CN109187773A - The measuring method of diquat dibromide or paraquat residual quantity in a kind of food - Google Patents
The measuring method of diquat dibromide or paraquat residual quantity in a kind of food Download PDFInfo
- Publication number
- CN109187773A CN109187773A CN201810656041.4A CN201810656041A CN109187773A CN 109187773 A CN109187773 A CN 109187773A CN 201810656041 A CN201810656041 A CN 201810656041A CN 109187773 A CN109187773 A CN 109187773A
- Authority
- CN
- China
- Prior art keywords
- paraquat
- diquat dibromide
- food
- sample
- mentioned steps
- 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
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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 present invention relates to the measuring methods of diquat dibromide or paraquat residual quantity in a kind of food.Sample pre-treatments of the invention are the diquat dibromide or paraquat extracted first with methanol aqueous solution in food samples, reselection C18 and PSA dispersive solid-phase extraction agent purifies extracting solution, high performance liquid chromatography-Quadrupole-time of flight mass spectrometry is finally combined, the qualitative and quantitative determination for remaining diquat dibromide or paraquat in food is realized by the accurate mass number of compound ions.Diquat dibromide in food or the matrix interference in paraquat residue detection is effectively reduced in the present invention, the rate of recovery of diquat dibromide or paraquat is up to 80.8%~97.3%, relative standard deviation is 3.5%~7.8%, quantitatively it is limited to 10 μ g/kg, its easy to operate, quick, accurate, high sensitivity and reproducible advantage are supplement and improvement to existing QuEChERS method.
Description
Technical field
The invention belongs to the determination techniques field of persticide residue, diquat dibromide or hundred grass in a kind of food are related in particular to
The measuring method of withered residual quantity.
Background technique
During the crop plantings such as water fruits and vegetables, Cereals, farmland weed generates crop yield and quality important
It influences.The use of herbicide in agricultural production not only saves a large amount of heavy weeding manual labors and weeding by machine's operation,
It is prior be the reduction of because of crop smothering caused by agricultural output and quality loss, obtain considerable economic benefit.But with
The concern of the food-safe problem of people, herbicide residue also receive much attention to the harm of human health.Such as belong to medium poison
The diquat dibromide or paraquat (diquat) chemical name 1,1 of property herbicide,-ethylene -4,4,-bipyridine cation belong to organic heterocyclic
Class nonselective herbicide.Be widely used in the crops such as potato, cotton, soybean, corn, sorghum, flax, sunflower urge it is withered, when
Remnants green portion and weeds are dried-up rapidly when crop maturity, can gather in ahead of time;Prevent and kill off for farmland weed: summer corn is no-tillage
Weeding, orchard weed growth animated period carry out weeds foliar treatment.Since it is to skin and the irritating effect of eyes.China, beauty
State, European Union and Japan and other countries have formulated residue limits standard to diquat dibromide or paraquat, more in water fruits and vegetables, fish, meat etc.
0.05~2mg/kg of maximum residue limit in kind food.Obviously with the popularization and use of diquat dibromide or paraquat, food is established
The detection method of diquat dibromide or paraquat residual quantity tool has very important significance in product.
The Sample Pretreatment Technique that existing QuEChERS method is got up as new development, be represent it is quick, simple, inexpensive,
Efficiently, stable and safety (Quick, Easy, Cheap, Effective, Rugged, Safe) sample-pretreating method.Have
The advantages that rate of recovery is high, and analysis pesticide range is wide, and processing speed is fast, and solvent usage amount is few, easy to operate.The world is recognized extensively at present
The AOAC 2007.01 of EN15662 and Official US's analytical chemistry Shi Xiehui that workable QuEChERS method has European Union to formulate
Standard method.Above-mentioned 2 methods are slightly different, but principle is identical, all include extract, 2 steps of purification: 1 with acetonitrile or contains
The acetonitrile of 1% acetic acid extracts sample, carries out water phase where salting-out extraction realizes acetonitrile and sample by the way that buffering salt mixture is added
Liquid-liquid separation;2 use dispersive solid-phase extraction agent and anhydrous magnesium sulfate to solution purification is extracted, and dispersive solid-phase extraction agent is according to sample
PSA, GCB, C18EC etc. may be selected in the property of product matrix and untested compound.But it all must be added to anhydrous magnesium sulfate divided by going
Remaining moisture in middle acetonitrile.But diquat dibromide or paraquat belong to highly polar quaternary ammonium compound, are highly soluble in water, hardly possible
To be extracted from water phase with acetonitrile, therefore sample pre-treatments can not be carried out using original QuEChERS method.Usual diquat dibromide or
Paraquat pre-treatment uses Solid Phase Extraction column purification, but method is more complex, and the rate of recovery is low, more demanding to operator;Or
Not purified direct detection, matrix interference is big, serious to instrumental pollution.Therefore seek and establishes adaptation diquat dibromide or paraquat it is residual
Staying the QuEChERS pre-treating method of detection is very important.
Summary of the invention
The object of the present invention is to provide the measuring methods of diquat dibromide or paraquat residual quantity in a kind of food, existing to make up
The deficiency of technology.
It is a further object of the present invention to provide a kind of sample-pretreating method, with make up the existing world be widely recognized as using
QuEChERS method is not used to the deficiency of diquat dibromide or paraquat residue detection.
Sample pre-treatments of the invention are the supplement and improvement to existing QuEChERS method, due to diquat dibromide or paraquat
It is highly soluble in the characteristic of water, causes existing QuEChERS method acetonitrile or the acetonitrile containing 1% the acetic acid salting-out extraction from water phase
Extraction diquat dibromide or the method for paraquat can not be practical, the present invention select methanol aqueous solution be Extraction solvent from sample directly
It extracts, ensure that the extraction efficiency of diquat dibromide or paraquat.It is existing because Extraction solvent is mainly water in purifying step
Anhydrous magnesium sulfate is added divided by the method for residual moisture in removal extracting solution and infeasible in method, therefore dispersion is used only in the present invention
Solid extracting agent purifies extracting solution, and is added without anhydrous magnesium sulfate, and dispersive solid-phase extraction agent can only select C18 and
PSA。
Therefore, diquat dibromide of the invention or paraquat sample detection, pre-treatment are to be extracted to eat first with methanol aqueous solution
Then diquat dibromide in product sample selects the agent of C18 and PSA dispersive solid-phase extraction to purify extracting solution, finally combine efficient
Liquid chromatogram-Quadrupole-time of flight mass spectrometry (LC-Q TOF) realizes food by the accurate mass number of compound ions
The accurate qualitative and quantitative analysis of middle residual diquat dibromide or paraquat.
Measuring method of the invention includes the following steps:
(1) it extracts
The food samples to homogenize are weighed in tool plug plastic centrifuge tube, adds methanol aqueous solution vortex oscillation, is centrifuged;
(2) it purifies
The supernatant of above-mentioned steps (1) acquisition is pipetted in plastic centrifuge tube, Dispersive solid phase extraction agent is added, is vortexed
Oscillation, centrifugation, Aspirate supernatant cross 0.22 μm of filter membrane, and gained sample liquid is to be determined;
(3) extraction standard working solution is prepared
Blank sample is handled by above-mentioned steps (1), (2), with the blank sample matrix solution in 10~1000 μ g/L models
Enclose interior preparation diquat dibromide or paraquat series of concentrations standard working solution;
(4) liquid chromatogram -- Quadrupole-time of flight mass spectrometry (LC-Q TOF) measurement
A) it quantitative determines: each concentration extraction standard working solution in step (3) being subjected to LC-Q TOF measurement, with each concentration
The chromatographic peak area of extraction standard working solution carries out regression analysis to its respective concentration, obtains standard working curve;In identical item
The sample liquid injection LC-Q TOF that step (2) obtains is measured under part, measures the color of diquat dibromide or paraquat in sample liquid
Spectral peak area substitutes into standard curve, obtains diquat dibromide or paraquat content in sample liquid, then the sample according to representated by sample liquid
Mass Calculation obtain diquat dibromide or paraquat residual quantity in sample.
B) qualitative determination: target compound in the sample liquid that detecting step (2) obtains, if its quasi-molecular ion chromatographic peak is protected
Stay the time consistent with extraction standard working solution;And target compound in its exact mass number extraction standard solution suitable with concentration
Exact mass number relative standard deviation be no more than 5ppm when, then judge that there are diquat dibromide or paraquats in the sample;On if
Stating two conditions cannot meet simultaneously, then judgement is free of diquat dibromide or paraquat.
The volumetric concentration of preferred methanol aqueous solution is 20% in above-mentioned steps (2).
Above-mentioned steps (2) mesostroma dispersive solid-phase extraction agent is made of C18 and PSA, C18 and PSA in every milliliter of extracting solution
Additional amount is respectively 50mg.
The mobile phase of liquid chromatogram is A: methanol and Mobile phase B in above-mentioned steps (4): containing 0.1% formic acid -5mmol/L first
Sour aqueous ammonium, using A:B volume ratio 20:80 isocratic elution, flow velocity: 0.2mL/min.
The chromatographic column of liquid chromatogram is hydrophilic chromatographic column (HILIC) in above-mentioned steps (4).
Mass Spectrometer Method uses electrospray ionization source (ESI) positive ion mode in above-mentioned steps (4), and capillary voltage is+4000V,
Atomization gas pressure is 275.8kPa, and dry gas is nitrogen, and dry temperature degree is 350 DEG C, and dry gas stream speed is 10.0L/min, ginseng
Than ion m/z121.050873 and m/z922.009798, scanning range 50-1100m/z.
Mass Spectrometer Method uses level-one full scan mode, the standard of diquat dibromide or paraquat quasi-molecular ion in above-mentioned steps (4)
True molecular weight 184.3322.
The vortex oscillation time in above-mentioned steps (1) and (2) is 1min.
Centrifugation 5000r/min in above-mentioned steps (1) and (2), 3~5min of centrifugation time.
The container including centrifuge tube that sample touches in above-mentioned steps (1)~(4) should be plastic material and be made.
The beneficial effects of the present invention are:
Diquat dibromide in food or the matrix interference in paraquat residue detection can be effectively reduced in the present invention, by this pre-treatment side
Method combination HPLC-Q TOF is applied to diquat dibromide or the qualitative confirmation of paraquat and quantitative detection in food.The present invention has operation letter
Just, quickly, accurately, high sensitivity and reproducible advantage, be the supplement and improvement to existing QuEChERS method.It is entirely capable of
Meet China and European Union, the U.S., Japan to the technical requirements of corresponding product safety detection, will be guarantee our people's food safety
And export abroad trade develops in a healthy way and provides strong technical support.
Specific embodiment
Now with following embodiment, the present invention will be described in detail, but is not to limit the scope of the invention.
Instrument and reagent used in the embodiment of the present invention:
T18Basic homogenizer (IKA, Germany);III type high speed freezing centrifuge (Hitachi, Japan) of CR21G;
MS3 type vortex mixer (IKA, Germany);- 6520 level four bars flight time mass spectrum of 1200 high performance liquid chromatography
(Agilent, USA);PSA dispersive solid-phase extraction agent (Agilent, USA);C18 dispersive solid-phase extraction agent (Agilent, USA).
Reagent: methanol (HPLC grades, Merke, Germany);Ammonium formate (HPLC grades, CNW, Germany);Formic acid (HPLC
Grade, CNW, Germany).
Diquat dibromide or paraquat standard substance: purity 99.0% is purchased from Dr Ehrenstorfer company of Germany.
Embodiment 1: the detection of diquat dibromide or paraquat residual quantity in apple
(1) sample pre-treatments
It weighs the apple sample 10.0g to homogenize to have in plug plastic centrifuge tube in 50mL, 10mL volumetric concentration 20% is added
Methanol aqueous solution, vortex 1min, 5000r/min are centrifuged 5min.After centrifugation, take 2mL supernatant extracting solution to being equipped with 100mg
In the centrifuge tube of C18 and 100mg PSA, vortex 1min, 5000r/min are centrifuged 3min.After taking supernatant to cross 0.22 μm of filter membrane,
Gained sample liquid is measured for liquid chromatogram-Quadrupole-time of flight mass spectrometry (LC-Q TOF).
(2) preparation of standard working solution
25 ± 0.1mg standard items are weighed in 25mL plastics volumetric flask, are dissolved with acetonitrile, constant volume obtains 1000.0 μ g/mL mark
Quasi- stock solution;It pipettes 1.0mL standard reserving solution to be placed in 100mL plastics volumetric flask, obtains 10.0 μ g/mL mark with acetonitrile constant volume
Quasi- intermediate fluid;
It uses and is detected the apple without diquat dibromide or paraquat as blank sample, prepared by above-mentioned pre-treatment step empty
The dilution of standard intermediate fluid vehicle solution is configured to 10,20,50,100,200,500,1000ng/mL by white matrix solution
Serial extraction standard working solution.
(3) liquid chromatogram-Quadrupole-time of flight mass spectrometry (LC-Q TOF) measures
Quantitative determination: each concentration extraction standard working solution in step (3) is subjected to LC-Q TOF measurement, with each concentration base
The chromatographic peak area of matter standard working solution carries out regression analysis to its respective concentration, obtains standard working curve;In the same terms
The lower sample liquid injection LC-Q TOF for obtaining step (2) is measured, and measures the chromatography of diquat dibromide or paraquat in sample liquid
Peak area substitutes into standard curve, obtains diquat dibromide or paraquat content in sample liquid, then the sample according to representated by sample liquid
Mass Calculation obtains diquat dibromide residual quantity in sample.
Wherein chromatographic condition are as follows: and BEH HILIC chromatographic column (2.1mm × 100mm, 1.7 μm;U.S. Waters);Mobile phase:
Methanol and contain 0.1% formic acid -5mmol/L ammonium formate water, with volume ratio 20:80 isocratic elution;Flow velocity: 0.2mL/min;Column temperature:
30℃;Sample volume: 2 μ L.
Wherein mass spectrometry parameters are as follows: electrospray ionization source (ESI) positive ion mode scanning;Dry 350 DEG C of temperature degree, dry gas stream speed
10L/min, atomization gas pressure 275.8kPa, capillary voltage 4kV, capillary outlet voltage 190V, scanning mode: level-one is swept entirely
It retouches, reference ion m/z121.050873 and m/z922.009798, scanning range 50-1100m/z.
Qualitative Identification: target compound in the sample liquid that detecting step (2) obtains, if its quasi-molecular ion chromatographic peak retains
Time is consistent with extraction standard working solution;And target compound in its exact mass number extraction standard solution suitable with concentration
When the relative standard deviation of exact mass number is no more than 5ppm, then judge that there are diquat dibromide or paraquats in the sample;If above-mentioned
Two conditions cannot meet simultaneously, then judgement is free of diquat dibromide or paraquat.
Standard working curve and detection limit:
Regression analysis is carried out to its respective concentration with the chromatographic peak area of extraction standard working solution, it is bent to obtain standard work
Line.Using testing concentration in the corresponding sample of 3 times of signal-to-noise ratio (S/N) as detection limit (LOD), 10 times of signal-to-noise ratio (S/N) are corresponding
Sample in testing concentration as quantitative limit (LOQ), obtain the detection limit and quantitative limit of each determinand.The results show that related
Coefficient is greater than 0.999, and quantitative limit and detection limit are respectively 10 μ g/kg and 5 μ g/kg.
Recovery of standard addition and repeatability:
It uses and is detected the apple without diquat dibromide or paraquat as blank sample, low middle high various concentration level is added
Diquat dibromide or paraquat standard solution press the progress determination of residual amount of above-mentioned processing step after adding 30min, will measurement concentration and agriculture
Pharmacology opinion addition concentration is compared, and obtains pesticide TIANZHU XINGNAO Capsul, and each pitch-based sphere is measured in parallel 6 times, obtains its opposite mark
Quasi- deviation.In 3 mark-on levels, the rate of recovery 80.8%~97.3% of diquat dibromide or paraquat, relative standard deviation (RSD)
It is 3.5%~7.8%, illustrates that the rate of recovery of the method for the present invention is higher, it is reproducible.
Obviously, the present invention can overcome the disadvantages that diquat dibromide in the prior art or paraquat residue detection are not available QuEChERS method
The technological deficiency of pre-treatment improves the sensitivity of LC-Q TOF detection, realizes that diquat dibromide or paraquat are remaining accurate in food
Analysis.
Above embodiment is only that preferred embodiments of the present invention will be described, is not carried out to the scope of the present invention
It limits, without departing from the spirit of the design of the present invention, this field ordinary skill technology makes technical solution of the present invention
All variations and modifications, claim of the invention should all be fallen into.
Claims (5)
1. the measuring method of diquat dibromide or paraquat residual quantity in a kind of food, it is characterised in that include the following steps:
(1) it extracts
The food samples to homogenize are weighed in tool plug plastic centrifuge tube, adds methanol aqueous solution vortex oscillation, is centrifuged;
(2) it purifies
The supernatant of above-mentioned steps (1) acquisition is pipetted in plastic centrifuge tube, Dispersive solid phase extraction agent is added, be vortexed vibration
It swings, is centrifuged, Aspirate supernatant crosses 0.22 μm of filter membrane, and gained sample liquid is to be determined;
(3) extraction standard working solution is prepared
Blank sample is handled by above-mentioned steps (1), (2), with the blank sample matrix solution within the scope of 10~1000 μ g/L
Prepare diquat dibromide or paraquat series of concentrations standard working solution;
(4) liquid chromatogram -- Quadrupole-time of flight mass spectrometry (LC-Q TOF) measurement
A) it quantitative determines: each concentration extraction standard working solution in step (3) being subjected to LC-Q TOF measurement, with each concentration matrix
The chromatographic peak area of standard working solution carries out regression analysis to its respective concentration, obtains standard working curve;Under the same conditions
The sample liquid injection LC-Q TOF that step (2) obtains is measured, the chromatographic peak of diquat dibromide or paraquat in sample liquid is measured
Area substitutes into standard curve, obtains diquat dibromide or paraquat content in sample liquid, then the matter of the sample according to representated by sample liquid
Diquat dibromide or paraquat residual quantity in sample is calculated in amount;
B) qualitative determination: target compound in the sample liquid that detecting step (2) obtains, if its quasi-molecular ion chromatographic peak retains
Between it is consistent with extraction standard working solution;And in its exact mass number extraction standard solution suitable with concentration target compound standard
When the relative standard deviation of true mass number is no more than limit value, then judge that there are diquat dibromide or paraquats in the sample;If above-mentioned
Two conditions cannot meet simultaneously, then judgement is free of diquat dibromide or paraquat;
Above-mentioned steps (2) mesostroma dispersive solid-phase extraction agent is made of C18 and PSA, and C18 and PSA is added in every milliliter of extracting solution
Amount is respectively 50mg;
The volumetric concentration of methanol aqueous solution is 20% in above-mentioned steps (1);
The mobile phase of liquid chromatogram is A: methanol and Mobile phase B in above-mentioned steps (4): containing 0.1% formic acid -5mmol/L ammonium formate
Aqueous solution, using A:B volume ratio 20:80 isocratic elution, flow velocity: 0.2mL/min;
The chromatographic column of liquid chromatogram is hydrophilic chromatographic column in above-mentioned steps (4);
Mass Spectrometer Method uses electrospray ionization source (ESI) positive ion mode in above-mentioned steps (4), and capillary voltage is+4000V, atomization
Atmospheric pressure is 275.8kPa, and dry gas is nitrogen, and dry temperature degree is 350 DEG C, and dry gas stream speed is 10.0L/min, reference from
Sub- m/z121.050873 and m/z922.009798, scanning range 50-1100m/z.
2. the measuring method of diquat dibromide or paraquat residual quantity in food as described in claim 1, it is characterized in that above-mentioned steps
(4) Mass Spectrometer Method uses level-one full scan mode in, and the accurate molecular masses of diquat dibromide or paraquat quasi-molecular ion are
184.3322。
3. the measuring method of diquat dibromide or paraquat residual quantity in food as described in claim 1, it is characterized in that above-mentioned steps
(1) the vortex oscillation time and in (2) is 1min.
4. the measuring method of diquat dibromide or paraquat residual quantity in food as described in claim 1, it is characterized in that above-mentioned steps
(1) the centrifugation 5000r/min and in (2), centrifugation time 3-5min.
5. the measuring method of diquat dibromide or paraquat residual quantity in food as described in claim 1, it is characterized in that above-mentioned steps
(1) container including centrifuge tube that sample touches in~(4) should be plastic material and be made.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810656041.4A CN109187773A (en) | 2018-06-23 | 2018-06-23 | The measuring method of diquat dibromide or paraquat residual quantity in a kind of food |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810656041.4A CN109187773A (en) | 2018-06-23 | 2018-06-23 | The measuring method of diquat dibromide or paraquat residual quantity in a kind of food |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109187773A true CN109187773A (en) | 2019-01-11 |
Family
ID=64948453
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810656041.4A Pending CN109187773A (en) | 2018-06-23 | 2018-06-23 | The measuring method of diquat dibromide or paraquat residual quantity in a kind of food |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109187773A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109959737A (en) * | 2019-04-10 | 2019-07-02 | 珠海天祥粤澳质量技术服务有限公司 | The detection method of paraquat in traditional Chinese medicinal material raw materials |
CN112730372A (en) * | 2020-11-26 | 2021-04-30 | 中国科学院合肥物质科学研究院 | Flexible surface enhanced Raman substrate, preparation method thereof and paraquat detection method |
CN114609284A (en) * | 2022-03-16 | 2022-06-10 | 广东工业大学 | Screening and verifying method of occupational combined pollution exposure biomarker based on human urine |
-
2018
- 2018-06-23 CN CN201810656041.4A patent/CN109187773A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109959737A (en) * | 2019-04-10 | 2019-07-02 | 珠海天祥粤澳质量技术服务有限公司 | The detection method of paraquat in traditional Chinese medicinal material raw materials |
CN112730372A (en) * | 2020-11-26 | 2021-04-30 | 中国科学院合肥物质科学研究院 | Flexible surface enhanced Raman substrate, preparation method thereof and paraquat detection method |
CN114609284A (en) * | 2022-03-16 | 2022-06-10 | 广东工业大学 | Screening and verifying method of occupational combined pollution exposure biomarker based on human urine |
CN114609284B (en) * | 2022-03-16 | 2023-06-02 | 广东工业大学 | Screening and verifying method of occupational composite pollution exposure biomarker based on human urine |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103822995B (en) | Determination method of residual amount of glufosinate, glyphosate and aminomethyl phosphoric acid in food | |
CN106053703A (en) | Method of detecting various plant growth regulators in foods at same time | |
CN105842357B (en) | Detect the method for dinotefuran and its metabolin UF, DN residual quantity in Cereals simultaneously | |
CN109187773A (en) | The measuring method of diquat dibromide or paraquat residual quantity in a kind of food | |
CN103822994B (en) | Method for measuring residual quantity of paraquat and diquat in food | |
CN110146616A (en) | The remaining detection method of pesticide in a kind of rice, rice stem | |
CN106153770A (en) | A kind of Solid-Phase Extraction liquid chromatography mass detection method of aquatic products glyphosate | |
CN109655570A (en) | The measuring method of prothioconazoles residual quantity in a kind of food | |
CN103837388A (en) | Pretreatment method for strong-polarity pesticide residue detection | |
CN104502515B (en) | A kind of LC-MS/MS assay method of four chlorantraniliprole residual quantities | |
CN104237414A (en) | Method for simultaneously detecting various preservatives remaining in orange with liquid chromatograph/mass spectrometer | |
CN103869038B (en) | The assay method of paraquat residual quantity in a kind of food | |
Aharonson et al. | Determination of residues of benomyl, its hydrolysis product, and thiabendazole in various crops | |
CN107462640A (en) | The method for determining breeding water Malachite Green and crystal violet residual quantity simultaneously | |
CN108535369A (en) | A kind of method of polybenzobisoxazole humulone residual quantity in detection wheat planting | |
CN107907606A (en) | The method of a variety of herbicides in a kind of while quick detection soil | |
CN106404958A (en) | Method for quickly detecting contents of plant growth regulators in vegetables | |
CN104730191B (en) | A kind of LC-MS/MS assay method of fluorine ether bacterium amide residual quantity | |
CN103123345A (en) | Method for rapidly detecting phenoxyacetic acid herbicide in soil | |
CN109459524A (en) | It is a kind of while measuring 6 kinds of pyrethroid pesticide remained methods in birds, beasts and eggs | |
CN104458968B (en) | The GC-EI-MS assay method of spiral shell worm ethyl ester residual quantity in a kind of fruits and vegetables | |
CN110988243A (en) | Ion chromatography-mass spectrometry detection method for glyphosate content in fruits | |
CN103217498A (en) | Method for detecting dicyandiamide in milk powder with LC-MS (liquid chromatography/mass spectrometry) and sample preparation method | |
CN113960197B (en) | Method for determining 39 pesticide residues in soil or sediment | |
CN105181870A (en) | Method for determining hymexazol residues in vegetables and fruits |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190111 |