CN112305131B - GC-Orbitrap-MS screening and analyzing method for pesticide residues in animal derived food - Google Patents
GC-Orbitrap-MS screening and analyzing method for pesticide residues in animal derived food Download PDFInfo
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- CN112305131B CN112305131B CN202011329130.1A CN202011329130A CN112305131B CN 112305131 B CN112305131 B CN 112305131B CN 202011329130 A CN202011329130 A CN 202011329130A CN 112305131 B CN112305131 B CN 112305131B
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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 GC-Orbitrap-MS screening and analyzing method for pesticide residues in animal derived food. The method comprises the following steps: (1) extraction: homogenizing an animal-derived food sample, mixing with an extraction solvent and extraction salt, performing oscillation extraction to obtain an extracting solution, and taking supernatant I; (2) purifying: mixing the supernatant I obtained in the step (1) with a purifying agent for purification, collecting a supernatant II, and filtering to obtain a sample solution to be liquid; (3) and (3) detecting by using a chromatographic mass spectrum: and (3) separating the pesticide residue in the sample liquid to be detected by adopting a gas chromatography, and then detecting by adopting Orbitrap-MS with an EI ion source to obtain the pesticide residue content in the animal-derived food. The method has the characteristics of high recovery rate, good precision, strong applicability, small dosage of organic reagents and the like, each technical index can meet the requirement of daily detection and analysis of various animal-derived foods, and important technical support is provided for the field of food safety.
Description
Technical Field
The invention relates to a GC-Orbitrap-MS screening and analyzing method for pesticide residues in animal derived food, belonging to the field of quality safety detection of agricultural products.
Background
Pesticides are indispensable auxiliary products in agricultural production, but pesticides and degradation products thereof can be enriched in animal bodies through food chains, and further harm human health. The pesticide has various types and greatly different chemical properties. The gas chromatography-electrostatic field orbital trap high-resolution mass spectrometry (GC-Orbitrap-MS) can provide accurate molecular mass and mass spectrum fragmentation information of a compound to be detected, has the advantages of high sensitivity, high accuracy, high resolution and the like, and is increasingly applied to analysis of pesticide residues in food.
The animal-derived food matrix is complex, and the traditional pretreatment method is complex in steps, long in time consumption and needs to consume a large amount of organic solvent. The QuEChERS method is a short-form quick, simple, low-cost, effective, durable and safe pretreatment method and is widely applied to extraction and purification treatment of pesticide residues in fruits and vegetables. Therefore, it is necessary to further optimize the QuEChERS method to be suitable for pretreatment of pesticide residues in animal-derived food to reduce the influence of the sample matrix on instrumental analysis.
Disclosure of Invention
The GC-Orbitrap-MS screening and analyzing method for the pesticide residues in the animal-derived food is simple to operate, high in sensitivity and good in reproducibility, and can be widely applied to screening and analyzing of various pesticide residues in the animal-derived food.
The GC-Orbitrap-MS analysis method for pesticide residues in animal derived food provided by the invention comprises the following steps:
(1) extraction: homogenizing an animal-derived food sample, mixing with an extraction solvent and extraction salt, performing oscillation extraction to obtain an extracting solution, and taking supernatant I;
(2) purifying: mixing the supernatant I obtained in the step (1) with a purifying agent for purification, collecting a supernatant II, and filtering to obtain a sample solution to be liquid;
(3) and (3) detecting by using a chromatographic mass spectrum: and separating the pesticide residue in the sample liquid to be detected by adopting a gas chromatography, and then detecting by adopting Orbitrap-MS with an EI ion source to obtain the pesticide residue content in the animal-derived food.
In the method, GC-Orbitrap-MS (gas chromatography-electrostatic field orbital trap) is used for high-resolution mass spectrometry.
The animal derived food applicable to the invention comprises at least one of chicken, pork, beef, mutton, duck, goose, chicken liver, pork liver and lamb liver.
In the above method, in the step (1), the extraction solvent may be acetonitrile, acetone, a mixture of acetonitrile and acetone at a volume ratio of 1:1, acetonitrile containing 1% formic acid, acetone containing 1% formic acid, a mixture of acetonitrile and acetone at a volume ratio of 1:1 containing 1% formic acid, acetonitrile containing 1% acetic acid, acetone containing 1% acetic acid, or a mixture of acetonitrile and acetone at a volume ratio of 1:1 containing 1% acetic acid; preferably, the mixture of acetonitrile and acetone in a ratio of 1:1 contains 1% acetic acid, and the above percentages refer to volume percentages, and the mixture ratio is volume ratio.
In the step (1), the volume ratio of the mass of the animal-derived food sample to the extraction solvent can be 1g: 2-5 mL, specifically 1g:2 mL;
the extracted salt can beThe mixture of anhydrous magnesium sulfate, sodium chloride, sodium bicarbonate, sodium citrate and disodium citrate can be mixed at a mass ratio of 4:1:5:1:0.5, and 4g anhydrous MgSO can be added when analyzing 5 + -0.05 g animal derived food sample4A mixture of 1g NaCl, 1g sodium citrate, 0.5g disodium citrate and 5g sodium bicarbonate is dewatered;
adding the extraction salt to remove water for 1-5 min, specifically 1 min;
the extract was centrifuged under the following conditions:
the temperature is 0-10 ℃, the rotating speed is 2500-10000 Xg, and the time is 5-10 min.
In the above method, in the step (2), the scavenger may be at least one of Primary and Secondary Amine (PSA), Graphitized Carbon Black (GCB), C18, anhydrous magnesium sulfate, EMR-Lipid (Enhanced Matrix Removal-Lipid, novel dispersed solid phase extraction material), Discovery DSC-18, ENVI-Carb, Z-Sep + and Z-Sep; preferably C18 and anhydrous magnesium sulfate, preferably at a weight ratio of 1:6, and when analyzing 5 + -0.05 g animal derived food sample, 150mg C18 and 900mg MgSO4 can be added4As a decontaminant.
In the method, in the step (2), the supernatant I is mixed with the purifying agent and then is subjected to vortex to realize purification, and then the supernatant II is obtained by centrifugation under the following conditions:
the temperature is 0-10 ℃, the rotating speed is 2500-5000 Xg, and the time is 5-10 min;
filtration was performed using a 0.22 μm filter.
In the method, in the step (3), the chromatographic column used in the gas chromatography is Trace-Pesticide II;
the gas chromatography column may specifically be of a specification of 30m x 0.25mm x 0.25 μm.
In the above method, in the step (3), the chromatographic conditions of the gas chromatography are as follows: the temperature rising procedure is as follows: maintaining the initial temperature at 40 deg.C for 1.5 min; heating to 90 deg.C at 25 deg.C/min, and maintaining for 1.5 min; heating to 180 ℃ at a speed of 25 ℃/min; heating to 280 ℃ at the speed of 5 ℃/min; heating to 300 deg.C at 10 deg.C/min, and maintaining for 3 min; the injection port temperature was 290 ℃ and the helium gas flow rate was 1.2 mL/min.
In the above method, in step (3), the mass spectrum conditions of the Orbitrap-MS are as follows: the ion source temperature is 280 ℃, the ionization energy is 70eV, and the current is 50 muA;
the ion scanning mode is a full scanning mode, the scanning range is 50-550m/z, the resolution of the full scanning mode is set to be 60,000FWHM, an internal standard reference solution is used for correcting the quality precision of the instrument in real time, and data acquisition and processing are carried out on mass spectrum detection through TraceFinder 4.1General quant software;
the adopted gas chromatography-mass spectrometer can be an active GC Orbitrap GC-MS system.
Pesticide residues suitable for analysis by the method of the invention include herbicides, insecticides, fungicides, acaricides, rodenticides and plant growth regulators.
The herbicide comprises 2- (2,4, 5-trichlorophenoxy) -propionic acid, 2- (4-chloro-2-methylphenoxy) propionic acid, 2,4, 5-nasal discharge methyl propionate, 2, 4-D-2-ethylhexyl ester, 2, 4-D propionic acid, 2, 4-D butyric acid, 2, 4-D butyl ester, 2, 6-dichlorobenzamide, 2-methyl-4, chloro-2-ethylhexyl ester, 2-methyl-4-chlorobutyl ester, 2 methyl-4-chloroisooctyl ester, 3-chloro-p-toluidine, 4-chlorophenoxyacetic acid, E-pyriminobac-methyl, atrazine/atrazine, prodiamine, Benfuresate, anilazine, metamifop, tribenuron-methyl, anisole, metamitron, mefenacet, fenzopyr, pyraflufen, fluazifop-butyl, haloxyfop-methyl, diflufenican, pyroxafen, metazachlor, mefenpyr-diethyl, proshlor, flumioxazin, thioureamide, dicamba, benazolin ethyl, prodazine, cufensulfuron-methyl, dimethomol, bromacil, propanil, dichlormid, dichlorvol, dichlorvos, dimethyl chlorophthalate, dimetal, triazophos, butachlor, butbifenther, butafenamide, butafenan, buthiuron, propyzamide, oxadiazon; oxadiargyl, oxadiargyl; benoxacor, oxazinone, fenoxaprop-ethyl, diacrylin, dimethachlor, dimethenamid, pendimethalin, clopyralid, trans-dodine, fenflurazone, furbenoxan, flurprimidol, diflufenzopyr sodium, haloxyfop-methyl, flupyrazamide, butafenacil, norflurazon, fluroxypyr-1-methylheptyl; fluroxypyr isooctyl ester, beflubutamid, fluridone, primisulfuron sodium, fluroxypyr, trifluralin, dithiopyr, flufenacet, fluroxypyr, fentrazine, heptanolachlor, molinate, diclofop-methyl, clethodim lithium, ciprofloxacin, cycloprozine, cyhalofop-methyl, triclopyr, hexazinone, cyclosulfuron, clomeprop-methyl, metalaxyl, metsulfuron-methyl, mefensulfuron-methyl, fenpyr-methyl, oxazazole, oxapyr-ethyl, benoxacor, cloquinate, clethoate, kularuron, quizalofop-ethyl, linon, fluazin-methyl, thiuron, chlortoluron, chlorphenamine, chlordiazepoxide, clomazone, clodinafop-methyl, chlorfluuron, halon, triflumuron, rythrin, fluroxypyr, prim, clomeprop, fluroxypyr, prim, clomeprop, bensulfuron-methyl, fluroxypyr, bensulfuron-methyl, benfluroxypyr, ben, benfluroxypyr, ben, benflurben, ben, benflurben, benflurbenflurben, ben, benflurbenflurben, ben, benflurbenflurbenflurben, ben, benflurbenflurben, ben, benflurben, ben, benflurbenflurben, ben, m, ben, benflurben, ben, m, ben, m, ben, benflurbenflurben, m, ben, benflurben, benflurbenflurben, benflurbenflurbenflurben, m, ben, cyclomethimazone, diafenthiuron, metamifop, propyzamide, prometryn, metribuzin, cyhalofop-methyl, metribuzin, cyhalofop-butyl, cyhalofop-methyl, propyzamide, propargyl, clodinafop-methyl, lactofen, cycloxydim, thiophenamine, thiazopyr, metribuzin, tralkoxydim, triclopyr, triazolam, dimesnac, dichlorate, anilofos, fenfluroxypyr, isoxadifen, dipheny, cis-oaten, terbutryn, terbuthylazine, deethylatrazine, diethylatrazine, terbutyralazine, terbuthylazine, terbinafine, at least one of penflufen, simetryn, simazine, simatong, dichlormid, pethoxamid, clethodim, sethoxydim, saflufuron, neodelphin, bromoxynil octanoate, bromobutyluramid, bromogluron, dichloram, avenyl, triallate, acetochlor, benfluralin, fluazifop-ethyl, fluoroglycofen-ethyl, acetochlor, ethofumesate, oxyfluorfen, propisochlor, metolachlor, ipratron, isoproturon, clomazone, isoxaflutole, isoacetochlor, butafosinate, imazaquin, dichlorphenate, indolone, sulfentram, indanthrone, isoxaflufen, ametryn, trumol, isoproxen, dimethomorph, penetryn, butralin, and carfentrazone-ethyl;
the pesticide comprises 2,3, 5-mixed carbofuran, 2,4' -dichlorodiphenyl, 2,4' -dicofol, 3,4, 5-mixed carbofuran, 4' -dichlorodiphenyl ketone, 4-dodecyl-2, 6-dimethyl morpholine (isomer mixture), E-methyl-chlorfenvinphos, N-diethyl-methyl pyrimidine phosphorus, o, p ' -dichlorodiphenyl, p ' -dichlorodiphenyl, beta-hexachlorodiphenyl, S-fenvalerate, alpha-hexachloro-ethyl, alpha-cypermethrin, beta-hexachloro, delta-hexachlorodiphenyl, Epsilon-hexahexa, aldrin, anethole, amifostine, tetramethrin, octamethiphos, octachlorostyrene, octachlorodipropyl ether, baaphos, bermuda, baotion, fenthion sulfone, fenthion sulfoxide, benzofenamiphos, thiophosphine, phenothrin, cyphenothrin, thiocyanobenzene, fenamiphos, fenoxycarb, pyriproxyfen, tebufenpyrad, pyrazofos, deentraniliprole, benzofuramethrin, benzofenamiphene, propaphos, prothiocarb, profenofos, propromazine, propoxur, bendiocarb, insecticidal cycurcarb, chlorfenafos, chlorfenphos, isofos, pyrethrum extract, fenamiphos, pyridaphenthion, phenthoate, dichlorvos, difenofos, dichlorvos extract, dichlorvos extract, dichlorvos, dich, Butafenapyr, butylpyrimidine phosphate, carbosulfan, pyridalyl, acetamiprid, chlorfenvinphos, loamidophos, chlorpyrifos oxide, parathion, paraoxon, noviflumuron, oxazaphos, bendiocarb, diazinon, naled, dioxacarb, vamidophos, trans-chlordane (gamma), trans-nonachlor, trans-chlordane, trans-permethrin, fenphos, fonofol, sulfoxaflor, furbendiocarb, vophos, fluvalinate, flufenamiphene, flupropathrin, flubencarb, fipronil sulfide, flufenoxuron, flonicamid, flusilate, fluoroformononetin, cyhalothrin, cyfluthrin, cyhalothrin, heptenophos, sulfofipronil, housefly, methamidophos, phorate sulfoxide, phorate, methidathion, pirphos, pirimiphos-methyl, chlorpyrifos-methyl, Methyl parathion, methyl paraoxon, methyl pyrimidophos, methyl systemic phosphorus, methyl bromophenol phosphorus, methyl disulfoton, methyl isothion, methiocarb sulfone, methothrin, carbaryl, fenpropathrin, metofluthrin, methoxychlor, monocrotophos, monocrotocarb, kaempferia, acamprosate, pirimicarb, carbofuran, quinalphos, dimethoate, bifenthrin, lindane, phosphamidon, thiopropaphos, thiobencarb, alpha-thiodan, beta-thiodan, thiodan sulfate, thiocyclophos, thiotepa, spirotetramat-mono-hydroxy, spirotetramat-keto-hydroxy, spirotetramat-enol-glucoside, spirotetramat, spirodiclofen, cyhalothrin, chlormephos, cypermethrin, chlormephos, malathion, fenthion, Malathion, mechlorfenthion, ethofenprox, kresoxim-methyl, pirimiphos, gossypol, methomyl, fenamiphos, ethoprophos, mirex, cyromazine, demeton, phoxim-S-sulfoxide, pyralid, tefluthrin, heptachlor, fenvalerate, anthelmintic, prallethrin, kadethrin, buprofezin, fosthiazate, triphenyl phosphate, trithion, triclosan, triazophos, chlordimeform, chlorfenapyr, fenib, fenitrole, fenitrothion, methidathion, resmethrin, bioallethrin, fenthion, cis-chlorthion, cis-cypermethrin, transfluthrin, phos, carbosulfan, terbufos-OXON, terbufos-oxonon, terbufos-OXON, terbufos-O-OXON, Aldicarb, aldicarb sulfone, aldicarb sulfoxide, demethyl-pirimicarb, debromorphophosphorus, exochlorhydric heptachlor, meclofenozide, pentachlorobenzene, pentachloranilide, pentachlorophenol, penconazole, allethrin, methoprene, phoxim, bromophos, bromocyantranilide, deltamethrin, chlorfenapyr, phosmet, phos-fon, oxydisup, oxyphenphos, chlordane oxide, oxydemeton-methyl, omethion, omethoate, oxyphenote, oxydisulphos, oxithion, isothion, disulfoton, ethiofen, dichlofen, ethithion, ethiofen, ethiofencarb, ethidium, ethiprole, ethidium, ethiofencarb, ethiprole, ethiofencarb, ethiprole, ethidium, At least one of nicotine, isoprocarb, endrin aldehyde, endrin ketone, isosulforaphane, isochlorophos, bensulide, indoxacarb, coumaphos, fosthier, synergistic ether, sulfotep, fenobucarb, Zuccarb and tolfenpyrad;
the bactericide comprises enestroburin, (E) -metominostrobin, (Z) -metominostrobin, 3, 5-dichloroaniline, 3-phenylphenol, 8-hydroxyquinoline, fenpyrazamine, chlorothalonil, fenpropathrin, fenpyroxate, benzovindiflupyr, benfluanid, metrafenone, difenoconazole, benalaxyl, fenpropidin, fenxamide-1, metominostrobin-2, phenoxyquinoline, pyrazofos, pyrimidazole, pyrazofos, penthiopyrad, pyrafluthrin, isopyrazam (isomer mixture), benzchlorotriazole, propiconazole, isoprothiolane, captafol, fenaminostrobin, fenamiphos, buthrimorph, eugenol, pyriproxyfen-2, picoxystrobin, oxadixyl, flutriafolan, flutriafol, furametpyr, furamex, and the like, furamex, Fluopyram, fluazinam, epoxiconazole-2, triflumizole, fluquinconazole, fluvaliconazole, flutolanil, fluconazole, flutolanil, procymidone, simeconazole, silthiofamid, cyprodinil, cyflufenamid, fenhexamid, griseofulvin, activated esters, hexaconazole, mebenflumetofen, methylfurosemide, tolclofos-methyl, metalaxyl, metoclopramide cry bacteria, fenbuconazole, myclobutanil, mefenoxam, dimethachlozil, bromuconazole, captan, biphenyl, bixafen, biphenyldiamine, bitertanol, phthalimide, thioneazole, hexachlorobenzene, spiroxamine, anisole, fenarimol, clonidine, fuberidazole, prochloraz, fenamidone, cyprodinil, azoxystrobin, pyrimethanil, triflumiron, pyraclostrobin, trifloxystrobin, primidon, pyraclostrobin, trifloxystrobin, pyrane, pyraclostrobin, trifloxystrobin, pyraclostrobin, prochloraz, and, At least one of triticonazole, mefenamate, mefenaminostrobin, cyhalodiamide, thifluzamide, triphenyltin hydroxide, triflumizole, tricyclazole, nitrapyrin, triadimenol, triadimefon, dodecamorph, diclorocyanid, propamocarb, tetraconazole, tetrachlorophthalide, tetrachloronitrobenzene, phthalidyl ester, hymexazol, debenzoquat, methamidozole, fenbuconazole, carboxin, trifloxystrobin, orysastrobin, pencycuron, penconazole, tebuconazole, probenazole, dimethomorph, diniconazole, fenamidone, iprovalicarb, bromothalonil, imibenazol-oxonon-debenzyl, nicotinoyl alkali, oxycarboxin, metconazole, epoxiconazole, ethirimol sulfonate, vinclozolin, ethoxyquin, iprobenfos, iprodione, imazalil, ethaboxam, ipconazole, and pyraclostrobin;
the acaricide comprises at least one of flutriafol, fenoxycarb, fenpyroximate, propylate miticide, pyridaben, fluazuron, fenpyroximate, fluazuron, hexaflumuron, flufenzine, noviflumuron, cyhalofenate, fenazaquin, bifenazate, chlorfenapyr, acarine, pyriminostrobin, fluacrypyrit, propargite, thiamethoxam, hexythiazox, dicofol, lufenuron, amitraz, bromopropylate, etoxazole and fenpyroximate;
the rodenticide comprises at least one of warfarin and morindate;
the plant growth regulator comprises at least one of 1-naphthylacetamide, paclobutrazol, flumetralin, cyprodinil, trinexapac-ethyl (free acid), jasmone, naphthylacetic acid, thionine, defoliation, uniconazole, imazalil and indridyl.
The method can screen and analyze 719 kinds of pesticide residues in the animal derived food.
The invention establishes a gas chromatography-high resolution mass of various pesticide residues in animal derived food aiming at the characteristics of complex matrix, high lipid and protein content and the like in the animal derived foodAnd (3) a spectrum detection method. The method is simple to operate, high in sensitivity and good in reproducibility, and can be widely applied to screening and analyzing of various pesticide residues in animal-derived food. The invention adopts 1:1 mixed solution of acetonitrile and acetone containing 1% acetic acid as an extractant, anhydrous MgSO4A mixture of NaCl, sodium citrate, disodium citrate and sodium bicarbonate as extraction salt, C18 and anhydrous MgSO4The mixture is used as a purifying agent, and an external standard method is used for quantification, so that the confirmation and quantitative analysis of various pesticide residues in animal-derived food are realized. The method has the characteristics of high recovery rate, good precision, strong applicability, small dosage of organic reagents and the like, each technical index can meet the requirement of daily detection and analysis of various animal-derived foods, and important technical support is provided for the field of food safety.
Drawings
FIG. 1 is a statistical histogram of the recovery of 197 pesticide residues using different extraction solvents.
FIG. 2 is a statistical histogram of the recovery of 197 pesticide residues using different extraction solvents plus acid.
FIG. 3 is a statistical histogram of the recovery of 197 pesticide residues using different extracted salts.
FIG. 4 is a statistical histogram of the recovery of 197 pesticide residues using different scavengers.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The instrument and reagent information in the following examples is as follows:
1. the instrument comprises the following steps: GC-Orbitrap-MS (Thermo Fisher Scientific, Exactive GC Orbitrap GC-MS system, chromatograph Trace 1310, autosampler TriPlus RSH); vortexer (IKA, germany); nitrogen blow dryer (Zymark corporation, usa); q ultra pure water device (Millipore corporation, usa); a refiner (Electrolux, Sweden); electronic balances (Sartorius, germany); high speed centrifuge (Thermo corporation, usa).
2. Reagent: the standard substance of pesticide residue is purchased from Tianjin Alta company of China (the purity is 96.2 percent to 99.9 percent); purifiers (PSA, GCB, C18, EMR-Lipid) were purchased from Agilent Inc. USA; purifiers (Discovery DSC-18, ENVI-Carb, Z-Sep +, Z-Sep) were purchased from Supelco, USA. Acetonitrile: carrying out chromatographic purification; acetone: carrying out chromatographic purification; methanol: carrying out chromatographic purification; ethyl acetate: carrying out chromatographic purification; formic acid (purity is more than or equal to 99.0%): carrying out chromatographic purification; acetic acid (purity is more than or equal to 99.0%): carrying out chromatographic purification; MgSO (MgSO)4: mass spectrum purification; NaCl: mass spectrum purification; sodium citrate: mass spectrum purification; disodium citrate salt: mass spectrum purification; sodium acetate: mass spectrum purification; sodium bicarbonate: and (5) mass spectrum purification.
3. Preparation of standard working solution:
preparing a stock solution: accurately weighing 5mg of standard substance, dissolving with 5mL of chromatographically pure ethyl acetate to prepare 1000 mug/mL stock solution, and storing in a refrigerator at 0-4 ℃ in a dark place in a sealed manner, wherein the storage life is 6 months.
Preparing a working solution: the right amount of stock solution is accurately transferred and diluted by chromatographic grade ethyl acetate to prepare working solutions with different concentrations when in use.
Examples 1,
1. The working conditions of the instrument are as follows:
chromatographic conditions are as follows:
the chromatographic conditions for the gas chromatography were as follows: the temperature rising procedure is as follows: maintaining the initial temperature at 40 deg.C for 1.5 min; heating to 90 deg.C at 25 deg.C/min, and maintaining for 1.5 min; heating to 180 ℃ at a speed of 25 ℃/min; heating to 280 ℃ at the speed of 5 ℃/min; heating to 300 deg.C at 10 deg.C/min, and maintaining for 3 min. The injection port temperature was 290 ℃ and the helium gas flow rate was 1.2 mL/min.
Mass spectrum conditions:
the mass spectrometry conditions for the Orbitrap-MS method with EI ion source were as follows: the ion source temperature was 280 ℃, the ionization energy was 70eV, and the current was 50 μ A. The ion scan mode was full scan mode (Fullscan mode), scan range 50-550m/z, resolution set at 60,000FWHM (200 m/z).
And (3) correcting the mass precision of the instrument in real time by using an internal standard reference solution, and acquiring and processing data for mass spectrum detection by using TraceFinder 4.1General Quan software. The molecular formulas, mass-to-charge ratios, retention times, detection limits, and other information of 197 kinds of pesticide residues are shown in table 1.
TABLE 1197 basic information and detection limits for pesticide residues
2. Sample pretreatment
(1) Extraction of
Accurately weighing 5g (+ -0.05 g) of homogenized animal-derived food sample (specifically beef) in a 50mL centrifuge tube, adding 10mL of a 1:1 mixture of acetonitrile containing 1% acetic acid and acetone as an extraction solvent, fully mixing, and vortexing for 60s to fully contact the sample with the extraction solution.
4g of anhydrous MgSO was added to the centrifuge tube41g NaCl, 1g sodium citrate, 0.5g disodium citrate and 5g sodium bicarbonate, shaking the mixture on a mechanical shaker for 1min, centrifuging at 8000 Xg at 4 ℃ for 5min, and taking the supernatant for later use.
(2) Purification
5mL of the supernatant was mixed with 150mg of C18 and 900mg of MgSO4After mixing well, vortex for 1min, centrifuge at 8000 Xg for 5min at 4 ℃. Taking 1mL of supernatant, passing through 0.22Filtering with a filter membrane of mum to obtain a sample solution a to be detected, and detecting on a computer.
3. Results of the experiment
(1) Optimization of extraction procedure
1) Optimization of extraction solvent
The pesticide compound can be dissolved in various organic reagents, and 8 extraction solvents of acetonitrile, acetone, ethyl acetate, methanol, acetone + ethyl acetate (5:5, v/v), acetonitrile + acetone (5:5, v/v), acetonitrile + methanol (5:5, v/v) are compared in the invention, and the results are shown in table 2. The effect of adding 1% formic acid, 1% acetic acid, 2% acetic acid to the system on recovery was then compared and the results are shown in Table 3.
With the range of recovery rates as abscissa and the number of pesticides within this range as ordinate, a statistical histogram of the recovery rates of 197 types of pesticide residues was prepared as shown in fig. 1 (in the figure, the indices are acetonitrile, acetone, ethyl acetate, methanol, acetone + ethyl acetate, acetonitrile + acetone, acetonitrile + methanol, etc., in order from left to right). It can be seen that when methanol is used as the extraction solvent, the matrix composition in the extraction solution is complex, which is not conducive to purification, and the recovery rate is poor; when the mixed solution of acetonitrile and acetone in the ratio of 1:1 is used as an extraction solvent, the recovery rate of the medicine is the maximum between 70 and 120 percent. When 1% acetic acid and 2% acetic acid are added into an extraction solvent, the pesticide recovery rate is 70% -120% and is 196, but when 1% acetic acid is added, the recovery rate is better, the recovery rate of 186 drugs is 90% -110%, as shown in fig. 2 (in a histogram in which 2% acetic acid is added, 70% -80%, 80% -90%, 90% -110%, 110% -120% and > 120% are sequentially arranged from left to right, in a histogram in which 1% acetic acid is added, 70% -80%, 80% -90%, 90% -110%, 110% -120% and > 120% are sequentially arranged, in a histogram in which 1% formic acid is added, 70% -80%, 80% -90%, 90% -110% and > 120% are sequentially arranged from left to right, and in a histogram in which no acetic acid is added, 70% -80% and 70% -80% are sequentially arranged from left to right, 80% -90%, 90% -110%, and > 120%). Therefore, in the experiment, a 1:1 mixture of acetonitrile and acetone in 1% acetic acid is preferably added as an extraction solvent.
TABLE 2 Effect of different extraction solvents on recovery
TABLE 3 Effect of extraction solvent plus acid on recovery
2) Optimization of extracted salt
Anhydrous MgSO (MgSO)4The sodium citrate and disodium citrate are used as buffering agents, so that the stability of pH is favorably maintained, and the addition of sodium bicarbonate is favorable for improving the recovery rate of acid-unstable pesticides. The invention compares the extraction efficiency of four groups of extracted salts, which are respectively as follows: 6g MgSO41.5g sodium acetate (first group), 4g MgSO41g NaCl, 1g sodium citrate, 0.5g disodium citrate (second group), 4g MgSO41g NaCl, 1g sodium citrate, 0.5g disodium citrate, 5g sodium bicarbonate (third group), 6g MgSO4, 1g sodium chloride (fourth group). As is clear from table 4 and fig. 4, the extraction effect of group 3 is higher than that of the other groups. Thus, 4g MgSO was chosen for the experiment41g NaCl, 1g sodium citrate, 0.5g disodium citrate, 5g sodium bicarbonate as extraction salts.
TABLE 4 Effect of different extracted salts on recovery
(2) Optimization of decontaminants
The contents of lipid, protein and the like in animal-derived food are high, and the matrixes with complex components can interfere the detection and analysis of pesticide residues, influence the quantitative accuracy and possibly cause damage to an analysis chromatographic column. Therefore, the selection of the scavenger is of great importance.
The invention combines common adsorbents and novel adsorbents, and the common adsorbents and the novel adsorbents are divided into the following 8 groups:
1、150mg C18、900mg MgSO4
2、400mg PSA、1200mg MgSO4
3、400mg PSA、400mg C18、1200mg MgSO4
4、400mg PSA、400mg C18、45mg GCB、1200mg MgSO4
5、400mg EMR-Lipid、400mg NaCl、1600mg MgSO4
6、300mg Z-Sep，900mg MgSO4
7、300mg Z-Sep+，900mg MgSO4
8、400mg Supelclean PSA，1200mg MgSO4，400mg Discovery DSC-18，400mg ENVI- Carb
by comparison, when C18+ MgSO is used4Recovery yields resulted in the highest amount of drug between 70% and 120% when used as a purging agent (results are shown in table 5 and figure 4). Thus, C18+ MgSO was the experimental choice4Is used as a purifying agent.
TABLE 5 Effect of different purification modes on recovery
(3) Optimization of detection conditions
The invention inspects the separation and retention effects of the common gas chromatography capillary chromatographic column on Pesticide compounds, when the Trace-Pesticide II chromatographic column is used, the 197 kinds of Pesticide compounds have the best separation effect, and simultaneously, the invention can keep lower column loss and higher chromatographic reproducibility when a large amount of samples are detected, so the Trace-Pesticide II chromatographic column is selected in the experiment.
After the chromatographic column is determined, the invention considers the common chromatographic temperature-rising program for pesticide residue detection, and finally determines the following temperature-rising program: maintaining the initial temperature at 40 deg.C for 1.5 min; heating to 90 deg.C at 25 deg.C/min, and maintaining for 1.5 min; heating to 180 ℃ at a speed of 25 ℃/min; heating to 280 ℃ at the speed of 5 ℃/min; heating to 300 deg.C at 10 deg.C/min, and maintaining for 3 min. The injection inlet temperature is 290 ℃, the helium gas flow rate is 1.2mL/min, each pesticide compound, especially isomers, can be effectively separated, and cross contamination among sample matrixes can be reduced.
3546 fragment ions were determined for 197 compounds under the following mass spectrometric conditions: the ion source temperature was 280 ℃, the ionization energy was 70eV, and the current was 50 μ A. The ion scan mode was a full scan mode (Fullscan mode), the scan range was 50-550m/z, the mass deviation of the measured value from the theoretical value was in the range of 0-4.96ppm, and therefore the mass deviation of the data analysis was set to 5 ppm. Different mass spectrum resolutions are tested, when 6 ten thousand resolutions are used, enough data acquisition points can be guaranteed, and data information with enough accuracy can be obtained, so that the mass spectrum resolution is set to be 6 ten thousand. And (3) correcting the mass precision of the instrument in real time by using an internal standard reference solution, and acquiring and processing data for mass spectrum detection by using TraceFinder 4.1General Quan software.
(4) Methodology investigation
And (4) quantifying by adopting an external standard method, and drawing a standard curve by using the peak area of the target pesticide residue to the corresponding mass concentration. When the quantitative ion and the qualitative ion of the compound are simultaneously detected and at least one of the qualitative ions is compared with the standard, the lowest concentration at which the ion ratio is + -15% is defined as the detection limit. The method can detect the concentration of 1000 mug/kg, does not need sample dilution when analyzing the actual sample containing high concentration pesticide residue level, and simplifies the experimental steps compared with other methods. The linear correlation coefficients of the method are all larger than 0.99, which indicates that the screening analysis method has good linear correlation.
Blank animal-derived food (animal-derived food without pesticide residue) is added with 100, 250 and 500 mug/kg of working solution respectively, and 6 parallel standard-adding recovery experiments on 3 levels are carried out. As can be seen from Table 6, all the recoveries of the pesticides were in the range of 70% to 120% in the high, medium and low levels, and the method was accurate. The relative standard deviation RSD values of all pesticides in the day and in the daytime are less than 20%, which indicates that the method has good repeatability. Therefore, the method has good accuracy and repeatability, and meets the requirements of food sanitation and agricultural product quality safety detection.
TABLE 6 recovery and standard deviation for different addition concentrations
The invention establishes a sample pretreatment method of pesticide residues in animal-derived food based on QuEChERS, and carries out screening analysis by using GC-Oribitrap-MS. The method adopts 1:1 mixed solution of acetonitrile containing 1% acetic acid and acetone as an extractant, C18 and magnesium sulfate as purificant, and adopts an external standard method for quantification after preparing a standard solution calibration curve, thereby realizing screening confirmation and quantitative analysis of 719 kinds of pesticide residues in animal-derived food. The method has the characteristics of high recovery rate, good repeatability, strong applicability, simplicity, rapidness and the like, each technical index can meet the requirement of daily detection and analysis of the animal derived food, and meanwhile, an important technical support is provided for the field of food safety.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, the scope of the present invention is not limited thereto, and various modifications and variations which do not require inventive efforts and which are made by those skilled in the art are within the scope of the present invention.
Claims (2)
1. A GC-Orbitrap-MS analysis method for pesticide residues in animal derived food comprises the following steps:
(1) extraction: homogenizing an animal-derived food sample, mixing with an extraction solvent and extraction salt, performing oscillation extraction to obtain an extracting solution, and taking supernatant I;
the volume ratio of the mass of the animal-derived food sample to the extraction solvent is 1g: 2-5 mL;
the extraction salt is a mixture of anhydrous magnesium sulfate, sodium chloride, sodium bicarbonate, sodium citrate and disodium citrate;
adding the extraction salt to remove water for 1-5 min;
the extract was centrifuged under the following conditions:
the temperature is 0-10 ℃, the rotating speed is 2500-10000 Xg, and the time is 5-10 min;
the animal derived food comprises at least one of chicken, pork, beef, mutton, duck, goose meat, chicken liver, pork liver and lamb liver;
the extraction solvent is a mixed solution of acetonitrile containing 1% acetic acid and acetone in a ratio of 1: 1;
(2) purifying: mixing the supernatant I obtained in the step (1) with a purifying agent for purification, collecting a supernatant II, and filtering to obtain a sample solution to be liquid;
the purifying agent is a mixture of C18 and anhydrous magnesium sulfate;
(3) and (3) detecting by using a chromatographic mass spectrum: separating the pesticide residue in the sample liquid to be detected by adopting a gas chromatography, and then detecting by adopting Orbitrap-MS with an EI ion source to obtain the pesticide residue content in the animal-derived food;
the chromatographic column adopted by the gas chromatography is Trace-Pesticide II;
the chromatographic conditions for the gas chromatography were as follows: the temperature rising procedure is as follows: maintaining the initial temperature at 40 deg.C for 1.5 min; heating to 90 deg.C at 25 deg.C/min, and maintaining for 1.5 min; heating to 180 ℃ at a speed of 25 ℃/min; heating to 280 ℃ at the speed of 5 ℃/min; heating to 300 deg.C at 10 deg.C/min, and maintaining for 3 min; the injection port temperature was 290 ℃ and the helium gas flow rate was 1.2 mL/min.
The mass spectrum conditions of the Orbitrap-MS are as follows: the ion source temperature is 280 ℃, the ionization energy is 70eV, and the current is 50 muA;
the ion scanning mode is a full scanning mode, the scanning range is 50-550m/z, the resolution of the full scanning mode is set to be 60,000FWHM, an internal standard reference solution is used for correcting the quality precision of the instrument in real time, and data acquisition and processing are carried out on mass spectrum detection through TraceFinder 4.1General quant software;
the pesticide residue comprises herbicide, insecticide, bactericide, acaricide, rodenticide and plant growth regulator;
the herbicide comprises 2- (2,4, 5-trichlorophenoxy) -propionic acid, 2- (4-chloro-2-methylphenoxy) propionic acid, 2,4, 5-nasal discharge methyl propionate, 2, 4-D-2-ethylhexyl ester, 2, 4-D propionic acid, 2, 4-D butyric acid, 2, 4-D butyl ester, 2, 6-dichlorobenzamide, 2-methyl-4, chloro-2-ethylhexyl ester, 2-methyl-4-chlorobutyl ester, 2-methyl-4-chloroisooctyl ester, 3-chloro-p-toluidine, 4-chlorophenoxyacetic acid, E-pyriminobac-methyl, atrazine, ethazine, prodiamine, propamocarb, barnyard grass, propamocarb, propham-ethyl, 3-chloro-p-toluidine, 4-chloro-4-o-ethyl, E-pyrimethanil, atrazine, ethazine, prodiamine, propamocarb-N-methyl, propamocarb-N-2-4-ethyl, 4-methyl-p-butyl-ethyl-4-butyl-ethyl-p-bencarb-4-ethyl, propham-p-bencarb-ethyl, propham-bencarb-p-bencarb-ethyl, bencarb-2-p-ethyl, p-ethyl, bencarb-p-ethyl, p-bencarb-p-bencarb-p-ethyl, p-bencarb-p-ben-p-ethyl, p-ben-p-bencarb-ben-p-ben-ethyl, p-o-p-ethyl, o-p, Bensulfuron-methyl, tribenuron-methyl, anisole, metamitron, mefenacet, fenpyroximate, fenpyrozamide, thioconazole, pyraflufen-ethyl, benfop-ethyl, metolachlor, flumioxazin, thiourel, dicamba, benazolin ethyl, prodazine, cufensulfuron-methyl, dimethofen, bromacil, bromfen, propanil, dichlobeturon, dichlorvos, dimethyl chlorophthalate, dimethomol, triazo, butachlor, butralin, butachlor, butafenamide, butazin, buthiuron, propyzamide, oxadiazon, oxadixyl, oxazicloziclodinium, diacryl, dimethenamid, pendimethalin, clopyralid, pyridinic acid, trans-oat-furbensulfuron, furbenfluridone, bentazone, metolachlor, clorfan, benflurazone, benfluralin, benazolin, benfluralin, benazolin, benfluralin, benazolin, flurprimidol, diflufenzopyr sodium, haloxyfop-methyl, flupyrazamide, butafenacil, fluroxypyr-1-methylheptyl, fluroxypyr-ethyl, fluorobutachlor, fluazinone, flupyrsulfuron-methyl sodium, flurazole, trifluralin, dithiopyr, flufenacet, fluoroelenic acid, fenclozine, heptanoyll, molinate, diclofop-methyl, benoxanone lithium, ciprofloxacin, cycloprozen-ethyl, cyhalofop-methyl, cyazone, cyclouron, cycloartemether, alachlor, metsulfrin, methabenzthiazone, dimethoate, oxaziclofenpyr-ethyl, linum, tebuconazole, cuckoo-methyl, quinoa-ethyl, linuron, tebufen, thiouron, metoclopramide, fluroxypyr, benfluroxypyr, benflur, Chlorsulfuron, chlorosulfonyl, clomeprop, clodinafop-propargyl, methylphosphonate, chlorsulfuron, chloroacetofloxacin, lofluazuron, lolium fluoroisopropyl, imazamox, pyriminobac-methyl, molinate, imazamox, diafenthiuron, dichlorphenazine, benfuresate, napropamide, propaquin, prosulfocarb, prometon, metribuzin, cyanazine, cyhaloxyfop, cyhalofop-butyl, norflurazon, propyzamide, propargyl, clodinafop-propargyl, lactofen-ethyl, thiazopyr, thiophenecarboxamide, thiazopyr, metribuzin, trin-methyl-norfluroxypyr, triclopyr, triazophos-amide, chlorbutan, fenbutan-ethyl, anilide, fenpropaquizafop-ethyl, isoxadifenon-bencarb, tebufenox, metamifop-ethyl, tebufenon-ethyl, tebufenozide, propyzamide, bencarb, benazolide, ben, Terbutryn, terbutone, desmethol, dethylatrazine, pentachloromethoxybenzene, penoxsulam, simetryn, simazine, dichlormid, dimethenamid, pethoxamid, clethodim, sethoxydim, amidosulfuron, neodelphin, bromoxynil octanoate, bromobutachlor, bromogluron, dichlorvos, avenanthramide, triallate, acetochlor, ibuflufen, fluoroglycofen-ethyl, at least one of acetometachlor, oxyfluorfen, propisochlor, metolachlor, ipropyn, isoproturon, clomazone, isoxaflutole, isoacetochlor, butafosinate, fenoxaprop-p, yinserin, indoxyl, amisulbrom, indanthrone, indoxachlor, ametryn, atrazine, trueol, shapexin, dimethomorph, paraquat, butralin and carfentrazone-ethyl;
the pesticide comprises 2,3, 5-mixed carbofuran, 2,4' -dichlorodiphenyl ketone, 2,4' -dicofol, 3,4, 5-mixed carbofuran, 4' -dichlorodiphenyl ketone, 4-dodecyl-2, 6-dimethyl morpholine, E-methyl chlorfenvinphos, N-diethyl-methyl pyrimidine phosphorus, o, p ' -dichlorodiphenyl, p ' -dichlorodiphenyl, S-fenvalerate, alpha-hexachloro-ethyl, beta-hexachloro-methyl, delta-hexachloro, epsilon-hexachloro, aldrin, Anethion, amikacin, tetramethrin, octamethrin, octachlorostyrene, octachlorodipropyl ether, chlorphos, captopril, baotion, fenthion, fenthiosulfone, fenthiosulfoxide, fenthiooxysulfone, fenthiosulfoxide, benchol, cyanophos, thiophosphine, phenothrin, cyphenothrin, thiocyanogen, fenamiphos, phenoxycarb, pyriproxyfen, tebufenpyrad, pyrazofos, deentraniliprole, resmethrin, benzofenamiprin, propathrin, prothiocarb, prothiocarpon, propoxyphene, propoxur, benfuracarb, oxadicarb, bensulide, fenclofos, chlorfenphos, fenamiphos, pyrethrum extract, dichlofenphos, pyridaphenthion, phenthoate, dicarb, dichlorvos, phosphaphenthion, dichlorvos, dinotefuran, fenapyr, pyraclofos, dichlorvos, diclofenthion, pyridalyl, acetamiprid, chlorfenvinphos, chlorloafos, chlorpyrifos oxide, parathion, paraoxon, polyfluorourea, oxazaphos, bendiocarb, diazinon, phosphorus dibromide, dioxacarb, vamidophos, trans-chlordane, trans-permethrin, fensulfofop, sulfofenfuracae, fluvalin, fluvalinate, fluoropyrimidinol, flupropathrin, flufenoxan, fipronil sulfide, flufenoxuron, flonicamid, silafluosilate, flucyclothrin, flucythrinate, lambda-cyhalothrin, heptenophos, sulfofipronil, housefly, methamidophos, phorate sulfone, phorate sulfoxide, methiphos, pirphos-methyl, pirimiphos-methyl, chlorpyrifos-methyl, methyl parathion, methyl paraoxon, methyl bensul, bensultrin, benfop, bensultrin, bencarb, Methyl systemic phosphorus, methyl bromphenthoate, methyl disulfate, methyl isoxathion, methyl sulfone, methothrin, carbaryl, fenpropathrin, metofluthrin, methoxychlor, monocarb, kaempferia galbana, anti-acarid, anti-aphid, carbofuran, quinalphos, dimethoate, bifenthrin, diflubenzuron, lindane, phosphamidon, thioprofos, thiofenphos, alpha-endosulfan, beta-endosulfan, endosulfan sulfate, thiocyclophos, thiotepa, spirotetramat-mono-hydroxy, spirotetramat-keto-hydroxy, spirotetramat-enol-glucoside, spiromesifen, spirodiclofen, lambda-cyhalothrin, chlormephos, chlorphrin, cypermethrin, chlormephos, phosphorus oxychloride, malathion, manganese, methomyl, ethofenproxy, ethofenprox, ethrin, ethofenprox, ethrin, ethofenphos, kresoxim, fenthion, fenpropathrin, kresoxim, fenpropathrin, thion, thiuron, clomiphos, thion, clomiphos, fenthion, clomiphos, fenpropathrin, fenthion, fenpropathrin, fenpropath, Pyrimidophos, gossypol, methiocarb, methomyl, fenamiphos, triazophos, desmethofen, cyromazine, dichlormid, demeton-S-sulfoxide, pyrathion, tefluthrin, heptachlor, fenvalerate, anthelmintic, prallethrin, kadethrin, buprofezin, fosthiazate, triphenyl phosphate, trithione, triclosan, triazophos, chlordimeform, fenvinphos, cyanophos, fenitrothion, methidathion, bioresmethrin, bioallethrin, paraquat, isochlorothion, cis-cypermethrin, transfluthrin, phos, metolcarb, carbochloprofen, terbufos sulfoxide, terbufos-OXON, terbufos-sulfone, terbufos-OXON, aldicarb, methiocarb-sulfone-methyl-sultap-methyl-ethyl, Aldicarb sulfoxide, demethyl-pirimicarb, bromobenzoate, exochlor, meclofenozide, pentachlorobenzene, pentachlorophen, pentachlorophenol, quintozene, penconazole, allethrin, methoprene, phoxim, bromophenyl phosphorus, chlorfenapyr, bromophos, cyantraniliprole, deltamethrin, chlorfenapyr, phos, phosmet, sulfoxophos, fenthion, oxyphenphos, chlordane oxide, oxydemeton-methyl sulfone, oxydemeton-methyl sulfoxide, omethoate, oxydisup, oximidothion, isoprofos, disulfoton, ethiofen, ethiofencarb, diethofencarb, ethiofencarb, isoprocarb, isosulfotolane, isosulfonicotine, isosulfomethabenzuron, isosulfomethacin, isosulfomethabenz, isosulfomethabenzuron, isobenfurbenfuradam, isosulfomethabenzuron, propathrin, isobendiothion, isobensulide, propathyrifos, isobensulbensulindate, isoflurbenomyl, etc, At least one of endrin aldehyde, endrin ketone, isosulforaphane, isochlorophos, bensulide, indoxacarb, coumaphos, foster phosphorus, synergistic ether, sulfotep, fenobucarb, zakhstan and tolfenpyrad;
the bactericide comprises enestroburin, (E) -metominostrobin, (Z) -metominostrobin, 3, 5-dichloroaniline, 3-phenylphenol, 8-hydroxyquinoline, fenpyrazamine, chlorothalonil, fenpropathrin, fenflurazole, benzovinfluanid, metrafenone, difenoconazole, benalaxyl, metamifop, fenpropidin, metominostrobin-1, metominostrobin-2, phenoxyquinoline, pyraclofos, pyrimidazole, pyrazosulfuron-ethyl, penthiopyrad, pyrafluthrin, isopyrazam, diclozoline, isoprothiolane, captafol, dixolone, diphenoxy, fenphos, fenpropimorph, pyrimorph, eugenol, picoxystrobin, oxadixyl, triadimenol, flutriafol, furametpyr, furamex, furametpyr, fluazinam, Epoxiconazole, epoxiconazole-2, triflumizole, fluquinconazole, fluvaliconazole, flutolanil, procymidone, flutriafol, silthiofam, cyproconazole, cyflufenamid, fenhexamid, griseofulvin, activated ester, hexaconazole, mebenfluanid, methylfurosemide, tolclofos-methyl, metalaxyl, metoclopramide cry bacteria, fenbuconazole, myclobutanil, mefenoxam, dimethachlon, bromuconazole, captan, biphenyl, bixafen, biphenyltriadimenol, phthalimide, metconazole, hexachlorobenzene, spiroxamine, chlorophenylmethyl ether, fenarimol, nicum, fuberidazole, mefenpyr, prochloraz, fenamidone, azoxystrobin, cyprodinil, azoxystrobin, ferimzone, imazalil, fenamidone, fenaminostrobilurin, triticale, fenaminostrobilum, fenamate, triticonazole, fenamiphos, fenaminostrobilurin, fenapyr, metominostrobilurin, prochloraz, trifloxystrobin, trifloxystroban, cyhalonil, trifloxystroban, prochloraz, proc, At least one of mefenapyr, cyanamide, thifluzamide, triphenyltin hydroxide, triflumizole, tricyclazole, trichloromethylpyridine, triadimenol, triadimefon, dodecacylmorpholine, dicloromethane, propamocarb, tetraconazole, tetrachlorophthalide, phthalidyl ester, hymexazol, debenzylimizole, fenbuconazole, carboxin, trifloxystrobin, oryzalin, pencycuron, tebuconazole, probenazole, dimethomorph, diniconazole, chlorfenapyr, iprovalicarb, bromacil-oxonon-debenzyl, nicotinoyl choline, oxycarboxin, metconazole, epoxiconazole, ethirimol, bupirimate, vinclozolin, ethoxyquin, iprobenfos, iprodione, imazalil, iprodione, ipconazole, and pyraclostrobin;
the acaricide comprises at least one of flutriafol, fenoxycarb, fenpyroximate, propylate miticide, pyridaben, fluazuron, fenpyroximate, fluazuron, hexaflumuron, flufenzine, noviflumuron, cyhalofenate, fenazaquin, bifenazate, chlorfenapyr, acarine, pyriminostrobin, fluacrypyrit, propargite, thiamethoxam, hexythiazox, dicofol, lufenuron, amitraz, bromopropylate, etoxazole and fenpyroximate;
the rodenticide comprises at least one of warfarin and morindate;
the plant growth regulator comprises at least one of 1-naphthylacetamide, paclobutrazol, flumetralin, cyprodinil, trinexapac-ethyl, jasmone, naphthylacetic acid, thionine, defoliant, uniconazole, imazalil and indate.
2. The analytical method of claim 1, wherein: in the step (2), the supernatant I is mixed with the purifying agent and then is subjected to vortex purification, and then the supernatant II is obtained by centrifugation under the following conditions:
the temperature is 0-10 ℃, the rotating speed is 2500-5000 Xg, and the time is 5-10 min;
filtration was performed using a 0.22 μm filter.
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| CN108896694B (en) * | 2018-07-05 | 2019-09-27 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of remaining LC-QToF-MS Screening analysis method of pesticide in animal food |
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