CN115406988A - Method for detecting residual quantity of sulfoketone in environmental sample - Google Patents

Method for detecting residual quantity of sulfoketone in environmental sample Download PDF

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CN115406988A
CN115406988A CN202211047761.3A CN202211047761A CN115406988A CN 115406988 A CN115406988 A CN 115406988A CN 202211047761 A CN202211047761 A CN 202211047761A CN 115406988 A CN115406988 A CN 115406988A
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acetonitrile
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何红梅
徐玲英
张昌朋
王祥云
李艳杰
蒋金花
赵学平
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Zhejiang Academy of Agricultural Sciences
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Abstract

The invention provides a method for detecting residual quantity of sulfoketone in an environmental sample, which comprises the following steps: (1) extracting: weighing a sample, adding acetonitrile to dissolve the sample, oscillating and filtering the sample twice, placing the filtrate in a measuring cylinder, oscillating the filtrate, standing the filtrate for layering, taking an acetonitrile layer and drying the acetonitrile layer to obtain an extract; (2) redissolution: ultrasonically dissolving the extract with acetonitrile water solution and formic acid to obtain purified solution; (3) purifying: and (3) taking the solid phase extraction column, pre-leaching, taking a purified liquid, loading the purified liquid, leaching with acetonitrile aqueous solution, finally eluting with acetonitrile, collecting the eluent, filtering the eluent to obtain a substance to be detected, and determining. The invention can be applied to the detection of the residual quantity of the tembotrione in water samples, soil and sediments, effectively avoids the matrix interference of the samples, and has higher accuracy, precision and sensitivity and high recovery rate.

Description

Method for detecting residual quantity of sulfoketone in environmental sample
Technical Field
The invention relates to the field of environmental detection, in particular to a method for detecting residual quantity of sulfoketone in an environmental sample.
Background
The tembotrione belongs to a triketone selective broad-spectrum herbicide, is mainly used for preventing and controlling broadleaf weeds and grassy weeds in corn and other crop fields, belongs to a 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor herbicide, and is registered and used in countries such as the United states, the British, australia, brazil and the like. In China, 2 pesticide preparation products are registered and used for preventing and controlling weeds in corn fields, and the chemical structural formula of the tembotrione is as follows:
Figure BDA0003822638540000011
at present, the information about the tembotrione mainly comprises product introduction, technical analysis, technical synthesis research, preparation control effect research, residual analysis method research in plant source food, residual research on corn and degradation research in soil, and the research on the tembotrione residual analysis method capable of detecting various environmental samples such as soil, sediment, water and the like at the same time and the national or industrial standard of the tembotrione residual detection method are not seen. With the registered use of tembotrions, tembotrions remaining in the environment present potential threats to the environment, living beings and humans, there is a need to establish an accurate, reliable, and versatile method for residue analysis.
The quache, li Fang, and others, in the article "quache-hplc-tandem mass spectrometry for determining tembotrion residue in plant-derived food" mentioned the pretreatment method of quache (Quick, easy, cheap, effective, rugged and Safe) and the lc-tandem mass spectrometry for determining tembotrion residue in plant-derived food (corn, rice, wheat, grape, apple, raisin, medlar, tomato, cucumber and cabbage); the addition recovery rate of 10 matrixes is 82.0-111.8%, the relative standard deviation is 3.0-14.9%, the matrix effect is-31.7-2.5%, and the matrix effect of only 3 matrixes is less than 10%. The QuEChERS pretreatment method is widely applied to pesticide residue detection in the food field due to the characteristics of rapidness, simplicity and the like, milligram-level graphitized carbon black powder (GCB), amino powder, ethylenediamine-N-Propyl Silane (PSA) and other powder are commonly used for impurity removal, but the impurity removal effect is limited, more impurities remain in a co-extraction solution, the pollution to an instrument is obvious, and the matrix effect is also obvious, so that the accurate qualitative and quantitative analysis is influenced; when the method is applied to solid samples in the environment such as soil, the method also has the defects of non-ideal extraction effect, limited sample capacity and the like. Therefore, it is necessary to establish a method for detecting the residual quantity of tembotrione for environmental samples, which solves the above problems.
Disclosure of Invention
The invention provides a method for detecting the residual quantity of tembotrione in an environmental sample, which sequentially comprises the steps of extracting, redissolving, purifying and measuring to detect the residual quantity of tembotrione in the environmental sample.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for detecting residual quantity of sulfoketone in an environmental sample comprises the following steps:
(1) Extraction: weighing a sample, adding acetonitrile for dissolution, wherein the mass ratio of the sample to the acetonitrile is 1g:2-4mL, oscillating and carrying out primary suction filtration, continuously adding acetonitrile into filter residues for dissolving, oscillating and carrying out secondary suction filtration, placing filtrate obtained in the two-time suction filtration into a measuring cylinder filled with sodium chloride, oscillating, standing for layering, taking an acetonitrile layer, and drying to obtain an extract;
(2) Redissolving: dissolving the extract with acetonitrile water solution mixed with formic acid to obtain purified solution;
(3) Purifying: taking a solid phase extraction column, pre-leaching, taking a purified liquid, loading the purified liquid, leaching with acetonitrile aqueous solution, finally eluting with acetonitrile, collecting the eluent, and filtering with a membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting the object to be detected by adopting an ultra-high performance liquid chromatography-mass spectrum/mass spectrum combination instrument.
Further, the ratio of the mass of the sample to the volume of the acetonitrile in the step (1) is 1g:4mL.
Further, the sample in the step (1) is soil, sediment or water sample.
Further, when the sample in the step (1) is a sediment, ammonia water needs to be added for dissolution, and the ratio of the mass of the sample to the volume of the ammonia water is 1g:0.1-0.4ml.
Further, when the sample in the step (1) is a sediment, the ratio of the mass of the sample to the volume of ammonia water is 1g:0.1ml.
Further, when the sample in the step (1) is soil, ammonia water and water are required to be added for dissolution, and the mass ratio of the sample to the volume of the ammonia water is 1g:0.1-0.4ml.
Further, when the sample in the step (1) is soil, the mass to volume ratio of the sample to ammonia water is 1g:0.1ml.
Further, in the step (2), 5mL of 20% acetonitrile water solution doped with formic acid is required to be added for ultrasonic dissolution every 1mL of acetonitrile layer, wherein the doping rate of formic acid is 2%.
Further, the purification material in the solid phase extraction column in the step (3) is selected from C 18 The rinsing was with 30% acetonitrile in water.
Further, the liquid phase measuring conditions in the step (4) are as follows: a chromatographic column: c 18 A reverse phase chromatography column; mobile phase: phase A is acetonitrile, phase B is 0.1% formic acid aqueous solution; gradient elution procedure: 0min, A is 50%;1min, A is 90%;3.5min, A is 90%;4min, A is 50%;5.0min, A is 50%; flow rate: column temperature 0.20 mL/min: sample volume at 40 ℃:2.00 mu L;
the mass spectrometry conditions are as follows: an ionization mode: ESI + Monitoring by adopting MRM multiple reactions; capillary voltage: 2.50kV; desolventizing temperature: 400 ℃; desolventizing agent gas flow: 800L/Hr; quantitative set, qualitative ion pair: 441.0>261.8*，441.0>340.9。
The invention has the following beneficial effects:
1. the method adopts a solid phase extraction purification method, and can effectively remove co-extraction impurities in the extracting solution by adding formic acid into the sample solution (namely the purified solution) and leaching with different polarity solutions in multiple steps during purification, thereby avoiding matrix interference of the sample and obtaining good detection effect. The method has the advantages of high accuracy, precision, sensitivity, small impurity interference and strong universality, and can effectively measure the tembotrione residue in environmental samples (soil, sediment and water).
2. The invention establishes a method for measuring the residual quantity of tembotrione in soil, sediment and water by using an ultra performance liquid chromatography-mass spectrometry/mass spectrometry (UPLC/MS/MS) method, wherein the minimum detection limit of the method is 0.00002mg/kg or mg/L, the quantification limit is 0.00007mg/kg or mg/L, the average recovery rate of tembotrione addition in the soil is 81.7-99.5%, and the RSD is 1.9-7.9%; the average recovery rate of the cyclic sulfoketone addition in the sediment is 75.8-84.0 percent, and the RSD is 2.5-9.2 percent; the average recovery rate of the sulfoketone in the water is 78.9-93.9%, the RSD is 1.9-8.7%, and compared with the addition recovery rate of the QuEChERS method which is 82.0-111.8%, and the standard deviation which is 3.0-14.9%, the addition recovery rate of the method is narrower in range and lower than the standard deviation, so that the method is more stable, and the accuracy and the sensitivity are higher.
3. According to the invention, multiple tests show that when an environmental sample is detected, the ratio of the sample mass to the volume of ammonia water to the volume of acetonitrile in the extraction step is 1g:0.1mL: when the volume is 4mL, the optimal extraction ratio is obtained; in the redissolution step, a 20% acetonitrile water solution doped with 2% formic acid is used as a solvent, so that the dissolution effect is best, and particularly, the subsequent sample loading and purification effect is better for a soil sample; used in the purification step
When the cyclosulfoketone is used as a solid phase extraction column of a purification material, the retention capacity of the cyclosulfoketone is strongest, which is beneficial to the separation of impurities, when the cyclosulfoketone is purified, a 20% acetonitrile water solution (doped with 2% formic acid) is firstly selected for sample loading, a 30% acetonitrile water solution is firstly used for leaching to remove the impurities, and finally, the cyclosulfoketone is completely eluted by acetonitrile with strong polarity, so that the recovery rate of the cyclosulfoketone is ensured.
Drawings
FIG. 1 is a liquid chromatography-mass spectrometry/mass spectrometry profile of a standard solution provided by the present invention;
FIG. 2 is a liquid chromatography-mass spectrometry/mass spectrometry profile of a water blank provided by the present invention;
FIG. 3 is a liquid chromatography-mass spectrometry/mass spectrometry profile of water recovery provided by the present invention;
FIG. 4 is a liquid chromatography-mass spectrometry/mass spectrometry profile of a soil blank provided by the present invention;
FIG. 5 is a liquid chromatography-mass spectrometry/mass spectrometry profile of soil recovery provided by the present invention;
FIG. 6 is a liquid chromatography-mass spectrometry/mass spectrometry profile of a deposit blank provided by the present invention;
FIG. 7 is a liquid chromatography-mass spectrometry/mass spectrometry profile of the deposit recovery provided by the present invention;
FIG. 8 shows a variation C provided by the present invention 18 A column chart of recovery of the solid phase extraction column;
FIG. 9 is a line graph of recovery per stage for an F column in accordance with the present invention at various ratios of eluting solvent;
fig. 10 is a line graph of the cumulative recovery of the F column provided by the present invention at various ratios of eluting solvent.
Detailed Description
In order to more specifically describe the present invention, the following detailed description is provided for the technical solution of the present invention with reference to the accompanying drawings and the specific embodiments. These descriptions are merely illustrative of how the invention may be carried out and do not limit the specific scope of the invention. The scope of the invention is defined in the claims.
Example 1
The embodiment provides a method for detecting residual quantity of sulfoketone in an environment sample, wherein the environment sample is paddy soil, and the method comprises the following steps:
(1) Extraction: weighing 20.0g of soil sample (accurate to 0.01 g), placing the soil sample in a 150mL triangular flask, adding 10mL of water and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring the filtrate into a 100mL measuring cylinder with a plug and containing 8g of sodium chloride, returning the filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, combining the filtrates in the measuring cylinder with the plug, violently shaking for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the acetonitrile layer in a flat-bottomed flask, rotating at 40 ℃, evaporating to dryness, and drying by nitrogen to obtain an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile water solution and 0.1mL of formic acid into a flat-bottomed flask filled with the extract in sequence, and performing ultrasonic dissolution to obtain a purified solution;
(3) Purifying: taking a solid phase extraction column C 18 Pre-leaching with 5mL of acetonitrile and 5mL of purified water in sequence, taking a purified solution for sampling, leaching with 2.5mL of 30% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting eluent, and filtering with a 0.22-micron filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument.
The conditions for the measurement were:
and (3) chromatographic column: waters ACQUITY
Figure BDA0003822638540000041
BEH C 18 (2.1×100mm，1.7μm)；
Column temperature: 40 ℃;
flow rate: 0.20mL/min;
mobile phase: the phase A is acetonitrile, the phase B is 0.1 percent formic acid water solution,
gradient elution procedure: 0min, A is 50%;1min, A is 90%;3.5min, A is 90%;4min, A is 50%;5.0min, A is 50%;
sample introduction amount: 2 mu L of the solution; quantifying by an external standard method;
mass spectrum conditions: the capillary voltage is 2.5kV, the desolventizing temperature is 400 ℃, and the desolventizing gas flow is 800L/Hr. The ionization being ESI + The detection mode is a multi-reaction monitoring scanning mode (MRM), and the quantitative ion pair and the qualitative ion pair are 441.0>261.8*，441.0>340.9。
And (3) measuring results: the sulfolone content in the sediment was determined to be 1.71mg/kg by the above procedure.
Example 2
The embodiment provides a method for detecting residual quantity of sulfoketone in an environment sample, wherein the environment sample is paddy soil, and the method comprises the following steps:
(1) Extraction: weighing 20.0g of soil sample (accurate to 0.01 g), placing the soil sample in a 150mL triangular flask, adding 8.0mL of water, 2.0mL of formic acid and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring filtrate into a 100mL stoppered measuring cylinder filled with 8g of sodium chloride, returning filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, combining filtrate in the stoppered measuring cylinder, violently oscillating for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the acetonitrile layer in a flat-bottomed flask, carrying out rotary evaporation at 40 ℃ for evaporation, and carrying out nitrogen blow-drying to obtain an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile water solution and 0.1mL of formic acid into a flat-bottomed flask filled with the extract in sequence, and performing ultrasonic dissolution to obtain a purified solution;
(3) Purifying: taking a solid phase extraction column C 18 Pre-leaching with 5mL of acetonitrile and 5mL of purified water in sequence, taking a purified solution for sampling, leaching with 2.5mL of 30% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting eluent, and filtering with a 0.22-micrometer filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions in this example were the same as in example 1.
And (3) measuring results: the cyclic sultone content of the sediment was determined to be 1.62mg/kg by the above procedure.
Example 3
The embodiment provides a method for detecting residual quantity of sulfoketone in an environment sample, wherein the environment sample is paddy soil, and the method comprises the following steps:
(1) Extraction: weighing 20.0g of soil sample (accurate to 0.01 g), placing the soil sample in a 150mL triangular flask, adding 8mL of water, 2mL of HCl (1 mol/L) and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring filtrate into a 100mL stoppered measuring cylinder filled with 8g of sodium chloride, returning filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, combining the filtrate in the stoppered measuring cylinder, violently oscillating for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the acetonitrile layer in a flat-bottomed flask, rotating to evaporate at 40 ℃ for evaporation, and drying by nitrogen to obtain an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile water solution and 0.1mL of formic acid into a flat-bottomed flask filled with the extract in sequence, and performing ultrasonic dissolution to obtain a purified solution;
(3) Medicine for treating rheumatismAnd (3) formation: taking a solid phase extraction column C 18 Pre-leaching with 5mL of acetonitrile and 5mL of purified water in sequence, taking a purified solution for sampling, leaching with 2.5mL of 30% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting eluent, and filtering with a 0.22-micron filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions in this example were the same as in example 1.
And (3) measuring results: the cyclic sultone content of the sediment was determined to be 1.75mg/kg by the above procedure.
Example 4
The embodiment provides a method for detecting residual quantity of sulfoketone in an environment sample, wherein the environment sample is paddy soil, and the method comprises the following steps:
(1) Extraction: weighing 20.0g of sediment sample (accurate to 0.01 g), placing the sediment sample in a 150mL triangular flask, adding 8.0mL of water, 2mL of ammonia water and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring the filtrate into a 100mL stoppered measuring cylinder filled with 8g of sodium chloride, returning the filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, carrying out suction filtration, combining the filtrates in the stoppered measuring cylinder, violently oscillating for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the acetonitrile layer in a flat-bottomed flask, carrying out rotary evaporation at 40 ℃ to dryness, and carrying out nitrogen blow-drying to obtain an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile water solution and 0.1mL of formic acid into a flat-bottomed flask filled with the extract in sequence, and performing ultrasonic dissolution to obtain a purified solution;
(3) Purifying: taking a solid phase extraction column C 18 Pre-leaching with 5mL of acetonitrile and 5mL of purified water in sequence, taking a purified solution for sampling, leaching with 2.5mL of 30% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting eluent, and filtering with a 0.22-micron filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions in this example were the same as in example 1.
And (3) measuring results: the sulfoketone content in the sediment was determined to be 1.92mg/kg by the above procedure.
Example 5
The embodiment provides a method for detecting residual quantity of sulfoketone in an environment sample, wherein the environment sample is paddy soil, and the method comprises the following steps:
(1) Extraction: weighing 20.0g of soil sample (accurate to 0.01 g), placing the soil sample in a 150mL triangular flask, adding 8mL of water, 2mL of 1mol/L NaOH and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring filtrate into a 100mL stoppered measuring cylinder filled with 8g of sodium chloride, returning filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, combining the two filtrates in the stoppered measuring cylinder, violently oscillating for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the acetonitrile layer in a flat-bottomed flask, rotating to evaporate to dryness at 40 ℃, drying by nitrogen and obtaining an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile water solution and 0.1mL of formic acid into a flat-bottomed flask filled with the extract in sequence, and performing ultrasonic dissolution to obtain a purified solution;
(3) Purifying: taking a solid phase extraction column C 18 Pre-leaching with 5mL of acetonitrile and 5mL of purified water in sequence, taking a purified solution for sampling, leaching with 2.5mL of 30% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting eluent, and filtering with a 0.22-micrometer filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions in this example were the same as in example 1.
And (3) measuring results: the content of tembotrione in the soil was determined to be 1.28mg/kg by the above procedure.
Example 6
The embodiment provides a method for detecting residual quantity of sulfoketone in an environment sample, wherein the environment sample is a soil sample, and the method comprises the following steps:
(1) Extraction: weighing 20.0g of soil sample (accurate to 0.01 g), placing the soil sample in a 150mL triangular flask, adding 6mL of water, 4.0mL of ammonia water and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring the filtrate into a 100mL measuring cylinder with a stopper containing 8g of sodium chloride, returning the filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, carrying out suction filtration, combining the two filtrates in the measuring cylinder with the stopper, violently oscillating for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the acetonitrile layer in a flat-bottomed flask, carrying out rotary evaporation at 40 ℃ for evaporation, and carrying out nitrogen blow drying to obtain an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile water solution and 0.1mL of acetic acid into a flat-bottomed flask filled with the extract in sequence, and performing ultrasonic dissolution to obtain a purified solution;
(3) Purifying: taking a solid phase extraction column C 18 Pre-leaching with 5mL of acetonitrile and 5mL of purified water in sequence, taking a purified solution for sampling, leaching with 2.5mL of 30% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting eluent, and filtering with a 0.22-micrometer filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions in this example were the same as in example 1.
And (3) measuring results: the content of tembotrione in the soil was determined to be 1.69mg/kg by the above procedure.
The values of the cyclic sulphonone content and the recovery rates of examples 1 to 6 are given in the following table:
example 1 Example 2 Example 3 Example 4 Example 5 Example 6
Extraction aid Water (W) Formic acid Hydrochloric acid Ammonia water Sodium hydroxide Aqueous ammonia
Measured value mg/kg 1.71 1.62 1.75 1.92 1.28 1.69
The recovery rate is high 85.5 81 87.5 96 64 84.5
Examples 1-6 analysis of results: from examples 1 to 4, it is understood that in the extraction operation in step (1), the extraction rate of tembotrione in soil is higher when an aqueous acetonitrile solution containing aqueous ammonia is used than when an aqueous acetonitrile solution, an aqueous acetonitrile solution containing formic acid, or an aqueous acetonitrile solution containing hydrochloric acid is used. The above results were obtained because the pKa value of tembotrione was 3.18, and addition of weak alkaline ammonia water made tembotrione in soil ionic state as compared with acidic environment, adsorption of tembotrione by soil in ionic state was weakened, and tembotrione was sufficiently dissolved in extract and completely extracted. In example 5, although the aqueous acetonitrile solution containing sodium hydroxide having a strong alkali was added to soil, the same extraction effect as that of weak alkali aqueous ammonia was obtained, the strong alkali of sodium hydroxide degraded the tembotrione, and the extraction effect of tembotrione was impaired. The table above shows the measured content and recovery rate of tembotrione in the soil when different extraction aids are added, and it can be seen from the content and recovery rate of tembotrione in examples 1-5 and the table above that the effect of using ammonia water as the extraction aid in the step (1) is the best.
Meanwhile, as can be seen from the comparison of the content values of the tembotrions and the recovery rate of example 4 and example 6, the step (1) of example 4 is the optimal extraction condition, that is, when the environmental sample is soil, the ratio of the mass of the sample to the volume of the ammonia water to the volume of the acetonitrile is 1g:0.1ml:4ml is the optimal extraction ratio.
Example 7
The embodiment provides a method for detecting residual quantity of sulfoketone in an environment sample, wherein the environment sample is a sediment, and the method comprises the following steps:
(1) Extraction: weighing 10.0g of sediment sample (accurate to 0.01 g), placing the sediment sample in a 150mL triangular flask, adding 2.0mL of ammonia water and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring the filtrate into a 100mL stoppered measuring cylinder filled with 8g of sodium chloride, returning the filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, combining the two filtrates in the stoppered measuring cylinder, violently oscillating for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the mixture in a flat-bottomed flask, rotating at 40 ℃ for evaporation to dryness, and drying by nitrogen to obtain an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile water solution and 0.1mL of formic acid into a flat-bottomed flask filled with the extract in sequence, and performing ultrasonic dissolution to obtain a purified solution;
(3) Purifying: taking a solid phase extraction column C 18 Pre-leaching with 5mL of acetonitrile and 5mL of purified water in sequence, taking a purified solution for sampling, leaching with 2.5mL of 50% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting eluent, and filtering with a 0.22-micrometer filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions of this example were the same as in example 1.
And (3) measuring results: the cyclic sultone content of the sediment was determined to be 2.04mg/kg by the above procedure.
Example 8
The embodiment provides a method for detecting residual quantity of sulfoketone in an environment sample, wherein the environment sample is a sediment, and the method comprises the following steps:
(1) Extraction: weighing 10.0g of sediment sample (accurate to 0.01 g), placing the sediment sample in a 150mL triangular flask, adding 2.0mL of ammonia water and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring the filtrate into a 100mL measuring cylinder with a stopper and containing 8g of sodium chloride, returning the filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, combining the two filtrates in the measuring cylinder with the stopper, violently shaking for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the acetonitrile layer in a flat-bottomed flask, rotating at 40 ℃ for evaporation to dryness, and carrying out nitrogen blow-drying to obtain an extract;
(2) Redissolving: sequentially adding 5.0ml of 20% acetonitrile water solution into a flat-bottomed flask filled with the extract, and ultrasonically dissolving to obtain a purified solution;
(3) Purifying: taking a solid phase extraction column C 18 Pre-leaching with 5mL of acetonitrile and 5mL of purified water in sequence, taking a purified solution for sampling, leaching with 2.5mL of 50% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting eluent, and filtering with a 0.22-micron filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions in this example were the same as in example 1.
And (3) measuring results: the cyclic sultone content of the sediment was determined to be 1.02mg/kg by the above procedure.
Example 9
The embodiment provides a method for detecting residual quantity of sulfoketone in an environmental sample, wherein the environmental sample is a water sample and comprises the following steps:
(1) Extraction: weighing 10.0mL of water sample, placing the water sample in a 100mL stoppered measuring cylinder filled with 8g of sodium chloride, adding 40mL of acetonitrile, violently shaking the stoppered measuring cylinder, standing for layering, absorbing 10mL of acetonitrile in a flat-bottomed flask, and concentrating in water at 40 ℃ to obtain an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile aqueous solution and 0.1mL of formic acid into a flat-bottomed flask filled with the extract in sequence to obtain a purified solution;
(3) Purifying: taking a solid phase extraction column C 18 Pre-spraying with 5mL acetonitrile and 5mL purified water in sequence, and collecting the purified solutionEluting with 2.5mL of 30% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting the eluent, and filtering with a 0.22-micron filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions of this example were the same as in example 1.
And (3) measuring results: the content of the tembotrione in the water is determined to be 1.95mg/L through the steps.
Example 10
The embodiment provides a method for detecting residual quantity of sulfoketone in an environmental sample, wherein the environmental sample is a water sample, and the method comprises the following steps:
(1) Extraction: weighing 10.0mL of water sample, placing the water sample in a 100mL stoppered measuring cylinder filled with 8g of sodium chloride, adding 40mL of acetonitrile, violently shaking the stoppered measuring cylinder, standing for layering, absorbing 10mL of acetonitrile in a flat-bottomed flask, and concentrating in water at 40 ℃ to obtain an extract;
(2) Redissolving: sequentially adding 5.0ml of 20% acetonitrile water solution into a flat-bottomed flask filled with the extract to obtain a purified solution;
(3) Purifying: taking a solid phase extraction column C 18 Pre-leaching with 5mL of acetonitrile and 5mL of purified water in sequence, taking a purified solution for sampling, leaching with 2.5mL of 30% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting eluent, and filtering with a 0.22-micrometer filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions in this example were the same as in example 1.
The measurement results are as follows: the content of the tembotrione in the water is determined to be 1.92mg/L through the steps.
Example 11
The embodiment provides a method for detecting residual quantity of sulfoketone in an environment sample, wherein the environment sample is paddy soil, and the method comprises the following steps:
(1) Extraction: weighing 20.0g of soil sample (accurate to 0.01 g), placing the soil sample in a 150mL triangular flask, adding 8mL of water, 2.0mL of ammonia water and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring filtrate into a 100mL stoppered measuring cylinder filled with 8g of sodium chloride, returning filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, combining the filtrate in the stoppered measuring cylinder, violently oscillating for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the acetonitrile layer in a flat-bottomed flask, rotating at 40 ℃ for evaporation, and drying by nitrogen to obtain an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile water solution and 0.1mL of formic acid into a flat-bottomed flask filled with the extract in sequence, and performing ultrasonic dissolution to obtain a purified solution;
(3) Purification: taking a solid phase extraction column C 18 Pre-leaching with 5mL of acetonitrile and 5mL of purified water in sequence, taking a purified solution for sampling, leaching with 2.5mL of 30% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting eluent, and filtering with a 0.22-micron filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions in this example were the same as in example 1.
And (3) measuring results: the content of the tembotrione in the soil is determined to be 1.95mg/kg through the steps.
Example 12
The embodiment provides a method for detecting residual quantity of sulfoketone in an environment sample, wherein the environment sample is paddy soil, and the method comprises the following steps:
(1) Extraction: weighing 20.0g of soil sample (accurate to 0.01 g), placing the soil sample in a 150mL triangular flask, adding 8mL of water, 2.0mL of ammonia water and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring the filtrate into a 100mL measuring cylinder with a plug and containing 8g of sodium chloride, returning the filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, carrying out suction filtration, combining the filtrates in the measuring cylinder with the plug, violently shaking for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the acetonitrile layer in a flat-bottomed flask, carrying out rotary evaporation at 40 ℃ to dryness, and carrying out nitrogen blow-drying to obtain an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile water solution into a flat-bottomed flask filled with the extract, and performing ultrasonic dissolution to obtain a purified solution;
(3) Purifying: taking a solid phase extraction column C 18 Pre-spraying with 5mL acetonitrile and 5mL purified water in sequence, collecting the purified solution, loading, eluting with 2.5mL30% acetonitrile water solution, eluting with 2.5mL acetonitrile, collecting the eluate, and filtering with 0.22 μm filter membrane to obtain the final productMeasuring an object;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions in this example were the same as in example 1.
And (3) measuring results: the content of tembotrione in the soil was determined to be <0.05mg/kg by the above procedure.
Example 13
The embodiment provides a method for detecting residual quantity of sulfoketone in an environment sample, wherein the environment sample is red soil, and the method comprises the following steps:
(1) Extraction: weighing 20.0g of soil sample (accurate to 0.01 g), placing the soil sample in a 150mL triangular flask, adding 8mL of water, 2.0mL of ammonia water and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring the filtrate into a 100mL measuring cylinder with a plug and containing 8g of sodium chloride, returning the filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, carrying out suction filtration, combining the filtrates in the measuring cylinder with the plug, violently shaking for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the acetonitrile layer in a flat-bottomed flask, carrying out rotary evaporation at 40 ℃ to dryness, and carrying out nitrogen blow-drying to obtain an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile water solution and 0.1mL of formic acid into a flat-bottomed flask filled with the extract in sequence, and performing ultrasonic dissolution to obtain a purified solution;
(3) Purification: taking a solid phase extraction column C 18 Pre-leaching with 5mL of acetonitrile and 5mL of purified water in sequence, taking a purified solution for sampling, leaching with 2.5mL of 30% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting eluent, and filtering with a 0.22-micrometer filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions in this example were the same as in example 1.
And (3) measuring results: the content of the tembotrione in the soil is determined to be 2.04mg/kg through the steps.
Example 14
The embodiment provides a method for detecting residual quantity of sulfoketone in an environment sample, wherein the environment sample is red soil, and the method comprises the following steps:
(1) Extraction: weighing 20.0g of soil sample (accurate to 0.01 g), placing the soil sample in a 150mL triangular flask, adding 8mL of water, 2.0mL of ammonia water and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring the filtrate into a 100mL measuring cylinder with a plug and containing 8g of sodium chloride, returning the filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, carrying out suction filtration, combining the filtrates in the measuring cylinder with the plug, violently shaking for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the acetonitrile layer in a flat-bottomed flask, carrying out rotary evaporation at 40 ℃ to dryness, and carrying out nitrogen blow-drying to obtain an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile water solution into a flat-bottomed flask filled with the extract, and performing ultrasonic dissolution to obtain a purified solution;
(3) Purifying: taking a solid phase extraction column C 18 Pre-leaching with 5mL of acetonitrile and 5mL of purified water in sequence, taking a purified solution for sampling, leaching with 2.5mL of 30% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting eluent, and filtering with a 0.22-micron filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry instrument. The measurement conditions of this example were the same as in example 1.
And (3) measuring results: the content of tembotrione in the soil was determined to be <0.05mg/kg by the above procedure.
Example 15
The embodiment provides a method for detecting residual quantity of sulfoketone in an environment sample, wherein the environment sample is moisture soil, and the method comprises the following steps:
(1) Extraction: weighing 20.0g of soil sample (accurate to 0.01 g), placing the soil sample in a 150mL triangular flask, adding 8mL of water, 2.0mL of ammonia water and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring the filtrate into a 100mL measuring cylinder with a plug and containing 8g of sodium chloride, returning the filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, carrying out suction filtration, combining the filtrates in the measuring cylinder with the plug, violently shaking for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the acetonitrile layer in a flat-bottomed flask, carrying out rotary evaporation at 40 ℃ to dryness, and carrying out nitrogen blow-drying to obtain an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile water solution and 0.1mL of formic acid into a flat-bottomed flask filled with the extract in sequence, and performing ultrasonic dissolution to obtain a purified solution;
(3) Purifying: taking a solid phase extraction column C 18 And using 5mL of acetonitrile and 5mL of purified water in sequencePre-leaching, sampling the purified solution, leaching with 2.5mL of 30% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting the eluent, and filtering with a 0.22-micrometer filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions in this example were the same as in example 1.
And (3) measuring results: the content of tembotrione in the soil was determined to be 1.73mg/kg by the above procedure.
Example 16
The embodiment provides a method for detecting residual quantity of sulfoketone in an environmental sample, wherein the environmental sample is moisture soil, and the method comprises the following steps:
(1) Extraction: weighing 20.0g of soil sample (accurate to 0.01 g), placing the soil sample in a 150mL triangular flask, adding 8mL of water, 2.0mL of ammonia water and 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, transferring filtrate into a 100mL stoppered measuring cylinder filled with 8g of sodium chloride, returning filter residue to the original triangular flask, adding 40mL of acetonitrile, oscillating for 30min, then carrying out suction filtration, combining the filtrate in the stoppered measuring cylinder, violently oscillating for about 1min, standing for layering, then sucking 10mL of acetonitrile layer, placing the acetonitrile layer in a flat-bottomed flask, rotating at 40 ℃ for evaporation, and drying by nitrogen to obtain an extract;
(2) Redissolving: adding 5.0mL of 20% acetonitrile water solution into a flat-bottomed flask filled with the extract, and performing ultrasonic dissolution to obtain a purified solution;
(3) Purification: taking a solid phase extraction column C 18 Pre-leaching with 5mL of acetonitrile and 5mL of purified water in sequence, taking a purified solution for sampling, leaching with 2.5mL of 30% acetonitrile aqueous solution, eluting with 2.5mL of acetonitrile, collecting eluent, and filtering with a 0.22-micrometer filter membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument. The measurement conditions in this example were the same as in example 1.
And (3) measuring results: the content of tembotrione in the soil was determined to be <0.05mg/kg by the above procedure.
The measured values and recoveries of the tembotrione of examples 7-16 are as follows:
Figure BDA0003822638540000131
examples 7-16 analysis of results: comparing examples 7 and 8, it was found that the influence of 5mL of 20% acetonitrile in water and 0.1mL of formic acid as the loading solvent in the next step on the detection results was larger when redissolving in step (2) than when using 5mL of 20% acetonitrile in water alone for the sediment samples;
comparing examples 9 and 10, it was found that, with respect to a water sample, the influence on the detection result when 5mL of 20% acetonitrile aqueous solution and 0.1mL of formic acid were used as the loading solvent in the next step is smaller in the reconstitution in step (2) than when 5mL of 20% acetonitrile aqueous solution was used alone;
comparing examples 11 and 12, examples 13 and 14, and examples 15 and 16, it was found that, with respect to the soil sample, the influence of 5mL of 20% acetonitrile aqueous solution and 0.1mL of formic acid as the loading solvent in the next step on the detection result upon reconstitution in step (2) was very large, compared to the case of using 5mL of 20% acetonitrile aqueous solution alone;
the use of 5mL of 20% acetonitrile aqueous solution and 0.1mL of formic acid in the redissolution is beneficial to the dissolution and subsequent purification of sediments and soil samples, and particularly for the soil samples, the subsequent sample loading and purification effects are better.
Next, after collecting and measuring the purified liquid samples obtained in the step (3) of examples 7 to 16, it was found that no cyclucone was detected after the purified liquid samples obtained in examples 7, 9, 10, 11, 13 and 15 were loaded, whereas 80% to 90% cyclucone was detected after the purified liquid samples obtained in examples 8, 12, 14 and 16, indicating that none of the cyclucones obtained in examples 8, 12, 14 and 16 was retained in the solid phase extraction column.
The above results are obtained because, in general, environmental water samples are relatively clean, sediments and soil matrix are relatively "miscellaneous", so that the co-extract in different environmental samples is greatly different, which causes significant difference in the effect of the co-extract on the solid-phase extraction purification of the tembotrione. The addition of formic acid during redissolution is beneficial to the retention of the tembotrion on the solid-phase extraction column, especially when the interference of a co-extract is large, the addition of formic acid in the sample loading solvent plays a key role in the retention of the tembotrion on the solid-phase extraction column, the pKa value of the tembotrion is 3.18, the addition of weak acid enables most of the tembotrion in the solution to be in a molecular state, the retention of the tembotrion on the solid-phase extraction column is enhanced, the subsequent steps are also beneficial to selecting non-polar acetonitrile for water-soluble leaching of impurities, the problem of matrix interference is solved, a good purification effect is achieved, and the influence of co-extraction impurities on certainty and quantitative analysis is reduced to the greatest extent. Selection of purification material and optimization of column passing condition
The optimization experiment is mainly aimed at the selection of the purification material in the step (3) and the column passing conditions, and tests are carried out by adopting the cyclic sulfoketone addition concentration of 2.0mg/kg or mg/L in the sample and selecting the implementation conditions of the embodiment 4.
Firstly, acidic alumina, neutral alumina, basic alumina and Florisil purification materials are selected in the test, a filling purification glass column is manufactured, the retention and adsorption capacities of petroleum ether/acetone, petroleum ether/ethyl acetate and acetonitrile/water to the tembotrione are measured, and specific results are shown in the following table.
Recovery rate of cyclic sulfonic acid ketone from different purification materials table:
Figure BDA0003822638540000141
Figure BDA0003822638540000151
from the above table, it can be seen that the acidic alumina purification material in the above purification materials has strong retention on the tembotrione, none of the three elution systems of petroleum ether/acetone, petroleum ether/ethyl acetate and acetonitrile/water elute the tembotrione, and the column recovery rates of the reagent systems of different proportions are all 0; the three purifying materials of neutral alumina, basic alumina and Florisil have strong retention to the cyclucone, petroleum ether/acetone and petroleum ether/ethyl acetate elution systems are difficult to elute the cyclucone, the column recovery rates of reagent systems with different proportions are all 0, the cyclucone can be eluted only under an acetonitrile/water elution system, but the stability of a self-made packed column is not enough, so C is also selected 18 As purifying materialThe solid phase extraction column of the material is subjected to a column passing test.
Secondly, 6 different brands of C are selected in the next test 18 Comparison of purification materials, 6 types C 18 The purification materials are named after A-F columns, model and manufacturer of which are Waters HLB (60 mg/3mL, waters Corp., USA), DIKAMA ProElut C 18 (500 mg/6mL, manufactured by Beijing Dima Techni Co., ltd.), agela Cleanert S C 18 SPE (500 mg/6mL, tianjin Bonner Ai Jieer Corp.), agela Cleanert S C 18 N-SPE (500 mg/6mL, tianjin Boner Ai Jieer Co.), BESEP C 18 H octadienyl modified silica (17% carbon Icad) (500 mg/6mL, volitant) and Spe-ed SPE C 18 18% (500 mg/6mL, applied separations, USA). The elution system for the test is acetonitrile water solution with different proportions, and the elution result is shown in figure 8. As can be seen from fig. 8, except for the F column, 55.8% to 88.8% of the tembotrione is eluted at the sample loading portion (20% acetonitrile aqueous solution) of the a-E column, and no tembotrione is eluted at the sample loading portion (20% acetonitrile aqueous solution) of the F column, so that it can be seen that the F column has the strongest retention capacity for tembotrione, which is favorable for separation of impurities, and is favorable for eluting to remove interfering impurities by selecting a combination of acetonitrile aqueous solutions with different polarities.
Again, the F column was selected for further optimization, and 20% (with 2% formic acid), 30%, 50%, 60%, 70%, 80%, 100% acetonitrile in water were used for rinsing, respectively, and the cyclic sultone in each section was measured, and the leaching recovery rate and the cumulative recovery rate in each section were calculated, and the results are shown in FIGS. 9-10. As can be seen from FIGS. 9-10, 20% (with 2% formic acid) of the acetonitrile aqueous solution and 30% of the acetonitrile aqueous solution failed to elute the tembotrion, but from 50% of the acetonitrile aqueous solution, the tembotrion was gradually eluted, and most of the tembotrion was eluted by 50% of the acetonitrile aqueous solution, 93.8% of the tembotrion was eluted when 70% of the acetonitrile aqueous solution was eluted, 99.5% of the tembotrion was eluted when 100% of the acetonitrile was eluted, and the concentration approaches to 100%, indicating that the tembotrion was substantially completely eluted. According to the experimental result, a 20% acetonitrile water solution (doped with 2% formic acid) is finally adopted for sample loading, a 30% acetonitrile water solution is adopted for rinsing to remove impurities, finally, the high-polarity acetonitrile is used for completely eluting the tembotrione, and the recovery rate of the tembotrione is ensured.
Method of verification test
1. The instrument comprises the following steps: waters UPLC-XEVO TQ-MS high performance liquid chromatography tandem mass spectrometry (Waters corporation, USA), OHAUS SPS402F electronic balance (0.01 g, ohaos, USA), AB104-S electronic balance (0.0001 g, mettler-Toliduo International trade (Shanghai) Limited), R-201 type rotary evaporator (Shanghai Shensheng biotechnology Limited), DHZ-DA full temperature type large container constant temperature oscillator (Taicang city laboratory instruments and Equipment factory).
2. Reagent: acetonitrile (chromatographically pure, merck, germany), acetonitrile (analytically pure, shanghai Ling Fenghua chemical reagents, ltd.), ammonia (analytically pure, high-crystalline fine chemical engineering, ltd.), sodium chloride (analytically pure, chemicals, ltd, santa, usa), formic acid (chromatographically pure, ACS, encco chemical reagents, usa), purified water (santa wa haha, ltd.), C 18 Small column (500 mg/6mL, applied separations, USA).
3. Conditions of instrumental analysis
Liquid phase conditions
A chromatographic column: waters ACQUITY
Figure BDA0003822638540000161
BEH C 18 (2.1×100mm，1.7μm)
Mobile phase: phase A is acetonitrile, phase B is 0.1% formic acid water solution
Gradient elution procedure: 0min, A is 50%;1min, A is 90%;3.5min, A is 90%;4min, A is 50%;5.0min, A is 50%
Flow rate: 0.20mL/min
Column temperature: 40 deg.C
Sample introduction volume: 2.00 mu L
Mass spectrum conditions: the ionization being ESI + The method adopts MRM multi-reaction monitoring, the capillary voltage is 2.50kV, the desolventizing temperature is 400 ℃, and the desolventizing gas flow is 800L/Hr. Quantitative ion pair 441.0>261.8*，441.0>340.9。
4. Linear relation of method
Accurately weighing 98% of tembotrione standard substance, and preparing with chromatographic pure acetonitrile to obtain 100mg/L standard stock solution. Diluting with chromatographic acetonitrile to obtain standard working solutions of 0.0050, 0.010, 0.020, 0.040, 0.080 and 0.10mg/L. Injecting sample according to the analysis condition of the instrument, drawing a standard curve of the tembotrione by concentration-peak area, wherein the regression equation is y =103210.4967x-92.6439 (R) 2 = 0.9987) where y is the area of the cyclic sulphonone peak and x is the standard solution concentration.
5. Method recovery and relative standard deviation
The standard solution of tembotrione with concentration of 2 grades is added into blank matrix (pH 4.0 buffer solution, pH7.0 buffer solution, pH9.0 buffer solution, canal water and West lake water) respectively, each grade is repeated for 5 times, the standard solution of tembotrione with concentration of 3 grades is added into blank matrix (moisture soil, red soil, paddy soil, west lake sediment and canal sediment) and each grade is repeated for 5 times, the soil is treated according to the steps of example 4, the sediment is treated according to the steps of example 7, and the water sample is treated according to the steps of example 9. After the environmental sample is processed, the recovery rate is determined by using the method for sampling by the instrument. The recovery rate of the tembotrione in a water sample and the coefficient of variation thereof are as follows:
Figure BDA0003822638540000171
the results for the recovery of tembotrione in soil and sediment and its coefficient of variation are given in the following table:
Figure BDA0003822638540000172
and (4) analyzing results: the table of the recovery rates and the variation coefficients of the cyclic sulfoketones in water samples, soils and sediments shows that the average recovery rate of the cyclic sulfoketones in the water is 78.9-93.9%, the RSD is 1.9-8.7%, the average recovery rate of the cyclic sulfoketones in the soils is 81.7-99.5%, the RSD is 1.9-7.9%, the average recovery rate of the cyclic sulfoketones in the sediments is 75.8-84.0%, and the RSD is 2.5-9.2%; the method adopts solvent standard sample calculation, the calculation results of the recovery rate all meet the analysis and detection requirements of pesticide residue, no obvious matrix effect exists, and the method is proved to have better recovery rate and repeatability and to be superior to the QuEChERS method; meanwhile, the method is used in the soil sample, has the highest recovery rate and the smallest coefficient of variation, and has the best measuring effect and higher accuracy when being applied to the soil sample. The linear range of the method is 0.005-0.1 mg/L, the lowest detection limit is calculated by 3 times of signal-to-noise ratio, the quantification limit is calculated by 10 times of signal-to-noise ratio, the lowest detection limit is 0.00002mg/kg or mg/L, and the quantification limit is 0.00007mg/kg or mg/L.
With reference to fig. 1 to 7, fig. 1 is a liquid chromatogram of a standard solution (0.005 mg/L), fig. 2 is a liquid chromatogram of a blank water sample, fig. 3 is a liquid chromatogram of a water sample added and recovered (0.05 mg/L), and as can be seen from fig. 1 to 3, the blank sample chromatogram has less interference and the response value background is low (< 6.266e + 002); FIG. 4 is a liquid phase map of a blank soil sample, FIG. 5 is a liquid phase map of laterite addition recovery (0.05 mg/kg), and as can be seen from FIGS. 4-5, the blank sample chromatogram has little interference and the response value is low (< 6.670e +002); FIG. 6 is a liquid phase map of a sediment blank sample, FIG. 7 is a liquid phase map of addition recovery (0.05 mg/kg) of sediment in West lake, and it can be known from FIGS. 6 and 7 that a blank sample chromatogram has little interference and a low response value background (< 1.124e + 003).
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be effected by one skilled in the art without departing from the spirit and scope of the invention, as defined in the appended claims.

Claims (10)

1. A method for detecting residual quantity of sulfoketone in an environmental sample is characterized by comprising the following steps:
(1) Extraction: weighing a sample, adding acetonitrile for dissolution, wherein the mass ratio of the sample to the acetonitrile is 1g:2-4mL, oscillating and carrying out primary suction filtration, continuously adding acetonitrile into filter residues for dissolving, oscillating and carrying out secondary suction filtration, placing filtrate obtained in the two-time suction filtration into a measuring cylinder filled with sodium chloride, oscillating, standing for layering, taking an acetonitrile layer, and drying to obtain an extract;
(2) Redissolving: dissolving the extract with aqueous acetonitrile solution doped with formic acid to obtain purified solution;
(3) Purifying: taking a solid phase extraction column, pre-leaching, taking a purified solution, loading, leaching with acetonitrile aqueous solution, eluting with acetonitrile, collecting an eluent, and filtering by a membrane to obtain a substance to be detected;
(4) And (3) determination: and detecting the object to be detected by adopting an ultra-high performance liquid chromatography-mass spectrum/mass spectrum combination instrument.
2. The method for detecting the residual quantity of tembotrione in an environmental sample according to claim 1, wherein the ratio of the mass of the sample to the volume of acetonitrile in the step (1) is 1g:4mL.
3. The method for detecting the residual quantity of tembotrione in an environmental sample according to claim 1, wherein the sample in step (1) is soil, sediment or water sample.
4. The method for detecting the residual quantity of the tembotrione in the environmental sample according to claim 3, wherein when the sample in the step (1) is a sediment, ammonia water is added for dissolution, and the ratio of the mass of the sample to the volume of the ammonia water is 1g:0.1-0.4ml.
5. The method for detecting the residual quantity of tembotrione in an environmental sample according to claim 4, wherein when the sample in step (1) is a sediment, the ratio of the mass of the sample to the volume of ammonia water is 1g:0.1ml.
6. The method for detecting the residual quantity of tembotrione in an environmental sample according to claim 3, wherein when the sample in step (1) is soil, ammonia water and water are added for dissolution, and the ratio of the mass of the sample to the volume of the ammonia water is 1g:0.1-0.4ml.
7. The method for detecting the residual quantity of tembotrione in an environmental sample according to claim 6, wherein when the sample in step (1) is soil, the ratio of the mass of the sample to the volume of ammonia water is 1g:0.1ml.
8. The method for detecting the residual amount of tembotrione in an environmental sample as claimed in claim 1, wherein 5mL of 20% acetonitrile-water solution mixed with formic acid is required to be added for ultrasonic dissolution in step (2) per 1mL of acetonitrile layer, wherein the mixing rate of formic acid is 2%.
9. The method according to claim 1, wherein the purifying material in the solid phase extraction column in step (3) is C 18 The rinsing was with 30% acetonitrile in water.
10. The method for detecting the residual quantity of tembotrione in an environmental sample as claimed in claim 1, wherein the liquid phase measurement conditions in step (4) are as follows: a chromatographic column: c 18 A reverse phase chromatography column; mobile phase: phase A is acetonitrile, phase B is 0.1% formic acid aqueous solution; gradient elution procedure: 0min, A is 50%;1min, A is 90%;3.5min, A is 90%;4min, A is 50%;5.0min, A is 50%; flow rate: column temperature 0.20 mL/min: sample volume at 40 ℃:2.00 mu L;
the mass spectrometry conditions are as follows: an ionization mode: ESI + Monitoring by adopting MRM multiple reactions; capillary voltage: 2.50kV;
desolventizing temperature: 400 ℃; desolventizing agent gas flow: 800L/Hr; quantitative ion pair: 441.0> < 261.8, 441.0> < 340.9.
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