CN105891362B - The remaining GC-MS/MS analysis methods of Multiple Pesticides in a kind of cigarette mainstream smoke condensate - Google Patents
The remaining GC-MS/MS analysis methods of Multiple Pesticides in a kind of cigarette mainstream smoke condensate Download PDFInfo
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- CN105891362B CN105891362B CN201610210976.0A CN201610210976A CN105891362B CN 105891362 B CN105891362 B CN 105891362B CN 201610210976 A CN201610210976 A CN 201610210976A CN 105891362 B CN105891362 B CN 105891362B
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract
The invention discloses a kind of remaining GC MS/MS analysis methods of Multiple Pesticides in cigarette mainstream smoke condensate, include the following steps：(1)：Pesticide standard sample solution is prepared, is measured by gas-chromatography tandem mass spectrum and is fitted to obtain standard curve；(2)：There is the cambridge filter of cigarette mainstream smoke condensate through acetonitrile mechanical shaking extraction trapping, extracting solution carries out centrifugal treating after being dispersed through liquid-liquid micro-extraction；Water is added into extracting solution and carbon tetrachloride carries 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；(3)：Sedimentary facies after centrifugation is measured under the conditions of the gas-chromatography tandem mass spectrum of step (1) again；And measurement result substitution standard curve is acquired into pesticide residual content in cigarette mainstream smoke condensate.Dispersive liquid-liquid microextraction technology is combined by the present invention with GC MS/MS, simplify sample handling procedure can make testing result it is more acurrate, it is stable, objectively react flue gas in pesticide residual condition.
Description
Technical field
The invention belongs to cigarette smoke the Detection Technologies of Pesticide Residues fields, relate generally to more in cigarette mainstream smoke condensate
The determination techniques of pesticide residue are planted, the remaining GC-MS/MS of Multiple Pesticides divides in specifically a kind of cigarette mainstream smoke condensate
Analysis method.
Background technology
Tobacco is during plantation, production and processing and storage, the use of unavoidable pesticide, thus related pesticide is caused to exist
Residual on tobacco leaf, cigarette is during burning and sucking and has part pesticide through being drawn into main flume.(the Zhang Hong such as Zhang Hongfei
It is non-, it radically reforms recklessly, Tang Gangling waits the rate of transform [J] the cigarettes of .29 kind organophosphorus pesticides into cigarette mainstream smoke condensate and stub
Careless science and technology, 2010 (07):39-42.) research shows that 29 kinds of organophosphorus pesticide moving into cigarette mainstream smoke condensate in pipe tobacco
Shifting rate is 0~6.3%, and (Wan Yilun, Zhang Hongfei, Gao Chuanchuan wait 126 kinds of pesticides in cigarette during burning and sucking for ten thousand firm human relations etc.
Migratory behaviour [J] Guizhou Agricultural Sciences, 2015 (05):101-106.) research shows that 126 kinds of pesticides are to cigarette mainstream in pipe tobacco
Average mobility in flue gas is 7.1%, and wherein endrin reaches as high as 31.7%, and variety classes pesticide is fired in cigarette
Migratory behaviour difference during suction is also very big, and Suckering agents average mobility highest, organophosphor, carbamate chemicals for agriculture etc. are flat
Equal mobility is relatively low.
Mainly there are gas chromatography, gas chromatography mass spectrometry method and liquid matter connection to the detection method of pesticide residue analysis in cigarette smoke
With etc., pretreatment process mainly has mechanical shaking extraction, accelerated solvent extraction etc.,
Such as, the Chinese patent literature of Publication No. CN104251897A discloses a kind of while measuring five kinds of differences in soil
The method of structure herbicide residue amount belongs to the remaining physico-chemical examination technique field of Pesticide Residue in Soil.It is exactly specifically to use
Dispersive solid-phase extraction combination 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.This method measurement sensitivity is low, and use scope is narrow, and the pesticide variety of analysis is less.
The Chinese patent literature of Publication No. CN102866215A disclose one grow tobacco and tobacco product in 20 kinds of pesticides
Remaining GC-MS/MS assay methods：By sample to be tested after water infiltration, acetonitrile and internal standard compound is added, then extraction of ocean eddies, salt
Analysis layering adds toluene and carries out liquid-liquid extraction, after taking supernatant to be dispersed through Solid Phase Extraction, with gas chromatography tandem mass spectrometry method
The method being measured.This method pre-treatment is comparatively laborious, and the sample type measured simultaneously is less.
Persticide residue in total particulate matter in mainstream smoke is relatively low, generally requires in pre-treatment operating process and is carried out to extract liquor
Concentration is in favor of detection and analysis, but cumbersome pre-treatment may result in the rate of recovery reduction of part pesticide, and testing result is inaccurate
Really.
Invention content
The purpose of the present invention is intended to provide a kind of having that the filter disc of cigarette mainstream smoke condensate is extracted, dispersion liquid by trapping
The method that gas chromatography tandem mass spectrometry (GC-MS/MS) is measured after liquid micro-extraction.This method can quickly, accurately detect cigarette
Multiple Pesticides residual in total particulate matter in mainstream smoke, measurement result are accurate, reproducible.
The remaining GC-MS/MS analysis methods of Multiple Pesticides in a kind of cigarette mainstream smoke condensate, include the following steps：
(1)：Pesticide standard sample solution is prepared, is measured and is fitted by gas chromatography tandem mass spectrometry (GC-MS/MS)
Obtain standard curve；
(2)：There is the cambridge filter of cigarette mainstream smoke condensate through acetonitrile mechanical shaking extraction trapping, extracting solution is dispersed through liquid
Centrifugal treating is carried out after liquid micro-extraction；
(3)：Sedimentary facies after centrifugation is measured under the conditions of the gas chromatography tandem mass spectrometry of step (1) again；And it will survey
Determine result substitution standard curve and acquires pesticide residual content in cigarette mainstream smoke condensate.
There are many possible remaining pesticide variety in cigarette mainstream flue gas, and content is relatively low, realize the Gao Ling of pesticide in flue gas
The detection difficulty of quick property is larger.The present invention carries out cigarette mainstream flue gas pesticide residue ingredient using dispersive liquid-liquid microextraction technology
Extraction blows instead of traditional nitrogen and waits concentration steps, simplifies sample handling procedure.In addition, by dispersive liquid-liquid microextraction technology
Be combined with GC-MS/MS, can make testing result it is more acurrate, it is stable, objectively react flue gas in pesticide residual condition.Mainstream smoke
Multiple types, multigroup other pesticide residue can be realized while be detected in gas granule phase substance, effectively improve detection efficiency.
It in step (1) and step (3), is measured using internal standard method, the internal standard compound of addition is triphenyl.
Such as, during preparing standard solution and testing sample solution (sedimentary facies), inner mark solution is added.The internal standard
Solution is the acetonitrile solution of triphenyl.Such as, the acetonitrile solution of the TPP (triphenyl) of a concentration of 20 μ g/mL.
In step (1), preparing standard sample solution processes is：
Standard sample of pesticide is weighed respectively, with acetone solution, then adds internal standard compound and with dilution in acetonitrile to concentration ladder
The standard solution containing various pesticides of degree；
Include alachlor, drinox, M 9834, benfluralin, α-six six six, β-six in the pesticide standard sample solution
Six or six, δ-six six six, lindane, Biphenthrin, butralin, Niran (suitable), Niran (anti-), 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, dieldrite, 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 acid
Ester, phonamiphos, Entex, fenvalerate, fluazifop, flucythrinate, flumetralim, heptachlor, Heptachlor epoxide-be anti-, epoxy
Heptachlor-is suitable, hexachloro-benzene, isopropalin, Isoprothiolane, metalaxyl, methoxychlor, isopropyl methoxalamine, mirex, nitrile bacterium azoles, gram
Careless enemy, penconazole, pendimethalin, Permethrin (suitable), Permethrin (anti-), thimet, Butacide, Aphox, pirimiphos-methyl, seven
Flumethrin, thionazin, triazolone, Triadimenol and trefanocide.
Such as, the manner of formulation of standard solution is：The various pesticide standards described in 0.01g (being accurate to 0.1mg) are weighed respectively
Product are placed in same 10mL volumetric flasks, and the mixed standard solution I of 1mg/mL is obtained with acetone solution and constant volume；Accurately pipette
0.2mL mixed standard solutions I, with acetonitrile constant volume, are configured to the mixing mark that each pesticide concentration is 2 μ g/mL in 100mL volumetric flasks
Quasi- solution II；The accurate mixed standard solution II for pipetting 0.01mL, 0.02mL, 0.05mL, 0.1mL, 0.2mL, 0.5mL and 1mL,
It is placed in 10mL volumetric flasks, it is accurate that 100 μ L inner mark solutions (acetonitrile solution of the TPP of a concentration of 20 μ g/mL) are added, it is fixed with acetonitrile
Hold to get 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 the completion of standard solution is prepared, when carrying out GC-MS/MS measurement, GC realizes the separation of ingredient in sample.MS realizes sample
The qualitative and quantitative analysis of ingredient in product.The detection parameters of GC and MS influence the separating degree of sample to be tested, detection limit very big.
In the present invention, in step (1) and step (3), when GC-MS/MS is measured, the chromatographic condition that uses for：
Chromatographic column：HP-5MS quartz capillary columns：30m×0.25mm×0.25μm；
Injector temperature：280℃；Temperature programming：60 DEG C of initial temperature with 40 DEG C/min rises to 120 DEG C after keeping 1min,
Again 310 DEG C are risen to 5 DEG C/min；Program after column：310 DEG C, keep 5min；
Splitless injecting samples do not shunt time 1min；
Carrier gas：Helium, purity 99.999%；
Constant current mode, flow velocity 1.2mL/min；Sample size：1μL.
The Mass Spectrometry Conditions used for：
Ionization energy 70eV；Heater current：35μA；Ion source temperature：300℃；Quadrupole rod temperature：180℃；Transmission line temperature
Degree：280℃；Q2 collision 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 and interior target retention time and mass spectrometry parameters (MRM) in standard solution are shown in Table 1.
Table 1
In step (1), standard solution selects quasi-molecular ions face after GC-MS/MS is analyzed, then with the two level of pesticide and internal standard compound
Product compares its respective concentration and carries out regression analysis, obtains standard curve.
Step (2) (i.e. fume sample pre-treatment) is parallel step, no elder generation with the drawing process (step (1)) of standard curve
Sequence afterwards.
In step (2), in main flume the remaining extracting method of pesticide by directly influence test result accuracy and
Confidence level.In the present invention, the granule phase substance of main flume is collected by cambridge filter, then acetonitrile is used to be extracted as dispersant.
Water and extractant are added into extracting solution again, fully shaking is then centrifuged, i.e., the granule phase substance of main flume is enriched with to extractant
In, then the extraction oxidant layer after centrifugation is measured.
Every cambridge filter presses ISO 3308：2000 methods collect the total particulate matter in mainstream smoke of 3-5 branch cigarette samples.Oscillation
In extraction process, every cambridge filter adds the acetonitrile of 15-25mL.
Preferably, mechanical shaking extraction process carries out on shaker, the frequency of oscillation of shaker is 150-180r/min, is shaken
It is 30-50min to swing extraction time.Further preferably, the frequency of oscillation of shaker is 150r/min, and the oscillation extraction time is
30min。
Preferably, adding water and carbon tetrachloride progress dispersive liquid-liquid microextraction into extracting solution, 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 adds volume
Than being 1:5:0.2.
For the extractant that the present invention uses for carbon tetrachloride, the organic principle that can be fully enriched in extracting solution makes testing result
It is more objective.
Preferably, in centrifugal process, centrifugal rotational speed 5000-6000r/min, centrifugation time 3-5min.Further
It is preferred that in centrifugal process, centrifugal rotational speed 5000r/min, centrifugation time 3min.
Such as, the preparation method (sample pretreatment process) of cigarette mainstream smoke condensate sample to be tested is：By ISO 3308：
After 2000 methods collect the total particulate matter in mainstream smoke of 4 cigarette samples, cambridge filter is removed；It is accurate that the work of 0.1mL internal standards is added
Liquid (inner mark solution, the acetonitrile solution of the TPP of a concentration of 20 μ g/mL) and 20mL acetonitriles are vibrated in conical flask with 150r/min
Extract 30min；It takes 1mL acetonitriles extracting solution to have in plug conical centrifuge tube in 10mL, 5mL water is added, adds 200 μ L, tetra- chlorinations
Carbon forms uniform emulsion after persistent oscillation 30s, organic molten with syringe suction foot after centrifuging 3min with 5000r/min
Liquid then carries out the GC-MS/MS analyses of step (3) in chromatography bottle.
The chromatographic condition and Mass Spectrometry Conditions of step (3) and being equal for step (1).
The high sensitivity of above-mentioned chromatographic condition and Mass Spectrometry Conditions, strong antijamming capability is easy to operate, reproducible, can
It detects, improves while realizing tens kinds of pesticides such as organophosphor, carbamate chemicals for agriculture in cigarette mainstream smoke condensate
Detection efficiency increases the scope of application of the present invention.The detection limit of the present invention is low, and it is fixed to be calculated with 10 times of signal-to-noise ratio (S/N=10)
Amount limit (LOQ), quantitative detection limit is between 0.03ng/cig~10ng/cig.The rate of recovery of the method for the present invention is high, reproducible,
Wherein, the rate of recovery 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 blows equal concentration steps by introducing dispersive liquid-liquid microextraction technology instead of traditional nitrogen, simplifies
Existing sample treatment, and more acurrate more stable measurement result can be provided.The method of the present invention has compared with prior art
There are following excellent results：
(1) the method for the present invention has been firstly introduced dispersive liquid-liquid microextraction technology applied to cigarette mainstream smoke condensate middle peasant
The analysis of medicine residual quantity, simplifies sample pre-treatments, and concentration effect is notable.
(2) the method for the present invention uses highly sensitive and strong anti-interference ability GC-MS/MS and is detected, therefore with behaviour
Make accurate, high sensitivity and reproducible advantage.
(3) examined while the method for the present invention realizes multiple types in cigarette mainstream smoke condensate, multigroup other pesticide residue
It surveys, improves detection efficiency.
Specific implementation mode
Following embodiment is implemented by aforesaid operations method：
Reagent：
Standard sample of pesticide：Alachlor, drinox, M 9834, benfluralin, α-six six six, β-six six six, δ-six six six,
Lindane, Biphenthrin, butralin, Niran (suitable), Niran (anti-), 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, dieldrite, 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 sulphur
Phosphorus, fenvalerate, fluazifop, flucythrinate, flumetralim, heptachlor, Heptachlor epoxide-are anti-, Heptachlor epoxide-is suitable, hexachloro-benzene,
Isopropalin, Isoprothiolane, metalaxyl, methoxychlor, isopropyl methoxalamine, mirex, nitrile bacterium azoles, pebulate, penconazole, diformazan
Penta spirit, Permethrin (suitable), Permethrin (anti-), thimet, Butacide, Aphox, pirimiphos-methyl, Tefluthrin, thionazin, three
Oxazolone, Triadimenol, trefanocide；It is standard items.
Internal standard compound：TPP is standard items.It is configured to acetonitrile solution (inner mark solution, the internal standard of the TPP of a concentration of 20 μ g/mL
Working solution)；
Acetonitrile, acetone, carbon tetrachloride are chromatography pure reagent.
Pure water meets the requirement of level-one water in GB/T 6682.
Instrument：
U.S.'s Agilent 7000B gas-chromatographies-triple quadrupole bar tandem mass spectrometer (GC-MS/MS)；Britain Si Rulin SM
450 linear type smoking machines；U.S.'s Labnet VtexMixer VX200 oscillators；German Sigma high speed freezing centrifuges.
Embodiment 1：
Step (1)：Prepare pesticide standard solution：
0.01g (being accurate to 0.1mg) various standard sample of pesticide are weighed, is placed in same 10mL volumetric flasks, uses acetone solution
And constant volume obtains the mixed standard solution I of 1mg/mL；0.2mL mixed standard solutions I accurately are pipetted in 100mL volumetric flasks, are used
Acetonitrile constant volume is configured to the mixed standard solution II that each pesticide concentration is 2 μ g/mL；It is accurate pipette 0.01mL, 0.02mL,
The mixed standard solution II of 0.05mL, 0.1mL, 0.2mL, 0.5mL and 1mL, are placed in 10mL volumetric flasks, accurate that 100 μ L are added
Inner mark solution, with acetonitrile constant volume to get 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 prepared various concentration is injected into GC-MS/MS, quantitative point that pesticide is carried out with internal standard method
Analysis, when GC-MS/MS is measured, the chromatographic condition that uses for：Chromatographic column：HP-5MS quartz capillary columns (30m ×
0.25mm×0.25μm)；Injector temperature：280℃；Temperature programming：60 DEG C of initial temperature, keep 1min after with 40 DEG C/min liters
310 DEG C are risen to 120 DEG C, then with 5 DEG C/min；Program after column：310 DEG C, keep 5min；Splitless injecting samples do not shunt the time
1min；Carrier gas：Helium (purity 99.999%)；Constant current mode, flow velocity 1.2mL/min；Sample size：1μL.Total run time
For 40.5min.
The Mass Spectrometry Conditions used for：Ionization energy 70eV；Heater current：35μA；Ion source temperature：300℃；Quadrupole rod temperature
Degree：180℃；Transmission line temperature：280℃；Q2 collision 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).It is a variety of
Pesticide and interior target retention time and mass spectrometry parameters are shown in Table 1.
It compares its respective concentration with pesticide and interior target two level selection ion peak areas and carries out regression analysis, obtain standard song
Line is shown in Table 2.
Detection limit：
The standard solution of embodiment 1 is added in blank extracting solution, and injects GC-MS/MS analyses, with 10 times of signal-to-noise ratio
(S/N=10) quantitative limit (LOQ) is calculated, for quantitative detection limit between 0.03ng/cig~10ng/cig, data are shown in Table 2.
Repeatability and recovery of standard addition：
Pesticide standard sample solution (a concentration of 100ng/mL) is added in blank filter disc sample, then carries out pre-treatment respectively
(step (2)) and GC-MS/MS are analyzed, and according to adding scalar sum measured value to calculate its rate of recovery, the results are shown in Table 2 (pesticide it is linear
Equation, regression coefficient, quantitative limit, the rate of recovery and repeatability (n=6)).
Table 2
As can be seen from Table 2, between 67.8%~119.6%, relative standard deviation (RSD) exists the rate of recovery of pesticide
Between 0.3%~11.4%, illustrate that the rate of recovery of the method for the present invention is high, it is reproducible.
Step (2)：Sample treatment (sample pre-treatments)：
By ISO 3308：After 2000 methods collect the total particulate matter in mainstream smoke of 4 cigarette sample A, cambridge filter is removed；It is accurate
0.1mL internal standards working solution (acetonitrile solution of the TPP of 20 μ g/mL) and 20mL acetonitriles is really added in conical flask, with 150r/min
Oscillation extraction 30min；It takes 1mL acetonitriles extracting solution to have in plug conical centrifuge tube in 10mL, 5mL water is added, adds 200 μ L tetrachloros
Change carbon and forms uniform emulsion after persistent oscillation 30s, it is organic with syringe suction foot after centrifuging 3min with 5000r/min
Solution is in chromatography bottle, analysis to be detected.
Step (3)：GC-MS/MS is measured：
Sample after extraction is measured, detection pesticide is measured and selects ion peak areas ratio with interior target two level, substitute into
Standard curve, the content for acquiring various pesticides in sample A total particulate matter in mainstream smoke are shown in Table 3.
Table 3
Note："-" expression is not detected
Embodiment 2：
As described in Example 1, difference lies in select another cigarette sample B, measure pesticide mesh in its total particulate matter in mainstream smoke
The content of mark object is shown in Table 4.
Table 4
Note："-" expression is not detected
Embodiment 3：
As described in Example 1, difference lies in select another cigarette sample C, measure pesticide mesh in its total particulate matter in mainstream smoke
The content of mark object is shown in Table 5.
Table 5
Note："-" expression is not detected
It is found by each embodiment, the Multiple Pesticides that this method can quickly, accurately detect in cigarette mainstream smoke condensate are residual
It stays, measurement result is accurate, reproducible；It can be achieved to detect while 60 Multiple Pesticides, detection efficiency is high.
Comparative example 1：
With embodiment 1 difference lies in, in step (2), acetonitrile extracting solution：Water：The volume ratio that adds of carbon tetrachloride is 1:5:
0.5.The agricultures such as Isoprothiolane, metalaxyl, Butacide, triazolone in the cigarette mainstream smoke condensate of the offer of embodiment 1 are provided
Medicine remains, and illustrates that enrichment times deficiency causes the object of lower content to be not detected when extractant volume is too big.
Comparative example 2：
With embodiment 1 difference lies in, in step (2), acetonitrile extracting solution：Water：The volume ratio that adds of carbon tetrachloride is 2:5:
0.2.Pesticide residue in the cigarette mainstream smoke condensate that embodiment 1 provides is not detected substantially, illustrates (to disperse when acetonitrile
Agent) volume it is too big when, solubility of the pesticide object in water phase increases, the extraction so as to cause carbon tetrachloride to object
Efficiency substantially reduces.
Comparative example 3：
Difference lies in step (2), using dichloromethane as extractant, substitute carbon tetrachloride with embodiment 1.As a result
It has been shown that, dispersive liquid-liquid microextraction have no the layering of water phase and organic phase, illustrate dichloromethane under the ratio after centrifuging in the process
Good extraction and separation effect cannot be reached.
Claims (5)
1. the remaining GC-MS/MS analysis methods of Multiple Pesticides in a kind of cigarette mainstream smoke condensate, which is characterized in that including
Following steps：
(1)：Pesticide standard sample solution is prepared, is measured and is fitted by gas chromatography tandem mass spectrometry (GC-MS/MS) and obtain
Standard curve；
Include alachlor, drinox, M 9834, benfluralin, α-six six six, β-six six in the pesticide standard sample solution
Six, δ-six six six, lindane, Biphenthrin, butralin, cis- Niran, trans- Niran, 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, dieldrite, 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 acid
Ester, phonamiphos, Entex, fenvalerate, fluazifop, flucythrinate, flumetralim, heptachlor, Heptachlor epoxide-be anti-, epoxy
Heptachlor-is suitable, hexachloro-benzene, isopropalin, Isoprothiolane, metalaxyl, methoxychlor, isopropyl methoxalamine, mirex, nitrile bacterium azoles, gram
Careless enemy, penconazole, pendimethalin, cis- Permethrin, trans- Permethrin, thimet, Butacide, Aphox, pirimiphos-methyl, seven fluorine
Pyrethroids, thionazin, triazolone, Triadimenol and trefanocide
(2)：There is the cambridge filter of cigarette mainstream smoke condensate through acetonitrile mechanical shaking extraction trapping, it is micro- that extracting solution is dispersed through liquid liquid
Centrifugal treating is carried out after extraction；Water is added into extracting solution and carbon tetrachloride carries 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；
(3)：Sedimentary facies after centrifugation is measured under the conditions of the gas chromatography tandem mass spectrometry of step (1) again；And it is tied measuring
Fruit substitutes into standard curve and acquires pesticide residual content in cigarette mainstream smoke condensate：
In step (1) and step (3), when GC-MS/MS is measured, the chromatographic condition that uses for：
Chromatographic column：HP-5MS quartz capillary columns：30m×0.25mm×0.25μm；
Injector temperature：280℃；Temperature programming：60 DEG C of initial temperature keeps rising to 120 DEG C with 40 DEG C/min after 1min, then with
5 DEG C/min rises to 310 DEG C；Program after column：310 DEG C, keep 5min；
Splitless injecting samples do not shunt time 1min；
Carrier gas：Helium, purity 99.999%；
Constant current mode, flow velocity 1.2mL/min；Sample size：1μL；
The Mass Spectrometry Conditions used for：
Ionization energy 70eV；Heater current：35μA；Ion source temperature：300℃；Quadrupole rod temperature：180℃；Transmission line temperature：280
℃；Q2 collision 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.
2. the remaining GC-MS/MS analysis methods of Multiple Pesticides in cigarette mainstream smoke condensate as described in claim 1,
It is characterized in that, in step (1) and step (3), is measured using internal standard method, the internal standard compound of addition is triphenyl.
3. the remaining GC-MS/MS analysis methods of Multiple Pesticides in cigarette mainstream smoke condensate as claimed in claim 2,
It is characterized in that, in step (1), standard solution selects quasi-molecular ions after GC-MS/MS is analyzed, then with the two level of pesticide and internal standard compound
Area compares its respective concentration and carries out regression analysis, obtains standard curve.
4. the remaining GC-MS/MS analysis methods of Multiple Pesticides in cigarette mainstream smoke condensate as described in claim 1,
It is characterized in that, mechanical shaking extraction process carries out on shaker, and the frequency of oscillation of shaker is 150-180r/min, when oscillation extraction
Between be 30-50min.
5. the remaining GC-MS/MS analysis methods of Multiple Pesticides in cigarette mainstream smoke condensate as described in claim 1,
It is characterized in that, in centrifugal process, centrifugal rotational speed 5000-6000r/min, centrifugation time 3-5min.
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