CN106248854A - A kind of measure the method for 100 kinds of pesticide residues in Chinese liquor - Google Patents
A kind of measure the method for 100 kinds of pesticide residues in Chinese liquor Download PDFInfo
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- CN106248854A CN106248854A CN201610790361.XA CN201610790361A CN106248854A CN 106248854 A CN106248854 A CN 106248854A CN 201610790361 A CN201610790361 A CN 201610790361A CN 106248854 A CN106248854 A CN 106248854A
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
Abstract
The invention discloses and a kind of measure the method for 100 kinds of persticide residues in Chinese liquor, including Wine Sample through decompression distillation except alcohol, organic solvent extraction, dispersive solid-phase extraction purifies, and measures the persticide residue in Chinese liquor with the triple quadrupole rods tandem mass spectrometry of gas chromatogram (GC MS/MS) being configured with programmed temperature sampling mouth after being centrifuged.This method can be prevented effectively from Chinese liquor ethanol to mass spectrographic interference, have easy and simple to handle, quick, solvent load is few, the feature such as accurate, sensitive.
Description
Technical field
The invention belongs to technical field of analytical chemistry, relate to the assay method of multiple types pesticide residues in a kind of Chinese liquor.
Background technology
Chinese liquor is using Cereals such as Sorghum vulgare Pers., Semen Tritici aestivi, Semen Maydiss as primary raw material, fermented, distill, store, blend and form.High
The Cereals such as fine strain of millet, Semen Tritici aestivi and Semen Maydis, in plantation and storage, may cause pesticide residues because of pollution or Misuse, this
Residual may enter wine body through distillation technogenic migration and bring food safety risk to Chinese liquor.At present, China not yet formulates Chinese liquor
Pesticide Residues limitation national standard, Chinese liquor pesticide residues method standard is also blank, and this is unfavorable for that Chinese liquor food is pacified
The monitoring of full blast danger and management and control, and the international development of Chinese liquor.
At present, rare about the research report of multiple types pesticide residue detection method in Chinese liquor both at home and abroad, conventional drinks
Beverage Pesticide Residues pre-treating method mainly has liquid-liquid extraction method (LLE), solid phase extraction (SPE), Solid-phase Microextraction
(SPME), dispersive solid-phase extraction method (d-SPE) etc..Analytical Techniques of Pesticide Residues mainly has a gas chromatography (GC), and gas chromatogram-
MS (GC-MS), high performance liquid chromatography (HPLC), Liquid Chromatography-Mass Spectrometry (LC-MS) etc..Place before these
Reason method and the detection of multi-pesticide residue in alcoholic strength is than relatively low wine of analytical technology major applications, such as Chinese patent CN
105334277 A disclose employing GC/MS and carry out the Pesticides Testing in wine.But the assay method of wine Pesticides is also
It is not suitable for the mensuration that Chinese liquor middle peasant is residual.This is because the main matrix in wine is polyphenol, sugar, pigment etc., analyzing
Journey is relatively easily removed, as pigment uses absorption just can remove.Therefore, the assay method that wine middle peasant is residual is relatively easy
Realize.Compared to wine, Chinese liquor has higher alcohol concentration, and analysis is had a great impact by the alcohol concentration of high concentration,
In GC-MS/MS, the ethanol of high concentration makes major part object produce matrix enhancement effect, mass spectrographic peak type is produced impact,
Make method poor stability, thus cause qualitative and quantitative inaccurate.Additionally, in Chinese liquor possibly together with abundant acid, ester, alcohol, aldehyde,
The flavor substances such as pyrazine, furfural and phenols, analyze trace pesticide residues from the most complicated substrate, use traditional solid phase to extract
The drawbacks such as following the example of (SPE) and have complex operation, solvent load is big, detection limit for height.
Due to the above-mentioned characteristic of Chinese liquor, when causing it to measure agriculture material such as residual grade, pre-treatment requirement is high, existing few in number
In the report of Chinese liquor Pesticide Residues detection method pertinent literature, its pesticide variety coverage rate is narrow, complex pretreatment, solvent load
Greatly, being easily generated false positive results, therefore, the multi-pesticide residue assay method inventing efficiently and accurately in a kind of Chinese liquor is the most necessary.
Summary of the invention
In order to solve Chinese liquor Detecting Pesticide analysis in prior art, kind is single, complex pretreatment, result are inaccurate
Defect, the invention provides a kind of efficiently, the method for multiple trace pesticide residues in Accurate Determining Chinese liquor.
The object of the invention is realized by techniques below means:
The invention provides a kind of gas chromatogram-triple quadrupole rods tandem mass spectrometry (GC-being configured with programmed temperature sampling mouth
MS/MS) method of Multiple Pesticides residual in Chinese liquor is measured.
Pre-treatment is that Wine Sample removes alcohol, acetonitrile extraction through decompression distillation, and dispersive solid-phase extraction purifies, and uses GC-after being centrifuged
MS/MS analyzes the persticide residue measured in Chinese liquor.
A kind of measure the method for 100 kinds of persticide residues in Chinese liquor more specifically, described, comprise the following steps:
S1. vacuum rotary steam removes alcohol and extraction: take Wine Sample in rotary evaporation bottle, decompression distillation, is moved by remaining sample
Enter in centrifuge tube, measure acetonitrile rinse rotary evaporation bottle at twice, and transfer in centrifuge tube, after vortex oscillation, add chlorination
Sodium, stands after vortex oscillation and makes acetonitrile phase be layered with aqueous phase.
S2. purify: pipette sample extraction supernatant in centrifuge tube, add dispersive solid-phase extraction material, vibrate immediately, whirlpool
It is centrifuged after the vibration of whirlpool, Aspirate supernatant filter membrane.
S3.GC-MS/MS measure: according in gas chromatography-mass spectrum/Mass Spectrometry Conditions determination step S2 filter after sample and
Standard working solution, mass spectrum uses SRM pattern to be acquired the qualitative, quantitative ion pair of each object；Pass through sample
Mass spectrum and relevant information, obtain its qualitative and quantitative result；Should be with the retention time of standard substance, qualitative ion time qualitative
Consistent to, abundance of ions ratio, and relative abundance tolerance is less than the scope of regulation, then can determine whether to exist in sample correspondence
Measured object；Standard curve method is used during quantitative determination；Further, for external standard method.
In said method, every 5～20mL Wine Sample, add 5～20mL acetonitriles, sodium chloride 3～6g sodium chloride: every 1mL
Decompression adds 150-200mg dispersive solid-phase extraction material except the supernatant of alcohol adds every milliliter of supernatant.
Described dispersive solid-phase extraction material is anhydrous magnesium sulfate and primary secondary amine PSA.Further, institute
The anhydrous magnesium sulfate further stated is 5-25:1-5 with the weight ratio of primary secondary amine PSA.Currently preferred
In embodiment, anhydrous magnesium sulfate is 6:1 with the weight ratio of primary secondary amine PSA.
In view of Wine Sample non-pigment, relative to corn vegetable sample, its substrate is more clean, uses anhydrous magnesium sulfate
Combining in conjunction with the scavenging material of PSA and purify acetonitrile extraction supernatant, anhydrous magnesium sulfate contains in extract for removing
Small part water, to avoid its injury to instrument；PSA polarity matrix components in the sorption extraction liquid, such as fatty acid, organic
Acid, aldehydes matter etc..And carry out experimental verification using parameters such as the response rate, precision, detection limits as performance assessment criteria.Experimental result
Display (table 1,2), the method response rate is the best with precision, it is adaptable to analyzes while trace multi-pesticide residue in Chinese liquor and measures.
In step S1, the revolution of rotary evaporation is 80-130rpm, and the pressure of pump is 20-80mbar, and bath temperature is 40-
45℃；Preferably, rotating speed: 100rpm；Pressure: 50mbar, temperature: 40 DEG C.When bath temperature is less than 40 DEG C, ethanol volatilization speed
Degree is slow, and when bath temperature is higher than 45 DEG C, part agriculture to be measured is residual can volatilize or degrade, such as major part organophosphorus insecticide.Send out
A person of good sense, through repeatedly groping experiment, finds under the conditions of above-mentioned rotation is steamed, and can quickly realize removing the big portion in Wine Sample
Divide ethanol, ensure that testing compound is not degraded simultaneously.In the present invention one preferred embodiment, consider rotation and steam effect
Steaming temperature with rotation steaming time and rotation, selection rotation steaming condition is: rotating speed: 100rpm；Pressure: 50mbar, temperature: 40 DEG C.This condition
Under, the Wine Sample of 10mL about 5min can revolve steaming to be terminated.
As preferably, in step S3, the condition determination of GC-MS/MS is following:
Chromatographic condition: sampling volume: 1 μ L；Sample introduction pattern: PTV Splitless injecting samples；Surge pressure: 150kPa (1min)；
Injection port initial temperature: 90 DEG C, is quickly ramped up to 280 DEG C with 10 DEG C/s after sample introduction；Capillary column: TR-Pesticide II
[(50% phenyl) methyl polysiloxane, μm+5m × 0.25,30m × 0.25mm × 0.25 μm Guard (pre-column)]；Carrier gas: He,
Purity >=99.999%；Flow rate of carrier gas: 1.2mL/min；Chromatographic column heating schedule: the heating schedule of chromatographic column is 88-92 DEG C of guarantor
Hold 4-6min, then rise to 175-185 DEG C with 20--30 DEG C/min, keep 14-16min, then rise to 270-with 4-6 DEG C/min
290 DEG C, keep 3-5min.
In the present invention one preferred embodiment, the heating schedule of chromatographic column be 90 DEG C keep 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 DEG C；Emission current: 50 μ A；Ion source: closed EI source；Collision atmospheric pressure:
1.2mTorr(Ar)；Solvent delay time: 7.0min；Scan pattern: MRM (monitoring of many reactive ions), uses " EZ-Method "
Establishing method, " Start time " is set as target compound starting point sweep time, for " target compound retention time RT-
0.75min ", it is set as target compound terminal sweep time at " End time ", for " target compound retention time RT+
0.75min”。
The present invention selects the TR-Pesticide residual post of II agriculture as analyzing chromatographic column, revises temperature programming bar by continuous
Part, makes relatively uniform being distributed on retention time axle of chromatographic peak, and the fixing condition optimized.
Mass Spectrometry Conditions selection strategy: mass spectrometric data drainage pattern is SRM pattern, SRM parameter includes monitoring ion pair, collision
The parameters such as energy and window sweep time.First pass through full scan acquisition retention time and abundance is higher, mass-to-charge ratio is relatively big, characteristic
Strong parent ion, uses different energy bombardment parent ions, obtains the second order ms figure under different-energy bombarding conditions, from two grades of matter
Select in spectrogram that abundance is higher, mass-to-charge ratio as daughter ion, and records the collision energy of correspondence compared with ion big, that characteristic is strong,
Near the collision energy of record, reduce energy level again, do second energy optimization and obtain optimum collision energy.Sweep time window one
As be set to " retention time ± 0.75min ", indivedual pesticide such as cypermethrin because of its isomeric exist occur four be connected
Chromatographic peak, its appearance time window is relatively wide, and therefore arrange its of window is " retention time ± 1.25min " sweep time,
Guarantee that target compound goes out peak at window sweep time set, can tolerate that the retention time of target compound is in certain journey simultaneously
Skew on degree.
As preferably, the compound method of step S3 Plays solution is:
1) single standard storing solution (100 μ g/mL)
Weigh every kind of pesticide standard material 0.01g respectively in different 100mL volumetric flasks, be accurate to 0.0001g, use first
Benzene dissolves and dilutes constant volume.Stored protected from light under the conditions of-18 DEG C, 6 months effect duration.
2) hybrid standard storing solution (2 μ g/mL)
Pipette each pesticide single standard storing solution 2mL in 100mL volumetric flask, use dilution in acetonitrile constant volume.Stored protected from light in-
Under the conditions of 18 DEG C, 3 months effect duration.
3) matrix matching standard working solution
Choose and do not contain the same type Wine Sample of pesticide residues to be measured as the type blank sample.Blank wine sample is pressed
Described pre-treating method obtains vehicle solution after processing, by vehicle solution, hybrid standard storing solution preparation substrate
Disposition row standard working solution.This solution should i.e. be joined and i.e. used.
As preferably, the detection method of the present invention can measure the pesticide of more than 100 kinds 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 analysis can be carried out
Drug compound all can use this method to measure.
The Cereals such as Sorghum vulgare Pers., Semen Tritici aestivi, Semen Maydis are as Chinese liquor primary raw material, in plantation and storage, may because polluting or
Misuse and cause pesticide residues, this residual may through distillation technogenic migration enter wine body and bring food safety to Chinese liquor
Risk.A kind of the detection method of Multiple Pesticides in Chinese liquor can be detected timely and effectively therefore, it is necessary to build.Existing containing wine
The detection method of essence beverage is mainly for wine, and shorter mention Chinese liquor.Because Chinese liquor and wine substrate have great
Difference.Compared to wine, containing substantial amounts of ethanol in Chinese liquor, possibly together with the flavor substance of multiple denier, these materials are equal
The Pesticides Testing of trace can be brought interference, cause wine detection method of the prior art not to be suitable for the detection of Chinese liquor.
The present invention have employed the pretreatment technology that decompression low temperature rotation is steamed, dispersive solid-phase extraction purifies first and examines with GC-MS/MS
Survey technology is integrated, can realize the 100 kinds of pesticide residues simultaneously measuring in Chinese liquor, in prior art, the mensuration side of alcoholic beverage
Method once can only measure tens kinds or a class medicine, such as Chinese patent CN 105334277 A, determines 52 in wine
Pesticides.And for Chinese liquor, a class residual pesticide therein typically can only be measured, such as Li Jun etc., (Li Jun, Wang Zhen, Pang Hongyu open
Skill thoroughbred horse, Guo Xiaoguan；Multiple pyrethroid pesticide remained detection method [J] in Chinese liquor；Brewing science and technology；11 phases in 2013) etc.
The pyrethroid pesticide determined in Chinese liquor；(Wang Rong, Yuan Dong, Fu great You, Li Yanqing, Tan Wenyuan, the Wu Fang such as Wang Rong
Green；Gas chromatography/mass spectrometry method measures the Organochlorine Pesticide Residues [J] in Chinese liquor；Brewing science and technology；12 phases in 2007) determine white
Organochlorine pesticide in wine；Li Yan waits clearly (Li Yanqing, Tan Wenyuan, Wang Rong, Yuan Dong, Wang Hairong；Methyl carbamate agriculture in Chinese liquor
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 kind of mensuration includes the pesticide such as organophosphor, organochlorine, pyrethroid, more
Having marked improvement, sample only need to be through single treatment, a pin sample introduction to complete 100 kinds of pesticide within 50 minutes residual
(not including pre-treatment) is measured while staying.
As well known to those skilled in the art, when using the mensuration that GC-MS/MS carries out compound, the compound of analysis is the most, right
Sample and pre-treatment also have the parameter request analyzed the highest.The present invention is by simple and quick pre-treatment, it is possible to realize 100 kinds
Measure while compound, and the detection limit that 100 kinds of pesticide are in Chinese liquor is less than 38 μ g/L less than 12 μ g/L, quantitative limit.At 4 μ
In the range of g/L～753 μ g/L, linearly dependent coefficient is more than 0.99.
One projecting point of the present invention is, will the decompression Sample Pretreatment Technique such as rotary evaporation, dispersive solid-phase extraction and height
Flux, high sensitivity, the GC-MS/MS detection technique integrated innovation of strong anti-interference ability, break through prior art detects limit for height,
Kind is few, be easily generated the technical bottleneck of false positive results in analysis simultaneously, it is achieved to more than hundred kinds pesticide in high concentration of alcohol Chinese liquor
The power of test simultaneously analyzed.In prior art, for the analysis of other spirituosity sample Pesticide Residues things, many employing liquid liquid
The pretreatment mode of extraction or Solid-Phase Extraction pretreatment technology, as Xue Jie etc. (Xue Jie, Zhang Jing, Liang Mengmeng, etc. in wine
The investigation [J] of pesticide residues. brewing science and technology, 2014 (7): 4-8) use liquid-liquid extraction and GC-MS to measure wine samples
In agriculture residual.Inventor the most once attempted the pre-treatment of liquid-liquid extraction: 58 kinds of pesticide of experimental selection are as object of study, respectively
With normal hexane and toluene, the pesticide of 10 μ g/L and 50 two concentration levels of μ g/L is carried out direct liquid-liquid extraction, before extraction, add chlorine
Change sodium, to saturated, investigates its response rate situation.Result shows, major part pesticide exists matrix enhancement effect in various degree, separately
Outward, owing to being affected by wine sample middle and high concentration ethanol content, when being repeatedly measured, peak shape is unstable, and liquid-liquid extraction needs a large amount of
Organic solvent.Solid-Phase Extraction then needed post, eluting, except multiple steps such as organic solvents, additionally, extraction column application cost
High.For above-mentioned problem, the present invention take vacuum rotary steam to remove dispersive solid-phase extraction purifies after alcohol, acetonitrile extraction strategy is to sample
Product process, time saving and energy saving, low cost, and little to follow-up analysis matrix effect.
The beneficial effect that the present invention reaches:
1. the present invention establishes the detection method that the gas chromatography-mass spectrum of Wine Sample Pesticide Residues thing is connected, simultaneously
100 kinds of pesticide residues are detected.
2. boiled off except the ethanol in Chinese liquor by the rotation under specified conditions.
3. reagent type is few, only need to add acetonitrile and sodium chloride extraction, and dispersed solid phase agent purifies, and consumption of organic solvent is little.
4. easy to be quick, pre-treatment is simple to operate, and 100 kinds of pesticide residues can measure in 50 minutes.
5. accurate, 100 kinds of pesticide detection limit in Chinese liquor is less than 38ug/L less than 12 μ g/L, quantitative limit.At 4 μ g/L～
In the range of 753 μ g/L, linearly dependent coefficient is more than 0.99.
Accompanying drawing explanation
The selective reaction monitoring total ion current figure of 100 kinds of pesticide of Fig. 1
Detailed description of the invention
Further illustrating technical scheme below by way of specific embodiment, specific embodiment does not represent this
The restriction of bright protection domain.Some nonessential amendments and adjustment that other people are made according to theory of the present invention still fall within this
Bright protection domain.Be will assist in by following example and understand the present invention, but be not intended to present disclosure:
Embodiment 1 GC-MS/MS measures the method for 100 Pesticide Residues in Chinese liquor
1. the configuration of standard solution:
1) single standard storing solution (100 μ g/mL)
Weigh every kind of pesticide standard material 0.01g respectively in different 100mL volumetric flasks, be accurate to 0.0001g, use first
Benzene dissolves and dilutes constant volume.Stored protected from light under the conditions of-18 DEG C, 6 months effect duration.
2) hybrid standard storing solution (2 μ g/mL)
Pipette each pesticide single standard storing solution 2mL in 100mL volumetric flask, use dilution in acetonitrile constant volume.Stored protected from light in-
Under the conditions of 18 DEG C, 3 months effect duration.
3) matrix matching standard working solution
Choose and do not contain the same type Wine Sample of target pesticide residues as the type blank sample.Blank wine sample is pressed
Described pre-treating method obtains vehicle solution after processing, by vehicle solution, hybrid standard storing solution preparation substrate
Disposition row standard working solution.This solution should i.e. be joined and i.e. used.
2. the pre-treatment of sample
2.1 decompressions are except alcohol and extraction: taking 10mL wine sample in the rotary evaporation bottle of 50mL, 100rpm, 50mbar, 40 DEG C subtract
Pressure distillation 5 minutes, moves into remaining sample in 50mL centrifuge tube, accurately pipettes 10mL acetonitrile rinse rotary evaporation at twice
Bottle, and transfer in 50mL centrifuge tube, vortex oscillation adds 3g sodium chloride after extracting 2min again, quiet after 2000rpm vortex oscillation 30s
Put and make acetonitrile phase and aqueous phase layering.
2.2 purify: pipette 1mL supernatant in containing scavenging material combination (containing 150mgMgSO4 and 25mgPSA) 2mL from
In heart pipe, the most hand-held vibration, 2000rpm vortex oscillation 5min, 6000rpm is centrifuged 5min, draws appropriate supernatant and crosses 0.22 μ
Treat that GC-MS-MS analyzes after m filter membrane, quantified by external standard method.
3. loading analysis
Instrument parameter is: instrument parameter is: chromatographic condition: sampling volume: 1 μ L；Sample introduction pattern: PTV Splitless injecting samples；
Surge pressure: 150kPa (1min)；Injection port initial temperature: 90 DEG C, is quickly ramped up to 280 DEG C with 10 DEG C/s after sample introduction；Capillary tube
Post: TR-Pesticide II [(50% phenyl) methyl polysiloxane, μm+5m × 0.25,30m × 0.25mm × 0.25 μm
Guard (pre-column)]；Carrier gas: He, purity >=99.999%；Flow rate of carrier gas: 1.2mL/min；Chromatographic column heating schedule: 90 DEG C of guarantors
Hold 5min, then rise to 180 DEG C with 25 DEG C/min, keep 15min, then rise to 280 DEG C with 5 DEG C/min, keep 4.5min；Color
Spectrum-mass spectrometer interface temperature: 290 DEG C.Mass Spectrometry Conditions: ion source temperature: 250 DEG C；Emission current: 50 μ A；Ion source: closed EI
Source；Collision atmospheric pressure: 1.2mTorr (Ar)；Solvent delay time: 7.0min；Scan pattern: MRM (monitoring of many reactive ions),
Using " EZ-Method " establishing method, " Start time " is set as target compound starting point sweep time, for " target chemical combination
Thing retention time RT-0.75min ", it is set as target compound terminal sweep time at " End time ", for " target compound
Retention time RT+0.75min ".The qualitative ion pair of each pesticide, quota ion are shown in Table 1 to, impact energy and retention time.
4. the mensuration of standard curve, detection limit, quantitative limit, the response rate and precision
The Wine Sample i.e. not containing pesticide to be measured with blank Wine Sample prepares the moon according to embodiment 2 sample pre-treatments step
Property matrix solution, with appropriate anima solution, blended standard solution, is configured to the standard curve of 7 Concentraton gradient, with
Object peak area obtains the range of linearity and linearly dependent coefficient as vertical coordinate, the concentration of object as abscissa, mapping；
Confirm detection limit (LOD) with target concentration during signal to noise ratio S/N >=3, confirm with target concentration during signal to noise ratio S/N >=10
Quantitative limit (LOQ).In negative Wine Sample, add 100 kinds of standard sample of pesticide of three concentration levels from low to high respectively, add
Adding concentration between 3.7～152.0 μ g/L, each level does three parallel sample, does 0 solvent blank and sample blank pair simultaneously
According to, process laggard Instrumental Analysis, each horizontal replication 6 times in described manner.
When adding concentration and being first concentration level of 3.7～25.0 μ g/L, the response rate 66.8%～122.1% it
Between, relative standard deviation is between 2.4%～19.1%；When standard sample of pesticide adds concentration at the second of 7.3～76.0 μ g/L
During concentration level, the response rate between 64.6%～123.5%, wherein have the response rate of 96 kinds of pesticide 70.0%～
Between 120.0%, the relative standard deviation of 100 kinds of pesticide is between 1.3%～18.4%；When add concentration 36.5～
During three concentration level of 152.0 μ g/kg, except α-Gamma Hexaochlorocyclohexane, cyfloxylate, triazophos the response rate respectively 60.6%,
69.2%, outside 123.8%, remaining pesticide response rate is all between 70.0%～120.0%, and relative standard deviation is 1.3%
～between 12.8%.100 kinds of pesticide detection limit (LOD) in Chinese liquor is 0.2～11.2 μ g/L, quantitative limit (LOQ) be 0.7～
37.5μg/L.In the range of 4 μ g/L～753 μ g/L, linearly dependent coefficient is 0.9937～1.0000.
The range of linearity of each pesticide, linearly dependent coefficient, detection limit and quantitative limit are shown in Table 1；Adding corresponding of each pesticide
The response rate and relative standard deviation under concentration level are shown in Table 2.
The retention time of the lower 100 kinds of pesticide of table 1 multiple-reaction monitoring pattern, monitoring ion pair, impact energy, the range of linearity, line
Property correlation coefficient, detection limit (LOD), quantitative limit (LOQ)
The average recovery rate of 2 100 kinds of pesticide three pitch-based sphere in Chinese liquor of table and relative standard deviation (n=6)
The selection of embodiment 2 Pretreatment
Vacuum rotary steam condition is groped: taking in the rotary evaporation bottle of 10mL wine sample 50mL, described according to the form below 3, condition is revolved
Steam.
Situation is steamed in rotation under table 3 different condition
Interpretation of result: from condition 1, condition 2 and condition 3, steam temperature, rotating speed, rotation steaming time conditions in identical rotation
Under, pressure is the highest, and slipping out liquid, to slip out speed the slowest, slips out liquid at 50mbar and slips out speed, and the rotation that can reach good is steamed
Effect；From condition 3, condition 4 and condition 5, in the case of other conditions are constant, temperature is the highest, slips out speed the fastest, temperature
Time too low, condensation slips out, but the too high meeting of temperature causes the decomposition of partial target pesticide.Consider rotation and steam effect and rotation steaming
Temperature is steamed in time and rotation, and selection rotation steaming condition is: revolution is 80-130rpm, and pressure is 20-80mbar, and bath temperature is 40-45
℃；It is further preferred that rotating speed: 100rpm；Pressure: 50mbar, temperature: 40 DEG C, time: 5min.
Claims (10)
1. the method measuring Chinese liquor Pesticide Residues, comprises the steps of
S1. except alcohol and extraction: take Wine Sample rotary evaporation and remove ethanol, remaining liq adds acetonitrile and sodium chloride mixing, quiet
Put and make aqueous layer and acetonitrile layer layering；
S2. purify: take after supernatant adds the concussion of dispersive solid-phase extraction material centrifugal, take supernatant through membrane filtration；
S3. GC-MS/MS measures: takes GC-MS/MS instrument on the liquid after filtering in step S2 and is measured.
Method the most according to claim 1, it is characterised in that: Wine Sample, acetonitrile, the ratio of sodium chloride three be: 5～
20mL Wine Sample: 5～20mL acetonitriles: 3～6g sodium chloride.
Method the most according to claim 1, it is characterised in that: every milliliter of supernatant adds 150-200mg dispersed solid phase extraction
Draw materials.
Method the most according to claim 1, it is characterised in that described dispersive solid-phase extraction material be anhydrous magnesium sulfate and
Primary secondary amine PSA: further, anhydrous magnesium sulfate with the ratio of weight and number of primary secondary amine PSA is
5-25∶1-5。
Method the most according to claim 4, it is characterised in that described anhydrous magnesium sulfate and primary secondary amine
The ratio of weight and number of PSA is 6: 1.
Method the most according to claim 1, it is characterised in that:
In step S1, the revolution of rotary evaporation is 80-130rpm, pressure 20-80mbar, and bath temperature is 40-45 DEG C.
Method the most according to claim 6, it is characterised in that:
In step S1, the revolution of rotary evaporation is 100rpm, pressure 50mbar, and bath temperature is 40 DEG C.
8. according to the method described in claim 1, it is characterised in that:
In step S3, gas chromatogram is configured with programmed temperature sampling mouth, and the heating schedule of chromatographic column is 88-92 DEG C and keeps 4-
6min, then rises to 175-185 DEG C with 20--30 DEG C/min, keeps 14-16min, then rises to 270-290 DEG C with 4-6 DEG C/min,
Keep 3-5min.
Method the most according to claim 8, it is characterised in that:
The heating schedule of chromatographic column be 90 DEG C keep 5min, then rise to 180 DEG C with 25 DEG C/min, keep 15min, then with 5 DEG C/
Min rises to 280 DEG C, keeps 4.5min.
10. according to the method described in claim 1, it is characterised in that in step S3,
The condition of chromatograph is:
Sampling volume: 1 μ L；
Sample introduction pattern: PTV Splitless injecting samples；
Surge pressure: 150kPa；
Injection port initial temperature: 90 DEG C, is quickly ramped up to 280 DEG C with 10 DEG C/s after sample introduction；
Capillary column: TR-Pesticide II；
Carrier gas: He, purity >=99.999%；
Flow rate of carrier gas: 1.2mL/min；
Chromatographic column heating schedule: 90 DEG C keep 5min, then rise to 180 DEG C with 25 DEG C/min, keep 15min, then with 5 DEG C/min
Rise to 280 DEG C, keep 4.5min；
Chromatography-mass spectroscopy interface temperature: 290 DEG C；
Mass Spectrometry Conditions is:
Ion source temperature: 250 DEG C；
Emission current: 50 μ A；
Ion source: closed EI source；
Collision atmospheric pressure: 1.2mTorr Ar；
Solvent delay time: 7.0min；
Scan pattern: MRM.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610790361.XA CN106248854B (en) | 2016-08-31 | 2016-08-31 | A kind of method of 100 kinds of pesticide residues in measure white wine |
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| CN109187784A (en) * | 2018-09-11 | 2019-01-11 | 中山出入境检验检疫局检验检疫技术中心 | A kind of headspace solid-phase microextraction of sea-buckthorn volatile oil compositions-gas chromatography mass spectrometry determination method |
| CN109254104A (en) * | 2018-09-26 | 2019-01-22 | 新疆农垦科学院 | The detection method of residues of organophosphate pesticides in a kind of grape wine |
| CN113325112A (en) * | 2021-06-08 | 2021-08-31 | 贵州茅台酒股份有限公司 | Method for simultaneously and rapidly detecting residual quantity of various pesticides |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109187784A (en) * | 2018-09-11 | 2019-01-11 | 中山出入境检验检疫局检验检疫技术中心 | A kind of headspace solid-phase microextraction of sea-buckthorn volatile oil compositions-gas chromatography mass spectrometry determination method |
| CN109187784B (en) * | 2018-09-11 | 2021-10-29 | 中山出入境检验检疫局检验检疫技术中心 | Headspace solid phase microextraction-gas chromatography-mass spectrometry detection and analysis method for sea buckthorn volatile oil component |
| CN109254104A (en) * | 2018-09-26 | 2019-01-22 | 新疆农垦科学院 | The detection method of residues of organophosphate pesticides in a kind of grape wine |
| CN113325112A (en) * | 2021-06-08 | 2021-08-31 | 贵州茅台酒股份有限公司 | Method for simultaneously and rapidly detecting residual quantity of various pesticides |
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| CN106248854B (en) | 2018-05-25 |
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