CN107764923A - The assay method of 6 kinds of agricultural chemicals in spice - Google Patents
The assay method of 6 kinds of agricultural chemicals in spice Download PDFInfo
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- CN107764923A CN107764923A CN201610682273.8A CN201610682273A CN107764923A CN 107764923 A CN107764923 A CN 107764923A CN 201610682273 A CN201610682273 A CN 201610682273A CN 107764923 A CN107764923 A CN 107764923A
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- G—PHYSICS
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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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N30/14—Preparation by elimination of some components
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- G—PHYSICS
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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
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Abstract
The present invention discloses a kind of assay method of 6 kinds of agricultural chemicals in spice, the concentration of 6 kinds of agricultural chemical compounds in spice sample is detected simultaneously with ultra high efficiency liquid phase series connection level Four bar flight time mass spectrum, this method comprises the following steps：The agricultural chemicals of spice sample is extracted, obtains testing sample solution；Testing sample solution is measured with ultra high efficiency liquid phase series connection level Four bar flight time mass spectrum；Standard curve is made with standard sample of pesticide, contrast conting obtains the pesticide concentration in testing sample solution.The present invention can solve the problems such as detection method complex pretreatment of prior art, detection trace farm chemical ingredients difficulty.
Description
Technical field
The present invention relates to the detection method of 6 in spice sample kind residues of pesticides, and superelevation is based on more particularly, to one kind
The method that 6 clock agricultures are residual in spice is detected while imitating liquid phase series connection level Four bar time-of-flight mass spectrometry (TOFMS) (UPLC-Q-TOF).
Background technology
It would generally ensure the healthy growth of plant using some agricultural chemicals in the planting process of spice plant, and adopt
After receiving and being made spice product, often can still there are some residues of pesticides in the quality on product, influenceing product.Cause
How residues of pesticides in spice are fast and accurately detected by this, turn into that those skilled in the art are of interest to be asked
Topic.
In the prior art, the analysis method for agricultural chemicals is had good manners combination (GC-MS) and LC-MS (LC-MS/MS)
Method.Using the gas chromatography mass spectrometry detection compounds being applied to thermostabilization and high volatility, there is certain limitation more.Liquid matter
The multiple-reaction monitoring pattern of combination (LC-MS/MS) generally use needs to use standard items to optimize instrument parameter, to unknown phase pair
Molecular mass and the compound of dissociation pathways can not often detect.In addition, the trace residues of pesticides in detection sample, there is also color
The problems such as spectral condition optimization is difficult, sample pre-treatments complexity.
Therefore, a kind of assay method for spice Pesticide Residues how is designed, it is solved prior art
In the presence of the defects of, become those skilled in the art's urgent problem to be solved.
The content of the invention
It is an object of the invention to provide a kind of 6 in spice kind agricultural chemicals (Hostathion, pyridine worm narrow, Buprofezin, more bacterium
Spirit, carbofuran, imidacloprid) assay method, allow its solve the detection method complex pretreatment of prior art, detection trace
The problems such as farm chemical ingredients difficulty.
To achieve these goals, (Hostathion, pyridine worm narrow 6 kinds of agricultural chemicals in a kind of spice of present invention offer, thiazine
Ketone, carbendazim, carbofuran, imidacloprid) assay method, with ultra high efficiency liquid phase series connection level Four bar flight time mass spectrum simultaneously to perfume (or spice)
The concentration of 6 kinds of agricultural chemical compounds is detected in pungent material sample, and this method comprises the following steps：
1) take homogeneous spice sample to be fitted into centrifuge tube, add acetonitrile, acutely concussion, centrifuging and taking 1 the after supersound process
One supernatant, the first supernatant is added into dispersing solid purifying pipe, acutely concussion, centrifugation takes one second supernatant again, with filter membrane
The second supernatant is handled, obtains a testing sample solution；
2) liquid chromatogram and Mass Spectrometry Conditions, including molecular formula, retention time, parent ion, daughter ion parameter are set, by super
Efficient liquid phase series connection level Four bar flight time mass spectrum is measured to testing sample solution, and it is molten that testing sample is obtained after Integral Processing
6 kinds of agricultural chemical compound peak area numerical value in liquid；
3) 6 kinds of agricultural chemical compound standard items of gradient concentration are entered with the liquid chromatogram and Mass Spectrometry Conditions same with step 2)
Row measure, is made standard curve, is compared with the peak area numerical value obtained by step 2) with standard curve, is calculated and treats test sample
The concentration of 6 kinds of agricultural chemical compounds in product solution.
Wherein, in step 1), it is fitted into weigh 5-10g homogeneous spice samples in centrifuge tube with cover, adds 10-15ml
Acetonitrile, acutely shakes 0.5-1min, and 5-10min is centrifuged under 4000-8000r/min after being ultrasonically treated 10-20min, take this
One supernatant, first supernatant is added into dispersing solid purifying pipe, then acutely concussion 0.5-1min, in 4000-8000r/min
Lower centrifugation 5-10min, second supernatant is taken, second supernatant is handled with 0.22 μm of organic filter membrane, it is molten to obtain the testing sample
Liquid.
Wherein, in step 1), it is fitted into weigh 5g homogeneous spice samples in centrifuge tube with cover, adds 10ml acetonitriles,
Acutely concussion 1min, 5min is centrifuged under 6000r/min after being ultrasonically treated 20min, first supernatant is taken, by first supernatant
Liquid adds dispersing solid purifying pipe, then acutely concussion 1min, centrifuges 5min under 6000r/min, takes second supernatant, with
0.22 μm of organic filter membrane handles second supernatant, obtains the testing sample solution.
Wherein, in step 1), the dispersing solid purifying pipe in also comprising 50mg PSA, 50mg C18,7.5mg GCB and
150mg MgSO4。
Wherein, in step 2), liquid phase chromatogram condition is：
Chromatographic column Acclaim RSLC120 C18 (100mm x 2.1mm, 2.2 μm)；The μ L of sampling volume 2；25 DEG C of column temperature；
Mobile phase A is 0.01% formic acid+5mM ammonium formates+water/methanol, wherein, water/methanol=90:10；Mobile phase B is 0.01% formic acid
+ 5mM ammonium formates+methanol；Flow velocity 0.2mL/min；Liquid phase condition of gradient elution is：0-0.1min, 1%B；0.1-3min, 1%-
40%B；3.1-14min, 40%B-100%B；14.1-16min 100%B；16.1-20min stop.
Wherein, in step 2), set molecular formula, retention time, parent ion, daughter ion parameter are following (table 1)：
Table 1：Molecular formula, retention time, parent ion, the daughter ion parameter of 6 kinds of agricultural chemical compounds
Wherein, in step 2), Mass Spectrometry Conditions are：
First mass spectrometric, using ESI ion guns, positive ion mode；Voltage is set as 5kV；Nebulizer pressure 6psi；Dry gas
Flow velocity 4L/min；Dry 200 DEG C of temperature degree；Broadband collision induced dissociation can (BBCID) 10-30eV；Mass range 100-
1500m/z。
Wherein, in step 3), making standard curve is：
First respectively prepare 6 kinds of agricultural chemical compound standard items, then with 1ppb, 2ppb, 5ppb, 10ppb, 20ppb,
50ppb gradient concentration, and with step 2) identical liquid chromatogram and Mass Spectrometry Conditions respectively to 6 kinds of agricultural chemical compound standard items
It is measured, integration obtains the peak area of 6 kinds of agricultural chemical compound standard items of gradient concentration, and regression equation and correlation is calculated
Coefficient (table 2)；
Table 2：The method range of linearity, regression equation and coefficient correlation (X：Peak area；Y：Concentration)
Wherein, in step 3), by 6 kinds of agricultural chemical compound peak area numerical tapes in the testing sample solution obtained by step 2)
In the regression equation for entering the standard curve obtained by step 3), the concentration of 6 kinds of agricultural chemical compounds in testing sample solution is obtained.
With prior art effect ratio, the present invention has significant technological progress, and its concrete principle and advantage are described as follows：
Ultra high efficiency liquid phase series connection level Four bar time-of-flight mass spectrometry (TOFMS) (UPLC-Q-TOF) used in the present invention is a kind of new
Method, mass resolution and accurate mass number function by its superelevation solve the deficiencies in the prior art.Especially for
During multi-component screening analysis, the database based on accurate molecular weight can include considerable compound, can carry out quick
Screening.Liquid chromatogram high resolution mass spectrum is typically by high performance liquid chromatography (HPLC) or ultrahigh pressure liquid phase chromatogram and high resolution mass spectrum string
Connection forms.High resolution mass spectrum can determine compound accurate molecular weight, pass through one-level, two by the mass resolution of its superelevation
The screening in level spectrum storehouse is screened and confirmatory analysis with matching to the trace components in complex matrices.By the mass resolution of superelevation
Rate, high resolution mass spectrum can distinguish impurity and common effluent in complex background, trace analysis be carried out, so as to reduce to sample
The requirement of pre-treatment, the situation difficult especially suitable for chromatographic condition optimization.European Union has issued 2002/657EC instructions within 2002
Mass-spectrometric technique is classified as to one of main confirmation technology, the analysis residual to agriculture can be realized accordingly.
Compared with the residual detection method of existing agriculture, use ultra high efficiency liquid phase of the invention series connection quadrupole rod flight time mass spectrum
Method that is residual to 6 kinds of agricultures in spice while being measured, use the extracting method (QuEChERS) of optimization and the color of optimization
Spectrum, Mass Spectrometry Conditions so that method pre-treatment of the invention is simple, analysis time is short, testing cost is low, and selective good, clever
Sensitivity is high, high resolution, and detection accuracy and detection efficiency all obtain great lifting.
Below in conjunction with the drawings and specific embodiments, the present invention will be described in detail, but not as a limitation of the invention.
Brief description of the drawings
The EIC figures that Fig. 1 is the UPLC-Q-TOF of 6 kinds of agricultural chemical compound standard items；
Fig. 2 a are the parent ion and daughter ion mass spectrum figure of imidacloprid；
Fig. 2 b are the parent ion and daughter ion mass spectrum figure that pyridine worm narrows；
Fig. 2 c are the parent ion and daughter ion mass spectrum figure of carbofuran；
Fig. 2 d are the parent ion and daughter ion mass spectrum figure of Hostathion；
Fig. 2 e are the parent ion and daughter ion mass spectrum figure of Buprofezin；
Fig. 2 f are the parent ion and daughter ion mass spectrum figure of carbendazim.
Wherein, reference：
1：Imidacloprid
2：Pyridine worm narrows
3：Carbendazim
4：Carbofuran
5：Hostathion
6：Buprofezin
Embodiment
For the technical characterstic of the present invention can be demonstrated, to allow those skilled in the art to be apparent from the present invention's
Structure, feature, occupation mode and technique effect, below by embodiment, and with reference to accompanying drawing, the solution of the present invention is entered
Row illustrates.But as described below is only to illustrate to be used, and is not intended as the limitation of the present invention.
To solve the problems such as detection method complex pretreatment of prior art, detection trace farm chemical ingredients difficulty, the present invention
A kind of measure side of 6 in spice kinds of agricultural chemicals (Hostathion, pyridine worm narrow, Buprofezin, carbendazim, carbofuran, imidacloprid) is provided
Method, the concentration of 6 kinds of agricultural chemical compounds in spice sample is entered simultaneously with ultra high efficiency liquid phase series connection level Four bar flight time mass spectrum
Row detection, this method comprise the following steps：
1) take homogeneous spice sample to be fitted into centrifuge tube, add acetonitrile, acutely concussion, centrifuging and taking 1 the after supersound process
One supernatant, the first supernatant is added into dispersing solid purifying pipe, acutely concussion, centrifugation takes one second supernatant again, with filter membrane
The second supernatant is handled, obtains a testing sample solution；
2) liquid chromatogram and Mass Spectrometry Conditions, including molecular formula, retention time, parent ion, daughter ion parameter are set, by super
Efficient liquid phase series connection level Four bar flight time mass spectrum is measured to testing sample solution, and it is molten that testing sample is obtained after Integral Processing
6 kinds of agricultural chemical compound peak area numerical value in liquid；
3) 6 kinds of agricultural chemical compound standard items of gradient concentration are entered with the liquid chromatogram and Mass Spectrometry Conditions same with step 2)
Row measure, is made standard curve, is compared with the peak area numerical value obtained by step 2) with standard curve, is calculated and treats test sample
The concentration of 6 kinds of agricultural chemical compounds in product solution.
In step 1), it is fitted into weigh 5-10g homogeneous spice samples in centrifuge tube with cover, adds 10-15ml acetonitriles,
Acutely concussion 0.5-1min, 5-10min is centrifuged under 4000-8000r/min after being ultrasonically treated 10-20min, takes first supernatant
Liquid, first supernatant is added into dispersing solid purifying pipe, then acutely concussion 0.5-1min, centrifuged under 4000-8000r/min
5-10min, second supernatant is taken, second supernatant is handled with 0.22 μm of organic filter membrane, obtains the testing sample solution.This point
Dissipate in Purify pipe also comprising 50mg PSA, 50mg C18,7.5mg GCB and 150mg MgSO4。
Preferably, in step 1), it is fitted into weigh 5g homogeneous spice samples in centrifuge tube with cover, adds 10ml second
Nitrile, acutely shakes 1min, centrifuges 5min under 6000r/min after being ultrasonically treated 20min, takes first supernatant, by this first
Supernatant adds dispersing solid purifying pipe, then acutely concussion 1min, centrifuges 5min under 6000r/min, takes second supernatant,
Second supernatant is handled with 0.22 μm of organic filter membrane, obtains the testing sample solution.
In step 2), liquid phase chromatogram condition is：
Chromatographic column Acclaim RSLC120 C18 (100mm x 2.1mm, 2.2 μm)；The μ L of sampling volume 2；25 DEG C of column temperature；
Mobile phase A is 0.01% formic acid+5mM ammonium formates+water/methanol, wherein, water/methanol=90:10；Mobile phase B is 0.01% formic acid
+ 5mM ammonium formates+methanol；Flow velocity 0.2mL/min；Liquid phase condition of gradient elution is：0-0.1min, 1%B；0.1-3min, 1%-
40%B；3.1-14min, 40%B-100%B；14.1-16min 100%B；16.1-20min stop.
Mass Spectrometry Conditions are：
First mass spectrometric, using ESI ion guns, positive ion mode；Voltage is set as 5kV；Nebulizer pressure 6psi；Dry gas
Flow velocity 4L/min；Dry 200 DEG C of temperature degree；Broadband collision induced dissociation can (BBCID) 10-30eV；Mass range 100-
1500m/z。
In addition, in step 2), set molecular formula, retention time, parent ion, daughter ion parameter are following (table 1)：
Table 1：Molecular formula, retention time, parent ion, the daughter ion parameter of 6 kinds of agricultural chemical compounds
In step 3), making standard curve is：
First respectively prepare 6 kinds of agricultural chemical compound standard items (standard concentration of method for building up is 10mg/mL), then with
1ppb, 2ppb, 5ppb, 10ppb, 20ppb, 50ppb gradient concentration, and with step 2) identical liquid chromatogram and mass spectrum bar
Part is measured to 6 kinds of agricultural chemical compound standard items respectively, and integration obtains the peak of 6 kinds of agricultural chemical compound standard items of gradient concentration
Area, regression equation and coefficient correlation (table 2) is calculated；
Table 2：The method range of linearity, regression equation and coefficient correlation (X：Peak area；Y：Concentration)
It refer to Fig. 1-Fig. 2 f.The EIC figures that Fig. 1 is the UPLC-Q-TOF of 6 kinds of agricultural chemical compound standard items；Fig. 2 a- Fig. 2 f
Parent ion and daughter ion mass spectrum figure for each agricultural chemical compound.
After making standard curve, by 6 kinds of agricultural chemical compound peak area numerical tapes in the testing sample solution obtained by step 2)
In the regression equation for entering the standard curve obtained by step 3), the concentration of 6 kinds of agricultural chemical compounds in testing sample solution is obtained.
Embodiment 1：
The present embodiment is for testing the residual detection detected of the agriculture in Hebei, two kinds of Henan area chilli powder.Should
With ultra high efficiency liquid phase series connection quadrupole rod time-of-flight mass spectrometry (TOFMS) (UPLC-Q-TOF) of the invention while detect 6 clock agriculture in spice
It is residual, according to following steps：
(1) to the extraction of agricultural chemicals to be measured in spice：
Weigh 5g homogeneous chilli powders to be fitted into 50ml centrifuge tube with cover, add 10ml acetonitriles, acutely shake 1min, ultrasound carries
20min is taken, 4000r/min centrifugation 5min, takes supernatant 1ml to add dispersing solid purifying pipe, acutely shakes 1min, 4000r/
Min centrifuges 5min.Take supernatant to cross 0.22 μm of organic filter membrane, be transferred to sample introduction in 1.5ml sample injection bottles and analyze.
(2) it is residual using liquid chromatogram high resolution mass spectrum measure spice middle peasant：
Sample solution enters in the case where the ultra performance liquid chromatography of setting connects the liquid phase chromatogram condition of quadrupole flight time mass spectrum
Sample is analyzed.
The liquid chromatogram parameter set in method is as follows：
Chromatographic column：Acclaim RSLC120 C18(100mm x 2.1mm,2.2μm)；Sample introduction concentration 10mg/ml；Sample introduction
The μ L of volume 2；25 DEG C of column temperature；Mobile phase A is 0.01% formic acid+5mM ammonium formates+water/methanol (90:10)；Mobile phase B is 0.01%
Formic acid+5mM ammonium formates+methanol；Flow velocity 0.2mL/min；LC condition of gradient elution is：0-0.1min, 1%B；0.1-3min,
1%-40%B；3.1-14min, 40%B-100%B；14.1-16min 100%B；16.1-20min 1%, stop.
The Mass Spectrometry Conditions parameter set in method is as follows：
First mass spectrometric, using ESI ion guns, positive ion mode；Voltage is set as 5kV；Nebulizer pressure 6psi；Dry gas
Flow velocity 4L/min；Dry 200 DEG C of temperature degree；Broadband collision induced dissociation can (BBCID) 10-30eV；Mass range：100-
1500m/z。
(referring to table 1) under the molecular formula of setting, retention time, parent ion, daughter ion Parameter Conditions, to given 6 kinds
Compound carries out Integral Processing, obtains the peak area numerical value of each compound, according to the standard curve of table 2, calculates concentration.
It is residual to the agriculture in Hebei, Henan area chilli powder to detect using this method, the residual content of measurement result, i.e. agriculture
Average data be shown in Table 3.
Table 3 chilli powder, 6 kinds of Pesticides Testing results
With prior art effect ratio, the present invention has significant technological progress, and its concrete principle and advantage are described as follows：
Ultra high efficiency liquid phase series connection level Four bar time-of-flight mass spectrometry (TOFMS) (UPLC-Q-TOF) used in the present invention is a kind of new
Method, mass resolution and accurate mass number function by its superelevation solve the deficiencies in the prior art.Especially for
During multi-component screening analysis, the database based on accurate molecular weight can include considerable compound, can carry out quick
Screening.Liquid chromatogram high resolution mass spectrum is typically by high performance liquid chromatography (HPLC) or ultrahigh pressure liquid phase chromatogram and high resolution mass spectrum string
Connection forms.High resolution mass spectrum can determine compound accurate molecular weight, pass through one-level, two by the mass resolution of its superelevation
The screening in level spectrum storehouse is screened and confirmatory analysis with matching to the trace components in complex matrices.By the mass resolution of superelevation
Rate, high resolution mass spectrum can distinguish impurity and common effluent in complex background, trace analysis be carried out, so as to reduce to sample
The requirement of pre-treatment, the situation difficult especially suitable for chromatographic condition optimization.European Union has issued 2002/657EC instructions within 2002
Mass-spectrometric technique is classified as to one of main confirmation technology, the analysis residual to agriculture can be realized accordingly.
Compared with the residual detection method of existing agriculture, use ultra high efficiency liquid phase of the invention series connection quadrupole rod flight time mass spectrum
Method that is residual to 6 kinds of agricultures in spice while being measured, use the extracting method (QuEChERS) of optimization and the color of optimization
Spectrum, Mass Spectrometry Conditions so that method pre-treatment of the invention is simple, analysis time is short, testing cost is low, and selective good, clever
Sensitivity is high, high resolution, and detection accuracy and detection efficiency all obtain great lifting.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. the assay method of 6 kinds of agricultural chemicals in a kind of spice, it is characterised in that during with the series connection level Four bar flight of ultra high efficiency liquid phase
Between mass spectrum the concentration of 6 kinds of agricultural chemical compounds in spice sample is detected simultaneously, this method comprises the following steps：
1) take homogeneous spice sample to be fitted into centrifuge tube, add acetonitrile, acutely concussion, after supersound process in centrifuging and taking one first
Clear liquid, the first supernatant is added into dispersing solid purifying pipe, acutely concussion, centrifugation is taken one second supernatant, handled with filter membrane again
Second supernatant, obtain a testing sample solution；
2) liquid chromatogram and Mass Spectrometry Conditions, including molecular formula, retention time, parent ion, daughter ion parameter are set, passes through ultra high efficiency
Liquid phase series connection level Four bar flight time mass spectrum is measured to testing sample solution, is obtained after Integral Processing in testing sample solution
6 kinds of agricultural chemical compound peak area numerical value；
3) 6 kinds of agricultural chemical compound standard items of gradient concentration are surveyed with the liquid chromatogram and Mass Spectrometry Conditions same with step 2)
It is fixed, standard curve is made, is compared with the peak area numerical value obtained by step 2) with standard curve, it is molten that testing sample is calculated
The concentration of 6 kinds of agricultural chemical compounds in liquid.
2. the assay method of 6 kinds of agricultural chemicals in spice according to claim 1, it is characterised in that in step 1), be
Weigh 5-10g homogeneous spice samples to be fitted into centrifuge tube with cover, add 10-15ml acetonitriles, acutely shake 0.5-1min, ultrasound
5-10min is centrifuged under 4000-8000r/min after processing 10-20min, takes first supernatant, first supernatant is added
Dispersing solid purifying pipe, then acutely concussion 0.5-1min, centrifuge 5-10min under 4000-8000r/min, take second supernatant
Liquid, second supernatant is handled with 0.22 μm of organic filter membrane, obtains the testing sample solution.
3. the assay method of 6 kinds of agricultural chemicals in spice according to claim 1, it is characterised in that in step 1), be
Weigh 5g homogeneous spice samples to be fitted into centrifuge tube with cover, add 10ml acetonitriles, acutely shake 1min, be ultrasonically treated 20min
5min is centrifuged under 6000r/min afterwards, takes first supernatant, first supernatant is added into dispersing solid purifying pipe, then it is acute
Violent shock swings 1min, and 5min is centrifuged under 6000r/min, takes second supernatant, and this is handled on second with 0.22 μm of organic filter membrane
Clear liquid, obtain the testing sample solution.
4. the assay method of 6 kinds of agricultural chemicals in the spice according to any one of claim 1-3, it is characterised in that in
In step 1), also comprising 50mg PSA, 50mg C18,7.5mg GCB and 150mg MgSO in dispersing solid purifying pipe4。
5. the assay method of 6 kinds of agricultural chemicals in spice according to claim 1, it is characterised in that in step 2), liquid
Phase chromatographic condition is：
Chromatographic column Acclaim RSLC120 C18；The μ L of sampling volume 2；25 DEG C of column temperature；Mobile phase A is 0.01% formic acid+5mM first
Sour ammonium+water/methanol, wherein, water/methanol=90:10；Mobile phase B is 0.01% formic acid+5mM ammonium formates+methanol；Flow velocity
0.2mL/min；Liquid phase condition of gradient elution is：0-0.1min, 1%B；0.1-3min, 1%-40%B；3.1-14min, 40%
B-100%B；14.1-16min 100%B；16.1-20min stop.
6. the assay method of 6 kinds of agricultural chemicals in spice according to claim 1 or 5, it is characterised in that in step 2)
In, set molecular formula, retention time, parent ion, daughter ion parameter are as follows：
7. the assay method of 6 kinds of agricultural chemicals in spice according to claim 1 or 5, it is characterised in that in step 2)
In, Mass Spectrometry Conditions are：
First mass spectrometric, using ESI ion guns, positive ion mode；Voltage is set as 5kV；Nebulizer pressure 6psi；Dry gas stream speed
4L/min；Dry 200 DEG C of temperature degree；Broadband collision induced dissociation energy 10-30eV；Mass range 100-1500m/z.
8. the assay method of 6 kinds of agricultural chemicals in spice according to claim 6, it is characterised in that in step 2), matter
Spectral condition is：
First mass spectrometric, using ESI ion guns, positive ion mode；Voltage is set as 5kV；Nebulizer pressure 6psi；Dry gas stream speed
4L/min；Dry 200 DEG C of temperature degree；Broadband collision induced dissociation energy 10-30eV；Mass range 100-1500m/z.
9. the assay method of 6 kinds of agricultural chemicals in spice according to claim 1, it is characterised in that in step 3), system
It is as standard curve：
6 kinds of agricultural chemical compound standard items are prepared respectively first, then with 1ppb, 2ppb, 5ppb, 10ppb, 20ppb, 50ppb
Gradient concentration, and 6 kinds of agricultural chemical compound standard items are surveyed respectively with step 2) identical liquid chromatogram and Mass Spectrometry Conditions
Fixed, integration obtains the peak area of 6 kinds of agricultural chemical compound standard items of gradient concentration, and regression equation and coefficient correlation is calculated,
It is as follows：
Wherein X is peak area, and Y is concentration.
10. the assay method of 6 kinds of agricultural chemicals in spice according to claim 9, it is characterised in that in step 3),
6 kinds of agricultural chemical compound peak area numerical value in testing sample solution obtained by step 2) are brought into the standard curve obtained by step 3)
In regression equation, the concentration of 6 kinds of agricultural chemical compounds in testing sample solution is obtained.
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