CN104990778A - A method for acquiring flue-cured tobacco physical sample natural matrix positive material containing carbendazim residues - Google Patents

A method for acquiring flue-cured tobacco physical sample natural matrix positive material containing carbendazim residues Download PDF

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CN104990778A
CN104990778A CN201510403852.XA CN201510403852A CN104990778A CN 104990778 A CN104990778 A CN 104990778A CN 201510403852 A CN201510403852 A CN 201510403852A CN 104990778 A CN104990778 A CN 104990778A
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carbendazim
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tobacco
tobacco leaf
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CN104990778B (en
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师君丽
孔光辉
李勇
逄涛
吴玉萍
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Yunnan Academy of Tobacco Agricultural Sciences
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Yunnan Academy of Tobacco Agricultural Sciences
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Abstract

The invention discloses a method for acquiring a flue-cured tobacco physical sample natural matrix positive material containing carbendazim residues. The method comprises the steps of spraying a concentration of 25 percent of carbendazol wettable powder on the cultivated tobacco plants, and the application dosage is 300g per mu; taking tobacco leaves at leaf positions of the tenth leaf, the eleventh leaf, and the twelfth leaf of each tobacco plant, sampling in 2 hours and on the 1st day, the 3rd day, the 5th day, the 7th day, the 10th day, the 14th day, the 21st day, the 28th day, the 35th day and the 42nd day after applying the carbendazol wettable powder, detecting the content of thiophanate-methyl residues, and drawing a changing curve; sampling on the 42nd day after applying the carbendazol wettable powder according to the changing curve, baking and crushing the picked tobacco leaves, and sieving the baked and crushed tobacco leaves through a 40-mesh sieve and mixing uniformly; wherein the content of the carbendazim in the flue-cured tobacco physical sample natural matrix positive material is 6.14+/-0.03mg/kg. According to the method, a natural/polluted matrix standard sample which is consistent with a real sample is prepared, and the natural/polluted matrix standard sample is used for analysis and quality control of the carbendazim residues in the flue-cured tobacco, the consistency of the extraction rates of the quality control sample and the real sample under the same condition can be guaranteed, and the prepared natural/polluted matrix standard sample is uniform, stable, and is easy to store and use.

Description

A kind of flue-cured tobacco matter sample natural basal body positive material acquisition methods residual containing carbendazim
Technical field
The invention belongs to the natural basal body matter sample preparing technical field of Detecting Pesticide Quality Control, be specifically related to a kind of flue-cured tobacco matter sample natural basal body positive material acquisition methods residual containing carbendazim.
Background technology
The matrix RM ten points shortcoming of Pesticides Testing aspect.Need in Detecting Pesticide to set up sterling standard substance and substrate standard substance control to meet Detection job, solve in analyzing run into problem, ensure the requirements such as result is accurate.The residue detection regulation documentation requirements of European Union adopts standard model to control Detection job, checking detection method.Adopt reinforced legal system for matrix RM, though prepare easy, but exist object and matrix in conjunction with situation with truly detect the not quite identical situation of sample, thus extraction, purification behavior may be caused and truly detect sample not parity problem, carbendazim uses extensively in leaf tobacco production, easily cause residual, the research had no at present containing the tobacco natural matrix RM of carbendazim is reported.The present invention adopts and is worked into the operations such as abrasive dust, packaging, uniformity testing, stability test from tobacco leaf dispenser, sampling, baking, to be prepared into expection contents level tobacco leaf in carbendazim residual natural basal body RM, the situation that this RM form and object thereof are combined with matrix is all with truly to detect sample completely the same, thus avoid the defect of reinforced matrix RM, ensure that testing result is accurate.
Summary of the invention
The object of the present invention is to provide a kind of flue-cured tobacco matter sample natural basal body positive material acquisition methods residual containing carbendazim.
The object of the present invention is achieved like this, and the described flue-cured tobacco matter sample natural basal body positive material acquisition methods residual containing carbendazim, comprises dispenser, detection and sample preparation operation, specifically comprise:
A, dispenser: to cigarette strain spray concentration 25% carbendazol wettable powder of cultivation, every mu of formulation rate is 300g;
B, monitoring: the tobacco leaf of the 10th, 11,12 leaf positions is got in every strain cigarette strain, respectively at 2 after dispenser hour, and sampling in 1,3,5,7,10,14,21,28,35,42 day, detect carbendazim residual content according to YC/T 405.1-2011, draw the change curve of carbendazim residual content;
C, sample preparation: according to change curve the 42nd day harvesting tobacco leaf after administration of carbendazim residual content, institute's priming is processed into dry tobacco leaf through overbaking, again dry tobacco leaf is ground into powdery, by mixing after 40 mesh sieves, namely obtain the described flue-cured tobacco matter sample natural basal body positive material residual containing carbendazim; In described flue-cured tobacco matter sample natural basal body positive material, the content of carbendazim is 6.41 ± 0.03mg/kg.
Acquisition methods of the present invention is by adjustment dispenser condition and characterization processes, can prepare and truly detect carbendazim retention analysis Quality Control nature/pollution matrix standard model in the on all four flue-cured tobacco of sample, ensure that Quality Control sample and the consistance detecting sample extraction ratio under same operation condition.Described acquisition methods is easy, efficient, prepared nature/pollution matrix standard model homogeneity, excellent in stability, store, transport, easy to use.
Accompanying drawing explanation
Fig. 1 is carbendazim standard product chromatogram.
Fig. 2 is the change curve of carbendazim residual content in fresh tobacco leaf butt after dispenser.
Fig. 3 is the logarithmic curve that dispenser plays number of days after carbendazim residual content and dispenser in fresh tobacco leaf butt and cured tobacco leaf butt on the 3rd.
Embodiment
The present invention is further illustrated below, but limited the present invention never in any form, and any conversion done based on training centre of the present invention or replacement, all belong to protection scope of the present invention.
The flue-cured tobacco matter sample natural basal body positive material acquisition methods residual containing carbendazim of the present invention, comprises dispenser, monitoring and sample preparation operation, specifically comprises:
Described dispenser is cigarette strain spray concentration 25% carbendazol wettable powder to cultivation, and every mu of formulation rate is 300g;
Described monitoring is the tobacco leaf getting the 10th, 11,12 leaf positions in the strain of every strain cigarette, respectively at 2 after dispenser hour, and sampling in 1,3,5,7,10,14,21,28,35,42 day, detect carbendazim residual content according to YC/T 405.1-2011, draw the change curve of carbendazim residual content;
Described sample preparation is the change curve according to carbendazim residual content, within after administration the 42nd day, pluck tobacco leaf, institute's priming is processed into dry tobacco leaf through overbaking, again dry tobacco leaf is ground into powdery, by mixing after 40 mesh sieves, namely obtain the described flue-cured tobacco matter sample natural basal body positive material residual containing carbendazim; In described flue-cured tobacco matter sample natural basal body positive material, the content of carbendazim is 6.41 ± 0.03mg/kg.
Because carbendazim is cleared up comparatively slow in tobacco leaf, after dispenser, 42 days residual quantities are still comparatively large, and the sample carbendazim now gathered is combined with tobacco leaf firmly, and Maturity of Tobacco Leaf is good, the positive material good stability of acquisition, and each side index is closer to tobacco leaf to be analyzed.
What described dispenser operation adopted is the dispenser of even spraying method, and only dispenser is once for every mu of vega.
The weather condition of described dispenser operation is: a Zhou Wuyu after the dispenser same day and dispenser, can have light rain after one week.
Cigarette seeding row spacing set in described dispenser operation is 50cm*120cm.
The application process of the carbendazol wettable powder used in described dispenser operation adds 15L water in 75g carbendazim, mixes and make spray application after carbendazim water suspension.
When carrying out tobacco leaf sampling in described monitoring operation, tobacco leaf leaf position determines by order from top to bottom.
In described monitoring operation, carbendazim residual content is the content to butt.
Detect the water percentage of tobacco leaf according to YC/T 31 in described monitoring operation, carbendazim residual content in fresh tobacco leaf to be converted into the value calculated according to butt, thus the monitoring result of carbendazim residual content in comparative analysis tobacco leaf on equal footing.
In described monitoring operation, tobacco sample needs to shred mixing immediately after winning, and adopt inquartation contracting sample, the 200g that keeps sample is in-20 DEG C of preservations.
In described sample preparation operation, institute's priming is processed into dry tobacco leaf through baking, the baking process adopted is: three-phase-drying for tobacco technique, and concrete technology refers to: Liu Chunkui, tobacco flue-curing technology [J], and farmers' gives advice, 05 phase in 2008.
In described sample preparation operation, dry tobacco leaf is ground into powdery, by mixing after 40 mesh sieves, refers to and carrying out thick homogenising by pulverizing the rear tobacco leaf powder crossing 40 mesh sieves through artificial stirring, then mixing with V-Mixer.
The running parameter of described V-Mixer is: 15r/min, 50min.
embodiment 1
---containing the acquisition of the flue-cured tobacco matter sample natural basal body positive material that carbendazim remains
Experiment place: Yuxi Hongta District Huang Guan modern tobacco agriculture Specialty Co-operative Organization, test area 166m 2.
Experiment material:
1) cigarette strain: kind is cloud and mist 87, cigarette seeding row spacing is 50cm*120cm, according to local leaf tobacco production technology normal management, cigarette strain well-grown.
2) reagent: the carbendazol wettable powder of 25%, Sichuan Guoguang Agrochemical Co., Ltd..
3) instrument: Ultra Performance Liquid Chromatography (Waters, US), AB Sciex QTRAP 5500 mass spectrum (American AB Sciex company).
Experimental technique:
1) dispenser: dispenser weather: sunny.Insecticide-applying way: adopt even spraying method, 166m 2vega sprays the carbendazim water suspension that 15L prepares altogether, and pesticide preparation method is: take 75g carbendazim in sprayer, add 15L water, mix.
2) monitor: the tobacco leaf getting the 10th, 11,12 leaf positions in the strain of every strain cigarette according to order from top to bottom, respectively at 2 after dispenser hour, and sampling in 1,3,5,7,10,14,21,28,35,42 day.Each sampling amount is 2kg, and tobacco sample returns to laboratory (about needing 1h) immediately after winning, chopping mixing, and adopt inquartation contracting sample, 200 g that keep sample are in-20 DEG C of preservations.
Detect carbendazim residual content according to YC/T 405.1-2011 liquid chromatography-tandem mass spectrometry instrument, the running parameter of liquid chromatography-tandem mass spectrometry instrument is:
Liquid phase chromatogram condition: chromatographic column: ACQUITY UPLC HSS T3 (column length 100mm, internal diameter 2.1mm, Stationary liquid particle diameter 1.8 μm); Column temperature: 30 DEG C; Sample size: 2 μ L; Flow velocity 0.4mL/min.Mobile phase A: water, Mobile phase B: acetonitrile.Gradient elution: 0 ~ 2min, 10% B; 2 ~ 5 min, 10% B ~ 70% B; 5 ~ 6 min, 70% B; 6 ~ 7 min, 70% B ~ 10% B; 7 ~ 8 min, 10% B.
Mass Spectrometry Conditions: ionization mode: electron spray ESI; Scan mode: positive ion scans; Monitoring mode: multiple-reaction monitoring; Spray voltage: 5000 V; Atomization gas pressure: 0.552MPa; Gas curtain atmospheric pressure: 0.138 MPa; Auxiliary heating atmospheric pressure: 0.552 MPa; Ion source temperature: 600 DEG C, monitoring ion pair 192.2/160.1(DP:65 V, CE:26V), 192.2/132(DP:65 V, CE:41 V).
Detect the water percentage of tobacco leaf according to YC/T 31 simultaneously, carbendazim residual content in fresh tobacco leaf to be converted into the value calculated according to butt, thus the monitoring result of carbendazim residual content in comparative analysis tobacco leaf on equal footing.
3) sample preparation: pluck fresh tobacco leaf 100kg on the 42nd day after administration, when sampling every strain cigarette, all plucks the fresh tobacco leaf of the 10th, 11,12 leaf positions according to order from top to bottom.The tobacco leaf won is put into hothouse baking, and the baking process adopted is: three-phase-drying for tobacco technique, and concrete technology refers to: Liu Chunkui, tobacco flue-curing technology [J], and farmers' gives advice, 05 phase in 2008.
The dry tobacco leaf comminutor that is processed into will be toasted to pulverize and by 40 mesh sieves, tobacco leaf powder after sieving carries out thick homogenising through artificial stirring, use V-Mixer with the speed of 15r/min again, mixing 50min, can obtain the described flue-cured tobacco matter sample natural basal body positive material residual containing carbendazim.
Experimental result:
1) prediction of positive material sampling date: after dispenser, in fresh tobacco leaf the change curve of carbendazim residual content (to butt) is as shown in Figure 2.As shown in Figure 2, tobacco leaf sprays two days its residual quantities in carbendazim water suspension back and declines rapidly, then declines gently.The reason that in the 2 days tobacco leaves in dispenser back, carbendazim residual content declines rapidly is the carbendazim that newly sprays in tobacco leaf surface also not strong bonded with it, simultaneously, due to this stage carbendazim water suspension mass concentration height, then corresponding vapour pressure is large, and therefore volatilization loss is obvious.Carbendazim residual content, after 2 days reduce rapidly, enters the period normally based on degraded and growth dilution.As shown in Figure 2, the change rapidly due to tobacco leaf carbendazim residual content in 2 days of dispenser back, after 3 days, carbendazim is slowly cleared up in tobacco leaf, after dispenser, 42 days residual quantities are still comparatively large, and now carbendazim is combined more firm with tobacco leaf, the positive material good stability of acquisition, and Maturity of Tobacco Leaf is good, each side index, closer to tobacco leaf to be analyzed, is therefore suitable for the positive material collecting prospective quality concentration in after dispenser the 42nd day.
Testing result after rejecting the dispenser back detection data of 2 days map to the logarithm value of number of days after dispenser, obtains the logarithmic curve that dispenser plays number of days after carbendazim residual content (to butt) and dispenser in fresh tobacco leaf on the 3rd, as shown in Figure 3.Linear equation Y=-3.319Ln (x)+18.382, the linearly dependent coefficient of this figure are: 0.9816.
In the tobacco leaf powder that after dispenser, fresh tobacco leaf and sample preparation are processed into, the change curve of carbendazim residual content (to butt) as shown in Figure 3.As shown in Figure 3, under same dispenser and testing conditions, in the tobacco leaf powder be processed into by sample preparation in figure, the change curve of carbendazim residual content can Date of Sampling of Predict masculine gender material, and the level of carbendazim residual content in fresh tobacco leaf during sampling.
Such as, within the present embodiment the 5th day after administration, the 14th day, the 28th day, the 42nd day, respectively fresh tobacco leaf is plucked, the every sub-sampling 2kg of fresh tobacco leaf to be measured, laboratory (about needing 1h) is returned to immediately after winning, chopping mixing, adopt inquartation contracting sample, 200 g that keep sample are in-20 DEG C of preservations.Baking tobacco leaves to be measured gets fresh tobacco leaf 20kg at every turn, after baking, sample preparation becomes tobacco leaf powder, testing result shows, get the residual content of carbendazim in fresh tobacco leaf (to butt) and be respectively 19.89mg/kg, 13.73mg/kg, 8.78mg/kg and 6.77mg/kg, the carbendazim residual content in cured tobacco leaf powder is 13.17mg/kg, 9.16mg/kg, 7.34mg/kg and 6.44 mg/kg
embodiment 2
---the described homogeneity research containing the flue-cured tobacco matter sample natural basal body positive material that carbendazim remains
Experiment material:
1) sample: the sample prepared by method described in embodiment 1, sample time is in November, 2013.
2) reagent: with embodiment 1.
3) instrument: with embodiment 1.
Experimental technique:
Tobacco leaf powder after toasting, pulverize, sieve, mixing is loaded brown sample bottle, every bottle of 10g, stick the sample label of band numbering, the methods of sampling: by sample bottle serial number, utilize the table of random numbers to randomly draw 18 bottles, every bottle is detected 3 times, and detection method is with embodiment 1.Result carries out homogeneity statistical analysis by F method of inspection, and detection data result and the results of analysis of variance are in table 1 and table 2.The F value < F0.05 of Determination of carbendazim residue (17,36)=1.915, P > 0.05.Result to show between bottle that difference is remarkable, i.e. between the bottle of this candidate RM, homogeneity all meets the requirements
The measurement data of homogeneity research between table 1 bottle
Bottle number Detected value 1(mg/kg) Detected value 2(mg/kg) Detected value 3(mg/kg) Mean value Variance
1 6.28 6.46 6.32 6.35 0.0089
2 6.37 6.49 6.52 6.46 0.0063
3 6.42 6.46 6.39 6.42 0.0012
4 6.49 6.51 6.37 6.46 0.0057
5 6.41 6.47 6.59 6.49 0.0084
6 6.57 6.36 6.41 6.45 0.0120
7 6.25 6.48 6.34 6.36 0.0134
8 6.32 6.49 6.54 6.45 0.0133
9 6.53 6.32 6.46 6.44 0.0114
10 6.37 6.46 6.29 6.37 0.0072
11 6.23 6.46 6.33 6.34 0.0133
12 6.39 6.57 6.35 6.44 0.0137
13 6.47 6.69 6.68 6.61 0.0154
14 6.38 6.56 6.24 6.39 0.0257
15 6.27 6.58 6.48 6.44 0.0250
16 6.42 6.68 6.53 6.54 0.0170
17 6.4 6.38 6.37 6.38 0.0002
18 6.28 6.58 6.24 6.37 0.0345
Homogeneity research variance analysis between table 2 bottle
Difference source SS df MS F value P value F Critical
Between bottle 0.248 17 0.015 1.127 0.368 1.915
In bottle 0.466 36 0.013
Amount to 0.714 53
embodiment 3
---the described stability study containing the flue-cured tobacco matter sample natural basal body positive material that carbendazim remains
Experiment material:
1) sample: the sample prepared by method described in embodiment 1, sample time monthly samples from January, 2014, in Dec, 2014.
2) reagent: with embodiment 1.
3) instrument: with embodiment 1.
Experimental technique:
Tobacco leaf powder after toasting, pulverize, sieve, mixing is put into sample bottle, every bottle of 10g, stick the sample label of band numbering, put into-20 DEG C of preservations, monthly sample once, carry out 12 months altogether, carry out under (in laboratory) repeatability condition owing to measuring, wherein also include the instability of measurement.Long-time stability result of study is in table 3 and table 4.Result shows, and p value is all greater than 0.05, represents that recurrence is inapparent (for 95% confidence level, P < 0.05 just becomes significant).Preserve and detect after 1 year, detection method is with embodiment 1.Result shows that this candidate RM is more stable in 1 year.
The stability data of carbendazim in table 3 flue-cured tobacco
Time/moon Detected value 1(mg/kg) Detected value 1(mg/kg) Detected value 1(mg/kg) Mean value (mg/kg)
1 6.41 6.38 6.43 6.41
2 6.36 6.37 6.38 6.37
3 6.43 6.47 6.45 6.45
4 6.39 6.41 6.43 6.41
5 6.46 6.42 6.47 6.45
6 6.36 6.35 6.39 6.37
7 6.39 6.37 6.4 6.39
8 6.42 6.43 6.44 6.43
9 6.37 6.39 6.42 6.39
10 6.45 6.43 6.47 6.45
11 6.41 6.41 6.37 6.40
12 6.42 6.44 6.43 6.43
The existing analysis of variance in regression table of table 4 long-time stability data
df SS MS F P
Regretional analysis 1 0.0002 0.0002 0.2483 0.6290
Residual error 10 0.0098 0.0010
Amount to 11 0.0101
embodiment 4
---described definite value and the uncertainty evaluation containing the flue-cured tobacco matter sample natural basal body positive material that carbendazim remains
Experiment material:
1) sample: the sample prepared by method described in embodiment 1, sample time is in May, 2014.
2) reagent: with embodiment 1.
3) instrument: with embodiment 1.
Experimental technique:
1) measure: according to YC/T 405.1-2011, definite value is carried out to the flue-cured tobacco matter sample natural basal body positive material residual containing carbendazim.The laboratory of participating in collaborative definite value has: countries tobacco Quality Supervision and Inspection Center, agricultural product quality supervision and inspection center of the Ministry of Agriculture (Kunming), Hongta Tobacco(Group) Co., Ltd. technique center, Hongyunhonghe Tobacco (Group) Co., Ltd. technique center, tobacco research institute of Yunnan Province, Inspection & Quanrantine Tech Center, Yunnan Entry and Exit Inspection & Quarant, Yunnan Prov Academy Of Agricultural Sciences, Agricultural Research Institute Of Environmental Resources, Institute of Analysis of Yunnan Province, Yunnan Institute for nationalities.The laboratory of participating in collaborative definite value all adopts liquid chromatography-tandem mass spectrometry instrument to detect, and replicate determination 3 times, definite value result is that the testing result in 9 laboratories is averaged, and testing result is in table 5.
2) characteristic value: participate in collaborative definite value laboratory and adopt liquid chromatography-tandem mass spectrometry instrument to detect (n 0=3), definite value carbendazim is finally averaged by 9 laboratory results, definite value 6.41mg/kg.The evaluation of characteristic value uncertainty is according to GB/T 15000.3-2008 " standard model work directive/guide (3) standard model: the rule of definite value and statistical method ", consider that mensuration, homogeneity, stability are to the contribution of characteristic value overall uncertainty, namely by measured value standard uncertainty (u char), standard uncertainty (u between bottle bb), stability criterion uncertainty (u sts) synthesis and expand (Coverage factor k=2) and evaluate characteristic value uncertainty (U cRM).Therefore U cRM=k(u 2 char+ u 2 bb+ u 2 lts+ u 2 sts) 1/2(getting k=2).Selected traffic condition is without the need to considering the instable additional uncertainty of transport, therefore u sts=0, candidate RM characteristic value is 6.41 ± 0.03mg/kg.
The laboratory detection result of the flue-cured tobacco matter sample natural basal body positive material that table 5 remains containing carbendazim
Table 6 one-way analysis of variance table
Difference source SS df MS
Between group 0.2943 8 0.0368
In group 0.0099 18 0.0006
Amount to 0.3042 26

Claims (9)

1., containing the flue-cured tobacco matter sample natural basal body positive material acquisition methods that carbendazim is residual, it is characterized in that comprising dispenser, monitoring and sample preparation operation, specifically comprise:
A, dispenser: to cigarette strain spray concentration 25% carbendazol wettable powder of cultivation, every mu of formulation rate is 300g;
B, monitoring: the tobacco leaf of the 10th, 11,12 leaf positions is got in every strain cigarette strain, respectively at 2 after dispenser hour, and sampling in 1,3,5,7,10,14,21,28,35,42 day, detect carbendazim residual content according to YC/T 405.1-2011, draw the change curve of carbendazim residual content;
C, sample preparation: according to change curve the 42nd day harvesting tobacco leaf after administration of carbendazim residual content, institute's priming is processed into dry tobacco leaf through overbaking, again dry tobacco leaf is ground into powdery, by mixing after 40 mesh sieves, namely obtain the described flue-cured tobacco matter sample natural basal body positive material residual containing carbendazim; In described flue-cured tobacco matter sample natural basal body positive material, the content of carbendazim is 6.41 ± 0.03mg/kg.
2. acquisition methods according to claim 1, is characterized in that in described dispenser operation, cigarette seeding row spacing is 50cm*120cm.
3. acquisition methods according to claim 1, is characterized in that the application process of the carbendazol wettable powder used in described dispenser operation adds 15L water in 75g carbendazim, mixes and makes spray application after carbendazim water suspension.
4. acquisition methods according to claim 1, is characterized in that in described monitoring operation, carbendazim residual content is the content to butt.
5. acquisition methods according to claim 1, it is characterized in that it being the water percentage detecting tobacco leaf according to YC/T 31 in described monitoring operation, carbendazim residual content in fresh tobacco leaf to be converted into the value calculated according to butt, thus the monitoring result of carbendazim residual content in comparative analysis tobacco leaf on equal footing.
6. acquisition methods according to claim 1, is characterized in that in described monitoring operation, tobacco sample needs to shred mixing immediately after winning, and adopt inquartation contracting sample, the 200g that keeps sample is in-20 DEG C of preservations.
7. preparation method according to claim 1, it is characterized in that, in described sample preparation operation, institute's priming is processed into dry tobacco leaf through baking, the baking process adopted is: three-phase-drying for tobacco technique.
8. preparation method according to claim 1, it is characterized in that, in described sample preparation operation, dry tobacco leaf is ground into powdery, by mixing after 40 mesh sieves, referring to and carrying out thick homogenising by pulverizing the rear tobacco leaf powder crossing 40 mesh sieves through artificial stirring, then mixing with V-Mixer.
9. preparation method according to claim 8, is characterized in that the running parameter of V-Mixer in described sample preparation operation is: 15r/min, 50min.
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CN106124269A (en) * 2016-07-29 2016-11-16 云南省烟草农业科学研究院 A kind of flue-cured tobacco matter sample natural basal body positive material acquisition methods containing zineb residual
CN106198145A (en) * 2016-07-29 2016-12-07 云南省烟草农业科学研究院 A kind of flue-cured tobacco matter sample natural basal body positive material acquisition methods containing Determination of Imidacloprid Residue
CN111610174A (en) * 2020-06-04 2020-09-01 云南省计量测试技术研究院 Preparation method of heavy metal-containing tobacco matrix standard substance

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