CN114910594A - Method for rapidly measuring glyphosate by synchronously extracting and deriving - Google Patents
Method for rapidly measuring 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 62
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- 229940097068 glyphosate Drugs 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 46
- 238000000605 extraction Methods 0.000 claims abstract description 35
- 238000001514 detection method Methods 0.000 claims abstract description 15
- 238000001212 derivatisation Methods 0.000 claims description 82
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound 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 48
- 239000003463 adsorbent Substances 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 31
- 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 24
- 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 23
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- 239000000575 pesticide Substances 0.000 abstract description 2
- 238000002203 pretreatment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 55
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- 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
- 230000009471 action Effects 0.000 description 4
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- 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
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 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
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- 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
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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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- 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 method for quickly determining glyphosate by synchronously extracting and deriving. In the pretreatment process of a sample to be detected, the method obtains the glyphosate sample pretreatment method with synchronous extraction and derivation by adopting the extraction reagent with the pH buffer characteristic and matching with the proper derivation reagent.
Description
Technical Field
The invention belongs to the technical field of pesticide detection, and particularly relates to a method for quickly determining glyphosate by synchronously extracting and deriving.
Background
Glyphosate is a systemic high-efficiency herbicide with biocidal property developed by the company montmorindo usa in the 70 th 20 th century. In recent years, with the large-area planting of transgenic glyphosate-resistant crops, the usage amount of glyphosate is larger and larger, and the glyphosate is the herbicide which is tolerated by the first transgenic crop with the usage amount in the world at present. 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 by enrichment of crops, so that the food safety of human beings is finally influenced. Therefore, in order to ensure the safety of agricultural products, monitoring of the residual condition of glyphosate in soil needs to be carried out, and the establishment of a related analysis and detection method is key.
Glyphosate is a highly polar compound that limits the application of many standard derivatization methods for conventional gas chromatography. Therefore, the high performance liquid chromatography is widely applied to glyphosate detection. Because of the lack of chromophoric and fluorescent groups, derivatization is necessary prior to detection by high performance liquid chromatography. The pretreatment of the existing high performance liquid chromatography detection method for glyphosate in soil generally comprises the steps of extraction, purification, derivatization and the like, for example, HJ1055-2019 adopts the mixed extract of sodium phosphate and sodium citrate for ultrasonic extraction, normal hexane purification and 9-fluorenylmethyl chloroformate derivatization; for example, patent CN110441448A adopts sodium phosphate ultrasonic extraction, n-hexane purification and 9-fluorenylmethyl chloroformate derivatization; for example, Wang Yun Ru et al used sodium bicarbonate ultrasonic extraction, 9-fluorenylmethylchloroformate derivatization and HLB column purification in the research of 'pre-column derivatization-solid phase extraction-high performance liquid chromatography fluorescence method for measuring glyphosate residue in soil'. The methods have the defects of complicated pretreatment steps, time consumption, easy introduction of human errors, secondary environmental pollution risk due to the introduction of organic solvents, and unsuitability for rapid and accurate detection of actual large-scale samples.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for rapidly measuring glyphosate by synchronously extracting and deriving, which finishes the steps of extracting and deriving in one step through online deriving, finishes the purification of an extracting solution by utilizing the dispersion solid-phase extraction and salting-out action of simple adsorbent particles, finishes the pretreatment of a glyphosate sample in soil or sediment in a green and efficient way, and solves the technical problems that the pretreatment step in the existing glyphosate measuring method is complicated, time-consuming, and the introduction of an organic reagent causes secondary environmental pollution, is not suitable for the pretreatment of a large-batch sample and the like.
In order to achieve the purpose, the invention provides a method for rapidly measuring glyphosate by synchronously extracting and deriving, which is characterized by comprising the following steps:
(1) sample extraction and derivatization: mixing a sample to be detected and diatomite to prepare a quicksand-shaped mixed sample, mixing the mixed sample with a tetraborate solution and a derivatization reagent, and performing online extraction and derivatization to obtain a derivatized extracting solution;
(2) dispersed solid phase extraction and salting-out purification: fully mixing a liquid phase obtained after 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 solid-liquid separation;
(3) and (3) carrying out qualitative and quantitative analysis and detection on the glyphosate in the purified aqueous phase extracting solution 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 a quicksand-shaped mixed sample.
Preferably, the derivatizing reagent of step (1) is an acetonitrile solution of 9-fluorenylmethyl chloroformate, wherein the concentration of 9-fluorenylmethyl chloroformate in the derivatizing reagent is 5 to 20 g/L; the concentration of tetraborate in the tetraborate solution is 0.05-0.10mol/L, and the tetraborate solution added into each gram of the sample to be detected is 2-5 ml; the volume ratio of the derivatization reagent to the tetraborate solution is 1:1-2: 1.
Preferably, the step (1) is to mix the mixed sample with a tetraborate solution and a derivatization reagent, and carry out online extraction and derivatization under the conditions of shaking, stirring or ultrasound, wherein the extraction and derivatization time is 1-2 hours.
Preferably, the step (2) is to perform solid-liquid separation of the derivatized extract obtained in the step (1), wherein the solid-liquid separation is centrifugal separation.
Preferably, the adsorbent particles of step (2) are C 18 Adsorbent particles.
Preferably, in the step (2), the liquid phase obtained after the solid-liquid separation of the extraction liquid obtained after the derivatization in the step (1) is fully mixed with sodium chloride and adsorbent particles, wherein the sodium chloride is added into the liquid phase to be saturated during the mixing, and the amount of the adsorbent particles added into the liquid phase is 0.02-0.1g per milliliter.
Preferably, in the step (2), the liquid phase obtained by performing solid-liquid separation on the derivatized extracting solution obtained in the step (1), sodium chloride and adsorbent particles are fully mixed by adopting vortex to dissolve the sodium chloride, the derivatized extracting solution is purified by utilizing the salting-out effect of the sodium chloride and the adsorption effect of the adsorbent particles, and the purified aqueous phase extracting solution is obtained by taking down the lower aqueous phase after standing and layering.
Preferably, the glyphosate in the purified aqueous phase extracting solution obtained in the step (2) is qualitatively and quantitatively analyzed by adopting high performance liquid chromatography or high performance liquid chromatography-mass spectrometry in the step (3).
Preferably, the sample to be tested is soil or sediment.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) the invention provides a glyphosate determination method, in the pretreatment process of a sample to be determined, an extraction reagent with pH buffer characteristic is adopted, and a proper derivatization reagent is matched, so that a pretreatment method for synchronously extracting and derivatizing is obtained.
(2) The method utilizes the salting-out phenomenon after the in-situ derivatization pretreatment of the sample, only needs to add a small amount of sodium chloride salt, can realize the layering of the acetonitrile solvent and the water phase brought by the derivatization process after dissolution, and can achieve the purification effect of the extracting solution and improve the enrichment multiple of the target object to obtain a lower detection limit of the method because the glyphosate derivative is easier to enter the water phase.
(3) The invention adds C in the step of extracting the sample 18 The purification of the extracting solution can be finished by the adsorbent particles and simple vortex pretreatment; compared with the traditional purification step, the method does not need expensive solid phase extraction column or toxic and harmful organic reagent liquid-liquid extraction purification, reduces uncontrollable human factors brought by fussy pretreatment steps, is simple to operate, and reduces the harm to secondary pollution of the environment.
(4) The method combines an online derivatization technology, a dispersed solid phase extraction technology and a salting-out technology, and compares the steps with a sample pretreatment step in high performance liquid chromatography for measuring glyphosate in soil and sediment (HJ 1055- 18 The purification of the extracting solution is completed by the adsorption effect of the adsorbent particles, and the pretreatment of the glyphosate in the soil or the sediment is completed in a green and efficient mode. Compared with the standard method, the method reduces the need of extracting the sample: 1. filtering, 2, adjusting pH, 3, filtering, 4, extracting by an organic solvent and other complicated pretreatment steps, so that the operation flow is simpler; the efficiency of pretreatment 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 detecting the glyphosate in the soil or the sediment.
(5) The method can effectively simplify the pretreatment process, save labor, reduce the use of a large amount of organic reagents, carry out online derivatization under the condition of external energy assistance, and simultaneously complete the extraction and derivatization of glyphosate in the sample; and the target enrichment times are further improved and the sample is purified by salting out and adsorbent dispersed solid phase extraction adsorption. 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 glyphosate determination method in an embodiment of the present invention.
FIG. 2 is a chromatogram of the product derived from the glyphosate standard of example 1.
FIG. 3 is a chromatogram of a direct assay of a sample of the matrix of example 1 after in-line derivatization (unpurified).
FIG. 4 is a chromatogram of a matrix sample after derivatization and purification by salting out and adsorbent-dispersed solid phase extraction in example 1.
FIG. 5 is a chromatogram of a sample obtained in comparative example 4 using an aqueous solution of sodium hydroxide as an extraction reagent and the other conditions were the same as in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a method for rapidly measuring glyphosate by 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 a tetraborate solution and a derivatization reagent, and carrying out online extraction and derivatization to obtain a derivatized extracting solution;
(2) dispersed solid phase extraction and salting-out purification: fully mixing a liquid phase obtained after 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 solid-liquid separation;
(3) and (3) carrying out qualitative and quantitative analysis on the glyphosate in the purified aqueous phase extracting solution obtained in the step (2).
In some embodiments, 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 a quicksand-shaped mixed sample.
In some embodiments, said derivatizing reagent of step (1) is a solution of 9-fluorenylmethyl chloroformate in acetonitrile, wherein said 9-fluorenylmethyl chloroformate is present in a concentration of 5 to 20 g/L; the concentration of the tetraborate solution is 0.05-0.10mol/L, and the tetraborate solution added into each gram of the sample to be detected is 2-5 ml; the volume ratio of the derivatization reagent to the tetraborate solution is 1:1-2: 1.
In some embodiments, step (1) mixes the mixed sample with a tetraborate solution and a derivatizing reagent, and performs on-line extraction and derivatization under shaking, stirring or ultrasonic conditions, wherein the extraction and derivatization time is 1-2 hours.
In some embodiments, the solid-liquid separation of step (2) is a vortex or centrifugal separation. In a preferred embodiment, the delamination in step (2) is achieved by using a vortex. The adsorbent particles in the step (2) are C 18 Adsorbent particles.
In some embodiments, in the step (2), the liquid phase obtained after the solid-liquid separation of the derivatized extraction liquid obtained in the step (1) is fully mixed with sodium chloride and adsorbent particles, wherein the sodium chloride is added to the liquid phase to reach saturation during the mixing, and the amount of the adsorbent particles added to the liquid phase is 0.02-0.1g per ml.
In some embodiments, in the step (2), the liquid phase obtained by performing solid-liquid separation on the derivatized extracting solution obtained in the step (1), sodium chloride and adsorbent particles are fully mixed by adopting vortex to dissolve the sodium chloride, the derivatized extracting solution is purified by utilizing the salting-out effect of the sodium chloride and the adsorption effect of the adsorbent particles, and the purified aqueous phase extracting solution is obtained by taking down the lower aqueous phase after standing and layering.
In some embodiments, the step (3) is used for qualitative and quantitative analysis and detection of glyphosate (in the form of glyphosate derivative) in the purified aqueous phase extract obtained in the step (2) by high performance liquid chromatography or high performance liquid chromatography-mass spectrometry.
In some embodiments, the present invention employs liquid chromatography conditions for high performance liquid chromatography detection: a stainless steel column with the diameter of 250mm multiplied by 4.6mm and the diameter of 5 mu m special for PAHs analysis column; mobile phase a (0.3% aqueous phosphoric acid), mobile phase B (acetonitrile); flow rate: 0.8 mL/min; column temperature: 30-40 ℃; sample injection amount: 20 μ L.
The method for rapidly measuring the glyphosate is suitable for measuring the glyphosate in soil and sediments, and also suitable for the application objects of national standard HJ 1055-2019.
In the experimental process, a plurality of extraction reagents are tried so as to realize the synchronous extraction and derivation. For example, a sodium hydroxide aqueous solution, an ammonia aqueous solution, a sodium citrate solution and other salts with a complexing function are respectively tried to be mixed with a sample to be extracted together with a derivatization reagent, however, when the extraction reagents are adopted, derivatization cannot be carried out at all, and synchronous operation of extraction and derivatization cannot be realized; or derivatives which may be derived but are not glyphosate and may be degradation products thereof. The reason for analyzing the above-mentioned reaction is that the above-mentioned reagent can only provide an alkaline environment but does not have a pH buffering property, when the derivatization process is coupled, the derivatization reagent 9-fluorenylmethylchloroformate hydrolysis side reaction can generate a large amount of hydrogen ions, the pH of the system is reduced, and the reaction is not suitable for the glyphosate derivatization reaction along with the reduction of the pH. For example, high concentration sodium hydroxide (0.1mol/L) is used as an extraction reagent, and the final system becomes acidic (pH is 2) as the reaction proceeds; although the citrate system has pH buffering characteristic, the buffering pH range is 3.0-6.6, and the pH of the system is still reduced along with the progress of the reaction, so that the progress of the glyphosate derivatization reaction is influenced. Different from other extraction reagents, the invention adopts tetraborate such as sodium tetraborate as the extraction reagent, probably because the tetraborate is widely used as a solvent for glyphosate derivatization of 9-fluorenylmethyl chloroformate and can provide an alkaline environment required by glyphosate extraction; meanwhile, the tetraborate has certain complexing capacity and can eliminate metal ion interference, so that the deriving and extracting efficiency is improved.
On-line derivatization refers to the simultaneous extraction and derivatization processes, also known as in-situ derivatization. The method is used for measuring the glyphosate in the soil and sediment, and the extraction and the derivation in the pretreatment are synchronously carried out, namely the pretreatment process is on-line derivation. The process may benefit primarily from the fact that tetraborate can be used as both an extraction reagent and to provide a suitable pH "microenvironment" for the derivatization reaction, however, it has also been found in experiments that online derivatization cannot be achieved when the amounts of extraction reagent and derivatization reagent do not match. The reason for this may be mainly two ways: firstly, the tetraborate is added in the form of aqueous solution, the amount of the added tetraborate at a fixed concentration determines the amount of moisture introduced into a system, and excessive introduction of the moisture inevitably promotes the hydrolysis of the derivatization agent 9-fluorenylmethyl chloroformate; secondly, the 9-fluorenylmethyl chloroformate is added in the form of acetonitrile solution, the existence of acetonitrile mainly promotes the dissolution of the 9-fluorenylmethyl chloroformate, the amount of acetonitrile introduced into a system is determined by the amount of the 9-fluorenylmethyl chloroformate added under a fixed concentration, and the dissolution of the 9-fluorenylmethyl chloroformate is difficult to ensure due to the insufficient introduction of the acetonitrile. The hydrolysis of 9-fluorenylmethylchloroformate, whether difficult or impossible to dissolve, inhibits the efficient progress of the derivatization reaction of the system. When the extraction and derivatization are carried out step by step, the requirement of the derivatization reaction can be met only by adding a small amount of sodium tetraborate solution into a few hundred milliliters of derivatization reagent, however, the online derivatization is carried out, 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 proceeding of the derivatization reaction, namely, the online derivatization is realized. The proportion of the solvent water and the acetonitrile under the proportioning condition is greatly improved relative to the dosage in national standard HJ1055-2019, and good conditions are provided for purifying derivative extracting solution through salting-out action.
When the invention is used for purifying the derivatized extracting solution obtained by on-line derivatization, saturated sodium chloride and adsorbent particles are added without organic reagent extraction or small column purification as in the traditional method, the derivatized extracting solution is purified by utilizing the salting-out action of the sodium chloride and the adsorption action of the adsorbent particles, and the target product is in a water phase after simple vortex and is kept stand for layering, so that the enrichment factor is improved while the purification is carried out.
Example 1
(1) A sample extraction step: weighing 2g (in terms of dry weight) of sample, adding 1g of diatomite, fully mixing uniformly and grinding to a quicksand shape; transferring to a clean 50mL pp centrifuge tube, adding 10mL of 0.05mol/L aqueous sodium tetraborate solution and 20mL of 10g/L acetonitrile 9-fluorenylmethyl chloroformate solution, covering the centrifuge tube, screwing, and performing online derivatization for 1h by using an ultrasonic instrument.
(2) Salting out and adsorbent particle purification: placing the centrifugal tube filled with the extracting solution in a centrifugal machine for high-speed centrifugation until solid-liquid separation; 10mL of the supernatant was taken and added with 0.3g of sodium chloride and 1.0g of 1.0g C 18 Placing the adsorbent particles in a 12mL centrifuge tube; vortex for 2min, standing for layering immediately after salt is dissolved; the lower aqueous phase was filtered into a sample vial and tested on the machine.
(3) And (3) analysis and test steps: and (3) testing the sample by adopting a high performance liquid chromatography combined fluorescence detector. Liquid chromatography conditions for the above tests: a stainless steel column with the diameter of 250mm multiplied by 4.6mm and the diameter of 5 mu m special for PAHs analysis column; mobile phase a (0.3% aqueous phosphoric acid), mobile phase B (acetonitrile); flow rate: 0.8 mL/min; column temperature: 35 ℃; sample introduction amount: 20 μ L. Table 1 shows the gradient elution conditions of HPLC, and Table 2 shows the wavelength selection conditions of the fluorescence detector.
TABLE 1 high Performance liquid chromatography gradient elution conditions
TABLE 2 fluorescence Detector wavelength selection conditions
Taking a proper amount of glyphosate standard use solution, diluting the glyphosate standard use solution with ultrapure water into a standard series with a linear range of 1-200 mu g/L, and carrying out pretreatment according to the same steps of the sample. The mass concentration (C) of the glyphosate is taken as an abscissa, the peak area (A) of the derivative of the glyphosate is taken as an ordinate, the linear regression equation is obtained, wherein A is 57359.0729 xC, and the correlation coefficient is 0.9998, so that the linear relation between the glyphosate and the fluorescence response peak area corresponding to the derivative product of the glyphosate in the mass concentration range of 1-200 mu g/L is good. According to the regulation of the revised technical guide of environmental monitoring and analysis method Standard (HJ 168-; and selecting actual soil matrix to carry out a standard addition recovery test, wherein the mass concentration of the added soil matrix is 0.05, 0.10 and 0.50mg/kg, each sample is prepared into 6 parallel samples, and the recovery rate and the relative standard deviation result of the measured result are shown in Table 3. As can be seen from Table 3, the glyphosate spiking 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 requirement of actual sample measurement. Compared with the traditional method, the method is efficient, accurate and green, and is suitable for analyzing and detecting actual large-batch samples.
TABLE 3 test results of recovery with addition of a standard
Table 3Results of tests for recovery
FIG. 1 is a flow chart of a glyphosate determination method in an embodiment of the present invention.
FIG. 2 is a chromatogram of a derivative product of the glyphosate standard substance in example 1, and it can be seen that the peak shape of the derivative product is sharp and symmetrical, and the interference of the derivative by-product is small.
FIG. 3 is a chromatogram of a direct assay of a sample of the substrate of example 1 after in-line derivatization (unpurified), showing that too strong a peak response of the derivatized by-product reduces the lifetime of the fluorescence detector and significantly interferes with the analytical quantitation of glyphosate.
FIG. 4 is a chromatogram of the matrix sample of example 1 after derivatization and purification by salting out and dispersive solid phase extraction adsorbent, and comparison with FIG. 3 shows that the derivatized by-products are effectively removed and the purification effect is good.
Comparative example 1
The other conditions are the same as example 1, except that 10mL of potassium dihydrogen phosphate aqueous solution with the concentration of 1g/L and 20mL of acetonitrile solution of derivatization reagent 9-fluorenylmethyl chloroformate with the concentration of 10g/L are used for on-line derivatization, and experiments show that even if a labeling experiment is carried out by using blank matrix quartz sand, the peak position of the glyphosate derivative still has strong interference, so that the method cannot complete qualitative and quantitative analysis.
Comparative example 2
The other conditions are the same as example 1, except that 10mL of ammonia water with the concentration of 0.5mol/L and 20mL of acetonitrile solution of a derivatization reagent 9-fluorenylmethylchloroformate with the concentration of 10g/L are used for online derivatization, and experiments show that when a standard addition experiment is carried out by using quartz sand as a matrix, a good derivatization effect is achieved, but when an actual soil sample standard addition experiment is carried out, the derivatization cannot be carried out, the product recovery rate is 0, and the conditions are not feasible.
Comparative example 3
Other conditions are the same as example 1, except that the online derivatization is carried out by using 10mL of aqueous solution of sodium hydroxide with the concentration of 0.05mol/L and 20mL of acetonitrile solution of derivatization reagent 9-fluorenylmethyl chloroformate with the concentration of 10g/L, and experiments show that the system after the derivatization is in a strong acid (pH <3) environment, and the derivatization efficiency in actual samples is 0, so that the derivatization cannot be carried out.
Comparative example 4
Other conditions are the same as example 1, except that 0.05mol/L sodium hydroxide aqueous solution and 20mL acetonitrile solution with the concentration of 10g/L derivatization reagent 9-fluorenylmethylchloroformate are subjected to online derivatization, and a proper amount of PSA is added as a dispersed solid phase extraction adsorbent, experiments show that the introduction of PSA is easy to degrade glyphosate under an alkaline environment, and the result is shown in FIG. 5, which indicates that PSA is not suitable for being used as the dispersed solid phase extraction adsorbent.
Comparative example 5
The other conditions are the same as example 1, except that the online derivatization is carried out by 10mL of sodium citrate aqueous solution with the concentration of 0.05mol/L and 20mL of acetonitrile solution with the concentration of 10g/L of derivatization reagent 9-fluorenylmethylchloroformate, and experiments show that the reaction obtains a derivatization product which is not glyphosate and is accompanied by the existence of other interference peaks, and the conditions are not suitable for the online derivatization.
Comparative example 6
The other conditions are the same as example 1, except that in an on-line 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, proper amounts of HC-C are respectively added 18 And LC-C 18 As a dispersed solid phase extraction adsorbent, experiments show that HC-C is introduced 18 And LC-C 18 The recovery rate of the adsorbent is reduced, which shows that C 18 The material is directly introduced into an online derivatization process, and can adsorb or complex glyphosate, so that the derivatization is incomplete.
Comparative example 7
Other conditions were the same as in example 1, except that the ratio by volume of the sodium tetraborate solution (0.05 mol/L) to the acetonitrile solution (10 g/L) of the derivatizing reagent 9-fluorenylmethylchloroformate was varied, and it was found experimentally that when the ratio of the two was higher than 1:1, the recovery of glyphosate derived product tends to decrease and become non-derivatizable with increasing ratio, indicating that the derivatization is less effective at this solvent ratio.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for rapidly measuring glyphosate 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, grinding to obtain a mixed sample, mixing the mixed sample with a tetraborate solution and a derivatization reagent, and performing online extraction and derivatization to obtain a derivatized extracting solution;
(2) dispersive solid-phase extraction and salting-out purification: fully mixing a liquid phase obtained after 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 solid-liquid separation;
(3) and (3) carrying out qualitative and quantitative analysis and detection on the glyphosate in the purified aqueous phase extracting solution obtained in the step (2).
2. The method according to claim 1, wherein in the step (1), the sample to be measured and the diatomite are mixed in a mass ratio of 1:2-2:1 and then ground to prepare a quicksand-like mixed sample.
3. The assay of claim 1 wherein said derivatizing reagent of step (1) is an acetonitrile solution of 9-fluorenylmethyl chloroformate, wherein the concentration of 9-fluorenylmethyl chloroformate in said derivatizing reagent is between 5 and 20 g/L; the concentration of tetraborate in the tetraborate solution is 0.05-0.10mol/L, and the tetraborate solution added into each gram of the sample to be detected is 2-5 ml; the volume ratio of the derivatization reagent to the tetraborate solution is 1:1-2: 1.
4. The assay method of claim 1, wherein step (1) comprises mixing the mixed sample with a tetraborate solution and a derivatizing reagent, and performing on-line extraction and derivatization under shaking, stirring or ultrasound conditions for 1 to 2 hours.
5. The method according to claim 1, wherein the step (2) comprises subjecting the derivatized extract obtained in the step (1) to solid-liquid separation, which is centrifugal separation.
6. The assay of claim 1, wherein the adsorbent particle of step (2) is C 18 Adsorbent particles.
7. The method according to claim 1, wherein the step (2) comprises mixing a liquid phase obtained by solid-liquid separation of the derivatized extract obtained in the step (1) with sodium chloride and adsorbent particles, wherein sodium chloride is added to the liquid phase to saturate the liquid phase during the mixing, and the amount of the adsorbent particles added per ml of the liquid phase is 0.02 to 0.1 g.
8. The method according to claim 1, wherein the step (2) comprises sufficiently mixing a liquid phase obtained by solid-liquid separation of the derivatized extract obtained in the step (1) with adsorbent particles and sodium chloride by vortexing to dissolve the sodium chloride, purifying the derivatized extract by salting out of the sodium chloride and adsorption of the adsorbent particles, and removing a lower aqueous phase after standing and layering to obtain a purified aqueous phase extract.
9. The assay of claim 1, wherein step (3) comprises performing qualitative and quantitative analysis of glyphosate in the purified aqueous extract obtained in step (2) by high performance liquid chromatography or high performance liquid chromatography-mass spectrometry.
10. The assay of claim 1, wherein the sample to be assayed is soil or sediment.
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