CN113433247A - Method for measuring pesticide residue - Google Patents

Method for measuring pesticide residue Download PDF

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Publication number
CN113433247A
CN113433247A CN202110802087.4A CN202110802087A CN113433247A CN 113433247 A CN113433247 A CN 113433247A CN 202110802087 A CN202110802087 A CN 202110802087A CN 113433247 A CN113433247 A CN 113433247A
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methyl
mass
ethyl
pesticide
flow rate
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白冰
张耀丹
司文帅
王守英
黄志英
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Shanghai Academy of Agricultural Sciences
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Shanghai Academy of Agricultural Sciences
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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
    • 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
    • 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
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers

Abstract

The invention discloses a method for determining pesticide residues, and belongs to the technical field of pesticide determination. Measuring the contents of various pesticide components in a sample to be measured by using an UPLC-QTOF-MS method, wherein the pesticide components simultaneously comprise an insecticide and a bactericide; the liquid chromatography conditions include: the mobile phase A is methanol, and the mobile phase B is ammonium acetate aqueous solution or formic acid aqueous solution; the flow rate is 0.3-0.5 mL/min; the elution procedure for mobile phase a was: 0-0.5min, 2%; 0.5-15min, 2-98%; 15-17min, 98%; 17-17.1min, 98-2%; 17.1-20min, 2%; the mass spectrometry conditions include: an electrospray ionization source is adopted, and a positive ion mode is adopted; full scan mode, scan mass range 50-1000m/z, etc. The method has good sensitivity, accuracy and precision, and can accurately and efficiently detect the residual quantity of the pesticide in the vegetables and fruits.

Description

Method for measuring pesticide residue
Technical Field
The invention relates to the technical field of pesticide determination, and particularly relates to a method for determining pesticide residues.
Background
In the agricultural production process, a large amount of pesticide needs to be applied to ensure the yield of agricultural products, but the pesticide residue problem of the agricultural products is always one of the main risk factors influencing the quality and safety of agricultural products in China. Currently, 1100 kinds of pesticides are applied to agricultural production in China, the types of the pesticides are various, the purposes of the pesticides are different, a list of the pesticides forbidden and authorized to be used on agricultural products such as vegetables and fruits is changed continuously, and a plurality of pesticides do not have related national, industrial or local standards, so that the daily monitoring of the pesticides is limited.
Most of the traditional pesticide residue detection technologies are targeted detection technologies based on gas/liquid chromatography, gas/liquid chromatography-mass spectrometry, gas/liquid chromatography-tandem mass spectrometry and the like. Due to the fact that agricultural product matrixes are complex, sample sources are wide, pesticides are various, concentration ranges are wide, and differences of physicochemical properties of screened objects are large, the existing targeted detection technology is difficult to comprehensively analyze or simultaneously analyze pesticides and toxic metabolites in agricultural products, and is difficult to effectively implement monitoring, prevention and control of multi-residue drugs in agricultural products.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for measuring pesticide residue, which can accurately and efficiently detect at least one residue of an insecticide and a bactericide in a sample to be measured.
The application can be realized as follows:
the application provides a method for measuring pesticide residues, which adopts a UPLC-QTOF-MS method to measure the content of various pesticide components in a sample to be measured, wherein the pesticide components simultaneously comprise an insecticide and a bactericide;
the liquid chromatography conditions during the assay included: the mobile phase A is methanol, and the mobile phase B is ammonium acetate aqueous solution or formic acid aqueous solution; the flow rate is 0.3-0.5 mL/min; the elution procedure for mobile phase a was: 0-0.5min, 2%; 0.5-15min, 2-98%; 15-17min, 98%; 17-17.1min, 98-2%; 17.1-20min, 2%;
the mass spectrometric conditions during the assay included: the ion source adopts an electrospray ionization source and a positive ion mode; a full scanning mode, wherein the scanning mass range is 50-1000 m/z; the flow rate of the air curtain is 32-38 psi; the flow rate of the spray gas is 48-52psi, and the flow rate of the auxiliary heating gas is 48-52 psi; ionization voltage5450 and 5550V; the temperature is 490-510 ℃; the de-clustering voltage is 78-82V; the collision energy is 20-50 eV; self-calibrating reference ion to mass to charge ratio of 609.28766C33H40N2O9(ii) a MS/MS mode reference feature ions comprising C with mass-to-charge ratio of 174.0913011H12NO, C with mass to charge ratio of 195.0652010H11O4C with a mass to charge ratio of 236.1281013H18NO3C with a mass to charge ratio of 365.1860022H25N2O3C with a mass to charge ratio of 397.2122023H29N2O4C with a mass to charge ratio of 448.1966023H30NO8C with a mass to charge ratio of 609.2806633H40N2O9。
In a preferred embodiment, the flow rate in the liquid chromatography conditions is 0.4mL/min and the flow rate of the gas curtain gas in the mass spectrometry conditions is 35 psi; the flow rate of the spray gas is 50psi, and the flow rate of the auxiliary heating gas is 50 psi; the ionization voltage is 5500V; the temperature is 500 ℃; the declustering voltage was 80V.
In an alternative embodiment, mobile phase B is an aqueous ammonium acetate solution having a concentration of 4.5 to 5.5mmol/L, preferably a concentration of 5 mmol/L.
In an alternative embodiment, the column temperature during liquid chromatography is 30-50 ℃, preferably 45 ℃.
In an alternative embodiment, the sample size during liquid chromatography is 3-5. mu.L, preferably 3. mu.L.
In an alternative embodiment, the method further comprises the following pretreatment of the sample to be tested: extracting the pulped slurry of the sample to be tested by using an extracting agent, then mixing with sodium chloride, centrifuging, taking supernate, mixing with water, and then filtering by using a membrane.
In an alternative embodiment, the extractant is acetonitrile.
In an optional embodiment, the extraction is performed by mixing the extractant with the slurry, performing vortex extraction for 15-25min, and performing ultrasonic extraction for 4-6 min.
In an alternative embodiment, the method further comprises the step of measuring the standard solution corresponding to the pesticide component according to the same conditions as the sample to be measured so as to compare the measurement results of the sample to be measured.
In alternative embodiments, the insecticide comprises 3-hydroxycarba, avermectin B1a, chlorothalofop, bayphos, fenthion sulfone, fenthion sulfoxide, thiophen, fenamiphos sulfone, fenamiphos sulfoxide, fenoxycarb, pyriproxyfen, imidacloprid, profenofos, propoxur, tebufenozide, pyrethrin I, pyrethrin II, diflubenzuron, pyridaphethione, phenthoate, fonofol, trichlorfon, dichlorvos, butanil, acetamiprid, chlorfenapyr, chlorpyrifos, parathion, spinosad A, spinosad D, bendiocarb, diazinon, fosfon, sulfofenphos-S-sulfoxide, dinotefuran, oxamyl, vortiofos, fluvalinate, flubendiamide, flubenflumuron, flufenoxuron, fipronil sulfone, flufenoxuron, sulfoxafluoride, flubenflumeturon, hexaflumuron, pyrifenozide, Fenvalerate, flucythrinate, heptenophos, chromafenozide, emamectin benzoate B1a, methamidophos, phorate sulfone, phorate sulfoxide, chlorpyrifos-methyl, phoxim-methyl, thiophosphoryl-methyl, pirimiphos-methyl, isoxathion-methyl, carbaryl, fenpropathrin, methoxyfenozide, monocrotophos, pirimicarb, carbofuran, quinalphos, dimethoate, bifenthrin, phosphamidon, thiophosphoryl, thiodicarb, cadusafos, spirotetramat-mono-hydroxy, spirotetramat-keto-hydroxy, spirotetramat-enol-glucoside, chlorantraniliprole, cyhalothrin, cypermethrin, imidacloprid, pyrazofos, malathion, methiocarb, ethrin, cyromazine, imibenclamide, chlorfluazuron, fenvalerate, thiacloprid, fenpyrazofos, methamidothion, methamphetamine B1, methamidophos, methophos, methomyl, sulbensulfenpropathyrifos, sulbensulbensulpirimibensulbensulbensulbensulbensulbensulbensulpirimibensulpirimibensulbensulpirimibensulpirimibensulpirimibensulpirimibensulindate, bensulpirimibensulbensulpirimibensulindate, bensulindate, benbenbenbenbenbenbensulindate, benbenbenbensulindate, benben, Thiacloprid, thiamethoxam, buprofezin, pyridalyl, triazophos, chlordimeform, hexaflumuron, fenitrothion, methidathion, oxamyl oxime, lufenuron, metoclopramide, terbufos sulfone, terbufos sulfoxide, aldicarb sulfone, aldicarb sulfoxide, demethylcarboxamido pirimicarb, demethylated pirimicarb, nitenpyram, phoxim, cyantraniliprole, deltamethrin, triazophos, phosmet, phos-sulphoxide, oxyphenphos, omethoate, oxydimothion, ivermectin, disulfoton, fosetyl, ethiprol, acephate, isoprocarb, indoxacarb, coumaphos, rotenone, fenitrothion, fenobuconazole, and fenbuconazole.
In a preferred embodiment, the insecticide includes both imidacloprid, acetamiprid, dinotefuran, flonicamid, hexaflumuron, chlorantraniliprole, cyhalothrin, cypermethrin, clothianidin, thiamethoxam, and triflumuron.
In alternative embodiments, the bactericide includes fenpyrazamine, benfluanid, metrafenone, difenoconazole, benalaxyl, zoxamide, fenpropidin, penthiopyrad, pyraclostrobin, isopyrazam, trichloramidone, propiconazole, prothioconazole, propoxymoline, isoprothiolane, fenoxanil, dinocap-phenol, edifenphos, coumoxystrobin, pyrisoxazole, boscalid, picoxystrobin, carbendazim, hymexazol, oxadixyl, famoxadone, flutriafol, fluopyram, flusilazole, epoxiconazole, triflumizole metabolite, flumorph, flutolanil, flutrianilide, procymidone, fludioxonil, silthiopham, cyproconazole, cyflufenamid, hexaconazole, fenflurazole, tolfenprophos-methyl, thiophanate-methyl, mefenoxaprop-methyl, benazol-ethyl, flufenamate, flufenacetronil, flufenapyr, flufenacetropa, Myclobutanil, bromuconazole, quinoxyfen, bitertanol, fenarimol, prochloraz-deaminazole, prochloraz-deimidazole carboxamido, fenamidone, dimoxystrobin, kresoxim-methyl, cyprodinil, azoxystrobin, pyrimethanil, triticonazole, mefenacet, cyazofamid metabolite, cyazoxystrobin, thifluzamide, thiabendazole, tricyclazole, triadimenol, triadimefon, mandipropamid, propamocarb, tetraconazole, thioprothioconazole, trifloxystrobin, pencycuron, penconazole, tebuconazole, dimethomoxamide, enestrobin, diniconazole, myclobutanil, metconazole, diethofencarb, bupirimate, iprobenfos, imazalil, amikazamide, ipconazole, pyraclostrobin, and imazacil.
In a preferred embodiment, the fungicide comprises both difenoconazole, pyraclostrobin, boscalid, carbendazim, fluopyram, thiophanate-methyl, myclobutanil, prochloraz, cyprodinil, azoxystrobin, pyrimethanil, triadimenol, triadimefon, propamocarb and ethirimol.
In an alternative embodiment, the pesticide composition further comprises at least one of a miticide, a molluscicide, a nematicide, and a synergist.
In an alternative embodiment, the acaricide comprises at least one of fenoxycarb, pyridaben, cyflumetofen, fenazaquin, bifenazate, spiromesifen, spirodiclofen, propargite, hexythiazox, clofentezine, etoxazole and fenpyroximate.
In a preferred embodiment, the acaricide comprises bifenazate.
In an alternative embodiment, the molluscicide includes at least one of methiocarb sulfone and methiocarb sulfoxide.
In alternative embodiments, the nematicide comprises at least one of fenamiphos and fosthiazate.
In a preferred embodiment, the nematicide comprises fosthiazate.
In an alternative embodiment, the synergist comprises a synergist ether.
In an alternative embodiment, the pesticide composition further comprises a herbicide.
In alternative embodiments, the herbicide includes ethametsulfuron, tribenuron, saflufenacil, metamitron, mefenacet, pyraflufen-ethyl, fluazifop-butyl, diflufenican, pyrazosulfuron-ethyl, pyraflufen-ethyl, prosulfuron, oxadiargyl, propanil, diuril, diuron, butachlor, buthiuron-methyl, propyzamide, oxadiazon, oxaziclomefone, metamitron, metamifop, pendimethalin, rimsulfuron, flurtamone, prosulfuron, fluazifop, haloxyfop, flupyrazamide, fomfen, flufenacet, thiofenacet, thiobencarb, diclofop, cyclosulfamuron, pyrifton, sulcotrione, sulfentrazone, meturon-methyl, iodosulfuron-methyl, mebendazole, benfurazone, metolachlorfen-ethyl, dimethenamid-p, dimethenamid-p-methyl, dimethenap-p-methyl, fenoxap-p, fenoxap-ethyl, fenoxaprop-p-ethyl, bensulfuron-methyl, bensulfuron-ethyl, bensulfuron-methyl, bensulfuron-ethyl, bensulfuron-methyl, bensulfuron-ethyl, bensulfuron-methyl, bensulfuron-ethyl, bensulfuron-methyl, bensulfuron-ethyl, bensulfuron-methyl, bensulfuron-ethyl, bensulfuron-methyl, bensulfuron-, Quizalofop-p-ethyl, linuron, chlorsulfuron, halosulfuron-methyl, fluroxypyr-ethyl, chlorsulfuron, chlorimuron-ethyl, imazaquin, imazethapyr, triasulfuron, cinosulfuron, pyrisulfuron, pyribenzoxim, propaquizafop, prometryn, metazosulfuron, metrizachlor, metribuzin, cyanazine, cyhalofop, propyzamide, clodinafop, lactofen, thifensulfuron-methyl, triflusulfuron, tralkoxydim, fenprophos, bensulam, diflufenican, terbuthylazine, phencyclamate, penoxsulam, simetryn, simazine, clethodim sulfoxide, sethoxydim, amidon, mesotrione, nicosulfuron, triasulfuron, carbenoxafen, ethoxyflurane, oxyfluorfen, isoxauron, prosulfuron, propafen, metosulam, nicosulfuron-methyl, At least one of clomazone, isoxaflutole, ametryn, atrazine, butralin, carfentrazone-ethyl, pinoxaden and flumetsulam.
In an alternative embodiment, the pesticide composition further comprises a plant growth regulator.
In an alternative embodiment, the plant growth regulator comprises at least one of diethyl aminoethyl hexanoate, paclobutrazol, flumetrazol, trinexapac-ethyl, forchlorfenuron, thidiazuron and uniconazole.
In an alternative embodiment, the sample to be tested is an agricultural product, preferably a fruit and/or vegetable.
The beneficial effect of this application includes:
the application establishes an analysis method for simultaneously and rapidly measuring high-flux various pesticides (at least comprising insecticides and bactericides) based on a high-resolution mass spectrometry technology, is simple to operate, and has the advantages that the linear correlation coefficient r of all the pesticides in the established detection method2Are all more than 0.990, the detection Limit (LOD) range is 0.6-10 mug/kg, the quantification Limit (LOQ) range is 2.0-30 mug/kg, and the quantification limit of 98.1 percent of pesticide is not more than 10 mug/kg. The method has accurate and reliable qualitative and quantitative determination, high sensitivity, and can effectively avoid false detection and missed detectionThe method can be used for high-throughput qualitative screening and quantitative analysis of various pesticide residues in vegetables and fruits.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The method for measuring the pesticide residue provided by the present application will be specifically described below.
The application provides a method for measuring pesticide residues, which measures the content of various pesticide components in a sample to be measured by adopting an UPLC-QTOF-MS (ultra high performance liquid chromatography-quadrupole time of flight mass spectrometry), wherein the pesticide components simultaneously comprise an insecticide and a bactericide.
In an alternative embodiment, the sample to be tested is an agricultural product, preferably a fruit and/or vegetable.
The liquid chromatography conditions during the assay included: the mobile phase A is methanol, and the mobile phase B is ammonium acetate aqueous solution or formic acid aqueous solution; the flow rate is 0.3-0.5mL/min (e.g., 0.3mL/min, 0.35mL/min, 0.4mL/min, 0.45mL/min, or 0.5 mL/min); the elution procedure for mobile phase a (gradient elution) was: 0-0.5min, 2%; 0.5-15min, 2-98%; 15-17min, 98%; 17-17.1min, 98-2%; 17.1-20min, 2%.
In a preferred embodiment, the mobile phase B is an aqueous ammonium acetate solution, which may have a concentration of, for example, 4.5 to 5.5mmol/L, preferably 5 mmol/L. That is, in a preferred embodiment, the mobile phase is complexed by methanol (mobile phase a) and an aqueous ammonium acetate solution (mobile phase B). The flow rate is preferably 0.4 mL/min.
In alternative embodiments, the column temperature during the above-described liquid chromatography may be 30-50 ℃, such as 30 ℃, 35 ℃, 40 ℃, 45 ℃ or 50 ℃, and the like, preferably 45 ℃. The amount of sample to be used in the liquid chromatography may be 3-5. mu.L, such as 3. mu.L, 3.5. mu.L, 4. mu.L, 4.5. mu.L or 5. mu.L, etc., preferably 3. mu.L.
Has been determinedThe mass spectrometry conditions in the process include: the ion source adopts an electrospray ionization source (ESI) and a positive ion mode; a full scanning mode, wherein the scanning mass range is 50-1000 m/z; the flow rate of the air curtain gas (CUR) is 32-38 psi; the flow rate of the spray gas (GS1) is 48-52psi, and the flow rate of the auxiliary heating gas (GS2) is 48-52 psi; the ionization voltage (ISVF) is 5450-5550V; the Temperature (TEM) is 490-510 ℃; the declustering voltage (DP) is 78-82V; the Collision Energy (CE) is 20-50 eV; self-calibrating reference ion to C with mass to charge ratio (m/z) of 609.2876633H40N2O9(ii) a MS/MS mode reference feature ions comprising C with mass-to-charge ratio of 174.0913011H12NO, C with mass to charge ratio of 195.0652010H11O4C with a mass to charge ratio of 236.1281013H18NO3C with a mass to charge ratio of 365.1860022H25N2O3C with a mass to charge ratio of 397.2122023H29N2O4C with a mass to charge ratio of 448.1966023H30NO8C with a mass to charge ratio of 609.2806633H40N2O9。
The flow rate of the air curtain gas can be 32psi, 33psi, 34psi, 35psi, 36psi, 37psi or 38psi, and can also be any other value within the range of 32-38 psi.
The flow rate of the spray may be 48psi, 49psi, 50psi, 51psi, 52psi, etc., or any other value within the range of 48-52 psi.
The flow rate of the auxiliary heating gas may also be 48psi, 49psi, 50psi, 51psi, 52psi, etc., or any other value within the range of 48-52 psi.
The ionization voltage may be 5450V, 5500V, 5550V, or any other value within the range of 5450 and 5550V.
The temperature may be 490 ℃, 495 ℃, 500 ℃, 505 ℃, 510 ℃ or the like, or may be any other value within the range of 490 ℃ and 510 ℃.
The declustering voltage can be 78V, 79V, 80V, 81V, 82V, etc., and can also be any other value within the range of 78-82V.
In a preferred embodiment, the flow rate of the gas curtain gas in the mass spectrometry conditions is 35 psi; the flow rate of the spray gas is 50psi, and the flow rate of the auxiliary heating gas is 50 psi; the ionization voltage is 5500V; the temperature is 500 ℃; the declustering voltage was 80V.
It should be noted that the specific materials used in the present application for the air curtain, the spraying air and the auxiliary heating air can refer to the prior art, and are not described herein in detail.
The time-of-flight mass spectrum has the advantages of accurate mass measurement and high resolution, has higher sensitivity and selectivity when acquiring information of precursor ions and fragment ions, can accurately measure the mass of molecules and fragment ions, further accurately determines the nature, avoids false detection and omission, can quickly and accurately screen multiple residual pesticides in unknown samples, and improves the efficiency and reliability of qualitative screening.
Before the detection, the method also comprises the following pretreatment of the sample to be detected: extracting the pulped slurry of the sample to be tested by using an extracting agent, then mixing with sodium chloride, centrifuging, taking supernate, mixing with water, and then filtering by using a membrane.
In a preferred embodiment, the extractant is acetonitrile. The acetonitrile is mainly used for extracting the pesticide components in the slurry, the extraction amount of impurities is small in the extraction process, and the recovery rate of the acetonitrile in the process of extracting various pesticides is within an acceptable range; if acetone is used, more impurities can be extracted, the subsequent measurement result is influenced, and the safety is poor.
In an alternative embodiment, the extraction may be performed by mixing the extractant with the slurry, followed by vortex extraction for 15-25min (e.g., 20min), and then ultrasonic extraction for 4-6min (e.g., 5 min).
The NaCl used in the pretreatment process can ensure that water and acetonitrile have good layering effect and can remove part of protein.
Specifically, the pretreatment may refer to: weighing 10-20g of homogenized sample to be tested (such as vegetables and fruits) in a 50mL polypropylene centrifuge tube, adding 10-20mL of acetonitrile, performing vortex extraction for 15-25min, performing ultrasonic extraction for 4-6min, then adding 3-5g of sodium chloride, performing vortex extraction for 1-2min, centrifuging at the rotation speed of 4800-5200r/min for 4-6min, taking 1mL of supernatant into a 10mL glass test tube, adding 1mL of ultrapure water, performing vortex mixing for 25-35s, filtering the extracting solution through a 0.22 mu m nylon filter, and bottling for testing.
In alternative embodiments, the insecticides in the present application may include, for example, 3-hydroxycarbibar, abamectin B1a, chlorothalonil, bayphos, fenthion sulfone, fenthion sulfoxide, fenthion, fenamiphos, fenoxycarb, pyriproxyfen, imidacloprid, profenofos, propoxur, tebufenozide, pyrethrin I, pyrethrin II, diflubenzuron, pyridaphone, phenthoate, disulfoton, trichlorfon, dichlorvos, butanil, acetamiprid, chlorfenapyr, chlorpyrifos, parathion, spinosad A, spinosad D, bendiocarb, diazinon, fenthion, sulfofenprophos, fenprophos-S-sulfoxide, dinotefuran, furacarb, fenthion, fluvalinate, fluvalicarb, flufenpropathrin, flubenuron, fipronil, flubensulponin, flubenfursulide, flufenpyr, flubensulide, flubenfursulide, flubensulide, etc, Chlorfluazuron, hexaflumuron, flucythrinate, novaluron, heptenophos, chromafenozide, emamectin B1a, methamidophos, phorate sulfone, phorate sulfoxide, chlorpyrifos-methyl, phophorus methyl sulfone, thiophosphoryl methyl, pirimiphos-methyl, isoxathion-methyl, carbaryl, fenpropathrin, methoxyfenozide, monocrotophos, pirimicarb, carbofuran, quinalphos, dimethoate, bifenthrin, phosphamidon, thiotepa, thiodicarb, spirotetramat-mono-hydroxy, spirotetramat-keto-hydroxy, spirotetramat-enol-glucoside, chlorantraniliprole, cyhalothrin, permethrin, cypermethrin, imidacloprid, chlorfenphos, malathion, methiocarb, ethrin, cyflufen, chlorfluazuron, metaflumizone, hydrazone, metaflumizozone, methabenzuron, chlorfenapyr, fenofos, fenthiuron, fenpyr, fenpropathrin, fenthiuron, chlorfenapyr, methabenzuron, methamidone, methamidothion, thiuron, thion, bensulindamine, thion, bensulbensulindamine, benfurbensulindac, benfurbenfurin, benfurbenfurbenfurbenfurbensulindac, benfurin, bensulindac, benfurbenfurbenfurin, benfurin, benfurbensultap, benfurbenfurbenfurin, benfurbenfurin, benfurbenfurbenfurin, benfurbenfurin, benfurin, benfurbenfurbenfurbenfurbenfurin, benfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurin, benfurbenfurin, benfurbenfurbenfurin, benfurin, benfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurin, benfurbenfurbenfurbenfurin, benfurin, bensulam, benfurin, benfurbenfurbenfurbensulam, benfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfur, Fenvalerate, clothianidin, thiacloprid, thiamethoxam, buprofezin, pyridalyl, triazophos, chlordimeform, triflumuron, fenitrothion, methidathion, oxamyl oxime, lufenuron, metocloprid, terbufos sulfone, terbufos sulfoxide, aldicarb sulfone, aldicarb sulfoxide, demethylcarboxamido pirimicarb, demethylcarbosulfan, nitenpyram, phoxim, cyantraniliprole, deltamethrin, aphidophos, phosmet, sulphoxide, oxyphenbutazone sulfone, omethoate, oximinothion, ivermectin, disulfoton sulfone, disulfoton sulfoxide, disulfoton, ethiprole (clear), spinetoram A, spinetoram B, ethion, etrimfos, acephate, isoprocarb, indoxacarb, coumaphos, rotenone, sulfotep, fenobucarb and tolfenpyrad.
In a preferred embodiment, the insecticide includes both imidacloprid, acetamiprid, dinotefuran, flonicamid, hexaflumuron, chlorantraniliprole, cyhalothrin, cypermethrin, clothianidin, thiamethoxam, and triflumuron.
In alternative embodiments, the bactericide may include, for example, fenpyrazamine, benfluanid, metrafenone, difenoconazole, benalaxyl, zoxamide, fenpropidin, penthiopyrad, pyraclostrobin, isopyrazam, benzytriazolol, propiconazole, prothioconazole, propoxymine, isoprothiolane, fenoxanil, fenamiphos, coumoxystrobin, pyrisoxazole, boscalid, picoxystrobin, carbendazim, hymexazol, oxadixyl, famoxadone, flutriafol, fluopyram, flusilazole, epoxiconazole, triflumizole metabolite, flumorph, flutolanil, flutriafol, flutrianilide, procymidone, fludioxonil, silthiopham, cyproconazole, cyhexamid, hexaconazole, tolanil, tolnaftate, thiophanate-methyl, metyl, metalaxyl, propamocarb, Fenbuconazole, myclobutanil, bromuconazole, quinoxyfen, bitertanol, fenarimol, prochloraz-deaminated imidazole, prochloraz-deimidazolam, fenamidone, dimoxystrobin, kresoxim-methyl, cyprodinil, azoxystrobin, pyrimethanil, triticonazole, mefenamide, cyazofamid metabolite, cyazoxystrobin, thifluzamide, thiabendazole, tricyclazole, triadimenol, triadimefon, mandipropamid, propamocarb, tetraconazole, thioconazole, trifloxystrobin, pencycuron, penconazole, tebuconazole, dinil, enestrobin, dimethomorph, diniconazole, valicarb, imicarb, metconazole, ethirimol, bupirimate, iprobenfos, imazalil, indazole, ipconazole, pyraclostrobin, and mepanid.
In a preferred embodiment, the fungicide comprises both difenoconazole, pyraclostrobin, boscalid, carbendazim, fluopyram, thiophanate-methyl, myclobutanil, prochloraz, cyprodinil, azoxystrobin, pyrimethanil, triadimenol, triadimefon, propamocarb and ethirimol.
In an alternative embodiment, the pesticide composition further comprises at least one of a miticide, a molluscicide, a nematicide, and a synergist.
Wherein the acaricide can comprise at least one of fenoxycarb, pyridaben, cyflumetofen, fenazaquin, bifenazate, spiromesifen, spirodiclofen, propargite, hexythiazox, clofentezine, etoxazole and fenpyroximate. In a preferred embodiment, the acaricide comprises bifenazate.
The molluscicide may include at least one of methiocarb sulfone and methiocarb sulfoxide.
The nematicide may include at least one of fenamiphos and fosthiazate. In a preferred embodiment, the nematicide comprises fosthiazate.
The synergist may for example comprise a synergist ether.
Further, the above-mentioned pesticide composition may further comprise a herbicide.
In alternative embodiments, herbicides can include, for example, ethametsulfuron, tribenuron, saflufenuron, metamitron, mefenacet, pyraflufen, diflufenican, pyrazosulfuron, pyraflufen, prosulfuron, oxadiargyl, propanil, diuril, diuron, butachlor, buthiuron, propathyride, propyzamide, oxadiazon, oxaziclomefone, metamifop, haloxyfop, fluazifop, flupyrazamide, fomfen, flufenacet, thiofenacet, thiocarb, diclofop, cyclosulfamuron, pyrifton, sulfometuron, sulfentrazone, meturon sodium salt, mesotrione, mebendazole, bifenox, dicofol, fenoxaprop-p-ethyl, fenoxaprop-p-ethyl, metosulam, metosul, Dimethenamid-p, quizalofop-p-ethyl, linuron, chlortoluron, halosulfuron-methyl, fluroxypyr-ethyl, chlorsulfuron, chlorimuron-ethyl, imazaquin, imazethapyr, triasulfuron, cinosulfuron, pyribensulfuron, pyribenzoxim, penflufen, prometryn, metazosulfuron, metribuzin, cyanazine, cyhalofop-butyl, propyzamide, clodinafop, lactofen-ethyl, thifensulfuron-methyl, prosulfuron, tralkoxydim, fenprophos, anilofos, diclofop, flubenfop-butyl, terbuthylazine, propaquizam, penoxsulam, simetryn, clethodim sulfone, clethodim sulfoxide, sethoxydim, amidosulfuron, mesotrione, nicosulfuron, triallate, fluoroglycofen-ethyl, ethoxyfen-ethyl, ethoxysulfuron, prosulfuron, propaferon, metosulam, bensulfuron-p-ethyl, bensulam, bensulfuron, bensulam, bensulfuron, bensulam, bensulfuron, bensulam, bensulfuron, bensulam, bensulfuron, bensulam, bensulfuron, bensulam, ben, At least one of isoproturon, clomazone, isoxaflutole, ametryn, atrazine, butralin, carfentrazone, pinoxaden, and flumetsulam.
Further, the above-mentioned pesticide composition may further comprise a plant growth regulator.
In alternative embodiments, the plant growth regulator may include, for example, at least one of diethyl aminoethyl hexanoate, paclobutrazol, flumetrazol, trinexapac-ethyl, forchlorfenuron, thidiazuron and uniconazole.
Preferably, the determination method provided by the application can at least simultaneously determine imidacloprid, acetamiprid, dinotefuran, flonicamid, hexaflumuron, chlorantraniliprole, cyhalothrin, cypermethrin, clothianidin, thiamethoxam, triflumuron, difenoconazole, pyraclostrobin, boscalid, carbendazim, fluopyram, thiophanate-methyl, myclobutanil, prochloraz, cyprodinil, azoxystrobin, pyrimethanil, triadimenol, triadimefon, propamocarb, ethirimol, bifenazate and fosthiazate in a sample to be determined.
Further, the assay method of the present application may further include: and (3) measuring the standard solution corresponding to the pesticide component to be detected according to the same conditions as the sample to be detected, and taking the measured result of the standard solution as a control.
Specifically, the standard solution can be prepared by: using acetone as a solvent, preparing a plurality of groups of standard solutions into a group of mixed standard solutions containing 1 mu g/mL of all pesticides, storing the mixed standard solutions at 4 ℃ in a dark place, and reconfiguring the mixed standard solutions once every two months.
In conclusion, the application can accurately and efficiently detect the 373 pesticides in the vegetables and fruits by combining the high-resolution mass spectrometry technology with a simple and quick pretreatment method, and can meet the trace detection and analysis of the residual pesticides in the vegetables and fruits. Linear correlation coefficient r of all pesticides in the detection method established by the application2Are all greater than 0.990. The detection Limit (LOD) is 0.6-10 mug/kg, the quantitative Limit (LOQ) is 2.0-30 mug/kg, and the quantitative limit of 98.1 percent of pesticide is not more than 10 mug/kg. When the strawberry is used as a matrix and the adding concentrations of the pesticides are respectively 10 mug/kg, 50 mug/kg and 100 mug/kg, the results of 6 parallel measurements of each level show that the recovery rate of 352 (94.4%) pesticides ranges from 70% to 120%, and the recovery rate of abamectin B1a in the rest 21 pesticides is 130% at the adding level of 10 mug/kg; the recovery rate of tribenuron-methyl, benzytriazole, propoxymine, buthiuron, pyrisoxazole, heptenophos, fenazaquin, bifenthrin, forchlorfenuron, imidaclothiz, ethofenprox, cyromazine, fenflurazole, prometryn, pencycuron, clethodim, sethoxydim, difenofos and metconazole is lower than 70% (30% -67%). The Relative Standard Deviation (RSD) of all pesticides was less than 20% (0.7% to 14.7%). The method has good sensitivity, accuracy and precision, is simple to operate, and can meet the requirements of relevant laws and policies at home and abroad on the analysis method of the pesticide residue in the vegetables and fruits.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The present example provides a method for measuring pesticide residue, which specifically comprises the following steps:
sample pretreatment: weighing 10g of homogenized sample to be detected (strawberry) in a 50mL polypropylene centrifuge tube, adding 10mL of acetonitrile, performing vortex extraction for 20min, performing ultrasonic extraction for 5min, then adding 5g of sodium chloride, performing vortex extraction for 1min, centrifuging for 5min at the rotating speed of 5000r/min, taking 1mL of supernatant into a 10mL glass test tube, adding 1mL of ultrapure water, performing vortex mixing for 30s, filtering the extracting solution through a 0.22 mu m nylon filter, and bottling for detection.
Preparing a standard solution: the twenty-six groups of standard solutions are prepared into a group of mixed standard solutions containing 1 mu g/mL of all pesticides by taking acetone as a solvent, and the mixed standard solutions are stored at 4 ℃ in a dark place and are reconfigured once every two months.
The contents of various pesticide components in a sample to be tested are measured by using an UPLC-QTOF-MS method according to the following conditions, and are compared with the measurement result of a standard solution under the same measurement conditions.
The liquid chromatography conditions during the assay included: the mobile phase A is methanol, and the mobile phase B is ammonium acetate aqueous solution with the concentration of 5 mmol/L; the flow rate is 0.4 mL/min; the elution procedure for mobile phase a (gradient elution) was: 0-0.5min, 2%; 0.5-15min, 2-98%; 15-17min, 98%; 17-17.1min, 98-2%; 17.1-20min, 2%; the column temperature was 45 ℃; the amount of sample was 3. mu.L.
The mass spectrometric conditions during the assay included: the ion source adopts an electrospray ionization source (ESI) and a positive ion mode; a full scanning mode, wherein the scanning mass range is 50-1000 m/z; the flow rate of the air curtain air (CUR) was 35 psi; the flow rate of the spray gas (GS1) was 50psi, and the flow rate of the auxiliary heating gas (GS2) was 50 psi; the ionization voltage (ISVF) is 5500V; the Temperature (TEM) was 500 ℃; the declustering voltage (DP) is 80V; collision Energy (CE) 35 ± 15 eV; self-calibrating reference ion to C with mass to charge ratio (m/z) of 609.2876633H40N2O9(ii) a MS/MS mode reference feature ions comprising C with mass-to-charge ratio of 174.0913011H12NO, C with mass to charge ratio of 195.0652010H11O4C with a mass to charge ratio of 236.1281013H18NO3C with a mass to charge ratio of 365.1860022H25N2O3C with a mass to charge ratio of 397.2122023H29N2O4C with a mass to charge ratio of 448.1966023H30NO8C with a mass to charge ratio of 609.2806633H40N2O9。
The instruments and reagents used in the above process include: high performance liquid chromatography (Waters Acquity I-Class, Waters Inc. USA) -quadrupole time-of-flight mass spectrometry (AB SCIEX tripleTOF 5600+, Waters ACQUITY UPLC HSS T3 column (100X 2.1mm, 1.8 μm, Waters Inc. USA), MX-F vortex mixer (Dragonlab Inc. China), 5415D centrifuge (Eppendorf Inc. USA), Milli-Q water purification system (Millipore Inc. USA), 0.22 μm nylon filter (Shanghai Anan Spectroscopy Inc. China).
Chromatographically pure methanol, acetonitrile and acetone (Merck, Germany), ammonium acetate (purity not less than 99.0%, Shanghai' an spectral Co., China), analytically pure sodium chloride (Shanghai Tantan, China), twenty groups of 100 μ g/mL and five groups of 10 μ g/mL certified pesticide mixed standard solutions (solvents are acetonitrile, methanol, toluene, n-hexane, acetone, etc.) purchased from Tianjin Altar science and technology Co., Ltd, China.
The method for verifying parameters and results of 373 kinds of pesticides determined by the UPLC-QTOF/MS method are shown in Table 1, wherein the adducts are + H, + NH4Or + Na.
TABLE 1 measurement results
Figure BDA0003165043200000141
Figure BDA0003165043200000151
Figure BDA0003165043200000161
Figure BDA0003165043200000171
Figure BDA0003165043200000181
Figure BDA0003165043200000191
Figure BDA0003165043200000201
Figure BDA0003165043200000211
Example 2
The present example provides a method for measuring pesticide residue, which specifically comprises the following steps:
sample pretreatment: weighing 15g of homogenized sample to be detected (cucumber) in a 50mL polypropylene centrifuge tube, adding 15mL of acetonitrile, performing vortex extraction for 15min, performing ultrasonic extraction for 4min, then adding 3g of sodium chloride, performing vortex extraction for 1.5min, centrifuging at the rotating speed of 4800r/min for 4min, taking 1mL of supernatant into a 10mL glass test tube, adding 1mL of ultrapure water, performing vortex mixing for 25s, filtering the extracting solution through a 0.22 mu m nylon filter, and bottling to be detected.
Preparing a standard solution: the twenty-six groups of standard solutions are prepared into a group of mixed standard solutions containing 1 mu g/mL of all pesticides by taking acetone as a solvent, and the mixed standard solutions are stored at 4 ℃ in a dark place and are reconfigured once every two months.
The contents of various pesticide components in a sample to be tested are measured by using an UPLC-QTOF-MS method according to the following conditions, and are compared with the measurement result of a standard solution under the same measurement conditions.
The liquid chromatography conditions during the assay included: the mobile phase A is methanol, and the mobile phase B is ammonium acetate aqueous solution with the concentration of 4.5 mmol/L; the flow rate is 0.35 mL/min; the elution procedure for mobile phase a (gradient elution) was: 0-0.5min, 2%; 0.5-15min, 2-98%; 15-17min, 98%; 17-17.1min, 98-2%; 17.1-20min, 2%; the column temperature is 30 ℃; the amount of sample was 4. mu.L.
The mass spectrometric conditions during the assay included: the ion source adopts an electrospray ionization source (ESI) and a positive ion mode; full scan mode, scan mass range of50-1000 m/z; the flow rate of the air curtain air (CUR) was 32 psi; the flow rate of the spray gas (GS1) was 48psi, and the flow rate of the auxiliary heating gas (GS2) was 50 psi; ionization voltage (ISVF) is 5450V; the Temperature (TEM) was 490 ℃; the declustering voltage (DP) is 78V; collision Energy (CE) 35 ± 15 eV; self-calibrating reference ion to C with mass to charge ratio (m/z) of 609.2876633H40N2O9(ii) a MS/MS mode reference feature ions comprising C with mass-to-charge ratio of 174.0913011H12NO, C with mass to charge ratio of 195.0652010H11O4C with a mass to charge ratio of 236.1281013H18NO3C with a mass to charge ratio of 365.1860022H25N2O3C with a mass to charge ratio of 397.2122023H29N2O4C with a mass to charge ratio of 448.1966023H30NO8C with a mass to charge ratio of 609.2806633H40N2O9。
Instruments and reagents refer to example 1.
Example 3
This example provides a method for measuring pesticide residue, which is similar to that of example 1
Sample pretreatment: weighing 20g of homogenized sample to be detected (grape) into a 50mL polypropylene centrifuge tube, adding 20mL of acetonitrile, performing vortex extraction for 25min, performing ultrasonic extraction for 6min, then adding 4g of sodium chloride, performing vortex extraction for 2min, centrifuging at the rotating speed of 5200r/min for 6min, taking 1mL of supernatant into a 10mL glass test tube, adding 1mL of ultrapure water, performing vortex mixing for 35s, filtering the extracting solution through a 0.22 mu m nylon filter, and bottling to be detected.
Preparing a standard solution: the twenty-six groups of standard solutions are prepared into a group of mixed standard solutions containing 1 mu g/mL of all pesticides by taking acetone as a solvent, and the mixed standard solutions are stored at 4 ℃ in a dark place and are reconfigured once every two months.
The contents of various pesticide components in a sample to be tested are measured by using an UPLC-QTOF-MS method according to the following conditions, and are compared with the measurement result of a standard solution under the same measurement conditions.
The liquid chromatography conditions during the assay included: the mobile phase A is methanol, and the mobile phase B is an ammonium acetate aqueous solution with the concentration of 5.5 mmol/L; the flow rate is 0.5 mL/min; the elution procedure for mobile phase a (gradient elution) was: 0-0.5min, 2%; 0.5-15min, 2-98%; 15-17min, 98%; 17-17.1min, 98-2%; 17.1-20min, 2%; the column temperature is 50 ℃; the amount of sample was 5. mu.L.
The mass spectrometric conditions during the assay included: the ion source adopts an electrospray ionization source (ESI) and a positive ion mode; a full scanning mode, wherein the scanning mass range is 50-1000 m/z; the flow rate of the air curtain air (CUR) was 38 psi; the flow rate of the spray gas (GS1) was 52psi, and the flow rate of the auxiliary heating gas (GS2) was 50 psi; ionization voltage (isff) is 5550V; the Temperature (TEM) was 510 ℃; the declustering voltage (DP) was 82V; collision Energy (CE) 35 ± 15 eV; self-calibrating reference ion to C with mass to charge ratio (m/z) of 609.2876633H40N2O9(ii) a MS/MS mode reference feature ions comprising C with mass-to-charge ratio of 174.0913011H12NO, C with mass to charge ratio of 195.0652010H11O4C with a mass to charge ratio of 236.1281013H18NO3C with a mass to charge ratio of 365.1860022H25N2O3C with a mass to charge ratio of 397.2122023H29N2O4C with a mass to charge ratio of 448.1966023H30NO8C with a mass to charge ratio of 609.2806633H40N2O9。
Instruments and reagents refer to example 1.
Example 4
This example differs from example 1 only in that: mobile phase B was 0.1 vt% aqueous formic acid.
Through measurement, the methods provided in example 2 and example 3 can also simultaneously detect the content of 373 pesticides in table 1.
In summary, the present application can accurately and efficiently detect the 373 kinds of pesticides in the vegetables and fruits by using the high resolution mass spectrometry technology in combination with the simple and fast pretreatment method, and can satisfy the trace detection and analysis of the multiple residual pesticides in the vegetables and fruits. The linear correlation coefficient r2 of all pesticides in the detection method established by the application is more than 0.990. The detection Limit (LOD) is 0.6-10 mug/kg, the quantitative Limit (LOQ) is 2.0-30 mug/kg, and the quantitative limit of 98.1 percent of pesticide is not more than 10 mug/kg. When the strawberry is used as a matrix and the adding concentrations of the pesticides are respectively 10 mug/kg, 50 mug/kg and 100 mug/kg, the results of 6 parallel measurements of each level show that the recovery rate of 352 (94.4%) pesticides ranges from 70% to 120%, and the recovery rate of abamectin B1a in the rest 21 pesticides is 130% at the adding level of 10 mug/kg; the recovery rate of tribenuron-methyl, benzytriazole, propoxymine, buthiuron, pyrisoxazole, heptenophos, fenazaquin, bifenthrin, forchlorfenuron, imidaclothiz, ethofenprox, cyromazine, fenflurazole, prometryn, pencycuron, clethodim, sethoxydim, difenofos and metconazole is lower than 70% (30% -67%). The Relative Standard Deviation (RSD) of all pesticides was less than 20% (0.7% to 14.7%). The method has good sensitivity, accuracy and precision, is simple to operate, and can meet the requirements of relevant laws and policies at home and abroad on the analysis method of the pesticide residue in the vegetables and fruits.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for measuring pesticide residue is characterized in that a UPLC-QTOF-MS method is adopted to measure the content of various pesticide components in a sample to be measured, wherein the pesticide components simultaneously comprise an insecticide and a bactericide;
the liquid chromatography conditions during the assay included: the mobile phase A is methanol, and the mobile phase B is ammonium acetate aqueous solution or formic acid aqueous solution; the flow rate is 0.3-0.5 mL/min; the elution procedure for mobile phase a was: 0-0.5min, 2%; 0.5-15min, 2-98%; 15-17min, 98%; 17-17.1min, 98-2%; 17.1-20min, 2%;
the mass spectrometric conditions during the assay included: the ion source adopts an electrospray ionization source and a positive ion mode; a full scanning mode, wherein the scanning mass range is 50-1000 m/z; qi (Qi)The flow rate of the curtain gas is 32-38 psi; the flow rate of the spray gas is 48-52psi, and the flow rate of the auxiliary heating gas is 48-52 psi; the ionization voltage is 5450-5550V; the temperature is 490-510 ℃; the de-clustering voltage is 78-82V; the collision energy is 20-50 eV; self-calibrating reference ion to mass to charge ratio of 609.28766C33H40N2O9(ii) a MS/MS mode reference feature ions comprising C with mass-to-charge ratio of 174.0913011H12NO, C with mass to charge ratio of 195.0652010H11O4C with a mass to charge ratio of 236.1281013H18NO3C with a mass to charge ratio of 365.1860022H25N2O3C with a mass to charge ratio of 397.2122023H29N2O4C with a mass to charge ratio of 448.1966023H30NO8C with a mass to charge ratio of 609.2806633H40N2O9。
2. The assay of claim 1, wherein the flow rate in the liquid chromatography condition is 0.4mL/min and the flow rate of the gas curtain gas in the mass spectrometry condition is 35 psi; the flow rate of the spray gas is 50psi, and the flow rate of the auxiliary heating gas is 50 psi; the ionization voltage is 5500V; the temperature is 500 ℃; the declustering voltage is 80V;
preferably, the mobile phase B is an ammonium acetate aqueous solution with the concentration of 4.5-5.5mmol/L, more preferably an ammonium acetate aqueous solution with the concentration of 5 mmol/L;
preferably, the column temperature during liquid chromatography is 30-50 ℃, more preferably 45 ℃;
preferably, the sample size during liquid chromatography is 3-5. mu.L, more preferably 3. mu.L.
3. The assay method according to claim 2, further comprising the following pretreatment of the sample to be tested:
extracting the pulped slurry of a sample to be detected by using an extracting agent, mixing with sodium chloride, centrifuging, taking supernate, mixing with water, and filtering by using a membrane;
preferably, the extractant is acetonitrile;
preferably, the extraction is carried out by mixing the extractant with the slurry, then carrying out vortex extraction for 15-25min, and then carrying out ultrasonic extraction for 4-6 min.
4. The method according to claim 1, further comprising performing measurement using a standard solution corresponding to the pesticidal component under the same conditions as the sample to be measured, for comparing the measurement results of the sample to be measured.
5. The assay of any one of claims 1-4 wherein the pesticide comprises 3-hydroxycarba, abamectin B1a, chlorothalofop, bafenofos, fenthion sulfone, fenthion sulfoxide, thiophenophos, fenamiphos sulfoxide, fenoxycarb, pyriproxyfen, imidacloprid, profenofos, propoxur, tebufenozide, pyrethrin I, pyrethrin II, diflubenzuron, pyridaphethione, phenthoate, trichlorfon, dichlorfon, butafenapyr, acetamiprid, chlorfenvinphos, chlorpyrifos, parathion, spinosad A, spinosad D, carbofuran, diazinon, fosfone, fenprophos-S-sulfoxide, dinotefuran, furacarb, fenthion, fluvalinate, fluvalicarb, flubendiamide, flubenfurazamide, flubenfurazanil, fipronil sulfone, fipronil, Flufenoxuron, sulfoxaflor, flonicamid, chlorfluazuron, hexaflumuron, flucythrinate, novaluron, chromafenozide, emamectin B1a, methamidophos, phorate sulfone, phorate sulfoxide, chlorpyrifos-methyl, demeton-methyl, thiophosphoryl-methyl, pirimiphos-methyl, metathion-methyl, anaxycarb, fenpropathrin, methoxyfenozide, monocrotophos, pirimicarb, carbofuran, quinalphos, dimethoate, bifenthrin, phosphamidon, thiophosphoryl, thiodicarb, cadusafos, spirotetramat-mono-hydroxy, spirotetramat-keto-hydroxy, spirotetramat-enol-glucoside, chlorantraniliprole, cyhalothrin, permethrin, cypermethrin, imidacloprid, malathion, fenoxycarb, methiocarb, Ethofenprox, cyromazine, chlorbenzuron, metaflumizone, fenvalerate, clothianidin, thiacloprid, thiamethoxam, buprofezin, pyridalyl, triazophos, chlordimeform, hexaflumuron, fenitrothion, methidathion, oxamyl oxime, lufenuron, metoclopramide, terbufos sulfone, terbufos sulfoxide, aldicarb sulfone, aldicarb sulfoxide, demethylcarboxamido pirimicarb, demethylcarboxim, nitenpyram, phoxim, bromocyantran, deltamethrin, pirimiphos, phos-sulphoxide, oxymethoprophos-sulfone, omethoate, oximinothion, ivermectin, fosulfone, fosetylphos-ethyl, fosmidophos, ethiprol, ethiprole (formonitrile), ethyl multiphos A, ethyl multipur B, ethiosulfuron, acephate, isoprocarb, indoxacarb, methidathion, coumaphos, ethiprole (qingkaemp), ethiprole, At least one of fenobucarb and tolfenpyrad;
preferably, the insecticide comprises imidacloprid, acetamiprid, dinotefuran, flonicamid, hexaflumuron, chlorantraniliprole, cyhalothrin, cypermethrin, clothianidin, thiamethoxam and triflumuron.
6. The assay method according to claim 5, wherein the bactericide comprises fenpyrazamine, benfluanid, metrafenone, difenoconazole, benalaxyl, zoxamide, fenpropidin, penthiopyrad, pyraclostrobin, isopyrazam, benzytriazolol, propiconazole, prothioconazole, propoxymine, isoprothiolane, fenoxanil, dinocap-phenol, edifenphos, coumoxystrobin, pyrisoxazole, boscalid, picoxystrobin, carbendazim, hymexazol, oxadixyl, famoxadone, flutriafol, fluopyram, flusilazole, epoxiconazole, triflumizole, fludioxozole metabolite, flumorphine, flutolanil, flutriafol, fluxapyroxafen, prochloraz, procymidone, fludioxonil, silthiofam, cyproconazole, fenhexamid, hexaconazole, fenpyraclostrobin, metolachloraz, tolanil, tolbutafosfamide, tolnaftophos, metolac, and a, Thiophanate-methyl, metalaxyl, fenbuconazole, myclobutanil, bromuconazole, quinoxyfen, bitertanol, fenarimol, prochloraz-deamidylimidazole, prochloraz-deimidazolam carboxamide, fenamidone, dimoxystrobin, kresoxim-methyl, cyprodinil, azoxystrobin, pyrimethanil, triticonazole, mefenamide, cyazofamid metabolite, cyazoxystrobin, thifluzamide, thiabendazole, tricyclazole, triadimenol, at least one of triadimefon, mandipropamid, propamocarb, tetraconazole, thioconazole, trifloxystrobin, pencycuron, penconazole, tebuconazole, dimethomorph, enestroburin, dimethomorph, diniconazole, valvacrol, imibenconazole, metconazole, diethofencarb, ethirimol, bupirimate, iprobenfos, imazalil, amisulbrom, ipconazole, pyraclostrobin, pyraoxystrobin and ametoctradin;
preferably, the bactericide comprises difenoconazole, pyraclostrobin, boscalid, carbendazim, fluopyram, thiophanate-methyl, myclobutanil, prochloraz, cyprodinil, azoxystrobin, pyrimethanil, triadimenol, triadimefon, propamocarb and ethirimol at the same time.
7. The method according to claim 6, wherein the pesticidal composition further comprises at least one of an acaricide, a molluscicide, a nematicide and a synergist;
preferably, the acaricide comprises at least one of fenoxycarb, pyridaben, cyflumetofen, fenazaquin, bifenazate, spiromesifen, spirodiclofen, propargite, hexythiazox, clofentezine, etoxazole and fenpyroximate; more preferably, the acaricide comprises bifenazate;
preferably, the molluscicide comprises at least one of methiocarb sulfone and methiocarb sulfoxide;
preferably, the nematicide comprises at least one of fenamiphos and fosthiazate; more preferably, the nematicide comprises fosthiazate;
preferably, the synergist comprises a synergist ether.
8. The assay method according to claim 7, wherein the pesticidal component further comprises a herbicide;
preferably, the herbicide includes ethametsulfuron, tribenuron-methyl, saflufenacil, metamitron, mefenacet, pyraflufen-ethyl, fluazifop-butyl, diflufenican, pyrazosulfuron-ethyl, prosulfocarb, propyrisulfuron, oxadiargyl, propanil, diuron, butachlor, buthiuron, propyzamide, oxadiazon, oxaziclomefone, metamifop, pendimethalin, rimsulfuron, flurtamone, triflusulfuron, flucarbazone, haloxyfen, flupyrazamide, fomesafen, flufenacet, thiofenacet, thiobencarb, diclofop-methyl, cyprosulfuron, pyrin-methyl, sulam, sulfluron-methyl, metsulfuron-methyl, imazamethamidone, benazolin-ethyl, dimethenamid-p-methyl, dimethenamid-p-ethyl, dimethenamid-methyl, fenoxap-ethyl, fenoxaprop-p-ethyl, thiuron-methyl, bensulfuron-methyl, benazolin, bensulfuron-methyl, Quizalofop-p-ethyl, linuron, chlorsulfuron, halosulfuron-methyl, fluroxypyr-ethyl, chlorsulfuron, chlorimuron-ethyl, imazaquin, imazethapyr, triasulfuron, cinosulfuron, pyrisulfuron, pyribenzoxim, propaquizafop, prometryn, metazosulfuron, metrizachlor, metribuzin, cyanazine, cyhalofop, propyzamide, clodinafop, lactofen, thifensulfuron-methyl, triflusulfuron, tralkoxydim, fenprophos, bensulam, diflufenican, terbuthylazine, phencyclamate, penoxsulam, simetryn, simazine, clethodim sulfoxide, sethoxydim, amidon, mesotrione, nicosulfuron, triasulfuron, carbenoxafen, ethoxyflurane, oxyfluorfen, isoxauron, prosulfuron, propafen, metosulam, nicosulfuron-methyl, At least one of clomazone, isoxaflutole, ametryn, atrazine, butralin, carfentrazone-ethyl, pinoxaden and flumetsulam.
9. The assay method of claim 8, wherein the pesticide composition further comprises a plant growth regulator;
preferably, the plant growth regulator includes at least one of diethyl aminoethyl hexanoate, paclobutrazol, flumetrazol, trinexapac-ethyl, forchlorfenuron, thidiazuron and uniconazole.
10. The assay method according to claim 1, wherein the sample to be assayed is an agricultural product;
preferably, the sample to be tested is fruit and/or vegetable.
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CN115128195A (en) * 2022-08-31 2022-09-30 北京市疾病预防控制中心 LC-MS/MS detection method for pesticide and veterinary drug residues in animal oil and vegetable oil

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