CN106248854B - A kind of method of 100 kinds of pesticide residues in measure white wine - Google Patents

Abstract

The invention discloses a kind of methods for measuring 100 kinds of persticide residues in white wine, including Wine Sample through vacuum distillation except alcohol, organic solvent extracts, dispersive solid-phase extraction purifies, with the persticide residue being configured in the triple quadrupole rods tandem mass spectrometries of gas-chromatography (GC MS/MS) the measure white wine of programmed temperature sampling mouth after centrifugation.This method can effectively avoid ethyl alcohol in white wine to mass spectrographic interference, having the characteristics that easy to operate, quick, solvent dosage is few, accurate, sensitive.

Description

A kind of method of 100 kinds of pesticide residues in measure white wine

Technical field

The invention belongs to technical field of analytical chemistry, it is related to a kind of assay method of a variety of pesticide residues in white wine.

Background technology

White wine be using Cereals such as sorghum, wheat, corns as primary raw material, it is fermented, distill, store, blending.It is high The Cereals such as fine strain of millet, wheat and corn may cause pesticide residue in plantation and storage due to pollution or Misuse, this Residual may migrate into wine body through distillation technique and bring food safety risk to white wine.At present, China not yet formulates white wine Middle Pesticide Residue national standard, pesticide residue analysis method standard is also blank in white wine, this is unfavorable for white wine food peace The monitoring of full blast danger and the international development of management and control and white wine.

At present, rare, common drinks is reported in the research both at home and abroad on multiple types pesticide residue detection method in white wine Pesticide residue pre-treating method mainly has liquid-liquid extraction method (LLE), solid phase extraction (SPE), Solid-phase Microextraction in drink (SPME), dispersive solid-phase extraction method (d-SPE) etc..Analytical Techniques of Pesticide Residues mainly has a gas chromatography (GC), and gas-chromatography- Mass Spectrometry (GC-MS), high performance liquid chromatography (HPLC), Liquid Chromatography-Mass Spectrometry (LC-MS) etc..Place before these Reason method and the detection of analytical technology major applications multi-pesticide residue in alcoholic strength is than relatively low grape wine, such as Chinese patent CN 105334277 A disclose the Pesticides Testing carried out using GC/MS in grape wine.However the assay method of pesticide is simultaneously in grape wine It is not suitable for the residual measure of white wine middle peasant.This is because the main matrix in grape wine is polyphenol, sugar, pigment etc., analyzing It is relatively easily removed in journey, as pigment uses absorption that can remove.Therefore, the residual assay method of grape wine middle peasant is relatively easy It realizes.Compared to grape wine, white wine has higher alcohol concentration, and the alcohol concentration of high concentration has a great impact to analysis, In GC-MS/MS, the alcohol of high concentration makes most of object generate matrix enhancement effect, be had an impact to mass spectrographic peak type, Make method stability poor, so as to cause qualitative and quantitative inaccuracy.In addition, in white wine also containing abundant acid, ester, alcohol, aldehyde, The flavor substances such as pyrazine, furfural and phenols analyze trace pesticide residue from the matrix of such complexity, are extracted using traditional solid phase Following the example of (SPE) has cumbersome, and solvent dosage is big, the detection drawbacks such as limit for height.

Due to the above-mentioned characteristic of white wine, it is caused to measure the residual height of the pre-treatment requirement when substances of agriculture, existing few in number In white wine in the report of pesticide residue detection method pertinent literature, pesticide variety covering surface is narrow, complex pretreatment, solvent dosage Greatly, false positive results are also easy to produce, therefore, the multi-pesticide residue assay method for inventing efficiently and accurately in a kind of white wine is extremely necessary.

The content of the invention

It is inaccurate in order to solve single white wine Detecting Pesticide analysis species in the prior art, complex pretreatment, result The defects of, the present invention provides a kind of efficient, a variety of trace pesticide residues in Accurate Determining white wine methods.

The object of the invention is realized by following technological means：

The present invention provides a kind of gas-chromatography-triple quadrupole rods tandem mass spectrometries (GC- for being configured with programmed temperature sampling mouth MS/MS the remaining method of Multiple Pesticides in white wine) is measured.

Pre-treatment removes alcohol, acetonitrile extraction for Wine Sample through vacuum distillation, and dispersive solid-phase extraction purification uses GC- after centrifugation MS/MS analyses measure the persticide residue in white wine.

More specifically, in a kind of measure white wine 100 kinds of persticide residues method, comprise the following steps：

S1. vacuum rotary steam removes alcohol and extraction：Wine Sample is taken in rotary evaporation bottle, is evaporated under reduced pressure, remaining sample is moved Enter in centrifuge tube, measure acetonitrile rinse rotary evaporation bottle, and being transferred in centrifuge tube at twice, chlorination is added in after vortex oscillation Sodium, standing after vortex oscillation makes acetonitrile phase be mutually layered with water.

S2. purify：Sample extraction supernatant is pipetted in centrifuge tube, dispersive solid-phase extraction material is added in, vibrates immediately, whirlpool It is centrifuged after the vibration of whirlpool, Aspirate supernatant filter membrane.

S3.GC-MS/MS is measured：According in gas chromatography-mass spectrum/Mass Spectrometry Conditions determination step S2 filter after sample and Standard working solution, mass spectrum are acquired the qualitative, quantitative ion pair of each object using SRM patterns；Pass through sample Mass spectrum and relevant information, obtain its qualitative and quantitative result；Retention time that should be with standard substance when qualitative, qualitative ion To, abundance of ions than consistent, and relative abundance tolerance is no more than defined scope, then can determine whether to exist in sample and correspond to Measured object；Calibration curve method is used during quantitative determination；Further, it is external standard method.

In the above method, every 5~20mL Wine Samples add in 5~20mL acetonitriles, sodium chloride 3~6g sodium chloride：Per 1mL Decompression adds in 150-200mg dispersive solid-phase extraction materials except the supernatant of alcohol adds in every milliliter of supernatant.

The dispersive solid-phase extraction material is anhydrous magnesium sulfate and primary secondary amine PSA.Further, institute The weight ratio of the further anhydrous magnesium sulfate stated and primary secondary amine PSA are 5-25：1-5.Currently preferred In embodiment, the weight ratio of anhydrous magnesium sulfate and primary secondary amine PSA are 6：1.

In view of Wine Sample non-pigment, compared with cereal vegetable sample, matrix is more clean, using anhydrous magnesium sulfate Acetonitrile extraction supernatant is purified with reference to the scavenging material combination of PSA, anhydrous magnesium sulfate is used to remove what is in extract liquor contained Small part water, to avoid its injury to instrument；PSA is used for the polarity matrix components in sorption extraction liquid, such as aliphatic acid, organic Acid, aldehydes matter etc..And experimental verification is carried out using parameters such as the rate of recovery, precision, detection limits as performance assessment criteria.Experimental result It shows (table 1,2), this method rate of recovery and precision are good, analyze and measure while trace multi-pesticide residue suitable for white wine.

In step S1, the revolution of rotary evaporation is 80-130rpm, and the pressure of pump is 20-80mbar, bath temperature 40- 45℃；Preferably, rotating speed：100rpm；Pressure：50mbar, temperature：40℃.When bath temperature is less than 40 DEG C, ethyl alcohol volatilization speed Degree is slow, and when bath temperature is higher than 45 DEG C, part agriculture to be measured is residual to volatilize or degrade, such as most of organophosphorus insecticide.Hair A person of good sense has found under the conditions of above-mentioned revolving by repeatedly groping to test, can quickly realize the big portion in removal Wine Sample Divide ethyl alcohol, while ensure that testing compound is not degraded.In a preferred embodiment of the invention, revolving effect is considered With revolving the time and revolving temperature, select revolving condition for：Rotating speed：100rpm；Pressure：50mbar, temperature：40℃.This condition Under, the Wine Sample about 5min of 10mL, which can be rotated, to be terminated.

Preferably, in step S3, the determination condition of GC-MS/MS is following：

Chromatographic condition：Sampling volume：1μL；Sample introduction pattern：PTV Splitless injecting samples；Surge pressure：150kPa(1min)； Injection port initial temperature：90 DEG C, 280 DEG C are quickly ramped up to 10 DEG C/s after sample introduction；Capillary column：TR-Pesticide II [(50% phenyl) methyl polysiloxane, 30m × 0.25mm × 0.25 μm+5m × 0.25 μm Guard (pre-column)]；Carrier gas：He, Purity >=99.999%；Flow rate of carrier gas：1.2mL/min；Chromatographic column temperature program：The temperature program of chromatographic column is 88-92 DEG C of guarantor 4-6min is held, then rises to 175-185 DEG C with 20--30 DEG C/min, 14-16min is kept, then 270- is risen to 4-6 DEG C/min 290 DEG C, keep 3-5min.

In an of the invention preferred embodiment, the temperature program of chromatographic column is 90 DEG C of holding 5min, then with 25 DEG C/ Min rises to 180 DEG C, keeps 15min, then rises to 280 DEG C with 5 DEG C/min, keeps 4.5min；Chromatography-mass spectroscopy interface temperature：290 ℃。

Mass Spectrometry Conditions：Ion source temperature：250℃；Emission current：50μA；Ion source：Closed EI sources；Collide atmospheric pressure： 1.2mTorr(Ar)；The solvent delay time：7.0min；Scan pattern：MRM (more reactive ion monitorings), using " EZ-Method " Setting method, " Start time " are set as target compound sweep time starting point, are " target compound retention time RT- 0.75min " is set as target compound sweep time terminal at " End time ", is " target compound retention time RT+ 0.75min”。

The present invention selects the residual column of TR-Pesticide II agricultures as analysis chromatographic column, by constantly changing temperature programming item Part makes chromatographic peak is relatively uniform to be distributed on retention time axis, and the condition of fixed optimization.

Mass Spectrometry Conditions selection strategy：Mass spectrometric data drainage pattern is SRM patterns, and SRM parameters include monitoring ion pair, collision The parameters such as energy and sweep time window.First by the way that full scan acquisition retention time and abundance are higher, mass-to-charge ratio is larger, characteristic Strong parent ion bombards parent ion using different energy, the second order ms figure under different-energy bombarding conditions is obtained, from two level matter The ion that abundance is higher, mass-to-charge ratio is larger, characteristic is strong is selected in spectrogram as daughter ion, and records corresponding collision energy, Energy level is reduced near the collision energy of record again, second energy is done and optimizes to obtain optimum collision energy.Sweep time window one As be arranged to " retention time ± 0.75min ", indivedual pesticides such as cypermethrin because its it is isomeric exist occur four be connected Chromatographic peak, appearance time window is relatively wide, therefore sets its sweep time window as " retention time ± 1.25min ", Ensure sweep time window appearance of the target compound in setting, while the retention time of target compound can be tolerated in certain journey Offset on degree.

Preferably, the preparation method of step S3 Plays solution is：

1) single standard storing solution (100 μ g/mL)

Each pesticide standard substance 0.01g is weighed respectively in different 100mL volumetric flasks, is accurate to 0.0001g, is used first Benzene dissolves and dilutes constant volume.Stored protected from light is under the conditions of -18 DEG C, the term of validity 6 months.

2) hybrid standard storing solution (2 μ g/mL)

Each pesticide single standard storing solution 2mL is pipetted in 100mL volumetric flasks, with dilution in acetonitrile constant volume.Stored protected from light in- Under the conditions of 18 DEG C, the term of validity 3 months.

3) matrix matching standard working solution

The same type Wine Sample for not containing pesticide residue to be measured is chosen as the type blank sample.Blank wine sample is pressed Vehicle solution is obtained after the pre-treating method processing, matrix is prepared with vehicle solution, hybrid standard storing solution With serial standard working solution.This solution should be with i.e. use.

Preferably, detection method of the invention can measure 100 kinds or more of pesticide in Wine Sample simultaneously, excellent The pesticide of choosing is cited by the table one in embodiment, but is not limited to table 1, as long as the agriculture of GC-MS/MS analyses can be carried out This method measure may be employed in drug compound.

The Cereals such as sorghum, wheat, corn as white wine primary raw material, plant and storage in, may because of pollution or Misuse and cause pesticide residue, this residual may migrate into wine body through distillation technique and bring food security to white wine Risk.Therefore, it is necessary to build a kind of detection method that can timely and effectively detect Multiple Pesticides in white wine.It is existing to contain wine The detection method of smart beverage is mainly for grape wine, and shorter mention white wine.Because white wine has great with grape wine matrix Difference.Compared to grape wine, containing substantial amounts of ethyl alcohol in white wine, also contain the flavor substance there are many denier, these substances are equal Interference can be brought to the Pesticides Testing of trace, grape wine detection method of the prior art is caused not to be suitable for the detection of white wine.

The present invention employs decompression low temperature revolving, the pretreatment technology of dispersive solid-phase extraction purification and GC-MS/MS and examines for the first time Survey technology is integrated, it can be achieved that measuring 100 kinds of pesticide residues in white wine, in the prior art, the measure side of alcoholic beverage simultaneously Method can only once measure tens kinds or a kind of drug, such as 105334277 A of Chinese patent CN, determine 52 in grape wine Middle pesticide.And for white wine, a kind of remains of pesticide therein can only be generally measured, such as (Li Jun, Wang Zhen, Pang Hongyu open Li Jun Skill thoroughbred horse, Guo Xiaoguan；A variety of pyrethroid pesticide remained detection methods [J] in white wine；Brewing science and technology；11 phases in 2013) etc. The pyrethroid pesticide determined in white wine；(Wang Rong, Yuan Dong, Fu great You, Li Yanqing, Tan Wenyuan, the Wu Fang such as Wang Rong It is green；Gas Chromatography-mass Spectrometry measures the Organochlorine Pesticide Residues [J] in white wine；Brewing science and technology；12 phases in 2007) determine it is white Organo-chlorine pesticide in wine；Li Yan waits clearly (Li Yanqing, Tan Wenyuan, Wang Rong, Yuan Dong, Wang Hairong；Methyl carbamate agriculture in white wine The GC/MS study on determination method of medicine residual quantity；Brewing science and technology [J]；6 phases in 2008).The present invention can simultaneously to 100 kinds or with On different types of pesticide be measured, the species of measure includes the pesticides such as organophosphor, organochlorine, pyrethroid, more With marked improvement, it is residual that sample only need to complete 100 kinds of pesticides by single treatment, a pin sample introduction and within 50 minutes It is measured while staying (not including pre-treatment).

Well known to those skilled in the art, when carrying out the measure of compound using GC-MS/MS, the compound of analysis is more, right The parameter request that sample and pre-treatment are also analyzed is higher.The present invention passes through simple and quick pre-treatment, it is possible to realize 100 kinds It is measured while compound, and detection limit of 100 kinds of pesticides in white wine, less than 12 μ g/L, quantitative limit is less than 38 μ g/L.In 4 μ In the range of the μ g/L of g/L~753, linearly dependent coefficient is more than 0.99.

A projecting point of the invention is, by the Sample Pretreatment Techniques such as decompression rotary evaporation, dispersive solid-phase extraction and height The GC-MS/MS detection technique integrated innovations of flux, high sensitivity, strong anti-interference ability, break through in the prior art detect limit for height, The technical bottleneck that species is few, is also easy to produce false positive results is analyzed simultaneously, is realized to hundred kinds or more pesticides in high ethano concentration white wine The detectability of analysis simultaneously.In the prior art, for the analysis of pesticide residue in other spirituosity samples, mostly using liquid liquid The pretreatment mode of extraction or Solid Phase Extraction pretreatment technology, such as (Xue Jie, Zhang Jing, Liang Mengmeng are waited in grape wine Xue Jie Investigation [J] brewing science and technologies of pesticide residue, 2014 (7):Wine samples 4-8) are measured using liquid-liquid extraction and GC-MS In agriculture it is residual.Inventor also once attempted the pre-treatment of liquid-liquid extraction：58 kinds of pesticides of experimental selection are as research object, respectively Direct liquid-liquid extraction is carried out to the pesticide of 10 μ g/L and 50 two concentration levels of μ g/L with n-hexane and toluene, chlorine is added in before extracting Change sodium to saturation, investigate its rate of recovery situation.The result shows that most of pesticide is there are different degrees of matrix enhancement effect, separately Outside, due to being influenced by wine sample middle and high concentration ethanol content, when being repeatedly measured, peak shape is unstable, and liquid-liquid extraction needs largely Organic solvent.Solid Phase Extraction then needed column, elution, except multiple steps such as organic solvent, in addition, extraction column application cost It is high.For it is above-mentioned the problem of, the present invention take vacuum rotary steam except alcohol, acetonitrile extraction after dispersive solid-phase extraction purify strategy to sample Product are handled, time saving and energy saving, at low cost, and small to subsequent analysis matrix effect.

The advantageous effect that the present invention reaches：

1. the present invention establishes the detection method of the gas chromatography-mass spectrum series connection of pesticide residue in Wine Sample, simultaneously 100 kinds of pesticide residues are detected.

2. pass through the ethyl alcohol in the revolving removal white wine under specified conditions.

3. reagent type is few, acetonitrile and sodium chloride extraction need to be only added, dispersed solid phase agent purifies, and consumption of organic solvent is small.

4. easy to be quick, pre-treatment is easy to operate, and 100 kinds of pesticide residues can measure completion in 50 minutes.

5. accurate, detection limit of 100 kinds of pesticides in white wine is less than 12 μ g/L, and quantitative limit is less than 38ug/L.4 μ g/L~ In the range of 753 μ g/L, linearly dependent coefficient is more than 0.99.

Description of the drawings

The selective reaction monitoring total ion current figure of 100 kinds of pesticides of Fig. 1

Specific embodiment

Below by way of the technical solution that specific embodiment further illustrates the present invention, specific embodiment is not represented to this hair The limitation of bright protection domain.Other people according to the present invention theory made some it is nonessential modification and adjustment still fall within this hair Bright protection domain.It will be helpful to understand the present invention by following examples, but do not limit present disclosure：

The remaining method of pesticide during 1 GC-MS/MS of embodiment is measured 100 in white wine

1. the configuration of standard solution：

1) single standard storing solution (100 μ g/mL)

Each pesticide standard substance 0.01g is weighed respectively in different 100mL volumetric flasks, is accurate to 0.0001g, is used first Benzene dissolves and dilutes constant volume.Stored protected from light is under the conditions of -18 DEG C, the term of validity 6 months.

2) hybrid standard storing solution (2 μ g/mL)

Each pesticide single standard storing solution 2mL is pipetted in 100mL volumetric flasks, with dilution in acetonitrile constant volume.Stored protected from light in- Under the conditions of 18 DEG C, the term of validity 3 months.

3) matrix matching standard working solution

The same type Wine Sample for not containing target pesticide residue is chosen as the type blank sample.Blank wine sample is pressed Vehicle solution is obtained after the pre-treating method processing, matrix is prepared with vehicle solution, hybrid standard storing solution With serial standard working solution.This solution should be with i.e. use.

2. the pre-treatment of sample

2.1 decompressions are except alcohol and extraction：Taking 10mL wine sample, 100rpm, 50mbar, 40 DEG C subtract in the rotary evaporation bottle of 50mL Pressure distillation 5 minutes, remaining sample is moved into 50mL centrifuge tubes, accurately pipettes 10mL acetonitriles rinse rotary evaporation at twice Bottle, and is transferred in 50mL centrifuge tubes, quiet after 2000rpm vortex oscillations 30s after vortex oscillation extraction 2min again plus 3g sodium chloride Putting makes acetonitrile phase be mutually layered with water.

2.2 purification：Pipette 1mL supernatants in combined containing scavenging material the 2mL of (containing 150mgMgSO4 and 25mgPSA) from In heart pipe, vibration is held immediately, and 2000rpm vortex oscillations 5min, 6000rpm centrifugation 5min draws appropriate supernatant and crosses 0.22 μ Treat that GC-MS-MS is analyzed after m filter membranes, quantified by external standard method.

3. loading is analyzed

Instrument parameter is：Instrument parameter is:Chromatographic condition：Sampling volume：1μL；Sample introduction pattern：PTV Splitless injecting samples； Surge pressure：150kPa(1min)；Injection port initial temperature：90 DEG C, 280 DEG C are quickly ramped up to 10 DEG C/s after sample introduction；Capillary Column：TR-Pesticide II [(50% phenyl) methyl polysiloxane, 30m × 0.25mm × 0.25 μm+5m × 0.25 μm Guard (pre-column)]；Carrier gas：He, purity >=99.999%；Flow rate of carrier gas：1.2mL/min；Chromatographic column temperature program：90 DEG C of guarantors 5min is held, then rises to 180 DEG C with 25 DEG C/min, keeps 15min, then 280 DEG C are risen to 5 DEG C/min, keeps 4.5min；Color Spectrum-mass spectrometer interface temperature：290℃.Mass Spectrometry Conditions：Ion source temperature：250℃；Emission current：50μA；Ion source：Closed EI Source；Collide atmospheric pressure：1.2mTorr(Ar)；The solvent delay time：7.0min；Scan pattern：MRM (more reactive ion monitorings), Using " EZ-Method " setting method, " Start time " is set as target compound sweep time starting point, is " target chemical combination Object retention time RT-0.75min " is set as target compound sweep time terminal at " End time ", is " target compound Retention time RT+0.75min ".Qualitative ion pair, quota ion pair, impact energy and the retention time of each pesticide are shown in Table 1.

4. standard curve, detection limit, quantitative limit, the measure of the rate of recovery and precision

It is that the Wine Sample without pesticide to be measured prepares the moon according to 2 sample pre-treatments step of embodiment with blank Wine Sample Property matrix solution with appropriate anima solution, blended standard solution, is configured to the standard curve of 7 concentration gradients, with Object peak area is as ordinate, and for the concentration of object as abscissa, mapping obtains the range of linearity and linearly dependent coefficient； Target concentration during with signal-to-noise ratio S/N >=3 confirms detection limit (LOD), and target concentration during with signal-to-noise ratio S/N >=10 confirms Quantitative limit (LOQ).100 kinds of standard sample of pesticide of three concentration levels from low to high are added in negative Wine Sample respectively, are added Adding concentration, each level does three parallel samples, while does 0 solvent blank and sample blank pair between 3.7~152.0 μ g/L According to handling laggard Instrumental Analysis in described manner, each horizontal replication 6 times.

When add concentration be 3.7~25.0 μ g/L the first concentration level when, the rate of recovery 66.8%~122.1% it Between, relative standard deviation is between 2.4%~19.1%；When standard sample of pesticide adds concentration the second of 7.3~76.0 μ g/L During concentration level, the rate of recovery between 64.6%~123.5%, wherein have the rate of recovery of 96 kinds of pesticides 70.0%~ Between 120.0%, the relative standard deviation of 100 kinds of pesticides is between 1.3%~18.4%；When addition concentration 36.5~ During three concentration level of 152.0 μ g/kg, except α-six six six, cyfloxylate, Hostathion the rate of recovery respectively 60.6%, 69.2%th, outside 123.8%, remaining pesticide rate of recovery is between 70.0%~120.0%, and relative standard deviation is 1.3% Between~12.8%.Detection limit (LOD) of 100 kinds of pesticides in white wine is 0.2~11.2 μ g/L, quantitative limit (LOQ) for 0.7~ 37.5μg/L.In the range of the μ g/L of 4 μ g/L~753, linearly dependent coefficient is 0.9937~1.0000.

The range of linearity, linearly dependent coefficient, detection limit and the quantitative limit of each pesticide are shown in Table 1；Each pesticide is accordingly adding The rate of recovery and relative standard deviation under concentration level are shown in Table 2.

The retention time of the lower 100 kinds of pesticides of 1 multiple-reaction monitoring pattern of table, monitoring ion pair, impact energy, the range of linearity, line Property related coefficient, detection limit (LOD), quantitative limit (LOQ)

The average recovery rate and relative standard deviation (n=6) of 2 100 kinds of pesticides of table, three pitch-based spheres in white wine

The selection of 2 Pretreatment of embodiment

Vacuum rotary steam condition is groped：In the rotary evaporation bottle for taking 10mL wine samples 50mL, condition is revolved described according to the form below 3 It steams.

Revolving situation under 3 different condition of table

Interpretation of result：From condition 1, condition 2 and condition 3, in identical revolving temperature, rotating speed, revolving time conditions Under, pressure is higher, and slipping out liquid, to slip out speed slower, slips out liquid in 50mbar and slips out speed, can reach good revolving Effect；From condition 3, condition 4 and condition 5, in the case that other conditions are constant, temperature is higher, and it is faster to slip out speed, temperature When too low, condensation slips out, but the excessively high decomposition that can cause partial target pesticide of temperature.Consider revolving effect and revolving Time and revolving temperature, select revolving condition for：Revolution is 80-130rpm, pressure 20-80mbar, bath temperature 40-45 ℃；It is further preferred that rotating speed：100rpm；Pressure：50mbar, temperature：40 DEG C, the time：5min.

Claims (4)

1. a kind of remaining method of pesticide in measure white wine, comprises the steps of：

S1. alcohol and extraction are removed：Wine Sample rotary evaporation is taken to remove ethyl alcohol, remaining liq adds in acetonitrile and sodium chloride mixing, quiet Putting is layered aqueous layer and acetonitrile layer；

S2. purify：Supernatant is taken to be centrifuged after adding in the concussion of dispersive solid-phase extraction material, supernatant is taken to pass through membrane filtration；

S3.GC-MS/MS is measured：GC-MS/MS instrument on the liquid after being filtered in step S2 is taken to be measured；

Wherein, in step S1, Wine Sample, acetonitrile, the ratio of sodium chloride three are：5~20mL Wine Samples：5~20mL second Nitrile：3~6g sodium chloride；

Wherein, in step S2, every milliliter of supernatant adds in 150-200mg dispersive solid-phase extraction materials；The dispersed solid phase extraction It draws materials as anhydrous magnesium sulfate and primary secondary amine PSA：Further, anhydrous magnesium sulfate and ethylenediamine-N- propyl silicon The ratio of weight and number of alkane PSA is 5-25：1-5；

Wherein, in step S1, the revolution of rotary evaporation is 80-130rpm, and pressure 20-80mbar, bath temperature is 40-45 DEG C；

Wherein, in step S3, the capillary column that uses for：TR-Pesticide II；Gas-chromatography is configured with programmed temperature sampling Mouthful, the temperature program of chromatographic column is 88-92 DEG C of holding 4-6min, then rises to 175-185 DEG C with 20-30 DEG C/min, keeps 14- 16min, then 270-290 DEG C is risen to 4-6 DEG C/min, keep 3-5min.

2. according to the method described in claim 1, it is characterized in that, the anhydrous magnesium sulfate and primary secondary amine The ratio of weight and number of PSA is 6：1.

3. according to the method described in claim 1, it is characterized in that：In step S1, the revolution of rotary evaporation is 100rpm, pressure 50mbar, bath temperature are 40 DEG C.

4. according to the method described in claim 1, which is characterized in that in step S3,

The condition of chromatography is：

Sampling volume：1μL；

Sample introduction pattern：PTV Splitless injecting samples；

Surge pressure：150kPa；

Injection port initial temperature：90 DEG C, 280 DEG C are quickly ramped up to 10 DEG C/s after sample introduction；

Carrier gas：He, purity >=99.999%；

Flow rate of carrier gas：1.2mL/min；

Chromatographic column temperature program：90 DEG C of holding 5min, then rise to 180 DEG C with 25 DEG C/min, keep 15min, then with 5 DEG C/min 280 DEG C are risen to, keeps 4.5min；

Chromatography-mass spectroscopy interface temperature：290℃；

Mass Spectrometry Conditions are：

Ion source temperature：250℃；

Emission current：50μA；

Ion source：Closed EI sources；

Collide atmospheric pressure：1.2mTorr Ar；

The solvent delay time：7.0min；

Scan pattern：MRM.