CN109239248A - The LC-Q-TOF detection method of Fipronil in egg and egg products - Google Patents
The LC-Q-TOF detection method of Fipronil in egg and egg products Download PDFInfo
- Publication number
- CN109239248A CN109239248A CN201811076040.9A CN201811076040A CN109239248A CN 109239248 A CN109239248 A CN 109239248A CN 201811076040 A CN201811076040 A CN 201811076040A CN 109239248 A CN109239248 A CN 109239248A
- Authority
- CN
- China
- Prior art keywords
- egg
- fipronil
- egg products
- detection method
- detected
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses the LC-Q-TOF detection method of Fipronil in egg and egg products, 0.1% formic acid acetonitrile solution, sodium chloride and anhydrous magnesium sulfate are sequentially added in egg and egg products to be measured, vortex concussion mixing obtains supernatant after centrifugation, supernatant carries out supercritical CO2Extraction, extract liquor are added 0.1% formic acid acetonitrile solution constant volume, the liquid to be detected after constant volume are injected into LC-Q-TOF and is detected after the drying of nitrogen room temperature.The present invention obtains the mass spectrogram of liquid to be detected by LC-Q-TOF, realizes the qualitative analysis to ingredient in liquid to be detected, so that screening goes out in egg and egg products to be measured whether contain Fipronil.And the concentration of egg and egg products institute to be measured containing fipronil is calculated according to chromatogram simultaneously, the detection of this detection method is limited to 0.4ug/Kg, far superior to other detection methods.The present invention can not only in egg to be measured and egg products the qualitative Fipronil of accurate screening, and can also accurate quantitative analysis Fipronil, the detection for Fipronil in egg and egg products provides convenience.
Description
Technical field
The present invention relates to the detection methods of Fipronil in egg and egg products, and in particular to Fipronil in egg and egg products
LC-Q-TOF detection method.
Background technique
Recently it is growed in intensity by " malicious egg " disturbance that insecticide Fipronil pollutes in Europe, not only results in Holland, ratio
The egg millions of with German retailer is forced undercarriage when sharp, and Britain, France have also been notified to asking from imported from Holland
Inscribe egg.Fipronil is a kind of broad spectrum pesticide, can kill flea, mite and lice, and people's such as large dosage is edible to can lead to liver function, kidney
Function and impaired Thyroid Function are classified as the chemicals of " having moderate toxicity to the mankind " by the World Health Organization.Although Fipronil
Rice-stem borer and leaf roll snout moth's larva can be prevented and treated, but it is extremely unfriendly to environment, i.e., can make to butterfly, the dragonfly etc. around crops
At influence, regulation disables Fipronil from China on October 1st, 2009.Currently, Fipronil can only be used to kill off domestic hygiene pest.
Regulation has been made to the maximum residue limit of Fipronil in countries in the world, is not quite similar, and specific details are shown in Table 1.Its
In, maximum residue limit of the Fipronil in cereal, vegetables is specified in China GB 2763-2014, however, its in eggs and
Maximum residue limit in birds does not make regulation.
Table 1
The detection method that the country is related to Fipronil at present mainly has: (1) fluorine worm in SN/T 1982-2007 import and export food
Nitrile determination of residual amount gas chromatography-mass spectrography；(2) naphthaleneacetamide, pyraflufen-ethyl, second worm in SN/T 4039-2014 export food
Measurement liquid chromatography-mass spectrography/mass spectrography of nitrile, Fipronil persticide residue；(3) 519 kinds of agricultures in GB/T23204-2008 tealeaves
The measurement gas chromatography-mass spectrography of medicine and related chemicals residual quantity.However, the prior art still has following problem: at present
The test sample of domestic Fipronil is mainly cereal and vegetables, including brown rice, corn, fresh edible maize, leek, spinach, balling are sweet
Indigo plant, common Chinese cabbage, celery, Chinese cabbage etc. are not directed to and also undisclosed about the Fipronil of eggs and egg products detection skill
Art.
Summary of the invention
In order to solve the test problems of Fipronil in eggs and egg products, the present invention proposes fluorine worm in a hatching egg and egg products
The LC-Q-TOF detection method of nitrile.
The purpose of the present invention will be realized by following technical method: the detection side LC-Q-TOF of Fipronil in egg and egg products
Method, sequentially adds 0.1% formic acid acetonitrile solution, sodium chloride and anhydrous magnesium sulfate in egg and egg products to be measured, vortex concussion mixing,
Supernatant is obtained after centrifugation, supernatant carries out supercritical CO20.1% formic acid is added after the drying of nitrogen room temperature in extraction, extract liquor
Liquid to be detected after constant volume is injected into LC-Q-TOF and detects by acetonitrile solution constant volume.
Preferably, in the egg and egg products Fipronil LC-Q-TOF detection method, the supercritical CO2When extraction
Using acetonitrile as entrainer, the volume ratio of supernatant and acetonitrile is 10:1.
Preferably, in the egg and egg products Fipronil LC-Q-TOF detection method, the supercritical CO2When extraction
The temperature of extraction kettle is 40~50 DEG C, and the pressure of extraction kettle is 40~50MPa, and the temperature of separating still is 30~40 DEG C, separating still
Pressure be 6~10MPa.
Preferably, in the egg and egg products Fipronil LC-Q-TOF detection method, the LC-Q-TOF is efficient
Liquid chromatography tandem level four bars time of-flight mass spectrometer is treated by high performance liquid chromatography series connection level four bars time-of-flight mass spectrometry (TOFMS)
Detection liquid is tested and analyzed.
Preferably, in the egg and egg products Fipronil LC-Q-TOF detection method, in the high performance liquid chromatography
Using C18Chromatographic column, 40 DEG C of the column temperature of chromatographic column eluted using methanol/water as eluent gradient, and the flow velocity of mobile phase is
0.2mL/min, sample volume are 2 μ L.
Preferably, in the egg and egg products Fipronil LC-Q-TOF detection method, pass through high performance liquid chromatography string
Connection level four bars time of-flight mass spectrometer obtains the mass spectrogram and fragment ion peak of liquid to be detected, analyzes in liquid mass spectrogram to be detected
Fragment ion peak is to determine whether contain Fipronil.
Preferably, in the egg and egg products Fipronil LC-Q-TOF detection method, pass through the high-efficient liquid phase color
Spectrum series connection level four bars time of-flight mass spectrometer obtains the chromatogram of liquid to be detected, according to peak face corresponding in liquid chromatography figure to be detected
Product, to calculate the content of middle Fipronil to be detected.
Preferably, in the egg and egg products Fipronil LC-Q-TOF detection method, by by the fluorine of various concentration
Worm nitrile standard items are injected separately into high performance liquid chromatography series connection level four bars time of-flight mass spectrometer, and record its corresponding peak face
Product, establishes the standard curve between the concentration of Fipronil and peak area, further according to the peak face of Fipronil in egg to be measured and egg products
Product, to calculate the content of Fipronil in egg and egg products to be measured.
Compared with prior art, the present invention is with following the utility model has the advantages that the present invention passes through high performance liquid chromatography series connection four
Grade bar flight time mass spectrum (LC-Q-TOF) instrument obtains the mass spectrogram of liquid to be detected, realize in liquid to be detected ingredient it is qualitative
Analysis, so that screening goes out in egg and egg products to be measured whether contain Fipronil.And simultaneously according to chromatogram calculate egg to be measured and
The concentration of egg products institute containing fipronil, the detection of this detection method are limited to 0.4ug/Kg, far superior to other detection methods.This hair
It is bright can not only in egg to be measured and egg products the qualitative Fipronil of accurate screening, and can also accurate quantitative analysis Fipronil, be egg and egg
The detection of Fipronil provides convenience in product.
Specific embodiment
For a better understanding of the invention, further specific elaboration is made to the present invention below by following embodiment, but not
It can be regarded as limitation of the invention, it is some nonessential according to made by foregoing invention content for those skilled in the art
It improves and adjusts, be also considered as and be within the scope of the present invention.
Embodiment 1
The LC-Q-TOF detection method of Fipronil in egg and egg products, is divided into: (1) drafting of Fipronil standard curve；(2)
The preparation of liquid to be detected；(3) detection of Fipronil.
(1) drafting of Fipronil standard curve
Fipronil standard items 0.0174g is weighed, using dilution in acetonitrile and 100mL is settled to, shakes up, be prepared into mass concentration
For the standard reserving solution of 173.6mg/L；Draw respectively described standard reserving solution 1.16mL, 2.89mL, 5.78mL, 11.56mL and
28.9mL is placed in 100mL volumetric flask, using dilution in acetonitrile to scale, is shaken up, be configured to mass concentration be 0.002mg/L,
The titer of 0.005mg/L, 0.010mg/L, 0.020mg/L and 0.050mg/L；Each 2 μ L of titer injection is drawn respectively
High performance liquid chromatography is connected in level four bars time of-flight mass spectrometer, and records the peak area of its corresponding chromatographic peak, establishes Fipronil
Concentration and peak area between standard curve.
(2) preparation of liquid to be detected
5.0g egg products to be measured are weighed, 0.1% formic acid acetonitrile solution of 10mL is sequentially added into egg products to be measured
(formic acid acetonitrile solution of 0.1% volume), 2g sodium chloride and 5g anhydrous magnesium sulfate, vortex concussion mixing, in 10000rad/min
Revolving speed under be centrifuged after obtain supernatant, supernatant carries out supercritical CO2Extraction.Supercritical CO2Using acetonitrile as folder when extraction
The volume ratio of band agent, supernatant and acetonitrile is 10:1, supercritical CO2The temperature of extraction kettle is 44 DEG C when extraction, the pressure of extraction kettle
Power is 46MPa, and the temperature of separating still is 33 DEG C, and the pressure of separating still is 8MPa.Extract liquor is added after the drying of nitrogen room temperature
Liquid to be detected after constant volume is injected into the high performance liquid chromatography series connection level four bars flight time by 0.1% formic acid acetonitrile solution constant volume
It is detected in mass spectrograph.
(3) detection of Fipronil
Using high performance liquid chromatography series connection level four bars time of-flight mass spectrometer, flown by high performance liquid chromatography series connection level four bars
Row time mass spectrum method tests and analyzes liquid to be detected.
The condition of high performance liquid chromatography are as follows: chromatographic column is Hypersil GOLD C18(1.9 μm, 100mm × 2.1mm)；Stream
Dynamic phase: methanol (A)/water (B), gradient elution: 0~5min, 30%~90% (A)；5~6.5min, 90% (A)；6.5~
7min, 90%~30% (A)；7~10min, 30% (A).The flow velocity of mobile phase is 0.2mL/min；Sample volume is 2 μ L；Column temperature
It is 40 DEG C；
The condition of level four bars time of-flight mass spectrometer are as follows: electro-spray ionization source (negative ion mode) detects voltage :-
Temperature: 4500V, atomization gas GS1:50, assisted atomization gas GS2:50, gas curtain gas CUR:30 450 DEG C, remove cluster voltage DP:-80, touch
Hit energy CE:-10, Product ion: collision voltage: -30, CES 15.
Mass spectral results analysis: from the interpretation of result of high performance liquid chromatography series connection level four bars time of-flight mass spectrometer, mass spectrogram
With quasi-molecular ion peak m/z 434.9347 [M-H] for base peak, main fragment ion is respectively m/z329.9620, and 277.9571,
398.9574 365.9371, it is shown in Table 2.Quasi-molecular ion peak m/z 434.9347 loses CClF3Generate 329 (M-H- of fragment m/z
CHClF3), lose C3H2F3NOS generates 277 (M-H-C of fragment m/z3H2F3NOS), lose HCL and generate 398 (M-H- of fragment m/z
HCL), CF is lost3Generate 365 (M-H-CF of fragment m/z3).Thus upper analysis, show that the molecular formula of this substance is
C12H4Cl2F6N4OS contains Fipronil to obtain in this egg products to be measured according to retrieval molecular formula.
Table 2
And further determined that using blank sample counter point, divide into the not blank sample of containing fipronil egg and egg products
Not Tian Jia the Fipronils of three known concentrations and detected through LC-Q-TOF after being handled using same method, with bare substrate sample
The molecular ion [M-H] 434.9347 of condition ratio, addition Fipronil sample is base peak, and main fragment ion is respectively m/z
329.9620,277.9571,398.9574,365.9371, it is further determined that in this egg products to be measured as a result, and contains Fipronil.
Chromatography: carrying out the standard curve of drawing Fipronil with peak area-mass concentration, and standard curve regression equation is
Y=aX+b (wherein a=2.49E+03, b=4.67E+03), the detection of related coefficient 0.998, Fipronil are limited to 0.4ug/
Kg.In addition concentration within the scope of 0.4-4.0ug/Kg, the rate of recovery is between 65%-108%, and details are shown in Table 3, and precision is in weight
The absolute difference of the measurement result independent twice obtained under denaturing conditions is no more than the 10% of arithmetic mean of instantaneous value.
Table 3
According to corresponding peak area in the above standard curve and liquid chromatography figure to be detected, to calculate middle fluorine to be detected
The content of worm nitrile.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. the LC-Q-TOF detection method of Fipronil in egg and egg products, it is characterised in that: successively add in egg and egg products to be measured
Enter 0.1% formic acid acetonitrile solution, sodium chloride and anhydrous magnesium sulfate, vortex concussion mixing obtains supernatant after centrifugation, supernatant into
Row supercritical CO20.1% formic acid acetonitrile solution constant volume is added after the drying of nitrogen room temperature in extraction, extract liquor, by after constant volume to
It is detected in detection liquid injection LC-Q-TOF.
2. the LC-Q-TOF detection method of Fipronil in egg according to claim 1 and egg products, it is characterised in that: described
Supercritical CO2Entrainer is used as using acetonitrile when extraction, the volume ratio of supernatant and acetonitrile is 10:1.
3. the LC-Q-TOF detection method of Fipronil in egg according to claim 1 and egg products, it is characterised in that: described
Supercritical CO2The temperature of extraction kettle is 40~50 DEG C when extraction, and the pressure of extraction kettle is 40~50MPa, and the temperature of separating still is
30~40 DEG C, the pressure of separating still is 6~10MPa.
4. the LC-Q-TOF detection method of Fipronil in egg according to claim 1 and egg products, it is characterised in that: described
LC-Q-TOF is high performance liquid chromatography series connection level four bars time of-flight mass spectrometer, passes through high performance liquid chromatography series connection level four bars flight
Time mass spectrum method tests and analyzes liquid to be detected.
5. the LC-Q-TOF detection method of Fipronil in egg according to claim 4 and egg products, it is characterised in that: described
C is used in high performance liquid chromatography18Chromatographic column, 40 DEG C of the column temperature of chromatographic column, using methanol/water as eluent gradient elute,
The flow velocity of mobile phase is 0.2mL/min, and sample volume is 2 μ L.
6. the LC-Q-TOF detection method of Fipronil in egg according to claim 4 and egg products, it is characterised in that: pass through
High performance liquid chromatography series connection level four bars time of-flight mass spectrometer obtains the mass spectrogram and fragment ion peak of liquid to be detected, analyzes to be checked
The fragment ion peak in liquid mass spectrogram is surveyed to determine whether containing Fipronil.
7. the LC-Q-TOF detection method of Fipronil in egg according to claim 4 and egg products, it is characterised in that: pass through
The high performance liquid chromatography series connection level four bars time of-flight mass spectrometer obtains the chromatogram of liquid to be detected, according to liquid chromatography to be detected
Corresponding peak area in figure, to calculate the content of middle Fipronil to be detected.
8. the LC-Q-TOF detection method of Fipronil in egg according to claim 7 and egg products, it is characterised in that: pass through
The Fipronil standard items of various concentration are injected separately into high performance liquid chromatography series connection level four bars time of-flight mass spectrometer, and are remembered
Its corresponding peak area is recorded, the standard curve between the concentration of Fipronil and peak area is established, further according to egg to be measured and egg products
The peak area of middle Fipronil, to calculate the content of Fipronil in egg and egg products to be measured.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811076040.9A CN109239248A (en) | 2018-09-14 | 2018-09-14 | The LC-Q-TOF detection method of Fipronil in egg and egg products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811076040.9A CN109239248A (en) | 2018-09-14 | 2018-09-14 | The LC-Q-TOF detection method of Fipronil in egg and egg products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109239248A true CN109239248A (en) | 2019-01-18 |
Family
ID=65058333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811076040.9A Pending CN109239248A (en) | 2018-09-14 | 2018-09-14 | The LC-Q-TOF detection method of Fipronil in egg and egg products |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109239248A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112630332A (en) * | 2020-12-14 | 2021-04-09 | 安徽标王农牧有限公司 | Embryo egg separation and purification system based on liquid chromatogram |
| CN112931295A (en) * | 2021-01-26 | 2021-06-11 | 成都小巨人畜牧设备有限公司 | Breed with low-cost laser egg counting system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080192251A1 (en) * | 2005-05-24 | 2008-08-14 | Basf Aktiengesellschaft | Method For Determining Residues in Plastics |
| CN107037163A (en) * | 2017-04-13 | 2017-08-11 | 浙江省农业科学院 | The pre-treating method of many residues of pesticides during a kind of determination of the environment is biological |
| CN107037149A (en) * | 2017-04-08 | 2017-08-11 | 中国热带农业科学院农产品加工研究所 | Ethiprole and its metabolite residue amount method for measuring in a kind of egg |
| CN107917974A (en) * | 2017-11-10 | 2018-04-17 | 韩超 | The detection method of ethiprole and its metabolite residue amount in egg |
| US10092852B2 (en) * | 2017-01-19 | 2018-10-09 | Metamorphic Alchemy & Distillations, Inc. | Method for removing contaminants from cannabinoid distillates |
-
2018
- 2018-09-14 CN CN201811076040.9A patent/CN109239248A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080192251A1 (en) * | 2005-05-24 | 2008-08-14 | Basf Aktiengesellschaft | Method For Determining Residues in Plastics |
| US10092852B2 (en) * | 2017-01-19 | 2018-10-09 | Metamorphic Alchemy & Distillations, Inc. | Method for removing contaminants from cannabinoid distillates |
| CN107037149A (en) * | 2017-04-08 | 2017-08-11 | 中国热带农业科学院农产品加工研究所 | Ethiprole and its metabolite residue amount method for measuring in a kind of egg |
| CN107037163A (en) * | 2017-04-13 | 2017-08-11 | 浙江省农业科学院 | The pre-treating method of many residues of pesticides during a kind of determination of the environment is biological |
| CN107917974A (en) * | 2017-11-10 | 2018-04-17 | 韩超 | The detection method of ethiprole and its metabolite residue amount in egg |
Non-Patent Citations (2)
| Title |
|---|
| MOURAD BOULAID ET AL: "Assessing supercritical fluid extraction for the analysis of fipronil, kresoxim-methyl, acrinathrin, and pyridaben residues in melon", 《JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH PART B》 * |
| 郭德华 等: "固相萃取－液相色谱－四极杆飞行时间质谱法快速筛查禽蛋及蛋制品中氟虫腈及其代谢物", 《色谱》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112630332A (en) * | 2020-12-14 | 2021-04-09 | 安徽标王农牧有限公司 | Embryo egg separation and purification system based on liquid chromatogram |
| CN112931295A (en) * | 2021-01-26 | 2021-06-11 | 成都小巨人畜牧设备有限公司 | Breed with low-cost laser egg counting system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Topuz et al. | Simultaneous determination of various pesticides in fruit juices by HPLC-DAD | |
| Liu et al. | Residue and risk assessment of pyridaben in cabbage | |
| González-Zamora et al. | Measurement of capsaicinoids in chiltepin hot pepper: a comparison study between spectrophotometric method and high performance liquid chromatography analysis | |
| Costa et al. | Determination of pesticides in lettuce using solid–liquid extraction with low temperature partitioning | |
| CN106442747B (en) | A kind of method that chloropyuril in fruits and vegetables, 2,4-D, paclobutrazol residual quantity are measured simultaneously using gas chromatography mass spectrometry | |
| Feng et al. | Residue analysis and risk assessment of pyrethrins in open field and greenhouse turnips | |
| Plattner | HPLC/MS analysis of Fusarium mycotoxins, fumonisins and deoxynivalenol | |
| CN102636581A (en) | Liquid chromatogram and fluorescence method for simultaneously detecting aflatoxin B1, ochratoxin A, zearalenone and citrinin in grains | |
| Daxenbichler et al. | Glucosinolates and derived products in cruciferous vegetables: gas-liquid chromatographic determination of the aglucon derivatives from cabbage | |
| CN109239248A (en) | The LC-Q-TOF detection method of Fipronil in egg and egg products | |
| Fan et al. | Simultaneous determination of pyraclostrobin, prochloraz, and its metabolite in apple and soil via RRLC-MS/MS | |
| Purcell et al. | Nodule gas exchange and water potential response to rapid imposition of water deficit | |
| CN112858542B (en) | Liquid chromatography mass spectrometry method for measuring atrazine, imidacloprid and metabolites thereof in leaves | |
| CN104502484B (en) | A kind of GC-NCI-MS measures the method that in fruits and vegetables, cyanogen insect amide is residual | |
| CN104535692B (en) | The LC-MS/MS assay method that in a kind of fruits and vegetables, four chlorantraniliproles are residual | |
| Tang et al. | Risk assessment of 369 pesticide residues in banana from Hainan province of China through UPLC-Q-TOF/MS | |
| Słowik-Borowiec et al. | QuEChERS-based methods for the determination of pesticide residues in a dill using gas chromatography with electron capture and nitrogen phosphorus detection | |
| Yan et al. | Simultaneous determination of nine pyrethroids in indoor insecticide products by capillary gas chromatography | |
| CN105954434A (en) | Method for detecting phenols spice | |
| Wang et al. | Analysis of the dissipation kinetics of thiophanate‐methyl and its metabolite carbendazim in apple leaves using a modified QuEChERS–UPLC–MS/MS method | |
| Hiemstra et al. | Determination of benzoylphenylurea insecticides in pome fruit and fruiting vegetables by liquid chromatography with diode array detection and residue data obtained in the Dutch national monitoring program | |
| Thornton | Determination of residues of Nemacur and its metabolites in plant and animal tissues | |
| ISHII et al. | A quantitative determination of 4-methylthio-3-butenyl glucosinolate in daikon (Raphanus sativus L.) roots by gas liquid chromatography | |
| CN104458968A (en) | GC-EI-MS (gas chromatography-electron impact ionization-mass spectrometry) measuring method of residual quantity of spirotetramat in fruit and vegetable | |
| Thornton et al. | Determination of residues of Metasystox-R and metabolite in plant and animal tissues and soil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190118 |