CN112924599A - Method for extracting and detecting bromofenoxanil residue in rice field environment - Google Patents
Method for extracting and detecting bromofenoxanil residue in rice field environment Download PDFInfo
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- 240000007594 Oryza sativa Species 0.000 title 1
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 11
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- AMWBKZHMFJEZRP-UHFFFAOYSA-N 3-fluorobenzene-1,2-dicarboxamide Chemical compound NC(=O)C1=CC=CC(F)=C1C(N)=O AMWBKZHMFJEZRP-UHFFFAOYSA-N 0.000 description 8
- 239000005901 Flubendiamide Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- ZGNITFSDLCMLGI-UHFFFAOYSA-N flubendiamide Chemical compound CC1=CC(C(F)(C(F)(F)F)C(F)(F)F)=CC=C1NC(=O)C1=CC=CC(I)=C1C(=O)NC(C)(C)CS(C)(=O)=O ZGNITFSDLCMLGI-UHFFFAOYSA-N 0.000 description 8
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- Physics & Mathematics (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
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Abstract
本发明公开了一种稻田环境中溴虫氟苯双酰胺残留的提取与检测方法，包括以下步骤：样品的采集与提取：分别采集稻田环境中的样品，再与提取剂混合，经涡旋提取得到样品的提取液，然后将所述提取液经除水、第一次离心后，取第一上清液，并与净化剂混合进行净化，再进行第二次离心并收集第二上清液，过滤后得到待测溶液；标准溶液的配制；利用超高效液相色谱法‑高分辨飞行时间质谱法(UHPLC‑ESI‑QTOF‑MS)检测。本方法可以高效的提取出稻田环境(稻田水、稻田土、稻株、稻谷、稻壳)中溴虫氟苯双酰胺的残留，并灵敏、精确的检测其残留量，以利于控制污染并确保食品和环境安全。
The invention discloses a method for extracting and detecting bromfenac residues in a paddy field environment, comprising the following steps: sample collection and extraction: respectively collecting samples in the paddy field environment, mixing with an extractant, and vortex extraction The extract of the sample is obtained, and then the extract is dewatered and centrifuged for the first time, and the first supernatant is taken, mixed with a purifying agent for purification, and then centrifuged for the second time to collect the second supernatant , filtered to obtain the solution to be tested; preparation of the standard solution; detection by ultra-high performance liquid chromatography-high-resolution time-of-flight mass spectrometry (UHPLC-ESI-QTOF-MS). The method can efficiently extract the residues of bromflubenzamide in the paddy field environment (paddy water, paddy soil, rice plants, rice, rice husks), and detect the residues sensitively and accurately, so as to control pollution and ensure Food and Environmental Safety.
Description
Technical Field
The invention relates to the technical field of pesticide residue determination, in particular to a method for extracting and detecting bromofenoxanil residue in a rice field environment.
Background
The bromofenoxanil fluorobenzene bisamide is a diamide compound (shown in table 1), is a novel pesticide jointly developed by basf and Mitsui chemical companies, has a novel action mechanism, has no cross resistance with the existing pesticide, and has a wide application prospect. The flubendiamide can be used for preventing and controlling pests on crops such as rice, vegetables, soybeans, burmese flower and the like, and can effectively prevent and control pests generating resistance to other insecticides.
TABLE 1 physicochemical Properties of Bromocha-fluorobenzene bisamide
At present, the ultrahigh performance liquid chromatography analysis method of the brotrochan difluoride in five kinds of soil is researched by the Chinese agriculture university, the high performance liquid chromatography analysis method of the 5% brotrochan difluoride suspending agent is researched by the Jiangxi agriculture university, and the detection analysis method of the brotrochan difluoride residue in the rice field environment by using the ultrahigh performance liquid chromatography-high resolution flight time mass spectrometry is not researched by people.
Therefore, it is an urgent need to solve the problems of the art to provide a method for detecting and extracting the residual bromofenoxanil in the rice field environment by using ultra-high performance liquid chromatography-high resolution time-of-flight mass spectrometry.
Disclosure of Invention
In view of the above, the invention provides a method for extracting and detecting the residual bromofenoxanil in a rice field environment, and provides a method for extracting the residual bromofenoxanil in the rice field environment (rice field water, rice field soil, rice plants, rice grains and rice hulls) and a detection method by using ultra-high performance liquid chromatography-high resolution time-of-flight mass spectrometry. The method can efficiently extract the residues of the bromofenoxanil in the rice field environment (rice field water, rice field soil, rice plants, rice husks and rice husks), and sensitively and accurately detect the residues, so as to be beneficial to controlling pollution and ensuring the safety of food and environment.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for extracting and detecting the residue of the brotrochan difluoride in a rice field environment comprises the following steps:
s1, collecting and extracting a sample:
collecting a sample, mixing with an extractant, extracting to obtain an extracting solution, dewatering the extracting solution, centrifuging for the first time, collecting a first supernatant, mixing with a purifying agent, purifying, centrifuging for the second time, collecting a second supernatant, and filtering to obtain a solution to be detected;
s2, preparation of a standard working solution:
the concentration of the prepared bromofenoxanil is 1000 mg.L-1The mother solution is diluted by acetonitrile to obtain standard working solution of the bromofenoxanil fluorobenzenediamide with different concentration gradients;
s3, determining the content of the brofenthiuron bisamide:
32) drawing a standard working curve:
determining standard working solutions of the bromofenoxanil fluorobenzene bisamide with different concentration gradients by using ultra-high performance liquid chromatography-high resolution flight time mass spectrometry, and performing regression analysis to obtain a standard working curve;
32) determining the content of the brofenpyrad:
and (3) determining the solution to be detected by using the ultra-high performance liquid chromatography-high resolution flight time mass spectrometry under the same condition, obtaining the content of the brotroche bisamide in the solution to be detected according to the standard working curve, and obtaining the content of the brotroche bisamide in the sample through conversion.
Preferably, in step S1, the sample includes paddy water, paddy soil, rice plants, rice and rice hulls;
wherein the paddy field soil, rice plant, paddy and rice hull are added with ultrapure water before the extractant is added. More specifically, 5mL of ultrapure water was added to 5g of paddy soil sample, 7mL of ultrapure water was added to 5g of paddy soil sample, and 10mL of ultrapure water was added to 5g of paddy soil sample and 5g of rice plant sample, respectively
The technical effect of adopting the technical scheme is as follows: after the sample is added with water and vortexed, a uniform-texture system can be formed, and the uniform-texture system can be in more sufficient contact with a subsequently added organic phase, so that the extraction efficiency is improved.
Preferably, in step S1, the extracting agent is acetonitrile or acetonitrile containing 0.1% formic acid by volume concentration, the extraction temperature is 15-35 ℃, and the extraction time is 5-10 min;
the water removal is realized by adding MgSO (MgSO) into the extracting solution4And NaCl, the water removal time is 2-5min, the MgSO4And the dosage ratio of NaCl to the extracting solution is as follows: (2-5) g: (2-5) g: (5-10) mL;
the temperature of the first centrifugation is 2-5 ℃, the rotating speed is 11000-15000rpm, and the time is 5-10 min.
Preferably, in step S1, the scavenger is MgSO4And adsorbent, said MgSO4The dosage ratio of the first supernatant to the first supernatant is (150- & ltSP & gt 200-): (1.5-2) mL, and the purification time is 1-5 min;
the temperature of the second centrifugation is 2-5 ℃, the rotating speed is 5000-.
Preferably, the adsorbent is PSA and the amount ratio to the first supernatant is: (50-100) mg: (1.5-2) mL, and is used for the purification treatment of paddy field water.
Preferably, the adsorbent is C18, and the amount ratio of the adsorbent to the first supernatant is: (50-100) mg: (1.5-2) mL, and is used for purifying paddy field soil and paddy.
Preferably, the adsorbent is a mixture of GCB and C18, and the ratio of GCB, C18 and the first supernatant is: (10-50) mg: (50-100) mg: (1.5-2) mL, and is used for purifying rice plants and rice hulls.
The technical effect of the technical method is as follows: PSA is a weak anion exchanger that extracts organic acids and carbohydrates from samples, C18 is a non-polar material used to remove non-polar and moderately polar compounds from polar samples, and GCB is an effective adsorbent used to remove pigments including chlorophyll and carotenoids.
Preferably, the filtration is performed using a 0.22 μm organic filter membrane.
Preferably, in step S2, the different gradient concentrations include 0.05mg/L, 0.5mg/L, 1mg/L, 2mg/L, 5mg/L, 10mg/L, 20mg/L and 50 mg/L.
Preferably, the chromatographic column used by the ultra-high performance liquid chromatography is an Agilent Eclipse XDB-C18 chromatographic column.
Preferably, the chromatographic conditions of the ultra-high performance liquid chromatography are as follows: the mobile phase consists of 0.1 percent formic acid water solution and acetonitrile, and the volume ratio is 25: 75; adopting isocratic elution mode, and eluting for 6 min; flow rate: 0.3 mL/min; column temperature: 40 ℃; sample introduction amount: 10 μ L.
The technical effect of the technical method is as follows: experiments prove that under the chromatographic conditions provided by the method, the impurity peak and the target peak can be completely separated, and the target peak has a beautiful shape.
Preferably, the conditions for high resolution time-of-flight mass spectrometry are as follows: the temperature of the heated electrospray ion source (HESI) was 200 ℃; the spraying voltage is 5500V; the temperature of the ion transmission tube is 550 ℃; an ion source gas 2; the ion source gas and the curtain gas are respectively 30psi, 145 psi and 30 psi; the positive ion collection adopts an HR MRM scanning mode; the collection range is 100-1400 Da; the first and second mass resolutions exceed 26000 and 25000FWHM, respectively; the collision Cell Energy (CE) was 35. + -.15 eV.
The technical effect of the technical method is as follows: experiments prove that under the mass spectrum condition provided by the method, the impurity peak and the target peak can be completely separated, and the target peak has a beautiful shape.
According to the technical scheme, compared with the prior art, the method for extracting and detecting the residues of the bromoantraniliprole in the rice field environment disclosed by the invention has the following beneficial effects:
(1) the invention provides a method for extracting bromofenoxanil residue in a rice field environment (rice field water, rice field soil, rice plants, rice and rice husks) and a detection method by using ultra-high performance liquid chromatography-high resolution flight time mass spectrometry. The method can efficiently extract the residues of the bromofenoxanil in the rice field environment (rice field water, rice field soil, rice plants, rice husks and rice husks), and sensitively and accurately detect the residues, so as to be beneficial to controlling pollution and ensuring the safety of food and environment.
(2) The invention provides the method for detecting the residual quantity of the flubendiamide in the paddy field environment (paddy field water, paddy field soil, rice plants, paddy rice and rice hulls), wherein the average recovery rate of the residual quantity of the flubendiamide is 85.82-97.46%, the average Relative Standard Deviation (RSD) is 3.29-8.15%, and the detection limit is 0.16-1.67 mu g/kg.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a graph showing a standard curve of bromobenzophenone bisamide in the example of the present invention.
FIG. 2 is a drawing showing a bromofenoxanil standard sample (5mg kg)-1) The liquid chromatogram of (1).
FIG. 3 is a drawing showing a standard sample (0.5 mg/kg) of bromofenoxanil added in the embodiment of the present invention-1) The liquid chromatogram of the rice field water sample.
FIG. 4 is a drawing showing a standard sample (1 mg. kg) of bromofenoxanil added in the embodiment of the invention-1) The liquid chromatogram of the paddy field soil sample.
FIG. 5 is a drawing showing a standard sample (1 mg. kg) of bromofenoxanil added in the embodiment of the present invention-1) The liquid chromatogram of the rice plant sample.
FIG. 6 is a drawing showing a standard sample (1 mg. kg) of bromofenoxanil added in the embodiment of the present invention-1) The liquid chromatogram of the rice hull sample.
FIG. 7 is a drawing showing a bromofenoxanil standard sample (1mg kg) added in the embodiment of the invention-1) The liquid chromatogram of the rice sample.
FIG. 8 is a graph showing the results of recovery of bromofenoxanil from paddy water with different solvents in the example of the present invention.
FIG. 9 is a graph showing the results of recovery of p-bromofenoxanil from different samples with different pH solvents in the examples of the present invention.
FIG. 10 is a graph showing the results of recovery of p-bromoxynil bisamide from different samples with different adsorbents in accordance with the present invention.
FIG. 11 is a graph showing the results of different adsorbent dosages on the recovery rate of the brotrochar benserdiamide from the rice straw and the rice husk in the example of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The test materials used in the examples include: a standard product of the brotrochan difluoride (the purity is more than or equal to 98.6 percent) and a 5 percent brotrochan difluoride suspending agent (Nippon Mitsui chemical Co., Ltd.); formic acid (more than or equal to 88%) (chromatographic purity); methanol (chromatographically pure); acetonitrile (chromatographically pure); sodium chloride (NaCl); anhydrous magnesium sulfate (MgSO)4) (ii) a GCB (i.e. graphitized carbon black adsorbent) (60 μm); PSA (i.e. ethylenediamine-N-propylsilane) (40 μm); c18(40 μm); ultrapure water; 0.22 μm organic membrane (Skyo Kagaku K.K.).
The instrument used in the examples included: ultra high performance liquid chromatography-high resolution time-of-flight mass spectrometer (model: SCIEX X500R, AB SCIEX corporation, usa), column: agilent Eclipse XDB-C18 column (2.1mm X100 mm X1.8 μm, Agilent USA), high-speed refrigerated centrifuge (model: 5810R, Eppendorf, Germany), vortex mixer (model: XH-D, Dalo apparatus Co., Ltd.), ten thousandth analytical balance (model: Mettler Toledo AL204, Shenzhen deep Borui apparatus Co., Ltd.), ultrasonic cleaner (model: SB-5200DT, New Intelligence Biotechnology Co., Ltd.), and high-speed pulverizer (model: FW80, Beijing Yongguang Bright medical apparatus Co., Ltd.).
The embodiment of the invention provides a method for extracting and detecting bromofenoxanil residues in a rice field environment, which comprises the following steps:
s1, collecting and extracting a sample:
collecting a sample, mixing with an extractant, extracting to obtain an extracting solution, dewatering the extracting solution, centrifuging for the first time, collecting a first supernatant, mixing with a purifying agent, purifying, centrifuging for the second time, collecting a second supernatant, and filtering to obtain a solution to be detected;
s2, preparation of a standard working solution:
the concentration of the prepared bromofenoxanil is 1000 mg.L-1The mother solution is diluted by acetonitrile to obtain standard working solution of the bromofenoxanil fluorobenzenediamide with different concentration gradients;
s3, determining the content of the brofenthiuron bisamide:
33) drawing a standard working curve:
determining standard working solutions of the bromofenoxanil fluorobenzene bisamide with different concentration gradients by using ultra-high performance liquid chromatography-high resolution flight time mass spectrometry, and performing regression analysis to obtain a standard working curve;
32) determining the content of the brofenpyrad:
and (3) determining the solution to be detected by using the ultra-high performance liquid chromatography-high resolution flight time mass spectrometry under the same condition, obtaining the content of the brotroche bisamide in the solution to be detected according to the standard working curve, and obtaining the content of the brotroche bisamide in the sample through conversion.
In order to further optimize the above technical solution, in step S1, the sample in the rice field environment includes rice field water, rice field soil, rice plants, rice and rice hulls, wherein the rice field soil, the rice plants, the rice and the rice hulls are added with ultrapure water before the extractant is added.
In order to further optimize the technical scheme, in the step S1, the extracting agent is acetonitrile or acetonitrile containing 0.1% formic acid by volume concentration, the extracting temperature is 15-35 ℃, and the extracting time is 5-10 min;
the operation of water removal is: adding MgSO 2 into the extractive solution4And NaCl, the water removal time is 2-5min, the MgSO4And the dosage ratio of NaCl to the extracting solution is as follows: (2-5) g: (2-5) g: (5-10) mL;
the temperature of the first centrifugation is 2-5 ℃, the rotating speed is 11000-15000rpm, and the time is 5-10 min.
In order to further optimize the above technical solution, in step S1, the purifying agent is MgSO4And a mixture of adsorbents, MgSO4The dosage ratio of the first supernatant to the first supernatant is (150- & ltSP & gt 200-): (1.5-2) mL, and the purification time is 1-5 min;
the temperature of the second centrifugation is 2-5 ℃, the rotation speed is 5000-.
In order to further optimize the technical scheme, the adsorbent is PSA, and the dosage ratio of the adsorbent to the first supernatant is as follows: (50-100) mg: (1.5-2) mL, and is used for the purification treatment of rice field water;
the adsorbent is C18, and the dosage ratio of the adsorbent to the first supernatant is as follows: (50-100) mg: (1.5-2) for the purification treatment of paddy fields and paddy;
the adsorbent is a mixture of GCB and C18, and the dosage ratio of GCB, C18 to the first supernatant is as follows: (10-50 mg, 50-100 mg, 1.5-2 mL) for cleaning rice plant and rice hull.
In order to further optimize the technical scheme, a 0.22 mu m organic filter membrane is adopted for filtration.
In order to further optimize the above technical solution, in step S2, the different gradient concentrations include 0.05mg/L, 0.5mg/L, 1mg/L, 2mg/L, 5mg/L, 10mg/L, 20mg/L and 50 mg/L.
In order to further optimize the technical scheme, the chromatographic column adopted by the ultra-high performance liquid chromatography is an Agilent Eclipse XDB-C18 chromatographic column.
In order to further optimize the technical scheme, the chromatographic conditions of the ultra-high performance liquid chromatography are as follows: the mobile phase consists of 0.1 percent formic acid water solution and acetonitrile, and the volume ratio is 25: 75; eluting for 6min by isocratic elution; flow rate: 0.3 mL/min; column temperature: 40 ℃; sample introduction amount: 10 μ L.
In order to further optimize the technical scheme, the conditions of the high-resolution time-of-flight mass spectrometry are as follows: the temperature of the heated electrospray ion source (HESI) was 200 ℃; the spraying voltage is 5500V; the temperature of the ion transmission tube is 550 ℃; an ion source gas 2; the ion source gas and the curtain gas are respectively 30psi, 145 psi and 30 psi; the positive ion collection adopts an HR MRM scanning mode; the collection range is 100-1400 Da; the first and second mass resolutions exceed 26000 and 25000FWHM, respectively; the collision Cell Energy (CE) was 35. + -.15 eV.
Example 1
The embodiment provides a method for extracting and detecting a residue of flubendiamide in a rice field environment, which comprises the following steps:
(1) field test setup
The field test was conducted in 2019 in 7 months in Zhongcounty, Zanzhou, Yichun city, Jiangxi province. The test was designed according to the "guide for testing pesticide residue" (NY/T788-2018) issued by the ministry of agriculture of the people's republic of China, and the area of each cell was 30m2(5 × 6m), three repeated cells are set per process. Blank cells were set as a control. Each cell is separated by irrigation ditches. Control treated plots did not use any pesticide during rice growth.
(2) Sample collection and extraction
2.1 sample Collection
The blank sample was obtained from a test field in which no brevibraside was applied to a prefecture, Zhonghamu, Yichun, Jiangxi province. Sampling was performed during the rice harvest period. Scooping 5 parts (1 kg each) of the paddy field water sample randomly with a beaker, mixing uniformly and filtering; randomly collecting 5 parts (1 kg each) of paddy field soil samples on the surface layer of 0-20cm deep soil, fully mixing the samples, air-drying, grinding, sieving by a 20-mesh sieve, and dividing into four equal parts to obtain 500g sub-samples; randomly harvesting 5 parts (1 kg each) of rice plant samples by using a pair of scissors, cutting the rice plants into 0.5cm long, and putting the rice plants into a high-speed crusher for crushing; at the rice maturity stage, 5 (1 kg per serving) ear samples were randomly collected and dehulled, the rice hulls and the rice were crushed separately, and all the rice hulls and rice samples were divided into 4 equal portions, 500g per serving. Samples were stored below-18 ℃ until use.
2.2 sample extraction
Sample pre-treatment refers to the QuEChERS method. Bromofenoxanil was extracted from the sample using acetonitrile as the extractant. Transferring 5mL of paddy field water sample into a 50mL centrifuge tube by using a pipette gun, adding 10mL of acetonitrile, carrying out 5min intense vortex by using a vortex mixer, and after the vortex is finished, carrying out 2g MgSO4And 2g NaCl were added to the tube and vortexed vigorously for 2min, then centrifuged using a high speed refrigerated centrifuge at 11000rpm for 5 min. Samples (5g) of paddy field soil, rice and rice hulls were treated in the same way except that each sample was treated with a volume of ultra pure water prior to the addition of acetonitrile: 5mL of ultrapure water was added to the paddy field soil sample, 7mL of ultrapure water was added to the paddy sample, and 10mL of ultrapure water was added to each of the rice hull and the rice plant sample. For all treatments, 1.5mL of supernatant was transferred to a 2.5mL centrifuge tube after high speed refrigerated centrifugation, and 150mg MgSO was added to the 2.5mL centrifuge tube in advance4And specific adsorbents: 50mg PSA (for paddy water), 50mgC18 (for paddy soil and paddy), and 10mg GCB +50mgC18 (for paddy water)In rice plants and hulls). 2.5mL was vortexed for 1 minute and then centrifuged at 5000rpm for 5 minutes. Finally, the supernatant is extracted by a syringe, filtered by an organic filter membrane with the diameter of 0.22 μm, and the filtrate is collected to a sample injection bottle for UHPLC-ESI-QTOF-MS analysis.
(3) Preparation of Standard solutions
0.1014g of a bromofenoxaprop-p-fluorobenzenediamide standard was weighed using an analytical balance (+ -0.0001 g) and placed in a 100mL volumetric flask. 85mL of acetonitrile was added to dissolve the mixture, and the mixture was subjected to dissolution-assisting for 20 minutes using an ultrasonic cleaner, cooled to room temperature, and allowed to stand for 40 minutes. Then, the solution will contain 1000 mg.L-1Mother liquor of the bromofenoxanil is shaken up and stored in a refrigerator at 3 ℃ until being used. The mother liquor was diluted with acetonitrile to give various gradient concentrations of fresh bromofenoxanil solutions (0.05, 0.5, 1, 2, 5, 10, 20 and 50 mg/L). And mixing the blank matrix solution after the sample pretreatment with the working solution to prepare a matrix standard solution.
(4) Detection by using UHPLC-ESI-QTOF-MS
Carrying out ultra-high performance liquid chromatography-high resolution flight time mass spectrometry UHPLC-ESI-QTOF-MS measurement on the standard working solution with different concentration gradients in the step S2, and carrying out regression analysis on the corresponding concentration of the standard working solution according to the chromatographic peak area of the standard working solution to obtain a standard working curve;
and (4) carrying out UHPLC-ESI-QTOF-MS measurement on the solution to be detected of the sample in the step S1 under the same condition, measuring the chromatographic peak area in the bromofenoxuron fluorobenzenediamide in the solution to be detected, substituting the chromatographic peak area into a standard curve to obtain the content of the bromofenoxuron fluorobenzenediamide in the solution to be detected, and converting to obtain the content of the bromofenoxuron fluorobenzenediamide in the sample.
The bromobenzodiamide residues were analyzed by Ultra High Performance Liquid Chromatography (UHPLC) with a mixed quadrupole time of flight (Q-TOF) mass spectrometer (abciexx 500R). The separation experiment was carried out at ambient temperature (30 ℃) in a mobile phase consisting of solvent A (0.1% formic acid) and solvent B (chromatographic grade acetonitrile) (25: 75, v/v) on an Agilent eclipse XDB-C18 column (2.1 mm. times.100 mm. times.1.8 μm). An equidistant elution step of 40% A was used, eluting at a flow rate of 0.3mL/min for 6 minutes. The column temperature was 40 ℃ and the sample size was 10. mu.L, and the samples were stored at 4 ℃. The spectral conditions were as follows: the temperature of the heated electrospray ion source (HESI) was 200 ℃; the spraying voltage is 5500V; the temperature of the ion transmission tube is 550 ℃; an ion source gas 2; the ion source gas and the curtain gas are respectively 30psi, 145 psi and 30 psi; positive ion collection adopts HRMRM scanning mode; the collection range is 100-1400 Da; the first and second mass resolutions exceed 26000 and 25000FWHM, respectively; the collision Cell Energy (CE) was 35. + -.15 eV.
(5) Analysis of detection results
1) And verifying the actual application effect of the method.
Based on the UHPLC-ESI-QTOF-MS method provided by the invention, the concentration of residual bromofenoxanil in 100 actual samples in the rice field is measured. The concentration range of the detection result is 0.95-14.86 mug/kg-1The maximum allowable residual limit of the product is lower than that specified by the national food safety standard of China and is 0.05 mg/kg-1. Therefore, the method can be used for measuring the residual quantity of the flubendiamide in the paddy field environment.
2) And (5) measuring linear correlation.
Under defined chromatographic conditions, a series of standard solutions of different mass concentrations were prepared for the determination. The mass concentration of the flubendiamide is taken as the abscissa, the peak area value is taken as the ordinate, and an Agilent liquid chromatography workstation is used for fitting a working curve to obtain a linear regression equation y which is 17.576x +1.4606 and a linear correlation coefficient r which is 0.9999, as shown in figure 1. Regression equation of bromofenoxanil in different samples (paddy water, paddy soil, rice plants, paddy and rice hulls), correlation coefficient (R)2) Detection Limits (LODs), quantitation Limits (LOQs), and matrix effects, as shown in table 1.
Table 1 regression equation, correlation coefficient, detection limit, quantitation limit and matrix effect of brobendiamide in different samples.
Normalized recovery and relative standard deviation of 3 concentrations of each sample plus standard in different samples (paddy water, paddy soil, rice plants, paddy and rice hulls)As shown in Table 2, the paddy water contents were 0.0.1, 0.05 and 0.5 mg/kg-1The standard substance of (1) is prepared by adding 0.1, 0.5, 1 mg/kg of the above-mentioned materials into paddy field soil, rice plant, paddy and rice husk-1The standard substance of (1).
Wherein, the standard sample of the chlorfenapyr fluorobenzene diamide (5mg kg)-1) The liquid chromatogram of (1) is shown in FIG. 2, and a bromofenoxanil standard (0.5 mg. kg)-1) The liquid chromatogram of the rice field water sample is shown in FIG. 3, and a standard sample of chlorfenapyr fluorobenzene diamide (1 mg. kg) is added-1) The liquid chromatogram of the paddy soil sample is shown in FIG. 4, and a standard sample of bromofenoxanil (1 mg. kg)-1) The liquid chromatogram of the rice plant sample is shown in FIG. 5, and a bromofenoxanil standard (1 mg/kg)-1) The liquid chromatogram of the rice hull sample is shown in FIG. 6, and a standard bromofenoxanil sample (1 mg. kg) is added-1) The liquid chromatogram of the rice sample is shown in FIG. 7.
3) And (4) optimizing the solvent.
In pesticide residue analysis, sample pretreatment and preparation are the most time consuming and complex processes. The chemical nature of the pesticide determines the solvents available for extraction: typical examples include acetone, ethyl acetate, acetonitrile, methanol and dichloromethane. The research compares the standard recovery rates of the five solvents in the rice field water sample, wherein the addition rates are respectively 0.01 and 0.1 mg/kg-1The highest recovery was found for the solvent acetonitrile (as shown in figure 8). In addition, acetonitrile is characterized by less interference of lipids and proteins, high compatibility with HPLC, and less co-extracted sample components compared to other solvents.
Then, a volume fraction (0.1%) of formic acid and sodium hydroxide (NaOH) were added to acetonitrile and the addition of 0.5 mg-kg of standard concentration was investigated-1The recovery of flubendiamide in five different samples to optimize the recovery. The results show that the addition of acid or base to acetonitrile did not significantly affect the recovery of flubendiamide from rice plant and rice hull samples. In the remaining three samples, the best recovery was achieved using acetonitrile without acid or base, with the recovered bromobenzophenone bisamide content being the closest to the addition level (as shown in fig. 9). Therefore, acetonitrile without acid or base was chosen as the extraction solvent for sample pre-treatment.
4) And (4) optimizing the adsorbent.
In order to obtain a satisfactory bromobenzophenone bisamide extract, PSA, C18 and GCB were compared as adsorbents in the QuEChERS program. PSA is a weak anion exchanger that extracts organic acids and carbohydrates from a sample; c18 is a non-polar material used to remove non-polar and moderately polar compounds from polar samples; GCB is an effective adsorbent for the removal of pigments (including chlorophyll) and carotenoids. Using MgSO4Partitioning with NaCl can produce a large upper layer and high recovery. Here, 50mg of each specific adsorbent (0.1 mg. kg) was used-1) And 150mg of MgSO4Extracting the bromoantraniliprole. The standard concentration is 0.1 mg/kg-1The average recovery rate of the bromine cyanide in various samples of different adsorbents is between 89.67% and 109.35% (as shown in figure 10), and meets the requirement of the agricultural industry standard of the people's republic of China (the recovery rate is 70% -120%).
The use of C18 in combination with GCB reduced interference due to the high pigment content in rice plants and hulls. In view of the high adsorption capacity of GCB on pigments, it is important to control the adsorbent dosage to prevent under-recovery. The standard concentration is 0.1 mg/kg-1Comparing the effect of GCB (5, 10, 15 and 20mg) at different doses on the recovery of bromocyanide (as shown in fig. 11), it can be seen that 10mg of GCB is most suitable for extracting brobenobinamide.
Thus, optimal conditions for the extraction and purification of brobendiamide by the QuEChERS program were obtained: the paddy field water is 50mg PSA +150mg MgSO4The paddy field soil and the paddy are 50mg of C18+150mg of MgSO4，50mg C18+10mg GCB+150mg MgSO4It can be used for rice plant and rice husk.
In conclusion, the invention provides a method for extracting the residue of the bromofenoxanil in the rice field environment (rice field water, rice field soil, rice plants, rice and rice hulls) and a detection method by using ultra-high performance liquid chromatography-high resolution time-of-flight mass spectrometry. The method can efficiently extract the residues of the bromofenoxanil in the rice field environment (rice field water, rice field soil, rice plants, rice husks and rice husks), and sensitively and accurately detect the residues, so as to be beneficial to controlling pollution and ensuring the safety of food and environment.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
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