CN111830165B - Method for pretreatment and simultaneous measurement of phosphine and dithiocarbamate substances - Google Patents
Method for pretreatment and simultaneous measurement of phosphine and dithiocarbamate substances Download PDFInfo
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Abstract
The invention belongs to the field of detection and analysis, and particularly relates to a method for pretreating a sample containing phosphine and dithiocarbamate compounds, which comprises the following steps: mixing a sample with an acidic stannous chloride ethanol solution, carrying out solid-liquid separation, and collecting a liquid phase substance; wherein the mixing and the solid-liquid separation are carried out at a temperature of not higher than 10 ℃. The invention also relates to a method for simultaneously determining the content of phosphine and dithiocarbamate compounds in a sample. The method can accurately and quickly measure the phosphine content and the dithiocarbamate compound content in the sample simultaneously.
Description
Technical Field
The invention belongs to the field of detection and analysis, and particularly relates to a method for pretreating a sample containing hydrogen phosphate and dithiocarbamate compounds, and also relates to a method for simultaneously determining the content of the hydrogen phosphate and dithiocarbamate compounds in the sample.
Background
With the signing and the taking effect of the tobacco control framework convention, the pressure of smoking and health in the tobacco industry is further strengthened, and the ninth tobacco component regulation and the tenth tobacco product disclosure regulation in the convention prompt the respective convention countries to set up regulations on the safety of tobacco products and more strictly limit the release amount of harmful components in smoke. As one of the contracting countries, china gradually strengthens scientific research and technical development of tobacco speciality in recent years, and establishes detection methods and limit requirements of partial chemical components.
Phosphine and dithiocarbamate compounds are two types of most common pesticide residues of tobacco. Phosphine (PH) 3 ) As a fumigant for preventing and controlling tobacco pests, the fumigant has been used for nearly 50 years, and at present, aluminum phosphide (AlP) is most widely used at home and abroad to absorb water and then hydrolyze to generate phosphine to kill the pests in the tobacco, and the method has good insecticidal effect. Phosphine is a highly toxic substance and is easily left in the dense tobacco during the fumigation process. The exposure of people to phosphine can easily cause the increase of blood phosphorus, influence the normal metabolism of the organism, and possibly cause neurasthenia syndrome, respiratory tract irritation and digestive tract irritation, and the like. In the existing method for measuring phosphine, a detection tube method and a detection test paper method are easy to operate, but have poor accuracy and stability and can only be used for qualitative analysis; although the chromatography has more accurate detection result and strong stability, the upper limit of detection is lower and the operation is more complicated. The dithiocarbamic acid ester compound is a general name of organic sulfur pesticides, is divided into thiram type and dyson type, is a fungicide with wide application in the world, can be used for preventing and treating more than 400 pathogens of more than 70 crops, and is mainly used for tobaccoPreventing and treating anthrax, rhizoctonia rot, root rot, brown spot or black shank, etc. However, with the widespread use of dithiocarbamates, it has been found that dithiocarbamates produce a metabolite called hexylene thiourea (ETU) in the metabolic processes of animals and plants, and ETU has carcinogenicity, teratogenicity and mutagenicity and can affect the function of thyroid gland for a long time, and is compiled in volume by the american occupational safety and health administration (OSrtA) as a carcinogen. Therefore, great attention is paid to the safety of dithiocarbamate compounds at home and abroad, and the international cooperative research and study center for tobacco science (CORESTA) agricultural chemical committee (ACAC) also sets the directive residual limits (GRLs) of dithiocarbamate compounds in tobacco as CS 2 Calculated) was 5.00mg/kg. There are currently internationally many methods for analyzing dithiocarbamate pesticide residues, including spectrophotometry, gas chromatography, and liquid chromatography. However, the method has the problems of complicated sample treatment, long detection time, influence on analysis flux and the like. In addition, the detection of phosphine and dithiocarbamate pesticide residues is carried out respectively at present, and the detection period is longer.
Therefore, a method for rapidly and accurately detecting the contents of phosphine and dithiocarbamate compounds simultaneously is needed.
Disclosure of Invention
The invention provides a method for pretreating a sample containing phosphine and a dithiocarbamate compound, which is simple to operate and high in extraction rate of phosphine and carbon disulfide converted from the dithiocarbamate compound. On the basis, the invention also provides a method for simultaneously measuring the content of phosphine and dithiocarbamate compounds in the sample, and the method can accurately and quickly simultaneously measure the content of phosphine and dithiocarbamate compounds in the sample.
In a first aspect, the present invention relates to a method for pre-treating a sample containing phosphine and a dithiocarbamate compound, comprising the steps of:
mixing a sample with an acidic stannous chloride ethanol solution, carrying out solid-liquid separation, and collecting a liquid phase substance; wherein the mixing and solid-liquid separation are carried out at a temperature of not more than 10 ℃.
In some embodiments of the first aspect of the invention, the mixing and solid-liquid separation are carried out at 1 ℃ to 9 ℃, for example at 2 ℃, 3 ℃, 4 ℃, 5 ℃, 6 ℃, 7 ℃ or 8 ℃.
In some embodiments of the first aspect of the present invention, the mixing is under shaking conditions.
In certain embodiments of the first aspect of the present invention, the rate of oscillation is between 1000 and 5000rpm, such as 2000rpm, 3000rpm, 4000rpm.
In some embodiments of the first aspect of the present invention, the period of oscillation is 5-60 min, such as 10min, 15min, 17min, 20min, 24min, 26min, 28min, 30min, 33min, 36min, 38min, 40min, 42min, 45min, 48min, 50min, 52min, 55min, 57min, 59min.
In some embodiments of the first aspect of the present invention, the oscillating condition is provided by a vortex oscillator.
In some embodiments of the first aspect of the present invention, the solid-liquid separation is performed by centrifugation.
In some embodiments of the first aspect of the present invention, the rotational speed of the centrifugation is 1000 to 18000rpm, such as 2000rpm, 3000rpm, 4000rpm, 5000rpm, 7000rpm, 8000rpm, 10000rpm, 12000rpm, 14000rpm, 15000rpm, 16000 rpm, 17000rpm.
In some embodiments of the first aspect of the present invention, the time for centrifugation is 1 to 10min, such as 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min.
In some embodiments of the first aspect of the present invention, after centrifugation, the supernatant is collected as a liquid phase.
In certain embodiments of the first aspect of the present invention, the solid-liquid separation is performed immediately after the mixing is complete.
In certain embodiments of the first aspect of the present invention, the acidic stannous chloride ethanol solution has a water content of 0.02% by weight or less, preferably 0.01% by weight or less, such as 0.015%, 0.01%, 0.008%, 0.005%, 0.003%, 0.001%.
In some embodiments of the first aspect of the present invention, the method has one or more of the following features 1) to 7):
1) The sample is selected from tobacco and tobacco products, preferably tobacco leaves, more preferably self-cured tobacco leaves, aromatic tobacco leaves and burley tobacco leaves;
2) The ratio of the sample to the acidic stannous chloride ethanol solution is 1 (1 to 30) g/mL, for example, 1;
3) The sample has a water content of ≦ 1% by weight, e.g., 0.5%, 0.2%, 0.1%, 0.007%, 0.005%, 0.001%;
4) The molar concentration of the stannous chloride in the acidic stannous chloride ethanol solution is 0.1-2 mol/L, such as 0.3mol/L, 0.5mol/L, 0.7mol/L, 0.9mol/L, 1mol/L, 1.2mol/L and 1.5mol/L;
5) The acidic stannous chloride ethanol solution has a pH of 2 to 6.5, e.g., 3, 4, 5, 6;
6) The acidic stannous chloride ethanol solution contains at least one aqueous solution selected from hydrochloric acid, sulfuric acid and nitric acid, preferably contains hydrochloric acid aqueous solution;
7) The method further comprises the following steps: storing the liquid phase at a temperature of not higher than 10 deg.C.
Without being bound by theory, the dithiocarbamate compounds in the sample react with stannous chloride under acidic conditions to produce carbon disulfide.
In certain embodiments of the first aspect of the present invention, the liquid phase comprises phosphine and carbon disulfide.
In some embodiments of the first aspect of the present invention, the stannous chloride ethanol solution is a solution of stannous chloride dissolved in ethanol.
The second aspect of the present invention relates to a method for simultaneously determining the content of phosphine and dithiocarbamate compounds in a sample, which comprises the following steps:
(1) Obtaining a liquid phase according to the method of the first aspect of the invention;
(2) And detecting the liquid phase substance by using a gas chromatography-mass spectrometer to obtain a detection result.
In certain embodiments of the second aspect of the present invention, the dithiocarbamate compound content of the sample is based on the carbon disulfide content.
In some embodiments of the second aspect of the present invention, in step (2), the operating conditions of the gas chromatograph comprise one or more of the following a to F:
A. the chromatographic column is an Elite-624 capillary column;
preferably, the column size is 60m × 320 μm × 1.8 μm;
B. the injection port temperature is 25-65 deg.C, such as 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C;
C. the temperature rising procedure of the column oven is as follows: maintaining the temperature at 40-60 deg.C (e.g. 45 deg.C, 50 deg.C, 55 deg.C, 58 deg.C) for 1-10 min (e.g. 2, 3, 4, 5, 6, 7, 8, 9 min), increasing the temperature at 30-50 deg.C/min (e.g. 35 deg.C/min, 40 deg.C/min, 45 deg.C/min) to 210-250 deg.C (e.g. 220 deg.C, 225 deg.C, 230 deg.C, 235 deg.C, 240 deg.C, 245 deg.C), and maintaining the temperature at 210-250 deg.C (e.g. 220 deg.C, 225 deg.C, 230 deg.C, 235 deg.C, 240 deg.C, 245 deg.C) for 2-13 min (e.g. 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 min);
D. the carrier gas is helium, and the purity of the preferred helium is 99.999%;
E. the carrier gas flow is 1-8 mL/min, such as 2, 3, 4, 5, 6, 7, 8mL/min;
F. the split ratio is (2-7): 1, such as 3:1, 4:1, 5:1, 6:1.
In some embodiments of the second aspect of the present invention, in step (2), the operating conditions of the mass spectrometer comprise one or more of the following a to d:
a. the temperature of the transmission line is 200-260 ℃, such as 210 ℃, 220 ℃, 230 ℃, 240 ℃ and 250 ℃;
b. the ion source temperature is 200 ℃ to 260 ℃, for example, 210 ℃, 220 ℃, 230 ℃, 240 ℃ and 250 ℃;
c. the detection mode is selected ion detection;
d. the detector voltage is 380V.
In some embodiments of the second aspect of the present invention, the phosphine has a qualitative fragment mass to charge ratio of 31, 32, 33 and/or 34 and a quantitative fragment mass to charge ratio of 33.
In some embodiments of the second aspect of the present invention, the carbon disulphide has a qualitative fragment mass to charge ratio of 76 and/or 78 and a quantitative fragment mass to charge ratio of 76.
In certain embodiments of the second aspect of the present invention, in step (2), the measurement is obtained by external standard quantitative analysis.
In some embodiments of the second aspect of the present invention, in step (2), phosphine and carbon disulfide in the liquid phase are detected by using a gas chromatography-mass spectrometer, the phosphine content and the carbon disulfide content in the liquid phase are obtained by using an external standard quantitative analysis method, and then the phosphine content and the dithiocarbamate content (in terms of carbon disulfide content) in the sample are calculated.
In the present invention, unless otherwise specified, wherein:
the term "tobacco" refers to an annual or perennial herb, hobby crop of the solanaceae family. There are more than 60 species of this genus, most of which are wild species. The main cultivated species are safflower tobacco and yellow flower tobacco. Both are native to south america and are naturally occurring amphidiploids. The safflower tobacco is also called common tobacco and is a tobacco seed for producing worldwide commodities. And various types are formed due to different modulation methods, seed sources, regions and cultivation measures: flue-cured tobacco, burley tobacco, maryland tobacco, cigar tobacco, smoking, aromatic tobacco, sun-cured red tobacco, sun-cured yellow tobacco, etc. There are many cultivars in each type. The yellow tobacco is cultivated in more of the Soviet Union and India, and a small amount of yellow tobacco is cultivated in Xinjiang, gansu and other places in China. The floral tobacco (N.alata Link and Otta) and the Pink blue tobacco (N.glauca Graham) in the genus are planted for appreciation.
The term "tobacco product" refers to a hobby commodity made from tobacco leaves. According to the characteristics of different types of tobacco leaves, different processing and manufacturing methods are applied to produce a variety of tobacco products so as to meet the preference requirements of different consumers. Including but not limited to conventional cigarettes.
The invention has the following beneficial effects:
1. the pretreatment method is simple to operate, has high extraction rate of phosphine in the sample, and has high extraction rate of carbon disulfide converted from dithiocarbamate compounds in the sample.
2. The determination method can accurately and quickly determine the phosphine content and the dithiocarbamate compound content in the sample simultaneously.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a flow chart of the method for simultaneously determining the contents of phosphine and dithiocarbamate compounds according to the present invention.
Detailed Description
Embodiments of the present invention will now be described more fully hereinafter with reference to the accompanying examples, in which some, but not all embodiments of the invention are shown. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
As shown in fig. 1:
(1) And (3) preparing standard solutions with series concentrations by using chromatographically pure phosphine and chromatographically pure carbon disulfide as standard substances respectively.
(2) Sample pretreatment: weighing 1g of flue-cured tobacco leaf sample (the weight content of water is 0.05 percent), placing the sample in a 50mL centrifuge tube, adding 10mL of ethanol solution (the weight content of water is 0.005 percent) containing 0.5mol/L stannous chloride and having a pH value of 6, oscillating the solution at 5 ℃ for 20min by using a vortex oscillator at an oscillation speed of 2000rpm, immediately performing centrifugal separation at 4 ℃, setting the centrifugal time to be 3min and the centrifugal speed to be 4000rpm, taking supernatant as a sample to be tested, and placing the sample in a chromatographic bottle to be stored at 4 ℃ for later use.
(3) And (3) detection: and detecting the sample to be detected and the standard solution with the series of concentrations by adopting a gas chromatography-mass spectrometer. Wherein the content of the first and second substances,
gas chromatography operating conditions: the chromatographic column is an Elite-624 capillary column, and the specification of the chromatographic column is 60m multiplied by 320 mu m multiplied by 1.8 mu m; the temperature of a sample inlet is 45 ℃; the temperature rising procedure of the column oven is as follows: keeping the temperature at 50 ℃ for 3min, then heating to 230 ℃ at the speed of 40 ℃/min, and keeping the temperature at 230 ℃ for 5min; the carrier gas is helium with the purity of 99.999 percent; the carrier gas flow is 2mL/min; the split ratio is 5:1, and the split gas enters mass spectrometry detection.
Mass spectrum operating conditions: the transmission line temperature is 230 ℃; the ion source temperature is 230 ℃; the voltage of the detector is 380V; the detection mode is selected ion detection (SIR).
The mass-to-charge ratio of qualitative fragments of phosphine is 31, 32, 33 and 34, and the mass-to-charge ratio of quantitative fragments is 33; the qualitative fragment mass to charge ratio of carbon disulfide was 76, 78, and the quantitative fragment mass to charge ratio was 76.
And (3) determining the quality by combining retention time with qualitative fragments, determining the quantity by using quantitative fragments, and calculating the residual quantity of phosphine and the residual quantity of dithiocarbamate compounds (calculated by carbon disulfide content) in the tobacco leaf sample by adopting an external standard quantitative analysis method (using the detection result of a series of concentration standard solutions).
The phosphine residual quantity and the dithiocarbamate residual quantity (in terms of carbon disulfide content) in cured tobacco leaf samples 1# to 2# are measured by the method, and the results are shown in table 1.
TABLE 1 detection results of flue-cured tobacco leaf samples
Example 2
As shown in fig. 1:
(1) And (3) preparing standard solutions with series concentrations by using chromatographically pure phosphine and chromatographically pure carbon disulfide as standard substances respectively.
(2) Sample pretreatment: weighing 10g of aromatic tobacco leaf sample (the weight content of water is 0.1 percent), placing the aromatic tobacco leaf sample into a 100mL centrifuge tube, adding 50mL of ethanol solution (the weight content of water is 0.008 percent) containing 0.5mol/L stannous chloride with the pH value of 5, carrying out oscillation treatment for 20min at 5 ℃ by adopting a vortex oscillation instrument at the oscillation speed of 3000rpm, then immediately carrying out centrifugal separation at 4 ℃, the centrifugation time is 3min, the centrifugation speed is 8000rpm, taking supernatant as a sample to be detected, and placing the sample into a chromatographic bottle to be stored at 4 ℃ for later use.
(3) And (3) detection: and detecting the sample to be detected and the standard solution with the series concentration by adopting a gas chromatography-mass spectrometer. Wherein the content of the first and second substances,
operating conditions of the gas chromatography: the chromatographic column is an Elite-624 capillary column, and the specification of the chromatographic column is 60m multiplied by 320 mu m multiplied by 1.8 mu m; the temperature of a sample inlet is 50 ℃; the temperature rising program of the column oven is as follows: maintaining at 50 deg.C for 3min, heating to 230 deg.C at 40 deg.C/min, and maintaining at 230 deg.C for 5min; the carrier gas is helium with the purity of 99.999 percent; the carrier gas flow is 2mL/min; the split ratio 2:1, the split gas enters mass spectrometry detection.
Mass spectrum operating conditions: the transmission line temperature is 230 ℃; the ion source temperature is 230 ℃; the detector voltage is 380V; the detection mode is selected ion detection (SIR).
The mass-to-charge ratio of qualitative fragments of phosphine is 31, 32, 33 and 34, and the mass-to-charge ratio of quantitative fragments is 33; the mass to charge ratio of the qualitative fragments of carbon disulfide was 76, 78, and the mass to charge ratio of the quantitative fragments was 76.
And (3) determining the quality by combining retention time with qualitative fragments, determining the quantity by using quantitative fragments, and calculating the residual quantity of phosphine and the residual quantity of dithiocarbamate compounds (calculated by carbon disulfide content) in the tobacco leaf sample by adopting an external standard quantitative analysis method (using the detection result of a series of concentration standard solutions).
The phosphine residual amount and the dithiocarbamate compound residual amount (in terms of carbon disulfide content) in the aromatic tobacco leaf samples 1# to 2# are measured by the method, and the results are shown in table 2.
TABLE 2 detection results of aromatic tobacco leaf samples
Example 3
As shown in fig. 1:
(1) And (3) preparing standard solutions with series concentrations by using chromatographically pure phosphine and chromatographically pure carbon disulfide as standard substances respectively.
(2) Sample pretreatment: weighing 10g of burley tobacco leaf sample (the weight content of water is 0.1 percent), placing the burley tobacco leaf sample into a 100mL centrifuge tube, adding 50mL of ethanol solution (the weight content of water is 0.01 percent) containing 0.5mol/L stannous chloride with the pH value of 4, carrying out oscillation treatment for 20min at 5 ℃ by using a vortex oscillator, wherein the oscillation rate is 3000rpm, then immediately carrying out centrifugal separation at 4 ℃, the centrifugation time is 3min, the centrifugation speed is 12000rpm, taking supernatant as a sample to be detected, and placing the sample into a chromatographic bottle to be stored at 4 ℃ for later use.
(3) And (3) detection: and detecting the sample to be detected and the standard solution with the series concentration by adopting a gas chromatography-mass spectrometer. Wherein the content of the first and second substances,
gas chromatography operating conditions: the chromatographic column is an Elite-624 capillary column, and the specification of the chromatographic column is 60m multiplied by 320 mu m multiplied by 1.8 mu m; the temperature of a sample inlet is 50 ℃; the temperature rising procedure of the column oven is as follows: maintaining at 50 deg.C for 3min, heating to 230 deg.C at 40 deg.C/min, and maintaining at 230 deg.C for 5min; the carrier gas is helium with the purity of 99.999 percent; the flow rate of carrier gas is 2mL/min; and the split ratio is 2:1, and the split gas enters mass spectrum detection.
Mass spectrum detection conditions: the transmission line temperature is 230 ℃; the ion source temperature is 230 ℃; the detector voltage is 380V; the detection mode is selective ion detection (SIR).
The mass-to-charge ratio of qualitative fragments of phosphine is 31, 32, 33 and 34, and the mass-to-charge ratio of quantitative fragments is 33; the qualitative fragment mass to charge ratio of carbon disulfide was 76, 78, and the quantitative fragment mass to charge ratio was 76.
The retention time is combined with the qualitative fragments for qualitative determination, the quantitative fragments for quantitative determination, and the phosphine residual quantity and the dithiocarbamate residual quantity (in terms of carbon disulfide content) in the tobacco leaf sample are calculated by an external standard quantitative analysis method (using the detection results of series concentration standard solutions), and the results are shown in table 3.
TABLE 3 detection results of burley tobacco leaf samples
Comparative example 1
The phosphine residual quantity of each tobacco sample in the examples 1 to 3 is independently measured by adopting a method of a document 'Lu Xinbo, flying and the like, measuring the phosphine residual quantity after tobacco fumigation by headspace gas chromatography, a Chinese tobacco science report, 2014,20 (4): 7-10'; according to the industrial standard YC/T405.4-2011, the method for measuring the residual quantity of various pesticides of tobacco and tobacco products part 4 comprises the following steps: determination of dithiocarbamate pesticide residue the method of gas chromatography-mass spectrometry combined method "alone determines the residue of dithiocarbamate compounds in each tobacco sample of examples 1-3; the results are shown in Table 4.
TABLE 4 results of independent determination of phosphine residual amount and dithiocarbamate compound residual amount in tobacco leaf samples
As can be seen from tables 1-4, compared with the above two methods for measuring the residual amount of phosphine and the residual amount of dithiocarbamate compounds, the method of the present invention can measure the residual amount of phosphine and the residual amount of dithiocarbamate compounds in tobacco leaves simultaneously.
Comparative example 2
The comparison method comprises the following steps: in the step (2), a vortex oscillator is adopted for oscillation treatment for 20min at the temperature of 20 ℃, the oscillation speed is 2000rpm, then centrifugal separation is immediately carried out at the temperature of 20 ℃, the centrifugal time is 3min, the centrifugal rotation speed is 4000rpm, and the supernatant is taken as a sample to be measured. The rest of the operation was the same as in example 1.
And (3) determining the residual amount of phosphine and the residual amount of dithiocarbamate compounds (calculated by carbon disulfide content) in cured tobacco leaf samples 1# to 2# according to the comparison method. Spiked samples were prepared according to the spiking levels in table 5. The comparison method is adopted to measure the residual hydrogen phosphide amount and the residual dithiocarbamate compound amount (in terms of carbon disulfide content) of the standard adding sample, then the standard adding recovery rate is calculated, the experiment is repeated for three times, and the average standard adding recovery rate is obtained, and the result is shown in 5. The method of example 1 was used to determine the residual amount of phosphine and the residual amount of dithiocarbamate (in terms of carbon disulfide content) in the spiked samples, the spiked recovery was calculated, and the experiment was repeated three times to obtain the average spiked recovery, the results of which are shown in table 6.
TABLE 5 average spiked recovery for the comparative processes
Table 6 average spiked recovery for the process of example 1
As can be seen from tables 5-6, the average spiking recovery for the comparative method was 78% -84%, whereas the average spiking recovery for the inventive method reached 92% -97%. Under the same standard adding level, compared with a comparison method, the method has higher average standard adding recovery rate, which shows that the method has higher accuracy for simultaneously measuring the residual quantity of phosphine and the residual quantity of dithiocarbamate compounds in tobacco leaves.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (18)
1. A method for simultaneously determining the content of phosphine and dithiocarbamate compounds in a sample comprises the following steps:
(1) Mixing a sample with an acidic stannous chloride ethanol solution, carrying out solid-liquid separation, and collecting a liquid phase substance; wherein the mixing and solid-liquid separation are carried out at a temperature of not more than 10 ℃, and the sample is selected from tobacco and tobacco products;
(2) Detecting the liquid phase substance by using a gas chromatography-mass spectrometer to obtain a detection result; wherein, the operating conditions of the gas chromatography comprise: the chromatographic column is an Elite-624 capillary column, and the temperature rise program of the column incubator is as follows: the temperature is maintained at 50 ℃ for 3min, then the temperature is increased to 230 ℃ at the speed of 40 ℃/min, and then the temperature is maintained at 230 ℃ for 5 min.
2. The method according to claim 1, wherein in step (1), the mixing is performed under shaking conditions.
3. The method according to claim 2, wherein in the step (1), the rate of oscillation is 1000 to 5000rpm.
4. The method according to claim 2, wherein in the step (1), the time of the oscillation is 5 to 60min.
5. The method of claim 2, wherein in step (1), the oscillating condition is provided by a vortex oscillator.
6. The method according to claim 1, wherein in the step (1), solid-liquid separation is performed by centrifugation.
7. The method according to claim 6, wherein in the step (1), the rotation speed of the centrifugal treatment is 1000 to 18000rpm.
8. The method according to claim 6, wherein in the step (1), the time for the centrifugal treatment is 1 to 10min.
9. The method according to claim 6, wherein in the step (1), after the centrifugation, the supernatant is collected as a liquid phase.
10. The process according to claim 1, wherein in the step (1), solid-liquid separation is carried out immediately after the mixing is completed.
11. The method according to claim 1, wherein in the step (1), the weight content of water in the acidic stannous chloride ethanol solution is less than or equal to 0.02 percent.
12. The method according to any one of claims 1 to 11, in step (1), characterized by one or more of the following 1) to 6):
1) The proportion of the sample to the acidic stannous chloride ethanol solution is 1 (1-30) g/mL;
2) The weight content of water in the sample is less than or equal to 1 percent;
3) The molar concentration of the stannous chloride in the acidic stannous chloride ethanol solution is 0.1-2 mol/L;
4) The pH value of the acidic stannous chloride ethanol solution is 2-6.5;
5) The acidic stannous chloride ethanol solution contains at least one aqueous solution selected from hydrochloric acid, sulfuric acid and nitric acid;
6) The method further comprises the following steps: storing the liquid phase at a temperature not higher than 10 deg.C.
13. The method of claim 1, wherein the sample is tobacco leaf.
14. The method of claim 1, wherein the sample is selected from flue-cured tobacco leaf, oriental tobacco leaf, and burley tobacco leaf.
15. The method of any one of claims 1 to 11, wherein in step (2), the operating conditions of the gas chromatograph comprise one or more of:
A. the specification of the chromatographic column is 60m multiplied by 320 mu m multiplied by 1.8 mu m;
B. the temperature of a sample inlet is 25-65 ℃;
C. the carrier gas is helium;
D. the flow rate of carrier gas is 1-8 mL/min; E. the split ratio is (2-7) to 1.
16. The method of claim 15 wherein the helium gas has a purity of 99.999% in item C.
17. The method of any one of claims 1 to 11, wherein in step (2), the operating conditions of mass spectrometry comprise one or more of the following a to d:
a. the temperature of the transmission line is 200-260 ℃;
b. the temperature of the ion source is 200-260 ℃;
c. the detection mode is selected ion detection;
d. the detector voltage is 380V.
18. The method according to any one of claims 1 to 11, wherein in step (2), the measurement result is obtained by external standard quantitative analysis.
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