CN118883790A - Extraction method and detection method for pesticides in water body - Google Patents
Extraction method and detection method for pesticides in water body Download PDFInfo
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- 238000000605 extraction Methods 0.000 title claims abstract description 348
- 239000000575 pesticide Substances 0.000 title claims abstract description 87
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- 238000001514 detection method Methods 0.000 title claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 209
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- YFGYUFNIOHWBOB-UHFFFAOYSA-N pirimicarb Chemical compound CN(C)C(=O)OC1=NC(N(C)C)=NC(C)=C1C YFGYUFNIOHWBOB-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000007788 liquid Substances 0.000 claims abstract description 66
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
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- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to the technical field of pesticide testing and analysis, and particularly relates to an extraction method and a detection method of pesticides in a water body. The invention provides an extraction method of pesticides in water, which comprises the following steps: preparing a water sample and a phosphate buffer solution with pH=6.5-7 into a sample phase solution, and extracting pesticides in the sample phase solution into a receiving phase solution by adopting a supported liquid film extraction method, wherein the pesticides are one or more selected from carbendazim, pirimicarb, triclopyr, diflubenzuron and antifeedant hydrazine. Based on the natural barrier effect of the membrane on macromolecular substances in the supported liquid membrane extraction method, the interference problem caused by a water sample matrix can be effectively overcome, and by selecting phosphate buffer solution with pH=6.5-7 as a sample phase background solution, pesticides with various properties can be ensured to be always in a neutral state, the mass transfer effect of the pesticides in the extraction process is ensured, and the extraction rate of the pesticides is greatly improved.
Description
Technical Field
The invention relates to the technical field of pesticide testing and analysis, in particular to an extraction method and a detection method of pesticides in a water body.
Background
In recent years, with the increase of the usage amount of pesticides, more and more pesticides enter the water body along with natural actions of rainwater, runoff and the like. Factors exceeding the standard of pesticide residue include unreasonable, unscientific and nonstandard pesticide use, lag detection means, unhealthy detection system and the like. These pesticides, which are long-standing in water samples, not only adversely affect the growth of aquatic animals and plants and the balance of water ecology, but also pose a threat to human health through bioaccumulation effects. In order to avoid harm to human body caused by pesticide residue in water, it is important to establish a green rapid and sensitive detection technology for pesticide residue.
In pesticide residue analysis, modern analysis techniques generally involve two core links: pretreatment of samples and detection and analysis of instruments. Sample pretreatment plays a main role in the whole analysis process, and the main steps comprise preparation, extraction, purification, concentration, derivatization and the like, so that target substances are effectively separated and enriched from complex samples, and meanwhile, interference of matrixes is reduced or eliminated to realize low-concentration detection of pesticides. At present, pesticide residue analysis mainly adopts technologies such as Solid Phase Extraction (SPE), microwave-assisted extraction (MAE), molecular imprinting extraction (MIT), supercritical Fluid Extraction (SFE), solid Phase Microextraction (SPME), liquid Phase Microextraction (LPME) and the like. The SPE, MAE, MIT, SFE technology has the defects of complex operation, time consumption and the like.
Sample pretreatment technology is evolving toward cheapness, greenness, miniaturization, and automation. The miniaturized sample pretreatment technology LPME integrating extraction and concentration has the advantages of high enrichment factor, low cost, simple device and the like, and is more and more popular with researchers. The method mainly comprises extraction modes such as single drop liquid phase microextraction (SDME), hollow fiber liquid phase microextraction (HF-LPME) and the like. SDME uses an organic extraction solvent suspended from the tip of a microinjector as an extraction solvent, either suspended above the sample phase solution or immersed in the sample phase. After extraction is completed, the extraction solvent is pumped back into the injector again, and the receiving phase solution is collected and directly enters an analysis instrument for quantitative analysis. This technique has been widely used for determining pesticide residues in various actual samples. However, this method results in poor stability of the extraction solvent suspended from the tip of the microinjector, and the volume of the extraction solvent is limited and not easily controlled, resulting in poor reproducibility of the experiment. The HF-LPME solves the problems of unstable extraction solvent and difficult control of volume, the method uses a hollow fiber tube to protect the organic solvent, and the volume of the organic solvent added into the hollow fiber is constant, but bubbles are easy to generate in the extraction process, so that the repeatability of the experiment is poor. In response to this problem, researchers have proposed that Polytetrafluoroethylene (PTFE) tubes or horn-like devices may be suspended from the needle end of the microinjector to increase the volume of the organic extraction solvent. However, these devices still present a risk of organic extraction reagent falling from the needle end.
The Chinese patent publication No. CN114213219B issued by 12/22/2023 discloses a method for recovering bisphenol A from a template molecule in a molecularly imprinted polymer elution waste liquid, which uses a sample phase solution as a donor phase and an alkaline solution as a receiving phase, and adopts a liquid film extraction technology to recover bisphenol A in the sample phase solution, and can realize the efficient recovery and purification of bisphenol A in the complex matrix elution waste liquid under the action of the selectivity of an extraction solvent loaded on a porous membrane and the self screening of the pore diameter of the porous membrane.
However, the extraction in the recovery method is that a large amount of template molecules with high concentration are extracted from the molecularly imprinted polymer elution waste liquid, and the extraction of low-concentration pesticides in water is poor.
Disclosure of Invention
The invention aims to provide an extraction method of pesticides in a water body, which solves the problem of poor extraction rate of pesticides in the water body in the prior art.
The second aim of the invention is to provide a method for detecting pesticides in water body, which solves the problem of poor pesticide extraction rate in water body in the prior art.
In order to solve the technical problems, the technical scheme of the extraction method of the pesticide in the water body is as follows:
The extraction method of the pesticide in the water body comprises the following steps: preparing a water sample and a phosphate buffer solution with pH=6.5-7 into a sample phase solution, and extracting pesticides in the sample phase solution into a receiving phase solution by adopting a supported liquid film extraction method, wherein the pesticides are one or more selected from carbendazim, pirimicarb, triclopyr, diflubenzuron and antifeedant hydrazine.
The invention improves the prior art, provides an extraction method of pesticides in water, which has obvious advantages in terms of sample purification based on the natural barrier effect of membranes on macromolecular substances in a supported liquid membrane extraction method, can effectively overcome the interference problem caused by water sample matrixes, and can ensure that pesticides with various properties are always in a neutral state by selecting phosphate buffer with pH value of 6.5-7 as sample phase background solution, ensure the mass transfer effect of the pesticides in the extraction process, greatly improve the extraction rate of the pesticides, and has good extraction effect, and the extraction rate of all pesticides is in the range of 78.70-90.00%.
The extraction method provided by the invention is based on extraction solvent carried by the membrane in the supported liquid membrane extraction method, the amount of the used organic extraction solvent is very small, only a few microliters is needed, the problem of environmental pollution caused by the large amount of the used organic solvent in the traditional extraction technology is avoided, the purification, enrichment and concentration are integrated, and the operation is convenient; in addition, the extraction method can be combined with a detection technology to provide a detection method for pesticide residues.
In order to further increase the extraction rate of pesticides, preferably, the extraction solvent in the supported liquid film extraction method is selected from octanone, nonanone, tributyl phosphate, undecanone and dihexyl ether in a volume ratio of (20-40): (80-60) one of the formed mixed solutions; the receiving phase solution is selected from one of hydrochloric acid solution, formic acid solution, acetic acid solution, trifluoroacetic acid solution, sodium hydroxide solution, sodium carbonate solution, sodium phosphate solution and potassium hydroxide solution. By selecting a specific extraction solvent, the efficient extraction of pesticides in the water body can be realized.
In order to further improve the extraction efficiency of the alkaline pesticide, preferably, when the pesticide is carbendazim and pirimicarb, the extraction solvent is selected from one of octanone, nonanone and tributyl phosphate, and the receiving phase solution is selected from one of hydrochloric acid solution, formic acid solution, acetic acid solution and trifluoroacetic acid solution.
In order to further improve the extraction efficiency of the acidic pesticide, preferably, when the pesticide is the herbicide, the diflubenzuron and the antifeedant hydrazine, the extraction solvent is undecanone and dihexyl ether according to the volume ratio of (20-40): (80-60), wherein the receiving phase solution is selected from one of sodium hydroxide solution, sodium carbonate solution, sodium phosphate solution and potassium hydroxide solution.
In order to further complete the extraction of the pesticide in the sample phase, it is preferred that the extraction is performed with shaking at a speed of 300-1000 rpm.
In order to further increase the extraction rate of the pesticide, the concentration of the receiving phase solution is preferably 100 to 120mmol/L.
In order to further improve the extraction efficiency and shorten the extraction time, preferably, the extraction temperature is 10-50 ℃, and the extraction time is 5-90 min.
In order to further improve the natural barrier effect on macromolecular substances and overcome the interference problem caused by water sample matrixes, preferably, the membrane adopted in the supported liquid membrane extraction method is a porous polypropylene fiber membrane, wherein the pore diameter of the porous polypropylene fiber membrane is 0.2 mu m, and the thickness of the porous polypropylene fiber membrane is 100 mu m to 200 mu m. The extraction solvent is coated on the porous polypropylene fiber membrane, and the method has remarkable advantages in terms of sample purification due to the selectivity characteristic of the organic extraction solvent and the natural barrier effect of the high-molecular porous membrane on the macromolecular substances, can effectively overcome the interference problem caused by a water sample matrix, and has the characteristics of simplicity and convenience in operation, short time consumption and strong sample purification capability.
The technical scheme of the method for detecting the pesticides in the water body is as follows:
The method for detecting the pesticide in the water body comprises the steps of extracting the pesticide to a receiving phase solution by adopting the extraction method of the pesticide in the water body, and detecting the receiving phase solution by adopting liquid chromatography-tandem mass spectrometry.
The method for detecting the pesticides in the water body provided by the invention has the advantages that the extraction method for extracting the pesticides in the water body is adopted, the extraction method has obvious advantages in the aspect of sample extraction, the interference problem caused by a water sample matrix can be effectively overcome, the extraction rate of the pesticides is greatly improved, the extraction effect is good, the extraction rate range of all pesticides is between 78.70% and 90.00%, the detection limit of the established detection method for the pesticides is between 0.011 and 0.090ng/mL, the quantitative limit is between 0.036 and 0.31ng/mL, the standard adding recovery rate under different concentrations is between 80% and 125%, the reproducibility is good, the stability is high, the average daily and daytime deviation is less than 10%, and the established detection method is environment-friendly, simple and convenient, has good purification effect and has potential advantages for quantitative analysis of various pesticides in the water sample.
In order to further improve the detection accuracy, preferably, the detection conditions in the liquid chromatography-tandem mass spectrometry detection are as follows: chromatographic column: watersDC18 column, column temperature: 25 ℃; sample injection amount: 5.0. Mu.L; flow rate: 0.3mL/min; mobile phase: the phase A is aqueous solution containing 0.1% formic acid, the phase B is acetonitrile, and a gradient elution mode is adopted.
More preferably, the gradient elution mode is: 0-0.5min, mobile phase 90% A-10% B;0.5-2min, the mobile phase is changed from 90% A-10% B to 60% A-40% B;2-5min, the mobile phase is changed from 60% A-40% B to 40% A-60% B;5-10min, the mobile phase is changed from 40% A-60% B to 35% A-65% B; at 10-17min, the mobile phase was changed from 35% A-65% B to 90% A-10% B.
Drawings
FIG. 1 is a diagram of a supported liquid membrane extraction apparatus used in example 1;
fig. 2 is a total ion flow diagram of the labeled pesticide in the sample phase solution and the receiving phase solution.
Detailed Description
The technical conception of the extraction method of pesticides in water body is as follows:
The extraction method of the pesticide in the water body comprises the following steps: preparing a water sample and a phosphate buffer solution with pH=6.5-7 into a sample phase solution, and extracting pesticides in the sample phase solution into a receiving phase solution by adopting a supported liquid film extraction method, wherein the pesticides are one or more selected from carbendazim, pirimicarb, triclopyr, diflubenzuron and antifeedant hydrazine.
The extraction method of pesticides in water provided by the invention has the advantages that the method is based on the natural barrier effect of the membrane on macromolecular substances in the supported liquid membrane extraction method, the interference problem caused by water sample matrixes can be effectively overcome, the pesticides with various properties can be always in a neutral state by selecting the phosphate buffer solution with pH=6.5-7 as a sample phase background solution, the mass transfer effect of the pesticides in the extraction process is ensured, the extraction rate of the pesticides is greatly improved, the extraction effect is good, and the extraction rate range of all pesticides is between 78.70% and 90.00%.
The extraction method provided by the invention is based on extraction solvent carried by the membrane in the supported liquid membrane extraction method, the amount of the used organic extraction solvent is very small, only a few microliters is needed, the problem of environmental pollution caused by the large amount of the used organic solvent in the traditional extraction technology is avoided, the purification, enrichment and concentration are integrated, and the operation is convenient; in addition, the extraction method can be combined with a detection technology to provide a detection method for pesticide residues.
In a specific embodiment, the shaking is performed in a thermostatic mixer.
In specific embodiments, the body of water is rainwater, tap water, and lake water.
In a specific embodiment, the water body is firstly subjected to coarse treatment, wherein the coarse treatment is to filter the water body through a filter membrane with the diameter of 0.45 mu m to remove particles; and then taking the water body after the rough treatment as a solvent to prepare phosphate buffer solution with pH value of 6.5-7.
The method for detecting the pesticide in the water body comprises the steps of extracting the pesticide to a receiving phase solution by adopting the extraction method of the pesticide in the water body, and detecting the receiving phase solution by adopting liquid chromatography-tandem mass spectrometry.
In a specific embodiment, the mass spectrometry conditions at the time of liquid chromatography-tandem mass spectrometry detection are: ion source: an electrospray ESI source; scanning mode: multiple reaction detection scan (MRM); scanning mode: a positive ion mode; ESI ion source temperature: 500 ℃; the quantitative ion pair of carbendazim is 192/160.2, the collision voltage is 22V, and the fragmentation voltage is 60V; the quantitative ion pair of the pirimicarb is 239.1/182, the collision voltage is 23V, and the fragmentation voltage is 50V; the quantitative ion pair of the herbicide is 263/207.1, the collision voltage is 17V, and the fragmentation voltage is 55V; the quantitative ion pair of the diflubenzuron is 311/157.8, the collision voltage is 20V, and the fragmentation voltage is 60V; the quantitative ion pair of the antifeedant hydrazine is 297.1/241.2, the collision voltage is 23V, and the fragmentation voltage is 50V.
Embodiments of the present invention will be further described with reference to the following specific examples. The chemical reagents referred to in the examples below, unless otherwise specified, are commercially available conventional products.
1. Specific examples of the method for extracting pesticides in Water of the present invention
Example 1
The extraction method of the pesticide in the water body in the embodiment is as follows:
(1) Crude treatment of three water samples: and filtering the collected rainwater, tap water and lake water through a filter membrane with the diameter of 0.45 mu m to remove particulate matters, thereby obtaining treated rainwater, tap water and lake water samples.
(2) Preparation of sample phase solution: respectively taking the treated rainwater, tap water and lake water as solvents to prepare 50mmol/LpH =6.8 phosphate buffer solution; in order to examine the influence of an actual sample matrix on the extraction effect, the treated lake water is used as a solvent to respectively prepare standard solutions (50 mmol/L of phosphate buffer solution with pH=6.8) containing a series of concentrations (0.1, 1, 10, 20, 40, 80, 100, 140, 180, 200, 400, 600, 800, 1000, 1200, 1400 mg/mL) of carbendazim and pirimicarb, so as to obtain lake water sample phase solutions of the carbendazim and the pirimicarb;
And (3) taking the treated rainwater, lake water and tap water as solvents, and preparing four types of carbendazim and pirimicarb standard solutions (pH=6.8 50mmol/L phosphate buffer solutions) with different concentrations of 20, 100, 500 and 1200ng/mL, so as to obtain four types of rainwater and tap water standard sample phase solutions with different concentrations respectively.
(3) Extraction: the supported liquid membrane extraction apparatus used in this example was, as shown in FIG. 1, a 2mL centrifuge tube was used as a sample chamber for holding a sample phase solution, a porous polypropylene fiber membrane having a pore diameter of 0.2 μm and a thickness of 200 μm was cut into a size of 1 cm. Times.1 cm, and then attached to the tip of a 1mL pipette, and the tip of the pipette was removed to serve as a receiving chamber; and (3) coating 10 mu L of tributyl phosphate on the porous polypropylene fiber membrane as a flat supporting liquid membrane, finally combining the receiving chamber and the sample chamber, enabling the liquid level of the sample phase solution to be just contacted with the porous polypropylene fiber membrane, and then injecting 200 mu L of receiving phase into the receiving chamber, wherein the receiving phase is 100mmol/L hydrochloric acid solution. Setting the temperature of the constant temperature mixing instrument to 25 ℃, oscillating at 1000rpm for 60min, starting the constant temperature mixing instrument, and carrying out supported liquid film extraction.
Example 2
The extraction method of the pesticide in the water body in the embodiment is as follows:
(1) Crude treatment of three water samples: and filtering the collected rainwater, tap water and lake water through a filter membrane with the diameter of 0.45 mu m to remove particulate matters, thereby obtaining treated rainwater, tap water and lake water samples.
(2) Preparation of sample phase solution: respectively taking the treated rainwater, tap water and lake water as solvents to prepare 50mmol/LpH =6.8 phosphate buffer solution; in order to examine the influence of the actual sample matrix on the extraction effect, the treated lake water is used as a solvent to respectively prepare standard solutions (phosphate buffer solution with pH=6.8 50 mmol/L) containing a series of concentrations (0.1, 1, 10, 20, 40, 80, 100, 140, 180, 200, 400, 600, 800, 1000, 1200, 1400 mg/mL) of the metazachlor, the diflubenzuron and the antifeedant hydrazine, so as to obtain lake water sample phase solutions of the metazachlor, the diflubenzuron and the antifeedant hydrazine;
And (3) taking the treated rainwater, lake water and tap water as solvents, preparing three standard solutions (pH=6.8 50mmol/L phosphate buffer solution) of chlorpyrifos, diflubenzuron and antifeedant hydrazine with different concentrations of 100, 500 and 1200ng/mL, and respectively obtaining three standard sample phase solutions of the rainwater and tap water with different concentrations.
(3) Extraction: the supported liquid film extraction apparatus and the extraction method of this embodiment are different from those of embodiment 1 with reference to embodiment 1 in that: the porous polypropylene fiber membrane was coated with 10. Mu.L of a mixed extraction solvent of undecone and dihexyl ether (40:60, v/v) and the receiving phase was 100mmol/L sodium hydroxide solution.
2. Specific examples of the method for detecting pesticides in Water body of the present invention
Example 3
The detection method of the pesticide in the water body in the embodiment is as follows:
After the extraction of the pesticide in the water body in the embodiment 1 is completed, taking out the solution of the receiving phase, and directly feeding the solution into a high performance liquid chromatography-tandem mass spectrometer (liquid chromatography-tandem mass spectrometry) to detect the content of the carbendazim and the pirimicarb, wherein the chromatographic conditions of the high performance liquid chromatography-tandem mass spectrometer are as follows: chromatographic column: waters DC18 column (2.1 mm. Times.150 mm,3.0 μm); column temperature: 25 ℃; sample injection amount: 5.0. Mu.L; flow rate: 0.3mL/min; mobile phase: phase A is aqueous solution containing 0.1% formic acid, and phase B is acetonitrile; the liquid chromatography adopts a gradient elution mode, and the elution conditions are as follows: 0-0.5min, mobile phase 90% A-10% B;0.5-2min, the mobile phase is changed from 90% A-10% B to 60% A-40% B;2-5min, the mobile phase is changed from 60% A-40% B to 40% A-60% B;5-10min, the mobile phase is changed from 40% A-60% B to 35% A-65% B; at 10-17min, the mobile phase was changed from 35% A-65% B to 90% A-10% B.
The mass spectrum conditions are as follows: ion source: an electrospray ESI source; scanning mode: multiple reaction detection scan (MRM); scanning mode: a positive ion mode; ESI ion source temperature: 500 ℃; the quantitative ion pair of carbendazim is 192/160.2, the collision voltage is 22V, and the fragmentation voltage is 60V; the quantitative ion pair of the pirimicarb is 239.1/182, the collision voltage is 23V, and the fragmentation voltage is 50V.
Example 4
The detection method of the pesticide in the water body in the embodiment is as follows:
after the extraction of the pesticide in the water body by adopting the extraction method of the embodiment 2 is completed, taking out the solution of the receiving phase, directly feeding the solution into a high performance liquid chromatography-tandem mass spectrometer (liquid chromatography-tandem mass spectrometry) to detect the content of the hexaflumuron, the tebufenozide and the antifeedant hydrazine, wherein the chromatographic conditions of the high performance liquid chromatography-tandem mass spectrometer are as follows: chromatographic column: waters DC18 column (2.1 mm. Times.150 mm,3.0 μm); column temperature: 25 ℃; sample injection amount: 5.0. Mu.L; flow rate: 0.3mL/min; mobile phase: phase A is aqueous solution containing 0.1% formic acid, and phase B is acetonitrile; the liquid chromatography adopts a gradient elution mode, and the elution conditions are as follows: 0-0.5min, mobile phase 90% A-10% B;0.5-5min, the mobile phase is changed from 90% A-10% B to 50% A-50% B; at 5-8min, the mobile phase was changed from 50% A-50% B to 15% A-85% B;8-12min, the mobile phase was changed from 15% A-85% B to 90% A-10% B.
The mass spectrum conditions are as follows: ion source: an electrospray ESI source; scanning mode: multiple reaction detection scan (MRM); scanning mode: a positive ion mode; ESI ion source temperature: 500 ℃; the quantitative ion pair of the herbicide is 263/207.1, the collision voltage is 17V, and the fragmentation voltage is 55V; the quantitative ion pair of the diflubenzuron is 311/157.8, the collision voltage is 20V, and the fragmentation voltage is 60V; the quantitative ion pair of the antifeedant hydrazine is 297.1/241.2, the collision voltage is 23V, and the fragmentation voltage is 50V.
3. Experimental example
Experimental example 1
The experimental example optimizes the extraction conditions, and the specific method is as follows:
Optimizing extraction conditions of supported liquid film extraction carbendazim and pirimicarb
1) Optimization of extraction solvent
The influence of 2-nitrophenyl octyl ether, dihexyl ether, n-heptanol, n-octanol, octanone, nonanone, undecanone, n-hexane, ethyl acetate, dichloromethane and tributyl phosphate on the extraction effect of the carbendazim and the pirimicarb is examined by taking a mixed standard solution of 0.5mg/L of the carbendazim and 0.5mg/L of the pirimicarb as a sample phase solution, and the extraction solvent is screened according to the extraction rate. See the following tests 1-1 to 1-11 for specific experimental details:
Test 1-1:
(1) Preparation of sample phase solutions
Preparing a mixed standard solution of 0.5mg/L carbendazim and 0.5mg/L pirimicarb: taking 100mg/L of mixed standard substance of carbendazim and pirimicarb, taking 50mmol/L of phosphate buffer solution with pH=6.8 as a solvent, preparing 0.5mg/L of mixed standard substance solution of carbendazim and pirimicarb, and taking the mixed standard substance solution as a sample phase solution for carrying out supported liquid film extraction.
(2) Extraction
Supported liquid film extraction apparatus and extraction method referring to example 1, the difference from example 1 is that: 10. Mu.L of 2-nitrophenyl octyl ether was coated on the porous polypropylene fiber membrane.
Test 1-2:
The extraction method of run 1-2 was essentially the same as run 1-1, except that: 10. Mu.L of dihexyl ether was coated on a porous polypropylene fiber membrane.
Test 1-3:
The extraction method for run 1-3 was essentially the same as run 1-1, except that: 10. Mu.L of n-heptanol was coated on the porous polypropylene fiber film.
Runs 1-4:
The extraction method for runs 1-4 was essentially the same as that for runs 1-1, except that: 10. Mu.L of n-octanol was coated on the porous polypropylene fiber membrane.
Test 1-5:
The extraction method for runs 1-5 was essentially the same as that for runs 1-1, except that: 10. Mu.L of octanone was coated on a porous polypropylene fiber membrane.
Runs 1-6:
The extraction method for runs 1-6 was essentially the same as that for runs 1-1, except that: 10. Mu.L of nonone was coated on a porous polypropylene fiber membrane.
Runs 1-7:
The extraction method for runs 1-7 was essentially the same as that for runs 1-1, except that: 10. Mu.L of undecone was coated on a porous polypropylene fiber film.
Runs 1-8:
The extraction method for runs 1-8 was essentially the same as that for runs 1-1, except that: 10. Mu.L of n-hexane was coated on the porous polypropylene fiber film.
Runs 1-9:
The extraction method for runs 1-9 was essentially the same as that for runs 1-1, except that: 10. Mu.L of ethyl acetate was coated on the porous polypropylene fiber membrane.
Test 1-10:
The extraction method for runs 1-10 was essentially the same as that for runs 1-1, except that: 10. Mu.L of methylene chloride was coated on the porous polypropylene fiber film.
Runs 1-11:
The extraction method for runs 1-11 was essentially the same as that for runs 1-1, except that: 10. Mu.L of tributyl phosphate was coated on a porous polypropylene fiber film.
The concentrations of carbendazim and pirimicarb in the receiving phase solution after the extraction is finished in the tests 1-1 to 1-11 are measured by adopting a high performance liquid chromatography tandem mass spectrometer, and the recovery rate (i.e. extraction rate) is calculated by the following specific calculation formula: recovery (%) = (C A×VA)/(CDi×VD) ×100%, where C A refers to the concentration of pesticide residue in the receiving phase after the end of extraction, C Di refers to the initial concentration of pesticide residue in the sample phase, and V A and V D refer to the volumes of the receiving phase and the sample phase, respectively. The extraction ratios are shown in Table 1, and the conditions of the test method for the HPLC tandem mass spectrometer are as shown in example 3.
Table 1 influence of different extraction solvents on extraction rates of carbendazim and pirimicarb (n=6)
As can be seen from Table 1, the extraction solvents with relatively high extraction rates for carbendazim and pirimicarb are octanone, nonanone and tributyl phosphate, wherein the extraction rate of tributyl phosphate is the highest.
2) Optimization of sample phase background solutions
100Mmol/L hydrochloric acid is used as a receiving phase solution, the influence of different sample phase background solutions (5, 10, 20 and 50mmol/LpH =6.8 phosphate buffer solutions) on the extraction effect of carbendazim and pirimicarb is examined, and the sample phase background solutions are screened according to the extraction rate. See the following tests 2-1 to 2-5 for specific experimental details:
Test 2-1:
(1) Preparation of sample phase solutions
Preparing a mixed standard solution of 0.5mg/L carbendazim and 0.5mg/L pirimicarb: taking 100mg/L of mixed standard substance of carbendazim and pirimicarb, taking 5mmol/L phosphate buffer solution with pH=6.8 as a solvent, preparing 0.5mg/L mixed standard substance solution of carbendazim and pirimicarb, and taking the mixed standard substance solution as a sample phase solution for carrying out supported liquid film extraction.
(2) Extraction
Supported liquid membrane extraction apparatus and extraction method reference is made to example 1.
Test 2-2:
The extraction method of run 2-2 was essentially the same as run 2-1, except that: 10mmol/L phosphate buffer at pH=6.8 was used as solvent.
Test 2-3:
The extraction method for run 2-3 was essentially the same as that for run 2-1, except that: 20mmol/L phosphate buffer at pH=6.8 was used as solvent.
Test 2-4:
the extraction method for run 2-4 was essentially the same as that for run 2-1, except that: 50mmol/L phosphate buffer at pH=6.8 was used as solvent.
And (3) measuring the concentrations of carbendazim and pirimicarb in the receiving phase solution after the extraction is finished by adopting a high performance liquid chromatography-tandem mass spectrometer (HPLC-MS) to test 2-4, and calculating the concentrations in the sample phase solution to obtain the extraction rate shown in the table 2, wherein the conditions of a testing party of the HPLC-MS are as shown in example 3.
Table 2 influence of different sample phase background solutions on extraction rates of carbendazim and pirimicarb (n=6)
As can be seen from Table 2, the 5-50 mmol/L phosphate buffer solutions all showed higher extraction rates for carbendazim and pirimicarb, with pH=6.8 and 50mmol/L phosphate buffer solution showing the highest extraction rate.
3) Optimization of the receiving phase solution
The mixed standard solution of 0.5mg/L carbendazim and 0.5mg/L pirimicarb is used as a sample phase solution, different solutions are used as receiving phase solutions to carry out supported liquid film extraction, the influence of the receiving phase solution on the extraction effect of the carbendazim and the pirimicarb is examined, and the receiving phase solution is screened according to the extraction rate. See the following tests 3-1 to 3-4 for specific experimental details:
test 3-1:
(1) Preparation of sample phase solutions
Preparing a mixed standard solution of 0.5mg/L carbendazim and 0.5mg/L pirimicarb: taking 100mg/L of mixed standard substance of carbendazim and pirimicarb, taking 50mmol/L of phosphate buffer solution with pH=6.8 as a sample phase, carrying out Jing Rongye, preparing 0.5mg/L of mixed standard substance solution of carbendazim and 0.5mg/L of pirimicarb, and taking the mixed standard substance solution as a sample phase solution for carrying out supported liquid film extraction.
(2) Extraction
Supported liquid membrane extraction apparatus and extraction method referring to example 1, the receiving phase solution was 100mmol/L hydrochloric acid solution.
Test 3-2:
The extraction method of run 3-2 was essentially the same as that of run 3-1, except that: the receiving phase solution is 100mmol/L formic acid solution.
Test 3-3:
The extraction method of run 3-3 was essentially the same as run 3-1, except that: the receiving phase solution is 100mmol/L trifluoroacetic acid solution.
Test 3-4:
The extraction method for run 3-4 was essentially the same as that for run 3-1, except that: the receiving phase solution is 100mmol/L acetic acid solution.
And (3) measuring the concentrations of carbendazim and pirimicarb in the receiving phase solution after the extraction is finished by adopting a high performance liquid chromatography-tandem mass spectrometer to test 3-1, and calculating the concentrations in the sample phase solution to obtain the extraction rate shown in table 3, wherein the conditions of a testing method of the high performance liquid chromatography-tandem mass spectrometer are as shown in example 3.
Table 3 influence of different receiver phase solutions on the extraction rates of carbendazim and pirimicarb (n=6)
As can be seen from Table 3, a 100mmol/L hydrochloric acid solution shows a higher extraction rate for carbendazim and pirimicarb.
4) Optimization of extraction time
The mixed standard solution of 0.5mg/L carbendazim and 0.5mg/L pirimicarb is used as a sample phase solution, the influence of the extraction time on the extraction effect of the carbendazim and the pirimicarb is examined, and the extraction time is screened according to the extraction rate. See tests 4-1 to 4-8 below for specific experimental details.
Test 4-1:
(1) Preparation of sample phase solutions
Preparing a mixed standard solution of 0.5mg/L carbendazim and 0.5mg/L pirimicarb: taking 100mg/L of mixed standard substance of carbendazim and pirimicarb, taking 50mmol/L of phosphate buffer solution with pH=6.8 as a sample phase, carrying out Jing Rongye, preparing 0.5mg/L of mixed standard substance solution of carbendazim and 0.5mg/L of pirimicarb, and taking the mixed standard substance solution as a sample phase solution for carrying out supported liquid film extraction.
(2) Extraction
Supported liquid film extraction apparatus and extraction method referring to example 1, the extraction time was 5min.
Test 4-2:
The extraction method of run 4-2 was essentially the same as that of run 4-1, except that: the extraction time is 10min.
Test 4-3:
the extraction method for run 4-3 was essentially the same as that for run 4-1, except that: the extraction time is 20min.
Run 4-4
The extraction method for run 4-4 was essentially the same as that for run 4-1, except that: the extraction time is 30min.
Runs 4-5
The extraction method for run 4-5 was essentially the same as that for run 4-1, except that: the extraction time is 45min.
Runs 4-6
The extraction method for run 4-6 was essentially the same as that for run 4-1, except that: the extraction time is 60min.
Runs 4-7
The extraction method for run 4-7 was essentially the same as that for run 4-1, except that: the extraction time was 75min.
Runs 4-8
The extraction method for run 4-8 was essentially the same as that for run 4-1, except that: the extraction time is 90min.
And (3) measuring the concentrations of carbendazim and pirimicarb in the receiving phase solution after the extraction is finished by adopting a high performance liquid chromatography-tandem mass spectrometer to test 4-1 to test 4-8, and calculating the concentrations in the sample phase solution to obtain the extraction rate shown in table 4, wherein the conditions of a testing method of the high performance liquid chromatography-tandem mass spectrometer are as shown in example 3.
Table 4 influence of different extraction times on extraction rates of carbendazim and pirimicarb (n=6)
As can be seen from Table 4, an extraction time of 60min shows a higher extraction rate for carbendazim and pirimicarb.
5) Optimization of extraction temperature
The mixed standard solution of 0.5mg/L carbendazim and 0.5mg/L pirimicarb is used as a sample phase solution, the influence of temperature on the extraction effect of the carbendazim and the pirimicarb is examined, and the temperature is optimized according to the extraction rate. See test 5-1 to test 5-5 below for specific experimental details.
Test 5-1:
(1) Preparation of sample phase solutions
Preparing a mixed standard solution of 0.5mg/L carbendazim and 0.5mg/L pirimicarb: taking 100mg/L of mixed standard substance of carbendazim and pirimicarb, taking 50mmol/L of phosphate buffer solution with pH=6.8 as a sample phase, carrying out Jing Rongye, preparing 0.5mg/L of mixed standard substance solution of carbendazim and 0.5mg/L of pirimicarb, and taking the mixed standard substance solution as a sample phase solution for carrying out supported liquid film extraction.
(2) Extraction
Supported liquid film extraction apparatus and extraction method referring to example 1, the temperature of the thermostatic mixing device was set to 10 ℃.
Test 5-2:
The extraction method of run 5-2 was essentially the same as run 5-1, except that: the temperature of the constant temperature mixer was set at 25 ℃.
Test 5-3:
The extraction method of run 5-3 was essentially the same as run 5-1, except that: the temperature of the constant temperature mixer was set at 30 ℃.
Test 5-4:
The extraction method for run 5-4 was essentially the same as that for run 5-1, except that: the temperature of the constant temperature mixer was set at 40 ℃.
Test 5-5:
The extraction method for run 5-5 was essentially the same as that for run 5-1, except that: the temperature of the constant temperature mixer was set at 50 ℃.
And (3) measuring the concentrations of carbendazim and pirimicarb in the receiving phase solution after the extraction is finished by adopting a high performance liquid chromatography-tandem mass spectrometer to test 5-1, and calculating the concentrations in the sample phase solution to obtain the extraction rate shown in table 5, wherein the conditions of a testing method of the high performance liquid chromatography-tandem mass spectrometer are as shown in example 3.
Table 5 influence of different extraction temperatures on extraction rates of carbendazim and pirimicarb (n=6)
As can be seen from Table 5, the extraction temperature was 25℃which showed a higher extraction rate for carbendazim and pirimicarb.
6) Optimization of oscillation speed
The mixed standard solution of 0.5mg/L carbendazim and 0.5mg/L pirimicarb is used as a sample phase solution, the influence of the oscillation speed on the extraction effect of the carbendazim and the pirimicarb is examined, and the oscillation speed is optimized according to the extraction rate. See tests 6-1 to 6-5 below for specific experimental details.
Test 6-1:
(1) Preparation of sample phase solutions
Preparing a mixed standard solution of 0.5mg/L carbendazim and 0.5mg/L pirimicarb: taking 100mg/L of mixed standard substance of carbendazim and pirimicarb, taking 50mmol/L of phosphate buffer solution with pH=6.8 as a sample phase, carrying out Jing Rongye, preparing 0.5mg/L of mixed standard substance solution of carbendazim and 0.5mg/L of pirimicarb, and taking the mixed standard substance solution as a sample phase solution for carrying out supported liquid film extraction.
(2) Extraction
Supported liquid film extraction apparatus and extraction method referring to example 1, the shaking speed of the thermostatic mixer was set at 300rpm.
Test 6-2:
the extraction method of run 6-2 was essentially the same as that of run 6-1, except that: the shaking speed of the thermostatic mixer was set at 400rpm.
Test 6-3:
the extraction method of run 6-3 was essentially the same as run 6-1, except that: the shaking speed of the thermostatic mixer was set at 600rpm.
Test 6-4:
the extraction method for run 6-4 was essentially the same as that for run 6-1, except that: the shaking speed of the thermostatic mixer was set at 800rpm.
Test 6-5:
the extraction method for run 6-5 was essentially the same as that for run 6-1, except that: the shaking speed of the constant temperature mixer was set at 1000rpm.
And (3) measuring the concentrations of carbendazim and pirimicarb in the receiving phase solution after the extraction is finished by adopting a high performance liquid chromatography-tandem mass spectrometer to test 6-1 to test 6-5, and calculating the concentrations in the sample phase solution to obtain the extraction rate shown in table 6, wherein the conditions of a testing method of the high performance liquid chromatography-tandem mass spectrometer are as shown in example 3.
TABLE 6 influence of different oscillation speeds on extraction rates of carbendazim and pirimicarb (n=6)
As can be seen from Table 6, the shaking speed was 1000rpm, which showed a higher extraction rate for carbendazim and pirimicarb.
Optimization of extraction conditions for extracting metazamide, diflubenzuron and antifeedant hydrazine by using supported liquid membrane
7) Optimization of extraction solvent
The mixed standard solution of 0.5mg/L of the triclopyr, 0.5mg/L of the diflubenzuron and 0.5mg/L of the antifeedant hydrazine is used as a sample phase solution, the influence of different membrane organic solvents on the extraction effects of the triclopyr, the diflubenzuron and the antifeedant hydrazine is examined, and the extraction solvents are optimized according to the extraction rate. See the following tests 7-1 to 7-16 for specific experimental details:
test 7-1:
(1) Preparation of sample phase solutions
Preparing a mixed standard solution of 0.5mg/L of triclopyr, 0.5mg/L of diflubenzuron and 0.5mg/L of antifeedant hydrazine: taking a mixed standard substance of 100mg/L of the herbicide, 100mg/L of the diflubenzuron and 100mg/L of the antifeedant hydrazine, taking 50mmol/L of phosphate buffer solution with pH=6.8 as a solvent, preparing a mixed standard substance solution of 0.5mg/L of the herbicide, 0.5mg/L of the diflubenzuron and 0.5mg/L of the antifeedant hydrazine, and taking the mixed standard substance solution as a sample phase solution for carrying out supported liquid film extraction.
(2) Extraction
Supported liquid membrane extraction apparatus and extraction method referring to example 2, 10 μl of a mixed solution of undecone and dihexyl ether (40:60, v/v) was coated on a porous polypropylene fiber membrane.
Test 7-2:
The extraction method of run 7-2 was essentially the same as that of run 7-1, except that: the porous polypropylene fiber membrane is coated with dihexyl ether.
Test 7-3:
The extraction method of run 7-3 was essentially the same as run 7-1, except that: 2-octanone is coated on the porous polypropylene fiber membrane.
Test 7-4:
The extraction procedure for run 7-4 was essentially the same as that for run 7-1, except that: coating undecanone on porous polypropylene fiber film.
Test 7-5:
the extraction method of run 7-5 was essentially the same as run 7-1, except that: n-hexane was coated on the porous polypropylene fiber membrane.
Test 7-6:
The extraction procedure for run 7-6 was essentially the same as that for run 7-1, except that: 2-nonone is coated on the porous polypropylene fiber membrane.
Test 7-7:
the extraction method for run 7-7 was essentially the same as that for run 7-1, except that: ethyl acetate was coated on the porous polypropylene fiber membrane.
Test 7-8:
the extraction method for run 7-8 was essentially the same as that for run 7-1, except that: n-heptanol is coated on the porous polypropylene fiber membrane.
Test 7-9:
The extraction method for run 7-9 was essentially the same as that for run 7-1, except that: a porous polypropylene fiber film was coated with a mixed solution of undecone and dihexyl ether (10:90, v/v).
Test 7-10:
The extraction method for run 7-10 was essentially the same as that for run 7-1, except that: a porous polypropylene fiber film was coated with a mixed solution of undecone and dihexyl ether (20:80, v/v).
Test 7-11:
the extraction method for run 7-11 was essentially the same as that for run 7-1, except that: a porous polypropylene fiber film was coated with a mixed solution of undecone and dihexyl ether (30:70, v/v).
Test 7-12:
The extraction method for run 7-12 was essentially the same as that for run 7-1, except that: a porous polypropylene fiber film was coated with a mixed solution of undecone and dihexyl ether (50:50, v/v).
Runs 7-13:
The extraction method for run 7-13 was essentially the same as that for run 7-1, except that: a porous polypropylene fiber film was coated with a mixed solution of undecone and dihexyl ether (60:40, v/v).
Runs 7-14:
The extraction method for run 7-14 was essentially the same as that for run 7-1, except that: a porous polypropylene fiber film was coated with a mixed solution of undecone and dihexyl ether (70:30, v/v).
Test 7-15:
the extraction procedure for run 7-15 was essentially the same as that for run 7-1, except that: a porous polypropylene fiber film was coated with a mixed solution of undecone and dihexyl ether (80:20, v/v).
Runs 7-16:
the extraction procedure for run 7-16 was essentially the same as that for run 7-1, except that: a porous polypropylene fiber film was coated with a mixed solution of undecone and dihexyl ether (90:10, v/v).
The concentrations of the hexaflumuron, the tebufenozide and the tebufenozide in the receiving phase solution after the extraction is completed are measured by using a high performance liquid chromatography-tandem mass spectrometer (HPLC-MS) to obtain the extraction rate shown in Table 7, and the conditions of the testing method of the HPLC-MS are as shown in example 4.
Table 7 effect of different extraction solvents on extraction rates of flubendiamide, diflubenzuron and picloram (n=6)
As can be seen from Table 7, the extraction solvents with relatively high extraction rates of the metazamide, the diflubenzuron and the antifeedant hydrazine are undecanone and dihexyl ether in a volume ratio of (20-40): (80-60), wherein the extraction rate of the mixed solution (40:60, v/v) of undecone and dihexyl ether is the highest.
8) Optimization of sample phase background solutions
100Mmol/L sodium hydroxide is taken as a receiving phase solution, the influence of different sample phase background solutions (5, 10, 20 and 50mmol/L phosphate buffer solution with pH=6.8) on the extraction effects of the chlorpyrifos, the diflubenzuron and the antifeedant hydrazine is examined, and the sample phase background solutions are screened according to the extraction rate. For specific experimental details, see examples 8-1 to 8-4 below:
Test 8-1:
(1) Preparation of sample phase solutions
Preparing a mixed standard solution of 0.5mg/L of triclopyr, 0.5mg/L of diflubenzuron and 0.5mg/L of antifeedant hydrazine: taking 100mg/L of mixed standard substance of the metazamide, 100mg/L of diflubenzuron and 100mg/L of antifeedant hydrazine, taking 5mmol/L of phosphate buffer solution with pH=6.8 as sample phase background solution (solvent), preparing 0.5mg/L of mixed standard substance solution of the metazamide, 0.5mg/L of diflubenzuron and 0.5mg/L of antifeedant hydrazine, and taking the mixed standard substance solution as sample phase solution for carrying out supported liquid film extraction.
(2) Extraction
Supported liquid membrane extraction apparatus and extraction method reference is made to example 2.
Test 8-2:
the extraction method of run 8-2 was essentially the same as run 8-1, except that: phosphate buffer at 10mmol/L ph=6.8 was used as sample phase background solution.
Test 8-3:
The extraction method of run 8-3 was essentially the same as run 8-1, except that: phosphate buffer at 20mmol/L ph=6.8 was used as sample phase background solution.
Test 8-4:
the extraction procedure for run 8-4 was essentially the same as that of run 8-1, except that: phosphate buffer at 50mmol/L ph=6.8 was used as sample phase background solution.
The concentrations of the hexaflumuron, the tebufenozide and the tebufenozide in the receiving phase solution after the extraction is completed in the tests 8-1 to 8-4 are measured by using a high performance liquid chromatography-tandem mass spectrometer, and calculated with the concentrations in the sample phase solution, so that the extraction rate is shown in table 8, and the conditions of the testing method of the high performance liquid chromatography-tandem mass spectrometer are referred to in example 4.
Table 8 effect of different sample phase background solutions on extraction of flubendiamide, diflubenzuron and picloram (n=6)
As can be seen from Table 8, 5 to 50mmol/L of phosphate buffer showed higher extraction rates for the herbicidal, diflubenzuron and the antifeedant hydrazine, wherein the pH=6.8 50mmol/L of phosphate buffer showed the highest extraction rate.
9) Optimization of the receiving phase solution
The method comprises the steps of taking 0.5mg/L of the mixed standard solution of the herbicide, 0.5mg/L of the diflubenzuron and 0.5mg/L of the antifeedant hydrazine as sample phase solutions, taking different solutions as receiving phases for carrying out supported liquid film extraction, examining the influence of the receiving phase solutions on the extraction effects of the herbicide, the diflubenzuron and the antifeedant hydrazine, and screening the receiving phases according to the extraction. See the following tests 9-1 to 9-4 for specific experimental details:
test 9-1:
(1) Preparation of sample phase solutions
Preparing a mixed standard solution of 0.5mg/L of triclopyr, 0.5mg/L of diflubenzuron and 0.5mg/L of antifeedant hydrazine: taking a mixed standard substance of 100mg/L of the herbicide, 100mg/L of the diflubenzuron and 100mg/L of the antifeedant hydrazine, taking 50mmol/L of phosphate buffer solution with pH=6.8 as a solvent, preparing a mixed standard substance solution of 0.5mg/L of the herbicide, 0.5mg/L of the diflubenzuron and 0.5mg/L of the antifeedant hydrazine, and taking the mixed standard substance solution as a sample phase solution for carrying out supported liquid film extraction.
(2) Extraction
Supported liquid membrane extraction apparatus and extraction process with reference to example 2, the receiving phase is 100mmol/L sodium hydroxide solution.
Test 9-2:
the extraction method of run 9-2 was essentially the same as run 9-1, except that: the receiving phase is 100mmol/L sodium carbonate solution.
Test 9-3:
the extraction method of run 9-3 was essentially the same as run 9-1, except that: the receiving phase is 100mmol/L sodium phosphate solution.
Test 9-4:
the extraction method for run 9-4 was essentially the same as that for run 9-1, except that: the receiving phase is 100mmol/L potassium hydroxide solution.
The concentrations of the hexaflumuron, the tebufenozide and the tebufenozide in the receiving phase solution after the extraction is completed in the tests 9-1 to 9-4 are measured by using a high performance liquid chromatography-tandem mass spectrometer, and calculated with the concentrations in the sample phase solution, so that the extraction rate is shown in the table 9, and the conditions of the testing method of the high performance liquid chromatography-tandem mass spectrometer are referred to in example 4.
Table 9 effect of different receiver phase solutions on extraction of flubendiamide, diflubenzuron and picloram (n=6)
As can be seen from Table 9, 100mmol/L sodium hydroxide and potassium hydroxide show better extraction rates for the pyribenzoxim, the diflubenzuron and the antifeedant hydrazine, wherein the extraction rates of the 100mmol/L sodium hydroxide for the pyribenzoxim, the diflubenzuron and the antifeedant hydrazine are higher.
10 Optimization of extraction time
The mixed standard solution of 0.5mg/L of the triclopyr, 0.5mg/L of the diflubenzuron and 0.5mg/L of the antifeedant hydrazine is used as a sample phase solution, the influence of the extraction time on the extraction effects of the triclopyr, the diflubenzuron and the antifeedant hydrazine is examined, and the extraction time is optimized according to the extraction rate. See the following tests 10-1 to 10-8 for specific experimental details:
Test 10-1:
(1) Preparation of sample phase solutions
Preparing a mixed standard solution of 0.5mg/L of triclopyr, 0.5mg/L of diflubenzuron and 0.5mg/L of antifeedant hydrazine: taking a mixed standard substance of 100mg/L of the herbicide, 100mg/L of the diflubenzuron and 100mg/L of the antifeedant hydrazine, taking 50mmol/L of phosphate buffer solution with pH=6.8 as a solvent, preparing a mixed standard substance solution of 0.5mg/L of the herbicide, 0.5mg/L of the diflubenzuron and 0.5mg/L of the antifeedant hydrazine, and taking the mixed standard substance solution as a sample phase solution for carrying out supported liquid film extraction.
(2) Extraction
Supported liquid film extraction apparatus and extraction method referring to example 2, the extraction time was 5min.
Test 10-2:
The extraction method of test 10-2 was essentially the same as that of test 10-1, except that: the extraction time is 10min.
Test 10-3:
The extraction method of test 10-3 was essentially the same as that of test 10-1, except that: the extraction time is 20min.
Test 10-4:
The extraction method for run 10-4 was essentially the same as that for run 10-1, except that: the extraction time is 30min.
Test 10-5:
The extraction method for run 10-5 was essentially the same as that for run 10-1, except that: the extraction time is 60min.
Test 10-6:
The extraction method for run 10-6 was essentially the same as that for run 10-1, except that: the extraction time was 75min.
Test 10-7:
the extraction method for run 10-7 was essentially the same as that for run 10-1, except that: the extraction time is 90min.
The concentrations of the hexaflumuron, the tebufenozide and the tebufenozide in the receiving phase solution after the extraction is completed in the tests 10-1 to 10-7 are measured by using a high performance liquid chromatography-tandem mass spectrometer, and calculated with the concentrations in the sample phase solution, so that the extraction rate is shown in table 10, and the conditions of the testing method of the high performance liquid chromatography-tandem mass spectrometer are referred to in example 4.
Table 10 effect of different extraction times on extraction rates of flubendiamide, diflubenzuron and picloram (n=6)
As can be seen from table 10, an extraction time of 60 and 90min shows a higher extraction rate for both chlorpyrifos, diflubenzuron and picloram, so that the extraction is more efficiently performed in order to further shorten the extraction time, and more preferably the extraction time is 60min.
11 Optimization of extraction temperature
The mixed standard solution of 0.5mg/L of the triclopyr, 0.5mg/L of the diflubenzuron and 0.5mg/L of the antifeedant hydrazine is used as a sample phase solution, the influence of the temperature on the extraction effects of the triclopyr, the diflubenzuron and the antifeedant hydrazine is examined, and the temperature is optimized according to the extraction rate. See the following tests 11-1 to 11-5 for specific experimental details:
test 11-1:
(1) Preparation of sample phase solutions
Preparing a mixed standard solution of 0.5mg/L of triclopyr, 0.5mg/L of diflubenzuron and 0.5mg/L of antifeedant hydrazine: taking a mixed standard substance of 100mg/L of the herbicide, 100mg/L of the diflubenzuron and 100mg/L of the antifeedant hydrazine, taking 50mmol/L of phosphate buffer solution with pH=6.8 as a solvent, preparing a mixed standard substance solution of 0.5mg/L of the herbicide, 0.5mg/L of the diflubenzuron and 0.5mg/L of the antifeedant hydrazine, and taking the mixed standard substance solution as a sample phase solution for carrying out supported liquid film extraction.
(2) Extraction
Supported liquid film extraction apparatus and extraction method referring to example 2, the temperature of the thermostatic mixing device was set to 10 ℃.
Test 11-2:
The extraction method of run 11-2 was essentially the same as run 11-1, except that: the temperature of the constant temperature mixer was set at 25 ℃.
Test 11-3:
The extraction method for run 11-3 was essentially the same as that for run 11-1, except that: the temperature of the constant temperature mixer was set at 30 ℃.
Test 11-4:
The extraction method for run 11-4 was essentially the same as that for run 11-1, except that: the temperature of the constant temperature mixer was set at 40 ℃.
Test 11-5:
the extraction method for run 11-5 was essentially the same as that for run 11-1, except that: the temperature of the constant temperature mixer was set at 50 ℃.
The concentrations of the hexaflumuron, the tebufenozide and the tebufenozide in the receiving phase solution after the completion of the extraction are measured by using a high performance liquid chromatography-tandem mass spectrometer for the tests 11-1 to 11-5, and calculated with the concentrations in the sample phase solution, so that the extraction rate is shown in table 11, and the conditions of the testing method of the high performance liquid chromatography-tandem mass spectrometer are referred to in example 4.
Table 11 influence of different extraction temperatures on extraction rates of flubendiamide, diflubenzuron and picloram (n=6)
As can be seen from Table 11, the extraction temperature of 25℃shows a better extraction rate for the hexaflumuron, the diflubenzuron and the picloram.
12 Optimization of oscillation speed
The mixed standard solution of 0.5mg/L of the triclopyr, 0.5mg/L of the diflubenzuron and 0.5mg/L of the antifeedant hydrazine is used as a sample phase solution, the influence of the oscillation speed on the extraction effects of the triclopyr, the diflubenzuron and the antifeedant hydrazine is examined, and the oscillation speed is optimized according to the extraction rate. See the following tests 12-1 to 12-5 for specific experimental details:
Test 12-1:
(1) Preparation of sample phase solutions
Preparing a mixed standard solution of 0.5mg/L of triclopyr, 0.5mg/L of diflubenzuron and 0.5mg/L of antifeedant hydrazine: taking a mixed standard substance of 100mg/L of the herbicide, 100mg/L of the diflubenzuron and 100mg/L of the antifeedant hydrazine, taking 50mmol/L of phosphate buffer solution with pH=6.8 as a solvent, preparing a mixed standard substance solution of 0.5mg/L of the herbicide, 0.5mg/L of the diflubenzuron and 0.5mg/L of the antifeedant hydrazine, and taking the mixed standard substance solution as a sample phase solution for carrying out supported liquid film extraction.
(2) Extraction
Supported liquid film extraction apparatus and extraction method referring to example 2, the shaking speed of the thermostatic mixer was set at 300rpm.
Test 12-2:
The extraction method for run 12-2 was essentially the same as that for run 12-1, except that: the shaking speed of the thermostatic mixer was set at 400rpm.
Test 12-3:
The extraction method for run 12-3 was essentially the same as that for run 12-1, except that: the shaking speed of the thermostatic mixer was set at 600rpm.
Test 12-4:
The extraction method for run 12-4 was essentially the same as that for run 12-1, except that: the shaking speed of the thermostatic mixer was set at 800rpm.
Test 12-5:
The extraction method for run 12-5 was essentially the same as that for run 12-1, except that: the shaking speed of the constant temperature mixer was set at 1000rpm.
The concentrations of the hexaflumuron, the tebufenozide and the tebufenozide in the receiving phase solution after the extraction is completed are measured by a high performance liquid chromatography-tandem mass spectrometer (HPLC-MS) to test 12-5, and calculated with the concentrations in the sample phase solution, so that the extraction rate is shown in Table 12, and the conditions of the test method of the HPLC-MS are as shown in example 4.
Table 12 influence of different oscillation speeds on extraction rates of flubendiamide, diflubenzuron and picloram (n=6)
As can be seen from Table 12, a shaking speed of 1000rpm shows a higher extraction rate for both chlorpyrifos, diflubenzuron and picloram.
Experimental example 2
The experimental example tests the detection limit, the quantitative limit and the standard adding recovery rate of pesticides.
1) Carbendazim and pirimicarb
The linear range, correlation coefficient, detection limit and quantitative limit can be obtained by carrying out liquid chromatography-tandem mass spectrometry test on the receiving phase solution after carrying out supported liquid film extraction on a series of lake water sample phase solutions of carbendazim and pirimicarb in the embodiment 1, and the calculation results are shown in table 13.
TABLE 13 Linear range, correlation coefficient, detection limit and quantification limit of carbendazim and pirimicarb
As can be seen from Table 13, the detection limit of the detection method for pesticides in water bodies provided by the invention can reach 0.011-0.022 ng/mL and the quantitative limit can reach 0.036-0.072 ng/mL.
The results of the liquid chromatography-tandem mass spectrometry test of the received phase solution after the supported liquid film extraction of the sample phase solutions of different concentrations of rainwater, lake water and tap water in example 1 are shown in table 14.
TABLE 14 labeled recovery of carbendazim and pirimicarb in lake, rainwater and tap water
As can be seen from Table 14, the labeled recovery rate of carbendazim and pirimicarb in lake water, rainwater and tap water with different concentrations is 85% -125%, the repeatability is good, the stability is high, and the average deviation in daily and daytime is less than 10%.
For comparison, a pure rainwater labeling solution without buffer solution was prepared, and the specific preparation method is as follows: four different concentrations of carbendazim and pirimicarb standard solutions (no phosphate buffer solution) are prepared by taking treated rainwater as a solvent, four different concentrations of pure rainwater standard sample phase solutions are respectively obtained, liquid film extraction is carried out, liquid chromatography-tandem mass spectrometry test is carried out on the receiving phase solution, and the standard recovery rate test results are shown in table 15. As can be seen from Table 15, the labeled recovery rates of carbendazim and pirimicarb at different concentrations in rainwater were only 56% -65% and 32% -47%, respectively, when no phosphate buffer solution was added, which were much lower than those when 50mmol/L of pH=6.8 phosphate buffer solution was contained (Table 14). The pH of the rainwater is slightly acidic, so that part of carbendazim and pirimicarb are in an ionic form, which is unfavorable for the extraction process, and the phosphate buffer solution with pH=6.8 can ensure that the pesticide almost exists in a molecular form in the extraction process, and ensure the mass transfer capacity of the pesticide.
TABLE 15 labeled recovery of carbendazim and pirimicarb in rainwater (phosphate-free buffer solution)
2) Herbicidal, diflubenzuron and antifeedant hydrazine
The linear range, correlation coefficient, detection limit and quantitative limit were calculated by carrying out liquid chromatography-tandem mass spectrometry test on the receiving phase solution after carrying out supported liquid film extraction on a series of lake water sample phase solutions of the concentrations of the hexaflumuron, the tebuconazole and the tebuconazole in example 2, and the calculation results are shown in table 16.
TABLE 16 Linear ranges, correlation coefficients, detection limits and quantification limits for flubendiamide, diflubenzuron and imazapyr
As can be seen from Table 16, the detection limit of the pesticide in the water body provided by the invention on the detection limit of the hexaflumuron, the diflubenzuron and the antifeedant hydrazine can reach 0.07-0.09 ng/mL, and the quantitative limit can reach 0.22-0.31 ng/mL.
After carrying out supported liquid film extraction on rainwater, lake water and tap water with different concentrations and carrying out liquid chromatography-tandem mass spectrometry test on a receiving phase solution, the total ion flow diagrams of the sample phase solution and the receiving phase solution with the labeled pesticide are shown as shown in figure 2, and as can be seen from figure 2, the actual sample contains more matrix interferents besides the labeled pesticide residue, no obvious matrix interferents are found in the receiving phase solution after the supported liquid film extraction, and the peak intensity of the labeled pesticide residue is obviously improved.
The results of the standard recovery test obtained by the liquid chromatography-tandem mass spectrometry test are shown in table 17.
TABLE 17 labeled recovery of herbicidal, diflubenzuron and anti-food hydrazine in lake water, rainwater and tap water
As can be seen from Table 17, the standard recovery rate of the chlorpyrifos, the diflubenzuron and the antifeedant hydrazine in lake water, rainwater and tap water with different concentrations is 80-123.51%, the repeatability is good, the stability is high, and the average deviation in the day and the daytime is less than 10%.
Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principles of the present invention.
Claims (10)
1. The extraction method of the pesticide in the water body is characterized by comprising the following steps of: preparing a water sample and a phosphate buffer solution with pH=6.5-7 into a sample phase solution, and extracting pesticides in the sample phase solution into a receiving phase solution by adopting a supported liquid film extraction method, wherein the pesticides are one or more selected from carbendazim, pirimicarb, triclopyr, diflubenzuron and antifeedant hydrazine.
2. The method for extracting pesticides in water body according to claim 1, wherein the extraction solvent in the supported liquid film extraction method is selected from octanone, nonanone, tributyl phosphate, undecanone and dihexyl ether in a volume ratio of (20-40): (80-60) one of the formed mixed solutions; the receiving phase solution is selected from one of hydrochloric acid solution, formic acid solution, acetic acid solution, trifluoroacetic acid solution, sodium hydroxide solution, sodium carbonate solution, sodium phosphate solution and potassium hydroxide solution.
3. The method for extracting agricultural chemical in water according to claim 2, wherein when the agricultural chemical is carbendazim or pirimicarb, the extraction solvent is one of octanone, nonanone and tributyl phosphate, and the receiving phase solution is one of hydrochloric acid solution, formic acid solution, acetic acid solution and trifluoroacetic acid solution.
4. The method for extracting pesticides in water body according to claim 2, wherein when the pesticides are chlorbenzuron, diflubenzuron and antifeedant hydrazine, the extraction solvent is undecanone and dihexyl ether in a volume ratio of (20-40): (80-60), wherein the receiving phase solution is selected from one of sodium hydroxide solution, sodium carbonate solution, sodium phosphate solution and potassium hydroxide solution.
5. The method for extracting pesticides in water as claimed in claim 1, wherein the shaking is performed during the extraction, and the shaking speed is 300-1000 rpm.
6. The method for extracting agricultural chemicals from a water body according to claim 2, wherein the concentration of the receiving phase solution is 100 to 120mmol/L.
7. The method for extracting agricultural chemicals from water according to claim 1, wherein the extraction temperature is 10 ℃ to 50 ℃ and the extraction time is 5min to 90min.
8. The method for extracting agricultural chemicals from water according to claim 1, wherein the membrane used in the supported liquid membrane extraction method is a porous polypropylene fiber membrane, and the pore size of the porous polypropylene fiber membrane is 0.2 μm, and the thickness of the porous polypropylene fiber membrane is 100 μm to 200 μm.
9. A method for detecting pesticides in a water body, characterized in that the pesticides are extracted to a receiving phase solution by adopting the extraction method of pesticides in a water body according to any one of claims 1 to 8, and the receiving phase solution is detected by adopting liquid chromatography-tandem mass spectrometry.
10. The method for detecting pesticides in water as claimed in claim 9, wherein the detection conditions in the liquid chromatography-tandem mass spectrometry detection are as follows: chromatographic column: watersDC18 column, column temperature: 25 ℃; sample injection amount: 5.0. Mu.L; flow rate: 0.3mL/min; mobile phase: the phase A is aqueous solution containing 0.1% formic acid, the phase B is acetonitrile, and a gradient elution mode is adopted.
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