CN111487330B - Detection method for glyphosate and metabolites thereof in various matrixes - Google Patents
Detection method for glyphosate and metabolites thereof in various matrixes Download PDFInfo
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Abstract
The invention discloses a detection method for various matrix glyphosate and metabolites thereof, which comprises the following steps: step S1), sample extraction: adding a sample into a buffer solution, and obtaining an extracting solution through centrifugal operation; step S2), performing derivatization treatment on the extracting solution; s3), enriching and purifying through a solid phase extraction column special for glyphosate to obtain a detection sample; and S4), detecting the content of the glyphosate in the obtained detection sample. The invention can greatly improve the recovery rate of glyphosate, has good purification effect and wide application range, can be applied to various matrixes, including matrixes with higher glyphosate content such as soybean, peanut, orange, tea and the like, has unified experimental method, greatly facilitates experimenters and saves time and labor cost.
Description
Technical Field
The invention relates to a method for detecting matrix glyphosate and metabolites thereof, in particular to a method for detecting various matrix glyphosate and metabolites thereof.
Background
Glyphosate (GLY) belongs to an internal absorption and conduction type broad-spectrum biocidal herbicide and is widely used for preventing and killing various weeds in farmlands, gardens, nursery gardens, railways, roads, forests, lakes and the like. Because of its high efficiency and low cost, it has been widely used in agricultural production. In recent years, with the increase of transgenic glyphosate-resistant crops, the dosage of glyphosate is increased year by year, and the glyphosate is a pesticide variety which is widely applied and has the largest yield in the world. Although glyphosate has been considered as a "safe" herbicide, if it is used in large quantities for a long time, it will inevitably affect diseases of agricultural products, and recently, studies have shown that glyphosate can accumulate in the environment and in organisms, and finally cause harm to human health, even cause cancer. Therefore, the detection of glyphosate is bound to be a hot trend and has important significance.
The existing national standard detection method (GB/T23750-2009, NY/T1096-2006 and the like) adopts a strong cation exchange column (CAX column) to purify and enrich glyphosate in a food matrix. In addition, some special glyphosate columns on the market adsorb impurities by using small solid-phase extraction columns, so that the purposes of purifying samples and detecting glyphosate are achieved. Meanwhile, the existing invention documents mention the method for effectively detecting the residual quantity of glyphosate by using a C18 column or an anion exchange column. However, these methods have problems of extremely low recovery rate, poor purification effect, and limited application range. Therefore, a small column and a matched experimental method which can effectively remove impurities, obtain higher recovery rate and can be applied to various different matrixes need to be found.
Disclosure of Invention
The present invention is to solve the above technical problems and to provide a method for detecting glyphosate and its metabolites in various matrices.
The invention relates to a detection method for various matrix glyphosate and metabolites thereof, which comprises the following steps: step S1), sample extraction: adding a sample into a buffer solution, and obtaining an extracting solution through centrifugal operation; step S2), performing derivatization treatment on the extracting solution; s3), enriching and purifying through a solid phase extraction column special for glyphosate to obtain a detection sample; and S4), detecting the content of the glyphosate in the obtained detection sample.
Further, the buffer solution in the step S1) is deionized water or acetonitrile water; the step S1) includes: weighing the uniform sample in a centrifuge tube, adding an internal standard, adding deionized water or acetonitrile water, carrying out vortex mixing, extraction and centrifugation, filtering the upper layer solution to another centrifuge tube, and taking part of the extract for derivatization.
Further, the step S2 includes: adding boric acid water solution and FMOC-Cl acetonitrile solution into the extractive solution, shaking, sealing, performing derivatization reaction at 40 + -5 deg.C, cooling to room temperature, and waiting for sample loading.
Further, the step S3 includes: filling a solid phase extraction column special for glyphosate, and activating a balance column by using acetonitrile and water in sequence; transferring the sample solution after the derivatization to the top of the solid phase extraction column; eluting the column with water, drying under low vacuum, eluting the small column with acetonitrile, drying, concentrating under nitrogen blowing, diluting to constant volume, adding sample vial, and testing by LC/MS/MS.
Further, the step S4 adopts a liquid chromatography-ultraviolet detector to perform detection according to the following conditions: a chromatographic column: athena UHPLC C18,2.1mm x 50mm, particle size 1.8 μm; the mobile phase is acetonitrile formate or ammonium acetate water solution; flow rate: 0.25mL/min; column temperature: 40 ℃; wavelength: 361nm; sample introduction amount: 10 μ L.
Further, an HC-C18 filler and a C8 filler are arranged in the solid phase extraction column special for glyphosate, and the weight mixing ratio of the HC-C18 filler to the C8 filler is 100-30.
Further, the content of the C8 filler is positively correlated with the mass percentage of the nonpolar impurities in the extract liquid of step S2, and when the mass percentage of the nonpolar impurities in the extract liquid is 0 to 2%, the weight mixing ratio of the HC-C18 filler to the C8 filler is 100; when the mass percentage of the nonpolar impurities in the extracting solution is 2-10%, the weight mixing ratio of the HC-C18 filler to the C8 filler is 70-50; when the mass percentage of the nonpolar impurities in the extracting solution is more than 10%, the weight mixing ratio of the HC-C18 filler to the C8 filler is 50-30.
Further, when the mass percentage of the protein in the matrix exceeds 20%, the step S1) selects acetonitrile water as the buffer solution, otherwise, deionized water is selected as the buffer solution.
Compared with the prior art, the invention has the following beneficial effects: the detection method for the glyphosate and the metabolites thereof with various matrixes, provided by the invention, can greatly improve the recovery rate of the glyphosate, has a good purification effect and a wide application range, can be applied to various matrixes, including matrixes with higher glyphosate contents such as soybean, peanut, orange, tea and the like, has unified experimental method, greatly facilitates experimenters, and saves time and labor cost.
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FIG. 1 is a schematic flow diagram of the detection method for various substrates glyphosate and its metabolites according to the present invention.
Detailed Description
The invention is further described below with respect to specific examples.
As described in the background art, the CAX column used in the current standard methods such as the national standard, the SAX column and the C18 column used in the existing patent documents, and the like, and the C18 and HLB columns used in the commercial products that have been proposed, wherein 1) the CAX column and the SAX column have the problem of low recovery rate, and the target object cannot be accurately detected and quantified; 2) The methods of adopting small columns such as C18 and HLB and the like all utilize an impurity removal mode, so that impurities cannot be completely removed, and instruments in subsequent detection steps can be damaged; 3) Other commercial columns are directed against the tea matrix. Therefore, the invention adopts the mixed filler as the glyphosate detection column for the first time, and simultaneously adopts the enrichment mode to collect the target object, thereby ensuring that the recovery rate is higher, simultaneously thoroughly removing impurities, simultaneously being applied to different types of matrixes and having wide application range.
The special solid phase extraction column for glyphosate is provided with HC-C18 filler and C8 filler, wherein the weight mixing ratio of the HC-C18 filler to the C8 filler is 100-30. Preferably, the content of the C8 filler is positively correlated with the mass percentage content of the non-polar impurities in the extracting solution of step S2, and when the matrix is simple fruits and vegetables, etc., and the mass percentage content of the non-polar impurities in the extracting solution is 0 to 2%, the weight mixing ratio of the HC-C18 filler to the C8 filler is 100; when the mass percentage of the nonpolar impurities in the matrix extracting solution is 2-10%, the weight mixing ratio of the HC-C18 filler to the C8 filler is 70-50; when the matrix is peanut, soybean and the like, and the mass percentage of the nonpolar impurities in the extracting solution is more than 10%, the weight mixing ratio of the HC-C18 filler to the C8 filler is 50-30.
The first embodiment is as follows: the glyphosate standard was enriched using a glyphosate-dedicated column (GLY cartridge) and a cation exchange resin column (CAX cartridge), respectively.
1. The method comprises the following specific steps:
1) And CAX columella: adding a standard substance into an aqueous solution, and activating as a sample solution (1): activating the CAX small column by water; (2) loading: loading the labeling solution to a CAX column; (3) leaching: leaching the CAX small column by using a small amount of water-hydrochloric acid-methanol solution; (4) elution: eluting the small column with water-hydrochloric acid-methanol solution, draining, collecting eluate, performing rotary evaporation, diluting to desired volume with the eluate, derivatizing, and detecting with liquid chromatography-mass spectrometry (LC/MS/MS);
2) Passing through GLY column: the standard was added to 5mL of the aqueous solution as a sample solution. Activation: activating a GLY cartridge with acetonitrile; and (2) balancing: equilibrating the GLY cartridge with water; (3) loading: loading the sample loading solution to a GLY column; 4) Leaching: leaching the GLY column with water, and draining; (5) elution: eluting the small column with acetonitrile, draining, collecting eluate, concentrating by nitrogen blowing, diluting with water to constant volume, derivatizing, adding part into sample vial for LC/MS/MS detection;
3) LC/MS/MS measurement conditions: 1) Liquid phase conditions column Athena UHPLC C18 (2.1 x 50mm,2.1mm is column internal diameter, 50mm is column length, particle size 1.8 um)
Flow rate: 0.25mL/min; column temperature: 40 ℃; sample introduction amount: 10ul of
2) Mass spectrum parameters:
ionization Mode: ESI +; 4000V for Capillary Voltage; gas Temp:350 ℃; gas flow:10L/min; nebulizer:40psi Delta EMV (+): 400; an acquisition mode: MRM; fragment Voltage:90V; dwell:50
Example two: the method takes soybeans as a matrix, and utilizes a special glyphosate column (GLY column) to enrich glyphosate target substances.
1. The method comprises the following specific steps:
1) And (3) sample extraction: weighing uniform samples, adding the internal standard into a centrifuge tube, adding acetonitrile for extraction, performing vortex mixing extraction and centrifugation, filtering an upper-layer solution into another centrifuge tube, and taking part of an extracting solution for derivatization;
2) Derivation of an extracting solution: adding sodium tetraborate water solution and FMOC-Cl acetonitrile solution into the extract, shaking up, sealing, performing derivatization reaction at 40 +/-5 ℃, cooling to room temperature, and waiting for sample loading;
3) Passing through GLY column: activation: activating the GLY cartridge with acetonitrile; and (2) balancing: equilibrating the GLY cartridge with water; (3) loading: loading the derivative extracting solution to a GLY small column; 4) Leaching: leaching the GLY small column by using water, and draining; (5) elution: eluting the small column with acetonitrile, draining, collecting eluate, concentrating with nitrogen, diluting with water to constant volume, mixing, adding part into sample vial for LC/MS/MS detection;
4) And LC/MS/MS measurement conditions, the detection conditions are the same as above.
Example three: the peanut is taken as a substrate, and a glyphosate target object is enriched by utilizing a glyphosate special column (GLY column).
1. The method comprises the following specific steps:
1) And sample extraction: weighing uniform samples, adding the internal standard into a centrifuge tube, adding acetonitrile for extraction, performing vortex mixing extraction and centrifugation, filtering an upper-layer solution into another centrifuge tube, and taking part of an extracting solution for derivatization;
2) Derivation of an extracting solution: adding sodium tetraborate water solution and FMOC-Cl acetonitrile solution into the extract, shaking up, sealing, performing derivatization reaction at 40 +/-5 ℃, cooling to room temperature, and waiting for sample loading;
3) Passing through GLY column: activation: activating a GLY cartridge with acetonitrile; and (2) balancing: equilibrating the GLY cartridge with water; (3) loading: loading the derivative extracting solution to a GLY small column; 4) Leaching: leaching the GLY column with water, and draining; (5) elution: eluting the small column with acetonitrile, draining, collecting eluate, concentrating by nitrogen blowing, diluting with water to desired volume, mixing, adding part into sample injection vial, and detecting by LC/MS/MS;
4) And LC/MS/MS measurement conditions, the detection conditions are the same as above.
Example four: orange is taken as a matrix, and a glyphosate target object is enriched by using a glyphosate special column (GLY column).
1. The method comprises the following specific steps:
1) And sample extraction: weighing uniform samples, adding the internal standard into a centrifuge tube, adding water for extraction, performing vortex mixing extraction and centrifugation, filtering the upper solution into another centrifuge tube, and taking part of the extract for derivatization;
2) Derivation of an extracting solution: adding sodium tetraborate water solution and FMOC-Cl acetonitrile solution into the extract, shaking up, sealing, performing derivatization reaction at 40 +/-5 ℃, cooling to room temperature, and waiting for sample loading;
3) Passing through GLY column: activation: activating a GLY cartridge with acetonitrile; and (2) balancing: equilibrating the GLY cartridge with water; (3) loading: loading the derivative extracting solution to a GLY small column; 4) Leaching: leaching the GLY column with water, and draining; (5) elution: eluting the small column with acetonitrile, draining, collecting eluate, concentrating by nitrogen blowing, diluting with water to desired volume, mixing, adding part into sample injection vial, and detecting by LC/MS/MS;
4) And LC/MS/MS measurement conditions, detection conditions are the same as above.
Example five: the tea is taken as a matrix, and a glyphosate target object is enriched by using a glyphosate special column (GLY column).
1. The method comprises the following specific steps:
1) And (3) sample extraction: weighing the uniform sample, adding the internal standard into a centrifuge tube, adding water for extraction, carrying out vortex mixing extraction and centrifugation, filtering the upper layer solution into another centrifuge tube, and taking part of the extracting solution for derivatization;
2) Derivation of an extracting solution: adding sodium tetraborate aqueous solution and FMOC-Cl acetonitrile solution into the extractive solution, shaking, sealing, performing derivatization reaction at 40 + -5 deg.C, cooling to room temperature, and loading;
3) Passing through GLY column: activation: activating the GLY cartridge with acetonitrile; and (2) balancing: equilibrating the GLY cartridge with water; (3) loading: loading the derivative extracting solution to a GLY small column; 4) Leaching: leaching the GLY small column by using water, and draining; (5) elution: eluting the small column with acetonitrile, draining, collecting eluate, concentrating by nitrogen blowing, diluting with water to desired volume, mixing, adding part into sample injection vial, and detecting by LC/MS/MS;
4) And LC/MS/MS measurement conditions, the detection conditions are the same as above.
Example one data comparison: enriching glyphosate standard substance by using glyphosate special column (GLY column) and CAX small column respectively
| GLY-1 | GLY-2 | Mean value of | CAX | |
| Percent recovery% | 93.18 | 91.05 | 92.115 | 0 |
The CAX column is adopted to enrich glyphosate, the recovery rate is 0, a target object cannot be detected, and the average recovery rate of the special glyphosate column (GLY) is more than 90%, so that the small column is proved to be capable of greatly improving the collection effect of glyphosate and having better performance of collecting glyphosate compared with the traditional CAX column.
Example two data: soybeans are used as a matrix, and a glyphosate target object is enriched by using a glyphosate special column (GLY column).
| GLY-1 | GLY-2 | GLY-3 | Mean value of | RSD value | |
| Percent recovery% | 99 | 105 | 98 | 100.67 | 3.64 |
Soybean is the most widely used glyphosate, and thus a complex matrix with high protein content is high in content. In a soybean matrix, the recovery rate of glyphosate can reach about 100%, and the parallelism is good, which shows that the performance of GLY column is excellent, and the experimental method can effectively collect the target glyphosate to achieve the purpose of detection.
Data in example three: the peanut is taken as a substrate, and a glyphosate target object is enriched by utilizing a glyphosate special column (GLY column).
| GLY-1 | GLY-2 | GLY-3 | Mean value of | RSD value | |
| Percent recovery% | 102 | 104 | 103 | 103 | 3.64 |
The peanut contains more fat, meanwhile, the glyphosate content is higher, the recovery rate of the glyphosate in the matrix can reach about 100%, the parallelism is good, the performance of the GLY column is excellent, and the experimental method can effectively collect the target glyphosate to achieve the detection purpose.
Example four data: orange is taken as a matrix, and a glyphosate target object is enriched by using a glyphosate special column (GLY column).
| GLY-1 | GLY-2 | GLY-3 | Mean value of | RSD value | |
| Percent recovery% | 104 | 106 | 98 | 103 | 4.13 |
In an orange matrix, the recovery rate of the glyphosate can also reach about 100%, the recovery rate is higher, the parallelism is good, and the performance of the GLY column is excellent.
Example five data: tea is taken as a matrix, and a glyphosate target object is enriched by using a glyphosate special column (GLY column).
| GLY-1 | GLY-2 | GLY-3 | Mean value of | RSD value | |
| Percent recovery% | 104 | 104 | 101 | 103 | 1.77 |
In the tea matrix, impurities are more, the recovery rate of glyphosate can also reach about 100% by using the method and a matched product for detection, the recovery rate is higher, the parallelism is good, the performance of a GLY column is excellent, and the experimental method can effectively collect the target glyphosate to achieve the detection purpose.
The invention has the following specific advantages:
1) The experimental method and the special glyphosate column used in cooperation can greatly improve the recovery rate of glyphosate, and the recovery rate of the glyphosate matched with the small CAX column on the market is 0 and cannot be detected by adopting a national standard method. The invention improves the detection accuracy of glyphosate, perfects the traditional detection method and provides extremely favorable conditions for the detection in the field.
2) The purification effect is good, and the purification effect is achieved by adopting an enrichment mode (absorbing a target object), so that the method is different from similar products and application methods in the market. The other brands of glyphosate detection pillars and corresponding methods in the current market all adopt purification methods for removing impurities, namely: impurities are adsorbed on the small columns, effluent liquid is collected to be detected, and the impurities have different properties due to the fact that the types of the sample matrixes containing glyphosate are numerous, and the impurities can not achieve a good purification effect by using the small columns of the same type to adsorb and purify the impurities. Therefore, during detection, more impurity peaks affect the quantification of target peaks, and meanwhile, the service life of the chromatographic column is greatly affected by the fact that more impurities enter the chromatographic column. The invention fills the blank of similar products and methods in the market and realizes the thorough purification of the matrix.
3) The experimental method and the glyphosate special column used in cooperation are wide in application range, can be applied to various matrixes, including matrixes with higher glyphosate content such as soybean, peanut, orange and tea, are unified, greatly facilitate experimenters, and save time and labor cost.
Although the present invention has been described with respect to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. A method for detecting a plurality of matrix glyphosate and metabolites thereof, comprising the steps of:
step S1), sample extraction: adding a sample into a buffer solution, and obtaining an extracting solution through centrifugal operation;
step S2), performing derivative treatment on the extracting solution; the method comprises the following steps: adding boric acid water solution and FMOC-Cl acetonitrile solution into the extractive solution, shaking, sealing, performing derivatization reaction at 40 + -5 deg.C, cooling to room temperature, and waiting for sample loading;
s3), enriching and purifying through a solid phase extraction column special for glyphosate to obtain a detection sample;
step S4), detecting the content of glyphosate in the obtained detection sample;
the step S3) comprises the following steps: filling a solid phase extraction column special for glyphosate, and activating the balance column by acetonitrile and water in sequence; transferring the sample solution after the derivatization to the top of the solid phase extraction column; eluting the column with water, drying under low vacuum, eluting the small column with acetonitrile, drying, concentrating by blowing nitrogen, diluting to constant volume, adding sample injection small bottle, and checking by LC/MS/MS;
the special solid-phase extraction column for glyphosate is internally provided with HC-C18 filler and C8 filler;
the content of the C8 filler is positively correlated with the mass percentage of the nonpolar impurities in the extracting solution in the step S2), and when the mass percentage of the nonpolar impurities in the extracting solution is 0 to 2%, the weight mixing ratio of the HC-C18 filler to the C8 filler is 70; when the mass percentage of the nonpolar impurities in the extracting solution is 2 to 10 percent, the mixing ratio of the HC-C18 filler to the C8 filler is 70 to 50; when the mass percentage of the nonpolar impurities in the extracting solution is more than 10%, the weight mixing ratio of the HC-C18 filler to the C8 filler is 50 to 30.
2. The detection method according to claim 1, wherein the buffer in step S1) is deionized water or acetonitrile water; the step S1) comprises the following steps: weighing the uniform sample in a centrifuge tube, adding an internal standard, adding deionized water or acetonitrile water, carrying out vortex mixing, extraction and centrifugation, filtering the upper layer solution to another centrifuge tube, and taking part of the extract for derivatization.
3. The detection method according to claim 1, wherein the step S4) is performed by using a liquid chromatography-ultraviolet detector under the following conditions: a chromatographic column: athena UHPLC C18,2.1mm x 50mm, particle size 1.8 μm; the mobile phase is acetonitrile formate or ammonium acetate water solution; flow rate: 0.25mL/min; column temperature: at 40 ℃; wavelength: 361nm; sample introduction amount: 10 μ L.
4. The detection method according to claim 1, wherein step S1) selects acetonitrile water as the buffer solution when the mass percentage of the protein in the matrix exceeds 20%, otherwise deionized water is selected as the buffer solution.
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Denomination of invention: Detection method for Glyphosate and its metabolites in various matrices Effective date of registration: 20230710 Granted publication date: 20221118 Pledgee: China Construction Bank Corporation Shanghai Xuhui sub branch Pledgor: Shanghai Anpu Experimental Technology Co.,Ltd. Registration number: Y2023310000358 |
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