CN108828101B - Method for determining diuron residues in sugarcane based on 3, 4-dichloroaniline - Google Patents
Method for determining diuron residues in sugarcane based on 3, 4-dichloroaniline Download PDFInfo
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- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical group CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 title claims abstract description 78
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- 239000012086 standard solution Substances 0.000 claims abstract description 29
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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
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention discloses a method for determining diuron residue in sugarcane based on 3, 4-dichloroaniline, which comprises the following steps: s1, determining an indicating component 3, 4-dichloroaniline of diuron thermal decomposition by adopting a gas chromatography-mass spectrometry combined technology; s2, sample pretreatment: extracting and purifying a sugarcane sample to obtain a sugarcane liquid to be detected; s3, preparing diuron standard solution with at least 6 concentrations; carrying out gas chromatography-electronic capture detector measurement on the prepared diuron standard solution with each concentration gradient, and drawing a standard working curve; and (4) determining the diuron content in the sugarcane to-be-detected liquid. By adopting the method, the diuron has good linear relation in the range of 0.01-5.0 mg/L, the correlation coefficients are all larger than 0.998, the detection limit is 0.007 mg/kg, the recovery rate of the diuron in the sugarcane juice is 89.2-111%, the relative standard deviation is 2.45-6.57%, and the accuracy and precision of the method can meet the requirement of pesticide residue analysis.
Description
Technical Field
The invention relates to the technical field of food safety, in particular to a method for determining diuron residue in sugarcane based on 3, 4-dichloroaniline.
Background
Diuron (Diuron) is a substituted urea herbicide, can effectively prevent and kill grassy weeds, broad-leaved weeds and algae, is not limited by regions and climatic conditions, is widely applied to crop fields such as sugarcane, corn, soybean and the like all over the country, has stable chemical property and long residual period, is persistent in the environment and has certain biological accumulation effect and toxic effect on the development of mammals, birds and fetuses and the health of human beings, according to the fact that the Diuron is issued and implemented in 24 days of 5 months and 5 months in 2015 as food safety national standard sugar GB 13104-2014', the original sanitary standard is upgraded to the national food safety standard, the use regulations of the limited standard of food additives and pollutants (such as pesticide residues, heavy metals and the like) are increased, wherein the maximum residual amount and the maximum use amount of GB2760-2014 and GB2762-2017 are respectively executed, therefore, in order to ensure the safety of sugar products and the environment, the analysis of the residual quantity of the sugar cane juice serving as the diuron sugar product raw material is very necessary.
At present, methods for detecting diuron in sugarcane mainly comprise acid hydrolysis gas chromatography-mass spectrometry, ultra-high liquid chromatography, liquid chromatography-mass spectrometry and other instrument analysis methods. Since diuron is decomposed when the temperature reaches over 180 ℃, qualitative and quantitative analysis of a gas chromatography is difficult, most researches adopt the liquid chromatography for analysis, but when the liquid chromatography-mass spectrometry is adopted, the detection cost is high, the consumption of a mobile phase reagent is large, and the requirements of quick, low-cost and environment-friendly detection are difficult to meet.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a method for determining diuron residue in sugarcane based on 3, 4-dichloroaniline.
The technical problem to be solved by the invention is realized by the following technical scheme:
the method for determining diuron residue in sugarcane based on 3, 4-dichloroaniline comprises the following steps:
s1, determining an indicating component 3, 4-dichloroaniline of diuron thermal decomposition by adopting a gas chromatography-mass spectrometry combined technology;
s2, sample pretreatment: extracting and purifying a sugarcane sample to obtain a sugarcane liquid to be detected;
s3, preparing diuron standard solution with at least 6 concentrations; carrying out gas chromatography-electronic capture detector determination on the prepared diuron standard solution with each concentration gradient, carrying out regression analysis on the corresponding concentration of the standard solution according to the chromatographic peak area of the standard solution, and drawing a standard working curve; and injecting the sugarcane to-be-detected liquid into a gas chromatography-electron capture detector under the same condition for determination, determining the chromatographic peak area of diuron in the sugarcane to-be-detected liquid, and substituting the chromatographic peak area into a standard working curve to obtain the diuron content in the sugarcane to-be-detected liquid.
Further, the conditions detected by the gas chromatography-electron capture detector are as follows: the type of the chromatographic column: rtx-5; size of chromatographic column: 30 m.times.250. mu.m.times.0.25. mu.m; the carrier gas is nitrogen with the purity of more than 99.999 percent; the flow rate of the carrier gas is 1.2 mL/min; the temperature of a sample inlet is 250 ℃; the temperature of the detector is 300 ℃; the column oven adopts a temperature program, and the temperature program is as follows: the initial temperature of the chromatographic column is 100 ℃, the temperature is increased to 200 ℃ at 20 ℃/min, then the temperature is increased to 230 ℃ at 8 ℃/min, and the temperature is kept for 2 min; sample introduction amount: 1 mu L of the solution; the split ratio is 1: 50.
Further, the specific operation of step S1 is: (1) establishing gas chromatography conditions; establishing mass spectrum conditions; (2) detecting a diuron standard solution with a certain concentration by using a gas chromatography-mass spectrometer under the condition of the step (1), and carrying out qualitative analysis on each thermal decomposition product in the diuron standard solution by combining retrieval of an American NIST standard spectrum library or other standard spectrum libraries according to an obtained total ion current chromatogram and a mass spectrogram to determine a main product 3, 4-dichloroaniline of diuron thermal decomposition; (3) preparing diuron standard solutions with different concentrations, detecting the prepared diuron standard solutions with various concentration gradients by using a gas chromatography-mass spectrometer under the condition of the step (1), carrying out selective ion monitoring SIM quantitative analysis, wherein the quantitative ions are ions with m/z 161, the concentration of the diuron is used as an abscissa, the peak height of the quantitative ions is used as an ordinate, and a standard working curve is drawn by adopting the linear regression of the least square method, and the linear correlation coefficient of the standard working curve is larger than 0.998.
Since diuron decomposes when the temperature reaches over 180 ℃, which causes difficulties in qualitative and quantitative analysis of gas chromatography, researchers in the field have long considered that the detection of diuron residues in sugarcane samples is not suitable for the gas chromatography-electron capture detector method. The applicant carries out qualitative and quantitative research on decomposition products generated by thermal decomposition of diuron in the gas chromatography analysis process by utilizing a gas chromatography-mass spectrometry combined technology through long-term deep research, finds out indicating components of diuron thermal decomposition and a relationship between the indicating components and a diuron stock solution through the chemical structure of the decomposition products of a mass spectrogram, confirms the feasibility and the accuracy of measuring diuron residue in a sugarcane sample by using a gas chromatography-electronic trap detection method, and has important significance on establishing a detection method for analyzing the diuron residue in the sugarcane sample by using a gas chromatography-electronic trap detector method.
Until now, there is no report about using 3, 4-dichloroaniline as qualitative and quantitative index of diuron in gas chromatography-electron capture detector method in food and agricultural products at home and abroad, before the application, the technicians in this field always put the focus on the research on how to use instrumental detection method other than gas chromatography-electron capture detector method to measure diuron residue with high efficiency, because of diuron's thermal instability, the technicians in this field have not paid close attention to the feasibility of using gas chromatography-electron capture detector method to measure diuron residue, the applicant has determined 3, 4-dichloroaniline as the indicating component of diuron thermal decomposition and the representative component of quantitative analysis through intensive research, and the 3, 4-dichloroaniline structure contains two chlorine elements with strong electronegativity and has strong response signal in the electron capture detector, the sensitivity is high, thereby providing a new way for rapidly detecting the trace diuron.
Further, establishment of gas chromatography conditions: the type of the chromatographic column: HP-5 MS; specification of chromatographic column: 30 m.times.250. mu.m.times.0.25. mu.m; the carrier gas is helium with the purity of more than 99.999 percent; the flow rate of the carrier gas is 1.2 mL/min; the temperature of the sample inlet is 250 ℃, the temperature of the detector is 300 ℃, and the column incubator adopts the temperature programming, the temperature programming is as follows: the initial temperature of the chromatographic column is 100 ℃, the temperature is increased to 200 ℃ at 20 ℃/min, then the temperature is increased to 230 ℃ at 8 ℃/min, and the temperature is kept for 2 min; sample introduction amount: 1 μ L, the split ratio is: 1: 5; establishing mass spectrum conditions: an ion source: an electron bombardment source; electron energy: 70 eV; gas chromatography-mass spectrometry interface temperature: 250 ℃; temperature of the quadrupole rods: 150 ℃; ion source temperature: 230 ℃, collection mode: the ion is selected to monitor SIM, and the quantitative ion of the 3, 4-dichloroaniline is the ion of m/z 161, and the qualitative ion is the ion of m/ z 161, 207, 126 and 63.
The sugarcane juice matrix is complex, contains more organic acids, phenols, metal ions, pigments, microorganisms and the like, can reduce the sensitivity and selectivity of detection results, and can cause great damage to chromatographic columns, ion sources, detectors and the like. Therefore, before performing instrumental analysis, it is usually necessary to adopt a proper sample pretreatment technique to avoid interference of the matrix on the analysis of the target substance, so as to improve the accuracy of the detection result.
Further, the sample pretreatment is as follows: (1) extraction: sucking 5.00 mL of cane juice, placing the cane juice in a 50 mL centrifuge tube, adding 5.0 mL of acetonitrile and 2.0 g of sodium citrate, carrying out rotary mixing for 1 min, carrying out ultrasonic extraction for 3min, placing the centrifuge tube in a centrifuge, centrifuging for 5 min at a speed of 5000 r/min, taking out supernatant, and placing the supernatant in a nitrogen blowing tube; continuously adding 5.0 mL of acetonitrile into the centrifuge tube, carrying out rotary mixing for 1 min, carrying out ultrasonic extraction for 3min, putting the centrifuge tube into a centrifuge, centrifuging for 5 min at a speed of 5000 r/min, taking out supernatant, putting the supernatant into the nitrogen blowing tube, blowing to be nearly dry, and carrying out constant volume treatment to 2.0 mL by using methanol to obtain an extracting solution; (2) purifying: transferring the extractive solution into a purification column, repeatedly pumping and pushing the piston for three times, and allowing the extractive solution to pass through the purification column to obtain eluate; then the eluent passes through a 0.22 micron microporous filter membrane and is transferred into a sample bottle to be tested on a computer.
Further, the frequency of ultrasonic extraction was 70 kHz and the temperature of ultrasonic extraction was 30 ℃.
In the invention, acetonitrile is used as an extraction solvent, compared with the conventionally used extraction solvent such as acetone and the like, the diuron in the sugarcane juice can be extracted to the maximum extent, and because the sugarcane juice contains a large amount of sugar substances such as sucrose, glucose, fructose and the like, the sugar substances are insoluble in the acetonitrile, and the acetonitrile is used as the extraction solvent, the interference of the sugar substances can be effectively reduced, so that the target substance has symmetrical chromatographic peak shape and low matrix effect.
Magnesium sulfate is usually added in the traditional extraction process at the same time, and the practice of the invention finds that the extraction efficiency of residual diuron in sugarcane juice can be greatly improved by replacing magnesium sulfate with sodium citrate.
Further, the purifying column comprises a column tube and a filler in the column tube, a piston is arranged in the column tube, and the piston can move along the axial direction of the column tube; the lower end of the column tube is provided with a liquid outlet tube; the filler comprises the following components: 3-12 parts of NANO carbon, 2-10 parts of modified mesoporous silica and 0.5 part of diatomite; the NANO carbon is filled in the bottom layer of the column tube, the modified mesoporous silica and the diatomite are mixed and filled in the upper layer of the column tube, and a polypropylene sieve plate is used for separation.
Further, the preparation method of the modified mesoporous silica comprises the following steps: drying the ordered mesoporous silica for 8-10 h at 75-85 ℃ to obtain pretreated ordered mesoporous silica; adding toluene into the pretreated ordered mesoporous silica, then adding 3-aminopropyltriethoxysilane and gamma-halopropyl trimethoxysilane, stirring and reacting in an oil bath constant-temperature heating magnetic stirrer, performing suction filtration after the reaction is finished, cleaning for 1-2 h by using isopropanol, and drying, wherein the mass volume ratio of the organic mesoporous silica to the toluene is 8g:1L, and the molar ratio of the ordered mesoporous silica to the 3-aminopropyltriethoxysilane to the gamma-halopropyl trimethoxysilane is 8.5: 0.6: 1.5.
According to the invention, 3-aminopropyltriethoxysilane and gamma-halopropyl trimethoxysilane are adopted to introduce organic functional groups to the surface of the mesoporous silica to synthesize novel functionalized mesoporous hydrogenated silica, and the addition ratio of the 3-aminopropyltriethoxysilane and the gamma-halopropyl trimethoxysilane is adjusted in the synthesis process, so that the surface functional degree of the mesoporous silica material can be effectively regulated and controlled, the functional groups are uniformly distributed, and the pore channel order degree of the mesoporous silica material is kept from being damaged. The modified mesoporous silica synthesized by the method can be used as a purification adsorbent to effectively remove phenolic substances in the extracting solution and reduce the adsorption on a target object.
The NANO carbon is a carbon-based NANO material, has the characteristics of hydrophobic surface, porosity, specific pi electron system and the like, and is easy to react with a target compound pi-pi, so that the NANO carbon can effectively reduce or eliminate the influence of a base material such as pigment, fat, metal ions and the like in a sample on a detection result, and is an ideal adsorbent and a purifying agent. The NANO carbon of the present invention is selected from commercially available products and the purification column of the present invention is an improvement over the commercially available Cleanert NANO carbon purification column from the Agela brand.
The diatomite has strong adsorption capacity, and technicians in the field usually do not adopt the diatomite when purifying the sugarcane extracting solution so as to avoid the diatomite from adsorbing pesticide residues in the sugarcane extracting solution, thereby influencing the accurate determination of the pesticide residues in the sugarcane. In the invention, a small amount of diatomite is added as one of the adsorbents and is used together with NANO carbon and modified mesoporous silica, so that the recovery of pesticide residues is not influenced, and on the contrary, the final purification effect is very remarkable.
According to the invention, through optimizing the performances of dozens of adsorbing materials, NANO carbon, modified mesoporous silica and diatomite are used as the adsorbents for the first time, and through optimizing the dosage and the proportion of the three materials and combining an application method, the purification requirement on the sugarcane extract is met, the matrix interferents of the sample can be removed to the greatest extent, the matrix effect can be obviously reduced, and the target pesticide cannot be adsorbed.
Further, the filler has a particle size in the range of 5 μm to 100 μm.
Furthermore, the sieve plate is of a grid structure with certain apertures
Further, the column tube is made of high-density polyethylene material or glass material.
In the existing purification column, all adsorbents are mixed and then filled, or various adsorbents are filled in layers, and in the invention, modified mesoporous silica and diatomite are mixed and filled and then are filled with NANO carbon in layers, and tests prove that the filling mode has better purification effect.
The invention has the following beneficial effects:
the feasibility of measuring the residual of the thermolabile substance diuron by adopting a gas chromatography-electron capture method is firstly determined, the linear relation of the diuron in the range of 0.01-5.0 mg/L is good, the correlation coefficients are all larger than 0.998, the detection limit is 0.007 mg/kg, the recovery rate of the diuron in sugarcane juice is 89.2% -111%, the relative standard deviation is 2.45% -6.57%, and the accuracy and precision of the method can meet the requirement of pesticide residue analysis.
Drawings
FIG. 1 is a GC-ECD chromatogram of a diuron standard solution at 0.5 mg/L;
FIG. 2 is a total ion current chromatogram of diuron standard solution at 0.5 mg/L;
FIG. 3 is a mass spectrum of 3, 4-dichloroaniline.
Detailed Description
The present invention will be described in detail with reference to examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.
Example 1
A method for determining an indicating component of diuron thermal decomposition in a gas chromatography-electron capture detector process, comprising the steps of:
(1) establishment of gas chromatography conditions: the type of the chromatographic column: HP-5 MS; specification of chromatographic column: 30 m.times.250. mu.m.times.0.25. mu.m; the carrier gas is helium with the purity of more than 99.999 percent; the flow rate of the carrier gas is 1.2 mL/min; the temperature of the sample inlet is 250 ℃, the temperature of the detector is 300 ℃, and the column incubator adopts the temperature programming, the temperature programming is as follows: the initial temperature of the chromatographic column is 100 ℃, the temperature is increased to 200 ℃ at 20 ℃/min, then the temperature is increased to 230 ℃ at 8 ℃/min, and the temperature is kept for 2 min; sample introduction amount: 1 μ L, the split ratio is: 1: 5; establishing mass spectrum conditions: an ion source: an electron bombardment source; electron energy: 70 eV; gas chromatography-mass spectrometry interface temperature: 250 ℃; temperature of the quadrupole rods: 150 ℃; ion source temperature: 230 ℃, collection mode: selecting ions for monitoring SIM, wherein the quantitative ions of 3, 4-dichloroaniline are m/z 161 ions, and the qualitative ions are m/ z 161, 207, 126 and 63 ions;
(2) detecting a diuron standard solution with a certain concentration (0.5 mg/L) by using a gas chromatography-mass spectrometer under the condition of the step (1), and qualitatively analyzing each thermal decomposition product in the diuron standard solution by combining with the retrieval of an American NIST standard spectrum library or other standard spectrum libraries according to an obtained total ion current chromatogram and a mass spectrum so as to determine a main product 3, 4-dichloroaniline of diuron thermal decomposition;
referring to fig. 1-3, when the diuron standard solution is subjected to gas chromatography detection, no diuron original form is found, but two decomposition products are formed simultaneously, and the main product of diuron thermal decomposition, namely 3, 4-dichloroaniline, is analyzed through a total ion chromatogram and a mass spectrogram.
(3) Preparing diuron standard solutions (0.01-5 ppm) with different concentrations, detecting the prepared diuron standard solutions with various concentration gradients by using a gas chromatography-mass spectrometer under the condition of the step (1), carrying out selective ion monitoring SIM quantitative analysis, quantifying ions with m/z 161, drawing a standard working curve by using the concentration of diuron as an abscissa and the peak height of the quantified ions as an ordinate and adopting linear regression of a least square method, and finding that a corresponding signal of 3, 4-dichloroaniline is in direct proportion to the concentration of diuron, wherein the linear correlation coefficient of the standard working curve is 0.9986.
Example 2
On the basis of example 1, the method for measuring diuron residues in sugarcane comprises the following steps:
s1, sample pretreatment: extracting and purifying a sugarcane sample to obtain a sugarcane liquid to be detected;
s2, preparing diuron standard solutions with 7 concentrations (0.01, 0.05, 0.1, 0.5, 1.0, 2.0 and 5.0 mg/L); carrying out gas chromatography-electronic capture detector determination on the prepared diuron standard solution with each concentration gradient, carrying out regression analysis on the corresponding concentration of the standard solution according to the chromatographic peak area of the standard solution, and drawing a standard working curve; and injecting the sugarcane to-be-detected liquid into a gas chromatography-electron capture detector under the same condition for determination, determining the chromatographic peak area of diuron in the sugarcane to-be-detected liquid, and substituting the chromatographic peak area into a standard working curve to obtain the diuron content in the sugarcane to-be-detected liquid.
Wherein, the detection conditions of the gas chromatography-electron capture detector are as follows: the type of the chromatographic column: rtx-5; size of chromatographic column: 30 m.times.250. mu.m.times.0.25. mu.m; the carrier gas is nitrogen with the purity of more than 99.999 percent; the flow rate of the carrier gas is 1.2 mL/min; the temperature of a sample inlet is 250 ℃; the temperature of the detector is 300 ℃; the column oven adopts a temperature program, and the temperature program is as follows: the initial temperature of the chromatographic column is 100 ℃, the temperature is increased to 200 ℃ at 20 ℃/min, then the temperature is increased to 230 ℃ at 8 ℃/min, and the temperature is kept for 2 min; sample introduction amount: 1 mu L of the solution; the split ratio is 1: 50.
The sample pretreatment comprises the following steps: (1) extraction: sucking 5.00 mL of cane juice, placing the cane juice in a 50 mL centrifuge tube, adding 5.0 mL of acetonitrile and 2.0 g of sodium citrate, carrying out rotary mixing for 1 min, carrying out ultrasonic extraction for 3min, placing the centrifuge tube in a centrifuge, centrifuging for 5 min at a speed of 5000 r/min, taking out supernatant, and placing the supernatant in a nitrogen blowing tube; continuously adding 5.0 mL of acetonitrile into the centrifuge tube, carrying out rotary mixing for 1 min, carrying out ultrasonic extraction for 3min, putting the centrifuge tube into a centrifuge, centrifuging for 5 min at a speed of 5000 r/min, taking out supernatant, putting the supernatant into the nitrogen blowing tube, blowing to be nearly dry, and carrying out constant volume treatment to 2.0 mL by using methanol to obtain an extracting solution; (2) purifying: transferring the extractive solution into a purification column, repeatedly pumping and pushing the piston for three times, and allowing the extractive solution to pass through the purification column to obtain eluate; then the eluent passes through a 0.22 micron microporous filter membrane and is transferred into a sample bottle to be tested on a computer. Wherein the frequency of ultrasonic extraction is 70 kHz, and the temperature of ultrasonic extraction is 30 ℃.
The purifying column comprises a column tube and a filler in the column tube, the column tube is made of high-density polyethylene material or glass material, the granularity of the filler ranges from 5 micrometers to 100 micrometers, a piston is arranged in the column tube, and the piston can move along the axial direction of the column tube; the lower end of the column tube is provided with a liquid outlet tube; the filler comprises the following components: 3-12 parts of NANO carbon, 2-10 parts of modified mesoporous silica and 0.5 part of diatomite; the NANO carbon is filled in the bottom layer of the column tube, the modified mesoporous silica and the diatomite are filled in the upper layer of the column tube in a mixed manner, a polypropylene sieve plate is used as separation, the sieve plate is of a grid structure with a certain aperture, and the preparation method of the modified mesoporous silica comprises the following steps: drying the ordered mesoporous silica for 8-10 h at 75-85 ℃ to obtain pretreated ordered mesoporous silica; adding toluene into the pretreated ordered mesoporous silica, then adding 3-aminopropyltriethoxysilane and gamma-halopropyl trimethoxysilane, stirring and reacting in an oil bath constant-temperature heating magnetic stirrer, performing suction filtration after the reaction is finished, cleaning for 1-2 h by using isopropanol, and drying, wherein the mass volume ratio of the organic mesoporous silica to the toluene is 8g:1L, and the molar ratio of the ordered mesoporous silica to the 3-aminopropyltriethoxysilane to the gamma-halopropyl trimethoxysilane is 8.5: 0.6: 1.5.
Example 3
Precision and recovery rate test
Using the sugarcane juice without diuron as blank samples, recovery tests were performed at addition levels of 0.01 mg/kg, 0.05 mg/kg, and 0.5 mg/kg for each sample, and 6 replicates for each addition level were measured by the method of example 2 to find the average recovery and relative standard deviation.
The above-mentioned embodiments only express the embodiments of the present invention, and the description is more specific and detailed, but not understood as the limitation of the patent scope of the present invention, but all the technical solutions obtained by using the equivalent substitution or the equivalent transformation should fall within the protection scope of the present invention.
Claims (7)
1. The method for determining diuron residue in sugarcane based on 3, 4-dichloroaniline comprises the following steps:
s1, determining an indicating component 3, 4-dichloroaniline of diuron thermal decomposition by adopting a gas chromatography-mass spectrometry combined technology;
s2, sample pretreatment: extracting and purifying a sugarcane sample to obtain a sugarcane liquid to be detected;
s3, preparing diuron standard solution with at least 6 concentrations; carrying out gas chromatography-electronic capture detector determination on the prepared diuron standard solution with each concentration gradient, carrying out regression analysis on the corresponding concentration of the standard solution according to the chromatographic peak area of the standard solution, and drawing a standard working curve; injecting the sugarcane to-be-detected liquid into a gas chromatography-electronic capture detector under the same conditions for detection, detecting the chromatographic peak area of diuron in the sugarcane to-be-detected liquid, substituting the chromatographic peak area into a standard working curve, and obtaining the diuron content in the sugarcane to-be-detected liquid;
the sample pretreatment comprises the following steps: (1) extraction: sucking 5.00 mL of cane juice, placing the cane juice in a 50 mL centrifuge tube, adding 5.0 mL of acetonitrile and 2.0 g of sodium citrate, carrying out rotary mixing for 1 min, carrying out ultrasonic extraction for 3min, placing the centrifuge tube in a centrifuge, centrifuging for 5 min at a speed of 5000 r/min, taking out supernatant, and placing the supernatant in a nitrogen blowing tube; continuously adding 5.0 mL of acetonitrile into the centrifuge tube, carrying out rotary mixing for 1 min, carrying out ultrasonic extraction for 3min, putting the centrifuge tube into a centrifuge, centrifuging for 5 min at a speed of 5000 r/min, taking out supernatant, putting the supernatant into the nitrogen blowing tube, blowing to be nearly dry, and carrying out constant volume treatment to 2.0 mL by using methanol to obtain an extracting solution; (2) purifying: transferring the extractive solution into a purification column, repeatedly pumping and pushing the piston for three times, and allowing the extractive solution to pass through the purification column to obtain eluate; then the eluent passes through a 0.22 micron microporous filter membrane and is transferred into a sample injection bottle to be tested on a computer;
the purifying column comprises a column tube and a filler in the column tube, wherein a piston is arranged in the column tube and can move along the axial direction of the column tube; the lower end of the column tube is provided with a liquid outlet tube; the filler comprises the following components: 3-12 parts of NANO carbon, 2-10 parts of modified mesoporous silica and 0.5 part of diatomite; the NANO carbon is filled in the bottom layer of the column tube, the modified mesoporous silica and the diatomite are mixed and filled in the upper layer of the column tube, and a polypropylene sieve plate is used for separation.
2. The method of claim 1, wherein the conditions detected by the gas chromatography-electron capture detector are: the type of the chromatographic column: rtx-5; size of chromatographic column: 30 m.times.250. mu.m.times.0.25. mu.m; the carrier gas is nitrogen with the purity of more than 99.999 percent; the flow rate of the carrier gas is 1.2 mL/min; the temperature of a sample inlet is 250 ℃; the temperature of the detector is 300 ℃; the column oven adopts a temperature program, and the temperature program is as follows: the initial temperature of the chromatographic column is 100 ℃, the temperature is increased to 200 ℃ at 20 ℃/min, then the temperature is increased to 230 ℃ at 8 ℃/min, and the temperature is kept for 2 min; sample introduction amount: 1 mu L of the solution; the split ratio was 1: 50.
3. The method as claimed in claim 1, wherein the specific operation of step S1 is: (1) establishing gas chromatography conditions; establishing mass spectrum conditions; (2) detecting a diuron standard solution with a certain concentration by using a gas chromatography-mass spectrometer under the condition of the step (1), and carrying out qualitative analysis on each thermal decomposition product in the diuron standard solution by combining retrieval of an American NIST standard spectrum library or other standard spectrum libraries according to an obtained total ion current chromatogram and a mass spectrogram to determine a main product 3, 4-dichloroaniline of diuron thermal decomposition; (3) preparing diuron standard solutions with different concentrations, detecting the prepared diuron standard solutions with various concentration gradients by using a gas chromatography-mass spectrometer under the condition of the step (1), carrying out selective ion monitoring SIM quantitative analysis, wherein the quantitative ions are ions with m/z 161, the concentration of the diuron is used as an abscissa, the peak height of the quantitative ions is used as an ordinate, and a standard working curve is drawn by adopting the linear regression of the least square method, and the linear correlation coefficient of the standard working curve is larger than 0.998.
4. The method of claim 3, wherein the establishment of gas chromatography conditions: the type of the chromatographic column: HP-5 MS; specification of chromatographic column: 30 m.times.250. mu.m.times.0.25. mu.m; the carrier gas is helium with the purity of more than 99.999 percent; the flow rate of the carrier gas is 1.2 mL/min; the temperature of the sample inlet is 250 ℃, the temperature of the detector is 300 ℃, and the column incubator adopts the temperature programming, the temperature programming is as follows: the initial temperature of the chromatographic column is 100 ℃, the temperature is increased to 200 ℃ at 20 ℃/min, then the temperature is increased to 230 ℃ at 8 ℃/min, and the temperature is kept for 2 min; sample introduction amount: 1 mu L with the split ratio of 1: 5; establishing mass spectrum conditions: an ion source: an electron bombardment source; electron energy: 70 eV; gas chromatography-mass spectrometry interface temperature: 250 ℃; temperature of the quadrupole rods: 150 ℃; ion source temperature: 230 ℃, collection mode: the ion is selected to monitor SIM, and the quantitative ion of the 3, 4-dichloroaniline is the ion of m/z 161, and the qualitative ion is the ion of m/z 161, 207, 126 and 63.
5. The method of claim 1, wherein the frequency of ultrasonic extraction is 70 kHz and the temperature of ultrasonic extraction is 30 ℃.
6. The method of claim 1, wherein the modified mesoporous silica is prepared by a method comprising: drying the ordered mesoporous silica for 8-10 h at 75-85 ℃ to obtain pretreated ordered mesoporous silica; adding toluene into the pretreated ordered mesoporous silica, then adding 3-aminopropyltriethoxysilane and gamma-halopropyl trimethoxysilane, stirring and reacting in an oil bath constant-temperature heating magnetic stirrer, performing suction filtration after the reaction is finished, cleaning for 1-2 h by using isopropanol, and drying, wherein the mass volume ratio of the organic mesoporous silica to the toluene is 8g:1L, and the molar ratio of the ordered mesoporous silica to the 3-aminopropyltriethoxysilane to the gamma-halopropyl trimethoxysilane is 8.5: 0.6: 1.5.
7. The method of claim 1, wherein the filler has a particle size in the range of 5 μ ι η to 100 μ ι η; the sieve plate is of a grid structure with a certain aperture; the column tube is made of high-density polyethylene material or glass material.
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