CN107907606A - The method of a variety of herbicides in a kind of while quick detection soil - Google Patents
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- CN107907606A CN107907606A CN201711089432.4A CN201711089432A CN107907606A CN 107907606 A CN107907606 A CN 107907606A CN 201711089432 A CN201711089432 A CN 201711089432A CN 107907606 A CN107907606 A CN 107907606A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention belongs to Pesticides Testing technical field, and the method for specifically providing a variety of herbicides in a kind of while quick detection soil, includes the following steps：Pedotheque and diatomite are weighed respectively, is added to after mixing in abstraction pool and carries out static extracting, obtain liquid to be clean；Wherein, using acetonitrile extraction solvent；Pipette liquid to be clean be placed in advance added with PSA, C18, anhydrous MgSO4 centrifuge tube in, vortex oscillation uniformly centrifuges afterwards, take supernatant liquor add ultra-pure water, then through 0.22 μm of organic membrane filtration, obtain prepare liquid；The prepare liquid obtained in step 2 is measured using superelevation liquid chromatogram triple level Four bar compounded linear ion trap mass spectrometries.Method provided by the invention, rate of extraction is fast, solvent consumption is few, extraction efficiency is high；Compensate for the residual MRM scan mode appearances in high selection of triple level Four bar instrument low content agricultures, but can not be got well second order ms figure the defects of, quickly solve the false positive issue of complex sample.
Description
Technical field
The present invention relates to Pesticides Testing technical field, and in particular to a variety of herbicides in a kind of while quick detection soil
Method.
Background technology
Not only species is more for farmland weed, density is big, the rapid harm of sprawling is serious, but also effects a radical cure very difficult, is always resistance
An important factor for hindering agriculture fast development.Since starting to apply farmland Application of Herbicides, to controlling Farmland weed, ensure
Higher yield of crops has played important function.But in the application process of herbicide, medicament also gets over the pollution problem in soil
More to protrude.One side Pesticide Residue in Soil, which remains, happens occasionally the drug injury problem of succession crop, such as milpa herbicide is such as
Improper use, still has poisoning to lower stubble wheat, and the green sulphur of highy potent herbicide used in wheatland is grand, though dosage is seldom, to lower stubble
The plant growths such as corn, rape, soybean and rice all have an impact；On the other hand, pesticide residue can also pass through contaminated soil and ground
Table water causes to seriously endanger hence into the food chain of the mankind to health.
It is a hot issue in current environment research that the research and application of herbicide and returning, which becomes, and at present, herbicide is in soil
The method of retention analysis has capillary electrophoresis CE, gas chromatography (GC), high performance liquid chromatography (HPLC), gas phase color in earth
Spectrum-mass spectrography (GC-MS), Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) etc., these methods respectively have an advantage and disadvantage, CE methods for
Though water sample analysis are with the deficiencies of certain advantage, Existing detector is single, method narrow application range；GC and HPLC detections
As a result there is a possibility that false positive is larger, it is in insufficient present on sensitivity and selectivity, the weeding for causing it to be measured
Agent species is limited；GC-MS, (LC-MS/MS) have certain advantage compared to GC and HPLC in sensitivity and selectivity, but by
Mostly relatively strong in the water solubility of herbicide, the polarity of pesticide is also relatively strong, and the herbicide that GC-MS can be analyzed is also limited, side
The detection limit of method can not completely arrive at the requirement of residue limits.LC-MS/MS is during the actual examination of pesticide examination, and one
As to be often regarded as pesticide ion pair " appearance " be to detect, be positive findings, but during atual detection due to matrix
It is complicated and disturb larger, false positive phenomenon often occurs, and then influence screening results correctness and examination report it is rigorous
Property.
The content of the invention
The defects of the purpose of the present invention is overcoming the prior art, there is provided a variety of herbicides in a kind of while quick detection soil
Method, using Accelerate solvent extraction technology extract soil in herbicide, rate of extraction is fast, solvent consumption is few, extraction efficiency is high,
The degree of automation is high, substantially reduces experimentation cost；With advantages such as high selectivity, high sensitivity, high throughputs, can quickly examine
Survey herbicide residual in soil.
For this reason, the present invention provides the method for a variety of herbicides in a kind of while quick detection soil, include the following steps：
Step 1：Pedotheque and diatomite are weighed respectively, are added to after mixing in abstraction pool and are carried out static extracting,
Obtain liquid to be clean；Wherein, using acetonitrile extraction solvent；
It there may exist the accumulation of sample in extraction process, so that extraction yield is reduced, therefore before extraction, using diatomite
Dispersed processing, to improve extraction yield.
Step 2：Pipette liquid to be clean be placed in advance added with PSA, C18, anhydrous MgSO4 centrifuge tube in, vortex oscillation is equal
Centrifugation after even, takes supernatant liquor to add ultra-pure water, then through 0.22 μm of organic membrane filtration, obtains prepare liquid；Add ultrapure
Water can improve mass spectrographic Ionization Efficiency during subsequent measurements.PSA is Medical PSA, can remove organic acid, pigment
With metal ion etc., improve clean-up effect.
Step 3：Using superelevation liquid chromatogram-triple level Four bar compounded linear ion trap mass spectrometry to obtained in step 2
Prepare liquid be measured.
Further, the step 1 is specially：1g pedotheques are weighed, 2g diatomite, adds 11ml's after mixing
In abstraction pool, static extracting is carried out by extractant of acetonitrile；
After static extracting, abstraction pool is eluted with 40% extractant equivalent to extraction pool volume, is then purged with nitrogen
100S, collects the extract after static extracting；Extract is settled to 10mL with acetonitrile, obtains liquid to be clean.
Elution be abstraction instrument after extraction, can be with the process of the clean extractant of certain volume elution sample
Realize between cycle-index with the extract in clean extractant displacement abstraction pool, improve extraction yield.
Nitrogen purging is that all extracts in flow path are purged in receiving flask with nitrogen, so as to ensure that high extraction is returned
Yield.
Further, the extraction conditions is：120 DEG C of extraction temperature, extracting pressure 10MPa, heating time 300s；It is static
Cycling extraction 2 times, each static extracting time 600s；
Further, the step 2 is specially：Pipette liquid 1mL to be clean be placed in advance added with 50mg PSA, 50mgC18,
In the 2mL centrifuge tubes of the anhydrous MgSO4 of 150mg, 2000r/min vortexs 2min, 5000r/min centrifugation 5min, takes supernatant liquor
0.5mL adds 0.5mL ultra-pure waters, then through 0.22 μm of organic membrane filtration, obtains prepare liquid.
Further, the step 3 is specially：
(1) a variety of herbicides are selected and determines the Mass Spectrometry Conditions of herbicide；
(2) the hybrid standard working solution of selected a variety of herbicides is prepared；
(3) analyzed with UPLC-Q-TRAP/MS methods, then using each herbicide concentration as abscissa, corresponding chromatographic peak
Area is ordinate, draws the standard working curve of every kind of herbicide；
(4) prepare liquid is injected in UPLC-Q-TRAP/MS systems, using MRM-IDA-EPI scan patterns, according to two pairs
MRM ion pairs, retention time and EPI library searchings determine herbicide species, and its peak area is brought into the mark of corresponding herbicide
Quasi- working curve, so as to obtain selected each weeding agent content in prepare liquid.
Further, the hybrid standard working solution of the selected a variety of herbicides of preparation is：100 μ L are pipetted respectively
And concentration be the herbicide standard solution of 100 μ g/mL in same 10mL volumetric flasks, with methanol dilution constant volume, with being made
To the hybrid standard working solution of a variety of herbicides, preserved at -18 DEG C.
Further, the hybrid standard working solution for preparing selected a variety of herbicides further comprises：With sky
Carclazyte earth sample substrate liquid is solvent, and by the solution after methanol dilution constant volume, it is molten to prepare hybrid standard work for dilution step by step
Liquid, its mass concentration are respectively 0.5,1,5,10,50,100 μ g/L.
Further, superelevation liquid chromatogram-triple level Four bar compounded linear ion trap mass spectrometry condition in the step 3
For：Using Kinetex SB-C18Chromatographic column, specification are 100 × 2.1mm, 1.7 μm；Column temperature：40℃；Sample size：3μL；A flows
It is mutually 0.1% formic acid solution, B mobile phases are methanol；
Gradient elution, the gradient elution program are as follows：0-10min, 50%-100%B；10.1-15min 100%-
100%B；15.1-20min 50%B；
Ionization pattern：Electron spray negative ions scan at the same time；Monitoring mode：MRM-IDA-EPI；Ionizing voltage：Holotype
Formula+5.5KV, negative mode -4.5KV；Gas curtain atmospheric pressure 241kPa；Atomization temperature：550℃；Atomization gas pressure：379kPai；Auxiliary
Atmospheric pressure：414kPa.
Further, pedotheque and diatomaceous mass ratio are 1: 2 in the step 1.
Beneficial effects of the present invention：The method of a variety of herbicides in provided by the invention this while quick detection soil,
Herbicide in soil is extracted using Accelerate solvent extraction technology, rate of extraction is fast, solvent consumption is few, extraction efficiency is high, automation
Degree is high, substantially reduces experimentation cost；Using superelevation liquid chromatogram-triple level Four bar compounded linear ion trap mass spectrometry technology
MRM-IDA-EPI scan modes, compared with traditional MRM scan modes, that is, completing the examination of herbicide can confirm respectively again
Herbicide residual, compensate for the residual MRM scan mode appearances in high selection of triple level Four bar instrument low content agricultures, but can not obtain
The defects of second order ms figure got well, quickly solve the false positive issue of complex sample.
Embodiment
With reference to embodiment, the present invention is furture elucidated.
Embodiment 1：
The method for present embodiments providing a variety of herbicides in a kind of while quick detection soil, used instrument and examination
Agent is：
AB SCIEX 5500Mass spectrometer system (American AB company), Shimadz μ LC-30A system (Japanese Shimadzus
Company), full-automatic pressurized liquid extraction instrument APLE-2000 (Beijing Jitian Instrument Co., Ltd.), vortex vortex mixer (German IKA
Company).
Acetonitrile, methanol：Chromatographic grade, Thermo Fischer Scient Inc.；Formic acid：Chromatographic grade, Shanghai Mike's woods biochemical technology have
Limit company；Butachlor, pyrazosulfuron, bensulfuron-methyl, dimethyl tetrachloride, bentazone, bispyribac-sodium, penoxsuam, Acetochlor, the third grass
Amine, mefenacet, Evil humulones, neburea, pendimethalin, benthiocarb, isopropyl methoxalamine, cyhalofop-butyl, symetryne, Sha barnyard grass
Phosphorus, Atrazine, nicosulfuron, prometryn, metribuzin, Zhong Dingtong, chloroxifenidium, ametryn：Mass concentration is 100 μ g/mL, pure
Spend >=99%, State Standard Matter Research Centre；Pedotheque picks up from multiple counties and cities of Jilin Province.
Include the following steps：
Step 1：1g pedotheques are weighed, 2g diatomite, adds in the abstraction pool of 11ml using acetonitrile as extraction after mixing
Solvent is taken to carry out static extracting；After static extracting, abstraction pool is eluted with 40% extractant equivalent to extraction pool volume, then
100S is purged with nitrogen, collects the extract after static extracting；Extract is settled to 10mL with acetonitrile, obtains liquid to be clean.
The extraction conditions is：120 DEG C of extraction temperature, extracting pressure 10MPa, heating time 300s；Quiet cycle extraction 2 times, every time
Static extracting time 600s；
Step 2：Liquid 1mL to be clean is pipetted to be placed in advance added with 50mg PSA, the 2mL of the anhydrous MgSO4 of 50mgC18,150mg
In centrifuge tube, 2000r/min vortexs 2min, 5000r/min centrifugation 5min, takes supernatant liquor 0.5mL to add 0.5mL ultra-pure waters,
Then through 0.22 μm of organic membrane filtration, prepare liquid is obtained.
Step 3：Using superelevation liquid chromatogram-triple level Four bar compounded linear ion trap mass spectrometry to obtained in step 2
Prepare liquid be measured.Specially：
(1) a variety of herbicides are selected and determines the Mass Spectrometry Conditions of herbicide；
The herbicide species used in agricultural production is very much, and the present invention establishes weeding in general quick measure soil
The remaining detection method of agent, have selected the investigation that common 25 kinds of herbicides are used for this method.In order to obtain the selectivity of higher
And sensitivity, this implementation is using herbicide standard solution to superelevation liquid chromatogram-triple level Four bar compounded linear ion trap mass spectrometry
Method analysis in herbicide qualitative, quantitative ion pair, go cluster voltage, collision energy to be optimized, the results are shown in Table 1.
Chromatographic condition is：Using Kinetex SB-C18Chromatographic column, specification are 100 × 2.1mm, 1.7 μm；A mobile phases are
0.1% formic acid solution, B mobile phases are methanol；Gradient elution.The gradient elution program is as follows：0-10min, 50%-100%
B；10.1-15min 100%-100%B；15.1-20min 50%B；Column temperature：40℃；Sample size：3μL.Mass Spectrometry Conditions are：Electricity
From pattern：Electron spray negative ions scan at the same time；Monitoring mode：MRM-IDA-EPI；Ionizing voltage：Holotype+5.5KV, bears
Pattern -4.5KV；Gas curtain atmospheric pressure 241kPa；Atomization temperature：550℃；Atomization gas pressure：379kPai；Assist gas pressure power：
414kPa。
(2) the hybrid standard working solution of selected a variety of herbicides is prepared；
In superelevation liquid chromatogram-triple level Four bar compounded linear ion trap mass spectrometry, matrix effect can seriously affect point
Quantitative result is analysed, in order to avoid matrix effect, the present embodiment prepares serial hybrid standard working solution using bare substrate, specifically
Be：Pipette 100 μ L respectively and concentration be the herbicide standard solution of 100 μ g/mL in same 10mL volumetric flasks, use first
Alcohol dilutes constant volume, the storing solution that mass concentration is 1 μ g/mL is obtained, using blank pedotheque matrix liquid as solvent, by above-mentioned storing solution
Hybrid standard working solution is prepared in dilution step by step, is preserved at -18 DEG C, mass concentration is respectively 0.5,1,5,10,50,
100μg/L。
(3) each 3 μ L of hybrid standard working solution of 25 kinds of weeding solvents of prepared various concentrations are drawn, are injected into
In UPLC-Q-TRAP/MS systems, its respective concentration is compared with the chromatographic peak area of the herbicide standard working solution of concentration known
Linear regression analysis is carried out, wherein y represents the chromatographic peak area of corresponding herbicide, and x represents the concentration of herbicide, 25 kinds of herbicides
Linear equation be shown in Table 2.
(4) prepare liquid is injected in UPLC-Q-TRAP/MS systems, using MRM-IDA-EPI scan patterns, according to two pairs
MRM ion pairs, retention time and EPI library searchings determine specific herbicide, and its peak area is brought into the mark of corresponding herbicide
Quasi- working curve, so as to obtain each weeding agent content in prepare liquid.
Common herbicide is following 25 kinds in existing agricultural production：Butachlor, pyrazosulfuron, bensulfuron-methyl, diformazan four
Chlorine, bentazone, bispyribac-sodium, penoxsuam, Acetochlor, pretilachlor, mefenacet, Evil humulones, neburea, pendimethalin,
Benthiocarb, isopropyl methoxalamine, cyhalofop-butyl, symetryne, anilofos, Atrazine, nicosulfuron, prometryn, metribuzin, Zhong Ding
Logical, chloroxifenidium, ametryn.
1 25 kinds of herbicide mass spectrum acquisition parameters of table
Linear relationship, detection limit, the quantitative limit of 2 each herbicide of table
Embodiment 2
Actually should to quickly detect the method for a variety of herbicides in soil while verifying that above-described embodiment 1 provides
Feasibility in, the present embodiment investigate the parameters such as its detection limit, quantitative limit, recovery of standard addition, precision.Its
In, respectively with the detection limit and quantitative limit of 3 times of signal-to-noise ratio and 10 times calculating, 25 kinds of herbicides, it the results are shown in Table 2.
The standard solution of a certain amount of 25 kinds of herbicides is added in the pedotheque of blank, then extracts, measure, calculate
The rate of recovery, comes the precision of computational methods, same sample average measurement 6 times with the relative standard deviation (RSD) of the rate of recovery.To returning
The investigation of yield comprises the following steps that：
1) 1g blank pedotheques are weighed, add thereto low (2 μ g/kg), in (10 μ g/kg), three kinds of high (50 μ g/kg)
The hybrid standard working solution of 25 kinds of herbicides of concentration, then adds the abstraction pool that 2g diatomite adds 11ml after mixing
In, carry out static extracting by extractant of acetonitrile；After static extracting, drenched with 40% extractant equivalent to extraction pool volume
Abstraction pool is washed, then purges 100S with nitrogen, collects the extract after static extracting；Extract is settled to 10mL with acetonitrile,
Obtain liquid to be clean.The extraction conditions is：120 DEG C of extraction temperature, extracting pressure 10MPa, heating time 300s；Quiet cycle
Extraction 2 times, each static extracting time 600s；
2) liquid 1mL to be clean is pipetted to be placed in advance added with the 2mL centrifugations of 50mg PSA, the anhydrous MgSO4 of 50mgC18,150mg
In pipe, 2000r/min vortexs 2min, 5000r/min centrifugation 5min, takes supernatant liquor 0.5mL to add 0.5mL ultra-pure waters, then
Through 0.22 μm of organic membrane filtration, prepare liquid is obtained.
3) 2) middle gained prepare liquid is injected in UPLC-Q-TRAP/MS systems, using MRM-IDA-EPI scan patterns, root
Specific herbicide is determined according to two pairs of MRM ion pairs, retention time and EPI library searchings, and its peak area is brought into embodiment 1
The standard working curve of corresponding herbicide, so that the concentration of every kind of herbicide in prepare liquid is obtained, then with the concentration after calculating
Value divided by the concentration value of addition, you can to obtain the TIANZHU XINGNAO Capsul of herbicide.
The present embodiment provide method recovery of standard addition and precision it is as shown in table 3.As shown in Table 3, it is of the present invention
For the herbicide rate of recovery in method between 75.91%~103.84%, RSD is not more than 10.21%, illustrates that the present invention establishes
The method rate of recovery and precision are good.
3 recovery of standard addition of table and precision
For LC/MS/MS during the actual examination of pesticide examination, it is to examine generally to be often regarded as pesticide ion pair " appearance "
Go out, be positive findings, but often occur that false positive shows since the complexity of matrix and interference are larger during atual detection
As, and then influence the correctness of screening results and the preciseness of examination report.For this reason, we use MRM-IDA-EPI patterns, will
MRM conditions after optimization inspire mode as EPI, and initial setting IDA parameters, analyze 10g/L mixed standard solutions.Knot
Fruit shows, when CE values are 20 and 35eV, can obtain enough fragment ion information, and include fragments characteristic ion.Build at the same time
The EPI spectrums storehouse of vertical object, for library searching of positive when qualitative, aids in qualitative analysis.MRM passages collection at the same time
Signal still can be used for quantitative analysis, compared with common MRM patterns, since EPI spectrograms enhance secondary fragment ions full scan
Spectrogram, its high sensitivity is in quadrupole rod mass spectrum, and confirmatory information is more rich, and the signal of MRM passages collection can still be used as and quantify
The data of analysis.Thus can effectively Aided Trace level or detection limit concentration samples qualitative analysis, solve biography well
Quadrupole rod MRM patterns of uniting are to difficult existing for the qualitative detection of low concentration sample.
The foregoing examples are only illustrative of the present invention, does not form the limitation to protection scope of the present invention, all
It is to be belonged to the same or similar design of the present invention within protection scope of the present invention.
Claims (9)
1. the method for a variety of herbicides in a kind of while quick detection soil, it is characterised in that include the following steps：
Step 1：Pedotheque and diatomite are weighed respectively, is added to after mixing in abstraction pool and carries out static extracting, are obtained
Liquid to be clean；Wherein, using acetonitrile extraction solvent；
Step 2：Pipette liquid to be clean be placed in advance added with PSA, C18, anhydrous MgSO4 centrifuge tube in, after vortex oscillation is uniform
Centrifugation, takes supernatant liquor to add ultra-pure water, then through 0.22 μm of organic membrane filtration, obtains prepare liquid；
Step 3：Using superelevation liquid chromatogram-triple level Four bar compounded linear ion trap mass spectrometry to being treated obtained in step 2
Liquid is surveyed to be measured.
2. the method as described in claim 1, it is characterised in that the step 1 is specially：Weigh 1g pedotheques, 2g diatoms
Soil, adds in the abstraction pool of 11ml after mixing, and static extracting is carried out by extractant of acetonitrile；
After static extracting, abstraction pool is eluted with 40% extractant equivalent to extraction pool volume, then purges 100S with nitrogen,
Collect the extract after static extracting；Extract is settled to 10mL with acetonitrile, obtains liquid to be clean.
3. according to the method described in claim 2, it is characterized in that：The extraction conditions is：120 DEG C of extraction temperature, extraction pressure
Power 10MPa, heating time 300s；Quiet cycle extracts 2 times, each static extracting time 600s.
4. according to the method described in claim 3, it is characterized in that：The step 2 is specially：Liquid 1mL to be clean is pipetted to be placed in
In advance added with 50mg PSA, the anhydrous MgSO4 of 50mgC18,150mg 2mL centrifuge tubes in, 2000r/min vortexs 2min, 5000r/
Min centrifuges 5min, takes supernatant liquor 0.5mL to add 0.5mL ultra-pure waters, then through 0.22 μm of organic membrane filtration, is treated
Survey liquid.
5. the method according to claim 1 or 4, it is characterised in that the step 3 is specially：
(1) a variety of herbicides are selected and determines the Mass Spectrometry Conditions of herbicide；
(2) the hybrid standard working solution of selected a variety of herbicides is prepared；
(3) analyzed with UPLC-Q-TRAP/MS methods, then using each herbicide concentration as abscissa, corresponding chromatographic peak area
For ordinate, the standard working curve of every kind of herbicide is drawn；
(4) prepare liquid is injected in UPLC-Q-TRAP/MS systems, using MRM-IDA-EPI scan patterns, according to two couples of MRM from
Son determines, retention time and EPI library searchings herbicide species, and the standard that its peak area is brought into corresponding herbicide works
Curve, so as to obtain selected each weeding agent content in prepare liquid.
6. the according to the method described in claim 5, it is characterized in that, hybrid standard for preparing selected a variety of herbicides
Working solution is：Pipette 100 μ L respectively and concentration is the herbicide standard solution of 100 μ g/mL in same 10mL volumetric flasks
In, with methanol dilution constant volume, preparation obtains the hybrid standard working solution of a variety of herbicides, is preserved at -18 DEG C.
7. the according to the method described in claim 6, it is characterized in that, hybrid standard for preparing selected a variety of herbicides
Working solution further comprises：Using blank pedotheque matrix liquid as solvent, the solution after methanol dilution constant volume dilutes step by step
Hybrid standard working solution is prepared, its mass concentration is respectively 0.5,1,5,10,50,100 μ g/L.
8. according to the method described in claim 5, it is characterized in that, superelevation liquid chromatogram-triple level Four bar is answered in the step 3
Linear ion trap mass spectrometry condition is：Using Kinetex SB-C18Chromatographic column, specification are 100 × 2.1mm, 1.7 μm；Column temperature：
40℃；Sample size：3μL；A mobile phases are 0.1% formic acid solution, and B mobile phases are methanol；
Gradient elution, the gradient elution program are as follows：0-10min, 50%-100%B；10.1-15min 100%-100%
B；15.1-20min 50%B；
Ionization pattern：Electron spray negative ions scan at the same time；Monitoring mode：MRM-IDA-EPI；Ionizing voltage：Holotype+
5.5KV, negative mode -4.5KV；Gas curtain atmospheric pressure 241kPa；Atomization temperature：550℃；Atomization gas pressure：379kPai；Aid in gas
Pressure：414kPa.
9. according to the method described in claim 1, it is characterized in that, pedotheque and diatomaceous mass ratio in the step 1
For 1: 2.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108918709A (en) * | 2018-07-12 | 2018-11-30 | 河北医科大学 | Screening, quantitative detecting method and the application of common herbicide in a kind of blood |
| CN110068622A (en) * | 2019-03-27 | 2019-07-30 | 黑龙江八一农垦大学 | Acetamide-group herbicides efficiently separates method and rapid detection method in miscellaneous beans |
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| CN110068622A (en) * | 2019-03-27 | 2019-07-30 | 黑龙江八一农垦大学 | Acetamide-group herbicides efficiently separates method and rapid detection method in miscellaneous beans |
| CN111398491A (en) * | 2020-04-27 | 2020-07-10 | 广东煜祺检测股份有限公司 | Method for detecting residual quantity of atrazine pesticide in sludge |
| CN113960196A (en) * | 2021-10-11 | 2022-01-21 | 太湖流域水文水资源监测中心（太湖流域水环境监测中心） | Method for on-line determination of sulfonylurea herbicide in water |
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