CN114910594B - Method for rapidly determining glyphosate by synchronously extracting and deriving - Google Patents
Method for rapidly determining glyphosate by synchronously extracting and deriving Download PDFInfo
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- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 54
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000001212 derivatisation Methods 0.000 claims abstract description 89
- 238000000605 extraction Methods 0.000 claims abstract description 48
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 35
- 238000001514 detection method Methods 0.000 claims abstract description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 54
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 46
- 239000003463 adsorbent Substances 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 26
- IRXSLJNXXZKURP-UHFFFAOYSA-N fluorenylmethyloxycarbonyl chloride Chemical compound C1=CC=C2C(COC(=O)Cl)C3=CC=CC=C3C2=C1 IRXSLJNXXZKURP-UHFFFAOYSA-N 0.000 claims description 23
- 239000011780 sodium chloride Substances 0.000 claims description 22
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 claims description 21
- 238000005185 salting out Methods 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 18
- 239000000284 extract Substances 0.000 claims description 17
- 239000007791 liquid phase Substances 0.000 claims description 17
- 238000000746 purification Methods 0.000 claims description 17
- 239000002689 soil Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000008346 aqueous phase Substances 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 12
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 12
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004445 quantitative analysis Methods 0.000 claims description 7
- 238000004451 qualitative analysis Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 3
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 239000006286 aqueous extract Substances 0.000 claims description 2
- 230000032798 delamination Effects 0.000 claims description 2
- 238000003260 vortexing Methods 0.000 claims description 2
- 238000003556 assay Methods 0.000 claims 1
- 230000010355 oscillation Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 239000000575 pesticide Substances 0.000 abstract description 2
- 238000002203 pretreatment Methods 0.000 abstract description 2
- 239000006174 pH buffer Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910021538 borax Inorganic materials 0.000 description 5
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 5
- 235000010339 sodium tetraborate Nutrition 0.000 description 5
- 239000004328 sodium tetraborate Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000002372 labelling Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 230000009261 transgenic effect Effects 0.000 description 3
- 238000002137 ultrasound extraction Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WSQCDHKJWQCQBB-UHFFFAOYSA-N acetonitrile 9H-fluoren-9-ylmethyl carbonochloridate Chemical compound CC#N.C1=CC=C2C(COC(=O)Cl)C3=CC=CC=C3C2=C1 WSQCDHKJWQCQBB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- 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)
- Spectroscopy & Molecular Physics (AREA)
- Cephalosporin Compounds (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to the technical field of pesticide detection, and particularly relates to a rapid glyphosate detection method by synchronously extracting and derivatizing. According to the method, in the pretreatment process of the sample to be detected, the extraction reagent with the pH buffer characteristic is adopted, and the proper derivatization reagent is matched, so that the glyphosate sample pretreatment method capable of synchronously carrying out extraction and derivatization is obtained.
Description
Technical Field
The invention belongs to the technical field of pesticide detection, and particularly relates to a rapid glyphosate detection method by synchronously extracting and derivatizing.
Background
Glyphosate is a highly potent herbicide with biocidal efficacy developed by the company mendo in the united states at 70 s of the 20 th century. In recent years, along with large-area planting of transgenic glyphosate-resistant crops, the use amount of glyphosate is larger and larger, and the transgenic glyphosate-resistant crop is the first transgenic crop tolerant herbicide in the world at present. Along with the wide use of glyphosate, the glyphosate is easy to be strongly combined with soil after entering the environment, so that pollution is caused, and meanwhile, the glyphosate is transmitted through the enrichment of crops, so that the food safety of human beings is finally influenced. Therefore, in order to ensure the safety of agricultural products, it is necessary to monitor the residual condition of glyphosate in soil, and it is critical to establish a related analysis and detection method.
Glyphosate is a highly polar compound that limits the application of many conventional gas chromatographic standard derivatization methods. Therefore, the high performance liquid chromatography is widely applied to the detection of glyphosate. Since the chromophore and fluorophore are absent, derivatization is necessary prior to detection by high performance liquid chromatography. Pretreatment of the existing high performance liquid chromatography detection method of glyphosate in soil generally comprises steps of extraction, purification, derivatization and the like, such as ultrasonic extraction of HJ1055-2019 by adopting mixed extract of sodium phosphate and sodium citrate, n-hexane purification and derivatization of 9-fluorenylmethyl chloroformate; for example, patent CN110441448a employs sodium phosphate ultrasonic extraction, n-hexane purification and 9-fluorenylmethyl chloroformate derivatization; for example Wang Yunru, sodium bicarbonate ultrasonic extraction, 9-fluorenylmethylchloroformate derivatization and HLB column purification are adopted in research of pre-column derivatization-solid phase extraction-high performance liquid chromatography fluorescence method for determining the residue of glyphosate in soil. The method has the defects of complicated pretreatment steps, time consumption and easy introduction of human errors, and simultaneously, the introduction of an organic solvent has the risk of secondary environmental pollution, so that the method is not suitable for rapid and accurate detection of actual mass samples.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a rapid glyphosate determination method which is synchronously performed by extraction and derivatization, wherein the steps of extraction and derivatization are completed in one step through online derivatization, the purification of an extracting solution is completed by utilizing the dispersion solid-phase extraction and salting-out actions of simple adsorbent particles, the pretreatment of glyphosate samples in soil or sediment is completed in a green and efficient way, and the technical problems that the pretreatment steps are complicated, time is wasted, organic reagents are introduced to cause secondary environmental pollution, and the like in the prior glyphosate determination method are solved.
In order to achieve the above purpose, the invention provides a rapid glyphosate determination method by synchronously extracting and deriving, which is characterized by comprising the following steps:
(1) Sample extraction and derivatization: mixing a sample to be detected with diatomite to prepare a quicksand-shaped mixed sample, mixing the mixed sample with a tetraborate solution and a derivatization reagent, and carrying out on-line extraction and derivatization to obtain a derivatized extract;
(2) Dispersion solid phase extraction and salting-out purification: fully mixing the liquid phase obtained after the solid-liquid separation of the derivatized extracting solution obtained in the step (1) with adsorbent particles and sodium chloride, purifying the derivatized extracting solution by utilizing the adsorption effect of the adsorbent particles and the salting-out effect of the sodium chloride, and obtaining a purified water phase extracting solution after the solid-liquid separation;
(3) And (3) carrying out qualitative and quantitative analysis and detection on the glyphosate in the purified aqueous phase extract obtained in the step (2).
Preferably, in the step (1), the sample to be detected and diatomite are mixed according to the mass ratio of 1:2-2:1 and then ground to prepare the quicksand-shaped mixed sample.
Preferably, the derivatizing agent in step (1) is an acetonitrile solution of 9-fluorenylmethyl chloroformate, wherein the concentration of 9-fluorenylmethyl chloroformate in the derivatizing agent is 5-20g/L; the concentration of tetraborate in the tetraborate solution is 0.05-0.10mol/L, and each gram of tetraborate solution added into the sample to be detected is 2-5 milliliters; the volume ratio of the derivatizing agent to the tetraborate solution is 1:1-2:1.
Preferably, step (1) mixes the mixed sample with tetraborate solution and derivatizing agent, and performs on-line extraction and derivatization under the conditions of shaking, stirring or ultrasound, wherein the extraction and derivatization time is 1-2 hours.
Preferably, step (2) is a solid-liquid separation of the derivatised extract obtained in step (1), said solid-liquid separation being a centrifugal separation.
Preferably, the adsorbent particles of step (2) are C 18 adsorbent particles.
Preferably, step (2) is to fully mix the liquid phase obtained after solid-liquid separation of the derivatised extract liquid obtained in step (1) with sodium chloride and adsorbent particles, wherein sodium chloride is added to the liquid phase to saturate the liquid phase during mixing, and the adsorbent particles are added in an amount of 0.02-0.1g per milliliter of the liquid phase.
Preferably, in the step (2), the liquid phase obtained after solid-liquid separation of the derivatized extraction liquid obtained in the step (1) is fully mixed with sodium chloride and adsorbent particles by vortex, so that the sodium chloride is dissolved, the derivatized extraction liquid is purified by salting-out action of the sodium chloride and adsorption action of the adsorbent particles, and the aqueous phase is taken out after standing and layering, so that the purified aqueous phase extraction liquid is obtained.
Preferably, the step (3) is to perform qualitative and quantitative analysis on the glyphosate in the purified aqueous phase extract obtained in the step (2) by adopting high performance liquid chromatography or high performance liquid chromatography-mass spectrometry.
Preferably, the sample to be measured is soil or sediment.
In general, the above technical solutions conceived by the present invention have the following beneficial effects compared with the prior art:
(1) According to the glyphosate determination method, in the pretreatment process of the sample to be detected, the extraction reagent with the pH buffering characteristic is adopted, and the proper derivatization reagent is matched, so that the pretreatment method for synchronously carrying out extraction and derivatization is obtained.
(2) According to the invention, salting-out phenomenon is utilized after sample in-situ derivatization pretreatment, only a small amount of sodium chloride salt is needed to be added, and after dissolution, delamination of solvent acetonitrile and water phase brought by the derivatization process can be realized, and because the glyphosate derivative is easier to enter the water phase, the process can achieve the effect of purifying the extracting solution, can also improve the enrichment multiple of the target object, and can obtain a lower detection limit of the method.
(3) According to the invention, C 18 adsorbent particles and simple vortex pretreatment are added in the sample extraction step, so that the purification of the extracting solution can be completed; compared with the traditional purification step, the method does not need to use an expensive solid-phase extraction column or use toxic and harmful organic reagent liquid-liquid extraction and purification, reduces uncontrollable human factors caused by complicated pretreatment steps, is simple to operate, and reduces the harm to secondary environmental pollution.
(4) According to the invention, an online derivatization technology, a dispersion solid-phase extraction technology and a salting-out technology are combined, and compared with the sample pretreatment steps in the high performance liquid chromatography for determination of soil and sediment glyphosate (HJ 1055-2019), the extraction and derivatization steps are completed in one step through online derivatization, the purification of an extracting solution is completed by utilizing the salting-out method and the adsorption effect of C 18 adsorbent particles, and the pretreatment of glyphosate in soil or sediment is completed in a green and efficient mode. Compared with a standard method, the method reduces the need for sample extraction: 1. filtering, 2, adjusting the pH value, 3, filtering, 4, carrying out complex pretreatment steps such as organic solvent extraction and the like, and enabling the operation flow to be simpler; the pretreatment efficiency of batch samples is improved, and the sample detection cost is reduced; the invention also reduces the use of a large amount of toxic and harmful organic reagents, and provides an efficient, accurate and green detection means for determining the glyphosate in soil or sediment.
(5) The invention can effectively simplify the pretreatment flow, save manpower and reduce the use of a large amount of organic reagents, and can complete the extraction and the derivatization of the glyphosate in the sample simultaneously by carrying out online derivatization under the condition of external energy assistance; through salting out and adsorbent dispersion solid phase extraction adsorption, the enrichment factor of the target object is further improved and the sample is purified. The method greatly reduces the difficulty of pretreatment, reduces the use of organic reagents, reduces the detection cost, improves the pretreatment efficiency, and can be successfully used for quantitative analysis of glyphosate in environmental soil and sediments.
Drawings
FIG. 1 is a flow chart of a method for determining glyphosate in accordance with an embodiment of the present invention.
FIG. 2 is a chromatogram of the glyphosate standard derived product of example 1.
FIG. 3 is a chromatogram of a direct test of a sample of the matrix of example 1 after on-line derivatization (unpurified).
FIG. 4 is a chromatogram of the matrix sample of example 1 after derivatization and purification by salting-out and solid phase extraction with adsorbent dispersion.
FIG. 5 is a chromatogram of a sample obtained in comparative example 4 using an aqueous sodium hydroxide solution as an extraction reagent under the same other conditions as in example 1.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a rapid glyphosate determination method for synchronously extracting and deriving, which comprises the following steps:
(1) Sample extraction and derivatization: mixing a sample to be detected with diatomite, grinding to obtain a mixed sample, mixing the mixed sample with tetraborate solution and a derivatization reagent, and carrying out on-line extraction and derivatization to obtain a derivatized extract;
(2) Dispersion solid phase extraction and salting-out purification: fully mixing the liquid phase obtained after the solid-liquid separation of the derivatized extracting solution obtained in the step (1) with adsorbent particles and sodium chloride, purifying the derivatized extracting solution by utilizing the adsorption effect of the adsorbent particles and the salting-out effect of the sodium chloride, and obtaining a purified water phase extracting solution after the solid-liquid separation;
(3) And (3) carrying out qualitative and quantitative analysis on the glyphosate in the purified aqueous phase extract obtained in the step (2).
In some embodiments, step (1) mixes the sample to be measured with diatomite according to a mass ratio of 1:2-2:1, and then grinds the mixture to prepare a quicksand-like mixed sample.
In some embodiments, the derivatizing agent of step (1) is an acetonitrile solution of 9-fluorenylmethyl chloroformate, wherein the concentration of 9-fluorenylmethyl chloroformate is 5-20g/L; the concentration of the tetraborate solution is 0.05-0.10mol/L, and each gram of tetraborate solution added into the sample to be detected is 2-5 milliliters; the volume ratio of the derivatizing agent to the tetraborate solution is 1:1-2:1.
In some embodiments, step (1) mixes the mixed sample with the tetraborate solution and the derivatizing agent, and performs on-line extraction and derivatization under shaking, stirring, or ultrasound conditions for a period of time ranging from 1 to 2 hours.
In some embodiments, the solid-liquid separation of step (2) is a vortex or a centrifuge. In a preferred embodiment, the layering can be achieved in step (2) by vortexing. The adsorbent particles in the step (2) are C 18 adsorbent particles.
In some embodiments, step (2) comprises mixing the liquid phase obtained after solid-liquid separation of the derivatized extract obtained in step (1) with sodium chloride and adsorbent particles thoroughly, wherein sodium chloride is added to the liquid phase to saturate the liquid phase during mixing, and the adsorbent particles are added in the range of 0.02-0.1g per milliliter of the liquid phase.
In some embodiments, the liquid phase obtained after solid-liquid separation of the derivatized extraction liquid obtained in step (1) is fully mixed with sodium chloride and adsorbent particles by vortex, so that sodium chloride is dissolved, the derivatized extraction liquid is purified by salting-out action of sodium chloride and adsorption action of adsorbent particles, and the aqueous phase is taken out after standing and layering, so that the purified aqueous phase extraction liquid is obtained.
In some embodiments, step (3) uses high performance liquid chromatography or high performance liquid chromatography mass spectrometry to perform qualitative and quantitative analytical detection of glyphosate (in the form of glyphosate derivatives) in the purified aqueous extract obtained in step (2).
In some embodiments, the present invention employs liquid chromatography conditions for high performance liquid chromatography detection: PAHs special analytical column 250mm x 4.6mm,5 μm stainless steel column; mobile phase a (0.3% phosphoric acid in water) mobile phase B (acetonitrile); flow rate: 0.8mL/min; column temperature: 30-40 ℃; sample injection amount: 20. Mu.L.
The rapid determination method of glyphosate provided by the invention is suitable for determination of glyphosate in soil and sediment, namely, the application objects of national standard HJ 1055-2019 are also suitable for the invention.
In the invention, various extraction reagents are tried in the experimental process, so that the extraction and the derivatization are synchronously carried out. For example, aqueous sodium hydroxide solution, aqueous ammonia solution, sodium citrate solution and other salts with complexing function are tried to be mixed with the sample to be extracted together with the derivatization reagent, however, when the extraction reagent is adopted, the derivatization can not be carried out at all, and the synchronous operation of the extraction and the derivatization can not be realized; or may be derived, but is derived not from glyphosate but possibly from a derivative of its degradation product. The reason for this analysis may be that the above extraction reagent only provides an alkaline environment but does not have pH buffering characteristics, and when coupling the derivatization process, the derivatization reagent 9-fluorenylmethylchloroformate hydrolysis side reaction generates a large amount of hydrogen ions, lowers the pH of the system, and is unsuitable for the glyphosate derivatization reaction. For example, high concentration sodium hydroxide (0.1 mol/L) is used as an extraction reagent, and the final system becomes acidic (pH of 2) as the reaction proceeds; although the citrate system has pH buffering characteristic, the pH of the citrate system ranges from 3.0 to 6.6, and the pH of the citrate system still decreases with the progress of the reaction, which affects the progress of the glyphosate derivative reaction. Unlike other extraction reagents, the present invention employs tetraborate, such as sodium tetraborate, as an extraction reagent, probably because of its wide use as a solvent for glyphosate derivatization as 9-fluorenylmethylchloroformate itself, while being able to provide the alkaline environment required for glyphosate extraction; meanwhile, tetraborate has certain complexing capacity, and can eliminate metal ion interference, so that the efficiency of derivative extraction is improved.
On-line derivatization means that the extraction process and the derivatization process are performed simultaneously, also known as in-situ derivatization. The invention measures glyphosate in soil and sediment, and extraction and derivatization in pretreatment are synchronously carried out, namely, the pretreatment process is online derivatization. This process enables the achievement of a pH "microenvironment" that may benefit primarily from tetraborate as both an extraction reagent and for the derivatization reaction, however, in experiments also found that on-line derivatization could not be achieved when the extraction reagent and derivatization reagent amounts were not matched. The reasons for this may be mainly two: firstly, tetraborate is added in the form of aqueous solution, the amount of the tetraborate added at a fixed concentration determines the amount of water introduced into the system, and excessive water introduction inevitably promotes the hydrolysis of the derivatization agent 9-fluorenylmethyl chloroformate; secondly, the addition of 9-fluorenyl methyl chloroformate is mostly carried out in the form of acetonitrile solution, the existence of acetonitrile mainly promotes the dissolution of 9-fluorenyl methyl chloroformate, the addition amount of acetonitrile introduced into a system is determined under a fixed concentration, and the insufficient introduction of acetonitrile is difficult to ensure the dissolution of 9-fluorenyl methyl chloroformate. Whether the hydrolysis or the difficult dissolution of 9-fluorenylmethyl chloroformate can inhibit the efficient progress of the system derivatization reaction. When the extraction and the derivatization are performed separately, generally, only a small amount of sodium tetraborate solution is added into hundreds of milliliters of derivatization reagent to meet the requirement of the derivatization reaction, however, the online derivatization is performed, and experiments show that the volume ratio of the extraction reagent to the derivatization reagent is in the range of 1:2-1:1 to ensure the smooth progress of the derivatization reaction, namely the online derivatization is realized. The proportion of solvent water and acetonitrile under the proportioning condition is greatly improved relative to the dosage in national standard HJ1055-2019, and a good condition is provided for purifying the derivative extracting solution by salting-out.
When the method is used for purifying the derivatized extract obtained by on-line derivatization, the method does not need to extract by an organic reagent or purify by a small column as in the traditional method, but adds saturated sodium chloride and adsorbent particles, purifies the derivatized extract by utilizing the salting-out effect of the sodium chloride and the adsorption effect of the adsorbent particles, stands and delaminates after simple vortex, and improves the enrichment factor of a target product in a water phase and purification.
Example 1
(1) Sample extraction: weighing 2g (dry weight) of the sample, adding 1g of diatomite, fully and uniformly mixing and grinding to form a quicksand shape; transfer to a clean 50mL pp centrifuge tube, add 10mL of aqueous sodium tetraborate at a concentration of 0.05mol/L and 20mL of acetonitrile at a concentration of 10g/L of 9-fluorenylmethyl chloroformate, cover the centrifuge tube and screw down, and assist in on-line derivatization for 1h by an ultrasonic instrument.
(2) Salting out and adsorbent particle purification: placing the centrifuge tube filled with the extracting solution into a centrifuge for high-speed centrifugation until solid-liquid separation; 10mL of supernatant was taken and added to a 12mL centrifuge tube with 0.3g of sodium chloride and 1.0g C 18 adsorbent particles; swirling for 2min, standing and layering immediately after salt is dissolved; the lower aqueous phase was filtered into sample vials and tested on-machine.
(3) Analysis and test steps: the test of the above samples was performed using a high performance liquid chromatography coupled with a fluorescence detector. Liquid chromatography conditions for the above detection: PAHs special analytical column 250mm x 4.6mm,5 μm stainless steel column; mobile phase a (0.3% phosphoric acid in water) mobile phase B (acetonitrile); flow rate: 0.8mL/min; column temperature: 35 ℃; sample injection amount: 20. Mu.L. Table 1 shows the conditions for high performance liquid chromatography gradient elution, and Table 2 shows the conditions for fluorescence detector wavelength selection.
TABLE 1 gradient elution conditions for high Performance liquid chromatography
TABLE 2 fluorescence detector wavelength selection conditions
And (3) diluting a proper amount of glyphosate standard use solution with ultrapure water to form a standard series with the linear range of 1-200 mu g/L, and performing pretreatment according to the same steps of the sample. The linear regression equation is A= 57359.0729 XC, and the correlation coefficient is 0.9998, which shows that the linear relation between the mass concentration of the glyphosate and the fluorescence response peak area corresponding to the derivatization product is good in the mass concentration range of 1-200 mug/L. According to the regulations of the environmental monitoring analysis method standard revision technical code (HJ 168-2020), 7 concentration samples which are close to the detection limit of the method are continuously measured by the method, the detection limit of the method is examined, the detection limit of the method is 0.019mg/kg, and the quantitative lower limit of the method is 0.076mg/kg through conversion of 4 times of the detection limit; and the actual soil matrix was selected for the standard addition recovery test, the mass concentrations of the addition were 0.05, 0.10 and 0.50mg/kg, respectively, 6 parallel samples were prepared for each sample, and the recovery rate and the relative standard deviation result of the measured results are shown in table 3. As shown in Table 3, the glyphosate standard recovery rate of the method is between 83.0% and 99.0%, the relative standard deviation of the measurement result is between 10.5% and 12.9%, and the accuracy and precision of the method can meet the measurement requirement of actual samples. Compared with the traditional method, the method is efficient, accurate and green, and is suitable for actual mass sample analysis and detection.
TABLE 3 labeling recovery test results
Table 3Results of tests for recovery
FIG. 1 is a flow chart of a method for determining glyphosate in accordance with an embodiment of the present invention.
FIG. 2 is a chromatogram of the derived product of the glyphosate standard of example 1, showing sharp symmetry of the peaks of the derived product and small interference of the derived by-products.
FIG. 3 is a chromatogram of a direct test of a substrate sample of example 1 after on-line derivatization (unpurified), showing that the peak response of the derivatized byproducts is too strong, which reduces the fluorescence detector lifetime and severely interferes with the analytical quantification of glyphosate.
FIG. 4 is a chromatogram of the matrix sample of example 1 after derivatization and purification by salting out and dispersion of solid phase extraction adsorbent, and comparing with FIG. 3, it can be seen that the derivatization by-product is effectively removed, and the purification effect is better.
Comparative example 1
Other conditions are different from those of example 1, in that 10mL of 1g/L potassium dihydrogen phosphate aqueous solution and 20mL of 10g/L derivatization reagent 9-fluorenylmethylchloroformate acetonitrile solution are used for online derivatization, and experiments show that even if a blank matrix quartz sand is used for a labeling experiment, the peak position of a glyphosate derivative still has strong interference, so that the method cannot complete qualitative and quantitative analysis.
Comparative example 2
Other conditions are the same as in example 1, except that 10mL of ammonia water with the concentration of 0.5mol/L and 20mL of acetonitrile solution of the derivatization reagent 9-fluorenylmethyl chloroformate with the concentration of 10g/L are used for online derivatization, and experiments show that the derivatization effect is better when the quartz sand is used as a matrix for the labeling experiment, but the derivatization cannot be performed when the actual soil sample labeling experiment is performed, and the product recovery rate is 0, so that the condition is not practical.
Comparative example 3
Other conditions are the same as in example 1, except that 10mL of aqueous sodium hydroxide solution with concentration of 0.05mol/L and 20mL of acetonitrile solution of derivatization reagent 9-fluorenylmethylchloroformate with concentration of 10g/L are used for online derivatization, and the experiment shows that the system after derivatization is in a strong acid (pH < 3) environment, and the derivatization efficiency in an actual sample is 0, so that the online derivatization cannot be performed.
Comparative example 4
Other conditions were the same as in example 1 except that 0.05mol/L aqueous sodium hydroxide solution was used for on-line derivatization with 20mL of acetonitrile solution of derivatization reagent 9-fluorenylmethylchloroformate at a concentration of 10g/L, and an appropriate amount of PSA was added as a dispersion solid phase extraction adsorbent, and it was found experimentally that the introduction of PSA easily resulted in degradation of glyphosate under alkaline conditions, and the results are shown in FIG. 5, indicating that PSA is unsuitable as an adsorbent for dispersion solid phase extraction.
Comparative example 5
Other conditions were the same as in example 1 except that 10mL of aqueous sodium citrate at a concentration of 0.05mol/L was used for on-line derivatization with 20mL of an acetonitrile solution of the derivatizing agent 9-fluorenylmethylchloroformate at a concentration of 10g/L, and it was found that the reaction resulted in a derivatization product other than glyphosate, accompanied by the presence of other interfering peaks, which was not suitable for on-line derivatization.
Comparative example 6
Other conditions are the same as in example 1, except that in an online derivatization system of 10mL of sodium tetraborate solution with the concentration of 0.05mol/L and 20mL of acetonitrile solution of derivatization reagent 9-fluorenylmethyl chloroformate with the concentration of 10g/L, a proper amount of HC-C 18 and LC-C 18 are respectively added to serve as dispersed solid phase extraction adsorbents, and experiments show that the recovery rate results of the adsorbents HC-C 18 and LC-C 18 are reduced, which means that the C 18 material is directly introduced into the online derivatization process to adsorb or complex glyphosate, so that derivatization is incomplete.
Comparative example 7
Other conditions are the same as in example 1, except that the volume ratio of the 0.05mol/L sodium tetraborate solution to the 10g/L acetonitrile solution of the derivatizing agent 9-fluorenylmethyl chloroformate is changed, and it is found that when the ratio is higher than 1:1, the recovery of the glyphosate derivative product tends to decrease and fail to derivative as the ratio increases, indicating that the derivatization is less effective at this solvent ratio.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (4)
1. The rapid glyphosate determination method by synchronously extracting and deriving is characterized by comprising the following steps:
(1) Sample extraction and derivatization: mixing a sample to be detected with diatomite according to a mass ratio of 1:2-2:1, grinding to prepare a quicksand mixed sample, mixing the mixed sample with a tetraborate solution and a derivatization reagent, and carrying out on-line extraction and derivatization under the conditions of oscillation, stirring or ultrasound, wherein the extraction and derivatization time is 1-2 hours; obtaining a derivatized extract; the derivatization reagent is an acetonitrile solution of 9-fluorenylmethyl chloroformate, and the concentration of the 9-fluorenylmethyl chloroformate in the derivatization reagent is 5-20 g/L; the concentration of tetraborate in the tetraborate solution is 0.05-0.10 mol/L, and each gram of tetraborate solution added into the sample to be detected is 5 milliliters; the volume ratio of the derivatizing agent to the tetraborate solution is 2:1; the sample to be detected is soil or sediment;
(2) Dispersion solid phase extraction and salting-out purification: fully mixing the liquid phase obtained after solid-liquid separation of the derivatized extraction liquid obtained in the step (1), sodium chloride and adsorbent particles, wherein sodium chloride is added into the liquid phase to saturate the liquid phase during mixing, the adsorbent particles added into each milliliter of the liquid phase are 0.02-0.1 g, the derivatized extraction liquid is purified by utilizing the adsorption effect of the adsorbent particles and the salting-out effect of the sodium chloride, and the purified aqueous phase extraction liquid is obtained after solid-liquid separation; the adsorbent particles are C 18 adsorbent particles;
(3) And (3) carrying out qualitative and quantitative analysis and detection on the glyphosate in the purified aqueous phase extract obtained in the step (2).
2. The method according to claim 1, wherein the step (2) is carried out by subjecting the derivatized extract obtained in the step (1) to solid-liquid separation, which is centrifugal separation.
3. The method according to claim 1, wherein the liquid phase obtained by solid-liquid separation of the derivatized extract obtained in step (1) is thoroughly mixed with adsorbent particles and sodium chloride by vortexing to dissolve sodium chloride, purifying the derivatized extract by salting-out of sodium chloride and adsorption of the adsorbent particles, standing for delamination, and removing a lower aqueous phase to obtain a purified aqueous phase extract.
4. The assay of claim 1 wherein step (3) uses high performance liquid chromatography or high performance liquid chromatography mass spectrometry to perform qualitative and quantitative analysis on the glyphosate in the purified aqueous extract obtained in step (2).
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