CN111855873A - Method for determining triazine herbicide residue in aquatic product by ultra-high performance liquid chromatography-tandem mass spectrometry - Google Patents
Method for determining triazine herbicide residue in aquatic product by ultra-high performance liquid chromatography-tandem mass spectrometry Download PDFInfo
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- CN111855873A CN111855873A CN202010677758.4A CN202010677758A CN111855873A CN 111855873 A CN111855873 A CN 111855873A CN 202010677758 A CN202010677758 A CN 202010677758A CN 111855873 A CN111855873 A CN 111855873A
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000003854 herbicide residue Substances 0.000 title claims abstract description 12
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 title claims abstract description 12
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- 238000001514 detection method Methods 0.000 claims abstract description 39
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- 238000004704 ultra performance liquid chromatography Methods 0.000 claims abstract description 13
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- 229910052786 argon Inorganic materials 0.000 claims description 4
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- 239000011780 sodium chloride Substances 0.000 claims description 4
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- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical group CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 21
- 241000252230 Ctenopharyngodon idella Species 0.000 description 21
- 238000011084 recovery Methods 0.000 description 17
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- MZZBPDKVEFVLFF-UHFFFAOYSA-N cyanazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)(C)C#N)=N1 MZZBPDKVEFVLFF-UHFFFAOYSA-N 0.000 description 10
- AAEVYOVXGOFMJO-UHFFFAOYSA-N prometryn Chemical compound CSC1=NC(NC(C)C)=NC(NC(C)C)=N1 AAEVYOVXGOFMJO-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000005621 Terbuthylazine Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- FZXISNSWEXTPMF-UHFFFAOYSA-N terbutylazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)(C)C)=N1 FZXISNSWEXTPMF-UHFFFAOYSA-N 0.000 description 6
- 239000005630 Diquat Substances 0.000 description 5
- SYJFEGQWDCRVNX-UHFFFAOYSA-N diquat Chemical compound C1=CC=[N+]2CC[N+]3=CC=CC=C3C2=C1 SYJFEGQWDCRVNX-UHFFFAOYSA-N 0.000 description 5
- ODCWYMIRDDJXKW-UHFFFAOYSA-N simazine Chemical compound CCNC1=NC(Cl)=NC(NCC)=N1 ODCWYMIRDDJXKW-UHFFFAOYSA-N 0.000 description 5
- MGLWZSOBALDPEK-UHFFFAOYSA-N simetryn Chemical compound CCNC1=NC(NCC)=NC(SC)=N1 MGLWZSOBALDPEK-UHFFFAOYSA-N 0.000 description 5
- IROINLKCQGIITA-UHFFFAOYSA-N terbutryn Chemical compound CCNC1=NC(NC(C)(C)C)=NC(SC)=N1 IROINLKCQGIITA-UHFFFAOYSA-N 0.000 description 5
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
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Abstract
The invention discloses a method for determining triazine herbicide residue in an aquatic product by ultra-high performance liquid chromatography-tandem mass spectrometry, which comprises the following steps: 1. preparing a mixed standard solution; 2. UPLC analysis and detection; 3. HESI-MS/MS analysis detection; 4. establishing a standard curve; 5. pretreatment of aquatic product samples; 6. and (5) detecting the sample to be detected. The method is simple, can quickly and accurately detect the residual quantity of the triazine herbicide in the aquatic product, has less matrix interference and accurate determination result.
Description
Technical Field
The invention relates to the technical field of physicochemical inspection of pesticide residues in aquatic products, in particular to a method for determining triazine herbicide residues in aquatic products by using ultra-high performance liquid chromatography-tandem mass spectrometry.
Background
Triazine herbicides (Triazine herbicides) are highly selective herbicides that act by inhibiting plant photosynthesis and have been used as early as 50 s in the 20 th century. The herbicide is widely applied to the control of various weeds, has large dosage, stable property and long lasting period, and has more and more attention to the harm to human health and environment. It has been reported that such compounds may cause human cancers and congenital defects, and at the same time interfere with the normal function of hormones, which have been included in the list of endocrine disrupter compounds in many countries of the world. At present, the detection of triazine herbicide residues is mainly focused on grains, vegetables and environmental samples, and relatively few methods are used for detecting the triazine herbicide residues in aquatic products.
In the prior art, the main technical method adopted for detecting the triazine herbicide residue in aquatic products is divided into two parts: sample pretreatment and instrument analysis and measurement, wherein the sample pretreatment mostly adopts solid phase extraction column purification, and the purification step is complicated and time-consuming; instrumental analysis has reported that gas chromatography tandem mass spectrometry (GC-MS/MS) is more frequently reported, but the stability and accuracy of the gas chromatography tandem mass spectrometry are poorer.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for determining triazine herbicide residue in an aquatic product by using ultra-high performance liquid chromatography-tandem mass spectrometry, the method is simple, the residual amount of triazine herbicide in the aquatic product can be rapidly and accurately detected, the matrix interference is less, and the determination result is accurate.
The technical scheme adopted for realizing the above purpose of the invention is as follows:
a method for determining triazine herbicide residue in aquatic products by ultra-high performance liquid chromatography-tandem mass spectrometry comprises the following steps
1. Preparing a mixed standard solution:
preparing N parts of mixed standard solutions with gradient concentration, wherein the triazine herbicides in each part of mixed standard solution are the same in type, the triazine herbicides in each part of mixed standard solution are the same in concentration, and the internal standard atrazine-D is contained in each part of mixed solution 5Mixing the internal standard substance atrazine-D in the standard solution5The concentrations of (A) were the same, and the internal standard substance atrazine-D5In the gradient concentration range of each triazine herbicide;
2. UPLC analysis and detection:
and (3) respectively carrying out UPLC analysis and detection on each mixed standard solution, wherein the UPLC conditions are as follows:
the chromatographic column adopts C18A chromatographic column, wherein a mobile phase adopts a mixed solution of an organic phase and a water phase, the organic phase is acetonitrile, the water phase is 0.1 wt% formic acid solution, the flow rate of the mobile phase is 0.3-0.4mL/min, and the mobile phase is eluted by adopting a gradient elution mode;
3. HESI-MS/MS analysis and detection:
the detection conditions of the HESI-MS/MS analysis are as follows:
the ion source is a heating atmospheric pressure electric spray source, positive ion mode scanning is carried out, a reaction monitoring mode is selected for determination, the spray voltage is 3000-: the purity of argon is more than or equal to 99.999, 2.0mTorr, the half-peak width of Q1 is 0.7, and the half-peak width of Q3 is 0.7;
after HESI-MS/MS analysis and detection, the peak area of the sub-ion of each triazine herbicide and the internal standard atrazine-D under each concentration can be obtained5The ratio of the peak areas of the daughter ions;
4. Establishing a standard curve:
taking the concentration of each triazine herbicide as an abscissa, and taking the peak area of the daughter ion of each triazine herbicide and an internal standard atrazine-D under each concentration5The ratio of the peak areas of the daughter ions is a vertical coordinate, drawing is carried out according to the data detected by each triazine herbicide, and a standard curve of each triazine herbicide is obtained after fitting, so that a function relation formula of the standard curve of each triazine herbicide is obtained;
5. pretreatment of aquatic product samples:
taking homogeneous muscle sample of aquatic animal, adding atrazine-D as internal standard substance5Sequentially adding acetonitrile, sodium chloride and anhydrous magnesium sulfate, performing vortex oscillation, centrifuging, collecting supernatant, repeatedly extracting, mixing the supernatants, evaporating the supernatant, dissolving the residue with solvent, and adding purifying agent such as ethylenediamine-N-Propylsilane (PSA) and octadecylsilane chemically bonded silica (C)18) And EMR-Lipid powder, centrifuging after vortex oscillation, and filtering the obtained supernatant with a microporous filter membrane to obtainTo a sample to be detected;
6. detecting a sample to be detected:
analyzing and detecting the sample to be detected according to the method in the step 2-3 to obtain the peak area of the sub-ion of each triazine herbicide and the internal standard atrazine-D 5The ratio of the peak area of the daughter ion is obtained by mixing the peak area of the daughter ion of each triazine herbicide with the peak area of the internal standard substance atrazine-D5Substituting the ratio of the ionic peak areas into the functional relation of the standard curve of the corresponding triazine herbicide to obtain the concentration of the corresponding triazine herbicide.
Further, the chromatographic column has a column length of 100mm, an inner diameter of 2.1mm, a packed particle size of 1.7 μm and a column temperature of 30 ℃.
Further, the conditions of the gradient elution are as follows:
the first stage is as follows: the elution time is 0-2min, wherein the volume percentage of the organic phase is 15-25%, and the volume percentage of the water phase is 75-85%;
and a second stage: the elution time is 3-5min, wherein the volume percentage of the organic phase is gradually increased from 15-25% to 90-95%, and the volume percentage of the aqueous phase is gradually decreased from 75-85% to 5-10%;
and a third stage: the elution time is 2-3min, wherein the volume percentage of the organic phase is 90-95%, and the volume percentage of the water phase is 5-10%;
a fourth stage: the elution time is 0.1-0.5min, wherein the volume percentage of the organic phase is gradually reduced from 90-95% to 15-25%, and the volume percentage of the aqueous phase is gradually increased from 5-10% to 75-85%;
the fifth stage: the elution time is 1.5-4min, wherein the volume percentage of the organic phase is 15-25%, and the volume percentage of the water phase is 75-85%.
Further, in step 5, the solvent is methanol or acetonitrile.
Furthermore, the microporous filter membrane is an organic microporous filter membrane, and the pore diameter of the microporous filter membrane is not more than 0.22 μm.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. according to the invention, the QuEChERS method is adopted to purify the samples, so that the time for purifying each aquatic product sample is greatly shortened, the conventional purifying agent is abandoned, the special purifying agent is adopted, the interference of the matrix is obviously reduced, the sensitivity and the accuracy are improved, and the residual condition of the triazine herbicide in the aquatic products can be accurately reflected.
2. The invention adopts an internal standard method and a special internal standard substance atrazine-D5Compared with the common external standard method, the method can eliminate the influence on the analysis result caused by the fluctuation of instruments and operation conditions, thereby improving the precision of measurement and the accuracy and reliability of the result.
Drawings
FIG. 1 is a graph comparing the results of recovering muscle tissue of grass carp blank by using example 1 and comparative example 1 and adding 11 triazine herbicides at a concentration of 20. mu.g/kg.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
1. Preparing a mixed standard solution:
Preparing 6 parts of mixed standard solution with gradient concentration by using an initial mobile phase (namely, the mobile phase used in the first elution stage), wherein each part of mixed standard solution contains 11 triazine herbicides, the 11 triazine herbicides are simazine, diquat, simetryn, atrazine, ametryn, atrazine, terbuthylazine, prometryn, cyanazine, terbutryn and prometryn, the concentration of each triazine herbicide in each part of mixed standard solution is the same, the concentration of each triazine herbicide in the 6 parts of mixed standard solution is 1.0 mu g/L, 5.0 mu g/L, 10 mu g/L, 20 mu g/L, 50 mu g/L and 100 mu g/L respectively, and an internal standard substance atrazine-D is added into each part of mixed standard solution5Mixing the internal standard substance atrazine-D in the standard solution5The concentration of (A) is 5 mu g/L;
2. UPLC analysis and detection:
performing UPLC analysis detection on each mixed standard solution, wherein the UPLC conditions are as follows:
the column used was a Waters ACQUITY BEH Shield RP18 column (100 mm. times.2.1 mm, 1.7 μm), column temperature: 30 ℃, sample introduction: 10 mu L of the solution; the mobile phase adopts a mixed solution of an organic phase and a water phase, the organic phase is acetonitrile, the water phase is 0.1 wt% formic acid solution, the flow rate of the mobile phase is 0.4mL/min, and the mobile phase is eluted by adopting a gradient elution mode, which comprises the following steps:
The first stage is as follows: the elution time is 2min, wherein the volume percentage of the organic phase is 20 percent, and the volume percentage of the water phase is 80 percent;
and a second stage: elution time 4min, wherein the volume percentage of the organic phase gradually increased from 20% to 90%, and the volume percentage of the aqueous phase gradually decreased from 80% to 10%;
and a third stage: the elution time is 2min, wherein the volume percentage of the organic phase is 90 percent, and the volume percentage of the water phase is 10 percent;
a fourth stage: the elution time is 0.1min, wherein the volume percentage of the organic phase is gradually reduced from 90% to 20%, and the volume percentage of the aqueous phase is gradually increased from 10% to 80%;
the fifth stage: the elution time is 1.9min, wherein the volume percentage of the organic phase is 20 percent, and the volume percentage of the aqueous phase is 80 percent;
3. HESI-MS/MS analysis and detection:
the detection conditions of the HESI-MS/MS analysis are as follows:
the ion source is a heating atmosphere piezoelectric spray source, positive ion mode scanning is carried out, a reaction monitoring mode is selected for determination, the spray voltage is 3500V, the evaporation temperature is 350 ℃, the temperature of an ion transmission capillary is 330 ℃, the flow rate of sheath gas is 40L/min, the auxiliary gas is 10L/min, and the collision gas and pressure are as follows: the purity of the argon is more than or equal to 99.999, 2.0mTorr, the half-peak width of Q1 is 0.7, the half-peak width of Q3 is 0.7, and the detection parameters of the triazine herbicides are shown in the following table 1:
Table 111 triazine herbicides and their internal standards parent ion, daughter ion and collision energy
Obtaining the triazine herbicides and atrazine-D according to the detection parameters of the triazine herbicides5The peak area of the ion of the triazine herbicide is obtained, and the peak area of the ion of each triazine herbicide and the area of the internal standard atrazine-D are obtained under each concentration5The ratio of the peak areas of the daughter ions;
4. establishing a standard curve:
taking the concentration of each triazine herbicide as an abscissa, and taking the peak area of the daughter ion of each triazine herbicide and an internal standard atrazine-D under each concentration5The ratio of the peak areas of the daughter ions is a vertical coordinate, drawing is carried out according to the data detected by each triazine herbicide, and a standard curve of each triazine herbicide is obtained after fitting, so that a functional relation (linear equation) of the standard curve of each triazine herbicide is obtained, the detection Limit (LOD) of the method is determined by the signal to noise ratio (S/N is more than or equal to 3) which is not less than 3 times, and the quantification Limit (LQD) of the method is determined by the signal to noise ratio (S/N is more than or equal to 10) which is not less than 10 times, and the specific results are as shown in the following table 2:
TABLE 211 Linear equations, Linear Range, correlation coefficients, detection limits and quantitation limits for the herbicides
5. Pretreatment of aquatic product samples:
weighing 5g (accurate to 0.01g) of homogenized grass carp muscle sample, placing the grass carp muscle sample in a 50mL centrifuge tube, and adding 100 mu L of 0.1mg/L internal standard atrazine-D 5Sequentially adding 10mL of acetonitrile, 3g of sodium chloride and 2g of anhydrous magnesium sulfate, carrying out vortex oscillation for 2min, then carrying out ultrasonic treatment for 5min, then centrifuging for 5min at 5000r/min, taking supernatant into a heart-shaped bottle, repeatedly extracting for 1 time, combining the supernatants into the heart-shaped bottle, evaporating the supernatant in the heart-shaped bottle at 40 ℃ to dryness, adding 2mL of methanol into residues, and carrying out vortex oscillation until the residues are dissolved to obtain a mixed solution for later use;
the mixture was placed in a 10mL centrifuge tube and 0.1g PSA, 0.1g 0.1g C were added sequentially18And 0.1g EMR-Lipid powder (Agilent Co.), vortexed for 1min, followed by shaking at 10000r/minFreezing and centrifuging for 5min, and filtering 1mL of supernatant with 0.22 μm nylon filter membrane to obtain a sample to be detected;
6. detecting a sample to be detected:
analyzing and detecting the sample to be detected according to the method in the step 2-3 to obtain the peak area of the sub-ion of each triazine herbicide and the internal standard atrazine-D5The ratio of the peak area of the daughter ion is obtained by mixing the peak area of the daughter ion of each triazine herbicide with the peak area of the internal standard substance atrazine-D5Substituting the ratio of the ionic peak areas into the functional relation of the standard curve of the corresponding triazine herbicide to obtain the concentration of the corresponding triazine herbicide.
7. Detecting the recovery rate and the precision;
Taking three homogeneous blank grass carp muscle tissue samples, respectively adding 11 triazine herbicide mixed standard solutions with low, medium and high concentrations to obtain three to-be-treated test samples, and pretreating the three to-be-treated samples according to the method in the step 5 of the embodiment 1 to obtain three to-be-treated test samples;
three test samples to be tested are detected according to the method of the step 6 in the embodiment, and the recovery rate, the day precision and the day precision are calculated as follows:
recovery (%) — actual assay concentration of spiked sample ÷ spiked concentration × 100%;
precision includes intra-day precision and inter-day precision. The in-day precision refers to the conformity degree between the measurement of the same adding concentration and different batches of standard adding samples in one day, and the in-day precision refers to the in-day precision calculated by continuously measuring the concentration of the standard adding samples in one week;
precision (%). standard deviation ÷ standard sample measured concentration mean x 100%.
And (3) detection results:
the detection results are shown in table 3, and table 3 shows the detection results of the standard recovery rate and precision of 11 triazine herbicides in the muscle tissue of grass carp by using an internal standard method, which specifically comprises the following steps:
table 311 normalized recovery and precision of herbicides in grass carp muscle tissue (n ═ 6)
As can be seen from Table 3, the recovery rate of the triazine herbicide is between 80% and 112%, and therefore the method for detecting the triazine herbicide in the aquatic product by adopting the internal standard method is high in accuracy and very reliable.
Comparative example 1
1. Preparing a mixed standard solution:
preparing 6 parts of mixed standard solution with gradient concentration by using an initial mobile phase, wherein each part of mixed standard solution contains 11 triazine herbicides, the 11 triazine herbicides are simazine, diquat, simetryn, atrazine, ametryn, atrazine, terbuthylazine, prometryn, cyanazine, terbutryn and prometryn, the concentration of each triazine herbicide in each part of mixed standard solution is the same, and the concentration of each triazine herbicide in the 6 parts of mixed standard solution is 1.0 mu g/L, 5.0 mu g/L, 10 mu g/L, 20 mu g/L, 50 mu g/L and 100 mu g/L respectively;
2. UPLC analysis and detection:
performing UPLC analysis detection on each mixed standard solution, wherein the UPLC conditions are as follows:
the column used was a Waters ACQUITY BEH Shield RP18 column (100 mm. times.2.1 mm, 1.7 μm), column temperature: 30 ℃, sample introduction: 10 mu L of the solution; the mobile phase adopts a mixed solution of an organic phase and a water phase, the organic phase is acetonitrile, the water phase is 0.1 wt% formic acid solution, the flow rate of the mobile phase is 0.4mL/min, and the mobile phase is eluted by adopting a gradient elution mode, which comprises the following steps:
The first stage is as follows: the elution time is 2min, wherein the volume percentage of the organic phase is 20 percent, and the volume percentage of the water phase is 80 percent;
and a second stage: elution time 4min, wherein the volume percentage of the organic phase gradually increased from 20% to 90%, and the volume percentage of the aqueous phase gradually decreased from 80% to 10%;
and a third stage: the elution time is 2min, wherein the volume percentage of the organic phase is 90 percent, and the volume percentage of the water phase is 10 percent;
a fourth stage: the elution time is 0.1min, wherein the volume percentage of the organic phase is gradually reduced from 90% to 20%, and the volume percentage of the aqueous phase is gradually increased from 10% to 80%;
the fifth stage: the elution time is 1.9min, wherein the volume percentage of the organic phase is 20 percent, and the volume percentage of the aqueous phase is 80 percent;
3. HESI-MS/MS analysis and detection:
the detection conditions of the HESI-MS/MS analysis are as follows:
the ion source is a heating atmosphere piezoelectric spray source, positive ion mode scanning is carried out, a reaction monitoring mode is selected for determination, the spray voltage is 3500V, the evaporation temperature is 350 ℃, the temperature of an ion transmission capillary is 330 ℃, the flow rate of sheath gas is 40L/min, the auxiliary gas is 10L/min, and the collision gas and pressure are as follows: the purity of the argon is more than or equal to 99.999, 2.0mTorr, the half-peak width of Q1 is 0.7, the half-peak width of Q3 is 0.7, and the detection parameters of the triazine herbicides are shown in the following table 4:
Table 411 parent ion, daughter ion and collision energy for triazine herbicides
The area of the daughter ion peak of each triazine herbicide under each concentration can be obtained according to the detection parameters of each triazine herbicide;
4. establishing a standard curve:
the concentration of each triazine herbicide is used as an abscissa, the area of a daughter ion peak of each triazine herbicide at each concentration is used as an ordinate, drawing is carried out according to data detected by each triazine herbicide, a standard curve of each triazine herbicide is obtained after fitting, so that a functional relation (linear equation) of the standard curve of each triazine herbicide is obtained, the detection Limit (LOD) of the method is determined by the signal to noise ratio (S/N is more than or equal to 3) which is not less than 3 times, and the quantitative Limit (LQD) of the method is determined by the signal to noise ratio (S/N is more than or equal to 10) which is not less than 10 times, and the specific results are shown in the following table 5:
TABLE 511 Linear Range, Linear equation, correlation coefficient, detection limits and quantitation limits for the herbicides
5. Pretreatment of aquatic product samples:
weighing 5g (accurate to 0.01g) of homogenized grass carp muscle sample, placing the grass carp muscle sample in a 50mL centrifuge tube, sequentially adding 10mL acetonitrile, 3g sodium chloride and 2g anhydrous magnesium sulfate, carrying out vortex oscillation for 2min, then carrying out ultrasonic treatment for 5min, then centrifuging for 5min at 5000r/min, taking supernatant into a heart-shaped bottle, repeatedly extracting for 1 time, combining the supernatant into the heart-shaped bottle, placing the supernatant in the heart-shaped bottle at 40 ℃, adding 2mL methanol into residues, carrying out vortex oscillation for evaporating to dryness until the residues are dissolved to obtain a mixed solution for later use;
The mixture was placed in a 10mL centrifuge tube and 0.1g PSA, 0.1C were added sequentially18And 0.1g of EMR-Lipid, carrying out vortex oscillation for 1min, then carrying out refrigerated centrifugation for 5min at 10000r/min, taking 1mL of supernatant, and filtering with a 0.22 mu m nylon filter membrane to obtain a sample to be detected;
6. detecting a sample to be detected:
and (3) analyzing and detecting a sample to be detected according to the method in the step 2-3 to obtain the daughter ion peak area of each triazine herbicide, and substituting the daughter ion peak area of each triazine herbicide into the functional relation formula of the corresponding standard curve of the triazine herbicide to obtain the concentration of the corresponding triazine herbicide.
7. And (3) detecting the recovery rate and the precision:
taking three homogeneous blank grass carp muscle tissue samples, respectively adding 11 triazine herbicide mixed standard solutions with low, medium and high concentrations to obtain three to-be-treated test samples, and pretreating the three to-be-treated samples according to the method of the step 5 in the comparative example 1 to obtain three to-be-treated control samples;
and (3) detecting three control samples to be detected according to the method of the step 6 in the comparative example 1, and calculating the recovery rate, the day precision and the day precision:
and (3) detection results:
the results are shown in table 6, and table 6 shows the results of detecting the standard recovery rate and precision of 11 triazine herbicides in the muscle tissue of grass carp by using an external standard method, which specifically includes the following steps:
Table 611 normalized recovery and precision of the herbicides in the muscle tissue of grass carp (n ═ 6)
As can be seen from Table 6, the recovery rate of the triazine herbicide is between 50% and 88%, and therefore, the accuracy of detecting the triazine herbicide in the aquatic product by adopting the external standard method is low, and the detection requirement cannot be met.
The mixed standard solution of 11 triazine herbicides with different concentrations is added into the muscle tissue of the blank grass carp, the recovery is carried out by adopting the methods of the example 1 and the comparative example 1, according to the results of the table 4 and the table 6, when the 11 triazine herbicides with 20 mug/kg are added, the recovery rate of each triazine herbicide is compared and shown in the figure 1, as can be seen from the figure 1, the recovery is carried out by adopting the internal standard method of the example 1, the recovery rate is 80-112%, and the recovery rate is 50-88% when the external standard method of the comparative example 1 is adopted, the standard recovery rate of terbuthylazine is only 54.5% at most, and the detection requirement cannot be met, therefore, the detection is carried out by adopting the method of the example 1, and the detection accuracy is high, and the detection is more accurate and reliable.
First, the matrix effect evaluation test of the method for determining triazine herbicide residue in aquatic products by ultra-high performance liquid chromatography-tandem mass spectrometry
The test method comprises the following steps:
1. the experimental group adopts the purifying reagents of PSA and C 18And EMR-Lipid, as follows:
1.1, taking the homogenized blank grass carp muscleTissue samples were pretreated according to the method of step 5 of comparative example 1, using 0.1g PSA, 0.1g 0.1g C as the decontamination reagent18And 0.1g of EMR-Lipid to obtain a blank grass carp matrix extracting solution 1;
1.2, preparing 6 parts of mixed standard solution with gradient concentration by using the blank grass carp matrix extracting solution 1, wherein each part of mixed standard solution contains 11 triazine herbicides, the 11 triazine herbicides are simazine, diquat, simetryn, atrazine, terbuthylazine, prometryn, cyanazine, terbutryn and prometryn, the concentration of each triazine herbicide in each part of mixed standard solution is the same, the concentration of each triazine herbicide in 6 parts of mixed standard solution is 1.0 mu g/L, 5.0 mu g/L, 10 mu g/L, 20 mu g/L, 50 mu g/L and 100 mu g/L, and an internal standard substance atrazine-D is added into each part of mixed solution5Mixing the internal standard substance atrazine-D in the standard solution5The concentrations of (A) and (B) were all 5. mu.g/L, and a matrix standard curve was established according to the method of example 1, steps 2 to 4;
1.3, Matrix Effect (ME) assessment:
using the formula ME ═ 1- (slope of substrate standard curve/slope of solvent standard curve) ]100% of the total amount of purified PSA and C, the results of the assay are shown in Table 7, where PSA and C are selected as the purifying reagents in Table 718And EMR-Lipid, the ME values of the respective substances are as follows:
TABLE 7 purification reagents PSA, C18And the ME value at EMR-Lipid
2. The control group 1 adopts the purifying reagents of PSA and C18The tests were carried out as follows:
2.1, taking a homogenized blank grass carp muscle tissue sample, pretreating according to the method of the step 5 in the comparative example 1, and selecting 0.1g of PSA and 0.1g C as purifying reagents18Obtaining a blank grass carp matrix extracting solution 2;
2.2, preparing 6 parts of mixed standard solution with gradient concentration by using the blank grass carp matrix extracting solution 2, wherein each part of mixed standard solution contains 11 triazine herbicides and 11 triazine herbicidesThe herbicides are simazine, diquat, simetryn, atrazine, cyhalozine, terbuthylazine, prometryn, cyanazine, terbutryn and prometryn respectively, the concentration of the triazine herbicides in each mixed standard solution is the same, the concentration of the triazine herbicides in 6 mixed standard solutions is 1.0 mug/L, 5.0 mug/L, 10 mug/L, 20 mug/L, 50 mug/L and 100 mug/L respectively, and the internal standard substance of atrazine-D is added into each mixed solution5Mixing the internal standard substance atrazine-D in the standard solution 5The concentrations of (A) and (B) were all 5. mu.g/L, and a matrix standard curve was established according to the method of example 1, steps 2 to 4;
2.3, Matrix Effect (ME) assessment:
using the formula ME ═ 1- (slope of substrate standard curve/slope of solvent standard curve)]100% of the total mass of the purified reagent, the results of the matrix effect of the method are shown in Table 8, Table 8 selects PSA and C for the purification reagents18The ME values of the respective substances are as follows:
TABLE 8 decontamination reagents PSA and C18ME value of time
3. The control group 2 was tested using EMR-Lipid as the decontamination reagent as follows:
3.1, taking a homogeneous blank grass carp muscle tissue sample, pretreating according to the method of the step 5 in the comparative example 1, and selecting 0.1g of EMR-Lipid as a purifying reagent to obtain a blank grass carp matrix extracting solution 3;
3.2, preparing 6 parts of mixed standard solution with gradient concentration by using the blank grass carp matrix extracting solution 3, wherein each part of mixed standard solution contains 11 triazine herbicides, the 11 triazine herbicides are simazine, diquat, simetryn, atrazine, terbuthylazine, prometryn, cyanazine, terbutryn and prometryn, the concentration of each triazine herbicide in each part of mixed standard solution is the same, the concentration of each triazine herbicide in 6 parts of mixed standard solution is 1.0 mu g/L, 5.0 mu g/L, 10 mu g/L, 20 mu g/L, 50 mu g/L and 100 mu g/L, and the internal standard substance atrazine-D is added into each part of mixed solution 5Each one of which is mixedCombining an internal standard substance atrazine-D in a standard solution5The concentrations of (A) and (B) were all 5. mu.g/L, and a matrix standard curve was established according to the method of example 1, steps 2 to 4;
3.3, Matrix Effect (ME) assessment:
the matrix effect of the method was examined using the formula ME ═ 1- (slope of matrix standard curve/slope of solvent standard curve) ] × 100%, and the results are shown in table 9, where table 9 selects the ME values for each substance when EMR-Lipid is used as the purification agent, as follows:
TABLE 9 ME value for EMR-Lipid as the decontamination reagent
A larger ME value indicates a more pronounced stromal effect, and a value of [ ME ] equal to or greater than 15% indicates the presence of a pronounced stromal effect. As can be seen by the test I, the purifying effects of the three groups of purifying reagents are obviously different, and PSA + C is used18Or EMR-Lipid purification, the | ME | of part of target herbicides is more than 15%, obvious matrix effect exists, which indicates that the purification effect is not ideal, and impurities such as fat in aquatic products interfere the analysis result, and PSA and C are adopted18And EMR-Lipid, all target herbicides | ME | are less than 15%, indicating that PSA, C are used18And the mixture of EMR-Lipid is used as a purifying agent, so that the purifying effect is optimal, the matrix effect caused by different aquatic product matrixes can be effectively eliminated, and the accuracy of the result is improved.
Claims (5)
1. A method for determining triazine herbicide residue in aquatic products by ultra-high performance liquid chromatography-tandem mass spectrometry is characterized by comprising the following steps
1.1, preparing a mixed standard solution:
preparing N parts of mixed standard solutions with gradient concentration, wherein the triazine herbicides in each part of mixed standard solution are the same in type, the triazine herbicides in each part of mixed standard solution are the same in concentration, and the internal standard atrazine-D is contained in each part of mixed solution5Mixing the internal standard substance atrazine-D in the standard solution5The concentrations of (A) were the same, and the internal standard substance atrazine-D5In the gradient concentration range of each triazine herbicide;
1.2, UPLC analysis and detection:
and (3) respectively carrying out UPLC analysis and detection on each mixed standard solution, wherein the UPLC conditions are as follows:
the chromatographic column adopts C18A chromatographic column, wherein a mobile phase adopts a mixed solution of an organic phase and a water phase, the organic phase is acetonitrile, the water phase is 0.1 wt% formic acid solution, the flow rate of the mobile phase is 0.3-0.4mL/min, and the mobile phase is eluted by adopting a gradient elution mode;
1.3, HESI-MS/MS analysis and detection:
the detection conditions of the HESI-MS/MS analysis are as follows:
the ion source is a heating atmospheric pressure electric spray source, positive ion mode scanning is carried out, a reaction monitoring mode is selected for determination, the spray voltage is 3000-: the purity of argon is more than or equal to 99.999, 2.0mTorr, the half-peak width of Q1 is 0.7, and the half-peak width of Q3 is 0.7;
After HESI-MS/MS analysis and detection, the peak area of the sub-ion of each triazine herbicide and the internal standard atrazine-D under each concentration can be obtained5The ratio of the peak areas of the daughter ions;
1.4, establishing a standard curve:
taking the concentration of each triazine herbicide as an abscissa, and taking the peak area of the daughter ion of each triazine herbicide and an internal standard atrazine-D under each concentration5The ratio of the peak areas of the daughter ions is a vertical coordinate, drawing is carried out according to the data detected by each triazine herbicide, and a standard curve of each triazine herbicide is obtained after fitting, so that a function relation formula of the standard curve of each triazine herbicide is obtained;
1.5, pretreatment of aquatic product samples:
taking homogeneous muscle sample of aquatic animal, adding atrazine-D as internal standard substance5Adding acetonitrile, sodium chloride and anhydrous magnesium sulfate in sequence, vortex oscillating, centrifuging, collecting supernatant, repeatedly extracting and mixing the supernatants, evaporating the supernatant to dryness, and collecting residueDissolving by using a solvent, adding a purifying agent, wherein the purifying agent is a mixture of ethylenediamine-N-propyl silane, octadecylsilane bonded silica gel and EMR-Lipid powder, performing vortex oscillation and centrifugation, and filtering the obtained supernatant by using a microporous filter membrane to obtain a sample to be detected;
1.6, detection of a sample to be detected:
analyzing and detecting the sample to be detected according to the method of the step 1.2-1.3 to obtain the peak area of the sub-ion of each triazine herbicide and the internal standard atrazine-D5The ratio of the peak area of the daughter ion is obtained by mixing the peak area of the daughter ion of each triazine herbicide with the peak area of the internal standard substance atrazine-D5Substituting the ratio of the ionic peak areas into the functional relation of the standard curve of the corresponding triazine herbicide to obtain the concentration of the corresponding triazine herbicide.
2. The method for determining triazine herbicide residue in aquatic products by ultra-high performance liquid chromatography-tandem mass spectrometry as claimed in claim 1, wherein the method comprises the following steps: the chromatographic column has a column length of 100mm, an inner diameter of 2.1mm, a packed particle size of 1.7 μm and a column temperature of 30 ℃.
3. The method for determining triazine herbicide residue in aquatic products by ultra high performance liquid chromatography-tandem mass spectrometry as claimed in claim 1, wherein the gradient elution conditions are as follows:
the first stage is as follows: the elution time is 0-2min, wherein the volume percentage of the organic phase is 15-25%, and the volume percentage of the water phase is 75-85%;
and a second stage: the elution time is 3-5min, wherein the volume percentage of the organic phase is gradually increased from 15-25% to 90-95%, and the volume percentage of the aqueous phase is gradually decreased from 75-85% to 5-10%;
And a third stage: the elution time is 2-3min, wherein the volume percentage of the organic phase is 90-95%, and the volume percentage of the water phase is 5-10%;
a fourth stage: the elution time is 0.1-0.5min, wherein the volume percentage of the organic phase is gradually reduced from 90-95% to 15-25%, and the volume percentage of the aqueous phase is gradually increased from 5-10% to 75-85%;
the fifth stage: the elution time is 1.5-4min, wherein the volume percentage of the organic phase is 15-25%, and the volume percentage of the water phase is 75-85%.
4. The method for determining triazine herbicide residue in aquatic products by ultra-high performance liquid chromatography-tandem mass spectrometry as claimed in claim 1, wherein the method comprises the following steps: in step 1.5, the solvent is methanol or acetonitrile.
5. The method for determining triazine herbicide residue in aquatic products by ultra-high performance liquid chromatography-tandem mass spectrometry as claimed in claim 1, wherein the method comprises the following steps: the microporous filter membrane is an organic microporous filter membrane, and the pore diameter of the microporous filter membrane is not more than 0.22 mu m.
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Application publication date: 20201030 Assignee: Xiantao Natural Source Ecological Breeding Professional Cooperative Assignor: YANGTZE RIVER FISHERIES Research Institute CHINESE ACADEMY OF FISHERY SCIENCES Contract record no.: X2024980011753 Denomination of invention: A method for determining triazine herbicide residues in aquatic products using ultra-high performance liquid chromatography tandem mass spectrometry Granted publication date: 20220923 License type: Common License Record date: 20240812 |