CN105891362A - GC-MS/MS method for analyzing multiple types of pesticide residues in cigarette main stream smoke grain phase substances - Google Patents

GC-MS/MS method for analyzing multiple types of pesticide residues in cigarette main stream smoke grain phase substances Download PDF

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CN105891362A
CN105891362A CN201610210976.0A CN201610210976A CN105891362A CN 105891362 A CN105891362 A CN 105891362A CN 201610210976 A CN201610210976 A CN 201610210976A CN 105891362 A CN105891362 A CN 105891362A
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pesticide
mainstream smoke
cigarette mainstream
smoke condensate
cigarette
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CN105891362B (en
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陈晓水
陆明华
杨洋
汤晓东
蒋佳磊
夏骏
潘凡达
李淑彪
斯文
王雨凝
朱书秀
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China Tobacco Zhejiang Industrial Co Ltd
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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
    • 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
    • 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
    • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
    • G01N2030/025—Gas chromatography
    • 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
    • G01N2030/062—Preparation extracting sample from raw material

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Abstract

The invention discloses a GC-MS/MS method for analyzing multiple types of pesticide residues in cigarette main stream smoke grain phase substances. The method comprises the following steps of 1, compounding a pesticide standard substance solution, and conducting measurement and fitting through a gas chromatography-tandem mass spectrum, so that a standard curve is obtained; 2, conducting vibrating extraction on a Cambridge filter disc which captures the main stream smoke grain phase substances through acetonitrile, conducting centrifugal treatment on an extracting solution after the extracting solution is subjected to microextraction through dispersion liquid, and adding water and carbon tetrachloride to the extracting solution for conducting dispersion liquid microextraction, wherein the adding volume ratio of the extracting solution to water to carbon tetrachloride is 1: (3-5): (0.05-0.2); 3, measuring sedimentary facies obtained after centrifugation under the condition of the gas chromatography-tandem mass spectrum used in step 1, and substituting the measurement result into the standard curve to obtain the pesticide residue content in the cigarette main stream smoke grain phase substances. According to the method, the dispersion liquid microextraction technology is combined with GC-MS/MS, the sample treatment procedure is simplified, and the detection result can reflect the condition of pesticide residues in the cigarette more accurately, stably and objectively.

Description

In a kind of cigarette mainstream smoke condensate, the GC-MS/MS of Multiple Pesticides residual analyzes Method
Technical field
The invention belongs to cigarette smoke the Detection Technologies of Pesticide Residues field, relate generally in cigarette mainstream smoke condensate many Planting the determination techniques of pesticide residues, in a kind of cigarette mainstream smoke condensate, the GC-MS/MS of Multiple Pesticides residual divides Analysis method.
Background technology
Nicotiana tabacum L. is during plantation, production and processing and storage, it is to avoid the not use of pesticide, thus results in relevant pesticide and exists Residual on Nicotiana tabacum L., Medicated cigarette has again part pesticide through being drawn in main flume during burning and sucking.(the Zhang Hong such as Zhang Hongfei Non-, recklessly radically reform, Tang Gangling, waits the .29 kind organophosphorus pesticide rate of transform [J] in cigarette mainstream smoke condensate and stub. cigarette Grass science and technology, 2010 (07): 39-42.) research show 29 kinds of organophosphorus pesticide moving in cigarette mainstream smoke condensate in tobacco shred Shifting rate is 0～6.3%, ten thousand firm human relations etc. (Wan Yilun, Zhang Hongfei, Gao Chuanchuan, etc. in Medicated cigarette, 126 kinds of pesticide are during burning and sucking Transfer behavior [J]. Guizhou Agricultural Sciences, 2015 (05): 101-106.) research shows that in tobacco shred, 126 kinds of pesticide are to Medicated cigarette main flow Average mobility in flue gas is 7.1%, and wherein endrin reaches as high as 31.7%, and variety classes pesticide fires at Medicated cigarette Transfer behavior difference during suction is the biggest, and Suckering agents average mobility is the highest, and organophosphor, carbamate chemicals for agriculture etc. are flat All mobilitys are relatively low.
The detection method of cigarette smoke pesticide residues mainly there are gas chromatography, gas chromatography mass spectrometry method and liquid matter connection With etc., pretreatment process mainly has mechanical shaking extraction, accelerated solvent extraction etc.,
As, the Chinese patent literature of Publication No. CN104251897A discloses one and measures five kinds of differences in soil simultaneously The method of structure herbicide residue amount, belongs to the physico-chemical examination technique field of Pesticide Residue in Soil residual.Use the most exactly Dispersive solid-phase extraction combines dispersive liquid-liquid microextraction, directly measures five kinds of different structures of three classes in soil with high performance liquid chromatograph The residual quantity of herbicide.The method measurement sensitivity is low, and range is narrow, and the pesticide variety of analysis is less.
The Chinese patent literature of Publication No. CN102866215A discloses one and grows tobacco and 20 kinds of pesticide in tobacco product The GC-MS/MS assay method of residual: by testing sample after water infiltration, adds acetonitrile and internal standard substance, then extraction of ocean eddies, salt Analysis layering, adds toluene and carries out liquid-liquid extraction, takes after supernatant is dispersed through Solid-Phase Extraction, with gas chromatography tandem mass spectrometry method The method being measured.The method pre-treatment is comparatively laborious, and the sample type simultaneously measured is less.
Persticide residue in total particulate matter in mainstream smoke is relatively low, it is generally required to carry out extract in pre-treatment operating process Concentration is beneficial to detection and analyzes, but the response rate that loaded down with trivial details pre-treatment may result in part pesticide reduces, and testing result is forbidden Really.
Summary of the invention
The purpose of the present invention aims to provide that a kind of filter disc that trapping has cigarette mainstream smoke condensate is extracted, dispersion liquid The method that after liquid micro-extraction, gas chromatography tandem mass spectrometry (GC-MS/MS) is measured.The method can quickly, accurately detect Medicated cigarette Multiple Pesticides residual in total particulate matter in mainstream smoke, measurement result is accurate, reproducible.
In a kind of cigarette mainstream smoke condensate, the GC-MS/MS of Multiple Pesticides residual analyzes method, comprises the following steps:
(1): preparation standard sample of pesticide solution, it is measured and matching by gas chromatography tandem mass spectrometry (GC-MS/MS) Obtain standard curve；
(2): trapping has the cambridge filter of cigarette mainstream smoke condensate be dispersed through liquid through acetonitrile mechanical shaking extraction, extracting solution Centrifugal treating is carried out after liquid micro-extraction；
(3): the sedimentary facies after Li Xin is measured under the conditions of the gas chromatography tandem mass spectrometry of step (1) again；And will survey Determine result substitution standard curve and try to achieve cigarette mainstream smoke condensate Pesticide Residues content.
The pesticide variety that may remain in cigarette mainstream flue gas is a lot, and content is relatively low, it is achieved the Gao Ling of flue gas Pesticides The detection difficulty of quick property is bigger.The present invention uses dispersive liquid-liquid microextraction technology to carry out cigarette mainstream flue gas pesticide residues composition Extract, instead of traditional nitrogen and the concentration step such as blow, simplify sample handling procedure.Additionally, by dispersive liquid-liquid microextraction technology Combine with GC-MS/MS, testing result can be made to react flue gas Pesticide Residues situation more accurately, stably, objectively.Mainstream smoke In gas granule phase substance, multiple types, many groups pesticide residues can realize detecting simultaneously, are effectively improved detection efficiency.
In step (1) and step (3), using internal standard method to be measured, the internal standard substance of interpolation is triphenyl.
As, during preparing standard solution and testing sample solution (sedimentary facies), add inner mark solution.Described internal standard Solution is the acetonitrile solution of triphenyl.As, concentration is the acetonitrile solution of the TPP (triphenyl) of 20 μ g/mL.
In step (1), preparation standard sample solution processes is:
Weigh standard sample of pesticide respectively, with acetone solution, then add internal standard substance and by dilution in acetonitrile to having concentration ladder The standard solution containing various pesticide of degree；
Described standard sample of pesticide solution comprises alachlor, drinox, M 9834, benfluralin, α-Gamma Hexaochlorocyclohexane, β-six Six or six, δ-Gamma Hexaochlorocyclohexane, gamma hch, Biphenthrin, butralin, Niran (suitable), Niran (instead), chlopyrifos, chlorpyrifos-methyl, different evil grass Ketone, cyfloxylate, lambda-cyhalothrin, cypermethrin, chlorthaldimethyl, DDD-o, p', DDD-p, p', DDE-o, p', DDE- P, p', DDT-o, p', DDT-p, p', diazinon, dieldrin, diphenamide, disulfoton, α-5a,6,9,9a-hexahydro-6,9-methano-2,4, β-5a,6,9,9a-hexahydro-6,9-methano-2,4,5a,6,9,9a-hexahydro-6,9-methano-2,4 sulphuric acid Ester, phonamiphos, fenthion, fenvalerate, fluazifop, flucythrinate, flumetralim, heptachlor, Heptachlor epoxide-anti-, epoxy Heptachlor-suitable, Perchlorobenzene, isopropalin, Isoprothiolane, metalaxyl, methoxychlor, isopropyl methoxalamine, mirex, nitrile bacterium azoles, gram Grass enemy, Wu Junzuo, pendimethalin, Permethrin (suitable), Permethrin (instead), thimet, Butacide, Aphox, pirimiphos-methyl, seven Flumethrin, thionazin, triazolone, Triadimenol and trefanocide.
As, the manner of formulation of standard solution is: weigh the various pesticide standards described in 0.01g (being accurate to 0.1mg) respectively Product, are placed in same 10mL volumetric flask, obtain the mixed standard solution I of 1mg/mL with acetone solution constant volume；Accurately pipette 0.2mL mixed standard solution I, in 100mL volumetric flask, uses acetonitrile constant volume, is configured to the mixing mark that each pesticide concentration is 2 μ g/mL Quasi-solution II；Accurately pipette the mixed standard solution II of 0.01mL, 0.02mL, 0.05mL, 0.1mL, 0.2mL, 0.5mL and 1mL, It is placed in 10mL volumetric flask, accurately adds the 100 μ L inner mark solutions acetonitrile solution of TPP of 20 μ g/mL (concentration be), fixed with acetonitrile Hold, obtain series standard working solution.The series standard solution concentration of preparation is: 2ng/mL, 4ng/mL, 10ng/mL, 20ng/ mL、40ng/mL、100ng/mL、200ng/mL。
After standard solution has been prepared, when carrying out GC-MS/MS mensuration, GC realizes the separation of composition in sample.MS realizes sample The qualitative and quantitative analysis of composition in product.The detection parameter of GC and MS is the biggest on separating degree, the detection limit impact of testing sample.
In the present invention, in step (1) and step (3), when GC-MS/MS measures, the chromatographic condition of employing is:
Chromatographic column: HP-5MS quartz capillary column: 30m × 0.25mm × 0.25 μm；
Injector temperature: 280 DEG C；Temperature programming: initial temperature 60 DEG C, rises to 120 DEG C with 40 DEG C/min after keeping 1min, 310 DEG C are risen to again with 5 DEG C/min；Program after post: 310 DEG C, keeps 5min；
Splitless injecting samples, does not shunt time 1min；
Carrier gas: helium, purity is 99.999%；
Constant current mode, flow velocity is 1.2mL/min；Sample size: 1 μ L.
The Mass Spectrometry Conditions used is:
Ionization energy 70eV；Heater current: 35 μ A；Ion source temperature: 300 DEG C；Quadrupole rod temperature: 180 DEG C；Transmission line temperature Degree: 280 DEG C；Q2 collides gas: nitrogen, purity 99.999%, flow 1.5mL/min；Quenching gas: helium, purity 99.999%, Flow 2.25mL/min；Solvent delay 5min；Scan mode: multiple-reaction monitoring.
Multiple Pesticides in standard solution and interior target retention time and mass spectrometry parameters (MRM) are shown in Table 1.
Table 1
In step (1), standard solution is after GC-MS/MS analyzes, then selects quasi-molecular ions faces with two grades of pesticide and internal standard substance Long-pending its respective concentration of comparison carries out regression analysis, obtains standard curve.
Step (2) (i.e. fume sample pre-treatment) is parallel step with the drawing process of standard curve (step (1)), without first Rear order.
In step (2), the extracting method of main flume Pesticide Residues by directly influence test result accuracy and Credibility.In the present invention, collected the granule phase substance of main flume by cambridge filter, then extract as dispersant with acetonitrile. In extracting solution, add water and extractant again, fully shake, be centrifuged subsequently, will main flume granule phase substance be enriched with to extractant In, then the extraction oxidant layer after centrifugal is measured.
Every cambridge filter is collected 3-5 by ISO 3308:2000 method and is propped up the total particulate matter in mainstream smoke of cigarette sample.Vibration During extraction, every cambridge filter adds the acetonitrile of 15-25mL.
As preferably, mechanical shaking extraction process is carried out on shaker, and the frequency of oscillation of shaker is 150-180r/min, shakes Swinging extraction time is 30-50min.Further preferably, the frequency of oscillation of shaker is 150r/min, and the oscillation extraction time is 30min。
As preferably, in extracting solution, add water and carbon tetrachloride carry out dispersive liquid-liquid microextraction, wherein, extracting solution: water: The volume ratio that adds of carbon tetrachloride is 1:3-5:0.05-0.2.Further preferably, extracting solution: water: carbon tetrachloride add volume Ratio is 1:5:0.2.
The extractant that the present invention uses is carbon tetrachloride, and the organic principle that can be fully enriched with in extracting solution makes testing result More objective.
As preferably, in centrifugal process, centrifugal rotational speed is 5000-6000r/min, and centrifugation time is 3-5min.Further Preferably, in centrifugal process, centrifugal rotational speed is 5000r/min, and centrifugation time is 3min.
As, the preparation method (sample pretreatment process) of cigarette mainstream smoke condensate testing sample is: by ISO 3308: After 2000 methods collect the total particulate matter in mainstream smoke of 4 cigarette samples, take off cambridge filter；Accurately add the work of 0.1mL internal standard Liquid (inner mark solution, concentration is the acetonitrile solution of the TPP of 20 μ g/mL) and 20mL acetonitrile, in conical flask, vibrate with 150r/min Extraction 30min；Take 1mL acetonitrile extraction liquid and fill in conical centrifuge tube in 10mL tool, add 5mL water, add 200 μ L tetra-chlorinations Carbon, continues vibration 30s, forms uniform emulsion, after being centrifuged 3min with 5000r/min, organic molten with syringe suction foot Liquid is in chromatograph bottle, and the GC-MS/MS carrying out step (3) subsequently analyzes.
The chromatographic condition of step (3) and Mass Spectrometry Conditions are equal to step (1).
Above-mentioned chromatographic condition and Mass Spectrometry Conditions highly sensitive, capacity of resisting disturbance is strong, simple to operate, reproducible, can Realize cigarette mainstream smoke condensate detects while tens kinds of pesticide such as organophosphor, carbamate chemicals for agriculture, improve Detection efficiency, adds the scope of application of the present invention.The detection limit of the present invention is low, and it is fixed to calculate with 10 times of signal to noise ratios (S/N=10) Amount limit (LOQ), quantitative detection limit is between 0.03ng/cig～10ng/cig.The response rate of the inventive method is high, reproducible, Wherein, the response rate of pesticide is between 67.8%～119.6%, and relative standard deviation (RSD) is between 0.3%～11.4%.
The method of the present invention by introduce dispersive liquid-liquid microextraction technology instead of traditional nitrogen blow wait concentration step, simplification Existing sample treatment, and it is provided that the most more stable measurement result.Compared with prior art the inventive method tool There is a following excellent results:
(1) the inventive method has been firstly introduced dispersive liquid-liquid microextraction technology and has been applied to cigarette mainstream smoke condensate middle peasant Medicine residual quantitative analysis, simplifies sample pre-treatments, and concentration effect is notable.
(2) the inventive method have employed the GC-MS/MS of high sensitivity and strong anti-interference ability and detects, and therefore has behaviour Make accurate, highly sensitive and reproducible advantage.
(3) examine while multiple types, many groups pesticide residues during the inventive method achieves cigarette mainstream smoke condensate Survey, improve detection efficiency.
Detailed description of the invention
Following example are pressed aforesaid operations method and are implemented:
Reagent:
Standard sample of pesticide: alachlor, drinox, M 9834, benfluralin, α-Gamma Hexaochlorocyclohexane, β-Gamma Hexaochlorocyclohexane, δ-Gamma Hexaochlorocyclohexane, Gamma hch, Biphenthrin, butralin, Niran (suitable), Niran (instead), chlopyrifos, chlorpyrifos-methyl, clomazone, cyfloxylate, Lambda-cyhalothrin, cypermethrin, chlorthaldimethyl, DDD-o, p', DDD-p, p', DDE-o, p', DDE-p, p', DDT-o, p', DDT-p, p', diazinon, dieldrin, diphenamide, disulfoton, α-5a,6,9,9a-hexahydro-6,9-methano-2,4, β-5a,6,9,9a-hexahydro-6,9-methano-2,4,5a,6,9,9a-hexahydro-6,9-methano-2,4 sulfuric ester, phonamiphos, times sulfur Phosphorus, fenvalerate, fluazifop, flucythrinate, flumetralim, heptachlor, Heptachlor epoxide-anti-, Heptachlor epoxide-suitable, Perchlorobenzene, Isopropalin, Isoprothiolane, metalaxyl, methoxychlor, isopropyl methoxalamine, mirex, nitrile bacterium azoles, pebulate, Wu Junzuo, diformazan Penta spirit, Permethrin (suitable), Permethrin (instead), thimet, Butacide, Aphox, pirimiphos-methyl, Tefluthrin, thionazin, three Oxazolone, Triadimenol, trefanocide；It is standard substance.
Internal standard substance: TPP, for standard substance.It is configured to acetonitrile solution (inner mark solution, the internal standard of the TPP that concentration is 20 μ g/mL Working solution)；
Acetonitrile, acetone, carbon tetrachloride, be chromatographically pure reagent.
Pure water, meets the requirement of one-level water in GB/T 6682.
Instrument:
U.S.'s Agilent 7000B gas chromatogram-triple quadrupole bar tandem mass spectrometer (GC-MS/MS)；Britain Si Rulin SM 450 linear type smoking machines；U.S.'s Labnet VtexMixer VX200 agitator；Germany's Sigma High speed refrigerated centrifuge.
Embodiment 1:
Step (1): preparation pesticide standard solution:
Weigh 0.01g (being accurate to 0.1mg) various standard sample of pesticide, be placed in same 10mL volumetric flask, use acetone solution And constant volume obtains the mixed standard solution I of 1mg/mL；Accurately pipette 0.2mL mixed standard solution I in 100mL volumetric flask, use Acetonitrile constant volume, is configured to the mixed standard solution II that each pesticide concentration is 2 μ g/mL；Accurately pipette 0.01mL, 0.02mL, The mixed standard solution II of 0.05mL, 0.1mL, 0.2mL, 0.5mL and 1mL, is placed in 10mL volumetric flask, accurately adds 100 μ L Inner mark solution, uses acetonitrile constant volume, obtains series standard working solution.The series standard solution concentration of preparation is: 2ng/mL, 4ng/ mL、10ng/mL、20ng/mL、40ng/mL、100ng/mL、200ng/mL。
The standard working solution of the variable concentrations prepared is injected GC-MS/MS, carries out quantitatively dividing of pesticide with internal standard method Analysis, when GC-MS/MS measures, the chromatographic condition of employing is: chromatographic column: HP-5MS quartz capillary column (30m × 0.25mm×0.25μm)；Injector temperature: 280 DEG C；Temperature programming: initial temperature 60 DEG C, with 40 DEG C/min liter after holding 1min To 120 DEG C, then rise to 310 DEG C with 5 DEG C/min；Program after post: 310 DEG C, keeps 5min；Splitless injecting samples, does not shunt the time 1min；Carrier gas: helium (purity is 99.999%)；Constant current mode, flow velocity is 1.2mL/min；Sample size: 1 μ L.Total run time For 40.5min.
The Mass Spectrometry Conditions used is: ionization energy 70eV；Heater current: 35 μ A；Ion source temperature: 300 DEG C；Quadrupole rod temperature Degree: 180 DEG C；Transmission line temperature: 280 DEG C；Q2 collides gas: nitrogen (purity 99.999%, flow 1.5mL/min), quenching gas Helium (purity 99.999%, flow 2.25mL/min)；Solvent delay 5min；Scan mode: multiple-reaction monitoring (MRM).Multiple Pesticide and interior target retention time and mass spectrometry parameters are shown in Table 1.
Select its respective concentration of ion peak areas comparison to carry out regression analysis with pesticide and interior target two grades, obtain standard bent Line, is shown in Table 2.
Detection limit:
In blank extracting solution, add the standard solution of embodiment 1, and inject GC-MS/MS analysis, with 10 times of signal to noise ratios (S/N=10) calculating quantitative limit (LOQ), quantitative detection limit is between 0.03ng/cig～10ng/cig, and data are shown in Table 2.
Repeatability and recovery of standard addition:
In blank filter disc sample, add standard sample of pesticide solution (concentration is 100ng/mL), carry out pre-treatment the most respectively (step (2)) and GC-MS/MS analyze, and calculate its response rate according to adding scalar sum measured value, (pesticide linear that the results are shown in Table 2 Equation, regression coefficient, quantitative limit, the response rate and repeatability (n=6)).
Table 2
As can be seen from Table 2, the response rate of pesticide is between 67.8%～119.6%, and relative standard deviation (RSD) exists Between 0.3%～11.4%, illustrate that the response rate of the inventive method is high, reproducible.
Step (2): sample treatment (sample pre-treatments):
Collect the total particulate matter in mainstream smoke of 4 cigarette sample A by ISO 3308:2000 method after, take off cambridge filter；Accurate Really addition 0.1mL internal standard working solution (acetonitrile solution of the TPP of 20 μ g/mL) and 20mL acetonitrile are in conical flask, with 150r/min Oscillation extraction 30min；Take 1mL acetonitrile extraction liquid and fill in conical centrifuge tube in 10mL tool, add 5mL water, add 200 μ L tetrachloros Change carbon, continue vibration 30s, form uniform emulsion, after being centrifuged 3min with 5000r/min, organic with syringe suction foot Solution in chromatograph bottle, analysis to be detected.
Step (3): GC-MS/MS measures:
Sample after extracting is measured, records detection pesticide and select ion peak areas ratio with interior target two grades, substitute into Standard curve, tries to achieve the content of various pesticide in sample A total particulate matter in mainstream smoke and is shown in Table 3.
Table 3
Note: " " expression does not detects
Embodiment 2:
As described in Example 1, difference is, selects another cigarette sample B, records its total particulate matter in mainstream smoke Pesticides mesh The content of mark thing is shown in Table 4.
Table 4
Note: " " expression does not detects
Embodiment 3:
As described in Example 1, difference is, selects another cigarette sample C, records its total particulate matter in mainstream smoke Pesticides mesh The content of mark thing is shown in Table 5.
Table 5
Note: " " expression does not detects
Being found by each embodiment, it is residual that this method can quickly, accurately detect the Multiple Pesticides in cigarette mainstream smoke condensate Staying, measurement result is accurate, reproducible；Detecting while can realizing 60 Multiple Pesticides, detection efficiency is high.
Comparative example 1:
It is with embodiment 1 difference, in step (2), acetonitrile extraction liquid: water: the volume ratio that adds of carbon tetrachloride is 1:5: 0.5.Do not detect the agricultures such as the Isoprothiolane in the cigarette mainstream smoke condensate that embodiment 1 provides, metalaxyl, Butacide, triazolone Medicine remains, and illustrates that, when extractant volume is the biggest, enrichment times deficiency causes the object of lower content not detect.
Comparative example 2:
It is with embodiment 1 difference, in step (2), acetonitrile extraction liquid: water: the volume ratio that adds of carbon tetrachloride is 2:5: 0.2.Pesticide residues in the cigarette mainstream smoke condensate that embodiment 1 provides do not detect substantially, illustrate (i.e. to disperse when acetonitrile Agent) volume the biggest time, pesticide object dissolubility in aqueous phase increases, thus causes the carbon tetrachloride extraction to object Efficiency is substantially reduced.
Comparative example 3:
It is with embodiment 1 difference, in step (2), uses dichloromethane as extractant, substitute carbon tetrachloride.Result Display, has no the layering of aqueous phase and organic facies, illustrate that dichloromethane is under this ratio during dispersive liquid-liquid microextraction after being centrifuged Good extract and separate effect can not be reached.

Claims (9)

1. in a cigarette mainstream smoke condensate, the GC-MS/MS of Multiple Pesticides residual analyzes method, it is characterised in that include Following steps:
(1): preparation standard sample of pesticide solution, it is measured by gas chromatography tandem mass spectrometry (GC-MS/MS) and matching obtains Standard curve；
(2): trapping having the cambridge filter of cigarette mainstream smoke condensate through acetonitrile mechanical shaking extraction, it is micro-that extracting solution is dispersed through liquid liquid Centrifugal treating is carried out after extraction；
(3): the sedimentary facies after Li Xin is measured under the conditions of the gas chromatography tandem mass spectrometry of step (1) again；And mensuration is tied Fruit substitutes into standard curve and tries to achieve cigarette mainstream smoke condensate Pesticide Residues content.
2. in cigarette mainstream smoke condensate as claimed in claim 1, the GC-MS/MS of Multiple Pesticides residual analyzes method, its Being characterised by, in step (1) and step (3), using internal standard method to be measured, the internal standard substance of interpolation is triphenyl.
3. in cigarette mainstream smoke condensate as claimed in claim 2, the GC-MS/MS of Multiple Pesticides residual analyzes method, its Being characterised by, in step (1), standard solution is after GC-MS/MS analyzes, then selects quasi-molecular ions with two grades of pesticide and internal standard substance Area ratio carries out regression analysis to its respective concentration, obtains standard curve.
4. in cigarette mainstream smoke condensate as claimed in claim 1, the GC-MS/MS of Multiple Pesticides residual analyzes method, its Being characterised by, mechanical shaking extraction process is carried out on shaker, and the frequency of oscillation of shaker is 150-180r/min, during oscillation extraction Between be 30-50min.
5. in cigarette mainstream smoke condensate as claimed in claim 1, the GC-MS/MS of Multiple Pesticides residual analyzes method, its It is characterised by, in extracting solution, adds water and carbon tetrachloride carries out dispersive liquid-liquid microextraction, wherein, extracting solution: water: carbon tetrachloride The volume ratio that adds be 1:3-5:0.05-0.2.
6. in cigarette mainstream smoke condensate as claimed in claim 1, the GC-MS/MS of Multiple Pesticides residual analyzes method, its Being characterised by, in centrifugal process, centrifugal rotational speed is 5000-6000r/min, and centrifugation time is 3-5min.
7. in cigarette mainstream smoke condensate as claimed in claim 1, the GC-MS/MS of Multiple Pesticides residual analyzes method, its Being characterised by, in step (1) and step (3), when GC-MS/MS measures, the chromatographic condition of employing is:
Chromatographic column: HP-5MS quartz capillary column: 30m × 0.25mm × 0.25 μm；
Injector temperature: 280 DEG C；Temperature programming: initial temperature 60 DEG C, rises to 120 DEG C with 40 DEG C/min after keeping 1min, then with 5 DEG C/min rises to 310 DEG C；Program after post: 310 DEG C, keeps 5min；
Splitless injecting samples, does not shunt time 1min；
Carrier gas: helium, purity is 99.999%；
Constant current mode, flow velocity is 1.2mL/min；Sample size: 1 μ L.
8. in cigarette mainstream smoke condensate as claimed in claim 7, the GC-MS/MS of Multiple Pesticides residual analyzes method, its Being characterised by, the Mass Spectrometry Conditions of employing is:
Ionization energy 70eV；Heater current: 35 μ A；Ion source temperature: 300 DEG C；Quadrupole rod temperature: 180 DEG C；Transmission line temperature: 280 ℃；Q2 collides gas: nitrogen, purity 99.999%, flow 1.5mL/min；Quenching gas: helium, purity 99.999%, flow 2.25mL/min；Solvent delay 5min；Scan mode: multiple-reaction monitoring.
9. in cigarette mainstream smoke condensate as claimed in claim 1, the GC-MS/MS of Multiple Pesticides residual analyzes method, its Be characterised by, described standard sample of pesticide solution comprises alachlor, drinox, M 9834, benfluralin, α-Gamma Hexaochlorocyclohexane, β- Gamma Hexaochlorocyclohexane, δ-Gamma Hexaochlorocyclohexane, gamma hch, Biphenthrin, butralin, Niran (suitable), Niran (instead), chlopyrifos, chlorpyrifos-methyl, different evil Oxadiazon, cyfloxylate, lambda-cyhalothrin, cypermethrin, chlorthaldimethyl, DDD-o, p', DDD-p, p', DDE-o, p', DDE-p, p', DDT-o, p', DDT-p, p', diazinon, dieldrin, diphenamide, disulfoton, α-5a,6,9,9a-hexahydro-6,9-methano-2,4, β-5a,6,9,9a-hexahydro-6,9-methano-2,4,5a,6,9,9a-hexahydro-6,9-methano-2,4 Sulfuric ester, phonamiphos, fenthion, fenvalerate, fluazifop, flucythrinate, flumetralim, heptachlor, Heptachlor epoxide-anti-, Heptachlor epoxide-suitable, Perchlorobenzene, isopropalin, Isoprothiolane, metalaxyl, methoxychlor, isopropyl methoxalamine, mirex, nitrile bacterium Azoles, pebulate, Wu Junzuo, pendimethalin, Permethrin (suitable), Permethrin (instead), thimet, Butacide, Aphox, methylpyrimidine Phosphorus, Tefluthrin, thionazin, triazolone, Triadimenol and trefanocide.
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