CN106324123B - The measuring method of persticide residue in tobacco and tobacco product - Google Patents
The measuring method of persticide residue in tobacco and tobacco product Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention discloses a kind of measuring methods of persticide residue in tobacco and tobacco product, belong to Detecting Pesticide field.Sample pre-treatments are easy to operate, quick in this method, and the removal efficiency of impurity and chaff interferent is high, can greatly shorten the processing time.Sample is after acetonitrile extracts first with anhydrous magnesium sulfate, sodium chloride, sodium citrate and DisodiumHydrogen Citrate purification, it is purified again with C18 and neutral alumina, other of pigment and tobacco plant tissue co-extraction object (such as fatty acid, chlorophyll) in tobacco can be effectively removed, the operations such as sample concentration, purification, derivative is avoided to cause the loss of pesticide composition to be measured.The measuring method has the advantage that, 1) since buccal cigarette is many kinds of, matrix difference is different, can not carry out quantitative analysis with calibration method using bare substrate, and Isotope Internal Standard Dilution Technique method can reduce influence of the matrix effect to quantitative result；2) easy to operate, quick, detection sensitivity is high, reproducible.
Description
Technical field
The present invention relates to a kind of measuring methods of persticide residue in tobacco and tobacco product, belong to Detecting Pesticide neck
Domain.
Background technique
Currently, the pesticide applied during tobacco growing mainly includes fungicide and insecticide.There are commonly more for fungicide
Bacterium spirit, nitrile bacterium azoles, penta bacterium spirit, Propamocarb, thiophanate-methyl, Triadimenol, triazolone and Fluoxastrobin, there are commonly pyridine worms for insecticide
Amidine and imidacloprid.In view of high residue risk of the above-mentioned pesticide in tobacco leaf, pesticide is residual in strict control tobacco and tobacco product
Allowance is the key that guarantee that tobacco product sucks safety.International tobacco research establishment (CORESTA) proposed in 2003
Guiding residue limits are given to 99 kinds of pesticides in tobacco, and monitor control index is extended to 120 kinds in 2013.
Sucking tobacco product is one of important form of new tobacco products, will not generate " environmental tobacco smoke ".State's collar extension
The typical additives of the smoke-free tobacco product containing type include sweetener, acid-base modifier, flavors and fragrances etc., manufacture craft it is more
Sample causes the based article to see outside, the larger difference in terms of physical characterization especially chemical index.Bagging oral containing type smokeless
Tobacco product is will to be directly loadable into pouch after the tobacco particle ground processing, and when use is put in oral cavity, without chewing,
Tobacco component passes through oral mucosal absorption after saliva is dissolved.Since pesticide residue is prevalent in tobacco, and tobacco is mouth
Primary raw material containing cigarette, therefore have pesticide residue in buccal cigarette unavoidably.But the type of buccal cigarette is more, matrix difference is different,
Quantitative analysis can not be carried out with calibration method using bare substrate.
Isotope Internal Standard Dilution Technique method can reduce influence (Isotope Dilution Mass Spectrometry of the matrix effect to quantitative result
The matrix effect of milk powder matrix drug residue is studied, and Yang is total, and 2013；Isotopic dilution-Solid Phase Extraction-LC/MS/MS method measurement
Bisphenol compound in dispensed food for baby, Gao Meng Jie etc., analytical chemistry), while the detection with higher of LC-MS/MS method
Sensitivity and stronger specificity, without making complete chromatographic isolation between analyte, sample pre-treatments are easy to operate, and analysis is surveyed
The examination time is short, it can be achieved that polymorphic type more remainss of pesticide whiles is analyzed.The patent of invention of publication No. CN105699538A discloses
A kind of measuring method of common pesticides content in cigarette mainstream flue gas, comprising: 1) sample pre-treatments: in flue gas trapping gas gas-phase objects
Acetonitrile and internal standard is added, vortex oscillation sequentially adds anhydrous magnesium sulfate, sodium chloride, sodium citrate and dihydrogen citrate after extracting
Anhydrous magnesium sulfate and PSA adsorbent (N- propyl ethylenediamine) is added in sodium, centrifuging and taking supernatant after vortex oscillation is extracted in supernatant,
Centrifuging and taking supernatant after vortex oscillation is extracted filters, to be measured after dilution constant volume；2) ultra performance liquid chromatography-tandem mass spectrum measurement: will
Solution to be measured injects UPLC-MS/MS system, chromatographic condition: UPLC HSST3 chromatographic column, 100 × 2.1mm, and 1.8 μm of partial size, stream
Dynamic phase A:0.1% aqueous formic acid, Mobile phase B: 0.1% formic acid methanol solution, flow velocity: 0.4mL/min, column temperature: 35 DEG C, sample introduction
Amount: 2 μ L, elution requirement: 0~2min (90%A-50%A), 2~2.4min (50%A-30%A), 2.4~4min (30%A-
20%A), 4~6min (20%A-5%A), 6~9.8min (5%A-5%A), 9.8~10min (5%A-90%A), 10~
12min (90%A-90%A)；Mass Spectrometry Conditions: electric spray ion source, spray voltage: 2.6kV, ionization temperature: 350 DEG C, atomization
Throughput: 800L/Hr, taper hole throughput: 50L/Hr, collision gas flow: 0.15mL/min, collision gas are argon gas, remaining gas
For nitrogen, residence time: 30msec, acquisition mode: cation MRM monitors ion pair and its corresponding collision energy is shown in Table 1.
The patent is extracted using acetonitrile, and extracts and purify sample using Dispersive solid phase extraction method, is analyzed and is surveyed through UPLC-MS/MS
Surely butralin in flue gas, carbendazim, imidacloprid, Isoprothiolane, metalaxyl, nitrile bacterium azoles, pendimethalin, Propamocarb, methyl sulphur are obtained
Bacterium spirit, triadimefon and triadimenol residual quantity, this method detection sensitivity is high, and selectivity is strong, but to pigment in tobacco etc. at
The removal effect divided is not good enough, and only with a kind of internal standard of TPP, the interference that cannot remove matrix effect not can be carried out accurate quantitative analysis.
Summary of the invention
The object of the present invention is to provide a kind of measuring methods of persticide residue in tobacco and tobacco product.
In order to achieve the goal above, the technical scheme adopted by the invention is that:
The measuring method of persticide residue in tobacco and tobacco product, the pre-treatment step including sample, specifically: in sample
Isotope mixing inner mark solution is added in product, acetonitrile is added after balance and extracts, adds anhydrous magnesium sulfate, sodium chloride, lemon
Lemon acid sodium and DisodiumHydrogen Citrate purifying, centrifuging and taking supernatant, is added C18 in supernatant and neutral alumina is net after purification
Change, filtering is after purification to get solution to be measured.
The tobacco product such as sucks tobacco product.
Following steps can be used in the preparation of the isotope mixing inner mark solution: respectively by each pesticide accordingly in target standard
Constant volume after product (such as deuterated object) are mixed with acetonitrile obtains each pesticide accordingly interior target standard reserving solution；It takes respectively a certain amount of each
Pesticide accordingly in target standard reserving solution, acetonitrile constant volume is used after mixing, obtains isotope mixing inner mark solution.
It is described to extract, purifying, purify the mode that vortex oscillation can be used, the whirlpool such as at 1800~2200rpm of revolving speed
Vibrate 1~6min.
5~10mL acetonitrile is added in every 1~2g sample in the extraction.
3~5g anhydrous magnesium sulfate, 1g sodium chloride, 1g sodium citrate and 0.5g lemon is added in every 1~2g sample in the purifying
Lemon acid disodium hydrogen.
40~60mg C18 and 40~60mg neutral alumina is added in every 1mL supernatant in the purification.C18 and neutral oxygen
Change aluminium and is purchased from Agilent Technologies.
The pesticide includes carbendazim, nitrile bacterium azoles, penconazole, Propamocarb, thiophanate-methyl, Triadimenol, triazolone, pyridine worm
Amidine, imidacloprid, Fluoxastrobin etc..
The measuring method of persticide residue in tobacco and tobacco product further includes the determination step of persticide residue, specifically
Are as follows: by solution to be measured inject liquid chromatography-tandem mass spectrometry system, within standard quantitative analysis, calculate in tobacco product
The residual quantity of pesticide；Liquid phase chromatogram condition are as follows: chromatographic column: Poroshell 120EC-C18, specification: 100mm × 3.0mm, partial size
2.7μm；Mobile phase A: 0.1% formic acid acetonitrile solution (volume fraction), Mobile phase B: 10mM formic acid aqueous ammonium, flow velocity:
0.4mL/min, column temperature: 40 DEG C, sample volume: 10 μ L, elution requirement (are specifically shown in the following table 1): 0~5min, 90%A-60%A, 5~
10min, 60%A-40%A, 10~15min, 40%A-10%A, 15~20min, 10%A-10%A, 20~20.1min,
10%A-90%A, 20.1~30min, 90%A-90%A；Tandem mass spectrum condition: electric spray ion source, ionization temperature: 500
DEG C, ionization voltage: 5500V, scanning mode: cation scanning, MRM type collection (parameter see the table below 2), atomization gas flow:
60psi, gas curtain throughput: 20psi, auxiliary heating throughput: 60psi, collision gas flow: 12psi, four kinds of gases are nitrogen
Gas.
1 eluent gradient elution requirement of table
Each pesticide of table 2 and its Isotopic Internal Standard monitoring ion pair remove cluster voltage and collision energy
Note: Fluoxastrobin is similar to imidacloprid property, and the two is using imidacloprid-d4 as internal standard；Other pesticides are with respectively right
The deuterated object answered is internal standard.
The inner mark method ration analysis are as follows: the hybrid standard working solution of series of concentrations is injected into liquid chromatography-tandem matter
Spectra system is made regression analysis with its corresponding concentration of ratio of each standard sample of pesticide interior target chromatographic peak area corresponding to its, is obtained
Standard curve；Solution to be measured is injected into liquid chromatography-tandem mass spectrometry system, obtains each detection pesticide interior target chromatography corresponding to its
The ratio of peak area substitutes into standard curve to get the concentration of each pesticide in solution to be measured.
Following steps can be used in the preparation of the hybrid standard working solution of the series of concentrations: respectively by the standard of each pesticide
Constant volume after product are mixed with acetonitrile obtains the standard reserving solution of each pesticide；The standard reserving solution of a certain amount of each pesticide is taken respectively, is mixed
Acetonitrile constant volume is used after conjunction, obtains hybrid standard stock solution；Above-mentioned hybrid standard stock solution is diluted to concentration ladder with acetonitrile
The hybrid standard working solution of degree is separately added into isotope mixing inner mark solution, as series of concentrations mixing mark in dilution
Quasi- working solution.
Beneficial effects of the present invention:
Sample pre-treatments are easy to operate, quick in the present invention, and the removal efficiency of impurity and chaff interferent is high, before capable of greatly shortening
Handle the time.Sample is first purified with anhydrous magnesium sulfate, sodium chloride, sodium citrate and DisodiumHydrogen Citrate after acetonitrile extracts, then
It is purified with C18 and neutral alumina, other of pigment and tobacco plant tissue co-extraction object in tobacco can be effectively removed (such as fat
Acid, chlorophyll etc.), avoid the operations such as sample concentration, purification, derivative from causing the loss of pesticide composition to be measured.
In the present invention 1) measuring method of tobacco product persticide residue has the advantage that since buccal cigarette type is numerous
More, matrix difference is different, can not carry out quantitative analysis with calibration method using bare substrate, and Isotope Internal Standard Dilution Technique method can
Reduce influence of the matrix effect to quantitative result；2) easy to operate, quick, detection sensitivity is high, reproducible, and detection limit exists
Between 0.002~0.011 μ g/g, recovery of standard addition is 85%~98%, and average relative standard's deviation is less than 6%.
Detailed description of the invention
Fig. 1 is the flow diagram of pesticide determination of residual amount method in the present invention；
Fig. 2 is the chromatography of ions figure of hybrid standard working solution 4 in embodiment 1；
Fig. 3 is the chromatography of ions figure of solution to be measured in embodiment 1.
Specific embodiment
Only invention is further described in detail for following embodiments, but does not constitute any limitation of the invention.
Instrument and reagent: 4000 quadrupole rod tandem mass spectrometer of API (American AB company)；Vortex oscillation instrument (U.S. Labnet
Company)；Sigma 3-30K centrifuge (German Sigma company)；166 electricity of 163 electronic balance (sensibility reciprocal 0.0001g) of AE and AE
Sub- balance (sensibility reciprocal 0.01g) (Mettler company, Switzerland).Pesticide is standard items；Acetonitrile, acetone, formic acid are the residual grade of agriculture.
Embodiment 1
The measuring method of persticide residue in buccal cigarette (flow diagram is shown in Fig. 1), comprising the following steps:
1) pre-treatment of sample
The purification of sample: it accurately weighs 1.0g buccal cigarette sample and has in plug centrifuge tube in 50mL, smash to pieces, 100 μ L10 μ are added
G/mL isotope mixing inner mark solution (each internal standard concentration is 10 μ g/mL in solution), it is small that juxtaposition balances 24 in a cool and dry place
When, uniformly to mix and exchange with measured matter completely, 10mL acetonitrile is added after balance, centrifuge tube is then placed in whirlpool and is mixed
On shaker, with 2000rpm rate oscillation 5min, then 3g anhydrous magnesium sulfate, 1g sodium chloride, 1g citric acid are added into centrifuge tube
Sodium and 0.5g DisodiumHydrogen Citrate (number of ions of DisodiumHydrogen Citrate is more compared with Sodium citrate, and effect of saltouing is more preferable), immediately
It is placed on whirlpool mixing shaker, with 2000rpm rate oscillation 5min, 3min is then centrifuged with 6000rpm rate.
The purification of sample: 50mg C18 and 50mg is added in 1.5mL centrifuge tube in the supernatant after pipetting 1mL centrifugation
Neutral alumina, on whirlpool mixing shaker with 2000rpm rate oscillation 2min, then with 6000rpm rate be centrifuged 3min, inhale
Supernatant is taken, is filtered through 0.45 μm of organic phase filter membrane, obtains solution to be measured.
The preparation steps of isotope mixing inner mark solution are as follows: it is accordingly interior to weigh 10mg (being accurate to 0.1mg) each pesticide respectively
Target standard items dissolve in 10mL volumetric flask, with acetonitrile and are settled to scale, obtain each pesticide accordingly interior target standard inventory
Liquid；Pipetting a certain amount of each pesticide respectively, accordingly interior target standard reserving solution is fixed with acetonitrile in the volumetric flask of the same 100mL
Hold to scale, obtain the isotope mixing inner mark solution of 10 μ g/mL, in be protected from light, preservation at -18 DEG C.
2) measurement of persticide residue
The preparation steps of the hybrid standard working solution of series of concentrations are as follows: weigh 10mg (being accurate to 0.1mg) each agriculture respectively
The standard items of medicine dissolve in 10mL volumetric flask, with acetonitrile and are settled to scale, obtain the standard reserving solution of each pesticide；It moves respectively
It takes the standard reserving solution of a certain amount of each pesticide in the volumetric flask of the same 100mL, is settled to scale with acetonitrile, obtain 10 μ
The hybrid standard stock solution of g/mL；20 μ L of hybrid standard stock solution, 50 μ L, 100 μ L, 250 μ L, 500 μ L, 1000 μ L are pipetted respectively
In the volumetric flask of 6 10mL, and it is separately added into the above-mentioned isotope mixing inner mark solution of 100 μ L and is had with acetonitrile constant volume
The hybrid standard working solution of concentration gradient.
The concentration of each standard sample of pesticide see the table below 3 in hybrid standard working solution.
The concentration of each standard sample of pesticide in the hybrid standard working solution of 3 series of concentrations of table
The hybrid standard working solution of series of concentrations is injected separately into liquid chromatography-tandem mass spectrometry system, liquid chromatogram item
Part are as follows: chromatographic column: Poroshell 120EC-C18, specification: 100mm × 3.0mm, 2.7 μm of partial size；Mobile phase A: 0.1% formic acid
Acetonitrile solution (volume fraction), Mobile phase B: 10mM formic acid aqueous ammonium, flow velocity: 0.4mL/min, column temperature: 40 DEG C, sample volume:
10 μ L, elution requirement (are shown in Table 1)；Tandem mass spectrum condition: electric spray ion source, ionization temperature: 500 DEG C, ionization voltage:
5500V, scanning mode: cation scanning, MRM type collection (parameter is shown in Table 2), atomization gas flow: 60psi, gas curtain throughput:
20psi, auxiliary heating throughput: 60psi, collision gas flow: 12psi, four kinds of gases are nitrogen；Measure each standard sample of pesticide
Unary linear regression equation (the retention time of each pesticide of the ratio of peak area and its corresponding internal standard peak area and its concentration relationship
And 4) relevant parameter see the table below, the selection chromatography of ions figure of hybrid standard working solution 4 is shown in Fig. 2.
Solution to be measured is injected into liquid chromatography-tandem mass spectrometry system, liquid chromatogram and tandem mass spectrum condition are same as above, and are obtained each
Detect the ratio of corresponding with its internal standard peak area of pesticide peak area, substitution standard curve obtains the dense of each pesticide in solution to be measured
Degree, wherein Fluoxastrobin 30ng/mL, carbendazim 28ng/mL, select chromatography of ions figure to see Fig. 3), then calculate in buccal cigarette
The residual quantity of each pesticide, result are 0.3 μ g/g of Fluoxastrobin, 0.28 μ g/g of carbendazim.
The retention time and relevant parameter of each pesticide of table 4
Embodiment 2
The measuring method of persticide residue in tobacco leaf, comprising the following steps:
1) pre-treatment of sample
The purification of sample: dry tobacco leaf is crushed, and accurately weighs 2.0g sample and has in plug centrifuge tube in 50mL, smashs to pieces, be added
100 μ L, 10 μ g/mL isotope mixing inner mark solution (with embodiment 1), juxtaposition balance 24 hours, after balance in a cool and dry place
10mL acetonitrile is added, then centrifuge tube is placed on whirlpool mixing shaker, with 2000rpm rate oscillation 5min, then to centrifugation
5g anhydrous magnesium sulfate, 1g sodium chloride, 1g sodium citrate and 0.5g DisodiumHydrogen Citrate are added in pipe, is immediately placed on whirlpool mixing vibration
It swings on instrument, with 2000rpm rate oscillation 5min, 3min is then centrifuged with 6000rpm rate.
The purification of sample: 50mg C18 and 50mg is added in 1.5mL centrifuge tube in the supernatant after pipetting 1mL centrifugation
Neutral alumina, on whirlpool mixing shaker with 2000rpm rate oscillation 2min, then with 6000rpm rate be centrifuged 3min, inhale
Supernatant is taken, is filtered through 0.45 μm of organic phase filter membrane, obtains solution to be measured.
2) measurement of persticide residue
Solution to be measured is injected into liquid chromatography-tandem mass spectrometry system, liquid chromatogram and tandem mass spectrum condition with embodiment 1,
The ratio of each detection pesticide peak area internal standard peak area corresponding with its is obtained, substitutes into the standard curve of embodiment 1, obtains to be measured
The concentration of each pesticide in solution, wherein Acetamiprid 120ng/mL, carbendazim 165ng/mL, then calculate each pesticide in tobacco leaf
Residual quantity, result be 1.2 μ g/g of Acetamiprid, 1.65 μ g/g of carbendazim.
In other embodiments of the invention, extract, purify and purification reagent dosage can appropriate adjustment, extract,
Each parameter can also appropriate adjustment in purifying and purification run.
Test example
Mark-on reclaims test: special that 0.10 μ of concentration is added in the sample for the accuracy for judging measuring method in embodiment 1
The mixed standard solution (being added together with isotope mixing inner mark solution) of g/g ibid carries out sample pre-treatments and subsequent measurements
Operation, mark-on reclaims test result see the table below 5.
Precision test: the mixed standard solution of 0.10 μ g/g of concentration is added in the sample, ibid carries out sample pre-treatments
And subsequent measurements operation, 5 repetitions are carried out altogether and are tested, and as a result see the table below 5.
5 rate of recovery of table and precision test result
Claims (4)
1. the measuring method of persticide residue in tobacco and tobacco product, it is characterised in that: pre-treatment step including sample and
The determination step of persticide residue；
The pre-treatment step of sample are as follows: isotope mixing inner mark solution is added in the sample, acetonitrile is added after balance and extracts,
Anhydrous magnesium sulfate, sodium chloride, sodium citrate and DisodiumHydrogen Citrate purifying are added, after purification centrifuging and taking supernatant, in supernatant
C18 and neutral alumina purification are added in liquid, filtering is after purification to get solution to be measured；
40 ~ 60mg C18 and 40 ~ 60mg neutral alumina is added in every 1mL supernatant in the purification；
The preparation steps of the isotope mixing inner mark solution are as follows: respectively by each pesticide accordingly in target standard items mix with acetonitrile
Constant volume afterwards obtains each pesticide accordingly interior target standard reserving solution；Each pesticide accordingly interior target standard reserving solution is taken respectively, after mixing
With acetonitrile constant volume, isotope mixing inner mark solution is obtained；
The pesticide include carbendazim, nitrile bacterium azoles, penconazole, Propamocarb, thiophanate-methyl, Triadimenol, triazolone, Acetamiprid,
Imidacloprid and Fluoxastrobin, corresponding Isotopic Internal Standard be followed successively by carbendazim-d3, nitrile bacterium azoles-d7, penconazole-d7, Propamocarb-d7,
Thiophanate-methyl-d6, Triadimenol-d4, triazolone-d4, Acetamiprid-d3, imidacloprid-d4, imidacloprid-d4；
The determination step of persticide residue are as follows: solution to be measured is injected into liquid chromatography-tandem mass spectrometry system, with inner mark method ration point
Analysis, calculates the residual quantity of pesticide in tobacco product；
Liquid phase chromatogram condition are as follows: chromatographic column: 120 EC-C18 of Poroshell, specification: 100mm × 3.0mm, 2.7 μm of partial size；Stream
Dynamic phase A:0.1% formic acid acetonitrile solution, Mobile phase B: 10mM formic acid aqueous ammonium, flow velocity: 0.4mL/min, column temperature: 40 DEG C, sample introduction
Amount: 10 μ L；Elution requirement: 0 ~ 5min, 90%A-60%A, 5 ~ 10min, 60%A-40%A, 10 ~ 15min, 40%A-10%A, 15 ~
20min, 10%A-10%A, 20 ~ 20.1min, 10%A-90%A, 20.1 ~ 30min, 90%A-90%A；Tandem mass spectrum condition: electron spray
Ion source, ionization temperature: 500 DEG C, ionization voltage: 5500V, scanning mode: cation scanning, MRM type collection, atomization gas
Flow: 60psi, gas curtain throughput: 20psi, auxiliary heating throughput: 60psi, collision gas flow: 12psi, four kinds of gases are equal
For nitrogen；
The inner mark method ration analysis are as follows: the hybrid standard working solution of series of concentrations is injected into liquid chromatography-tandem mass spectrometry system
System makees regression analysis with its corresponding concentration of ratio of each standard sample of pesticide interior target chromatographic peak area corresponding to its, obtains standard
Curve；Solution to be measured is injected into liquid chromatography-tandem mass spectrometry system, obtains each detection pesticide interior target chromatographic peak face corresponding to its
Long-pending ratio substitutes into standard curve to get the concentration of each pesticide in solution to be measured；
The preparation of the hybrid standard working solution of the series of concentrations uses following steps: respectively by the standard items and second of each pesticide
Constant volume after nitrile mixing, obtains the standard reserving solution of each pesticide；The standard reserving solution for taking a certain amount of each pesticide respectively, is used after mixing
Acetonitrile constant volume obtains hybrid standard stock solution；Above-mentioned hybrid standard stock solution is diluted to mixing with concentration gradient with acetonitrile
Standardization working solution is separately added into isotope mixing inner mark solution in dilution, and as series of concentrations hybrid standard works
Solution.
2. measuring method according to claim 1, it is characterised in that: the extraction, purifying, purification are all made of vortex oscillation
Mode.
3. measuring method according to claim 1, it is characterised in that: 5 ~ 10mL second is added in every 1 ~ 2g sample in the extraction
Nitrile.
4. measuring method according to claim 3, it is characterised in that: it is anhydrous that 3 ~ 5g is added in every 1 ~ 2g sample in the purifying
Magnesium sulfate, 1g sodium chloride, 1g sodium citrate and 0.5g DisodiumHydrogen Citrate.
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