CN114354773A - Detection method of pyrethroid pesticide residue in dairy product - Google Patents
Detection method of pyrethroid pesticide residue in dairy product Download PDFInfo
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- 239000000447 pesticide residue Substances 0.000 title claims abstract description 23
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- 238000001514 detection method Methods 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims abstract description 33
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Abstract
The invention provides a method for detecting pyrethroid pesticide residue in dairy products, which comprises the following steps: mixing a sample to be detected with an acidified first organic solvent to obtain a mixture so as to extract residual pyrethroid pesticide in the sample to be detected; adding sodium chloride into the mixture, uniformly mixing, centrifuging, and collecting supernatant; transferring the supernatant to a solid phase extraction column, and collecting all effluent liquid; drying the effluent, redissolving the effluent by using a second organic solvent, and filtering the redissolved solution to obtain filtrate; the filtrate was measured by gas chromatography-tandem mass spectrometry. The pretreatment method provided by the invention is simple to operate, short in time consumption and capable of accurately and quickly detecting the pyrethroid pesticide residue.
Description
Technical Field
The invention belongs to the technical field of food detection, and particularly relates to a method for detecting pyrethroid pesticide residue in dairy products.
Background
Pyrethroid pesticides are insecticides modified from the structure of the natural product pyrethrin and are widely used all over the world. Although pyrethroid has lower toxicity, as a neurotoxic agent, research shows that the pyrethroid can have interference effect on endocrine function and has certain correlation with tumors. If it remains in the food, there is a risk of threatening human health.
In order to guarantee food safety and human health, GB 2763-2019 'maximum residue limit of pesticides in national food safety standards' issued by the 2019 nation stipulates the maximum residue limits of 6 pyrethroid pesticides such as bifenthrin, cyhalothrin, cyfluthrin, cypermethrin, ethofenprox and fenvalerate in raw milk, and the maximum residue limits are 0.2mg/kg, 0.01mg/kg, 0.05mg/kg, 0.02mg/kg and 0.1mg/kg respectively. However, there are some limitations to the detection method given, such as: cyhalothrin and cypermethrin can be executed according to the method of GB/T23210-2008, a large amount of organic reagents are consumed in the experimental process, the steps are relatively complicated, and a rotary evaporator is required to concentrate the solvent; cyfluthrin and ethofenprox have no recommended detection methods. In addition, GB 23200.85-2016 provides a method for detecting various pyrethroids in milk and dairy products, and the whole experiment needs two times of solid phase extraction column purification and three times of nitrogen blowing concentration, and is time-consuming and labor-consuming. The pretreatment methods of the prior documents are mainly developed by a matrix solid phase dispersion method (such as Chenmei yog, journal of analytical testing, 2019), a solid phase microextraction method (such as Zhujie, journal of Chinese food sanitation, 2007), a solid phase extraction column method (such as Song dynasty, China Dairy industry, 2016), a QuEChERS method (such as Xiaodao Gao, Chinese Dairy, 2010) and the like, and the methods have one or more defects of inconvenient operation, large solvent usage amount, long pretreatment time, narrow applicable range of dairy matrixes and the like. Therefore, methods for determining the content of bifenthrin, cyhalothrin, cyfluthrin, cypermethrin, ethofenprox and fenvalerate in the dairy still need to be developed and improved.
Disclosure of Invention
The invention aims to provide a method for detecting pyrethroid pesticide residue in dairy products, which promotes protein precipitation in the dairy products by adopting acidified organic solvents, thereby better removing impurities, leading the purity of the extracted pyrethroid pesticide to be higher and leading the detection result to be quicker and more accurate.
According to one aspect of the invention, the method for detecting the pyrethroid pesticide residue in the dairy product comprises the following steps:
mixing a sample to be detected with an acidified first organic solvent to obtain a mixture so as to extract residual pyrethroid pesticide in the sample to be detected;
adding sodium chloride into the mixture, uniformly mixing, centrifuging, and collecting supernatant;
carrying out solid phase extraction on the supernatant, and collecting all effluent liquid;
drying the effluent, redissolving the effluent by using a second organic solvent, and filtering the redissolved solution to obtain filtrate;
the filtrate was measured by gas chromatography-tandem mass spectrometry.
Preferably, the first organic solvent is one or more of acetonitrile and ethyl acetate, and the acid for acidifying the first organic solvent is one or both of formic acid and acetic acid; the second organic solvent is one or more of n-hexane, ethyl acetate and acetone.
Preferably, the amount of the acid used is 0.2 to 0.6% by mass of the first organic solvent.
Preferably, the amount of sodium chloride is 0.25-1.0g per 1g of sample to be tested.
Preferably, the pyrethroid pesticide includes one or more of bifenthrin, cyhalothrin, cyfluthrin, cypermethrin, ethofenprox and fenvalerate.
Preferably, the dairy product is liquid milk, milk powder, yoghurt or cheese.
Preferably, the solid phase extraction step employs an Oasis PRiME HLB solid phase extraction column.
Preferably, the Oasis PRiME HLB solid phase extraction column has any one of the packing specifications of 60mg, 150mg or 200mg, and is used directly without activation
Preferably, the centrifugation step is carried out at 4-10 ℃.
Preferably, the mass spectrum parameter conditions of the gas chromatography-tandem mass spectrometry are as follows:
for bifenthrin, the ion pair is two or three selected from 181.0>165.9, 181.0>179.0 and 165.1> 163.6;
for cyhalothrin, the ion pair is two or three selected from 208.1>180.9, 180.9>151.9 and 197> 141.1;
for cyfluthrin, the ion pair is two or three selected from 226>206, 163>127, and 163> 91.1;
for cypermethrin, the ion pair is two or three selected from 163>127, 163>91.1 and 180.9> 151.9;
for ethofenprox, the ion pair is two or three selected from 163.1>107.1, 163.1>135.1 and 163.1> 77.1;
for fenvalerate, the ion pair is two or three selected from 167>125, 125>89 and 167> 89.
The determination method disclosed by the invention has the advantages of simple pretreatment operation, short time consumption, less used organic solvent, good extraction and separation effects, quick and accurate detection result and very strong application value.
Drawings
Further objects, features and advantages of the present invention will become apparent from the following description of embodiments of the invention, with reference to the accompanying drawings, in which:
FIG. 1 is a bifenthrin Selective Response Monitoring (SRM) chromatogram at a concentration of 250ng/mL in a milk-based standard curve of example 1;
FIG. 2 is a cyhalothrin Selective Response Monitoring (SRM) chromatogram at a concentration of 250ng/mL in a standard curve for a milk base according to example 1;
FIG. 3 is a Cyhalothrin Selective Response Monitoring (SRM) chromatogram at a concentration of 250ng/mL in a standard curve for milk base of example 1;
FIG. 4 is a cypermethrin Selective Response Monitoring (SRM) chromatogram at a concentration of 250ng/mL in a standard curve for milk base of example 1;
FIG. 5 is a permethrin Selective Response Monitoring (SRM) chromatogram at a concentration of 250ng/mL in a milk-based standard curve of example 1;
FIG. 6 is a fenvalerate Selective Response Monitoring (SRM) chromatogram at a concentration of 250ng/mL in a standard curve for milk base of example 1;
FIG. 7 shows the recovery rates of the pesticide residues corresponding to different proportions of acetonitrile formate at a concentration of 50. mu.g/kg in comparative example 1;
FIG. 8 shows the recovery rates of pesticide residues corresponding to different qualities of sodium chloride at a concentration of 50. mu.g/kg in comparative example 2;
FIG. 9 shows the recovery rates of pesticide residues corresponding to solid phase extraction columns of different specifications at a concentration of 50. mu.g/kg in comparative example 3.
Detailed Description
Technical features, objects and advantages of the present invention will be more clearly understood and appreciated by those skilled in the art. It should be understood that the following detailed description is merely exemplary, and the technical solution of the present invention is not limited to the specific embodiments listed below.
The method for detecting the pyrethroid pesticide residue in the dairy product comprises the steps of extraction, centrifugal separation, solid phase extraction, re-dissolution and determination.
The dairy product detected by the invention can be liquid milk, milk powder, yoghourt or cheese. The pyrethroid pesticide comprises one or more of bifenthrin, cyhalothrin, cyfluthrin, cypermethrin, ethofenprox and fenvalerate, and preferably the six pesticide components are detected simultaneously.
The method comprises the following steps of extracting pyrethroid pesticides from a sample to be detected, wherein the extraction step comprises the step of mixing the sample to be detected with an acidified first organic solvent to obtain a mixture so as to extract the pyrethroid pesticides left in the sample to be detected.
The first organic solvent is one or more of acetonitrile and ethyl acetate, preferably acetonitrile. The acid used to acidify the first organic solvent is one or both of formic acid and acetic acid, preferably formic acid. Wherein the amount of the acid is 0.2-0.6%, preferably 0.2-0.4% of the mass of the first organic solvent.
The centrifugation step comprises adding sodium chloride to the mixture obtained in the extraction step, preferably by vortexing, and centrifuging to collect the supernatant. Centrifugation is preferably carried out at 10000 r/min. The centrifugation step is carried out at cryogenic conditions, preferably at 4-10 ℃.
The solid phase extraction step comprises passing the supernatant through a solid phase extraction column. Preferably, the supernatant is transferred directly to a solid phase extraction column and the entire effluent is collected. The solid phase extraction column is an Oasis prisme HLB solid phase extraction column commercialized by waters technologies (shanghai) ltd, and the specification of the packing is preferably 60mg, 150mg or 200mg, and most preferably 60 mg.
The redissolving step comprises blow-drying the effluent, preferably with nitrogen, to remove the acidified first organic solvent from the effluent, specifically, the blow-drying temperature of nitrogen may be 40 ℃; and re-dissolving the effluent with a second organic solvent after drying. The second organic solvent may be one or more of n-hexane, ethyl acetate and acetone.
1. The determination step is carried out by gas chromatography-tandem mass spectrometry. The conditions for the mass spectral parameters are preferably as shown in table 1. The mass spectrum parameter conditions for each pyrethroid pesticide include at least two pairs of ion pairs in table 1, and most preferably, one pair is a quantitative ion pair and the other or both pairs are qualitative ion pairs.
TABLE 1
In conclusion, the pretreatment method for determining the pyrethroid pesticide residue is simple, rapid, environment-friendly and economical to operate. Compared with the national standard GB/T23210-2008, the amount of the organic solvent used in the extraction process is small, and the supernatant obtained by centrifugal separation can be directly loaded for solid-phase extraction without concentration. Compared with the national standard GB 23200.85-2016, the whole process only needs one column passing and one solvent concentration, the used solid phase extraction column can be used without activation, and after the supernatant is transferred to the solid phase extraction column, the organic solution obtained by filtration is directly collected by adopting the principle of impurity adsorption, so that the experimental steps are further simplified, and the use of the organic solvent is saved.
In addition, compared with the method in the prior art, the detection method provided by the invention has the characteristics of simplicity in operation, small solvent consumption, short pretreatment time, wide applicable sample variety range to be detected and the like. The method adopts gas chromatography-tandem mass spectrometer for detection, can well reduce matrix interference, has quick and accurate detection result, can simultaneously detect 6 pyrethroid pesticide residues such as bifenthrin, cyhalothrin, cyfluthrin, cypermethrin, ethofenprox, fenvalerate and the like in the dairy product, and has strong application value.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
The methods used in the following examples are conventional methods unless otherwise specified, and the reagents used are commercially available reagents unless otherwise specified.
Examples
Example 1
(1) Reagent:
water: primary water according with GB/T6682;
acetonitrile: pesticide residue grade;
n-hexane: pesticide residue grade;
ethyl acetate: pesticide residue grade.
(2) Preparing a standard solution:
bifenthrin, cyhalothrin, cyfluthrin, cypermethrin, ethofenprox and fenvalerate standard substance: the concentration was 0.1 mg/mL.
6 mixed standard working solutions of pyrethroid pesticides: accurately measuring 1.0mL of each standard substance solution in a 10mL volumetric flask respectively, diluting the solution to 10mL with n-hexane, mixing uniformly, and preparing a mixed standard substance intermediate solution with the concentration of 10 mug/mL; and further taking 1.0mL of the intermediate solution of the standard substance in a 10mL volumetric flask, and diluting the volume to 10mL by using normal hexane to obtain the working solution of the mixed standard substance with the concentration of 1 mu g/mL. Storing at 4 deg.C or below 4 deg.C for 1 month.
(3) Sample pretreatment:
weighing 2.0g of pure milk in a 30mL centrifuge tube with a plug, mixing with 10mL of 0.2% acetonitrile formate, and performing vortex oscillation for 5min to extract a target substance; adding 1.0g of sodium chloride into the mixture, carrying out vortex oscillation for 5min, centrifuging for 5min at 4 ℃ under the condition of 10000r/min, and collecting 5mL of supernatant; directly transferring the supernatant to an Oasis PRIME HLB solid phase extraction column, and collecting all effluent liquid; blowing the obtained effluent to be nearly dry in a water bath at 40 ℃ by using nitrogen, adding 1.0mL of n-hexane solution for redissolving, filtering the mixture by a filter membrane with the diameter of 0.22 mu m, and measuring the mixture by using a gas chromatography-tandem mass spectrometer.
(4) The measurement conditions were as follows:
chromatographic conditions
A chromatographic column: 5% phenyl-methyl polysiloxane quartz capillary chromatography column (HP-5 MS); chromatographic temperature-raising procedure: maintaining at 40 deg.C for 1.5min, programming at 25 deg.C/min to 90 deg.C, maintaining for 1.5min, programming at 25 deg.C/min to 180 deg.C, programming at 5 deg.C/min to 300 deg.C, and maintaining for 5 min; and (3) sample introduction mode: no split-flow sample introduction.
Conditions of Mass Spectrometry
An ionization mode: an electron impact source (EI); the monitoring mode is as follows: selective Reaction Monitoring (SRM), quantitative ion pairs, qualitative ion pairs and collision voltages of 6 pyrethroid pesticides are as shown in table 1 above in the summary of the invention; the Selective Reaction Monitoring (SRM) chromatograms of 6 pyrethroid pesticides are displayed by spectrograms of 250ng/mL concentration points in a milk substrate standard curve, and the corresponding spectrograms are shown in figures 1 to 6.
(5) Drawing of standard curve
Blowing the blank substrate solution with nitrogen, adding a certain volume of mixed standard substance working solution, diluting with n-hexane to a constant volume of 1.0mL, preparing a series of substrate mixed standard working solutions with the concentrations of 0ng/mL, 5ng/mL, 10ng/mL, 20ng/mL, 50ng/mL, 100ng/mL and 250ng/mL in sequence, measuring by using a gas chromatography-mass spectrometer, and drawing a standard curve by using the peak area of the target compound quantitative ion as a vertical coordinate and the mass concentration of the target compound standard solution as a horizontal coordinate.
(6) Sample assay
And sampling the sample liquid to be detected to obtain the peak area of the target object, and obtaining the corresponding on-machine concentration according to the standard curve.
(7) Calculation of results
In the formula:
x represents the residual quantity of the tested components in the sample, namely mu g/kg;
c- - -the concentration of the measured component solution obtained from the standard working curve, ng/mL;
v- - -sample solution volume, mL;
m-mass of the sample represented by the sample solution, g;
f- - -dilution factor;
1000- -conversion factor.
(8) Method quantitative limit verification
Combining the sample, adding standard solutions with different mass concentrations by using a blank matrix sample, measuring the concentration corresponding to the signal-to-noise ratio equal to 10 by using a gas chromatography-tandem mass spectrometer, and finally determining the limit of quantitation to be 5 mu g/kg.
(9) Standard curve and linearity verification
The standard curves and the correlation coefficients of 6 pyrethroid pesticides were obtained by plotting the standard curves of example 1(5), as shown in table 2.
TABLE 2
| Compound (I) | Standard curve | Correlation coefficient |
| Biphenthrin | Y＝4.391*105X+1.299*105 | 0.9998 |
| Cyhalothrin | Y＝1.066*105X+9.059*104 | 0.9997 |
| Cyhalothrin | Y＝5.746*104X+3.188*104 | 0.9995 |
| Cypermethrin | Y＝8.869*104X+5.468*104 | 0.9996 |
| Ether chrysanthester | Y＝3.496*105X+5.647*104 | 0.9994 |
| Fenvalerate | Y＝1.462*105X+6.026*104 | 0.9997 |
As can be seen from Table 2, the concentrations of the 6 pyrethroid pesticides and the peak areas have good linear relations, and the correlation coefficients are all larger than 0.9900, which meets the requirements of GB/T27404-.
(10) Verification of recovery and precision
A blank pure milk sample is added with 1 time, 2 times and 10 times of quantitative limit three levels (n is 6) respectively to carry out a standard addition recovery experiment. The results of the measurement, recovery and precision of the spiked samples are shown in Table 3 below.
TABLE 3
As can be seen from Table 3, when the addition amount is 5 mug/kg, 10 mug/kg and 50 mug/kg, the recovery rate ranges of the 6 pyrethroid pesticides are 62.4-108%, 93.6-109% and 73.5-90.0%, and the recovery rate of the method meets the requirement of GB/T27404-2008; the relative standard deviation ranges of the 6 pyrethroid pesticides are 3.4-13%, 2.6-5.1% and 3.1-5.7%, and the method precision meets the requirement of GB/T27404-2008.
Example 2
In this example, a commercially available milk powder of a certain brand was selected and used for the experiment of the pesticide residue addition recovery rate. The specific method comprises the following steps:
weighing 2.0g of milk powder into a 30mL centrifuge tube with a plug, adding the mixed standard solution of the example 1 into the centrifuge tube, and fully and uniformly mixing to obtain a milk powder sample to be detected with the mass concentration of 50 mug/kg. Adding 5mL of pure water, mixing with 10mL of 0.2% acetonitrile formate, and performing vortex oscillation for 5min to extract a target substance; adding 1.0g of sodium chloride into the mixture, carrying out vortex oscillation for 5min, centrifuging at 4 ℃ under the condition of 10000r/min, and collecting 5mL of supernatant; directly transferring the supernatant to an Oasis PRIME HLB solid phase extraction column, and collecting all effluent liquid; blowing the obtained effluent to be nearly dry in a water bath at 40 ℃ by using nitrogen, adding 1.0mL of n-hexane solution for redissolving, filtering the mixture by a filter membrane with the diameter of 0.22 mu m, and measuring the mixture by using a gas chromatography-tandem mass spectrometer.
The chromatographic conditions and mass spectrometric conditions were specifically the same as in example 1.
Matrix standard curve a blank milk powder matrix was used and the formulation procedure was the same as in example 1.
The results of measurement by gas chromatography-tandem mass spectrometry are shown in table 4.
TABLE 4
Example 3
In this example, a commercially available yogurt of a certain brand was selected and subjected to an experiment of the recovery rate of pesticide residue. The specific method comprises the following steps:
weighing 2.0g of the yogurt to be detected in a 30mL centrifuge tube with a plug, adding the mixed standard solution in the embodiment 1 into the centrifuge tube, and fully and uniformly mixing to obtain a yogurt sample to be detected with the mass concentration of 50 mug/kg. Adding 3mL of pure water, mixing with 10mL of 0.2% acetonitrile formate, and performing vortex oscillation for 5min to extract a target substance; adding 1.0g of sodium chloride into the mixture, carrying out vortex oscillation for 5min, centrifuging at 4 ℃ under the condition of 10000r/min, and collecting 5mL of supernatant; directly transferring the supernatant to an Oasis PRIME HLB solid phase extraction column, and collecting all effluent liquid; blowing the obtained effluent to be nearly dry in a water bath at 40 ℃ by using nitrogen, adding 1.0mL of n-hexane solution for redissolving, filtering the mixture by a filter membrane with the diameter of 0.22 mu m, and measuring the mixture by using a gas chromatography-tandem mass spectrometer.
The chromatographic conditions and mass spectrometric conditions were specifically the same as in example 1.
Matrix standard curve a blank yogurt matrix was used and the formulation procedure was the same as in example 1.
The results of measurement by gas chromatography-tandem mass spectrometry are shown in table 5.
TABLE 5
Example 4
In this example, a commercially available cheese of a certain brand was selected and subjected to an experiment for the recovery rate of pesticide residue. The specific method comprises the following steps:
weighing 2.0g of cheese to be detected in a 30mL centrifuge tube with a plug, adding the mixed standard solution in the embodiment 1 into the centrifuge tube, and fully and uniformly mixing to obtain a cheese sample to be detected with the mass concentration of 50 mug/kg. Adding 10mL of pure water, mixing with 10mL of 0.2% acetonitrile formate, and performing vortex oscillation for 5min to extract a target substance; adding 1.0g of sodium chloride into the mixture, carrying out vortex oscillation for 5min, centrifuging at 4 ℃ under the condition of 10000r/min, and collecting 5mL of supernatant; directly transferring the supernatant to an Oasis PRIME HLB solid phase extraction column, and collecting all effluent liquid; blowing the obtained effluent to be nearly dry in a water bath at 40 ℃ by using nitrogen, adding 1.0mL of n-hexane solution for redissolving, filtering the mixture by a filter membrane with the diameter of 0.22 mu m, and measuring the mixture by using a gas chromatography-tandem mass spectrometer.
The chromatographic conditions and mass spectrometric conditions were specifically the same as in example 1.
Matrix standard curve a blank cheese matrix was used and the formulation procedure was the same as in example 1.
The results of measurement by gas chromatography-tandem mass spectrometry are shown in table 6.
TABLE 6
Comparative example 1
The recovery of 6 pyrethroid pesticide residues was determined in the same manner as in example 1, except that the formic acid content of the acidified acetonitrile in step (2) was different. Specifically, the acidified acetonitrile used in this comparative example had formic acid contents of 0.2%, 0.4% and 0.6%, respectively. The results of the experiment are shown in FIG. 7.
Comparing the data in fig. 7, it can be seen that the recovery of the target was optimal for acidified acetonitrile with a formic acid content of 0.2%, and that the average recovery of bifenthrin, cyhalothrin, cyfluthrin, cypermethrin, ethofenprox and fenvalerate were 80.1%, 89.3%, 88.9%, 86.6%, 78.9% and 85.0% in that order.
Comparative example 2
The recovery of 6 pyrethroid pesticide residues was determined in the same manner as in example 1, except that the amount of sodium chloride used in step (2) was different. Specifically, the amounts of sodium chloride used in this comparative example were 0.5g, 1.0g, 1.5g, and 2.0g, respectively. The results of the experiment are shown in FIG. 8.
As can be seen from comparison of the data in fig. 8, the recovery rate of the target was the best when the mass of sodium chloride used was 1.0g, and the average recovery rates of bifenthrin, cyhalothrin, cyfluthrin, cypermethrin, ethofenprox and fenvalerate were 88.6%, 92.8%, 91.8%, 92.0%, 90.0% and 90.1% in this order.
Comparative example 3
The recovery rates of 6 pyrethroid pesticide residues were determined in the same manner as in example 1, except that the Oasis PRiME HLB solid phase extraction column packing specifications used in step (3) were different. Specifically, the specifications of the solid phase extraction column packing used in this comparative example were 60mg, 150mg, and 200mg, respectively. The results of the experiment are shown in FIG. 9.
Comparing the data in fig. 9, it can be seen that the recovery rate of the target substance is the best when the packing specification of the solid phase extraction column is 60mg, and the average recovery rates of bifenthrin, cyhalothrin, cyfluthrin, cypermethrin, etofenprox and fenvalerate are 84.9%, 90.8%, 85.7%, 86.9%, 84.5% and 86.1% respectively.
The foregoing is only a preferred embodiment of the present invention. It will be appreciated that various modifications, combinations, alterations, and substitutions of the details and features of the invention may be made by those skilled in the art without departing from the spirit and nature of the invention. Such modifications, combinations, alterations and substitutions are also to be understood as being included within the scope of the invention as claimed.
Claims (10)
1. A method for detecting pyrethroid pesticide residue in dairy products is characterized by comprising the following steps:
mixing a sample to be detected with an acidified first organic solvent to obtain a mixture so as to extract residual pyrethroid pesticide in the sample to be detected;
adding sodium chloride into the mixture, uniformly mixing, centrifuging, and collecting supernatant;
carrying out solid phase extraction on the supernatant, and collecting all effluent liquid;
drying the effluent, redissolving the effluent by using a second organic solvent, and filtering the redissolved solution to obtain filtrate;
the filtrate was measured by gas chromatography-tandem mass spectrometry.
2. The detection method according to claim 1, wherein the first organic solvent is one or more of acetonitrile and ethyl acetate, and the acid for acidifying the first organic solvent is one or both of formic acid and acetic acid; the second organic solvent is one or more of n-hexane, ethyl acetate and acetone.
3. The detection method according to claim 2, wherein the amount of the acid is 0.2 to 0.6% by mass of the first organic solvent.
4. The assay of claim 1, wherein the amount of sodium chloride is from about 0.25 to about 1.0g of sodium chloride per 1g of sample to be assayed.
5. The detection method according to claim 1, wherein the pyrethroid pesticide includes one or more of bifenthrin, cyhalothrin, cyfluthrin, cypermethrin, ethofenprox and fenvalerate.
6. The detection method according to claim 1, wherein the dairy product is liquid milk, milk powder, yogurt or cheese.
7. The method of claim 1, wherein the solid phase extraction step is performed using an Oasis PRiME HLB solid phase extraction column.
8. The method of detecting according to claim 7, wherein the Oasis PRiME HLB solid phase extraction column has any one of a packing specification of 60mg, 150mg, or 200mg, and is used without activation.
9. The detection method according to claim 1, wherein the centrifugation step is carried out at 4 to 10 ℃.
10. The detection method of claim 5, wherein the mass spectrum parameter conditions of the gas chromatography-tandem mass spectrometry are as follows:
for bifenthrin, the ion pair is two or three selected from 181.0>165.9, 181.0>179.0 and 165.1> 163.6;
for cyhalothrin, the ion pair is two or three selected from 208.1>180.9, 180.9>151.9 and 197> 141.1;
for cyfluthrin, the ion pair is two or three selected from 226>206, 163>127, and 163> 91.1;
for cypermethrin, the ion pair is two or three selected from 163>127, 163>91.1 and 180.9> 151.9;
for ethofenprox, the ion pair is two or three selected from 163.1>107.1, 163.1>135.1 and 163.1> 77.1;
for fenvalerate, the ion pair is two or three selected from 167>125, 125>89 and 167> 89.
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