CN111896654B - Method for analyzing acetochlor in ginger and metabolites EMA and HEMA thereof - Google Patents
Method for analyzing acetochlor in ginger and metabolites EMA and HEMA thereof Download PDFInfo
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Abstract
The invention discloses an analysis method of acetochlor in ginger and metabolites EMA and HEMA thereof, which adopts a high performance liquid chromatography-mass spectrometry combined method for detection, and verifies the effectiveness and accuracy of the method by adding a recovery test. The adding concentration range of the three medicines in the ginger is set to be 0.01-1 mg/kg, the recovery rate of the acetochlor is 70-81 percent, and the RSD is 3.0-4.8 percent; the recovery rate of EMA is 84-94%, and the RSD is 3.1-7.9%; the recovery rate of HEMA is 84-92%, and RSD is 0.8-2.3%. Provides a reliable detection method for researching the metabolism of acetochlor in ginger applied with acetochlor, and simultaneously increases a new mode for detecting the residual quantity of the acetochlor in crops.
Description
Technical Field
The invention relates to the technical field of pesticide residue detection, in particular to an analysis method of acetochlor in ginger and metabolites EMA and HEMA thereof.
Background
The chemical name of acetochlor is 2-ethyl-6-methyl-N-ethoxymethyl-alpha-chloroacetanilide, which is a widely applied selective preemergence herbicide, and the selective preemergence herbicide mainly inhibits the growth of cells by inhibiting protein synthesis, so that the growth of weed buds and roots is stopped, and the weeding effect is further achieved. Based on the good weeding effect of acetochlor, the herbicide is widely applied to the control of various farmland weeds. Acetochlor can generate metabolites EMA (2-methyl-6-ethyl aniline) and HEMA (1- (2-amino-3-methylphenyl) ethane-1-alcohol) in plant cells, and the 2 metabolites have strong toxicity and can bring great hidden danger to the safety of agricultural products and food.
The existing detection method of the acetochlor is only a gas chromatography and gas chromatography-mass spectrometry combined method, and both detection methods have limitations and cannot quickly, conveniently and accurately detect the residual amount of the acetochlor. Also, there is no detection method for EMA and HEMA, which are metabolites of acetochlor, and there is no method for detecting 3 substances by using a liquid chromatography-mass spectrometry combined method.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides an analysis method of acetochlor and its metabolites EMA and HEMA in ginger, and the method can simultaneously, simply, quickly and accurately detect the acetochlor and its metabolites EMA and HEMA in ginger matrix.
The invention provides an analysis method of acetochlor in ginger and metabolites EMA and HEMA thereof, which adopts a high performance liquid chromatography-mass spectrometry combined method for detection, wherein the conditions of the high performance liquid chromatography are as follows: the chromatographic column is a Shim-pack XR-ODS II chromatographic column, the mobile phase A is formic acid aqueous solution with the volume fraction of 0.1 percent, the mobile phase B is acetonitrile, the flow rate is 0.3mL/min, gradient elution is carried out,
the gradient elution procedure was: within 0-1.0min, the proportion of the mobile phase A is 70 percent, and the proportion of the mobile phase B is 30 percent; within 1.0-3.0min, the proportion of the mobile phase A is gradually changed from 70% to 5%; the proportion of the mobile phase A is maintained at 5 percent within 3.0-4.0 min; within 4.0-4.01min, the proportion of the mobile phase A is gradually changed from 5% to 70%; the proportion of the mobile phase A is maintained at 70 percent within 4.01-6.0 min;
the mass spectrum conditions are as follows: the ion source is an electrospray ion source under atmospheric pressure, a positive ion mode and a triple quadrupole mass analyzer, the interface voltage is 4.5kv, the DL tube temperature is 250 ℃, the heating block temperature is 400 ℃, the atomization gas flow is 3L/min, the drying gas flow is 15L/min, and the collision gas is argon; the monitoring mode is a multi-reaction monitoring mode.
Preferably, the multiple reaction monitoring conditions for acetochlor are: the mass-to-charge ratio of the qualitative ion pair is 270.20>133.15, 270.20>148.20, 270.20>224.20, and the mass-to-charge ratio of the quantitative ion pair is 270.20>224.20; wherein, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 270.20> -133.15 are-29V, -34 and-25V respectively, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 270.20> -148.20 are-13V, -18 and-14V respectively, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 270.20> -224.20 are-28V, -11 and-14V respectively, and the residence time is 35msec respectively.
The symbol ">" in the above-described ion pair is a symbol commonly used by those skilled in the art to represent the ion pair.
The Q1pre deviation voltage, the collision voltage CE, and the Q3pre deviation voltage are specific expressions of the liquid chromatography-mass spectrometer of shimadzu corporation, japan.
Preferably, the multiple reaction monitoring conditions of EMA are: the mass-to-charge ratios of the qualitative ion pairs are 135.90>, 91.15, 135.90>, 108.10 and 135.90>, 117.10, and the mass-to-charge ratios of the quantitative ion pairs are 135.90>, 91.15; wherein, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 135.90>91.15 are-29V, -22 and-15V respectively, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 135.90>108.10 are-30V, -18 and-18V respectively, and the residence time of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 135.90>117.10 are-29V, -20 and-21V respectively, are 35msec.
Preferably, the multiple reaction monitoring conditions for HEMA are: the mass-to-charge ratio of the qualitative ion pair is 152.15>91.10, 152.15>119.20 and 152.15>134.10, and the mass-to-charge ratio of the quantitative ion pair is 152.15> < 134.10; wherein, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 152.15>91.10 are-17V, -35 and-30V respectively, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 152.15>119.20 are-10V, -22 and-22V respectively, and the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 152.15>134.10 are-17V, -12 and-23V respectively, and the residence time is 35msec.
Preferably, the size of the Shim-pack XR-ODS II column is 2.0 mmi.d.times.75 mm.
Preferably, the column temperature is 35 ℃.
Preferably, the sample size is 1 μ L.
Preferably, the specific detection steps are: taking an acetochlor standard substance, an EMA standard substance and a HEMA standard substance, preparing series of standard working solutions with different concentrations by using a ginger blank matrix extracting solution, sampling and drawing a standard curve to obtain a linear regression equation, then taking a ginger extracting solution to be detected for sampling, and calculating the content of acetochlor and metabolites EMA and HEMA thereof in ginger through the linear regression equation.
Preferably, the ginger blank matrix is a ginger sample without acetochlor and its metabolites EMA, HEMA.
Preferably, the preparation method of the ginger blank matrix extracting solution is the same as that of the ginger extracting solution to be detected, and the preparation method comprises the following steps: weighing 2.000g of crushed and uniformly mixed ginger to be detected, uniformly mixing the crushed and uniformly mixed ginger with 10mL of acetonitrile in a vortex manner, carrying out ultrasonic treatment for 10min, then adding 1-2 g of sodium chloride, uniformly mixing the mixture in a vortex manner, centrifuging the mixture, transferring 1-2 mL of supernatant, uniformly mixing the supernatant with 50mg of N-propyl ethylenediamine, 50mg of octadecylsilane chemically bonded silica gel and 100mg of anhydrous magnesium sulfate in a vortex manner, standing the mixture, taking the supernatant, and filtering the supernatant through a 0.22 mu m organic filter membrane.
To demonstrate the effectiveness of the validation method, acetochlor, EMA and HEMA addition recovery tests in ginger were performed for this purpose, with the following results:
when the adding concentration of the acetochlor on the ginger is 0.01-1 mg/kg, the recovery rate is 70-81%, and the RSD is 3.0-4.8%; when the addition concentration of EMA on ginger is 0.01-1 mg/kg, the recovery rate is 84-94%, and the RSD is 3.1-7.9%; when the addition concentration of HEMA on the ginger is 0.01-1 mg/kg, the recovery rate is 84-92%, and the RSD is 0.8-2.3%; the recovery rate and the relative standard deviation meet the requirements of NY/T788-2018.
The minimum detection amount of acetochlor and metabolites EMA and HEMA thereof in ginger is 2pg, the limit of quantitation is 0.01mg/kg, and the limit of quantitation can also meet the requirement of the maximum residue limit at home and abroad (GB 2763-2019 specifies that the maximum residue limit of acetochlor in ginger is 0.05 mg/kg).
Has the beneficial effects that:
the invention uses LC-MS/MS (high performance liquid chromatography-mass spectrometry) analysis technology, finds out the instrument data acquisition conditions which are not mutually influenced according to the properties of the compounds, and simultaneously detects acetochlor, EMA and HEMA; simultaneously determining the nature of the substance to be detected through retention time and ion abundance ratio; the preparation method of the ginger solution to be detected is changed, and the proper extraction reagent (acetonitrile), extraction reagent (sodium chloride) and purification reagent (N-propylethylenediamine, octadecylsilane chemically bonded silica gel and anhydrous magnesium sulfate) are selected, so that the pretreatment time of the ginger to be detected is shortened, the detection conditions of an instrument are researched and optimized, the sensitivity and resolution of the instrument are improved to solve the problem of impurity interference caused by complex ginger matrix, and meanwhile, a new mode is added for detecting the residual quantity of acetochlor and metabolites thereof in crops, and the method is a convenient and efficient detection method.
Drawings
FIG. 1 is a standard curve of acetochlor in a standard working solution of example 1.
FIG. 2 is a standard curve of EMA in a standard working solution of example 1.
FIG. 3 is a standard curve of HEMA in a standard working solution of example 1.
FIG. 4 is an extracted ion current chromatogram of an air-white solvent in example 1.
FIG. 5 is an extracted ion current chromatogram of the ginger blank matrix extract in example 1.
FIG. 6 is an extracted ion current chromatogram of acetochlor, EMA and HEMA in the standard working solution of example 1.
Fig. 7 is an extracted ion current chromatogram of the ginger extract to be tested in example 1.
FIG. 8 is an extracted ion current chromatogram of an extract liquid of sample A in example 2.
FIG. 9 is an extracted ion current chromatogram of an extract solution of sample B in example 2.
FIG. 10 is an extracted ion current chromatogram of an extract liquid of sample C in example 2.
FIG. 11 is an extracted ion current chromatogram of an extract liquid of sample D in example 2.
FIG. 12 is an extracted ion current chromatogram of an extract solution of sample E in example 2.
FIG. 13 is an extracted ion current chromatogram of an extract solution of sample F in example 2.
Detailed Description
The technical means of the present invention will be described in detail below with reference to specific examples.
The main apparatus comprises:
liquid chromatography-mass spectrometer (LCMS-8040), shimadzu corporation, japan;
one in ten-thousandth electronic balance (AUW-220D), shimadzu corporation, japan;
vortex mixer (XH-D), shanghai Hano instruments, inc.;
water bath constant temperature oscillator (GY 2016-SW), manufactured by yoyo instruments ltd, japan;
centrifuge (TDZ 5-WS), hunan instruments laboratory Instrument development, inc.
The main reagents are as follows:
acetochlor standard substance (purity 99.6%); EMA standard substance (purity 99.3%); HEMA standard (99.5% pure); acetone (chromatographically pure); acetonitrile (chromatographically pure); sodium chloride (analytically pure); pure water (primary water); n-propylethylenediamine (40-60 μm); octadecylsilane bonded silica ((40-60 μm)) anhydrous magnesium sulfate (analytical grade).
Example 1
A method for analyzing acetochlor and metabolites EMA and HEMA thereof in ginger adopts a liquid chromatography tandem mass spectrometer LCMS-8050 for detection by Shimadzu corporation in Japan, wherein the conditions of high performance liquid chromatography are as follows: the chromatographic column is a Shim-pack XR-ODS II chromatographic column (2.0 mmi.d is multiplied by 75 mm), the mobile phase A is formic acid aqueous solution with the volume fraction of 0.1 percent, the mobile phase B is acetonitrile, the flow rate is 0.3mL/min, the column temperature is 35 ℃, the sample injection amount is 1 mu L, gradient elution is carried out,
the gradient elution procedure was: within 0-1.0min, the proportion of the mobile phase A is 70 percent, and the proportion of the mobile phase B is 30 percent; the proportion of the mobile phase A is gradually changed from 70% to 5% within 1.0-3.0 min; the proportion of the mobile phase A is maintained at 5 percent within 3.0-4.0 min; within 4.0-4.01min, the proportion of the mobile phase A is gradually changed from 5% to 70%; the proportion of the mobile phase A is maintained at 70 percent within 4.01-6.0 min;
the mass spectrum conditions are as follows: the ion source is an electrospray ion source under atmospheric pressure, a positive ion mode and a triple quadrupole mass analyzer, the interface voltage is 4.5kv, the DL tube temperature is 250 ℃, the heating block temperature is 400 ℃, the atomization gas flow is 3L/min, the drying gas flow is 15L/min, and the collision gas is argon; the monitoring mode is a multi-reaction monitoring mode;
the multiple reaction monitoring conditions for acetochlor, EMA, HEMA are shown in table 1:
TABLE 1 multiple reaction monitoring conditions for acetochlor, EMA, HEMA
Note: plus ". Sup." indicates the quantitative ion.
Solution preparation:
blank solution: and (3) acetonitrile.
The pretreatment process of the blank matrix of the ginger is the same as that of the ginger to be detected.
Sample preparation: taking blank ginger or ginger to be detected, cutting the blank ginger or the ginger to be detected into small blocks by a stainless steel cutter, uniformly mixing the small blocks in a stainless steel basin, dividing the small blocks by a quartering method, uniformly crushing the divided samples by a crusher, sealing and storing the crushed samples, and making marks for later use.
Extracting the ginger blank matrix: precisely weighing 2.004g of crushed and uniformly mixed ginger blank matrix into a 50mL centrifuge tube, adding 10mL acetonitrile, uniformly mixing by vortex, carrying out ultrasonic extraction for 10min, then adding 2g of sodium chloride, carrying out vortex for 1min, centrifuging for 3min at 4000r/min, precisely transferring 1.5mL of supernatant into the centrifuge tube filled with 50mg of N-propyl ethylenediamine, 50mg of octadecylsilane chemically bonded silica gel and 100mg of anhydrous magnesium sulfate, carrying out vortex for 1min, standing for 3min, taking the supernatant, and filtering through a 0.22 mu m organic filter membrane to obtain the ginger blank matrix extracting solution.
The ginger extract to be detected: precisely weighing 2.005g of crushed and uniformly mixed ginger to be detected into a 50mL centrifuge tube, adding 10mL of acetonitrile, carrying out vortex mixing, carrying out ultrasonic extraction for 10min, then adding 2g of sodium chloride, carrying out vortex mixing for 1min, centrifuging for 3min at 4000r/min, precisely transferring 1.5mL of supernate into the centrifuge tube filled with 50mg of N-propylethylenediamine, 50mg of octadecylsilane bonded silica gel and 100mg of anhydrous magnesium sulfate, carrying out vortex mixing for 1min, standing for 3min, taking supernate, and filtering through an organic filter membrane of 0.22 mu m to obtain the ginger extracting solution to be detected.
Standard working solution: respectively weighing (to the accuracy of 0.00001 g) appropriate amounts of acetochlor standard substance, EMA standard substance and HEMA standard substance, respectively dissolving with chromatographic pure acetone, and sequentially preparing standard stock solutions with the concentration of 1000 mg/L; then precisely transferring appropriate amounts of 3 standard stock solutions into the same volumetric flask, diluting with the ginger blank matrix extract, and fixing the volume to prepare series of standard working solutions with different concentrations.
The operation method comprises the following steps: setting instrument parameters according to the chromatographic and mass spectrum conditions, editing a batch processing table after the instrument is stabilized, and sequentially collecting a reagent blank solvent, a ginger blank matrix extracting solution, a series of standard working solutions and a ginger extracting solution to be detected; analyzing the collected data, drawing a standard curve to obtain a linear regression equation, and calculating the content of acetochlor, EMA and HEMA in the ginger to be detected according to the linear regression equation by an external standard method.
FIG. 1 is a standard curve of the acetochlor standard substance in example 1, wherein the abscissa is the concentration X of the acetochlor standard substance, the ordinate is the peak area f (X) of the acetochlor standard substance, the linear regression equation obtained is f (X) =2516770x +10857.5 2 =0.9998833; the table on the right in FIG. 1 is the corresponding peak areas for different concentrations (mg/L) of acetochlor in the standard working solution.
FIG. 2 is a standard curve of the EMA standard substance in example 1, the abscissa is the concentration X of the EMA standard substance, the ordinate is the peak area Y of the EMA standard substance, the linear regression equation obtained is f (X) =4919950x +23079.7, R is 2 =0.9998459; the table on the right in FIG. 2 shows the peak areas corresponding to different concentrations (mg/L) of EMA in the standard working solution.
FIG. 3 is a standard curve of the HEMA standard substance in example 1, wherein the abscissa is the concentration X of the HEMA standard substance, the ordinate is the peak area Y of the HEMA standard substance, the linear regression equation obtained is f (X) =4144330x +33897.1 2 =0.9994565; the table on the right in FIG. 3 shows the peak areas corresponding to different concentrations (mg/L) of HEMA in the standard working solution.
According to the linear regression equation, the concentration C of acetochlor, EMA and HEMA in the ginger extracting solution to be detected can be calculated Test object Then, the residual quantity X of acetochlor, EMA and HEMA in the ginger to be detected is calculated according to the following formula Test object 。
The calculation formula of the residual quantity of acetochlor, EMA and HEMA in the ginger to be detected is as follows:
X test object ＝C Test object ×V 0 /m Ginger (fresh ginger)
In the formula:
X test object -the residual amount of test substance in ginger in mg/kg;
C test object -the concentration of the test substance in mg/L of ginger extract;
V 0 -the volume of extraction reagent added, L, when preparing ginger extract;
m ginger (fresh ginger) Weighing the mass, kg, of the ginger to be tested.
The content of acetochlor, EMA and HEMA in the ginger is respectively measured to be 0.036mg/kg, 0.045mg/kg and 0.044mg/kg.
Typical extracted ion flow chromatograms are shown in fig. 4-7.
FIG. 4 is an extracted ion current chromatogram of the white solvent in example 1.
FIG. 5 is an extracted ion current chromatogram of the ginger blank matrix extract in example 1.
FIG. 6 is an extracted ion current chromatogram of acetochlor, EMA and HEMA in the standard working solution of example 1, wherein the retention time of acetochlor is 4.402min, the retention time of EMA is 3.314min and the retention time of HEMA is 0.937min.
Fig. 7 is an extracted ion current chromatogram of the ginger extract to be tested in example 1, in which the retention time of acetochlor is 4.403min, the retention time of EMA is 3.307min, and the retention time of HEMA is 0.937min.
Example 2 recovery test
The residual amounts of acetochlor, EMA and HEMA in the samples were measured by adding samples of known concentrations according to the method and detection conditions of example 1, and the recovery rates were calculated.
The experimental process comprises the following steps:
weighing 6 parts of ginger blank matrix, weighing 2.000g of standard stock solutions (same as example 1) with the serial numbers of A, B, C, D, E and F in each part, respectively diluting the stock solutions to different concentrations, adding the stock solutions to the ginger blank matrix A, B, C, D, E and F, and uniformly mixing the stock solutions to ensure that the adding concentrations of acetochlor, EMA and HEMA in the A and B samples are 0.01mg/kg; C. the adding concentration of acetochlor, EMA and HEMA in the sample D is 0.05mg/kg; E. the adding concentrations of acetochlor, EMA and HEMA in the F sample are all 1.0mg/kg; then standing the sample for 2h;
the ginger extract to be tested was processed according to the method of the ginger extract to be tested in example 1 to obtain the extracts of samples a, B, C, D, E and F, respectively.
The blank solvent, ginger blank matrix extract and standard working solution were the same as in example 1.
The operation method comprises the following steps: setting instrument parameters according to the chromatographic and mass spectrum conditions, editing a batch processing table after an instrument is stabilized, and sequentially collecting a reagent blank solvent, a ginger blank matrix extracting solution, a series of standard working solutions and extracting solutions A, B, C, D, E and F; analyzing the collected data, drawing a standard curve to obtain a linear regression equation, calculating the content of acetochlor, EMA and HEMA in the samples A, B, C, D, E and F according to the linear regression equation by an external standard method, and calculating the recovery rate of the samples.
The sample recovery rate calculation formula is as follows:
in the formula: x is recovery (%); c 1 The detection value of the ginger blank matrix sample after pesticide is added is mg/kg; c 0 The concentration value of the actually added pesticide in the blank sample is mg/kg.
The results of the recovery calculation are shown in Table 2.
TABLE 2 calculated results of recovery
Typical extracted ion flow chromatograms are shown in fig. 8-13.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (10)
1. An analysis method of acetochlor in ginger and metabolites EMA and HEMA thereof is characterized in that a high performance liquid chromatography-mass spectrometry combined method is adopted for detection, wherein the conditions of the high performance liquid chromatography are as follows: the chromatographic column is a Shim-pack XR-ODS II chromatographic column, the mobile phase A is formic acid aqueous solution with the volume fraction of 0.1 percent, the mobile phase B is acetonitrile, the flow rate is 0.3mL/min, gradient elution is carried out,
the gradient elution procedure was: within 0-1.0min, the proportion of the mobile phase A is 70 percent, and the proportion of the mobile phase B is 30 percent; within 1.0-3.0min, the proportion of the mobile phase A is gradually changed from 70% to 5%; the proportion of the mobile phase A is maintained at 5 percent within 3.0-4.0 min; within 4.0-4.01min, the proportion of the mobile phase A is gradually changed from 5% to 70%; the proportion of the mobile phase A is maintained at 70 percent within 4.01-6.0 min;
the mass spectrum conditions are as follows: the ion source is an electrospray ion source under atmospheric pressure, a positive ion mode and a triple four-level rod mass analyzer, the interface voltage is 4.5kV, the temperature of a DL tube is 250 ℃, the temperature of a heating block is 400 ℃, the flow rate of atomized gas is 3L/min, the flow rate of dry gas is 15L/min, and collision gas is argon; the monitoring mode is a multi-reaction monitoring mode.
2. The method for analyzing the acetochlor and the metabolites EMA and HEMA of the ginger as claimed in claim 1, wherein the multiple reaction monitoring conditions of the acetochlor are as follows: the mass-to-charge ratio of the qualitative ion pair is 270.20>133.15, 270.20>148.20, 270.20>224.20, and the mass-to-charge ratio of the quantitative ion pair is 270.20>224.20; wherein, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 270.20> -133.15 are-29V, -34 and-25V respectively, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 270.20> -148.20 are-13V, -18 and-14V respectively, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 270.20> -224.20 are-28V, -11 and-14V respectively, and the residence time is 35msec respectively.
3. The method for analyzing EMA and HEMA in ginger, which are acetochlor and metabolites thereof, according to claim 1 or 2, wherein the multiple reaction monitoring conditions of EMA are as follows: the mass-to-charge ratios of the qualitative ion pairs are 135.90>, 91.15, 135.90>, 108.10 and 135.90>, 117.10, and the mass-to-charge ratios of the quantitative ion pairs are 135.90>, 91.15; wherein, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 135.90>91.15 are-29V, -22 and-15V respectively, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 135.90>108.10 are-30V, -18 and-18V respectively, and the residence time of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 135.90>117.10 are-29V, -20 and-21V respectively, are 35msec.
4. The method for analyzing the acetochlor and the metabolites EMA and HEMA of ginger as claimed in claim 1, wherein the multiple reaction monitoring conditions of HEMA are as follows: the mass-to-charge ratio of the qualitative ion pair is 152.15>91.10, 152.15>119.20 and 152.15>134.10, and the mass-to-charge ratio of the quantitative ion pair is 152.15> < 134.10; wherein, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 152.15>91.10 are-17V, -35 and-30V respectively, the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 152.15>119.20 are-10V, -22 and-22V respectively, and the deviation voltage of Q1pre, the deviation voltage of collision voltage CE and Q3pre corresponding to the ion pair 152.15>134.10 are-17V, -12 and-23V respectively, and the residence time is 35msec.
5. The method for analyzing EMA and HEMA of acetochlor and metabolites thereof in ginger as claimed in claim 1, wherein the size of a Shim-pack XR-ODS II chromatographic column is 2.0 mm.d x 75mm.
6. The method for analyzing the acetochlor and the metabolites EMA and HEMA of the ginger as claimed in claim 1, wherein the column temperature is 35 ℃.
7. The method for analyzing EMA and HEMA as acetochlor and metabolites thereof in ginger according to claim 1, wherein the sample amount is 1 μ L.
8. The method for analyzing the acetochlor and the metabolites EMA and HEMA of the ginger as claimed in claim 1, wherein the specific detection steps are as follows: taking an acetochlor standard substance, an EMA standard substance and a HEMA standard substance, preparing series of standard working solutions with different concentrations by using a ginger blank matrix extracting solution, sampling and drawing a standard curve to obtain a linear regression equation, then taking a ginger extracting solution to be detected for sampling, and calculating the content of acetochlor and metabolites EMA and HEMA thereof in ginger through the linear regression equation.
9. The method for analyzing acetochlor and its metabolites EMA and HEMA in ginger according to claim 8, wherein the ginger blank matrix is a ginger sample without acetochlor and its metabolites EMA and HEMA.
10. The method for analyzing the acetochlor and the metabolites EMA and HEMA thereof in the ginger according to claim 8, wherein the preparation method of the ginger blank matrix extracting solution is the same as the preparation method of the ginger extracting solution to be detected, and the methods are as follows: weighing 2.000g of crushed and uniformly mixed ginger to be detected, uniformly mixing the crushed and uniformly mixed ginger with 10mL of acetonitrile in a vortex manner, carrying out ultrasonic treatment for 10min, then adding 1-2 g of sodium chloride, uniformly mixing the mixture in a vortex manner, centrifuging the mixture, transferring 1-2 mL of supernatant, uniformly mixing the supernatant with 50mg of N-propyl ethylenediamine, 50mg of octadecylsilane chemically bonded silica gel and 100mg of anhydrous magnesium sulfate in a vortex manner, standing the mixture, taking the supernatant, and filtering the supernatant through a 0.22 mu m organic filter membrane.
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