CN107037149B - Fipronil and its metabolite residue amount method for measuring in a kind of egg - Google Patents
Fipronil and its metabolite residue amount method for measuring in a kind of egg Download PDFInfo
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G01N30/04—Preparation or injection of sample to be analysed
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- G01N30/12—Preparation by evaporation
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Abstract
The present invention relates to Fipronil in a kind of egg and its metabolite residue amount methods for measuring.The measuring method of Fipronil and its metabolite residue amount includes: sample preparation in egg of the present invention；Sample pre-treatments；Organic solvent extracts；Solid-phase extraction column removes pigment impurity, and nitrogen, which is blown to, closely to be done, and with mobile phase dissolved residue, solution is analyzed through membrane filtration for UPLC-TQD；The preparation of standard solution；High performance liquid chromatography-tandem mass instrument measurement, etc. processes.Method of the invention, easy to operate, quickly, high degree of automation, extraction efficiency is fast, the rate of recovery and reproducible, it can be achieved that Fipronil and its metabolite residue amount while measure in egg.
Description
Technical field
The present invention relates to Fipronil in a kind of egg and its metabolite residue quantity measuring methods, and in particular in a kind of egg
The high performance liquid chromatography-tandem mass instrument method of 4 kinds of pesticide residue determinations, belongs to the physico-chemical examination technique field of pesticide residue.
Background technique
In recent years, with the development of Chinese national economy, the people are food-safe in life gradually to be mentioned with quality requirement
Height, but for current social situation development, present in food safety accident still happen occasionally.Food safety is
One big problem concerning national economy is to be related to everyone health problem the most basic, the even more following food industries hair
The core link of exhibition.Therefore reinforce just seeming especially heavy to the detection of content of chemical substances various in food in current work
It wants.
Fipronil and its metabolin are a kind of Phenylpyrazole insecticides, to a series of pests such as aphid, Ye Chan and flies
There is very high insecticidal activity.Studies have shown that such medical instrument has chronic neurotoxicity effect, it is decided to be C class carcinogen.Phenyl
Pyrazoles medicine is extra-high (severe toxicity) to the toxicity of aquatic shellfish fish, shrimp, crab, also higher to the toxicity of honeybee.Fipronil pair
Light is more sensitive, and Photolysis Half in water is 3.6h, and Photolysis Half in the soil is 34 days.Fipronil is through photodissociation or oxygen
4 kinds of toxic metabolites are formed after changing reduction.Wherein there is the toxicity of 2 kinds of metabolins to be higher by parent raw medicine to the 10 of mammalian toxicity
Times or more, and fat has enrichment in vivo.It is destructive in view of the high risk and its height of Fipronil and its metabolin, I
State on October 1st, 2009 starts that the medicine is prohibited/limited the use of, destructive in view of the high risk and its height of Fipronil and its metabolin,
Fipronil remains the attention for also having caused the states such as America and Europe, Japan in food, and has formulated stringent limit standard.
Currently, domestic there is no the Liquid Chromatography-Tandem Mass Spectrometry analysis side of Fipronil and its metabolin while measurement in egg
Method, document report mainly have gas chromatography, gas chromatographymass spectrum, liquid-mass chromatography method to measure one of pesticide, do not report also
Measure the Fipronil and its metabolin in egg simultaneously by high performance liquid chromatography tandem mass spectrum instrument.Reported foreign literature
In, using the Fipronil in gas chromatography-mass spectrometry (GC/MS) detection vegetables, but not yet it is used for egg sample.
Summary of the invention
It is a kind of easy to operate the purpose of the present invention is overcoming the deficiencies of the prior art and provide, quickly, high degree of automation,
Extraction efficiency is high, the rate of recovery and reproducible, while measuring the side of the Fipronil in egg and its metabolin persticide residue
Method.
For the purpose for realizing foregoing invention, the technical solution adopted by the present invention is as follows: Fipronil and its generation in a kind of egg
The method for thanking to the object determination of residual amount, includes the following steps:
(1) sample preparation: egg sample is rubbed, homogenate, freezen protective；
(2) sample pre-treatments: accurately weighing and be homogenized uniform egg sample 2g through step (1), be placed in 50mL polypropylene from
In heart pipes, 5 mL acetonitriles are added and are used as crude extract, after homogeneous 1min, vibrate 10 min, at 4 DEG C, is centrifuged with 8000 r/min,
Supernatant is extracted in chicken heart bottle, obtains extracting solution；Sediment repeats to extract 1 time with 5 mL acetonitriles, merges extracting solution twice, is added
2mL isopropanol is concentrated into 50 DEG C of Rotary Evaporators and closely does, obtains concentrate；2.0mL methanol+and dichloromethane are added in concentrate
The mixed solution dissolved residue of alkane mixes, obtains solution to be clean；Solid-phase extraction column is successively used to methanol, the 5mL methanol+two of 5mL
The mixed solution of chloromethanes elutes in advance, conditioning is poured into immediately when solvent liquid level reaches solid-phase extraction column absorption layer surface
Solution to be clean is stated, receives eluent with 15mL graduated centrifuge tube, is rinsed and is burnt with methanol+methylene chloride mixed solution of 5mL
After cup, solid-phase extraction column is eluted, and be repeated once；The graduated centrifuge tube for filling 10mL eluent is placed on nitrogen evaporator, in water
It under the conditions of 50 DEG C of bath temperature, is dried with nitrogen, is settled to 1.0mL with acetonitrile+ultrapure water mixed solution, mixed on vortex mixer
It is even, through 0.22 μm of organic membrane filtration, measured for high performance liquid chromatography-tandem mass instrument；The mixing of the methanol+methylene chloride
Methanol and methylene chloride volume ratio are 1:99 in solution；Acetonitrile and ultrapure water volume in the mixed solution of the acetonitrile+ultrapure water
Than for 1:1；
(3) preparation of standard solution: hybrid standard working solution dilution in acetonitrile is configured to have the mixed of graded series concentration
Standardization working solution, with acetonitrile+ultrapure water mixed solution constant volume；In the mixed solution of the acetonitrile+ultrapure water acetonitrile with it is ultrapure
Water volume ratio is 1:1；
(4) high performance liquid chromatography-tandem mass instrument measures: working solution injection is furnished with to the high-efficient liquid phase color of triple level four bars
In spectrum-tandem mass spectrometer instrument, ultra performance liquid chromatography-tandem mass spectrum measurement is carried out；
(5) qualitative: when carrying out sample measurement, if the retention time one of the chromatographic peak retention time of detection and standard items
It causes, and after background correction in sample mass spectrum, selected ion occurs and abundance is than the abundance of ions with standard items
Than consistent, then it can determine whether that there are this agricultural chemical compounds in sample；
(6) quantitative: it is quantitative with external standard calibration curve method, to reduce influence of the matrix effect to dosing accuracy, using base
Matter matching working solution does standard curve, and guarantees surveyed compound response within the scope of instrument is linear；
(7) residual quantity calculation formula is as follows:
In formula: the persticide residue (mg/kg) in w- sample；Upper machine measurement concentration (ng/mL) of M-；V- constant volume
(mL)；V1It extracts volume (mL)；V2Point take volume (mL)；M- sample sample weighting amount V1It extracts volume (g).
Step (2) described neutral alumina column is using acidic oxidation aluminium powder as the chromatographic column of solid phase extraction filler, solid phase
In extraction column, the additional amount of neutral alumina aluminium powder is that 1 gram of neutral alumina aluminium powder is added in every gram of sample；The neutral alumina
Powder in Muffle furnace 400 DEG C before use, dry.
The graded series concentration of step (3) the hybrid standard working solution is 1.0 ng/mL, 2.0 ng/mL, 5.0 ng/
ML, 10.0 ng/mL, 20.0 ng/mL and 50.0 ng/mL.
Preferably, step (1) the freezen protective temperature is -18 DEG C.
Further, step (2) volume that acetonitrile is added is that 5.0 mL are added in every gram of sample.
Fipronil and its method of the metabolite residue amount determination of residual amount are applied in detection egg in egg of the invention
Persticide residue；In particular for detecting the residual quantity of Fipronil and its metabolin in egg simultaneously.
The graded series concentration of step (3) the hybrid standard working solution is 1.0 ng/mL, 2.0 ng/mL, 5.0 ng/
ML, 10.0 ng/mL, 20.0 ng/mL and 50.0 ng/mL.
Preferably, used ultra performance liquid chromatography determination condition is as follows: UPLC ACQUITY BEHC18 column, 50 ×
2.1 mm, 1.7 μm；Mobile phase A is acetonitrile, and Mobile phase B is the ammonium acetate solution of 5mmol/L；Flow velocity: 0.3mL/min；Column temperature:
40℃；Sample volume: 10 μ L；Used eluent gradient and time conditions are shown in Table 1；
1 eluent gradient of table and time
。
Preferably, used Mass Spectrometry Conditions are as follows: ion source: ESI, negative ion mode；Capillary voltage: 4.0 kv；
Ion source temperature: 110 DEG C；350 DEG C of desolvation temperature；Desolventizing gas flow: 800 L/ hr；Cone hole backflow airflow amount 50
L/ hr；Orifice potential: 40 v；Scanning mode: multiple-reaction monitoring (MRM)；It used monitoring ion pair, orifice potential and touches
It hits energy condition and is shown in Table 2, wherein band * is quantitative fragment ion；
2 Fipronil of table and its metabolin monitoring ion pair, orifice potential and collision energy
。
The beneficial effects of the present invention are: with Fipronil and its metabolite residue amount, processing operation in this method detection egg
Simply, quickly, high degree of automation, it is pesticide residue in a kind of rate of recovery and reproducible measurement egg that extraction efficiency is high
The method of amount；The method of the present invention can measure four kinds of Fipronil in egg, fluorine formonitrile HCN, Fipronil sulfone and Fipronil sulfoxide pesticides simultaneously
Residual quantity.
Detailed description of the invention
Fig. 1: Fipronil, fluorine formonitrile HCN, 4 kinds of pesticides of Fipronil sulfone and Fipronil sulfoxide standard liquid chromatograph figure (concentration is
20.0 ng/mL), condition is monitored according to the MRM of Fipronil and its metabolin, is followed successively by Fipronil sulfone, fluorine from 1 to 4 in mass spectrogram
Worm nitrile, Fipronil sulfoxide and fluorine formonitrile HCN.
Fig. 2: egg sample blank spectrogram.
Fig. 3: egg sample mark-on spectrogram (concentration is 20.0 ng/mL).
Specific embodiment
The present invention is described in further details below by example, these examples are only used to illustrate the present invention, and unlimited
The scope of the present invention processed.
Embodiment 1 use method of the invention, as follows respectively measure 5 egg samples in Fipronil, fluorine first
Nitrile, Fipronil sulfone and Fipronil sulfoxide residual quantity:
(1) sample preparation: 5 egg samples are rubbed into homogenate respectively, freezen protective under the conditions of -18 DEG C obtains frozen samples；
(2) sample pre-treatments: accurately weighing and be homogenized uniform egg sample 2g through step (1), be placed in 50mL polypropylene from
In heart pipes, 5 mL acetonitriles are added and are used as crude extract, after homogeneous 1min, vibrate 10 min, at 4 DEG C, is centrifuged with 8000 r/min,
Supernatant is extracted in chicken heart bottle, obtains extracting solution；Sediment repeats to extract 1 time with 5 mL acetonitriles, merges extracting solution twice, is added
2mL isopropanol is concentrated into 50 DEG C of Rotary Evaporators and closely does, obtains concentrate；2.0mL methanol+and dichloromethane are added in concentrate
Mixed solution (volume ratio 1:99) dissolved residue of alkane mixes, obtains solution to be clean；Solid-phase extraction column is successively used to 5mL's
Methanol, 5mL methanol+methylene chloride mixed solution (volume ratio 1:99) elution, conditioning in advance, when solvent liquid level reaches solid phase
When extraction column adsorbs layer surface, above-mentioned solution to be clean is poured into immediately, eluent is received with 15mL graduated centrifuge tube, with 5mL's
After methanol+methylene chloride mixed solution (volume ratio 1:99) rinses beaker, solid-phase extraction column is eluted, and be repeated once；It will
The graduated centrifuge tube for filling 10mL eluent is placed on nitrogen evaporator, under the conditions of 50 DEG C of bath temperature, is dried with nitrogen, with acetonitrile+
The mixed solution of ultrapure water is settled to 1.0mL, mixes on vortex mixer, through 0.22 μm of organic membrane filtration, for efficient liquid
Phase chromatography-tandem mass spectrometer measurement；
(3) preparation of standard solution: hybrid standard working solution dilution in acetonitrile is configured to have the mixed of graded series concentration
Standardization working solution, with acetonitrile: ultrapure water (volume ratio 1:1) mixed solution constant volume；
(4) high performance liquid chromatography-tandem mass instrument measures: working solution injection is furnished with to the high-efficient liquid phase color of triple level four bars
In spectrum-tandem mass spectrometer instrument, high performance liquid chromatography-tandem mass measurement is carried out；
(5) qualitative: when carrying out sample measurement, if the retention time one of the chromatographic peak retention time of detection and standard items
It causes, and after background correction in sample mass spectrum, selected ion occurs and abundance is than the abundance of ions with standard items
Than consistent, then it can determine whether that there are this agricultural chemical compounds in sample；
(6) quantitative: it is quantitative with external standard calibration curve method, to reduce influence of the matrix effect to dosing accuracy, using base
Matter matching working solution does standard curve, and guarantees surveyed compound response within the scope of instrument is linear；As a result in 2 chickens
2 kinds of pesticides are detected in egg sample, the results are shown in Table 3；
(7) residual quantity calculation formula is as follows:
In formula: the persticide residue (mg/kg) in w- sample；Upper machine measurement concentration (ng/mL) of M-；V- constant volume
(mL)；V1It extracts volume (mL)；V2Point take volume (mL)；M- sample sample weighting amount.
The content of remains of pesticide in 3 egg sample of table
The measurement of repeatability and the rate of recovery: negative egg sample is respectively adopted, and (feminine gender refers to that 4 kinds of pesticides are equal in the sample
Without detection) it is measured, the detection limit of analyte is determined with 3 times of signal-to-noise ratio, and the quantitative limit of analyte is determined with 10 times of signal-to-noise ratio,
In conjunction with the rate of recovery and sample size, the quantitative detection of method is limited to 0.01mg/kg, using in sample add standard solution method,
Recovery of standard addition experiment is carried out to two kinds of pesticides under same sample treatment, the results are shown in Table 4.
4 kinds of pesticides carry out recovery of standard addition and standard deviation (n=5) in 4 egg of table
。
The linear and detection limit of 5 kinds of target compounds is shown in Ultra Performance Liquid Chromatography instrument tandem mass spectrometer measurement egg sample
Table 5.
5 Ultra Performance Liquid Chromatography instrument tandem mass spectrometer of table measures the linear and detection of 5 kinds of target compounds in egg sample
It limits (n=5)
Embodiment described above only describe the preferred embodiments of the invention, is not to of the invention
Range is defined, and without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technology of the invention
The various changes and improvements that scheme is made should all be fallen into the protection scope that claims of the present invention determines.
Claims (6)
1. Fipronil and its metabolite residue amount method for measuring in a kind of egg, characterized by the following steps:
(1) sample preparation: egg sample is rubbed, homogenate, freezen protective；
(2) it sample pre-treatments: accurately weighs and is homogenized uniform egg sample 2g through step (1), be placed in 50mL polypropylene centrifuge tube
In, 5mL acetonitrile is added and is used as crude extract, after homogeneous 1min, vibrates 10min and is centrifuged at 4 DEG C with 8000r/min, in extraction
Clear liquid obtains extracting solution in chicken heart bottle；Sediment repeats to extract 1 time with 5mL acetonitrile, merges extracting solution twice, and 2mL isopropyl is added
Alcohol is concentrated into 50 DEG C of Rotary Evaporators and closely does, obtains concentrate；The mixing of 2.0mL methanol+and methylene chloride is added in concentrate
Solution dissolved residue mixes, obtains solution to be clean；Solid-phase extraction column is successively used to methanol, the 5mL methanol+methylene chloride of 5mL
Mixed solution elutes in advance, conditioning is poured into above-mentioned to be clean immediately when solvent liquid level reaches solid-phase extraction column absorption layer surface
Solution receives eluent with 15mL graduated centrifuge tube, after rinsing beaker with methanol+methylene chloride mixed solution of 5mL, elution
Solid-phase extraction column, and be repeated once；The graduated centrifuge tube for filling 10mL eluent is placed on nitrogen evaporator, at 50 DEG C of bath temperature
Under the conditions of, it is dried with nitrogen, is settled to 1.0mL with acetonitrile+ultrapure water mixed solution, is mixed on vortex mixer, through 0.22 μ
The organic membrane filtration of m is measured for high performance liquid chromatography-tandem mass instrument；Methanol in the mixed solution of the methanol+methylene chloride
It is 1:99 with methylene chloride volume ratio；Acetonitrile and ultrapure water volume ratio are 1:1 in the mixed solution of the acetonitrile+ultrapure water；
Step (2) solid-phase extraction column is homemade neutral alumina column, is filled out using neutral alumina aluminium powder as Solid Phase Extraction
Expect, in solid-phase extraction column, the additional amount of neutral alumina aluminium powder is that 1 gram of neutral alumina aluminium powder is added in every gram of sample；In described
Property alumina powder in Muffle furnace 400 DEG C before use, dry；
(3) preparation of standard solution: hybrid standard working solution dilution in acetonitrile is configured to the mixing mark with graded series concentration
Quasi- working solution, with acetonitrile+ultrapure water mixed solution constant volume；Acetonitrile and ultrapure water body in the mixed solution of the acetonitrile+ultrapure water
Product is than being 1:1；
(4) high performance liquid chromatography-tandem mass instrument measures: working solution injection is furnished with to the high performance liquid chromatography-of triple level four bars
In tandem mass spectrometer instrument, ultra performance liquid chromatography-tandem mass spectrum measurement is carried out；Ultra performance liquid chromatography determination condition is as follows:
UPLC ACQUITY BEHC18 column, 50 × 2.1mm, 1.7 μm；Mobile phase A is acetonitrile, and Mobile phase B is the ammonium acetate of 5mmol/L
Solution；Flow velocity: 0.3mL/min；Column temperature: 40 DEG C；Sample volume: 10 μ L；Used eluent gradient and time conditions are as follows: stream
The dynamic time: 0min, 0.50min, 3.00min, 3.10min, 5.00min, eluent gradient are successively mobile phase As: 20%,
20%, 80%, 20%, 20%, Mobile phase B: 80%, 80%, 20%, 80%, 80%；Mass Spectrometry Conditions are as follows: ion source: ESI,
Negative ion mode；Capillary voltage: 4.0kv；Ion source temperature: 110 DEG C；350 DEG C of desolvation temperature；Desolventizing gas flow:
800L/hr；Cone hole backflow airflow amount 50L/hr；Orifice potential: 40v；Scanning mode: multiple-reaction monitoring (MRM)；Wherein, it is adopted
Monitoring ion pair, orifice potential and collision energy condition are specific as follows:
A. Fipronil: parent ion 434.8, quantitative fragment ion 250.0, orifice potential -35v, collision energy -25v；Parent ion
434.8, daughter ion 330.0, orifice potential -35, collision energy -15v；
B. fluorine formonitrile HCN: parent ion 386.9, quantitative fragment ion 351.0, orifice potential -30v, collision energy -15v；Parent ion
386.9, daughter ion 282.0, orifice potential -30v, collision energy -30v；
C. Fipronil sulfone: parent ion 450.9, quantitative fragment ion 282.0, orifice potential -35v, collision energy -25v；Parent ion
450.9, daughter ion 415.0, orifice potential -35v, collision energy -15v；
D. Fipronil sulfoxide: parent ion 418.9, quantitative fragment ion 262.0, orifice potential -30v, collision energy -25v；Mother from
Son 418.9, daughter ion 314.0, orifice potential -30v, collision energy -20v；
(5) calculating of determination of residual amount result: with retention time to Fipronil, fluorine formonitrile HCN, Fipronil sulfone, four kinds of Fipronil sulfoxide
Pesticide carries out qualitative analysis, the quantitative analysis of four kinds of pesticides is carried out with peak area, with external standard method calculated result.
2. Fipronil and its metabolite residue amount method for measuring in a kind of egg according to claim 1, it is characterised in that:
The egg sample crude extract is acetonitrile, extracts volume 10mL.
3. Fipronil and its metabolite residue amount method for measuring in a kind of egg according to claim 1, it is characterised in that:
Step (3) is described have its concentration of the hybrid standard working solution of graded series concentration be respectively 1.0ng/mL, 2.0ng/mL,
5.0ng/mL, 10.0ng/mL, 20.0ng/mL and 50.0ng/mL.
4. Fipronil and its metabolite residue amount method for measuring in a kind of egg according to claim 1, it is characterised in that:
Step (1) the freezen protective temperature is -18 DEG C.
5. Fipronil and its metabolite residue amount method for measuring in a kind of egg according to claim 1, it is characterised in that:
Step (2) it is described be added elution solid-phase extraction column eluting solvent be methanol+methylene chloride mixed solution, wherein methanol with
Methylene chloride volume ratio is 1:99.
6. Fipronil and its metabolite residue amount method for measuring in a kind of egg according to claim 1, it is characterised in that:
Residual quantity applied to Fipronil and its metabolin in detection egg.
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| CN107917974A (en) * | 2017-11-10 | 2018-04-17 | 韩超 | The detection method of ethiprole and its metabolite residue amount in egg |
| CN108362812B (en) * | 2018-02-11 | 2021-11-02 | 梁雪琪 | Method for detecting fipronil and its metabolite in animal-derived food |
| CN108445128B (en) * | 2018-03-01 | 2020-05-26 | 中国热带农业科学院农产品加工研究所 | Method for measuring residual amount of carbamate drugs in eggs |
| CN108287152B (en) * | 2018-04-03 | 2020-11-24 | 江南大学 | Method for rapidly detecting fipronil by utilizing illumination and surface enhanced Raman spectroscopy |
| CN108535379A (en) * | 2018-04-12 | 2018-09-14 | 韩超 | The detection method of test quantity of fluoride in tea worm nitrile and its metabolite fluorine formonitrile HCN, ethiprole thioether, ethiprole sulfone |
| CN109239248A (en) * | 2018-09-14 | 2019-01-18 | 河源出入境检验检疫局综合技术服务中心 | The LC-Q-TOF detection method of Fipronil in egg and egg products |
| CN110261515B (en) * | 2019-07-31 | 2021-11-12 | 江西省农业科学院农产品质量安全与标准研究所 | Method for detecting residual quantity of fipronil in livestock and poultry hair |
| CN113009057B (en) * | 2020-10-22 | 2023-11-07 | 重庆医科大学 | Method for detecting neonicotinoid insecticides and metabolites in urine by solid phase extraction-ultra-high performance liquid chromatography-tandem mass spectrometry |
| CN114414321A (en) * | 2021-12-02 | 2022-04-29 | 浙江省农业科学院 | Fipronil sulfone residue analysis standard substance candidate in egg powder and preparation method thereof |
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2017
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