CN112946128A - Pretreatment method and quantitative detection method of triazine herbicide - Google Patents
Pretreatment method and quantitative detection method of triazine herbicide Download PDFInfo
- Publication number
- CN112946128A CN112946128A CN202110146390.3A CN202110146390A CN112946128A CN 112946128 A CN112946128 A CN 112946128A CN 202110146390 A CN202110146390 A CN 202110146390A CN 112946128 A CN112946128 A CN 112946128A
- Authority
- CN
- China
- Prior art keywords
- sample
- pipe body
- triazine
- solution
- triazine herbicides
- 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
- 239000004009 herbicide Substances 0.000 title claims abstract description 83
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 32
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002203 pretreatment Methods 0.000 title claims abstract description 20
- 238000001514 detection method Methods 0.000 title claims description 22
- 239000000523 sample Substances 0.000 claims abstract description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 35
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 32
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 32
- 238000002470 solid-phase micro-extraction Methods 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012488 sample solution Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000009987 spinning Methods 0.000 claims abstract description 3
- RQVYBGPQFYCBGX-UHFFFAOYSA-N ametryn Chemical compound CCNC1=NC(NC(C)C)=NC(SC)=N1 RQVYBGPQFYCBGX-UHFFFAOYSA-N 0.000 claims description 38
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 claims description 38
- AAEVYOVXGOFMJO-UHFFFAOYSA-N prometryn Chemical compound CSC1=NC(NC(C)C)=NC(NC(C)C)=N1 AAEVYOVXGOFMJO-UHFFFAOYSA-N 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 238000000605 extraction Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 241000283973 Oryctolagus cuniculus Species 0.000 claims description 14
- 239000012086 standard solution Substances 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 210000002700 urine Anatomy 0.000 claims description 9
- 239000003480 eluent Substances 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 8
- 210000002966 serum Anatomy 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- RQBBFKINEJYDOB-UHFFFAOYSA-N acetic acid;acetonitrile Chemical compound CC#N.CC(O)=O RQBBFKINEJYDOB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012472 biological sample Substances 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000013535 sea water Substances 0.000 claims description 6
- 239000008399 tap water Substances 0.000 claims description 6
- 235000020679 tap water Nutrition 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000004811 liquid chromatography Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000009656 pre-carbonization Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 210000002381 plasma Anatomy 0.000 claims description 2
- 239000002349 well water Substances 0.000 claims description 2
- 235000020681 well water Nutrition 0.000 claims description 2
- 238000001471 micro-filtration Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 13
- 239000003463 adsorbent Substances 0.000 abstract description 8
- 239000012982 microporous membrane Substances 0.000 abstract description 7
- 239000007790 solid phase Substances 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000012496 blank sample Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000010812 external standard method Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004853 microextraction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000447 pesticide residue Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 241001313857 Bletilla striata Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000004464 cereal grain Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000012421 spiking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001195 ultra high performance liquid chromatography Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 210000003932 urinary bladder Anatomy 0.000 description 1
Images
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
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
- G01N30/8634—Peak quality criteria
-
- 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
- G01N2030/042—Standards
- G01N2030/047—Standards external
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)
- Engineering & Computer Science (AREA)
- Quality & Reliability (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention discloses a pretreatment method of triazine herbicide, which comprises the following steps: adding a proper amount of hydrochloric acid into a sample to be detected, and uniformly mixing to obtain a sample solution to be detected; adding the sample solution to be tested into an activated spinning integrated column solid phase micro-extraction device, and centrifuging for 1min at 2500 r/min; discarding the solution in the cannula; 2mL of acetonitrile/acetic acid solution with the volume ratio of 30:70 is added into the device, and the mixture is centrifuged for 1min at 1000 r/min; the eluate in the thimble was collected and filtered through a 0.22 μm microporous membrane. According to the invention, coconut shell biochar is filled into a self-prepared centrifugal sleeve to be used as a small solid-phase micro-extraction device, and the biochar is used as a solid-phase adsorbent to extract triazine herbicides, so that the method is green, environment-friendly, rapid, high in target recovery rate, high in sensitivity and good in accuracy.
Description
Technical Field
The invention relates to a pretreatment method and a quantitative detection method of triazine herbicides, belonging to the technical field of analysis and detection of pesticide residues.
Background
Triazine herbicides are highly effective selective herbicides for inhibiting plant photosynthesis, are widely used worldwide, and make important contributions to the development of agriculture. However, the problems of pesticide residue, environmental pollution, food safety and the like are brought when the triazine herbicide is used in large quantity and even abused, so that the research and development of the detection technology of the triazine herbicide are of great significance. In the detection technology of triazine herbicides, a pretreatment method is adopted to treat a sample so as to quickly and efficiently separate and enrich the triazine herbicides.
In the prior art, the pretreatment methods of triazine herbicides include liquid-liquid extraction, liquid-liquid microextraction, solid-phase extraction, dispersed solid-phase extraction, solid-phase microextraction and the like. Most of the adsorbents used in solid phase extraction, solid phase microextraction, dispersed solid phase extraction and the like are molecular imprinting materials synthesized by a laboratory and other nano materials such as metal frames, carbon nano tubes and the like. The synthesis of the material needs a large amount of organic reagents, the characterization of the material needs special equipment, the equipment cost is high, and the whole extraction process is long in time consumption. Therefore, if the green, environment-friendly and efficient solid phase adsorbent can be used for extracting the triazine herbicide in the environmental matrix, the time of the whole pretreatment process is shortened, and the development significance of pretreatment methods such as solid phase extraction, dispersed solid phase extraction and solid phase micro-extraction is great.
Disclosure of Invention
Aiming at the prior art, the invention provides a pretreatment method and a quantitative detection method of triazine herbicides. According to the method, the biochar prepared from biomass waste coconut shells is used as a solid-phase adsorbent of a solid-phase microextraction method to extract the triazine herbicide, and a small solid-phase microextraction device is prepared, so that the method is green, environment-friendly, rapid and high in target object recovery rate; the rear end is connected with the liquid chromatogram for detection, and the detection method has high sensitivity and good accuracy.
The invention is realized by the following technical scheme:
a pretreatment method of triazine herbicides comprises the following steps: adding a proper amount of hydrochloric acid into a sample to be detected, and uniformly mixing to obtain a sample solution to be detected; adding the sample solution to be tested into an activated spinning integrated column solid phase microextraction (MSC-SPME) device, and centrifuging; discarding the solution in the cannula; adding the acetonitrile-acetic acid mixed solution into the device, and centrifuging; and collecting the eluent in the sleeve, and filtering to obtain a pretreatment sample which can be used for High performance liquid chromatography (HPLC-UV) detection of the triazine herbicide.
The MSC-SPME device has the following structure: the device comprises two sleeved pipe bodies, wherein one end of the pipe body positioned on the outer side is opened, and the other end of the pipe body is closed; the two ends of the pipe body positioned on the inner side are both opened, the two pipe bodies are sleeved together, and the pipe body positioned on the inner side is communicated with the pipe body positioned on the outer side; the pipe body positioned at the inner side is sequentially filled with a filling substrate, coconut shell biochar and a filling substrate from bottom to top.
Further, in the specific preparation, a centrifuge tube (for example, a centrifuge tube with a specification of 1.5 mL) can be used as the tube body for self-preparation: the lower end of the centrifuge tube is cut off and discarded by a blade as a tube body located inside.
Further, the coconut shell biochar is prepared by the following method: air drying the waste coconut shells, crushing into small blocks (for example, crushing into small blocks of 1cm multiplied by 1 cm), placing into a ceramic crucible, covering and sealing, then firing in a muffle furnace, raising the temperature to 200 ℃ at a heating rate of 10 ℃/min, and carrying out pre-carbonization at a constant temperature for 2 hours; then heating to 700 ℃ at the heating rate of 10 ℃/min and carrying out anaerobic calcination for 3 h; cooling, grinding and sieving with a 100-mesh sieve to obtain the coconut shell biochar.
Further, the filling amount of the coconut shell biochar is 300 mg.
Further, the filling substrate is selected from cotton wool.
Further, the activation method comprises the following steps: adding 1mL of ultrapure water and 1mL of methanol into the MSC-SPME device, centrifuging at 3000r/min for 1min, and activating the coconut shell biochar.
Further, the sample to be detected is selected from a water sample or a biological sample. The water sample is selected from tap water, underground water, well water, river water, lake water or seawater; the biological sample is selected from urine, serum or plasma, such as human urine, rabbit serum, and rabbit plasma.
Furthermore, the dosage of the sample to be detected is 100 muL, the pH value of the hydrochloric acid is 1, and the dosage is 900 muL.
Further, the centrifugation conditions at the time of extraction were: centrifuging at 2500r/min for 1 min.
Further, in the acetonitrile-acetic acid mixed solution, the volume ratio of acetonitrile to acetic acid is 30: 70.
Further, the amount of the acetonitrile-acetic acid mixed solution added was 2 mL.
Further, the centrifugation conditions at elution were: centrifuging at 1000r/min for 1 min.
Further, a 0.22 μm microporous membrane was used for filtration.
A quantitative detection method of triazine herbicides comprises the following steps:
(1) making a standard curve: preparing a standard solution of triazine herbicide by using methanol as a solvent, measuring chromatographic peak retention time and chromatographic peak area of each component in the standard solution of triazine herbicide by HPLC-UV, and drawing a standard curve of concentration-chromatographic peak area (the chromatographic peak retention time is adopted for qualitative determination, the chromatographic peak area is adopted for quantitative determination, and an external standard method is adopted for quantitative determination, namely, the concentration of the herbicide is taken as a horizontal coordinate, and the chromatographic peak area is taken as a vertical coordinate for drawing the standard curve).
The standard solution contains three triazine herbicides: atrazine, ametryn and prometryn, wherein the concentration ranges of the components are respectively as follows: 10-10000 ng/mL of atrazine, 200-10000 ng/mL of ametryn and 200-10000 ng/mL of prometryn.
(2) HPLC-UV determination: and (3) carrying out HPLC-UV determination on the prepared pretreatment sample, and substituting the determination result into a standard curve, thereby calculating the concentration of the triazine herbicide in the sample to be determined.
Further, the conditions of the HPLC-UV determination are as follows: liquid chromatography instrument model: agilent 1260Infinity II; a chromatographic column: the model is Pursuit 5C18, the specification is 5 μm particle size, 4.6mm × 150 mm; sample introduction amount: 20 mu L of the solution; column temperature: 25 ℃; a detector: a diode array detector; detector wavelength: 222 nm; the mobile phase was methanol/water 70/30 (v/v).
The pretreatment method and the quantitative detection method of the triazine herbicide have the following advantages:
(1) the pretreatment time of the sample is greatly shortened, and the experiment cost is saved: the method adopts a self-prepared centrifugal tube sleeve as extraction equipment, adopts a centrifuge for driving, finishes sample loading in 1 minute under the condition of low rotating speed, finishes sample elution in 1 minute, and is simple and quick compared with the traditional solid phase extraction; in addition, the centrifuge can be used for simultaneously loading and eluting a plurality of samples at one time, so that the problem of time consumption in the treatment of large-flux biological samples is solved.
(2) Green and environment-friendly: the coconut shell is adopted to prepare the biochar, so that the purpose of recycling waste is achieved. The solid phase adsorbent adopted by the prior art is a conventional adsorbent or a nano material, the cost of the adsorbent is high, and the extraction reproducibility problem is the bottleneck of the adsorption performance. The coconut shell biochar adopted by the method is the reutilization of the biomass solid waste, the material is natural, and the experimental loss is reduced.
(3) The loss of manpower and material resources is greatly reduced by self-prepared solid phase microextraction small equipment. Compared with the traditional solid phase micro-extraction fiber, the method has low cost and can realize batch processing of samples by adopting the self-made centrifugal sleeve; more importantly, the small-sized centrifuge can be brought to a test site for rapid extraction.
The various terms and phrases used herein have the ordinary meaning as is well known to those skilled in the art.
Drawings
FIG. 1: schematic of the self-prepared centrifugal extraction cartridge of the present invention.
FIG. 2: tap water air and standard adding recovery chromatograms, wherein the standard adding concentration of the 3 triazine herbicides is 2 mug/mL; a is a blank sample and b is a labeled sample. ATR: atrazine; AME: ametryn; PROM: prometryn.
FIG. 3: blank lake water and labeled recovery chromatograms, wherein the labeled concentrations of the 3 triazine herbicides are respectively 2 mug/mL; a is a blank sample and b is a labeled sample. ATR: atrazine; AME: ametryn; PROM: prometryn.
FIG. 4: the chromatogram map is recovered by adding standard of seawater air and air, wherein the standard adding concentration of 3 triazine herbicides is 2 mug/mL respectively; a is a blank sample and b is a labeled sample. ATR: atrazine; AME: ametryn; PROM: prometryn.
FIG. 5: a chromatogram map for recovering human urinary bladder and rhizoma bletillae with a standard, wherein the standard concentrations of 3 triazine herbicides are respectively 2 mug/mL; a is a blank sample and b is a labeled sample. ATR: atrazine; AME: ametryn; PROM: prometryn.
FIG. 6: a chromatogram map for recovering the clear rhizoma bletillae from rabbit blood by adding a standard, wherein the standard adding concentrations of the 3 triazine herbicides are respectively 2 mug/mL; a is a blank sample and b is a labeled sample. ATR: atrazine; AME: ametryn; PROM: prometryn.
FIG. 7: a chromatogram map for recovering bletilla striata in rabbit plasma by adding standard substances, wherein the standard substance concentration of 3 triazine herbicides is 2 mug/mL respectively; a is a blank sample and b is a labeled sample. ATR: atrazine; AME: ametryn; PROM: prometryn.
FIG. 8: the influence of the using amount of the coconut shell biochar on the adsorption capacity (Q), wherein the standard adding concentration of the 3 triazine herbicides is 10 mu g/mL respectively; ATR: atrazine; AME: ametryn; PROM: prometryn Q: adsorption capacity.
FIG. 9: the influence of eluent types on the extraction recovery rate, wherein the standard adding concentration of 3 triazine herbicides is 10 mug/mL; ATR: atrazine; AME: ametryn; PROM: prometryn R: and (4) recovering rate.
FIG. 10: the influence of the elution speed on the extraction recovery rate, wherein the standard adding concentration of the 3 triazine herbicides is 10 mug/mL respectively; ATR: atrazine; AME: ametryn; PROM: prometryn R: and (4) recovering rate.
FIG. 11: the influence of the sample loading rotating speed on the extraction recovery rate, wherein the standard adding concentration of the 3 triazine herbicides is 10 mug/mL respectively; ATR: atrazine; AME: ametryn; PROM: prometryn R: and (4) recovering rate.
FIG. 12: the effect of eluent volume on extraction recovery, wherein the spiking concentrations of the 3 triazine herbicides are 10 mug/mL respectively; ATR: atrazine; AME: ametryn; PROM: prometryn R: and (4) recovering rate.
Detailed Description
The present invention will be further described with reference to the following examples. However, the scope of the present invention is not limited to the following examples. It will be understood by those skilled in the art that various changes and modifications may be made to the invention without departing from the spirit and scope of the invention.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
Detailed description of the preferred embodiment
1. Preparation of MSC-SPME small equipment
As shown in FIG. 1, two 1.5mL centrifuge tubes were taken, the lower end of one 1.5mL centrifuge tube was cut off and discarded by a razor blade, a small amount of absorbent cotton was filled, 300mg of coconut shell charcoal was filled in a self-made 1.5mL centrifuge tube, and the upper layer was filled with a small amount of absorbent cotton, and the centrifuge tube was housed inside another new 1.5mL centrifuge tube. The device is placed in a centrifuge, 1mL of ultrapure water and methanol are sequentially added, and the coconut shell biochar is activated after centrifugation at 3000r/min for 1 min.
The coconut shell biochar is prepared by the following method: air-drying the waste coconut shells, crushing the dried waste coconut shells into small pieces of 1cm multiplied by 1cm, placing the small pieces in a ceramic crucible, covering and sealing the ceramic crucible, then firing the ceramic crucible in a muffle furnace, raising the temperature to 200 ℃ at a heating rate of 10 ℃/min, and carrying out pre-carbonization for 2 hours at constant temperature; then heating to 700 ℃ at the heating rate of 10 ℃/min and carrying out anaerobic calcination for 3 h; cooling, grinding and sieving with a 100-mesh sieve to obtain the coconut shell biochar.
2. MSC-SPME method
Respectively putting 100 mu L of tap water, lake water, seawater, human urine, rabbit serum and rabbit plasma in 5mL glass centrifuge tubes, respectively adding 900 mu L of HCl solution with pH value of 1, and uniformly mixing to obtain uniform solution; adding the 1mL sample solution into the activated device, and centrifuging at 2500r/min for 1 min; discarding the solution in the cannula; 2mL of acetonitrile/acetic acid solution (30:70, v/v) was added to the apparatus and centrifuged at 1000r/min for 1 min. Collecting the eluate in the sleeve, filtering with 0.22 μm microporous membrane, and detecting by HPLC-UV.
3. HPLC-UV detection method
(1) Preparing a standard solution of triazine herbicide (comprising atrazine, ametryn and prometryn) by using methanol as a solvent, and measuring the chromatographic peak retention time and the chromatographic peak area of each component in the standard solution of triazine herbicide by HPLC-UV. The three herbicides are qualitative by chromatographic peak retention time, and quantitative by chromatographic peak area. The quantitative method adopts an external standard method, namely a standard curve of the triazine herbicide is drawn by taking the concentration of the herbicide as a horizontal coordinate and taking the chromatographic peak area as a vertical coordinate, wherein the triazine herbicide comprises atrazine, ametryn and prometryn, the concentration ranges of the components are respectively 10-10000 ng/mL of atrazine and 200-10000 ng/mL of ametryn and prometryn; the concentration of triazine herbicide in each sample was calculated using a standard curve.
(2) The HPLC-UV conditions for determining the triazine herbicides are as follows:
liquid chromatography instrument model: agilent 1260Infinity II; a chromatographic column: the model is Pursuit 5C18, the specification is 5 μm particle size, 4.6mm × 150 mm; sample introduction amount: 20 mu L of the solution; column temperature: 25 ℃; a detector: a diode array detector; detector wavelength: 222 nm; the mobile phase was methanol/water 70/30 (v/v).
The HPLC-UV condition is adopted to determine the mixed standard solution of the 3 triazine herbicides, the separation effect of the standard sample is better, the peak shape is symmetrical, the base line is stable, and the condition of the instrument is suitable. Under the chromatographic conditions, the retention time of the triazine herbicide is respectively as follows: atrazine 5.4min, ametryn 6.9min, prometryn 9.2min, as shown in figure 2, figure 3, figure 4, figure 5, figure 6 and figure 7.
(3) And (3) quantitatively analyzing the triazine herbicide in the sample by adopting an external standard method.
No 3 triazine herbicides were detected in tap water, lake water, sea water, human urine, rabbit serum and rabbit plasma samples, and the blank and labeled chromatograms are shown in FIG. 2, FIG. 3, FIG. 4, FIG. 5, FIG. 6 and FIG. 7.
The invention adopts the self-made centrifugal extraction sleeve as a small extraction device to carry out solid-phase micro-extraction, and compared with the traditional solid-phase extraction method, the method is simple and quick; compared with commercial solid phase extraction and solid phase micro-extraction equipment, the device has the advantages of low price, energy conservation and environmental protection. Table 1 compares the aspects of the method for pretreating samples of triazine herbicides, such as extraction packing, extraction time, extraction method, extraction equipment, and the like, with the pretreatment method of the present invention, as shown in table 1.
TABLE 1 comparison of sample pretreatment methods for triazine herbicides
From the above comparison and summary, the present invention has the following advantages compared with the prior art:
(1) the adopted self-prepared centrifugal sleeve is used for loading samples for 1 minute in the whole extraction process, and is eluted for 1 minute, so that the time for sample pretreatment is greatly shortened;
(2) compared with expensive multi-walled carbon nanotubes, graphene and the like adopted in the prior art, the biomass solid waste-biological carbon prepared from coconut shells is adopted as the adsorption filler, so that the experiment cost is greatly saved; in addition, the coconut shell biochar is simple in preparation process, does not need to consume a large amount of organic reagents, and is green and environment-friendly compared with the molecular imprinting filler; in the invention, coconut shell biochar is used as the adsorption filler of MSC-SPME, and multi-medium environmental samples such as water samples, urine samples and blood samples are applied, and experimental results prove that the MSC-SPME method has high recovery rate, and the few impurities in the extracted sample images can be easily seen from the attached drawings 2-7, so that the method can also effectively remove matrix interference without additionally adding other purification methods such as solid phase extraction and the like.
(3) The main equipment of the invention is two centrifugal tubes of 1.5mL, a peristaltic pump, a solid phase extraction device and a solid phase micro-extraction device are not needed, the equipment is simple and easy to operate, and the invention is suitable for daily laboratory operation and on-site rapid extraction and detection.
Specific example two-way optimization of extraction conditions by single factor alternation
1. Influence of coconut shell biochar usage
10, 20, 50, 100, 150 and 200mg of coconut shell biochar are accurately weighed respectively and added into 5mL of sample solutions (the concentrations are all 10 mu g/mL) of 3 triazine herbicides (atrazine, ametryn and prometryn) with the pH value of 1. And (3) carrying out ultrasonic treatment for 5min after vortex mixing, centrifuging for 5min at 3000r/min, filtering the supernatant through a 0.22-micron filter membrane, transferring the filtered supernatant into a chromatographic sampling bottle, and carrying out machine detection. The measurement result shows (figure 8) that when the adding amount of the coconut shell biochar is 100mg, the change of the adsorption capacity (Q) of the three herbicides tends to be stable, the adsorption effect under the condition is good, and the difference of extraction efficiency is not large when the amount of the coconut shell biochar is continuously increased, so that 300mg is selected as the optimal adding amount.
2. Influence of eluent type
Adding 1mL of sample solution (the concentrations of atrazine, ametryn and prometryn are all 10 mug/mL) into the activated centrifugal sleeve, and centrifuging for 1min at 2500 r/min; discarding the solution in the cannula; 2mL of methanol, acetonitrile, methanol/acetic acid (30:70, v/v), acetonitrile/acetic acid solution (30:70, v/v) and acetic acid were added to the above apparatus, respectively, and centrifuged at 1000r/min for 1 min. Collecting the eluate in the sleeve, filtering with 0.22 μm microporous membrane, and detecting by HPLC-UV. The results showed that the acetonitrile/acetic acid solution (30:70, v/v) was the most effective for eluting the three herbicides, and therefore the acetonitrile/acetic acid solution (30:70, v/v) was selected as the optimum condition for the subsequent experiments (fig. 9).
3. Influence of the elution speed
Adding 1mL of sample solution (the concentrations of atrazine, ametryn and prometryn are all 10 mug/mL) into the activated centrifugal sleeve, and centrifuging for 1min at 2500 r/min; discarding the solution in the cannula; 2mL of acetonitrile/acetic acid solution (30:70, v/v) was added to the above apparatus, and centrifuged at 500, 1000, 1500, 2000 and 2500r/min for 1 min. Collecting the eluate in the sleeve, filtering with 0.22 μm microporous membrane, and detecting by HPLC-UV. The results show that the extraction effect is best when the elution speed is 1000r/min, so the elution speed is 1000r/min (FIG. 10).
4. Influence of sample application speed
Adding 1mL of sample solution (the concentrations of atrazine, ametryn and prometryn are all 10 mug/mL) into the activated centrifugal sleeve, and centrifuging for 1min at 500r/min, 1000r/min, 1500 r/min, 2000 r/min and 2500r/min respectively; discarding the solution in the cannula; 2mL of acetonitrile/acetic acid solution (30:70, v/v) was added to the apparatus and centrifuged at 1000r/min for 1 min. Collecting the eluate in the sleeve, filtering with 0.22 μm microporous membrane, and detecting by HPLC-UV. The results show that the extraction effect is best when the rotation speed is 2500r/min, so the sample loading rotation speed is 2500r/min (FIG. 11).
5. Effect of eluent volume
Adding 1mL of sample solution (the concentrations of atrazine, ametryn and prometryn are all 10 mug/mL) into the activated centrifugal sleeve, and centrifuging for 1min at 2500 r/min; discarding the solution in the cannula; 0.3, 0.5, 1, 1.5 and 2mL acetonitrile/acetic acid solutions (30:70, v/v) were added to the apparatus and centrifuged at 1000r/min for 1 min. Collecting the eluate in the sleeve, filtering with 0.22 μm microporous membrane, and detecting by HPLC-UV. The result shows that when the volume of the elution solution is 2mL, the extraction effect of the atrazine and the prometryn is the best; while 1.5mL of the eluent volume gave the best effect for the extraction of ametryn, 2mL of the eluent volume was chosen for the simultaneous extraction of the three herbicides (fig. 12).
Third embodiment linear range, regression equation, and detection limits of the first embodiment method
The concentration C is used as the abscissa and the peak area A is used as the ordinate to draw a standard curve, so that the 3 herbicides have good linearity and correlation coefficient (R) in the concentration range2) Are all greater than 0.99, and as shown in table 2, the detection Limit (LOD) of each herbicide was calculated as 3-fold signal-to-noise ratio, and the LODs of the 3 triazine herbicides atrazine, ametryn, and prometryn were 3.3, 66.7, and 66.7ng/mL, respectively.
TABLE 2 Linear Range, regression equation, correlation coefficient and detection limits for triazine herbicides
Fourth embodiment of the invention the recovery and precision of the process of the invention
Respectively putting 100 mu L of tap water, lake water, seawater, human urine, rabbit serum and rabbit plasma (no herbicide is detected) into 5mL glass centrifuge tubes, respectively adding 900 mu L of HCl solution with pH value of 1, and uniformly mixing to obtain uniform solutions; 3 herbicide mixed standard solutions with different concentration levels are respectively added, the addition level of the triazine herbicide is 0.5-2 mu g/mL, each concentration level is parallel to 3 samples, and the sample pretreatment and the chromatographic condition determination are carried out according to the method of the specific embodiment. The average recovery of each herbicide and its standard deviation (i.e., SD) were calculated using external standard quantification, and the results are shown in table 3, and the sample blank and spiked chromatograms are shown in fig. 2, fig. 3, fig. 4, fig. 5, fig. 6, and fig. 7.
Table 3 results of recovery of herbicide added to urine, rabbit serum and rabbit plasma samples (n ═ 3)
As can be seen from Table 3, the average recovery rates of the 3 triazine herbicides atrazine, ametryn and prometryn are 73-119%, 76-120% and 70-112% respectively, and the corresponding SD rates are 1.8-9.1%, 0.6-9.8% and 1.0-9.3% respectively, which shows that the method has good accuracy and repeatability.
The above examples show that the MSC-SPME-HPLC-UV method can be used for detecting triazine herbicides in water samples and biological samples, the MSC-SPME method is simple, rapid and low in consumption, a large amount of organic reagents are not required for extraction, and the solid phase adsorbent is prepared by using biomass solid waste-coconut shells, so that waste recycling is realized. The HPLC-UV method provides high sensitivity for the detection of such herbicides. The result proves that the method is sensitive and rapid, and can be popularized as a method for measuring triazine herbicides.
The above examples are provided to those of ordinary skill in the art to fully disclose and describe how to make and use the claimed embodiments, and are not intended to limit the scope of the disclosure herein. Modifications apparent to those skilled in the art are intended to be within the scope of the appended claims.
Reference documents:
[1] the method is characterized in that the triazine herbicide in the environmental water sample is determined by Lixiameng, Shaozun, Wangxxukun, Zhuyawen, Zhang Wenyu, Gaoshi, Zhang En and magnetic tea seed shell activated carbon solid phase extraction-ultra high performance liquid chromatography/mass spectrometry, and the scientific analysis report is 2020,36(2), 183-plus 188.
[2] Bauximin, zhangteng, shouzichu, resize, xu 21180, wu friendship, pretty, magnetic ionic liquid graphene-solid phase extraction of triazine herbicides in water, industrial water treatment 2020,40(11), 106-.
[3] The method is characterized in that the method comprises the following steps of (1) xuli, Zhuqing, Wang Xiujuan, Lijilong, Von Ji, Bi Jinlong, Wang Shi, dynamic matrix solid phase dispersion-ionic liquid two-water-phase microextraction and high performance liquid chromatography are combined to detect the triazine herbicide in the cereal grain, and the food science is 2020, https:// kns.cnki.net/kcms/detail/11.2206.TS.20201015.1415.042.html.
[4] Konghui, Zhang Meng, Guli, Shi Jun, Han Ying, molecular imprinting solid phase extraction of triazine herbicides in tobacco leaves-high performance liquid chromatography detection, chemical science and technology, 2018,26(6),17-21.
[5]Zucheng Qin,Yanxiao Jiang,Huilan Piao,Jingkang Li,Shuo Tao,Pinyi Ma,Xinghua Wang,Daqian Song,Ying Sun,MIL-101(Cr)/MWCNTs-functionalized melamine sponges for solid-phase extraction of triazines from corn samples,and their subsequent determination by HPLC-MS/MS,Talanta,2020,211,120676-120686.
[6]Diana Angélica Varela-Martínez,Miguel
González-Curbelo,Javier González-Sálamo,Javier Hernández-Borges,Analysis of pesticides in cherimoya and gulupa minor tropical fruits using AOAC 2007.1and ammonium formate QuEChERS versions:A comparative study,Microchemical Journal,2020,157,104950-104958.
[7]Xingqiang Wu,Shigang Shen,Hongyuan Yan,Yanan Yuan,Xi Chen,Efficient enrichment and analysis of atrazine and its degradation products in Chinese Yam using accelerated solvent extraction and pipette tip solid-phase extraction followed by UPLC–DAD,Food Chemistry,2021,337,127752-127760.
Claims (10)
1. A pretreatment method of triazine herbicides is characterized in that: adding hydrochloric acid into a sample to be detected, and uniformly mixing to obtain a sample solution to be detected; adding a sample solution to be tested into an activated spinning integrated column solid phase micro-extraction device, and centrifuging; discarding the solution in the cannula; adding the acetonitrile-acetic acid mixed solution into the device, and centrifuging; and collecting the eluent in the sleeve, and filtering to obtain a pretreatment sample.
2. The pretreatment method for triazine herbicides according to claim 1, wherein: the MSC-SPME device has the following structure: the device comprises two sleeved pipe bodies, wherein one end of the pipe body positioned on the outer side is opened, and the other end of the pipe body is closed; the two ends of the pipe body positioned on the inner side are both opened, the two pipe bodies are sleeved together, and the pipe body positioned on the inner side is communicated with the pipe body positioned on the outer side; the pipe body positioned at the inner side is sequentially filled with a filling substrate, coconut shell biochar and a filling substrate from bottom to top.
3. The pretreatment method for triazine herbicides according to claim 2, wherein: the coconut shell biochar is prepared by the following method: air-drying the waste coconut shells, crushing the waste coconut shells into small pieces, placing the small pieces in a ceramic crucible, covering and sealing the ceramic crucible, then firing the ceramic crucible in a muffle furnace, raising the temperature to 200 ℃ at a heating rate of 10 ℃/min, and carrying out pre-carbonization at a constant temperature for 2 hours; then heating to 700 ℃ at the heating rate of 10 ℃/min and carrying out anaerobic calcination for 3 h; cooling, grinding and sieving with a 100-mesh sieve to obtain the coconut shell biochar.
4. The pretreatment method for triazine herbicides according to claim 2, wherein: the filling amount of the coconut shell biochar is 300mg/1.5mL of an inner side pipe body;
or/and: the filling substrate is selected from absorbent cotton.
5. The pretreatment method for triazine herbicides according to claim 1, wherein: the sample to be detected is selected from a water sample or a biological sample;
or/and: the activation method comprises the following steps: adding ultrapure water and methanol into an MSC-SPME device, centrifuging, and activating coconut shell biochar;
or/and: the dosage of the sample to be detected is 100 mu L, the pH value of the hydrochloric acid is 1, and the dosage is 900 mu L;
or/and: the centrifugation conditions during extraction were: centrifuging at 2500r/min for 1 min;
or/and: in the acetonitrile-acetic acid mixed solution, the volume ratio of acetonitrile to acetic acid is 30: 70;
or/and: the adding amount of the acetonitrile-acetic acid mixed solution is 2 mL;
or/and: the centrifugation conditions at elution were: centrifuging at 1000r/min for 1 min;
or/and: the filtration was carried out using a 0.22 μm microfiltration membrane.
6. The pretreatment method for triazine herbicides according to claim 5, wherein: the water sample is selected from tap water, underground water, well water, river water, lake water or seawater; the biological sample is selected from urine, serum or plasma, such as human urine, rabbit serum, and rabbit plasma.
7. A pretreatment device is characterized in that: the device comprises two sleeved pipe bodies, wherein one end of the pipe body positioned on the outer side is opened, and the other end of the pipe body is closed; the two ends of the pipe body positioned on the inner side are both opened, the two pipe bodies are sleeved together, and the pipe body positioned on the inner side is communicated with the pipe body positioned on the outer side; the pipe body positioned at the inner side is sequentially filled with a filling substrate, coconut shell biochar and a filling substrate from bottom to top.
8. A quantitative detection method of triazine herbicides is characterized in that: the method comprises the following steps:
(1) making a standard curve: preparing a standard solution of triazine herbicide by using methanol as a solvent, treating the standard solution by adopting the pretreatment method of any one of claims 1-6, measuring the chromatographic peak retention time and the chromatographic peak area of each component in the standard solution of triazine herbicide by HPLC-UV, and drawing a standard curve of concentration-chromatographic peak area;
(2) HPLC-UV determination: treating a sample to be tested by adopting the pretreatment method of any one of claims 1 to 7, carrying out HPLC-UV measurement, and substituting the measurement result into a standard curve so as to calculate the concentration of the triazine herbicide in the sample to be tested.
9. The method for quantitatively detecting triazine herbicides according to claim 8, wherein: the standard solution contains three triazine herbicides: atrazine, ametryn and prometryn, wherein the concentration ranges of the components are respectively as follows: 10-10000 ng/mL of atrazine, 200-10000 ng/mL of ametryn and 200-10000 ng/mL of prometryn.
10. The method for quantitatively detecting triazine herbicides according to claim 8, wherein: the conditions of the HPLC-UV determination are as follows: liquid chromatography instrument model: agilent 1260Infinity II; a chromatographic column: the model is Pursuit 5C18, the specification is 5 μm particle size, 4.6mm × 150 mm; sample introduction amount: 20 mu L of the solution; column temperature: 25 ℃; a detector: a diode array detector; detector wavelength: 222 nm; the mobile phase is methanol/water 70/30 volume ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110146390.3A CN112946128A (en) | 2021-02-03 | 2021-02-03 | Pretreatment method and quantitative detection method of triazine herbicide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110146390.3A CN112946128A (en) | 2021-02-03 | 2021-02-03 | Pretreatment method and quantitative detection method of triazine herbicide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112946128A true CN112946128A (en) | 2021-06-11 |
Family
ID=76241897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110146390.3A Pending CN112946128A (en) | 2021-02-03 | 2021-02-03 | Pretreatment method and quantitative detection method of triazine herbicide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112946128A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120164286A1 (en) * | 2002-03-11 | 2012-06-28 | Pawliszyn Janusz B | Solid-phase microextraction coatings and methods for their preparation |
| CN110227425A (en) * | 2019-07-05 | 2019-09-13 | 山西农业大学 | The application of triazine herbicide in a kind of magnetism effervescent tablet and preparation method thereof and extraction water |
| CN210175513U (en) * | 2019-06-28 | 2020-03-24 | 上海洁诺德塑胶制品有限公司 | Packing tube |
| CN111257460A (en) * | 2020-02-25 | 2020-06-09 | 中国水产科学研究院黄海水产研究所 | Detection method of triazine herbicide and metabolite thereof in shellfish |
| CN111855873A (en) * | 2020-07-15 | 2020-10-30 | 中国水产科学研究院长江水产研究所 | Method for determining triazine herbicide residue in aquatic product by ultra-high performance liquid chromatography-tandem mass spectrometry |
-
2021
- 2021-02-03 CN CN202110146390.3A patent/CN112946128A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120164286A1 (en) * | 2002-03-11 | 2012-06-28 | Pawliszyn Janusz B | Solid-phase microextraction coatings and methods for their preparation |
| CN210175513U (en) * | 2019-06-28 | 2020-03-24 | 上海洁诺德塑胶制品有限公司 | Packing tube |
| CN110227425A (en) * | 2019-07-05 | 2019-09-13 | 山西农业大学 | The application of triazine herbicide in a kind of magnetism effervescent tablet and preparation method thereof and extraction water |
| CN111257460A (en) * | 2020-02-25 | 2020-06-09 | 中国水产科学研究院黄海水产研究所 | Detection method of triazine herbicide and metabolite thereof in shellfish |
| CN111855873A (en) * | 2020-07-15 | 2020-10-30 | 中国水产科学研究院长江水产研究所 | Method for determining triazine herbicide residue in aquatic product by ultra-high performance liquid chromatography-tandem mass spectrometry |
Non-Patent Citations (8)
| Title |
|---|
| AKIRA N 等: "Extraction of amphetamines and methylenedioxyamphetamines from urine using a monolithic silica disk-packed spin column and high-performance liquid chromatography–diode array detection", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| LI WT 等: "Effects of tall fescue biochar on the adsorption and desorption of atrazine in different types of soil", 《ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH》 * |
| TANG L 等: "Removal of trace organic pollutants (pharmaceuticals and pesticides) and reduction of biological effects from secondary effluent by typical granular activated carbon", 《SCIENCE OF THE TOTAL ENVIRONMENT》 * |
| 张永杰 等: "《钢铁低碳高能效共性难题技术研发与应用》", 31 August 2019, 冶金工业出版社 * |
| 李剑锋 等: "改性木屑对阿特拉津的吸附特性", 《东北林业大学学报》 * |
| 李小蒙 等: "磁性茶籽壳活性炭固相萃取-超高效液相色谱/质谱法测定环境水样中三嗪类除草剂", 《分析科学学报》 * |
| 李桂杰 等: "微波辅助水蒸汽结合上浮溶剂固化法快速萃取谷物中三嗪类除草剂", 《分析化学》 * |
| 陈珏敏 等: "液液萃取-高效液相色谱法测定地表水中阿特拉津", 《环境与发展》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109270190B (en) | Method for measuring residual quantity of 101 pesticides in medlar | |
| CN108663471B (en) | Method for determining contents of multiple endocrine disruptors in estuary sediments | |
| US4541268A (en) | Method and device for the sampling of trace elements in gases, liquids, solids or in surface layers | |
| CN107589203B (en) | Method for simultaneously detecting three cannabinol compounds in hemp by SPE-HPLC | |
| CN108362786B (en) | Rapid solvent extraction analysis method for N, N-dimethylformamide in soil | |
| CN102841161A (en) | Gas chromatography-mass spectrometric detection method for octyl phenol and nonyl phenol in aquatic products | |
| CN114504842B (en) | Cotton fiber support liquid phase extraction device and application thereof in drug concentration detection | |
| Serrano et al. | Fullerenes as sorbent materials for benzene, toluene, ethylbenzene, and xylene isomers preconcentration | |
| CN110907558A (en) | Method for detecting aniline in soil | |
| CN113391015A (en) | Method for detecting 14 phenolic compounds in soil | |
| CN104549593A (en) | Functional pipetting head with double purification functions of ultra-filtration and solid extraction and application of functional pipetting head | |
| CN104807688B (en) | A kind of method of micro polycyclic aromatic hydrocarbon in extracting and enriching large volume environmental water sample | |
| CN105044262A (en) | Water polychlorinated biphenyl dispersive solid-phase extraction gas chromatography detection method | |
| CN112684070B (en) | Method for measuring semi-volatile organic compounds in solid waste | |
| CN108918747B (en) | Method for rapidly screening and quantitatively determining pesticide residues in tobacco by combining filter head type solid-phase extraction with GC-QTOF/MS | |
| Xie et al. | Determination of polynuclear aromatic hydrocarbons in aerosol by solid-phase extraction and gas chromatography–mass spectrum | |
| Sohrabi et al. | Pre‐concentration of trace amount of bisphenol A in water samples by palm leaf ash and determination with high‐performance liquid chromatography | |
| CN103197009A (en) | Measuring method of residual quantity of preservatives | |
| CN112946128A (en) | Pretreatment method and quantitative detection method of triazine herbicide | |
| CN102728101A (en) | Solid-phase extracting column and application thereof | |
| CN110879165A (en) | Sample pretreatment method of organochlorine pesticide residue sample | |
| CN105891387A (en) | Enrichment method for detecting hydrophilic amino acid | |
| Rodríguez-Palma et al. | A modified micro-solid phase extraction device for in-port elution and injection into portable liquid chromatography: A proof-of-concept study | |
| Zhao et al. | Sensitive determination of phenols in environmental water samples with SPE packed with bamboo carbon prior to HPLC | |
| CN111239277B (en) | Method and kit for determining N-dimethyl nitrosamine in water and application |
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: 20210611 |