
Compared with the prior art, the research has obvious advantages:
1. the research can determine the residues of 93 pesticides and 16 biotoxins in aquatic products, and the sensitivity is high, and the detection limit is 0.02 mu g/kg-0.2 mu g/kg.
2. The research combines QuEChERS and UPLC-QOxacteveOrbitrap to establish 93 pesticides and 16 biotoxin residues in aquatic product products, and the method is simple, rapid, accurate, high in sensitivity and good in precision.
3. Compared with the traditional detection method, the method is simple, rapid and accurate in research, high in sensitivity and good in precision, and is suitable for detecting aquatic product samples in a large scale.
[ description of the drawings ]
FIG. 1 is a total ion flow graph of 109 target compound standards at a concentration of 5 ng/mL;
FIG. 2 is one of the partial target compound chromatograms;
FIG. 3 is a second partial target compound chromatogram;
FIG. 4 is a third partial target compound chromatogram;
FIG. 5 is four of a partial target compound chromatogram;
FIG. 6 is a fifth partial target compound chromatogram;
FIG. 7 is a sixth of a partial target compound chromatogram;
FIG. 8 is a seventh of a partial target compound chromatogram;
FIG. 9 is an eighth of a partial target compound chromatogram;
FIG. 10 is a ninth of partial target compound chromatogram;
FIG. 11 is ten of a partial target compound chromatogram;
FIG. 12 is eleven of partial target compound chromatograms;
FIG. 13 is a twelve-fold chromatogram of a portion of the target compound;
FIG. 14 is thirteen of a partial target compound chromatogram;
note: the target compound names of FIGS. 2-14 are shown in Table 1.
[ detailed description ] embodiments
The determination of the control parameters for researching the optimal conditions mainly comprises the selection of an extraction solvent and the optimization of an adsorbent which influence the efficiency of QuEChERS, and the optimization of QOxactveterbitrap mass spectrum conditions.
Selection of QuEChERS extraction solvent:
the invention selects acetonitrile, 1% acetonitrile solution of formic acid, ethyl acetate and methanol solution as extraction solvent, the result shows that ethyl acetate and methanol can only partially recover target compound, wherein 16 biotoxin residues can not be recovered when ethyl acetate is used as extraction solvent, and Kewensan, carbendazim, tricyclazole, fenamiphos, anilinophosphosulfone, aldicarb sulfone, aldicarb sulfoxide, fenamidone, furalaxyl, chlordimeform, patulin, HT-2 toxin, zeaenone, T-2 toxin, aflatoxin, deoxynivalenol, diacetyl sickle-knife-blade enol, neosolanum-enol, nivalenol and fusarenone 22 residual target compounds can not be recovered when methanol is used as extraction solvent; when acetonitrile and 1% acetonitrile formate are used as extraction solvents, 109 target compounds can be recovered, but when 1% acetonitrile formate is used as an extraction solvent, the recovery rate of part of toxin target compounds and pesticide residue target compounds is lower than 40%, acetonitrile solution is used as an extraction solvent, and the recovery rate of 109 target compounds is higher than 70%, so that acetonitrile is selected as an extraction solvent.
Optimization of QuEChERS adsorbent: the currently used adsorbents mainly include PSA (n-propylethylenediamine), MgSO4, GCB (graphitized carbon black), aminopropyl silica gel (NH)2) And C18. C18 is relatively suitable for removing hydrophobic impurities such as lipid, but the recovery of HT-2 is seriously influenced by adding C18; aminopropyl silica gel (NH)2) The adsorbent is mainly used for removing strong anions such as sulfonate and the like in aquatic product products, has similar effect with PSA, and does not need to be selected in consideration of detection cost; PSA is a weak anion exchanger, primarily used for the removal of fatty acids; the GCB is mainly used for removing pigment substances and is helpful for clarifying the extract liquor; MgSO4 is mainly used for adsorbing water in extraction solvent acetonitrile, and finally, the optimal selection of removing sample matrix interference and ensuring sensitivity is determined by adding 50-200 mg of PSA, 20-100 mg of GCB and 600-1200 mg of MgSO4, and preferably 100mg of PSA, 50mg of GCB and 900mg of MgSO 4.
Influence of salt concentration the mass fraction of inorganic salts in the aqueous solution has a certain influence on the extraction efficiency of the target. In the method, QuEChERS requires a certain amount of salt, because the salt is added to increase the ionic strength, the solubility of a target compound in an aqueous phase is reduced, and the partition coefficient of the target compound in an organic phase is improved; however, when the salt concentration is too high, the viscosity of the sample solution becomes large, and the electrostatic force between the target and the salt ion is increased, resulting in a decrease in the mass transfer capacity thereof, thereby decreasing the recovery rate. The method verifies that NaCl (0.00-2.0 g) is added into the extraction solution, and the influence of salt effect on the recovery rate is examined. Experiments show that the recovery rate increases with the increase of the salt concentration when 0.00-1.0 g of NaCl is added, and the recovery rate is the largest when 1.0g of NaCl is added; then salt is added continuously, and the recovery rate is reduced. Therefore, the experiment was selected to add 1.0g NaCl.
In the optimization method of the concentration condition, the extract to be concentrated contains acetonitrile at most, and then contains a small amount of water, because the boiling point of the acetonitrile is high, the nitrogen-blowing concentration or rotary evaporation concentration time is long, and the mixed solution also contains a small amount of water which is difficult to completely evaporate, so that the accuracy of the final result is influenced. Under the condition of high temperature for a long time, the target compound is also degraded to some extent. The method selects a parallel sample quantitative concentrator to carry out reduced pressure concentration on a sample extracting solution, gropes the concentration condition, and determines the concentration temperature to be 40 ℃; the condensation temperature is 5 ℃; the vacuum degree is reduced in a gradient manner (250mbar10min, 100mbar10min, 20mbar concentration to dryness), and 24 sample extracts can be treated simultaneously in one time by the method, and the complete evaporation is only required for 1.5 h.
The method for optimizing QOxactvetorbitrap mass spectrum conditions comprises the steps of performing primary full scanning on 109 targets in a positive and negative ion switching mode in a flow injection mode, performing primary full scanning by using a primary parent ion full scanning mode of QOxctive high-resolution mass spectrum and a data-dependent secondary ion scanning mode (FullMS/dd-MS2), setting a mass number range (m/z 100-1000) covering the targets, performing primary full scanning, and establishing a target list of secondary scanning by using the theoretical mass number (table 1) of each compound. In the actual scanning process, when primary ions in a target list are found by primary full scanning and the signal intensity exceeds a preset value, a data-dependent sub-ion scanning mode is triggered, and further secondary ion full-scanning mass spectrum information corresponding to the accurate mass number of the primary ions is obtained, so that qualitative confirmation is realized. According to the requirements of the drug residue detection validation method according to European Union 2002/657/EC, 4 identification points are required for validation detection. In the experiment, 1 monitoring ion pair is finally determined for each substance to be detected through the optimization and screening of the mass spectrum parameters so as to meet the requirement of the European Union drug residue detection confirmation.
The present invention will be described in more detail with reference to specific embodiments.
Example (b):
(1) preparing a standard solution:
accurately weighing carbaryl (the purity is more than or equal to 98.9 percent), carbofuran (the purity is more than or equal to 98.3 percent), 3-hydroxy carbofuran (the purity is more than or equal to 98.0 percent), isoprocarb (the purity is more than or equal to 98.5 percent), methomyl (the purity is more than or equal to 99.1 percent), omethoate (the purity is more than or equal to 99.0 percent), acetamiprid (the purity is more than or equal to 98.1 percent), chlorsulfuron (the purity is more than or equal to 98.5 percent), diniconazole (the purity is more than or equal to 99.0 percent), edifenphos (the purity is more than or equal to 99.0 percent), fenpyroximate (the purity is more than or equal to 99.4 percent), imazalil (the purity is more than or equal to 99.0 percent), mefenoxamine (the purity is more than or equal to 98.7 percent), paclobutrazol (the purity is more than or equal to 99.0 percent), phoxim (the purity is more than or equal to 99.0 percent), pirimicarb (the purity is more than or equal to 98.7 percent), tebuconazole (the, Carbendazim (purity is more than or equal to 99.0%), pyrimethanil (purity is more than or equal to 99.0%), fenamiphos (purity is more than or equal to 98.5%), phosphosulfolane (purity is more than or equal to 99.0%), aldicarb (purity is more than or equal to 99.2%), aldicarb sulfoxide (purity is more than or equal to 99.0%), alachlor (purity is more than or equal to 99.5%), chlorpyrifos (purity is more than or equal to 99.0%), chlorpyrifos-methyl (purity is more than or equal to 99.9%), dichlorvos (purity is more than or equal to 99.2%), dimethoate (purity is more than or equal to 98.5%), ethion (purity is more than or equal to 99.0%), fenpropathrin (purity is more than or equal to 99.0%), fenfluroxypyr (purity is more than or equal to 99.0%), fluvalinate (purity is more than or equal to 99.0%), fluvalicarb-99.5%), pyrithion (purity is more than or equal to 99.0%), fluvalicarb (purity is more than or equal to 99., Myclobutanil (purity 100%), parathion (ethyl parathion) (purity more than or equal to 99.5%), phorate (purity more than or equal to 98.9%), pirimiphos (purity more than or equal to 99.0%), profenofos (purity more than or equal to 98.2%), quinalphos (purity more than or equal to 96.0%), tebufenpyrad (purity more than or equal to 99.5%), tetraconazole (purity more than or equal to 99.6%), methidathion (purity more than or equal to 99.1%), azathion (purity more than or equal to 97.8%), butoxycarb (purity more than or equal to 91.3%), clothianidin (purity more than or equal to 98.9%), fenamidone (purity more than or equal to 96.9%), furalaxyl (purity more than or equal to 98.5%), monocrotophos (purity more than or equal to 99.0%), pyraclostrobin (purity more than or equal to 93.9%), phos (purity more than or equal to 99.8%), chlordiazepoxide (purity more than or equal to 97.8%), and bensulide (purity more than or equal to 99.3%), pyrazosulfuron-2.8%) Propiconazole (purity is more than or equal to 99.0 percent), simetryn (purity is more than or equal to 98.9 percent), thidiazuron (purity is more than or equal to 99.0 percent), antimycin (purity is more than or equal to 99.0 percent), chlordimeform (purity is more than or equal to 97.1 percent), fenpropathrin (purity is more than or equal to 98.0 percent), oxydisup (purity is more than or equal to 95.7 percent), thiophosphoryl sulfone (purity is more than or equal to 98.0 percent), thiophosphoryl sulfoxide (purity is more than or equal to 99.5 percent), cyhalothrin (purity is more than or equal to 98.4 percent), iprobenfos (purity is more than or equal to 97.5 percent), phenthoate (purity is more than or equal to 98.1 percent), phorate (purity is more than or equal to 95.7 percent), methrin-sulfofenvalerate (purity is more than or equal to 93.6 percent), fenphos (purity is more than or equal to 98.7 percent), triazophos (purity is more than or equal to 99.2 percent), diclofenoxaprop-ethyl (purity is more than or equal, Diclofop-methyl (purity is more than or equal to 99.8%), pyributicarb (purity is more than or equal to 92.1%), aflatoxin B1 (purity is more than or equal to 99.6%), aflatoxin B2 (purity is more than or equal to 99.0%), aflatoxin G1 (purity is more than or equal to 99.0%), aflatoxin G2 (purity is more than or equal to 99.0%), aflatoxin M1 (purity is more than or equal to 99.9%), aflatoxin M2 (purity is more than or equal to 99.5%), patulin (purity is more than or equal to 99.1%), HT-2 toxin (purity is more than or equal to 99.0%), T-2 toxin (purity is more than or equal to 99.0%), zearalenone (purity is more than or equal to 99.3%), aflatoxin (purity is more than or equal to 99.6%), deoxynivalenol (purity is more than or equal to 95.0%), diacetyl-sickle-enol (purity is more than or equal to 95.0%), fusarium-nivalenol (purity is more than or equal to 95.0%), fusarium, dissolving in 5mL volumetric flasks with acetonitrile, diluting to a constant volume to obtain standard stock solution with mass concentration of 1mg/mL, and storing in a refrigerator at 4 deg.C;
mixing standard working solution: accurately sucking a proper amount of stock solution, and preparing mixed standard working solution with corresponding concentration of 1 mug/mL by using acetonitrile;
(2) QuEChERS extraction and purification of samples:
accurately weighing 5.0g (accurate to 0.01g) of uniformly crushed aquatic product sample into a 50mL centrifuge tube with a plug, adding 1mL of water, 1.0g of sodium chloride and 10mL of acetonitrile, performing vortex oscillation for 2min, performing ultrasonic extraction for 10min, centrifuging at 5 ℃ for 10min at 13000r/min, transferring the supernatant to a reactor, and putting 900mgMgSO 2 mg in advance4Swirling and oscillating for 5min in a 15mL centrifuge tube containing 100mg of n-propyl ethylenediamine (PSA) and 50mg of Graphitized Carbon Black (GCB), centrifuging for 10min at 13000r/min at 5 ℃, and transferring the supernatant into a 30mL glass tube to obtain a sample extracting solution;
(3) concentration: concentrating the sample extractive solution at 40 deg.C under reduced pressure with a parallel quantitative concentrator, concentrating to dryness at condensation temperature of 5 deg.C under vacuum degree gradient of 250mbar, 10min, 100mbar, 10min, and 20mbar, dissolving the residue with methanol water solution (methanol: water: 25:75, v/v) by vortex, filtering the extractive solution with 0.2 μm filter membrane, and measuring with ultra high performance liquid chromatography-high resolution mass spectrometer;
(4) analyzing by using an ultra-high performance liquid chromatography-high resolution mass spectrometer, wherein the analysis parameters are as follows:
and (3) chromatography: c18150mm × 2.1mm, 3.3 μm; column temperature: 40 ℃; sample introduction amount: 10 mu L of the solution; mobile phase: a was a 5mmol 0.1% aqueous ammonium formate solution and B was a 5mmol 0.1% methanolic ammonium formate solution. Gradient elution procedure for 0-2.0 min, keeping 25% of B; 2.0-7.0 min, linearly changing the proportion of the mobile phase B from 25% to 65%; 7.0-8.0 min, linearly changing the proportion of the mobile phase B from 65% to 90%; keeping 90% of B for 8.0-12.0 min; keeping 25% of B for 12.1-15 min;
mass spectrum: the temperature of a heating electrospray ion source is 350 ℃, the ion transmission temperature is 320 ℃, the sheath gas is 40 units, the auxiliary gas is 40 units, the capillary voltage is 3.2KV, and the temperature of an ion transmission pipe is 325 ℃; fullscan/ddms2 Scan mode: the collection range is 80-1000 Da, and positive and negative switching collection is carried out; the resolution of the primary mass spectrum is 70000FWHM, and the resolution of the secondary mass spectrum is 17500 FWHM; the collision cell energy NCE was 20, 40, 60 eV.
In the research, the accurate mass number of ion fragments is calculated through primary full scanning and secondary ion full scanning of a mass spectrometer, and the mass spectrometer is fitted with a mass spectrum to determine that each substance to be detected has 1 monitoring ion pair for qualitative confirmation. The results are shown in tables 2 and 3.
Table 2: linear range, linear equation and correlation coefficient of 109 target compounds
Figure BDA0002779532390000151
Figure BDA0002779532390000161
Figure BDA0002779532390000171
Figure BDA0002779532390000181
Figure BDA0002779532390000191
Figure BDA0002779532390000201
Table 3: recovery and relative standard deviation of negative sample
Figure BDA0002779532390000202
Figure BDA0002779532390000211
Figure BDA0002779532390000221
Figure BDA0002779532390000231
Figure BDA0002779532390000241
Figure BDA0002779532390000251
Figure BDA0002779532390000261
Figure BDA0002779532390000271
Figure BDA0002779532390000281
Figure BDA0002779532390000291
Figure BDA0002779532390000301
Figure BDA0002779532390000311
Verification example:
19 batches of aquatic product samples are detected by using the research method, wherein dimethoate is detected in 1 batch of samples, and the detected content is 5.6 mu g/kg; methomyl was detected in another 1 lot of samples, with a detected content of 13.9. mu.g/kg.
The research adopts the QuEChERS method to carry out pretreatment on the sample, and effectively reduces the interference influence of the matrix on target compounds (comprising 93 pesticides and 16 biotoxins). Meanwhile, the quantitative and qualitative analysis of the target compound can be accurately carried out by utilizing the Q-active high-resolution analysis capability, and the phenomenon of false positive is avoided.

Claims (6)

1. A detection method for rapidly screening various pesticides and biotoxins in aquatic product products is characterized by comprising the following steps:
(1) preparing a standard solution;
preparing standard stock solution, accurately weighing standard substances, dissolving the standard substances in respective 5mL volumetric flasks by using acetonitrile, fixing the volume to a scale, preparing the standard stock solution with the mass concentration of 1mg/mL, and storing the standard stock solution in a refrigerator at 4 ℃;
preparing mixed standard working solution, accurately sucking a proper amount of stock solution, and preparing mixed standard working solution with corresponding concentration of 1 microgram/mL by using acetonitrile;
(2) QuEChERS extraction and purification of samples:
accurately weighing 5.00g of uniformly crushed aquatic product sample to be accurate to 0.01g, adding 1mL of water, 1.0g of sodium chloride and 10mL of acetonitrile into a 50mL centrifuge tube with a plug, carrying out vortex oscillation for 2min, then carrying out ultrasonic extraction for 10min, centrifuging for 10min at 5 ℃ at 13000r/min, transferring the supernatant to a sample which is placed in advance and 600-1200 mg of MgSO (MgSO) MgSO (MgSO) in advance4Swirling and oscillating for 5min in a 15mL centrifuge tube containing 50-200 mg of n-propyl ethylenediamine and 20-100 mg of graphitized carbon black, centrifuging for 10min at 13000r/min at 5 ℃, and transferring the supernatant into a 30mL glass tube to obtain a sample extracting solution;
(3) concentration: concentrating the sample extractive solution at 40 deg.C under reduced pressure with a parallel quantitative concentrator, dissolving the residue with methanol (water: 25: 75) v/v methanol water solution by vortex, filtering the extractive solution with 0.2 μm filter membrane, and measuring with ultra high performance liquid chromatography-high resolution mass spectrometer;
(4) ultra-high performance liquid chromatography-high resolution mass spectrometer analysis.
2. The detection method for rapidly screening a plurality of pesticides and biotoxins in aquatic product products according to claim 1, wherein the standard substance comprises:
carbaryl with the purity of more than or equal to 98.9 percent, carbofuran with the purity of more than or equal to 98.3 percent, 3-hydroxy carbofuran with the purity of more than or equal to 98.0 percent, isoprocarb with the purity of more than or equal to 98.5 percent, methomyl with the purity of more than or equal to 99.1 percent, dimethoate with the oxidation purity of more than or equal to 99.1 percent, acetamiprid with the purity of more than or equal to 98.1 percent, chlorsulfuron with the purity of more than or equal to 98.5 percent, diniconazole with the purity of more than or equal to 99.0 percent, edifenphos with the purity of more than or equal to 99.4 percent, imazalil with the purity of more than or equal to 99.0 percent, mefenoxam with the purity of more than or equal to 98.7 percent, paclobutrazol with the purity of more than or equal to 99.0 percent, fosetyl with the purity of more than or equal to 99.0 percent, phoxim with the purity of more than or equal to 99.0 percent, thiacloprid with the purity of more than or equal to 0 percent, triazophos with the purity of more than or equal to 98.95 percent, propiconazole with the purity of more than or equal to 0 percent, thiacloprid with the purity, Chlorpyrifos with the purity of more than or equal to 99.0 percent, fenamiphos with the purity of more than or equal to 99.5 percent, fenamiphos with the purity of more than or equal to 98.5 percent, anilinophosulfone with the purity of more than or equal to 99.0 percent, aldicarb with the purity of more than or equal to 99.2 percent, alachlor with the purity of more than or equal to 99.5 percent, chlorpyrifos with the purity of more than or equal to 99.0 percent, chlorpyrifos methyl with the purity of more than or equal to 99.9 percent, dichlorvos with the purity of more than or equal to 99.2 percent, dimethoate with the purity of more than or equal to 98.5 percent, ethion with the purity of more than or equal to 99.0 percent, fenthion with the purity of more than or equal to 98.0 percent, fenpyrazofos with the purity of more than or equal to 99.5 percent, fluvalicarb with the purity of more than or equal to 99.0 percent, fluvalicarb with the purity of more than or equal to 100 percent, fenthion with the purity of more than or equal to 99.0 percent, fenthion, fenpyraclofos, fenthion with the purity of more than or equal to 99.0 percent, fenthion, fen, Profenofos with purity of more than or equal to 98.2 percent, quinalphos with purity of more than or equal to 96.0 percent, tebufenpyrad with purity of more than or equal to 99.5 percent, tetraconazole with purity of more than or equal to 99.6 percent, methidathion with purity of more than or equal to 99.1 percent, azathion with purity of more than or equal to 97.8 percent, butoxycarb with purity of more than or equal to 91.3 percent, clothianidin with purity of more than or equal to 98.9 percent, fenamidone with purity of more than or equal to 96.9 percent, furalaxyl with purity of more than or equal to 98.5 percent, monocrotophos with purity of more than or equal to 99.0 percent, pyrafluanid with purity of more than or equal to 93.9 percent, phosmet with purity of more than or equal to 99.0 percent, fenzopyr with purity of more than or equal to 96.8 percent, subtilon with purity of more than or equal to 97.6 percent, diuron with purity of more than or equal to 99.3 percent, fenpropathrin with purity of more than or equal to 99.0 percent, fenpropathrin with purity of more than or equal to 99.1 percent, fenpropathrin with purity of more than or equal to 99., Thiodichlofop with the purity of more than or equal to 98.1 percent, fenthion with the purity of more than or equal to 98.0 percent, fenthion with the purity of more than or equal to 95.7 percent, fenthion sulphoxide with the purity of more than or equal to 99.5 percent, cyhalothrin with the purity of more than or equal to 98.4 percent, iprobenfos with the purity of more than or equal to 97.5 percent, phenthoate with the purity of more than or equal to 98.1 percent, phorate with the purity of more than or equal to 95.7 percent, phorate with the purity of more than or equal to 93.6 percent, fenpropathrin with the purity of more than or equal to 98.7 percent, triazophos with the purity of more than or equal to 99.2 percent, diclofop-methyl-ethyl with the purity of more than or equal to 99.4 percent, quizalofop-ethyl with the purity of more than or equal to 94.5 percent, cypermethrin with the purity of more than or equal to 99.52 percent, fenpropathrin with the purity of more than or equal to 87.0 percent, aflatoxin with the purity of more than or equal to 99.8 percent, diclofop-P-, Aflatoxin M2 with the purity of more than or equal to 99.5 percent, patulin with the purity of more than or equal to 99.1 percent, HT-2 toxin with the purity of more than or equal to 99.0 percent, T-2 toxin with the purity of more than or equal to 99.0 percent, zearalenone with the purity of more than or equal to 99.3 percent, aflatoxin with the purity of more than or equal to 99.6 percent, deoxynivalenol with the purity of more than or equal to 95.0 percent, diacetyl sickle knife fungus enol with the purity of more than or equal to 95.0 percent, neosolanum sickle fungus enol with the purity of more than or equal to 95.0 percent, nivalenol with the purity of more than or equal to 95.0 percent, and fusarium enone with the purity of more than or equal.
3. The detection method for rapidly screening multiple pesticides and biotoxins in aquatic product products according to claim 1, wherein 900mg MgSO is selected as purification filler for QuEChERS purification filler4100mg of n-propylethylenediamine and 50mg of graphitized carbon black.
4. The detection method for rapidly screening the various pesticides and biotoxins in the aquatic product according to claim 1, wherein the condensation temperature of the parallel quantitative concentrator is 5 ℃, and the vacuum degree is reduced in a gradient manner of 250mbar, 10min, 100mbar, 10min and 20mbar until the concentration is dry.
5. The detection method for rapidly screening various pesticides and biotoxins in aquatic products according to claim 1, wherein the parameters of the ultra-high performance liquid chromatography-high resolution mass spectrometer are as follows:
and (3) chromatography: c18150mm × 2.1mm, 3.3 μm; column temperature: 40 ℃; sample introduction amount: 10 mu L of the solution; mobile phase: a is 5mmol of 0.1% ammonium formate aqueous solution, B is 5mmol of 0.1% ammonium formate methanol solution, gradient elution program is 0-2.0 min, and 25% of B is kept; 2.0-7.0 min, linearly changing the proportion of the mobile phase B from 25% to 65%; 7.0-8.0 min, linearly changing the proportion of the mobile phase B from 65% to 90%; keeping 90% of B for 8.0-12.0 min; keeping 25% of B for 12.1-15 min;
mass spectrum: the temperature of a heating electrospray ion source is 350 ℃, the ion transmission temperature is 320 ℃, the sheath gas is 40 units, the auxiliary gas is 40 units, the capillary voltage is 3.2KV, and the temperature of an ion transmission pipe is 325 ℃;
full scan/ddms2 scan mode: the collection range is 80-1000 Da, and positive and negative switching collection is carried out; the resolution of the primary mass spectrum is 70000FWHM, and the resolution of the secondary mass spectrum is 17500 FWHM; the collision cell energy NCE was 20, 40, 60 eV.
6. The detection method for rapidly screening multiple pesticides and biotoxins in aquatic product products according to claim 1, wherein the adsorbent used for purifying the supernatant in the step (2) is 900mg MgSO 24100mg of n-propylethylenediamine and 50mg of graphitized carbon black.
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