CN113325112A - Method for simultaneously and rapidly detecting residual quantity of various pesticides - Google Patents
Method for simultaneously and rapidly detecting residual quantity of various pesticides Download PDFInfo
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Abstract
The application belongs to the technical field of analytical chemistry, and particularly relates to a simultaneous rapid detection method for multiple types of pesticide residues. Comprises the steps of organic solvent extraction, dispersive solid phase extraction purification, and determination of pesticide residue in a sample by gas chromatography-triple quadrupole tandem mass spectrometry (GC-MS/MS) with a temperature programming injection port after purification. The method can effectively avoid the interference of high-content pigment in the sample, has the characteristics of simple and rapid operation, small solvent consumption, accuracy, sensitivity and the like, belongs to an environment-friendly green chemical analysis method, and has small harm to human bodies and environment.
Description
Technical Field
The application belongs to the technical field of analytical chemistry, and particularly relates to a simultaneous rapid detection method for multiple types of pesticide residues.
Background
In recent years, food safety issues such as "clenbuterol" event, escherichia coli epidemic, england bovine spongiform encephalopathy, "dioxin" in belgium, "listeria in the united states," sudan red "event in the world, etc. are continuously occurring at home and abroad, and are continuously exposed to media, and thus, the public has not paid attention to the food safety issues. The pesticide is one of the most important technical means and production data in the agricultural production activities in the world at present. Because of inherent chemical properties and improper use of pesticides, the quality of agricultural products which are the bottom layer and the most important ring of the human food chain is more and more threatened and influenced by the pesticides, the situation of pesticide residue is more severe when economic benefits are maximized and the awareness of the pesticides is insufficient, and the direct consequences are serious pollution of the agricultural products, serious standard exceeding of the pesticide residue and various poisoning accidents caused by the pesticides are frequent.
The analysis of pesticide residue in food is a complex trace analysis technology, and the pretreatment technologies widely applied at present mainly comprise a solid-phase micro-extraction technology, a solid-phase extraction technology, a molecularly imprinted polymer technology and the like. The newer detection technologies mainly comprise a tandem mass spectrometry detection technology, a time of flight mass spectrometry (TOF-MS) technology, a full two-dimensional gas chromatography mass spectrometry detection technology and the like, and the application of the new chromatography-mass spectrometry combined technology enables pesticide residue analysis to be developed from the original method of determining one or more pesticide residues by means of a chromatographic method to the method of simultaneously determining various different types of pesticide residues, so that high-flux, high-sensitivity qualitative and quantitative analysis of multi-component pesticides is realized.
The fruit and fruit wine has high nutritive value, so that it is popular with consumer and has very high economic value. In order to facilitate the safety and quality control of fruit and fruit wine-making food, it is necessary to establish an analysis method for simultaneously detecting various pesticide residues in fruit and fruit wine-making. However, few literature reports on rapid detection of multiple pesticide residues in fruit and fruit wine making are available at present. In the currently effective national recommended standards of detection methods for pesticide residues in fruits such as GB/T19648-2006, GB/T20769-2008 and GB/T14553-2003, a sample is mostly purified by a purification column in a pretreatment method, the operation is complex, the analysis time is long, false positive results are easy to occur by using unipolar mass spectrometry, and more time is consumed for further confirmation, so that the detection efficiency is low.
Aiming at the problems of high pigment content and complex matrix possibly existing in fruit and fruit wine making, it is necessary to develop a method for simultaneously and rapidly detecting various pesticide residues.
Disclosure of Invention
The application provides a method for simultaneously and rapidly detecting various pesticide residues, which comprises the step of purifying a sample by using a dispersed solid phase extraction material, wherein the dispersed solid phase extraction material comprises a mixture of anhydrous magnesium sulfate, ethylenediamine-N-Propyl Silane (PSA) and Graphitized Carbon Black (GCB).
The main interferents in the food matrix are lipid substances, organic acids, carbohydrates, sterols, etc., and the materials commonly used for purification are C18, PSA, GCB, etc. C18 is used for adsorbing lipid substances and some nonpolar interferents in the sample; PSA is used for adsorbing polar matrix components in extractive solution, such as fatty acid, organic acid, phenols and pigment; GCB is mainly used for removing pigments in a matrix, but has strong adsorbability, so that part of pesticides are not easy to elute, and the recovery rate is low. In use, several purifying materials are combined according to a certain proportion, and the recovery rate of the target object is ensured while the purifying effect is achieved. However, what ratio of decontaminating material is best for different samples is unknown to those skilled in the art, and further exploration is required to find the best combination of decontaminating agent for different samples.
In some embodiments, the weight part ratio of the anhydrous magnesium sulfate, the ethylenediamine-N-propyl silane and the graphitized carbon black in the mixture is (40-80): (5-15): (1-3); in some embodiments, the weight ratio of the anhydrous magnesium sulfate, the ethylenediamine-N-propyl silane, and the graphitized carbon black in the mixture is 60:10 (1-3); more preferably 60:10: 3.
In some embodiments, the dispersed solid phase extraction material is selected from the group consisting of the QuEChERS reagent packages 5982-.
In some embodiments, the detection method comprises the steps of:
s1, extraction: adding acetonitrile into a sample, performing vortex oscillation, and taking a supernatant;
s2, purification: adding the supernatant prepared in the step S1 into a dispersed solid phase extraction material, performing vortex oscillation, centrifuging, and filtering the supernatant with a filter membrane;
s3, GC-MS/MS measurement: the liquid filtered in step S2 was subjected to GC-MS/MS analysis.
In some embodiments, in the step S1, the rotation speed of vortex oscillation is 1500-3000rpm, and the time of vortex oscillation is 2-10 minutes.
In some embodiments, the rotational speed of the vortex oscillation is 2000rpm and the time of the vortex oscillation is 5 minutes.
In some embodiments, the vortexing is followed by adding a QuEChERS reagent pack for a second vortexing.
In some embodiments, the supernatant is centrifuged after the second vortexing.
In some embodiments, the ratio of the supernatant to the dispersed solid phase extraction material in step S2 is 150-300mg of the dispersed solid phase extraction material per ml of supernatant.
In some embodiments, in the step S2, the rotation speed of vortex oscillation is 1500-3000rpm, and the time of vortex oscillation is 2-10 minutes; in some embodiments, the rotational speed of the vortex oscillation is 2000rpm and the time of the vortex oscillation is 5 minutes.
In some embodiments, the rotation rate of centrifugation is 8000-12000r/min, and the centrifugation time is 5-20 minutes; in some embodiments, the centrifugation is performed at a rotational speed of 10000r/min for a period of 10 minutes.
In some embodiments, the filtration membrane is an organic phase filtration membrane; preferably, the organic phase filter is a 0.22 μm organic phase filter.
In some embodiments, in the step S3, the temperature raising procedure of the chromatographic column is to maintain at 88-92 ℃ for 4-6min, then raise the temperature at 20-30 ℃/min to 175-185 ℃ for 14-16min, then raise the temperature at 4-6 ℃/min to 270-290 ℃ for 3-5 min; in some embodiments, the temperature program for the chromatography column is 90 ℃ for 5min, then 25 ℃/min to 180 ℃ for 15min, then 5 ℃/min to 280 ℃ for 4.5 min.
In some embodiments, the chromatographic conditions are: sample introduction volume: 1 mu L of the solution; sample introduction mode: PTV non-shunting sample injection; the Surge pressure: 150kPa (1 min); initial temperature of a sample inlet: the temperature is increased to 280 ℃ rapidly at 10 ℃/s after sample injection at 90 ℃; capillary column: TR-Pesticide II [ (50% phenyl) methylpolysiloxane, 30 m.times.0.25 mm.times.0.25 μm +5 m.times.0.25 μm (pre-column) ]; carrier gas: he with the purity of more than or equal to 99.999 percent; flow rate of carrier gas: 1.2 mL/min; temperature program of chromatographic column: maintaining at 90 deg.C for 5min, heating to 180 deg.C at 25 deg.C/min, maintaining for 15min, heating to 280 deg.C at 5 deg.C/min, and maintaining for 4.5 min; transmission line temperature: 290 deg.c.
In some embodiments, the mass spectrometry conditions are: ion source temperature: 250 ℃; emission current: 50 muA; an ion source: a closed EI source; collision gas pressure: 1.2mTorr (Ar); solvent delay time: 7.0 min; scanning mode: SRM (selective reaction monitoring), using the Method of EZ-Method setting, "Start time" is set as the starting point of the scanning time of the target compound and is the retention time RT-0.75min of the target compound, and "End time" is set as the End point of the scanning time of the target compound and is the retention time RT +0.75min of the target compound.
Mass spectrum condition selection strategy: the mass spectrum data acquisition mode is an SRM mode, and SRM parameters comprise parameters such as monitoring ion pairs, collision energy and scanning time windows. Ion pairs and collision energies of a portion of pesticides are obtained by retrieving or querying relevant documents from the Thermo Fisher agricultural residues library (SRM Transitions). And (3) firstly, obtaining retention time and a primary mass spectrogram by full scanning of other pesticides, selecting ions with high abundance, large mass-to-charge ratio and strong characteristics from the primary mass spectrogram as parent ions, bombarding the parent ions by adopting different energies to obtain a corresponding secondary mass spectrogram, selecting ions with high abundance, large mass-to-charge ratio and strong characteristics from the secondary mass spectrogram as daughter ions, and recording corresponding collision energy. The scanning time window is generally set as 'retention time +/-0.75 min', four connected chromatographic peaks appear on an individual pesticide such as cypermethrin due to the existence of isomers, the peak appearance time window is relatively wide, and therefore the scanning time window is set as 'retention time +/-1.25 min', the target compound is ensured to appear in the set scanning time window, and meanwhile, the retention time of the target compound can be tolerated to be shifted to a certain extent.
In some embodiments, the scan pattern of the mass spectrum is: and (6) SRM.
In some embodiments, the test sample of the test method comprises fruit and fruit wines; in some embodiments, the fruit is selected from at least one of blueberry, grape, apple, peach, and green plum; in some embodiments, the fruit wine is selected from at least one of blueberry wine, grape wine, apple wine, peach wine, and green plum wine.
In some embodiments, the detection method further comprises step S0, homogenizing: homogenizing the sample to prepare a sample solution.
In some embodiments, the pesticide is selected from at least one of organochlorine, organophosphorus, organonitrogen, pyrethroid, triazole, and heterocyclic pesticides.
In some embodiments, the organochlorine pesticide is selected from at least one of o, p ' -DDD, o, p ' -DDE, o, p ' -DDT, p ' -DDD, p ' -DDE, p-DDT, alpha-endosulfan, alpha-hexachlorocyclohexane, beta-endosulfan, beta-hexachlorocyclohexane, gamma-hexachlorocyclohexane, delta-hexachlorocyclohexane, aldrin, chlorothalonil, dieldrin, dichlorosol, endosulfan sulfate, chlordane-trans, chlordane-cis, mirex, heptachlor, trichlorfone, ethacrylonitril, ethacridine, and endrin.
In some embodiments, the organophosphorus pesticide is selected from at least one of fenthion, thiophenyl, prothioconazole, fenamiphos, chlorpyrifos, parathion, diazinon, vozaphos, oryzophos, phorate, chlorpyrifos-methyl, pirimiphos-methyl, captan, quinalphos, chlorzofos, malathion, fenamiphos, pyrathion, triazophos, fenitrothion, methidathion, fenamiphos, terbufos, bromothion, disulfoton, ethiofenphos, ethion, and iprobenfos.
In some embodiments, the organonitrogen pesticide is selected from at least one of benalaxyl, propoxur, napropamide, oxadixyl, pendimethalin, trifluralin, alachlor, metalaxyl, pirimicarb, methiocarb, triadimefon, chlordimehypo, penconazole, metolachlor, and isoproylin.
In some embodiments, the pyrethroid-based pesticide is selected from at least one of cyfluthrin, lambda-cyhalothrin, bifenthrin, permethrin, cypermethrin, tefluthrin, fenvalerate, and deltamethrin.
In some embodiments, the triazole pesticide is selected from at least one of difenoconazole, myclobutanil, and uniconazole.
In some embodiments, the heterocyclic pesticide is selected from at least one of isoprothiolane, and clomazone.
In some embodiments, the pesticide is selected from disulfotoxin, metosulam, captafol, propoxur, fenamiphos, trifluralin, fluchlor, chlorfenapyr, captan, phorate, alpha-hexahexa, clonidine, clomazone, gamma-hexa, beta-hexa, terbufos, diazinon, disulfoton, chlorothalonil, clozapine, heptafluthrin, delta-hexa, pirimicarb, iprobenfos, chlorpyrifos-methyl, alachlor, heptachlor, metalaxyl, pirimiphos-methyl, pirfenidone, methidathion, methiocarb, malathion, metolachlor, aldrin, chlorpyrifos, fenthion, dichlorvos, parathion, triadimefon, butralin, bromophos, metamifop, isoprocarb, pendimethalin, penconazole, fenvinphos, quinacr, chlordane-antis, methidathion, o, at least one of p '-DDE, alpha-endosulfan, chlordane-cis, disulfuryl sulfone, flumetralin, naprophos, isoprothiolane, dieldrin, p' -DDE, uniconazole, o, p '-DDD, myclobutanil, endrin, aclonifen, beta-endosulfan, dicofol, oxadixyl, o, p' -DDT, p '-DDD, ethion, triazophos, benalaxyl, cumic ether, endosulfan sulfate, p' -DDT, synergistic ether, phenthophos, bifenthrin, trichlorfone, vomethidathion, dichlorfluthrin, fenthion, oryzophos, ethiofen, deltamethrin, azoxystrobin, famoxadone, permethrin, cyfluthrin, cypermethrin, fenvalerate, and dimethomorphine.
In some embodiments, the pesticide is selected from the group consisting of dichlorvos, metocloprid, heptenophos, propoxur, demeton-methyl, fenamiphos, chlorfenapyr, trifluralin, flumetsulam, captan, phorate, alpha-hexaxas, clonidine, isoxadim, beta-hexaxas, gamma-hexahexahexaxas, terbufos, diazinon, chlorothalonil, disulfoton, clozapon, delta-hexaxas, tefluthrin, pirimicarb, iprobenfos, chlorpyrifos-methyl, parathion-methyl, alachlor, carbaryl, benzothiadiazole, metalaxyl, pirimiphos-methyl, methidathion, triafolan, metolachlor, chlopyrifos, fenphos-methyl, fenthion, dichlorvos, parathion, triadimefon, pyrone, bromthion, isophen, pendimethalin, diclofen, epoxy-p, diclofen-p, and cloquinclorac-p, Captan, quinalphos, folpet, chlordane-trans, methidathion, o, p ' -DDE, alpha-endosulfan, disulfurone, chlordane-cis, napropamide, profenon, isoprothiolane, dieldrin, uniconazole, p ' -DDE, o, p ' -DDD, endrin, aclonifen, beta-endosulfan, dicofol, oxadixyl, o, p ' -DDT, p ' -DDD, ethion, triazophos, cumyl ether, benalaxyl, endosulfan, p, p' -DDT, thiophenyl, chlorantraniliprole, bifenthrin, methoxyDDT, dicofol, vozaphos, mirex, lambda-cyhalothrin, dichlofluthrin, diclofop, quizalofop-p-ethyl, deltamethrin, famoxadone, triadimenol, permethrin, cyfluthrin, cypermethrin, and cyhalothrin.
In some embodiments, the pesticide is selected from benzothiadiazole, alachlor, aldrin, alpha-endosulfan, acephate, oryzanol, azoxystrobin, benalaxyl, flumetum, beta-endosulfan, bifenthrin, bromacil, bromophos, butralin, captan, captafol, captan, carbaryl, chlorantraniliprole, chlordane-cis, chlordane-trans, chlordimeform, chlorfenphos, cumquat, chlorothalonil, chlorpyrifos-methyl, dichlorvos, dicofol, clomazone, cyfluthrin, cypermethrin, deltamethrin, endothos, methylphos sulfone, diazinon, dichlorvos, nicum, difenoconazole, dimethomorphine, metamifop-p, disulfoton, ben, indian, ben, benfurazon, benazol, benfurazon, benazol, benfurazon, benazol, benfurazol, benazol, benfurazon, benfurazol, benazol, benfurazol, benazol, benazolin, benfurazolin, benazolin, benazol, benfurazol, benazolin, benazol, benazolin, benfurazol, benazol, benfurazolin, benazolin, fenamiphos, famoxadone, pyraclofos, fenitrothion, fenthion, fenvalerate, flucythrinate, fluvalicarb, folpet, heptachlor, epoxy heptachlor-trans, heptenophos, iprobenfos, clomiphos, isoprotulin, isoprothiolane, lambda-cyhalothrin, malathion, metalaxyl, methidathion, methiocarb, metoxydt, metolachlor, metoclopramide, metalaxyl, imazalil, myclobutanil, alachlor, aclonifen, o, p '-DDD, o, p' -DDE, o, p '-DDT, oxadixyl, p' -DDD, p '-DDE, p' -DDT, parathion, methyl parathion, pendimethalin, penconazole, permethrin, phorate, phosmet, triazophos, pirimicarb, pirimiphos, propoxur, mephos, quinalphos, At least one of tefluthrin, terbufos, triclocarban, triadimefon, triadimenol, triazophos, trifluralin, uniconazole, alpha-hexahexa, beta-hexa, gamma-hexa, and delta-hexa.
It is well known to those skilled in the art that the more compounds analyzed, the higher the requirements for the sample and the pretreatment and also the parameters analyzed when the compounds are measured by GC-MS/MS. The method can realize simultaneous determination of 95 compounds in fruits and fruit wine by simple and rapid pretreatment (QuEChERS), effectively reduces the interference of a sample matrix, and meets the analysis requirements of multiple pesticide residues on the performance parameters of the method such as quantitative limit, accuracy and precision.
Drawings
FIG. 1 is a total ion flow diagram of Selective Response Monitoring (SRM) of 95 pesticides in a blueberry substrate.
FIG. 2 is a comparison of the color of the supernatant clarified by the four clarification combinations of example 2. Wherein, the leftmost sample is the color of the supernatant before purification; sample A represents purified by 5982-; b samples represent purification via 5982-; c sample represents purified by 5982-; d samples represent purified by 5982-.
FIG. 3 is a comparison of the full scan chromatograms for the four purification conditions in example 2. Wherein, the sample A is purified by 5982-5021; b samples represent purging via 5982-; c sample represents purified by 5982-; d samples represent purified by 5982-.
FIG. 4 is a total ion flow diagram of Selective Response Monitoring (SRM) of 95 pesticides in blueberry wine.
FIG. 5 is a comparison of the pigment removal performance under the three decontamination conditions of example 6. Wherein, the sample A is purified by 5982-5021; b represents the sample purified by 5982-; sample C represents purified 5982-.
FIG. 6 is a comparison of chromatograms for three purging conditions in example 6. Wherein A represents a sample purified by 5982-5021; b represents a sample purified by 5982-; c represents the sample purified by 5982-5321.
Detailed Description
The technical solutions of the present invention are further illustrated by the following specific examples, which do not represent limitations to the scope of the present invention. Other insubstantial modifications and adaptations of the present invention in accordance with its teachings are within the scope of the invention.
Example 1QuEChERS-GC-MS/MS method for determining 95 pesticide residues in blueberries
The blueberry is high in pigment content, and in the determination of multiple pesticide residues, in order to avoid the pollution of the blueberry to an analysis instrument as much as possible, higher requirements are put forward on sample pretreatment. While removing the pigment, the recovery rate of simultaneous analysis of various pesticides is ensured. The national standards for detecting pesticide residues in the existing effective fruits mainly comprise GB/T19648-2006, GB/T20769-2008, GB/T14553-2003 and the like, wherein the GB/T19648-2006 adopts acetonitrile for homogenate extraction and then is subjected to solid phase extraction and purification, the GC-MS analysis is carried out after solvent exchange, and the sample treatment is complex, the solvent consumption is large, and false positive easily occurs; the pretreatment of GB/T20769-2008 and GB/T14553-2003 samples is complicated, and the gas chromatography of GB/T14553-2003 is easy to generate false positive results.
The detection method for simultaneously determining 95 pesticide residues in the blueberries by the QuEChERS-GC-MS/MS method is established in the embodiment, and the technology has the advantages of simple and quick pretreatment, solvent saving, high sensitivity and capability of effectively eliminating false positive results.
1. Instruments and reagents
Thermo Scientific Trace GC Ultra-TSQ Quantum XLS gas chromatograph-triple quadrupole tandem mass spectrometer (ThermoFisher Scientific, USA); Talboys/Standard Multi-Tube vortex shaker (Talboys, USA); HITACHI CR22G III high speed centrifuge (Hitachi, Japan); a refiner (Omni Corp., USA).
Acetonitrile, toluene (chromatographically pure, TEDIA reagents, usa); QuEChERS reagent kit 5982-; QuEChERS reagent pack 5982-5021(150mg anhydrous MgSO)4+25mgPSA) (Agilent, USA); QuEChERS reagent pack 5982-5121(150mg anhydrous MgSO)4+25mgPSA +25mgC18) (Agilent, USA); QuEChERS reagent pack 5982-5221(150mg anhydrous MgSO)4+25mgPSA +2.5mgGCB) (Agilent, USA); QuEChERS reagent pack 5982-5321(150mg anhydrous MgSO)4+25mgPSA +7.5mgGCB) (Agilent, USA); 0.22 μm organic phase filter (Agilent Corp.); 95 kinds of pesticide standard substances and internal standard triphenyl phosphate (AccuStandard company). Wherein GCB is graphitized carbon black and PSA is ethylenediamine-N-propyl silane.
Sample preparation: blueberry (purchased from a certain market in Guizhou).
2. Standard solution preparation
Toluene is used for preparing a mixed standard solution with the concentration of 7.0-40.0 mg/L and a 20mg/L internal standard triphenyl phosphate (TPP) working solution, and the mixed standard solution and the TPP working solution are stored in a refrigerator at the temperature of-18 ℃ for later use.
3. Sample pretreatment
3.1 sample preparation
Taking a representative sample according to a national standard fresh fruit and vegetable sampling method GB/T8855-2008, chopping the representative sample, homogenizing the cut representative sample by a homogenizer, and storing the cut representative sample at a low temperature for later use.
3.2 extraction
Weighing 10g (accurate to 0.01g) of sample, placing in a 50mL centrifuge tube with a cover, adding 10mL acetonitrile and 400 μ L TPP internal standard working solution, and vortexing at 2000rpm for 5 minutes; optionally, add QuEChERS reagent package (part number: 5982-.
3.3 purification
Sucking 1mL of the supernatant into a 2mL centrifuge tube filled with a QuEChERS reagent pack (part number: 5982-5221 or 5982-5321), immediately shaking the sample by hand, carrying out vortex oscillation at 2000rpm for 5min, centrifuging at 10000r/min for 10min, sucking the purified solution to pass through a 0.22 mu m organic phase filter membrane, and then carrying out GC-MS/MS analysis and internal standard method quantification.
4. Conditions of the experiment
4.1 chromatographic conditions: sample introduction volume: 1 mu L of the solution; sample introduction mode: PTV non-shunting sample injection; the Surge pressure: 150kPa (1 min); initial temperature of a sample inlet: the temperature is increased to 280 ℃ rapidly at 10 ℃/s after sample injection at 90 ℃; capillary column: TR-Pesticide II [ (50% phenyl) methylpolysiloxane, 30 m.times.0.25 mm.times.0.25 μm +5 m.times.0.25 μm (pre-column) ]; carrier gas: he with the purity of more than or equal to 99.999 percent; flow rate of carrier gas: 1.2 mL/min; temperature program of chromatographic column: maintaining at 90 deg.C for 5min, heating to 180 deg.C at 25 deg.C/min, maintaining for 15min, heating to 280 deg.C at 5 deg.C/min, and maintaining for 4.5 min; transmission line temperature: 290 deg.c.
4.2 Mass Spectrometry conditions: ion source temperature: 250 ℃; emission current: 50 muA; an ion source: a closed EI source; collision gas pressure: 1.2mTorr (Ar); solvent delay time: 7.0 min; scanning mode: SRM (selective reaction monitoring), adopting an EZ-Method setting Method, wherein the Start time is set as the starting point of the scanning time of the target compound and is the retention time RT-0.75min of the target compound, and the End time is set as the End point of the scanning time of the target compound and is the retention time RT +0.75min of the target compound. The qualitative ion pair, the quantitative ion pair, the collision energy and the retention time of each pesticide are shown in a table 1, and the total ion flow diagram is shown in the table 1.
TABLE 1 Retention time, monitoring ion-pair, Collision energy, Linear Range, Linear correlation coefficient, quantitation Limit for 95 pesticides in Multi-reaction monitoring mode
Example 2QuEChERS-GC-MS/MS method for determining 95 pesticide residues in blueberry-comparison of sample purification conditions
The sample purification method is the key of sample pretreatment, and in order to avoid the interference of a complex matrix on a test result and the pollution to an analysis system, the sample purification requires that the proper recovery rate of a target object is ensured under the condition that the sample is as clean as possible. In the existing effective national standards GB/T19648-2006 and GB/T20769-2008 for detecting pesticide residues in fruits, samples are purified in a column passing mode, the operation steps generally comprise activation, sample loading, leaching, elution and the like, and the defects of complex operation, time and labor consumption and large solvent consumption are overcome. The method adopts a QuEChERS method to purify the extracting solution, and is high-efficient, simple and convenient.
The essence of the QuEChERS method is that the dispersed solid phase extraction material is used for adsorbing impurities in the extracting solution so as to achieve the purpose of sample purification. The commonly used dispersed solid phase extraction materials are C18, GCB, PSA, anhydrous magnesium sulfate and the like. Wherein, the anhydrous magnesium sulfate removes redundant moisture in the supernatant, thereby avoiding the moisture from entering the chromatographic column to damage the instrument; c18 is used for adsorbing lipid substances and some nonpolar interferents in the sample; PSA is used for adsorbing polar matrix components in extractive solution, such as fatty acid, organic acid, phenols, etc.; GCB is used mainly for pigment removal. In practical application, the type and the amount of the dispersed solid phase extraction material are selected according to the characteristics of the matrix and the type of the analyzed target substance, and the purification effect and the recovery rate are used as evaluation criteria. The blueberry sample has very high pigment content, and how to remove pigment and impurity interference is the key of the method.
This example investigated the purification effect of 4 purification conditions on the supernatant, and 4 purification combinations were: 5982-5021: 150mg anhydrous MgSO4+25mg PSA; 5982-5121: 150mg anhydrous MgSO4+25mg PSA +25mg C18; 5982-5221: 150mg anhydrous MgSO4+25mg PSA +2.5mg GCB; 5982-5321: 150mg anhydrous MgSO4+25mg PSA +7.5mg GCB. The comparison of the colors of the 4 purification combinations after the supernatant liquid purification is shown in FIG. 2, wherein the two purification combinations of 5982-; 5982 the color of the sample purified by 5221 is lighter, which indicates that the removal effect of the pigment is general; 5982-.
In this example, GC-MS full scan analysis was also performed on blank samples under 4 purification conditions, 1mL of supernatant was purified, and the sample injection amount, temperature program, mass spectrometry parameters, and other instrumental analysis methods were the same as in example 1.
The experimental result is shown in fig. 2, among the four purification conditions, the sample purified by 5982-; the number of chromatographic peaks of the sample under the purification conditions of 5982-; the chromatographic peak under the purification condition of 5982-; on the whole, the number and the response intensity of chromatographic peaks under the four purification conditions correspond to the color shades of the four chromatographic peaks.
Based on the above results, the present example selects two purification combinations of 5982-.
As shown in Table 2, the recovery rates of the 95 pesticides after purification of 5982-5221 and 5982-5321 are 71.8-112.6% and 75.4-112.0% respectively when the addition concentration is in the range of 14.0-201.5. mu.g/kg, and the recovery rates under both purification conditions meet the requirement of multi-pesticide residue analysis. However, considering that the 5982-. TABLE 25982 recovery of 95 pesticides under the two purification conditions 5221 and 5982 5321
Example 3QuEChERS-GC-MS/MS method for determining 95 pesticide residues in blueberries-linear relation of method and method quantitative limit
The linear range refers to that the concentration of the target substance and a detection signal (peak height, peak area and the like) are in a linear correlation relationship in a certain concentration range, the accuracy and the precision requirements can be met, and the chromatographic analysis generally requires that the correlation coefficient (R2) is greater than 0.99. The method quantitative limit is the lowest concentration of the analysis method for quantitatively determining the target object in the sample, and is an important index for measuring the sensitivity of the analysis method. In the experiment, a blank blueberry sample is selected to prepare a negative matrix solution according to the steps of '3 and sample pretreatment' in example 1, an internal standard is not added during operation, a proper amount of negative matrix solution, a mixed pesticide standard solution and an internal standard working solution are used to prepare 7 concentration points containing the equivalent internal standard with the concentration of 3-766 [ mu ] g/L, the peak area ratio of a target object to the internal standard is used as a longitudinal coordinate, the concentration of the target object is used as a horizontal coordinate, and a linear range and a linear correlation coefficient are obtained by plotting; the limit of quantitation (LOQ) is determined as the concentration of the target at a signal-to-noise ratio S/N.gtoreq.10.
The results show that the peak area ratios of the target substances and the internal standard and the mass concentration thereof are in good linear relation in the corresponding mass concentration range, the correlation coefficient is between 0.9945 and 1.0000, the quantitative limit LOQ of the method is between 1.6 mu g/kg and 20.5 mu g/kg, the quantitative limit of 59 pesticides is below 10 mu g/kg, and the linear range, the linear correlation coefficient and the LOQ of each pesticide are shown in Table 1.
Example 4QuEChERS-GC-MS/MS method for determining 95 pesticide residues in blueberries
Accuracy refers to the proximity of a measured value to a true value, and is used to indicate the accuracy of the analysis result, usually expressed as the recovery of spiked values. Precision is the proximity between measurements made on the same sample when the same sample is tested in duplicate by a particular method, and is indicative of the reproducibility of the assay, usually expressed in terms of standard deviation and relative standard deviation. In the experiment, a blank blueberry sample is selected, pesticides with high, medium and low levels are respectively added within the adding concentration range of 14.0-403.0 mug/kg, each adding concentration is repeatedly measured for 6 times, and the recovery rate and Relative Standard Deviation (RSD) of each pesticide are calculated, and the result is shown in Table 3. The experimental results show that: when the adding concentration is in a first level of 14.0-80.6 mug/kg, the recovery rate is 70.2-119.8%, and the RSD is 0.9-11.6%; when the adding concentration is at a second level ranging from 35.0 mug/kg to 201.5 mug/kg, the recovery rate is between 75.7% and 110.2%, and the RSD is between 1.3% and 14.3%; when the concentration is added at a third level ranging from 70.0 mug/kg to 403.0 mug/kg, the recovery rate is between 70.4% and 115.8%, and the RSD is between 0.8% and 11.6%. The accuracy and precision can meet the analysis requirement of multiple pesticide residues.
TABLE 35982 & 5321 purification conditions recovery and precision of 95 pesticides
Example 5QuEChERS-GC-MS/MS method for determining 95 pesticide residues in blueberry wine
The blueberry wine is a fruit wine, and is prepared by refining blueberries serving as raw materials by adopting a special process. Pesticide residues can be caused by environmental pollution or illegal use of blueberries in the planting process, and the risk can be introduced into the wine body in a migration mode and the like, so that the establishment of a method for detecting the multiple pesticide residues in the blueberry wine is very necessary. At present, few reports are available on relevant literatures for detecting pesticide residues in blueberry wine. In the existing effective residual national recommended standard GB/T23206 for pesticides and related chemicals in fruit and vegetable juice and fruit wine, the detection technology adopts the steps of firstly extracting a sample by using acidified acetonitrile, and then purifying the sample by passing through a purification column, and the method has the defects of large solvent consumption and complex operation.
In the embodiment, a liquid-liquid extraction technology is used for extracting samples, a QuEChERS technology is used for purifying the samples, a GC-MS/MS detection technology is used for detecting the samples, and a detection method for simultaneously determining 95 pesticide residues in blueberry wine by a QuEChERS-GC-MS/MS method is established. The method has the characteristics of simplicity and convenience in operation, solvent saving, rapidness and the like, and is suitable for production enterprises to carry out rapid qualitative and quantitative screening on the blueberry wine for multiple pesticide residues.
1. Instruments and reagents
Thermo Scientific Trace GC Ultra-TSQ Quantum XLS gas chromatograph-triple quadrupole tandem mass spectrometer (ThermoFisher Scientific, USA); Talboys/Standard Multi-Tube vortex shaker (Talboys, USA); HITACHI CR22G III high speed centrifuge (Hitachi, Japan).
Acetonitrile, toluene (chromatographically pure, TEDIA reagents, usa); QuEChERS reagent pack 5982-5021(150mg anhydrous MgSO)4+25mg PSA) (Agilent Inc., USA), QuEChERS reagent pack 5982-5221(150mg anhydrous MgSO)4+25mg PSA +2.5mg GCB) (Agilent, USA), QuEChERS reagent pack 5982-5321(150mg anhydrous MgSO)4+25mgPSA +7.5mgGCB) (Agilent, USA); 0.22 μm organic phase filter (Agilent Corp.); 95 kinds of pesticide standard substances (AccuStandard company).
Sample preparation: blueberry wine (purchased from a certain market in Guizhou).
2. Standard solution preparation
Preparing a mixed standard solution with the concentration of 7.0-40.0 mg/L by using toluene, and storing the mixed standard solution in a refrigerator at the temperature of-18 ℃ for later use.
3. Sample pretreatment
3.1 extraction
Taking 5mL of sample, placing the sample in a 50mL centrifuge tube with a cover, adding sodium chloride for saturation, adding 5mL of acetonitrile, carrying out vortex oscillation at 2000rpm for 5 minutes, standing, taking supernatant after the mixture is layered, and purifying.
3.2 purification
Sucking 1mL of the supernatant into a 2mL centrifuge tube filled with a QuEChERS reagent pack (part number: 5982-5021, 5982-5221 or 5982-5321), immediately shaking by hand, vortexing at 2000rpm for 5min, centrifuging at 10000r/min for 10min, sucking the supernatant through a 0.22 mu m organic phase filter membrane, performing GC-MS/MS analysis, and quantifying by an external standard method (establishing a standard curve: preparing a mixed standard solution with toluene at a concentration of 7.0-40.0 mg/L, and storing in a refrigerator at-18 ℃ for later use).
4. Conditions of the experiment
4.1 chromatographic conditions: sample introduction volume: 1 mu L of the solution; sample introduction mode: PTV non-shunting sample injection; the Surge pressure: 150kPa (1 min); initial temperature of a sample inlet: the temperature is increased to 280 ℃ rapidly at 10 ℃/s after sample injection at 90 ℃; capillary column: TR-Pesticide II [ (50% phenyl) methylpolysiloxane, 30 m.times.0.25 mm.times.0.25 μm +5 m.times.0.25 μm (pre-column) ]; carrier gas: he with the purity of more than or equal to 99.999 percent; flow rate of carrier gas: 1.2 mL/min; temperature program of chromatographic column: maintaining at 90 deg.C for 5min, heating to 180 deg.C at 25 deg.C/min, maintaining for 15min, heating to 280 deg.C at 5 deg.C/min, and maintaining for 4.5 min; transmission line temperature: 290 deg.c.
4.2 Mass Spectrometry conditions: ion source temperature: 250 ℃; emission current: 50 muA; an ion source: a closed EI source; collision gas pressure: 1.2mTorr (Ar); solvent delay time: 7.0 min; scanning mode: SRM, adopting an EZ-Method setting Method, wherein the Start time is set as the starting point of the scanning time of the target compound and is the retention time RT-0.75min of the target compound, and the End time is set as the End point of the scanning time of the target compound and is the retention time RT +0.75min of the target compound. The qualitative ion pair, quantitative ion pair, collision energy and retention time of each pesticide are shown in table 4, and the total ion flow diagram is shown in fig. 4.
TABLE 495 retention time of pesticides, monitor ion pair, collision energy, linear range, linear correlation coefficient and quantitative limit
Example 6QuEChERS-GC-MS/MS method for determining 95 pesticide residues in blueberry wine-comparison of sample purification conditions
In the current effective national recommended standard GB/T23206 for pesticide and related chemical residue in fruit and vegetable juice and fruit wine, a sample is purified by passing through a purification column, and the method is not friendly to experimenters and environment due to large solvent consumption, and is complex to operate, time-consuming and labor-consuming. In the research, a QuEChERS technology is adopted to purify the sample, and the principle of the QuEChERS technology is that the adsorption material and the extracting solution are fully mixed and interacted to adsorb impurities so as to achieve the purpose of purifying the sample. The blueberry wine contains more pigments, sugar and the like, the substances are difficult to gasify and easily pollute an instrument sample inlet system, and other volatile impurities in a matrix easily pollute an ion source to reduce the sensitivity of the instrument, so that the effective purification of a sample is very important. Common purification materials are PSA, C18, GCB, and the like. PSA is used for adsorbing polar matrix components in extractive solution, such as fatty acid, organic acid, phenols and small amount of pigment; c18 is used to remove some non-polar interferents from the sample; the GCB has a sheet structure, can better adsorb molecules with a plane structure, and has a very obvious adsorption effect on pigments in a sample. In addition, since the supernatant liquid contains a small amount of water, a small amount of anhydrous magnesium sulfate is added in the purification step to remove excess water and thus protect the apparatus.
The experiment compares the capacity of removing pigment in the blueberry wine extracting solution under three purification conditions. The three purification combinations are respectively: QuEChERS reagent pack 5982-5021(150mg anhydrous MgSO)4+25mg PSA); QuEChERS reagent pack 5982-5221(150mg anhydrous MgSO)4+25mg PSA +2.5mg GCB); QuEChERS reagent pack 5982-5321(150mg anhydrous MgSO)4+25mg PSA +7.5mg GCB). As a result, as shown in FIG. 5, the supernatants were colorless and transparent under all of the three purification conditions, and the pigments in the samples were removed well.
On the basis of the experiment, the recovery rate of 95 pesticides under three purification conditions is investigated. Blank blueberry wine samples are selected in the experiment, and 95 pesticide standards are added into the blank blueberry wine samples, so that the concentration range of the blank blueberry wine samples is 7.0 mu g/L-201.5 mu g/L. As shown in Table 5, the recovery rates of 95 pesticides remained under the purification conditions of 5982-5021 were 72.2-121.1%, the recovery rates under the purification conditions of 5982-5221 were 65.9-124.3%, and the recovery rates under the purification conditions of 5982-5321 were 67.7-125.1%. The recovery rate under the three purification conditions meets the analysis requirement of the residue of various trace pesticides.
Recovery of 595 pesticide residues under three decontamination conditions
Based on the above results, in order to select an optimal purification mode, in this embodiment, GC-MS full scan is performed on blank samples under 3 purification conditions, the chromatogram is as shown in fig. 6, the chromatogram peaks of the samples purified by 5982-; the chromatographic peak under the purification condition of 5982-; 5982, the number of chromatogram peaks under the purification condition of 5321 is the least, and the response intensity is the lowest, which shows that properly increasing the usage amount of GCB is beneficial to improving the purification effect, and the purification effect is the best of the three.
By combining the results, the pigment removal effect and the standard recovery rate under the 3 purification conditions both meet the requirement of multi-pesticide residue analysis, and can be used for purifying samples for multi-pesticide residue analysis in blueberry wine, but the samples are relatively dirty under the purification conditions of 5982-. Comprehensively considering the pigment removal effect, the standard addition recovery rate and the instrument maintenance frequency, the method selects 5982-5321 as the purification condition for the pretreatment of the blueberry wine.
Example 7QuEChERS-GC-MS/MS method for determining 95 pesticide residues in blueberry wine-Linear relationship of method and method quantitative limit
In the experiment, a blank blueberry wine sample is selected to prepare a matrix blank solution according to the steps of '3 and sample pretreatment' in example 5, a proper amount of the matrix blank solution and a mixed pesticide standard substance are used for preparing a standard curve with 7 concentration gradients, the peak area of a target object is taken as the ordinate, the concentration of the target object is taken as the abscissa, and a linear range and a linear correlation coefficient are obtained by plotting; the limit of quantitation (LOQ) is determined as the concentration of the target at which the S/N ratio is 10 or more. The results show that the peak area of each target substance and the mass concentration thereof have good linear relation in the mass concentration range of 4 mu g/L-766.0 mu g/L, the correlation coefficient is 0.9906-1.0000, the quantitative limit LOQ of the method is 1.5 mu g/L-43.7 mu g/L, and the linear range, the linear correlation coefficient and the LOQ of each pesticide are shown in Table 4.
Example 8QuEChERS-GC-MS/MS method for determining 95 pesticide residues in blueberry wine-method accuracy and precision
95 pesticide standards with two concentration levels of high and low are respectively added into a blank blueberry wine sample, the adding concentration is 7.0-201.5 mu g/L, three levels are made in parallel, the steps of 3 and sample pretreatment in the embodiment 5 are carried out, then the mixture is analyzed by an instrument, each level is repeatedly measured for 6 times, and the recovery rate and the precision of the method are calculated.
As shown in Table 6, the recovery rate was between 66.7% and 123.2% and the relative standard deviation was between 1.2% and 19.2% when the 95 pesticides were added at a first concentration level of 7.0. mu.g/L to 63.0. mu.g/L; when the addition concentration of the 95 pesticides is at a second concentration level of 35.0-201.5 mug/L, the recovery rate is 64.6-123.5%, and the relative standard deviation is 0.6-18.1%. The accuracy and precision can meet the analysis requirement of multiple pesticide residues.
Recovery and relative standard deviation of 695 pesticide residues at two addition levels under the conditions of 5982-
Claims (10)
1. The method for simultaneously and rapidly detecting the residual quantity of various pesticides is characterized by comprising the step of purifying a sample by using a dispersed solid-phase extraction material, wherein the dispersed solid-phase extraction material comprises a mixture of anhydrous magnesium sulfate, ethylenediamine-N-propyl silane and graphitized carbon black.
2. The method according to claim 1, wherein the weight ratio of the anhydrous magnesium sulfate, the ethylenediamine-N-propyl silane and the graphitized carbon black in the mixture is (40-80): (5-15): (1-3);
preferably, the weight part ratio of the anhydrous magnesium sulfate, the ethylenediamine-N-propyl silane and the graphitized carbon black in the mixture is 60:10 (1-3); more preferably 60:10: 3;
preferably, the dispersed solid phase extraction material is selected from the group consisting of the QuEChERS reagent kit 5982-5221 or 5982-5321.
3. The detection method according to claim 1, comprising the steps of:
s1, extraction: adding acetonitrile into a sample, performing vortex oscillation, and taking a supernatant;
s2, purification: adding the supernatant prepared in the step S1 into a dispersed solid phase extraction material, performing vortex oscillation, centrifuging, and filtering the supernatant with a filter membrane;
s3, GC-MS/MS measurement: the liquid filtered in step S2 was subjected to GC-MS/MS analysis.
4. The detecting method according to claim 3, wherein in the step S1, the rotational speed of vortex oscillation is 1500-3000rpm, and the time of vortex oscillation is 2-10 minutes;
preferably, the rotation speed of the vortex oscillation is 2000rpm, and the time of the vortex oscillation is 5 minutes;
preferably, after the vortex oscillation, adding a QuEChERS reagent package to perform secondary vortex oscillation;
preferably, the supernatant is centrifuged after the second vortexing.
5. The detecting method according to claim 3, wherein in the step S2, the ratio of the supernatant to the dispersed solid phase extracting material is 150-300mg of the dispersed solid phase extracting material per ml of the supernatant;
preferably, the weight part ratio of the anhydrous magnesium sulfate, the ethylenediamine-N-propyl silane and the graphitized carbon black in the mixture is (40-80): (5-15): (1-3);
preferably, the weight part ratio of the anhydrous magnesium sulfate, the ethylenediamine-N-propyl silane and the graphitized carbon black in the mixture is 60:10 (1-3); more preferably 60:10: 3;
preferably, the dispersed solid phase extraction material is selected from the group consisting of the QuEChERS reagent kit 5982-5221 or 5982-5321.
6. The detecting method according to claim 3, wherein in the step S2, the rotational speed of vortex oscillation is 1500-3000rpm, and the time of vortex oscillation is 2-10 minutes;
preferably, the rotation speed of vortex oscillation is 2000rpm, and the time of vortex oscillation is 5 minutes;
preferably, the rotating speed of the centrifugation is 8000-12000r/min, and the centrifugation time is 5-20 minutes;
preferably, the rotating speed of the centrifugation is 10000r/min, and the centrifugation time is 10 minutes;
preferably, the filtration is performed with an organic phase filtration membrane;
preferably, the organic phase filter is a 0.22 μm organic phase filter.
7. The detecting method according to claim 3, wherein in the step S3, the temperature raising procedure of the chromatographic column is that the temperature is raised to 88-92 ℃ for 4-6min, then raised to 175-185 ℃ at 20-30 ℃/min for 14-16min, then raised to 270-290 ℃ at 4-6 ℃/min for 3-5 min;
preferably, the temperature raising program of the chromatographic column is to maintain at 90 ℃ for 5min, then raise the temperature to 180 ℃ at 25 ℃/min, maintain for 15min, then raise the temperature to 280 ℃ at 5 ℃/min, maintain for 4.5 min;
preferably, the scan pattern of the mass spectrum is: and (6) SRM.
8. The test method according to any one of claims 1 to 7, wherein the sample to be tested comprises at least one of fruit and fruit wine;
preferably, the fruit is selected from at least one of blueberry, grape, apple, peach, and green plum;
preferably, the fruit wine is selected from at least one of blueberry wine, cider wine, peach wine, and green plum wine.
9. The assay of claim 8, further comprising step S0, homogenizing: homogenizing the sample to prepare a sample solution.
10. The detection method according to any one of claims 1 to 7, wherein the pesticide is at least one selected from the group consisting of organochlorine, organophosphorus, organonitrogen, pyrethroid, triazole and heterocyclic pesticides;
preferably, the organochlorine pesticide is selected from at least one of o, p ' -DDD, o, p ' -DDE, o, p ' -DDT, p ' -DDD, p ' -DDE, p-DDT, alpha-endosulfan, alpha-hexachloroethane, beta-endosulfan, beta-hexachloroethane, gamma-hexachloroethane, delta-hexachloroethane, aldrin, chlorothalonil, dieldrin, chlorthal, endosulfan-trans, chlordane-cis, mirex, heptachlor, dicofol, and endrin;
preferably, the organophosphorus pesticide is selected from at least one of fenthion, thiophenophos, prothioconazole, fenamiphos, chlorfenphos, parathion, diazinon, vozaphos, oryphos, phorate, chlorpyrifos-methyl, pirimiphos-methyl, captan, quinalphos, chlorzofos, malathion, fenamiphos, pyrathion, triazophos, fenitrothion, methidathion, metocloprid, terbufos, bromophos, disulfoton, ethion sulfoxide, ethion, and iprobenfos;
preferably, the organic nitrogen pesticide is selected from at least one of benalaxyl, propoxur, alachlor, oxadixyl, pendimethalin, trifluralin, alachlor, metalaxyl, pirimicarb, methiocarb, triadimefon, chlordimeform, dibenzamide, penconazole, metolachlor and isoproylin;
preferably, the pyrethroid pesticide is at least one selected from cyfluthrin, lambda-cyhalothrin, bifenthrin, permethrin, cypermethrin, tefluthrin, fenvalerate and deltamethrin;
preferably, the triazole pesticide is selected from at least one of difenoconazole, myclobutanil and uniconazole;
preferably, the heterocyclic pesticide is selected from at least one of isoprothiolane, and clomazone;
preferably, the pesticide is selected from disulfotoxin, metoclopramide, captafol, propoxur, fenamiphos, trifluralin, flumetsulam, chlorfenapyr, captan, phorate, alpha-hexaxagon, niclosamide, clomazone, gamma-hexaxagon, beta-hexaxagon, terbufos, diazinon, disulfoton, chlorothalonil, clozapyr, tefluthrin, delta-hexaxagon, pirimicarb, iprobenfos, chlorpyrifos-methyl, alachlorethan, heptachlor, metalaxyl, pyraclofos-methyl, pirfenitrofos-methyl, methiocarb, malathion, metolachlor, aldrin, chlorpyrifos, fenthion, dichlorvos, parathion, triadimefon, butralin, bromophos, metamifop-propathyrifos, pendimethalin, penconazole, fenvinphos, chlordane-trans, methidathion, o, p' -thion, DDE, alpha-DDS, beta-hexathion, beta-hexaflumetsulam, benazolin, bensulam, benazolin, bensulam, benazolin, bensulam, benazolin, bensulam, benazolin, bensulam, benazolin, bensulam, At least one of chlordane-cis, disulfotone, flumetralin, alachlor, prothioconazole, isoprothiolane, dieldrin, p ' -DDE, uniconazole, o, p ' -DDD, myclobutanil, endrin, aclonifen, beta-endosulfan, dicofol, oxadixyl, o, p ' -DDT, p ' -DDD, ethion, triazophos, benalaxyl, cumyl ether, endosulfan, p ' -DDT, diethofezin, phenthophos, bifenthrin, trichlorfon, vomethidathion, cyhalothrin, diclofluvalinate, orythion, ethylvalbuthion, deltamethrin, azoxystrobin, famoxadone, permethrin, cyfluthrin, cypermethrin, fenvalerate, difenoconazole, and dimethomorphine;
preferably, the pesticide is selected from the group consisting of dichlorvos, metocloprid, heptenophos, propoxur, methyl systemic phos, fenamiphos, chlorfenamidine, trifluralin, flumetsulam, captan, phorate, alpha-hexaxagon, clonidine, isoxathone, beta-hexaxagon, gamma-hexahexaxagon, terbufos, diazinon, chlorothalonil, disulfoton, isazofos, delta-hexahexaxagon, tefluthrin, pirimicarb, iprobenfos, chlorpyrifos-methyl, parathion-methyl, alachlor, carbaryl, benzothiadiazole, metalaxyl, pirimiphos-methyl, methidathion, triafol, bromucon, dichlorphenamide, isoprothiolane, pendimethalin, clofenamate, clofenaminostrobin, butachlor, quinacr, quinacrine, quinclorac, At least one of folpet, chlordane-trans, methidathion, o, p '-DDE, alpha-endosulfan, disulfprofulfone, chlordane-cis, napropamide, profenofos, isoprothiolane, dieldrin, uniconazole, p' -DDE, o, p '-DDD, endrin, aclonidin, beta-endosulfan, dicofol, oxadixyl, o, p' -DDT, p '-DDD, ethion, triazophos, cumyl ether, benalaxyl, endosulfan, p' -DDT, thiophosphoryl, chlorantraniliprole, bifenthrin, methoxyDDT, trichlorfone, phosate, mirex, lambda-cyhalothrin, captafos, quizalofop, deltamethrin, famoxadone, triadimenol, permethrin, cyhalothrin, cypermethrin, and flucythrinate;
preferably, the pesticide is selected from benzothiadiazole, alachlor, aldrin, alpha-endosulfan, oryzanol, azoxystrobin, benalaxyl, flufenacet, beta-endosulfan, bifenthrin, bromacil, fenthion, butralin, captan, captafol, captan, carbaryl, chlorantraniliprole, chlordane-cis, chlordane-trans, chlordimeform, chlorfenvinphos, cumquat, chlorothalonil, chlorpyrifos-methyl, dichlorvos, dicofol, clomazone, cyfluthrin, cypermethrin, deltamethrin, thiophosphoryl, methyl endosulfan, diazinon, dichlorvos, nicamide, dieldrin, difenoconazole, dimethomorphine, disulfoton, endosulfan, isoldrin, thion, ethion, fenamidone, famoxadone, carvone, disulfoton, ben, benazol, ben, benazolin, benfurazon, benazolin, benazol, benfurazol, benazol, benfurazolin, benazolin, benazol, benazolin, benazol, benfurazol, benfurazolin, benazol, benfurazol, benazol, benazolin, benfurazol, benazol, benfurazol, benazol, benfurazolin, benfurazol, benazol, benfurazolin, benazolin, benfurazol, benazolin, benfurazolin, benazolin, benazol, benazolin, benazol, benazolin, benfurazol, benfurazolin, benazolin, benazol, benfurazolin, benazolin, benfurazolin, benfur, Pyralid, fenitrothion, fenthion, fenvalerate, cyfluthrin, flumetralin, folpet, heptachlor, epoxy heptachlor-trans, heptenophos, iprobenfos, clofenphos, isoproturon, isoprothiolane, lambda-cyhalothrin, malathion, metalaxyl, methidathion, methiocarb, methoxyDDT, metolachlor, metoclopramide, mirex, imazapyr, myclobutanil, fenacet, aclonifen, o, p '-DDD, o, p' -DDE, o, p '-DDT, oxadixyl, p' -DDD, p '-DDE, p' -DDT, parathion, methyl parathion, pendimethalin, penconazole, permethrin, phorate, profenofos, pirimicarb, pirimiphos, prothioconazole, quinalphos, fluthrin, tebuthion, tebufenofos, tebuconazole, clofos, cyhalofos, propaphos, clofos, cyhalofos, clofos, cyhalofos, At least one of triadimefon, triadimenol, triazophos, trifluralin, uniconazole, alpha-hexahexa, beta-hexa, gamma-hexa, and delta-hexa.
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