CN104129829B - A kind of effervescent tablet for extracting organic pollutant and preparation and application method thereof - Google Patents
A kind of effervescent tablet for extracting organic pollutant and preparation and application method thereof Download PDFInfo
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- CN104129829B CN104129829B CN201410373662.3A CN201410373662A CN104129829B CN 104129829 B CN104129829 B CN 104129829B CN 201410373662 A CN201410373662 A CN 201410373662A CN 104129829 B CN104129829 B CN 104129829B
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Abstract
The invention belongs to trace organic pollutant in water and extract detection method technical field, particularly a kind of effervescent tablet for extracting organic pollutant and preparation and application method thereof.The inventive method first with citric acid, sodium bicarbonate and 1-undecyl alcohol for raw material, prepare this novel effervescent tablet, and the triazine be applied in sampling point extraction water sample, contrasting with traditional method can sampling position extracting directly in the wild, substantially reduce the number the usage quantity of organic solvent and significantly shorten the pre-treatment time, and reducing workload and transportation cost.The present invention simultaneously establishes the mass spectrographic analytical procedure of ultrahigh pressure liquid phase chromatographic tandem triple level Four bar after extraction water sample, and its detection limit is low, sensitivity is higher, linear relationship is good, can be used for the mensuration of five kinds of triazine herbicide agricultural chemicals in water.
Description
Technical field
The invention belongs to trace organic pollutant in water and extract detection method technical field, particularly a kind of effervescent tablet for extracting organic pollutant and preparation and application method thereof.
Background technology
Because increasing organic pollutant, as sterilant, polychlorobiphenyl, polycyclic aromatic hydrocarbons and PPCPs, in ambient water, (as river, in lake and ocean water) is detected, so the pollution level of water surrounding obtains great attention.In order to assess the risk of water pollutions, the organic pollutant detecting underwater trace is accurately very important.After traditional method needs that sample collecting is gone back to laboratory, just can further extract and analyze.If at sampling point extracting directly, not only workload and transportation cost can reduce, and can also improve the precision of result; Especially in remote districts, after sampling point extracts and terminates, as long as carry the sample bottle of the Extraction solvent containing small volume, transport and storage is convenient to.
Summary of the invention
Not enough for prior art, the invention provides a kind of effervescent tablet for extracting organic pollutant and preparation and application method thereof.
For extracting an effervescent tablet for organic pollutant, described effervescent tablet is made up of citric acid, sodium bicarbonate and 1-undecyl alcohol Homogeneous phase mixing.
In described effervescent tablet, the massfraction of citric acid, sodium bicarbonate and 1-undecyl alcohol respectively is 38.1% ~ 40.2%, 49.9% ~ 52.8%, 7.0% ~ 12.0%.
A kind of preparation method of the effervescent tablet for extracting organic pollutant, get citric acid and the abundant ground and mixed of sodium bicarbonate is even, 1-undecyl alcohol is added in ground citric acid and sodium bicarbonate mixture, again fully ground and mixed evenly after, get the mixture of gained citric acid, sodium bicarbonate and 1-undecyl alcohol, compacting obtains effervescent tablet.
Citric acid and sodium bicarbonate are dried two hours at 90 DEG C, is stored in moisture eliminator for subsequent use; Get citric acid (7.62g ~ 8.04g) and sodium bicarbonate (9.98g ~ 10.56g) (mol ratio of citric acid and sodium bicarbonate is 1:3) in mortar respectively, grinding is until obtain the powder mixed; Then 1-undecyl alcohol (1.4 ~ 2.4mL, 20g deduct citric acid and sodium bicarbonate quality income value is the amount of adding 1-undecyl alcohol) is added drop-wise on gained powder, carries out second time grinding afterwards until obtain the powder mixed; Take the powder that appropriate (1g) gained mixes, obtain effervescent tablet (at 0.4MPa pressure 5s) by tabletting machine compacting; Gained effervescent tablet sealed type storage (be stored under sealing bag is placed in 4 DEG C of temperature and store).
A kind of application method of the effervescent tablet for extracting organic pollutant, described effervescent tablet for extracting the method for organic pollutant is: in containing organic sample water, put into described effervescent tablet, after effervesce end of processing, Extraction solvent floats over ullage, take out a certain amount of Extraction solvent, and add interior mark, be mixed with testing sample.
Described organic pollutant is triazine herbicide.
Described triazine herbicide is one or more in atrazine, prometryn, terbuthylazine, terbutryn and ametryn.
Water sampling 10mL ~ 35mL is in glass test tube (40mL), add sodium-chlor (every milliliter of water sample adds 0.25g sodium-chlor) and regulate ionic strength, effervescent tablet is put into water, carries out effervesce process, in effervesce process, temperature controls at 20 DEG C ~ 40 DEG C; After effervesce end of processing, 1-undecyl alcohol swims in solution top with drops; Finally, transfer in sample introduction interpolation pipe with pipettor by the 1-undecyl alcohol of 35 μ L, the methanol solution being the simazine of 0.2mg/kg with 35 μ L concentration mixes, and obtains testing sample, and described simazine is mark in instrument.
Gained testing sample uses ultrahigh pressure liquid phase chromatographic tandem triple level Four bar mass spectrum (UHPLC-MS/MS) to detect.
Beneficial effect of the present invention is:
The present invention adopts a kind of novel effervescent tablet directly to carry out pre-treatment to water sample at sampling point, then by 5 kinds of triazine herbicides in ultrahigh pressure liquid phase chromatographic tandem triple level Four bar mass spectroscopy water.The method has prepared this novel effervescent tablet first, and the triazine be applied in sampling point extraction water sample, contrasting with traditional method can sampling position extracting directly in the wild, substantially reduce the number the usage quantity of organic solvent and significantly shorten the pre-treatment time, and reducing workload and transportation cost.The present invention simultaneously establishes the mass spectrographic analytical procedure of ultrahigh pressure liquid phase chromatographic tandem triple level Four bar after extraction water sample, and its detection limit is low, sensitivity is higher, linear relationship is good, can be used for the mensuration of five kinds of triazine herbicide agricultural chemicals in water.
Embodiment
The invention provides a kind of effervescent tablet for extracting organic pollutant and preparation and application method thereof, below in conjunction with embodiment, the present invention will be further described.
One, instrument and reagent:
ThermoFisherTSQQuantumAccessMAX system (ThermoFisher company of the U.S.), joins Dionex
tMultiMate
tM3000 ultrahigh pressure liquid phase chromatograms, electric spray ion source (ESI) and triple level Four bar mass spectrum.
Simazine, prometryn, terbutryn, ametryn, atrazine and terbuthylazine standard specimen, all buy in Inst. of Environment Protection & Scientific Research Monitor, Ministry of Agric, becomes the working solution of desired concn during use with methanol dilution.
Two, effervescent tablet preparation:
Citric acid and sodium bicarbonate are dried two hours at 90 DEG C, is stored in moisture eliminator for subsequent use; Get 8.04g citric acid and 10.56g sodium bicarbonate respectively in mortar, grinding is until obtain the powder mixed; Then the 1-undecyl alcohol of 1.4mL is added drop-wise on gained powder, carries out second time grinding afterwards until obtain the powder mixed; Take the powder (the 1-undecyl alcohols containing 70 μ L) that 1g gained mixes, after 0.4MPa pressure 5s, obtain effervescent tablet by tabletting machine; Gained effervescent tablet is stored under sealing bag is placed in 4 DEG C of temperature and stores.
Three, the pre-treatment (sample preparation) of triazine herbicide in water:
Interpolation sample water sample adds a certain amount of hybrid standard liquid and fully mixes latter standing 1 day, prepares extraction.
Extraction conditions: contriver has carried out contrasting optimizing (referring to hereafter leaching process condition optimizing) to extraction conditions emphatically, comprise NaCl addition, the volume of water, the volume of solvent, the optimization of Extracting temperature and sample pH value parameter, step is with optimal conditions:
1, water sampling 10mL is in the glass test tube of 40mL, adds 2.5g sodium-chlor and regulates ionic strength.
2, be placed in water by effervescent tablet, carry out effervesce process, period has a large amount of bubble to produce, and in effervesce process, temperature controls at 20 DEG C ~ 40 DEG C, and effervesce process probably continues 2.5min.
3, after effervesce end of processing, 1-undecyl alcohol swims in solution top with drops.
4, transfer in sample introduction interpolation pipe with pipettor by the 1-undecyl alcohol of 35 μ L, the methanol solution being the simazine of 0.2mg/kg with 35 μ L concentration mixes, and obtains testing sample, and described simazine is mark in instrument.
Four, the pre-treatment (stratographic analysis) of triazine herbicide in water:
Water sample after treatment, the mass spectroscopy of ultrahigh pressure liquid phase chromatographic tandem triple level Four bar is adopted to detect, chromatographic fraction testing conditions is HypersilGOLDC18column (100 × 2.1mmi.d., 3 μm) chromatographic column, sample size is 1 μ L, the mixed solution of moving phase to be acetonitrile and massfraction the be first aqueous acid of 0.1%, in described mixed solution, acetonitrile and massfraction are the volume ratio of the first aqueous acid of 0.1% is 7:3, flow velocity is 0.3mL/min, column temperature is 30 DEG C, analysis time 2.5min.
Mass spectrum partial condition is five kinds of analytes and simazine all ionizations under positive ion mode in electric spray ion source (ESI).Spray voltage is 3000V, and capillary temperature is 350 DEG C, and gasification temperature is 200 DEG C, and sheath atmospheric pressure is about 35psi, and auxiliary air vale flow velocity is 15arbitrary unit.Argon gas (wherein argon gas volume fraction is more than 99.999%) is by as collision gas, and its pressure is set to 1.5mTorr simultaneously, and Selective reaction monitoring (SRM) pattern, impact energy voltage and lens voltage are listed in table 1.
The Mass Spectrometry Conditions data sheet of table 1, compound
Note: wherein * represents quota ion.
Five, optimization:
Extraction conditions is one of important factor affecting the method rate of recovery, and appropriate extraction conditions effectively can improve the rate of recovery of target components.The important factor of this effect of extracting comprises NaCl addition, the volume of water, the volume of solvent, Extracting temperature and sample pH value.In each sample introduction sample, in simazine, target concentration is 0.1mg/kg.Be optimized with five above-mentioned target compounds and interior target ratio.
1, the impact of NaCl addition:
Adsorbent amount is one of important factor affecting the magnetic solid phase extraction method rate of recovery.
Method starting condition is: water sampling 15mL is in 40mL centrifuge tube, ionic strength is regulated to add the NaCl of different amount respectively, the effervescent tablet of the 1-undecyl alcohol containing 100 μ L is put into water has a large amount of bubbles to produce simultaneously, period, temperature should maintain 35 DEG C, after effervesce terminates, 1-undecyl alcohol swims in ullage with drops.With pipettor, the 1-undecyl alcohol of 50 μ L is transferred to the methanol solution being the simazine of 0.2mg/kg with 50 μ L concentration in sample introduction interpolation pipe to mix, to be detected.Change NaCl addition to make respectively to add in simazine before mark, in water sample respectively containing 0, the NaCl of 0.05g/mL, 0.1g/mL, 0.15g/mL, 0.20g/mL, 0.25g/mL, 0.3g/mL.In blank mark-on experiment, the relative peak area of 5 kinds of target analytes all reaches maximum value at the NaCl of 0.3g/mL.Blank mark-on experimental result is in table 2.
Table 2, NaCl addition affect data sheet to relative peak area
2, the impact of volume of water:
Method starting condition is: get different water gaging sample in 40mL centrifuge tube, ionic strength is regulated to add NaCl respectively, the concentration of NaCl in water sample is made to be 0.20g/mL, effervescent tablet containing 100 μ L1-undecyl alcohols is put into water has a large amount of bubbles to produce simultaneously, period, temperature should maintain 35 DEG C, after effervesce terminates, 1-undecyl alcohol swims in ullage with drops.With pipettor, the 1-undecyl alcohol of 50 μ L is transferred to the methanol solution being the simazine of 0.2mg/kg with 50 μ L concentration in sample introduction interpolation pipe to mix, to be detected.The volume of water sampling is respectively 10mL, 15mL, 20mL, 25mL, 30mL, 35mL.In experiment, the relative peak area of 5 kinds of target analytes increases with the volume reduction of water sample.The volume of water of final 10mL is selected, and the results are shown in Table 3.
Table 3, volume of water affect data sheet to relative peak area
3, the impact of Extraction solvent volume:
Method starting condition is: water sampling 15mL is in 40mL centrifuge tube, ionic strength is regulated to add NaCl, the concentration of NaCl in water sample is made to be 0.20g/mL, the effervescent tablet of the 1-undecyl alcohol containing 100 μ L is put into water has a large amount of bubbles to produce simultaneously, period, temperature should maintain 35 DEG C, after effervesce terminates, 1-undecyl alcohol swims in ullage with drops.With pipettor, a certain amount of 1-undecyl alcohol is transferred to the methanol solution being the simazine of 0.2mg/kg with 50 μ L concentration in sample introduction interpolation pipe to mix, to be detected.The volume changing 1-undecyl alcohol is respectively 70 μ L, 80 μ L, 90 μ L, 100 μ L, 110 μ L, 120 μ L.In experiment, the relative peak area of 5 kinds of target analytes increases with the volume reduction of 1-undecyl alcohol.The volume of final 70 μ L1-undecyl alcohols is selected, and the results are shown in Table 4.
Table 4, Extraction solvent volume affect data sheet to relative peak area
4, the impact of temperature:
Method starting condition is: water sampling 15mL is in 40mL centrifuge tube, ionic strength is regulated to add NaCl, the concentration of NaCl in water sample is made to be 0.20g/mL, the effervescent tablet of the 1-undecyl alcohol containing 100 μ L is put into water has a large amount of bubbles to produce simultaneously, period should maintain certain temperature, after effervesce terminates, 1-undecyl alcohol swims in ullage with drops.With pipettor, the 1-undecyl alcohol of 50 μ L is transferred to the methanol solution being the simazine of 0.2mg/kg with 50 μ L concentration in sample introduction interpolation pipe to mix, to be detected.Change temperature and be respectively 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C.In experiment, the relative peak area variation with temperature of 5 kinds of target analytes does not significantly change, and the results are shown in Table 5.
Table 5, temperature affect data sheet to relative recovery
5, the impact of pH value
Method starting condition is: water sampling 15mL is in 40mL centrifuge tube, ionic strength is regulated to add NaCl, the concentration of NaCl in water sample is made to be 0.20g/mL, the effervescent tablet of the 1-undecyl alcohol containing 100 μ L is put into water has a large amount of bubbles to produce simultaneously, period should maintain 35 DEG C, pH is certain value, and after effervesce terminates, 1-undecyl alcohol swims in ullage with drops.With pipettor, the 1-undecyl alcohol of 50 μ L is transferred to the methanol solution being the simazine of 0.2mg/kg with 50 μ L concentration in sample introduction interpolation pipe to mix, to be detected.Change pH value and be respectively 5,6,7,8,9,10.In experiment, the relative peak area of 5 kinds of target analytes does not significantly change with the change of pH, the results are shown in Table 6.
Table 6, pH value affect data sheet to relative recovery
For checking optimize after the validity of method, use interpolation five kinds of triazine herbicides ultrapure water as sample, the result is as table 7:
The result data sheet of table 7, optimization method
Note: a. is by adding analyte acquisition (n=5) that concentration is 5 μ g/L; B.A is relative peak area; C is concentration (μ g/L).
Six, embodiment is surveyed:
In order to the feasibility of verification method in actual sample, collect municipal tap water, neighbouring reservoir water and river water are as actual sample.The sample gathered except the prometryn containing 0.087 μ g/L in reservoir water, does not contain other evaluating objects things through conventional methods analyst result.Add target analytes, the concentration of added target analytes in sample solution is made to be respectively 0.1 μ g/L and 1 μ g/L, the results are shown in Table 8a, 8b and 8c, wherein relative recovery (RR) is by calculating the rate of recovery in ultrapure water as 100%.
Table 8a, optimization method are applied to the test result data table in tap water sample
Table 8b, optimization method are applied to the test result data table in river water sample
Table 8c, optimization method are applied to the test result data table in reservoir water sample
Claims (8)
1. for extracting an effervescent tablet for organic pollutant, it is characterized in that: described organic pollutant is triazine herbicide, described effervescent tablet is made up of citric acid, sodium bicarbonate and 1-undecyl alcohol Homogeneous phase mixing.
2. a kind of effervescent tablet for extracting organic pollutant according to claim 1, it is characterized in that: in described effervescent tablet, the massfraction of citric acid, sodium bicarbonate and 1-undecyl alcohol respectively is 38.1% ~ 40.2%, 49.9% ~ 52.8%, 7.0% ~ 12.0%.
3. a kind of effervescent tablet for extracting organic pollutant according to claim 1, is characterized in that: described triazine herbicide is one or more in atrazine, prometryn, terbuthylazine, terbutryn and ametryn.
4. the preparation method of a kind of effervescent tablet for extracting organic pollutant according to claims 1 to 3 any one claim, it is characterized in that: get citric acid and the abundant ground and mixed of sodium bicarbonate is even, 1-undecyl alcohol is added in ground citric acid and sodium bicarbonate mixture, again fully ground and mixed evenly after, get the mixture of gained citric acid, sodium bicarbonate and 1-undecyl alcohol, compacting obtains effervescent tablet.
5. the preparation method of a kind of effervescent tablet for extracting organic pollutant according to claim 4, is characterized in that: citric acid and sodium bicarbonate are dried two hours at 90 DEG C, be stored in moisture eliminator for subsequent use; Get citric acid and sodium bicarbonate respectively in mortar, grinding is until obtain the powder mixed; Then 1-undecyl alcohol is added drop-wise on gained powder, carries out second time grinding afterwards until obtain the powder mixed; Take the powder that appropriate gained mixes, obtain effervescent tablet by tabletting machine compacting; Gained effervescent tablet sealed type storage.
6. the application method of a kind of effervescent tablet for extracting organic pollutant according to claims 1 to 3 any one claim, it is characterized in that, described effervescent tablet for extracting the method for organic pollutant is: in containing organic sample water, put into described effervescent tablet, after effervesce end of processing, Extraction solvent floats over ullage, take out a certain amount of Extraction solvent, and add interior mark, be mixed with testing sample.
7. the application method of a kind of effervescent tablet for extracting organic pollutant according to claim 6, it is characterized in that: water sampling 10mL ~ 35mL is in glass test tube, add sodium-chlor and regulate ionic strength, effervescent tablet is put into water, carry out effervesce process, in effervesce process, temperature controls at 20 DEG C ~ 40 DEG C; After effervesce end of processing, 1-undecyl alcohol swims in solution top with drops; Finally, transfer in sample introduction interpolation pipe with pipettor by the 1-undecyl alcohol of 35 μ L, the methanol solution being the simazine of 0.2mg/kg with 35 μ L concentration mixes, and obtains testing sample, and described simazine is mark in instrument.
8. the application method of a kind of effervescent tablet for extracting organic pollutant according to claim 7, is characterized in that: gained testing sample uses ultrahigh pressure liquid phase chromatographic tandem triple level Four bar mass spectrum to detect.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107843666B (en) * | 2017-11-07 | 2020-08-07 | 山西农业大学 | Method for rapidly detecting organic pollutants in water |
| CN109289815B (en) * | 2018-10-24 | 2021-05-21 | 温州医科大学 | Magnetic effervescent tablet, magnetic effervescent tablet assisted dispersion solid phase microextraction method, heavy metal detection method and application |
| US11119011B2 (en) | 2019-02-12 | 2021-09-14 | National Tsing Hua University | Method for extracting and detecting volatile organic compounds |
| CN110227425B (en) * | 2019-07-05 | 2022-07-12 | 山西农业大学 | Magnetic effervescent tablet, preparation method thereof and application of magnetic effervescent tablet in extracting triazine herbicides in water |
| CN110308231A (en) * | 2019-07-18 | 2019-10-08 | 山西农业大学 | A kind of method of phenols endocrine disruptors in rapidly extracting plastics package drink |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10212286A1 (en) * | 2002-03-20 | 2004-04-01 | Krüger Gmbh & Co. Kg | Effervescent tablet production, e.g. for medicinal, food or detergent applications, by forming premix of solid acid and liquid polyol, mixing with active agent and carbonate and directly pressing to tablets |
| CN101049121A (en) * | 2007-05-15 | 2007-10-10 | 云南龙润药业有限公司 | Effervesce pieces of tea beverage, preparing method |
| CN102132819A (en) * | 2011-03-30 | 2011-07-27 | 苏州先阔生物科技有限公司 | Oligosaccharide-contained effervescent tablet |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090004270A1 (en) * | 2006-01-06 | 2009-01-01 | Amerilab Technologies, Inc. | Method of using guava extract |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10212286A1 (en) * | 2002-03-20 | 2004-04-01 | Krüger Gmbh & Co. Kg | Effervescent tablet production, e.g. for medicinal, food or detergent applications, by forming premix of solid acid and liquid polyol, mixing with active agent and carbonate and directly pressing to tablets |
| CN101049121A (en) * | 2007-05-15 | 2007-10-10 | 云南龙润药业有限公司 | Effervesce pieces of tea beverage, preparing method |
| CN102132819A (en) * | 2011-03-30 | 2011-07-27 | 苏州先阔生物科技有限公司 | Oligosaccharide-contained effervescent tablet |
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