CN102854271A - Method for measuring residues of three phenoxy carboxylic acid pesticides in tobacco and tobacco products - Google Patents
Method for measuring residues of three phenoxy carboxylic acid pesticides in tobacco and tobacco products Download PDFInfo
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Abstract
The invention discloses a method for measuring residues of three phenoxy carboxylic acid pesticides in tobacco and tobacco products. The method is characterized by comprising the following steps of: digesting a sample by using acetonitrile; adding anhydrous magnesium sulfate, sodium chloride, sodium citrate and sodium hydrogen citrate to oscillate for layering; and subsequently, performing dispersive solid-phase extraction, and directly measuring the pesticide residues of 2,4-drop, 2,4,5-mucus and dicamba in the tobacco and tobacco products through liquid chromatogram-tandem mass spectrometry. According to the method, the defects of the sample treatment method in the prior art are overcome, and the sample pretreatment method and the instrument detection conditions are optimized aiming at the tobacco products; and compared with the prior art, the method has the beneficial effects that the sample pretreatment process is simple and rapid, derivatization is not required, and the method has the advantages that operation is accurate, sensitivity is high and repeatability is high.
Description
Technical field
The invention belongs to the physical and chemical inspection technical field of tobacco and tobacco product Pesticide Residues, relate generally in tobacco and the tobacco product 2,4-drips, the determination techniques of three kinds of chlorobenzene oxycarboxylic acid pesticide residue amounts such as 2,4,5-tears and Mediben.
Background technology
Tobacco is as sucking product, its persticide residue problem has become the important component part in the smoking safety issue, tobacco and tobacco product residues of pesticides figureofmerit are the important contents of various countries in the tobacco product quality control, the key factor that has become international market tobacco leaf evaluation and chosen also is the important content that carries out commodity inspection in the tobacco international trade.Phenoxy acetic acid class material is the herbicide of developing the earliest and coming into operation.Because the advantages such as it is cheap, weeding speed, herbicidal spectrum are wider play a significant role aborning, are widely used in wheat, corn and rice terrace and prevent and kill off broad leaved weed always.Yet such herbicide is subjected to environmental baseline, the impact of crop growth phase larger on the security of crop, and misapplication may produce heavier poisoning; Simultaneously, such herbicide is easy to the poisoning of broad leaf crop generation on every side broad leaf crop sensitivity, drift and high volatility.In use, finding has certain endocrine disturbing effect to people, animal, along with the day by day increase of such herbicide use amount and usable range, and its residual in crop and the harm that human health and environment cause also more and more paid close attention to by people.Research and development is the problem of paying close attention in the world for the detection technique of this pesticide residue thing.China and other each states have all formulated strict residue limits, must not detect such as Japan's regulation 2,4,5-tears, and the international food code council, Japan waits 2 of formulation, and it is 0.05 mg/kg that 4-drops in limiting the quantity of in most agricultural product.CORESTA agricultural chemicals advisory committee (ACAC) in 118 kinds of agricultural chemicals directiveness residue limits tables formulating in 2008 with Mediben, 2,4-drips and 2,4, the limiting the quantity of of organochlorine herbicide agricultural chemicals such as 5-tears are decided to be respectively 0.20 mg/kg, 0.20 mg/kg and 0.05 mg/kg, China's tobacco business is not also formulated the limit standard of tobacco organochlorine herbicide residue at present.Because this compounds polarity is large, poor stability, be difficult for gasification, needs with measuring with gas chromatography or gas chromatography mass spectrometry method behind diazomethane or the boron trifluoride butanol derivs.The mensuration vapor-phase chromatography of YC/T 181-2004[People's Republic of China (PRC) tobacco business standard YC/T 181-2004 tobacco and tobacco product organochlorine herbicide persticide residue] stipulated in tobacco and the tobacco product 2,4-drips, 2,4, the assay method of 3 kinds of chlorobenzene oxycarboxylic acid class agricultural chemicals such as 5-tears and Mediben, for the detection of such persticide residue provides the analysis foundation, but this method is through using gas chromatography determination behind the derivatization.Derivatization reagent diazomethane and boron trifluoride butanols toxicity are stronger, and whole operation steps is more loaded down with trivial details, analysis cost is higher, the sense cycle of single sample is longer.Have no other bibliographical information of this type of Pesticides Testing in the tobacco.
About more for the report of the residual mensuration of phenoxy carboxylic acid in soil, water, rice, paddy rice and the textile, and the report of phenoxy carboxylic acid herbicides multi-residue analysis adopts gas chromatography or gas chromatography mass spectrometry to measure more.Phenoxy acetic acid class herbicide in the LC-MS/MS tobacco has no report.This experiment adopts high performance liquid chromatography-tandem mass to 3 kinds of residual analyses of phenoxy carboxylic acid herbicides in the tobacco, and to sample extraction with the condition such as separate and be studied, set up and measured 3 kinds of analytical approachs that how residual phenoxy carboxylic acid herbicides is in the tobacco, method is easy, quick, clean-up effect is better, and all technical all meets the requirement of residue detection.
Summary of the invention:
Purpose of the present invention is intended to overcome the prior art defective, a kind of employing Dispersive solid phase extraction tobacco and tobacco product Pesticide Residues are provided, need not the complicated processes such as derivatization, directly with in liquid chromatography tandom mass spectrometry determination tobacco and the tobacco product 2,4-drips, and 2,4, the assay method of three kinds of phenoxy carboxylic acid persticide residues such as 5-tears and Mediben, the method can fast, accurately detect three kinds of phenoxy carboxylic acid persticide residues in tobacco and the tobacco product, and measurement result is accurate, mensuration is disturbed few.
The objective of the invention is to be achieved through the following technical solutions:
One grow tobacco and tobacco product in the assay method of three kinds of phenoxy carboxylic acid persticide residues, with acetonitrile sample is carried out lixiviate, add again anhydrous magnesium sulfate and sodium chloride, sodium citrate, the Sodium citrate vibration impels its layering, disperse subsequently Solid-Phase Extraction, directly measure in tobacco and the tobacco product 2 with liquid chromatography-tandem mass spectrometry, 4-drips, and 2,4,5-tears and Mediben persticide residue.Concrete steps are as follows:
The extraction of a, sample: accurately take by weighing 2 g samples (being accurate to 0.01 g) in 50 mL tools lid centrifuge tube, add 10 mL water, vibrate until sample is fully infiltrated by water; Pipette 10 mL acetonitriles to centrifuge tube after leaving standstill 10 min, add 200 μ L acetic acid, then centrifuge tube is placed on the vortex mixing shaker, with 2000 rpm rate oscillations, 1 min; Centrifuge tube is placed keep 10 min under-18 ℃ of conditions, then in centrifuge tube, add 4 g anhydrous magnesium sulfates and 1 g sodium chloride, 1 g sodium citrate and 0.5 g Sodium citrate, immediately on whirlpool mixing shaker, with 2000 rpm rate oscillations, 2 min, then with centrifugal 10 min of 4000 rpm speed;
B, sample purification: pipette supernatant 1.0 mL in 1.5 mL centrifuge tubes, add 150 mg anhydrous magnesium sulfates and 25 mg PSA adsorbents, on whirlpool mixing shaker with 2000 rpm rate oscillations, 2 min, with centrifugal 2 min of 6000 rpm speed; Draw supernatant through 0.45 μ m organic phase membrane filtration, pipette 200 μ L, add 800 μ L acetonitriles, detect with LC-MS/MS;
C, the preparation of standard operation solution: take by weighing respectively three kinds of agricultural chemicals of 0.01g (2,4-drips, 2,4,5-tears and Mediben) standard items in different 10mL volumetric flasks, also finally be mixed with the standard operation solution of the various agricultural chemicals with concentration gradient with dilution in acetonitrile; Pipette respectively above-mentioned standard operation solution 200 μ L and 200 μ L blank samples and extract solution, then add 600 μ L acetonitriles, be mixed with matrix hybrid standard working solution;
D, liquid chromatography tandom mass spectrometry determination: the pesticide standard working solution of the variable concentrations for preparing more than the absorption, inject liquid chromatography-tandem mass spectrometer;
The calculating of e, persticide residue measurement result
Carry out the quantitative test of persticide residue with external standard method, namely with the chromatographic peak area of agricultural chemicals with its respective concentration is carried out regretional analysis, obtain typical curve, related coefficient is more than or equal to 0.999, sample after extracting is measured, record the chromatographic peak area that detects agricultural chemicals, the substitution typical curve is tried to achieve 2 in the sample, 4-drips, the residual quantity of the agricultural chemicals such as 2,4,5-tears and Mediben.
The manner of formulation of described standard operation solution is as follows: take by weighing respectively 0.01 g 2,4-drips, 2,4, and three kinds of standard sample of pesticide of 5-tears and Mediben are used the dilution in acetonitrile constant volume to 10 different mL volumetric flasks, make the standard reserving solution of 1.0 mg/mL; Pipette respectively above three kinds of agricultural chemicals single standard storing solution 1.0 mL in 100 mL volumetric flasks, be settled to scale with dilution in acetonitrile; Join to get hybrid standard storing solution (10 μ g/mL); Pipette respectively hybrid standard storing solution 25 μ L, 50 μ L, 100 μ L, 250 μ L in 500 μ L and 1000 μ L to the 6 10 mL volumetric flask, use the acetonitrile constant volume; The concentration of each standard operation solution is respectively 0.025 μ g/mL, 0.05 μ g/mL, 0.1 μ g/mL, 0.25 μ g/mL, 0.5 μ g/mL, 1.0 μ g/mL; Pipette respectively above-mentioned standard operation solution 200 μ L and 200 μ L blank samples and extract the solution mixing, and add 600 μ L acetonitriles; Each solution concentration is respectively 0.005 μ g/mL, 0.01 μ g/mL, 0.02 μ g/mL, 0.05 μ g/mL, 0.1 μ g/mL, 0.2 μ g/mL.
The liquid phase chromatogram condition that adopts is: chromatographic column: Atiantis dC18 (150 mm * 2.1 mm, 3 um, U.S. Waters company); Mobile phase: mobile phase A is acetonitrile, and Mobile phase B is water (containing 0.1 % formic acid), isocratic elution, and mobile phase A and Mobile phase B ratio are 50: 50, flow velocity: 0.3 mL/min; Column temperature: 30 ℃; Sample size: 5 μ L; The mass spectrum condition that adopts: scan mode: negative ion scanning; Electric spray ion source (ESI); The atomization gas flow is 60 psi; Gas curtain airshed 18 psi; The auxiliary heating airshed is 60 psi; 500 ℃ of ionization temperature; The collision airshed is 10 psi; 4 kinds of gases are nitrogen; The residence time is 100 msec; Ionization voltage 5500 V, negative ion MRM type collection.The MRM parameter sees Table 1.
Table 1 mass spectrum condition
* quota ion
Method of the present invention has overcome the deficiency of prior art sample treatment, has optimized sample-pretreating method and instrument testing conditions for tobacco sample, compared with prior art has following excellent results:
⑴ the inventive method sample pretreatment process is simple, has greatly shortened the extraction pre-treatment time of each tobacco sample.Industry standard " the mensuration vapor-phase chromatography of YC/T 181-2004 tobacco and tobacco product organochlorine herbicide persticide residue ", dichloromethane extraction is adopted in this standard method, with trimethyl parent sulfur oxide solution active carbon, Gas Chromatography-Mass Spectrometry, its pretreatment process complexity is time-consuming, is unfavorable for high flux sample fast detecting.
The inventive method is carried out lixiviate with offal with acetonitrile, adds anhydrous magnesium sulfate, sodium chloride etc. again and impels its layering, gets at last extract and disperses Solid-Phase Extraction.The method improves extraction efficiency, can extract altogether thing (fatty acid, chlorophyll etc.) to other of the pigment in the tobacco and tobacco plant tissue again and play preferably adsorption cleaning effect, the pesticide composition loss to be measured of having avoided sample concentration, purification, the process such as derivative to cause makes again experimental implementation more simple, quick.
⑵ the derivatization reagent that industry standard " the mensuration vapor-phase chromatography of YC/T 181-2004 tobacco and tobacco product organochlorine herbicide persticide residue " is used is harmful to health, thereby has limited their use; Thereby the present invention need not derivatization makes pretreatment process become fairly simple.
(3) the inventive method has advantages of accurate, the highly sensitive and good reproducibility of operation.
1. the detectability of the inventive method:
With 2 of variable concentrations, 4-drips, and 2,4,5-tears and Mediben pesticide standard working solution inject LC-MS/MS, calculates detectability (LOD) with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), and detectability is between 0.007 μ g/g-0.02 μ g/g.
2. the repeatability of the inventive method and recovery of standard addition:
Add 2,4-and drip in tobacco sample, then the standard solution of 2,4,5-tears and Mediben agricultural chemicals carries out pre-treatment and LC-MS/MS and analyzes, and calculate its recovery according to adding the scalar sum measured value, the results are shown in Table 2.As can be seen from Table 2, the recovery of three kinds of agricultural chemicals is between 95%-110.0%, and average relative standard deviation (RSD) illustrates that the recovery of the inventive method is high, good reproducibility less than 8%.
The recovery of three kinds of phenoxy carboxylic acid agricultural chemicals of table 2 and repeatability (n=6)
Description of drawings
Fig. 1 is assay method process flow diagram of the present invention (this figure is as Figure of abstract).
Embodiment
The present invention is described further below in conjunction with example, but is not restriction the present invention.
Example 1:
1. instrument and reagent:
Agricultural chemicals: 2,4-drips, and 2,4,5-tears and Mediben are standard items; Acetonitrile, acetic acid are the residual level of farming.
API 4000 quadrupole rod tandem mass spectrometers; Vortex shaker (U.S. Labnet company); Sigma 3-30K hydro-extractor (German Sigma company); AE 163 electronic balances (sensibility reciprocal: 0.0001g) with AE 166 electronic balances (sensibility reciprocal: 0.01g) (Switzerland Mettler company).
2. sample preparation:
Accurately take by weighing 2 g samples (being accurate to 0.01 g) in 50 mL tools lid centrifuge tube, add 10 mL water, vibrate until sample is fully infiltrated by water.Pipette 10 mL acetonitriles to centrifuge tube after leaving standstill 10 min, add 200 μ L acetic acid, then centrifuge tube is placed on the vortex mixing shaker, with 2000 rpm rate oscillations, 1 min.Centrifuge tube is placed keep 10 min under-18 ℃ of conditions, then in centrifuge tube, add 4 g anhydrous magnesium sulfates and 1 g sodium chloride, 1 g sodium citrate and 0.5 g Sodium citrate, immediately on whirlpool mixing shaker, with 2000 rpm rate oscillations, 2 min, then with centrifugal 10 min of 4000 rpm speed.
Pipette supernatant 1.0 mL in 1.5 mL centrifuge tubes, add 150 mg anhydrous magnesium sulfates and 25 mg PSA adsorbents, on whirlpool mixing shaker with 2000 rpm rate oscillations, 2 min, with centrifugal 2 min of 6000 rpm speed.Draw supernatant through 0.45 μ m organic phase membrane filtration, pipette 200 μ L, then add 800 μ L acetonitriles, detect with LC-MS/MS.
3. prepare standard operation solution: take by weighing respectively three kinds of agricultural chemicals of 0.01 g (2,4-drips, 2,4,5-tears and Mediben) standard items (being accurate to 0.0001 g) to 10 different mL volumetric flasks, use the dilution in acetonitrile constant volume, make the standard reserving solution of 1.0 mg/mL.Then pipette respectively above three kinds of agricultural chemicals single standard storing solution 1.0 mL in 100 mL volumetric flasks, be settled to scale with dilution in acetonitrile.Join to get the hybrid standard storing solution of 10 μ g/mL.Pipette respectively the mixing storing solution of certain volume in 10 mL volumetric flasks, use the dilution in acetonitrile constant volume, namely be mixed with the pesticide standard working solution of variable concentrations, standard sequence: 0.025 μ g/mL, 0.05 μ g/mL, 0.1 μ g/mL, 0.25 μ g/mL, 0.5 μ g/mL, 1.0 μ g/mL.Pipette respectively above-mentioned standard operation solution 200 μ L and 200 μ L blank samples and extract the solution mixing, then add 600 μ L acetonitriles.Respectively these standard solution being carried out LC-MS/MS analyzes.
4. assay method: the pesticide standard working solution of the variable concentrations for preparing is injected LC-MS/MS, and each standard specimen peak area (y) and its concentration (x) are carried out linear regression analysis, obtain typical curve.Sample liquid to be measured after extracting is measured, recorded the chromatographic peak area of agricultural chemicals, the substitution typical curve is tried to achieve 2 in the sample, and 4-drips with 2,4,5-tears content and is respectively 0.09 μ g/g and 0.12 μ g/g.
The LC-MS/MS condition that adopts is: chromatographic column: Atiantis dC18 (150 mm * 2.1 mm, 3 um, U.S. Waters company); Mobile phase: mobile phase A is acetonitrile, and Mobile phase B is water (containing 0.1 % formic acid), isocratic elution, and mobile phase A and Mobile phase B ratio are 50: 50, flow velocity: 0.3 mL/min; Column temperature: 30 ℃; Sample size: 5 μ L.Scan mode: negative ion scanning; Electric spray ion source (ESI); The atomization gas flow is 60 psi; Gas curtain airshed 18 psi; The auxiliary heating airshed is 60 psi; 500 ℃ of ionization temperature; The collision airshed is 10 psi; 4 kinds of gases are nitrogen; The residence time is 100 msec; Ionization voltage 5500 V, negative ion MRM type collection, the MRM parameter sees Table 1.
Be the accuracy of determination methods, add 2 of 0.1 μ g/g in this sample, 4-drips, 2,4,5-tears and Mediben standard solution, carry out the same sample pre-treatments, record 2,4-with LC-MS/MS and drip, 2,4,5-tears and Mediben are selected the quasi-molecular ions area, the substitution typical curve, try to achieve this moment sample in 2,4-drips, 2,4,5-tears and Mediben content are respectively 0.18 μ g/g, 0.20 μ g/g and 0.09 μ g/g, namely 2,4-drips, and 2,4, the recovery of standard addition of 5-tears and Mediben is 94.7%, 90.9% and 90.0%, illustrates that the method is accurately.
Example 2: according to example 1 described method, select another tobacco sample, the residual quantities that record in the sample 2,4 and Mediben are respectively 0.12 μ g/g and 0.18 μ g/g.
Example 3: according to example 1 described method, select another tobacco sample, record in the sample 2,4,5-tears content is 0.22 μ g/g.
Claims (4)
- One grow tobacco and tobacco product in the assay method of three kinds of phenoxy carboxylic acid persticide residues, it is characterized in that: with acetonitrile sample is carried out lixiviate, add again anhydrous magnesium sulfate and sodium chloride, sodium citrate, the Sodium citrate vibration impels its layering, disperse subsequently Solid-Phase Extraction, directly measure in tobacco and the tobacco product 2 with liquid chromatography-tandem mass spectrometry, 4-drips, and 2,4,5-tears and Mediben persticide residue.
- 2. the assay method of three kinds of phenoxy carboxylic acid persticide residues in tobacco according to claim 1 and the tobacco product, it is characterized in that: these assay method concrete steps are as follows:The extraction of a, sample: accurately take by weighing 2 g samples in 50 mL tools lid centrifuge tube, add 10 mL water, vibrate until sample is fully infiltrated by water; Pipette 10 mL acetonitriles to centrifuge tube after leaving standstill 10 min, add 200 μ L acetic acid, then centrifuge tube is placed on the vortex mixing shaker, with 2000 rpm rate oscillations, 1 min; Centrifuge tube is placed keep 10 min under-18 ℃ of conditions, then in centrifuge tube, add 4 g anhydrous magnesium sulfates and 1 g sodium chloride, 1 g sodium citrate and 0.5 g Sodium citrate, immediately on whirlpool mixing shaker, with 2000 rpm rate oscillations, 2 min, then with centrifugal 10 min of 4000 rpm speed;B, sample purification: pipette supernatant 1.0 mL in 1.5 mL centrifuge tubes, add 150 mg anhydrous magnesium sulfates and 25 mg PSA adsorbents, on whirlpool mixing shaker with 2000 rpm rate oscillations, 2 min, with centrifugal 2 min of 6000 rpm speed; Draw supernatant through 0.45 μ Lm organic phase membrane filtration, pipette 200 μ L, add 800 μ L acetonitriles, detect with LC-MS/MS;The preparation of c, standard operation solution: take by weighing respectively 0.01g 2,4-drips, and 2,4,5-tears and Mediben standard items are in different 10mL volumetric flasks, with dilution in acetonitrile and finally be mixed with the standard operation solution of the various agricultural chemicals with concentration gradient; Pipette respectively above-mentioned standard operation solution 200 μ L and 200 μ L blank samples and extract solution, then add 600 μ L acetonitriles, be mixed with matrix hybrid standard working solution;D, liquid chromatography tandom mass spectrometry determination: the pesticide standard working solution of the variable concentrations for preparing more than the absorption, inject liquid chromatography-tandem mass spectrometer;The calculating of e, persticide residue measurement resultCarry out the quantitative test of persticide residue with external standard method, namely with the chromatographic peak area of agricultural chemicals with its respective concentration is carried out regretional analysis, obtain typical curve, related coefficient is more than or equal to 0.999, sample after extracting is measured, record the chromatographic peak area that detects agricultural chemicals, the substitution typical curve is tried to achieve 2 in the sample, 4-drips, the residual quantity of the agricultural chemicals such as 2,4,5-tears and Mediben.
- 3. the assay method of three kinds of phenoxy carboxylic acid persticide residues in tobacco according to claim 1 and the tobacco product, it is characterized in that: the manner of formulation of described standard operation solution is as follows: take by weighing respectively 0.01 g 2,4-drips, 2,4, three kinds of standard sample of pesticide of 5-tears and Mediben are to 10 different mL volumetric flasks, use the dilution in acetonitrile constant volume, make the standard reserving solution of 1.0 mg/mL; Pipette respectively above three kinds of agricultural chemicals single standard storing solution 1.0 mL in 100 mL volumetric flasks, be settled to scale with dilution in acetonitrile; Join to get hybrid standard storing solution (10 μ g/mL); Pipette respectively hybrid standard storing solution 25 μ L, 50 μ L, 100 μ L, 250 μ L in 500 μ L and 1000 μ L to the 6 10 mL volumetric flask, use the acetonitrile constant volume; The concentration of each standard operation solution is respectively 0.025 μ g/mL, 0.05 μ g/mL, 0.1 μ g/mL, 0.25 μ g/mL, 0.5 μ g/mL, 1.0 μ g/mL; Pipette respectively above-mentioned standard operation solution 200 μ L and 200 μ L blank samples and extract the solution mixing, and add 600 μ L acetonitriles; Each solution concentration is respectively 0.005 μ g/mL, 0.01 μ g/mL, 0.02 μ g/mL, 0.05 μ g/mL, 0.1 μ g/mL, 0.2 μ g/mL.
- 4. the assay method of three kinds of phenoxy carboxylic acid persticide residues in tobacco according to claim 1 and the tobacco product, it is characterized in that: the liquid phase chromatogram condition of employing is: chromatographic column: Atiantis dC18 (150 mm * 2.1 mm, 3 um, U.S. Waters company); Mobile phase A is acetonitrile, and Mobile phase B is water (containing 0.1 % formic acid), isocratic elution, and mobile phase A and Mobile phase B ratio are 50: 50, flow velocity: 0.3 mL/min; Column temperature: 30 ℃; Sample size: 5 μ L; The mass spectrum condition that adopts: scan mode: negative ion scanning; Electric spray ion source (ESI); The atomization gas flow is 60 psi; Gas curtain airshed 18 psi; The auxiliary heating airshed is 60 psi; 500 ℃ of ionization temperature; The collision airshed is 10 psi; 4 kinds of gases are nitrogen; The residence time is 100 msec; Ionization voltage 5500 V, negative ion MRM type collection.
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| CN103149313B (en) * | 2013-02-06 | 2014-12-03 | 中国烟草总公司四川省公司 | Method for determining residual amount of dicamba in tobacco |
| CN103149289A (en) * | 2013-02-06 | 2013-06-12 | 中国烟草总公司四川省公司 | Method for determining residual amount of 2, 4-D in tobacco |
| CN103149313A (en) * | 2013-02-06 | 2013-06-12 | 中国烟草总公司四川省公司 | Method for determining residual amount of dicamba in tobacco |
| CN103175911A (en) * | 2013-02-06 | 2013-06-26 | 中国烟草总公司四川省公司 | Method for measuring 2,4,5-T residual quantity in tobaccos |
| CN103123345A (en) * | 2013-02-06 | 2013-05-29 | 中国烟草总公司四川省公司 | Method for rapidly detecting phenoxyacetic acid herbicide in soil |
| CN103123345B (en) * | 2013-02-06 | 2015-03-18 | 中国烟草总公司四川省公司 | Method for rapidly detecting phenoxyacetic acid herbicide in soil |
| CN103175911B (en) * | 2013-02-06 | 2015-01-21 | 中国烟草总公司四川省公司 | Method for measuring 2,4,5-T residual quantity in tobaccos |
| CN103149289B (en) * | 2013-02-06 | 2014-08-20 | 中国烟草总公司四川省公司 | Method for determining residual amount of 2, 4-D in tobacco |
| CN103217496A (en) * | 2013-03-28 | 2013-07-24 | 国家烟草质量监督检验中心 | Method for measuring contents of humectants in cigarette cut tobacco by GC/FID (Gas Chromatography/hydrogen Flame Ionization Detector) |
| CN103293266B (en) * | 2013-06-08 | 2014-09-10 | 国家烟草质量监督检验中心 | GC-MS/MS (gas chromatography-tandem mass spectrometry) method for analyzing dinitroaniline pesticide residue in tobacco and tobacco product |
| CN103293266A (en) * | 2013-06-08 | 2013-09-11 | 国家烟草质量监督检验中心 | GC-MS/MS (gas chromatography-tandem mass spectrometry) method for analyzing dinitroaniline pesticide residue in tobacco and tobacco product |
| CN104756985A (en) * | 2014-01-02 | 2015-07-08 | 刘勤学 | Applications of pesticide dicamba and composition of pesticide dicamba as tobacco bud inhibitor |
| CN103698463A (en) * | 2014-01-16 | 2014-04-02 | 国家烟草质量监督检验中心 | LC-MS/MS (liquid chromatography-mass spectrometry/mass spectrometry) method for analyzing residual quantity of phenoxy carboxylic acid herbicides in tobaccos |
| CN104172455A (en) * | 2014-08-25 | 2014-12-03 | 国家烟草质量监督检验中心 | Method for using ultraviolet rays to remove pesticide residues in tobacco |
| CN104777251A (en) * | 2015-04-13 | 2015-07-15 | 中国烟草总公司郑州烟草研究院 | Method for detecting various pesticide residues in tobacco by utilizing multiwalled carbon nanotube |
| CN109212070A (en) * | 2018-09-24 | 2019-01-15 | 丁立平 | Gas chromatography that is a kind of while measuring four kinds of benzoic acid herbicides in cereal |
| CN115219624A (en) * | 2022-07-14 | 2022-10-21 | 唐山市食品药品综合检验检测中心(唐山市农产品质量安全检验检测中心、唐山市检验检测研究院) | Rapid detection method for 33 forbidden pesticide residues in traditional Chinese medicinal materials |
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