CN103226139A - Process for analyzing gas-phase total components in cigarette mainstream smoke through airbag-thermal desorption-gas chromatography/mass spectrometry method - Google Patents
Process for analyzing gas-phase total components in cigarette mainstream smoke through airbag-thermal desorption-gas chromatography/mass spectrometry method Download PDFInfo
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- 229910052802 copper Inorganic materials 0.000 claims description 9
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- MECFLMNXIXDIOF-UHFFFAOYSA-L zinc;dibutoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CCCCOP([S-])(=S)OCCCC.CCCCOP([S-])(=S)OCCCC MECFLMNXIXDIOF-UHFFFAOYSA-L 0.000 claims description 4
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention relates to a process for analyzing gas-phase total components in a cigarette mainstream smoke through an airbag-thermal desorption-gas chromatography/mass spectrometry method. The process allows an airbag, an adsorption sampling tube, a syringe pump and a thermal desorber-gas chromatograph/mass spectrometer, utilizes the airbag to collect a cigarette mainstream smoke, allows the smoke in the airbag to be adsorbed to the adsorption sampling tube through the syringe pump, and utilizes the thermal desorber-gas chromatograph/mass spectrometer to desorb, age, detect and qualitatively and quantitatively analyze, so the advantages of each of above instruments are used, the repeatability is improved, the relative standard deviations of most measured substances in the gas-phase full components are below 5%, and the repeatability is substantially better than the previously-reported repeatability.
Description
Technical Field
The invention relates to a method for analyzing gas-phase total components in cigarette mainstream smoke by an air bag-thermal desorption-gas/mass combination method, belonging to the technical field of detection and analysis of gas-phase components in cigarette smoke.
Background
Cigarette smoke is a known system with the most complex composition, and more than 5000 chemical components identified from the cigarette smoke exist in two phases of gas and particles at present. According to the research reports at home and abroad, the technical difficulty of selective harm reduction aiming at grain phase components is high, and gas phase components are selectively adsorbed by harm reduction materials of the filter due to high diffusion speed when passing through the filter, so that the key point of selective harm reduction is placed on the gas phase components, but the reproducibility and sensitivity of most gas phase analysis methods are not ideal. In order to correctly evaluate the selective reduction function of the harm reduction material on the cigarette mainstream smoke, research and test work of all gas-phase components in the cigarette mainstream smoke is very necessary.
The gas bag-thermal desorption-gas/mass combination method is used for analyzing the gas phase total components in the cigarette mainstream smoke, the advantages of the gas bag sampling and the thermal desorption technology are combined, firstly, a Tedler gas bag is used for collecting the mainstream smoke of 20 cigarettes, a syringe type injection pump is used for quantitatively transferring a certain volume of smoke into a Carbotrap300 adsorption sampling tube for the first time, and then the thermal desorption technology-gas/mass combination instrument (ATD-GC/MS) method is used for qualitative analysis of the gas phase total components and quantitative analysis of partial compounds in the cigarette mainstream smoke. Because the sampling time, the sampling speed and the volume of the syringe type injection pump are highly controllable and very precise, the repeatability is greatly improved, the relative standard deviation of most of measured objects in all components of gas phase is below 5 percent, and the repeatability is obviously superior to that of the past report.
Disclosure of Invention
The invention aims to overcome the defects and provides a method for analyzing gas phase total components in cigarette mainstream smoke by an air bag-thermal desorption-gas/mass spectrometry.
The invention is realized by the following technical scheme:
an air bag-thermal desorption-gas/mass combination method for analyzing gas-phase total components in cigarette mainstream smoke comprises the following steps:
(1) connecting the air bag to a smoking machine, and collecting main stream smoke generated by the smoking machine;
(2) inserting one end of an adsorption sampling tube into the air bag, connecting one end of the adsorption sampling tube to an injection pump in a sealing manner, pumping cigarette smoke in the air bag into the adsorption sampling tube through the injection pump, and sealing two ends of the adsorption sampling tube by using a sealing copper cap for later use after adsorption is finished;
(3) desorbing and aging the flue gas adsorbed in the adsorption sampling tube by using a thermal desorption instrument, and then detecting by using a gas chromatography/mass spectrometer;
(4) carrying out qualitative analysis on the detection result;
(5) preparing standard samples of smoke component substances to be detected, introducing the standard samples into an adsorption sampling tube, determining the response of each standard sample by using a thermal desorption instrument-gas chromatography/mass spectrometer, establishing a linear regression working curve of the ratio of the chromatographic peak area and the internal standard peak area of each standard sample component to the standard sample concentration, and taking the amount at the 3-time signal-to-noise ratio as the detection limit of the determination method;
(6) and carrying out quantitative analysis on the detection result.
Wherein,
preferably, the smoking machine is a Borgwaldt200A model 20 tunnel rotary smoking machine; the relevant parameters of the turntable smoking machine are set as follows: preheating by a smoking machine at 22 +/-2 ℃ for more than 20 min; the wind speed of the smoking machine is 10-50cm/s, preferably 20-40 cm/s; the smoking machine has a suction capacity of 10-90mL, preferably 30-50 mL.
Preferably, the air bag is a Tedler air bag, so that the deposition of cigarette smoke on the air bag can be reduced; the air bag is connected with the air outlet of the smoking machine through a sampling hose and is used for collecting the main stream smoke of the cigarettes.
Preferably, the injection pump is an LSP02-1B injection pump; the maximum stroke of the syringe pump is 140mm, the stroke resolution: 0.156 μm, line speed range: 5 mu m/min-130 mm/min.
Preferably, the adsorption sampling tube is a three-section composite adsorption sampling tube Carbotrap300, and two ends of the adsorption sampling tube are provided with sealing copper caps; the sealing copper cap is selected from Swagelok copper caps.
Preferably, the thermal desorption instrument is a TurboMatrix ATD thermal desorption instrument; the gas chromatograph/mass spectrometer adopts a HP7890A gas chromatograph and an HP5975C mass spectrometer which are combined; the thermal desorption instrument is connected with the gas chromatography/mass spectrometer through a heating and heat-preserving transmission line.
Preferably, the desorption conditions in the step (3) are as follows: he: 10.0 psi; a valve: 200 ℃; pre-blowing: 1-3 min; first-stage desorption: the temperature is 250-280 ℃, the desorption flow is 40mL/min, the inlet split flow is 40mL/min, and the TenaxTA (60-80 meshes) adsorbent is enriched at-30 ℃; secondary desorption: the temperature is 250-280 ℃, the time is 2min, and the outlet split flow is 30 mL/min. Transmission line temperature: 200-220 ℃.
Preferably, the aging conditions in step (3) are as follows: he: 10.0 psi; a valve: 220 ℃; pre-blowing: 1-3 min; aging temperature: 280-300 ℃; aging time: 30 min; carrier gas flow: 40 mL/min; inlet flow splitting: 40 mL/min.
Preferably, the working conditions of the gas chromatograph/mass spectrometer in the step (3) are as follows: supelco VOCOL capillary column, 60m 0.32mm 1.8 um; temperature programming: 35 deg.C (10min), 3.5 deg.C/min to 180 deg.C, 10 deg.C/min to 210 deg.C (5 min); gas chromatography and mass spectrometer transmission interface temperature: 230 ℃; and (3) a mass spectrometer detection mode: SCAN, scanning range is 10 amu-300 amu.
And (4) performing qualitative analysis by adopting mass spectrum library retrieval.
In the step (5), a methanol solution of the to-be-detected smoke component substances and the internal standard substances with certain concentrations is prepared as working mother liquor, the rest of the standard samples are obtained by diluting the working mother liquor step by using methanol, and the relative proportion of the to-be-detected smoke component substances in each level of the standard samples is 0.05: 0.1: 0.2: 0.5: 1; the content of the internal standard substance in each grade of standard sample is the same; then, the adsorption sampling tube is connected to a sample inlet of a gas chromatograph packed column, and each level of standard sample is introduced into the adsorption sampling tube by using an automatic sample injector; and then, desorbing and aging the standard sample substances adsorbed in the adsorption sampling tube by using a thermal desorption instrument, measuring the response of each standard sample by using a gas chromatography/mass spectrometer, and establishing a working curve.
Preferably, the instrument parameters of the process of introducing the standard sample into the adsorption sampling tube are set as follows: he, constant current: 100mL/min, 20min, sample size: 1.0 μ L, injection port temperature: 150 ℃, furnace temperature: 30 ℃; and (3) setting the operating parameters of the thermal desorption instrument and the gas chromatography/mass spectrometer for analysis in the same step.
Preferably, the internal standard substance is deuterated benzene.
In the step (5), the working curve is a linear regression working curve of the ratio of the chromatographic peak area of the smoke component substances in the standard sample to the chromatographic peak area of the internal standard substance to the concentration of the smoke component substances in the standard sample.
In the step (6), the content (mu g/cig) of the gas phase in the mainstream smoke of each cigarette is calculated according to the chromatographic peak area of each component of the unknown sample, the peak area ratio of the internal standard and the linear regression working curve, and the calculation formula is as follows:
as: the chromatographic peak area of the substance to be detected; a. theIS: internal standard chromatographic peak area; RF: response factors of the standard sample (calculated according to a linear regression working curve); n: the number of suction ports; c: conversion factor
The invention has the technical effects and advantages that:
(1) the air bag collection and the heat desorption pipe are used for collecting and sampling, the advantages of the air bag collection and the heat desorption pipe can be combined to timely collect and store the smoke for a long time, and an operator can simultaneously perform sample loading analysis after continuously collecting the smoke of all cigarettes, so that the working efficiency can be greatly improved
(2) The sampling time, rate and volume of the syringe pump are highly controllable, which can greatly improve the repeatability of the method.
(3) The adsorption-thermal desorption/gas chromatography-mass spectrometry combination is subjected to secondary desorption by a condensation reheating method, and then transferred to a gas chromatograph through a heating and heat-preserving transmission line, so that the effect of high enrichment can be achieved.
(4) The gas circuit of the thermal desorption instrument is redesigned, and no matter what state, the outlet shunting gas sweeps the capillary column inlet all the time, so that the background signal is greatly reduced, and certain contribution is made to improving the sensitivity and the repeatability.
Drawings
FIG. 1 shows a gas bag-thermal desorption gas/mass spectrometry combined analysis apparatus system for analyzing gas phase total components in mainstream smoke of cigarettes
FIG. 2 separation chromatogram of gas phase components on VOCOL analytical column
Reference numerals:
1. an air bag; 2. a flue gas sample inlet; 3. adsorbing a sampling tube; 4. a sampling hose connected with the air bag; 5. an injector; 6. an injection pump; 7. a smoking machine; 8. a cigarette holder; 9. cigarettes; 10. a catcher (a cambridge filter disc is arranged in the catcher); 11. a suction unit; 12. a connection duct to the suction unit.
Detailed Description
The technical solution of the present invention is illustrated by specific examples below. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
A method for analyzing gas phase total components in cigarette mainstream smoke by an air bag-thermal desorption-gas/mass combination method is used for qualitative analysis of certain brand cigarettes, and comprises the following steps: (the device is shown in FIG. 1)
(1) Generating flue gas
Preheating a Borgwaldt200A model 20-channel rotary disc smoking machine at 22 +/-2 ℃ for 20min, adjusting the air speed and the smoking capacity of the smoking machine, and performing the cigarette smoking mode according to the ISO standard. The wind speed of the smoke suction machine is 20 cm/s; the smoking capacity was 35mL, the smoking time was 2s/puff, the interval per puff was 58s, and the smoke of 20 cigarettes was collected by a Tedler air bag.
(2) Diverting flue gas
After the smoke of 20 cigarettes is collected by a Tedler air bag, after 2min, 60mL of smoke is transferred into a Carbontrap300 adsorption sampling tube by using an LSP02-1B injection pump (the maximum stroke of the injection pump is 140mm, the stroke resolution is 0.156 μm, the linear speed range is 5 μm/min-130mm/min, 60 mL/min), and after the transfer is finished, the two ends of the adsorption sampling tube are sealed by a Swagelok copper cap to be tested.
(3) Flue gas composition detection
Desorbing and aging the adsorption sampling tube by using a Turbomatrix ATD thermal desorption instrument, then carrying out flue gas analysis by using an HP7890A gas chromatograph and an HP5975C mass spectrometer, and connecting the thermal desorption instrument with the gas chromatograph/mass spectrometer through a heating and heat-preserving transmission line; the desorption and aging conditions of the adsorption sampling tube on the thermal desorption instrument are as follows:
the desorption conditions are as follows: he, 10.0 psi; a valve: 200 ℃; pre-blowing: 1 min; first-stage desorption: the temperature is 280 ℃, the desorption flow is 40mL/min, the inlet split flow is 40mL/min, and the Tenax TA (60-80 meshes) adsorbent is enriched at minus 30 ℃; secondary desorption: keeping the temperature at 280 ℃ for 2min, and shunting at an outlet for 30 mL/min; transmission line temperature: at 210 ℃.
Aging conditions are as follows: he: 10.0psi, valve: at 220 ℃, pre-blowing: 1min, aging temperature: 300 ℃, aging time: 30min, carrier gas flow: 40mL/min, inlet split: 40 mL/min.
Gas chromatography-mass spectrometry conditions: supelco VOCOL capillary column, 60m 0.32mm 1.8 um; temperature programming: 35 ℃ (10min), 3.5 ℃/min up to 180 ℃, 10 ℃/min up to 210 ℃ (5min), gas chromatography and mass spectrometer transmission interface temperature: 230 ℃; and (3) a mass spectrometer detection mode: SCAN, scanning range is 10 amu-300 amu.
(4) Qualitative analysis
The detection result spectrum was subjected to mass spectrometry using Willey7n.1 library to identify 67 chemical substances, which are shown in FIG. 2 and Table 1.
TABLE 1 gas phase all composition analysis results
Example 2
A method for analyzing gas phase total components in mainstream smoke of cigarettes by an air bag-thermal desorption-gas/mass combination method is used for qualitatively and quantitatively analyzing partial gas phase components of 1, 3-butadiene, isoamyl diene, acrylonitrile, benzene, toluene, styrene, acetone, crotonaldehyde and the like of 2R4F standard cigarettes, and is compared with literature reports:
1. preparation of Standard working curves
When a part of measured components in a mainstream smoke gas phase substance are quantitatively measured by an internal standard method, the internal standard substance adopts deuterated benzene, and a methanol solution of the measured components and the internal standard substance is used as a working mother liquor concentration (5 th-level standard solution, see table 2); diluting the rest standard solutions with methanol step by step. The relative proportion of the concentration of the measured substance in each grade of standard solution is as follows: (1): (2): (3): (4): (5) = 0.05: 0.1: 0.2: 0.5: 1. the internal scalar quantity in each level of standard solution is the same as the working mother solution.
TABLE 21 amounts of each substance in the working mother liquors
| Chemical substance | Content of 1 μ L (μ g) |
| 1, 3-butadiene | 7.2 |
| Isoamyl chloride | 172.6 |
| Acrylonitrile | 8.1 |
| Benzene and its derivatives | 17.6 |
| Toluene | 34.6 |
| Styrene (meth) acrylic acid ester | 2.3 |
| Acetone (II) | 80.0 |
| Crotonaldehyde | 8.6 |
| Dibutanone | 32.4 |
| Butyraldehyde | 16.0 |
| Acetonitrile | 39.5 |
| 2, 5-bis (methylfuran) | 9.0 |
| Ethylbenzene production | 4.3 |
| Deuterated benzene (internal standard) | 19.0 |
Connecting the adsorption sampling tube to a sample inlet of a gas chromatograph packed column, and introducing 1-5-level standard solution into the adsorption sampling tube by using an automatic sample injector; the instrument parameters are as follows: he, constant current: 100mL/min, 20min, sample size: 1.0 μ L, injection port temperature: 150 ℃, furnace temperature: at 30 ℃. Determining the response of each standard substance by using a thermal desorption instrument-gas chromatography/mass spectrometer combined method, and establishing a working curve; the operating parameters of the thermal desorption apparatus and the GC/MS apparatus were set as in example 1.
The working curve verification is shown in table 3:
TABLE 3 Standard working Curve validation
2. The detection process of the smoke components of the 2R4F standard cigarette is the same as that of the example 1.
3. Quantitative analysis
According to the calculation formula: calculating the content of gas-phase components in the mainstream smoke of each cigarette;
wherein, As: the chromatographic peak area of the substance to be detected; AIS: chromatographic peak area of the internal standard; RF: response factors of the standard sample; n: the number of suction ports; c: the number of the conversion factors is such that,
the suction capacity is 35mL/min, the cigarette count is 20, the sampling volume is 60mL, and the analysis result is shown in Table 4: wherein the results of the analysis of each of the substances other than styrene were slightly lower than those of styrene were within the reported range of 2R4F, andand 2R4F, wherein the content mean deviation of the results of isoamyl dilene and acetone and 2R4F is within 5%; while styrene is less effective, primarily because it is a two-phase distribution in mainstream smoke, the analysis herein is directed to the gas phase constituents only. In different cigarette smoke, the two-phase distribution ratio of the styrene is approximately between 0.181 and 0.455, and according to the ratio, the measured result of the styrene is similar to the reported result of 2R 4F. The analysis result of the method is relatively reliable.
TABLE 4 analysis results of gas phase components of part of mainstream smoke in cigarette samples
Claims (10)
1. An air bag-thermal desorption-gas/mass combination method for analyzing gas-phase total components in cigarette mainstream smoke comprises the following steps:
(1) connecting the air bag to a smoking machine, and collecting main stream smoke generated by the smoking machine;
(2) inserting one end of an adsorption sampling tube into the air bag, connecting one end of the adsorption sampling tube to an injection pump in a sealing manner, pumping cigarette smoke in the air bag into the adsorption sampling tube through the injection pump, and sealing two ends of the adsorption sampling tube by using a sealing copper cap for later use after adsorption is finished;
(3) desorbing and aging the flue gas adsorbed in the adsorption sampling tube by using a thermal desorption instrument, and then detecting by using a gas chromatography/mass spectrometer;
(4) carrying out qualitative analysis on the detection result;
(5) preparing standard samples of smoke component substances to be detected, introducing the standard samples into an adsorption sampling tube, determining the response of each standard sample by using a thermal desorption instrument-gas chromatography/mass spectrometer, establishing a linear regression working curve of the ratio of the chromatographic peak area and the internal standard peak area of each standard sample component to the standard sample concentration, and taking the amount at the 3-time signal-to-noise ratio as the detection limit of the determination method;
(6) and carrying out quantitative analysis on the detection result.
2. The method according to claim 1, wherein the smoking machine is a Borgwaldt200A model 20 tunnel rotary smoking machine; the relevant parameters of the turntable smoking machine are set as follows: the preheating temperature is 22 +/-2 ℃, and the preheating time is more than 20 min; the wind speed is 10-50 cm/s; the suction capacity was 10-90 mL.
3. The method of claim 1, wherein the air bag is a Tedler air bag connected to the outlet of the smoking machine by a sampling hose for collecting mainstream smoke from the cigarette.
4. The method of claim 1, wherein the syringe pump is an LSP02-1B syringe pump; the maximum stroke of the syringe pump is 140mm, the stroke resolution: 0.156 μm, line speed range: 5 mu m/min-130 mm/min.
5. The method as claimed in claim 1, wherein the adsorption sampling tube is a three-section composite adsorption sampling tube Carbotrap300, and two ends of the adsorption sampling tube are provided with sealing copper caps; the sealing copper cap is selected from Swagelok copper caps.
6. The method of claim 1, wherein the thermal desorber is a TurboMatrix ATD thermal desorber; the gas chromatograph/mass spectrometer adopts a HP7890A gas chromatograph and an HP5975C mass spectrometer which are combined; the thermal desorption instrument is connected with the gas chromatography/mass spectrometer through a heating and heat-preserving transmission line.
7. The method of claim 7, wherein the desorption conditions in step (3) are as follows: he: 10.0 psi; a valve: 200 ℃; pre-blowing: 1-3 min; first-stage desorption: the temperature is 250-280 ℃, the desorption flow is 40mL/min, the inlet split flow is 40mL/min, and the Tenax TA (60-80 meshes) adsorbent is enriched at-30 ℃; secondary desorption: the temperature is 250-280 ℃, the time is 2min, and the outlet split flow is 30 mL/min. Transmission line temperature: 200-220 ℃.
8. The method of claim 1, wherein the aging conditions of step (3) are: he: 10.0 psi; a valve: 220 ℃; pre-blowing: 1-3 min; aging temperature: 280-300 ℃; aging time: 30 min; carrier gas flow: 40 mL/min; inlet flow splitting: 40 mL/min.
9. The method of claim 1, wherein the operating conditions of the GC/MS in step (3) are: supelco VOCOL capillary column, 60m 0.32mm 1.8 um; temperature programming: 35 deg.C (10min), 3.5 deg.C/min to 180 deg.C, 10 deg.C/min to 210 deg.C (5 min); gas chromatography and mass spectrometer transmission interface temperature: 230 ℃; and (3) a mass spectrometer detection mode: SCAN, scanning range is 10 amu-300 amu.
10. The method according to claim 1, wherein in the step (5), methanol solutions of the to-be-detected smoke component substances and the internal standard substance with certain concentrations are prepared as working mother liquor, and the rest of the standard samples are obtained by diluting the working mother liquor with methanol step by step, wherein the relative ratio of the to-be-detected smoke component substance concentrations in each standard sample is 0.05: 0.1: 0.2: 0.5: 1; the content of the internal standard substance in each grade of standard sample is the same; then, the adsorption sampling tube is connected to a sample inlet of a gas chromatograph packed column, and each level of standard sample is introduced into the adsorption sampling tube by using an automatic sample injector; and then, desorbing and aging the standard sample substances adsorbed in the adsorption sampling tube by using a thermal desorption instrument, measuring the response of each standard sample by using a gas chromatography/mass spectrometer, and establishing a working curve.
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| CN105784887A (en) * | 2016-03-09 | 2016-07-20 | 上海烟草集团有限责任公司 | Ageing device for thermal desorption pipes and ageing method thereof |
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| CN110296874B (en) * | 2019-07-18 | 2022-07-12 | 湖南中烟工业有限责任公司 | Cigarette product smoke trapping device, smoking machine and trapping method |
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